JP6627880B2 - Fluoroxyoxyalkylene group-containing polymer-modified phosphonic acid derivative, surface treatment agent containing the derivative, and surface treatment method using the surface treatment agent - Google Patents

Description

  The present invention relates to a fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative, a surface treatment agent containing the derivative, and a surface treatment method using the surface treatment agent, and in particular, has excellent water / oil repellency and fingerprint wiping property. The present invention relates to a fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative capable of providing a treated surface, a surface treating agent containing the derivative, and a method for treating a surface of an article or an optical article using the surface treating agent.

  In general, perfluorooxyalkylene group-containing compounds have properties such as water and oil repellency, chemical resistance, lubricity, mold release, and antifouling properties because their surface free energy is very small. Utilizing this, it is industrially widely used as a water / oil repellent / soil repellent for paper / fiber, a lubricant for magnetic recording media, an oil repellent for precision equipment, a release agent, a cosmetic, a protective film, and the like.

  However, its properties mean that it is non-adhesive and non-adhesive to other substrates at the same time, and even if a perfluorooxyalkylene group-containing compound can be applied to the substrate surface, It was difficult to make the coating adhere directly to the substrate surface.

  On the other hand, a silane coupling agent is well known as a material for bonding an organic compound to the surface of a substrate such as glass or cloth, and is widely used as a coating agent for various substrate surfaces. The silane coupling agent has an organic functional group and a reactive silyl group (in particular, a hydrolyzable silyl group) in one molecule. The hydrolyzable silyl group causes a self-condensation reaction due to moisture in the air or the like to form a film. The coating becomes a durable and strong coating by the chemical and / or physical bonding of the hydrolyzable silyl group to the surface of glass or cloth.

  Patent Literature 1 proposes a fluorooxyalkylene group-containing polymer-modified silane represented by the following formula (I).

(In the formula (I), Rf ¹ is a divalent linear fluorooxyalkylene group containing 5 to 100 repeating units of —C _d F _2d O— (d is an integer of 1 to 6, and each repeating unit is A and B are, independently of each other, an Rf ² group or a group represented by the following formula (II), wherein Rf ² is F, H, and the terminal is a —CF ₃ group or — A monovalent fluorine-containing group which is a CF ₂ H group, wherein in the following formula (II), Q is a divalent organic group, Z is a silalkylene structure or a silarylene structure, and a siloxane bond. Wherein 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, b is 1 to 6, c is an integer of 1 to 5.)

  Glass treated with the fluorooxyalkylene group-containing silane is excellent in wiping dirt and can provide a material having excellent adhesion, but it is difficult to directly adhere to a surface other than glass or silicon dioxide (silica). It was difficult.

  Recently, there has been an increasing demand for technologies that make it difficult for fingerprints to be attached to the surface of displays and housings of electronic devices and the like to improve appearance and visibility, and technologies that make it easier to remove dirt. Development of a material that can adhere to surfaces other than (silica) is desired.

  In addition, with the shift of electronic devices from stationary type to portable type and signal input type from button type to touch panel type, the number of opportunities to directly touch the electronic device is increasing. The types of substrates that need to be easily wiped have been diversified. Examples of the substrate include metal oxides and resins other than glass. In addition, it is desirable that the water- and oil-repellent layer covering the surface of the touch panel display or the wearable terminal has a low dynamic friction coefficient from the viewpoint of preventing scratches and wiping off fingerprints. Therefore, development of a water- and oil-repellent layer having a low dynamic friction coefficient is also required. In addition, these terminals often perform dirt wiping work, and thus require wear resistance.

JP 2013-11702A

  Therefore, an object of the present invention is to provide a water-repellent oil-repellent property, low dynamic friction property, dirt wiping property, mold release property, abrasion resistance, and a fluorooxyalkylene group-containing film which forms a film excellent in adhesion to a substrate. It is an object of the present invention to provide a polymer-modified phosphonic acid derivative, a surface treatment agent containing the same and having durability capable of maintaining performance for a long period of time, and a method of treating the surface of an article or an optical article with the surface treatment agent.

  The present inventors have conducted intensive studies to solve the above problems, and as a result, have a fluorooxyalkylene group-containing polymer in the main chain structure, and have phosphonic acid groups (alkali metal phosphonate groups and phosphonate ester groups). The following compounds having three at the terminal are capable of forming a water- and oil-repellent layer having excellent abrasion resistance to metal oxides by adhering to the metal oxide, and having excellent wiping properties and low dynamic friction after application. Heading, the present invention has been completed.

  That is, the present invention provides the following fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative and a surface treatment agent containing the derivative, and a step of treating the surface of an article, an optical article, a touch panel display, or the like using the surface treatment agent. Including a surface treatment method. In the present invention, the “phosphonic acid derivative” means that it is at least one selected from phosphonic acid having the modifying group and an alkali metal salt, an alkyl ester, an aryl ester, and a triorganosilyl ester of the phosphonic acid. I do.

[1]
A fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative represented by the following formula (1):

（式（４−１）〜（４−８）中、ｈは２〜１０の整数であり、Ｒはそれぞれ独立に非置換又は置換の炭素数１〜５のアルキル基又は炭素数６〜１０のアリール基である。）

（式（５−１）〜（５−４）中、ｉは１〜１０の整数であり、ｊは１〜１００の整数であり、Ｒはそれぞれ独立に非置換又は置換の炭素数１〜５のアルキル基又は炭素数６〜１０のアリール基である。）

(In the formula (1), A is a monovalent fluorine-containing group whose terminal is a —CF ₃ group, and Rf ¹ 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 - fluoro oxyalkylene group represented by, d are each independently 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 is 3 to 200, and each unit shown in parentheses is randomly B is a single bond or a divalent linking group selected from the group consisting of the following formulas (4-1) to (4-8) , D is a carbon atom or a silicon atom, and E is each independently a single bond, an oxygen atom, either diorganosiloxane group, Q is formula X is a divalent linking group having silicon atoms at both terminals selected from the group consisting of (5-1) to (5-4) , and X is each independently a hydrogen atom, an alkali metal atom, an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms, an aryl group, or J ₃ Si- (J is an unsubstituted or substituted 1 to 5 carbon atoms alkyl or aryl group independently.) in a monovalent group represented by And a and b are each independently an integer of 2 to 20.)

(In the formulas (4-1) to (4-8), h is an integer of 2 to 10, and R is each independently an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms or a C 6-10 alkyl group. An aryl group.)

(In formulas (5-1) to (5-4), i is an integer of 1 to 10, j is an integer of 1 to 100, and R is each independently an unsubstituted or substituted carbon number of 1 to 5. Is an alkyl group or an aryl group having 6 to 10 carbon atoms.)

[2]
A is a perfluoroalkyl group having 1 to 6 carbon atoms,
B is a single bond or a divalent linking group selected from the group consisting of formulas (4-1), (4-2) and (4-3);
The fluorooxy according to [1], wherein Q is a divalent linking group having silicon atoms at both terminals selected from the group consisting of formulas (5-1), (5-2) and (5-4). An alkylene group-containing polymer-modified phosphonic acid derivative.

(In the formulas (4-1) to (4-3), h is an integer of 2 to 10, and in the formulas (5-1), (5-2) and (5-4), i is 1 to 10. J is an integer of 1 to 100, and R is each independently an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.)

[ 3 ]
The fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative according to [1] or [2] , wherein Rf ¹ is a divalent linear fluorooxyalkylene group represented by the following formula (3).

（式（３）中、ｄはそれぞれ独立に０〜５の整数であり、ｐ＝１〜８０、ｑ＝１〜８０、ｒ＝０〜１０、ｓ＝０〜１０、ｐ＋ｑ＝５〜１００を満たす整数であり、かつ、ｐ＋ｑ＋ｒ＋ｓは１０〜１００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。）

(In the formula (3), d is each independently an integer of 0 to 5, p = 1 to 80, q = 1 to 80, r = 0 to 10, s = 0 to 10, and p + q = 5 to 100. It is an integer that satisfies, p + q + r + s is 10 to 100, and each unit shown in parentheses may be randomly bonded.)

[ 4 ]
[1] to a surface treatment agent containing at least one of the fluorooxyalkylene group-containing polymer-modified phosphonic San誘 conductor according to any one of [3].

[ 5 ]
A method for treating the surface of an article, comprising a step of treating the surface of the article using the surface treating agent according to [ 4 ].
[ 6 ]
A surface treatment method for an optical article, comprising a step of treating the surface of the optical article using the surface treatment agent according to [ 4 ].
[ 7 ]
A surface treatment method for a touch panel display, comprising a step of treating the surface of the touch panel display using the surface treatment agent according to [ 4 ].

  The fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the present invention has excellent adhesion to a substrate, and can provide a coating excellent in water / oil repellency, low dynamic friction, and dirt wiping properties, and can be used for various coatings. It can be used effectively for a long period of time.

  Hereinafter, the present invention will be described in more detail.

  The fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the present invention is represented by the following formula (1).

(In the formula (1), A is a monovalent fluorine-containing group whose terminal is a —CF ₃ group or a group represented by the following formula (2), and Rf ¹ 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 - fluoro represented by An oxyalkylene group, d is each independently 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 is 3 to 200; Each unit shown in parentheses may be randomly bonded, B is a single bond or a divalent linking group having an unsubstituted or substituted alkylene structure at any terminal, and D is a carbon atom or a silicon atom. Atom and E are independently connected , An oxygen atom, or a diorganosiloxane group, Q is a divalent linking group having silicon atoms at both ends, and X is each independently a hydrogen atom, an alkali metal atom, an unsubstituted or substituted carbon number. 1-5 alkyl group, a monovalent group represented by aryl group, or J ₃ Si- (J is an unsubstituted or substituted alkyl or aryl group of 1 to 5 carbon atoms independently.), a and b are each independently an integer of 2 to 20.)

(In the formula (2), B, D, E, Q, X, a and b each have the same meaning as the formula (1).)

The fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the present invention may be a monovalent fluorooxyalkylene group-containing polymer residue (A-Rf ¹ ) whose terminal is blocked with a —CF ₃ group, or a divalent fluorooxyalkylene. The group-containing polymer residue (Rf ¹ ) and the phosphonic acid group ((— (CH ₂ ) _b —PO (OH) ₂ ) or (— (CH ₂ ) _b —PO (OX) ₂ ) are converted to dimethylsilylene Group, a diorganosilylene group such as a diethylsilylene group or a diphenylsilylene group, or a divalent linking group containing any one of a diorganopolysiloxane group such as a dimethylpolysiloxane group, a diethylpolysiloxane group, and a diphenylpolysiloxane group. It has a bonded structure, and has three phosphonic acid groups at one end of the molecular chain, or three at each end of the molecular chain. Is (i.e., a total of six in one molecule) having phosphonic acid or a derivative thereof (an alkali metal salt of said phosphonic acid, alkyl esters, aryl esters and at least one selected from the triorganosilyl ester).

In the above formula (1), Rf ¹ is a linear or branched fluorooxyalkylene group represented by the following formula.

In the formula, d is each independently 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 is 3 to 200, and is shown in parentheses. Each unit may be linked randomly. The total (p + q + r + s + t) of the repeating units of the fluorooxyalkylene group is from 3 to 200, preferably from 10 to 150, more preferably from 15 to 80.
Specific examples of Rf ¹ containing the above repeating unit include the following.

(Wherein, d 'is the same as d, p' is the same as p, q 'is the same as q, and r', s ', and t' are each an integer of 1 or more. , And the upper limit is the same as the upper limit of r, s, and t.)

Above all, for applications where importance is placed on slipperiness, such as touch panels, Rf ¹ is preferably a divalent linear fluorooxyalkylene group represented by the following formula (3) from the viewpoint of low dynamic friction.

(In the formula (3), d is each independently an integer of 0 to 5, p = 1 to 80, q = 1 to 80, r = 0 to 10, s = 0 to 10, and p + q = 5 to 100. It is an integer that satisfies, p + q + r + s is 10 to 100, and each unit shown in parentheses may be randomly bonded.)

In the above formula (1), A is a monovalent fluorine-containing group whose terminal is a —CF ₃ group or a group represented by the above formula (2), and when A is a fluorine-containing group (that is, In the case where A-Rf ¹ is a monovalent fluorooxyalkylene group-containing polymer residue having a terminal CF ₃ group blocked, A is a perfluoroalkyl group having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms. Among them, a —CF ₃ group and a —CF ₂ CF ₃ group are more preferable.

  In the above formulas (1) and (2), a and b are integers of 2 to 20, preferably 2 to 10.

In the above formula (1) and (2), Q is a divalent silicon-containing linking group having a silicon atom at both terminals, - _{(CH 2) a} - group and - _{(CH 2) b} - the base It is a linking group, and is preferably a divalent silicon-containing organic group having 4 to 120 carbon atoms, particularly 6 to 80 carbon atoms, particularly 6 to 40 carbon atoms. The organic group is a diorganopolysiloxane group such as a dimethylpolysiloxane group, a diethylpolysiloxane group, a diphenylpolysiloxane group, a methylphenylpolysiloxane group, or an unsubstituted or substituted C1-C12 group. One type selected from the group consisting of divalent silicon-containing organic groups each of which is terminated with a diorganosilylene group such as a dimethylsilylene group, a diethylsilylene group, or a diphenylsilylene group at both terminals of the divalent hydrocarbon group, or It is preferable to use two or more types.

  Here, as the hydrocarbon group in the unsubstituted or substituted divalent hydrocarbon group having 1 to 12 carbon atoms, both ends of which are blocked with a diorganosilylene group, methylene group, ethylene group, propylene group (trimethylene group, Methylene group), butylene group (tetramethylene group, methylpropylene group), alkylene group such as hexamethylene group, octamethylene group, arylene group such as phenylene group, norbornyl group, or a combination of two or more of these groups (alkylene group) An arylene group, a norbornyl-alkylene group, etc.), in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, chlorine, bromine, and iodine. It may be present, and among them, an unsubstituted or substituted alkylene group having 1 to 3 carbon atoms or a phenylene group is preferable.

In the above formulas (1) and (2), B is a single bond or a divalent linking group having an unsubstituted or substituted alkylene structure at either end, and the fluorooxyalkylene group-containing polymer residue (Rf ¹ ) And a carbon or silicon atom (D). The divalent linking group includes, for example, an unsubstituted or halogen-substituted alkylene structure having 1 to 20, preferably 2 to 12 carbon atoms in its structure, and includes an oxygen atom (ether bond), an amide Containing one or more heteroatom-containing structures such as a group, an N-methyl-substituted amide group, an N-phenyl-substituted amide group, a phenylene group, a diorganosilylene group, a triorganosilyl group, and a silanol group. There may be. Specific examples of B include a single bond or a divalent linking group shown below.

(In the formula, h is an integer of 2 to 10, and Me is a methyl group.)

(In the formula, h is an integer of 2 to 10, and Me is a methyl group.)

  For example, Q includes the following groups.

(In the formula, i is an integer of 1 to 10, j is an integer of 1 to 100, Me is a methyl group, and Ph is a phenyl group.)

The fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the present invention is a compound represented by the above formula (1), wherein X is each independently a hydrogen atom, an alkali metal atom, an unsubstituted or substituted carbon atom having 1 to 5 carbon atoms. alkyl group, an aryl group, or J ₃ Si- (J is independently an unsubstituted or substituted alkyl or aryl group having 1 to 5 carbon atoms.) is a monovalent group represented by, where Examples of the alkali metal include sodium and potassium.

  The fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the present invention provides a cured film having excellent adhesion to a substrate, water / oil repellency, low dynamic friction, mold release, dirt wiping, and abrasion resistance. And can be effectively used for a long time in various coating applications. Also, it is easy to wipe off dirt, and is suitable as a coating for spectacle lenses, antireflection films, polarizing plates, TVs, touch panel displays, wearable terminals, tablet PCs, watches, mobile phones, decorative articles, and precision molds.

The fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative represented by the above formula (1) can be produced, for example, by the following method.
First, a compound having three unsaturated bonding groups added to the terminal of a perfluorooxyalkylene group-containing polymer is obtained by a known method.
Next, a fluorooxyalkylene group-containing polymer having three unsaturated bond groups at the terminal and an organosilicon compound having two SiH bonds are added in a fluorine-based solvent to an addition reaction catalyst such as a chloroplatinic acid / vinylsiloxane complex. Under a temperature of 40 to 120 ° C., preferably 60 to 100 ° C., for 1 to 72 hours, preferably 3 to 24 hours, after which the solvent and unreacted materials are reacted at 80 to 150 ° C., preferably 90 to 120 ° C. By distilling off under reduced pressure, a fluorooxyalkylene group-containing polymer having a terminal SiH group can be obtained.
Next, the polymer and a phosphonic acid ester having an unsaturated bond group at a terminal thereof are reacted at 40 to 120 ° C., preferably 60 to 100 ° C. in a fluorine-based solvent in the presence of an addition reaction catalyst such as a chloroplatinic acid / vinylsiloxane complex. , For 1 to 72 hours, preferably 3 to 24 hours, and thereafter, the solvent and unreacted substances are distilled off under reduced pressure at 80 to 150 ° C, preferably 90 to 120 ° C, to thereby modify the fluorooxyalkylene group-containing polymer. A phosphonate ester can be obtained.
Furthermore, a fluorooxyalkylene group-containing polymer-modified phosphonic acid can be obtained by hydrolyzing the ester. The hydrolysis can be carried out by reacting with a large amount of water in the presence of an acid such as hydrochloric acid or sulfuric acid. Further, when the ester group is a trimethylsilyl ester group, a fluorooxyalkylene group-containing polymer-modified phosphonic acid can be obtained only by stirring with water at room temperature.

  Examples of the fluorooxyalkylene group-containing polymer having three unsaturated bonding groups at the molecular chain terminals include the following.

Examples of Rf ¹ in the above formula include the following structures.

  The surface treating agent of the present invention contains the fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the present invention as a main component.

  In the surface treatment agent of the present invention, a type having a phosphonic acid group at one end and a type having a phosphonic acid group at both ends may be mixed. The type having a phosphonic acid group at one end has higher water / oil repellency, a lower dynamic friction coefficient, and is superior in abrasion resistance as compared with the type having a phosphonic acid group at both ends. On the other hand, the type having phosphonic acid groups at both ends is superior to the type having phosphonic acid groups at one end in that surface modification is possible even in thin film coating. Therefore, it is preferable to mix a type having a phosphonic acid group at one end with a type having a phosphonic acid group at both ends and use it as a surface treatment agent according to the application.

  Further, the surface treatment agent of the present invention may contain a non-functional fluorooxyalkylene group-containing polymer, and the non-functional fluorooxyalkylene group-containing polymer is a total of one-terminal hydrolyzable polymer and both-terminal hydrolysable polymer. It is advantageous to include 5 to 120 parts by mass, preferably 10 to 60 parts by mass with respect to 100 parts by mass in order to achieve both a low dynamic friction coefficient and durability.

  In addition, the surface treatment agent may contain a solvent in addition to the non-functional fluorooxyalkylene group-containing polymer, and it is preferable that the surface treatment agent is dissolved in an appropriate solvent before coating. Examples of such a solvent include fluorine-modified aliphatic hydrocarbon solvents (pentafluorobutane, decafluoropentane, perfluorohexane, perfluoroheptane, methoxyperfluoroheptene, perfluorooctane, perfluorocyclohexane, perfluoro1, 3-dimethylcyclohexane, etc.), fluorine-modified aromatic hydrocarbon solvents (m-xylenehexafluoride, 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, perfluorotripe) Butylamine, petroleum benzene, mineral spirits, toluene, xylene, etc., ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ether solvents (tetrahydrofuran, diethyl ether, etc.), ester solvents ( Examples thereof include ethyl acetate and the like, and alcohol solvents (such as isopropyl alcohol). Of these, fluorine-modified solvents are preferable in terms of solubility, wettability, etc., and methyl perfluorobutyl ether, ethyl perfluorobutyl ether, methoxyperfluoroheptene, decafluoropentane, pentafluorobutane, and perfluorohexane are preferred. And m-xylene hexafluoride are more preferable, and ethyl perfluorobutyl ether, decafluoropentane, pentafluorobutane and perfluorohexane are particularly preferable.

  The solvent may be a mixture of two or more kinds thereof. The optimum concentration of the fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative to be dissolved in the solvent varies depending on the treatment method, but is 0.01 to 50% by mass, particularly 0.03% by mass. It is preferably about 25% by mass.

  The surface treating agent can be applied to the substrate by a known method such as a wet coating method (brush coating, dipping, spraying, inkjet), a vapor deposition method, and the like. The curing temperature varies depending on the curing method, but is preferably in the range of 80 ° C to 200 ° C. The curing humidity is preferably performed under humidification in order to accelerate the reaction.

  The thickness of the cured film (fluorine layer) is preferably 50 nm or less, particularly preferably 2 to 20 nm, and more preferably 4 to 15 nm.

  The substrate treated with the surface treatment agent is not particularly limited, and may be of various materials such as paper, cloth, metal and oxides thereof, glass, plastic, ceramic, quartz, and sapphire. It is preferable that they have water and oil repellency, low dynamic friction properties, and antifouling properties.

The surface of the substrate may be subjected to a hard coat treatment or an antireflection treatment. In order to further improve the adhesion, as a primer layer, a metal oxide layer (TiO ₂ , Al ₂ O ₃ , ZrO ₂ , Ta ₂ O ₅ , ITO, AgO, CuO, etc.) treatment, vacuum plasma treatment, atmospheric pressure Known treatment methods such as plasma treatment, itro treatment, UV treatment, VUV (vacuum ultraviolet) treatment, alkali treatment, and acid treatment may be used.

  Articles treated with the surface treatment 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 operation panels Liquid crystal display, organic EL display, plasma display, touch panel display, medical equipment such as spectacle lens, camera lens, lens filter, sunglasses, gastric camera, copier, protective film, anti-reflection film And other optical articles. Further, it can be used as a nozzle for an ink jet printer or a spray device, or as a liquid repellent for resist. Since the surface treatment agent of the present invention prevents fingerprints, sebum, and oil from adhering to the article and can easily wipe off dirt, it is particularly useful for eyeglass lenses, smartphones, PCs, touch panel displays such as smart watches, and transportation. It is particularly useful as a water- and oil-repellent layer of an instrument panel of a device.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

  The test methods used in the examples and comparative examples are as follows.

[Method of evaluating water / oil repellency]
Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), the water contact angle of the cured film and the contact angle with oleic acid were measured at 25 ° C. and 40% humidity. The water contact angle was measured one second after a 2 μl droplet was deposited on the sample surface. The oleic acid contact angle was measured one second after a 4 μl droplet was deposited on the sample surface.

[Dynamic friction coefficient]
The dynamic friction coefficient with respect to Bencott (made by Asahi Kasei Corporation) was measured using a surface property tester (HEIDON 14FW manufactured by Shinto Kagaku Co., Ltd.) under the following conditions.
Contact area: 10 mm x 30 mm
Load: 100g

[Magic ink wiping properties]
Using the cured film prepared below, apply an oil-based magic ("Hi Mackey" manufactured by Zebra Corporation) to the treated surface, and wipe off the magic ink after wiping with a rubbing tester (manufactured by Shinto Kagaku) under the following conditions. Was visually evaluated using the following indices.
Test environment conditions: 25 ° C, humidity 40%
Wipe material: Tissue paper (Kami Shoji Co., Ltd. Elmore) fixed to the tip of the tester that comes in contact with the sample.
Travel distance (one way): 20mm
Moving speed: 1800mm / min
Contact area: 10 mm x 30 mm
Load: 500g
◎: It can be easily and completely wiped off by one round trip wiping operation.
： １: A small amount of ink remains in the reciprocating wiping operation.
Δ: About half the ink remains in the reciprocating wiping operation.
X: It cannot be wiped off at all.

[Wear resistance test]
Using a reciprocating abrasion tester (HEIDON 30S manufactured by Shinto Kagaku Co., Ltd.), an abrasion resistance test of the cured film was performed under the following conditions.
Evaluation environment conditions: 25 ° C, humidity 40%
Abrasive material: Eight nonwoven fabrics were stacked and fixed on the tip (10 mm × 30 mm) of a tester that was in contact with the sample.
Load: 1kg
Rubbing distance (one way): 40mm
Rubbing speed: 4,800 mm / min
Number of round trips: 3000 round trips

Example 1
Step (1i)
150 g of tetrahydrofuran and 300 g of 1,3-bistrifluoromethylbenzene were mixed into a reaction vessel, and 160 ml of a 0.7 M (molar concentration) allylmagnesium bromide solution was added dropwise. Subsequently, after slowly adding 300 g of the compound represented by the following formula (1a), the mixture was heated at 60 ° C. for 4 hours.

  After completion of the heating, the mixture was cooled to room temperature, and the solution was dropped into 300 g of a 1.2 M aqueous hydrochloric acid solution to stop the reaction. After the lower layer of the fluorine compound layer was recovered by a liquid separation operation, the layer was washed with acetone. The lower fluorine compound layer after the washing was recovered again, and the solvent and unreacted materials were distilled off to obtain 301 g of the following formula (1b).

  300 g of the compound (1b), 50 g of allyl bromide, and 0.6 g of tetrabutylammonium iodide were mixed. Subsequently, after adding 23 g of sodium hydroxide, the mixture was heated at 70 ° C. for 6 hours. After completion of the heating, the mixture was cooled to room temperature, and an aqueous hydrochloric acid solution was added dropwise. After the lower layer of the fluorine compound layer was recovered by a liquid separation operation, the layer was washed with acetone. The lower fluorine compound layer after the washing was recovered again, and the remaining solvent was distilled off under reduced pressure. By repeating the above operation, 295 g of the following formula (1c) was obtained.

Step (1ii)
Next, 20 g of the compound (formula (1c)) obtained in the above step (1i), 30 g of 1,3-trifluoromethylbenzene, 7.6 g of 1,2-bis (dimethylsilyl) ethane, and chloroplatinic acid / vinyl 0.005 g of a toluene solution of a siloxane complex (containing 1.25 × 10 ⁻⁹ mol as Pt alone) was mixed and reacted at 80 ° C. for 3 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 20 g of a liquid product. The obtained compound was measured by ¹ H-NMR, and it was confirmed that the compound represented by the following formula (1d).

Step (1iii)
Next, 20 g of the compound (formula (1d)) obtained in the above step (1ii), 30 g of 1,3-trifluoromethylbenzene, 5.1 g of diethyl allylphosphonate, and a toluene solution of chloroplatinic acid / vinylsiloxane complex 0 0.005 g (containing 1.25 × 10 ⁻⁹ mol as Pt alone) was reacted at 90 ° C. for 48 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 21 g of a liquid product. The obtained mixture was measured by ¹ H-NMR, and was confirmed to be the following formula (1e).

Step (1iv)
Next, 20 g of the compound (formula (1e)) obtained in the above step (1iii), 30 g of 1,3-trifluoromethylbenzene, 10 g of diethyl ether and 4.4 g of bromotrimethylsilane were mixed, and the mixture was mixed at 70 ° C. for 24 hours. Reacted. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 20 g of a liquid product. The obtained mixture was measured by ¹ H-NMR, and was confirmed to be the following formula (1f).

¹ H-NMR (TMS standard, ppm) data of the compound of the above formula (1f) (hereinafter, referred to as “compound 1”) is shown below.

Step (1v)
Next, 20 g of the compound 1 of the formula (1f) was added to a solution obtained by mixing 100 g of water and 50 g of acetone, and the mixture was stirred at 20 ° C. for 3 hours and allowed to stand for 1 hour. Thereafter, the lower layer was taken out and the solvent was distilled off under reduced pressure to obtain 15 g of a liquid product. The obtained mixture was confirmed to be the following formula (1 g) by ¹ H-NMR.

The ¹ H-NMR (TMS standard, ppm) data of the compound of the above formula (1 g) (hereinafter, referred to as “compound 2”) is shown below.

Example 2
Step (2i)
20 g of the compound (formula (1c)) obtained in Example 1, 30 g of 1,3-trifluoromethylbenzene, 45 g of 1,4-bis (dimethylsilyl) benzene, and a toluene solution of a chloroplatinic acid / vinylsiloxane complex were added. 005 g (containing 1.25 × 10 ⁻⁹ mol as Pt alone) were reacted at 80 ° C. for 5 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 23 g of a liquid product. The obtained compound was measured by ¹ H-NMR, and it was confirmed that the compound represented by the following formula (2c).

Step (2ii)
Next, 20 g of the compound (formula (2c)) obtained in the above step (2i), 30 g of 1,3-trifluoromethylbenzene, 6.0 g of diethyl allylphosphonate, and a toluene solution of chloroplatinic acid / vinylsiloxane complex 0 0.005 g (containing 1.25 × 10 ⁻⁹ mol as Pt alone) was reacted at 90 ° C. for 48 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 25 g of a liquid product. The obtained mixture was measured by ¹ H-NMR, and it was confirmed that the mixture represented by the following formula (2d).

Step (2iii)
Next, 20 g of the compound (formula (2d)) obtained in the above step (2ii), 30 g of 1,3 trifluoromethylbenzene, 10 g of diethyl ether and 5.5 g of bromotrimethylsilane were mixed, and reacted at 70 ° C. for 24 hours. I let it. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 21 g of a liquid product. The obtained mixture was measured by ¹ H-NMR, and was confirmed to be the following formula (2e).

¹ H-NMR (TMS standard, ppm) data of the compound of the above formula (2e) (hereinafter, referred to as “compound 3”) is shown below.

Example 3
Step (3i)

20 g of the compound represented by the above formula (3b), 30 g of 1,3-trifluoromethylbenzene, 45 g of 1,4-bis (dimethylsilyl) benzene, 0.005 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (as Pt alone) 1.25 × 10 ⁻⁹ mol) and reacted at 80 ° C. for 5 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 22 g of a liquid product. The obtained compound was measured by ¹ H-NMR, and it was confirmed to be the following formula (3c).

Step (3ii)
Next, 20 g of the compound (formula (3c)) obtained in the above step (3i), 30 g of 1,3-trifluoromethylbenzene, 7.0 g of diethyl allylphosphonate, and a toluene solution of chloroplatinic acid / vinylsiloxane complex 0 0.005 g (containing 1.25 × 10 ⁻⁹ mol as Pt alone) was reacted at 90 ° C. for 48 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 28 g of a liquid product. The obtained mixture was measured by ¹ H-NMR, and it was confirmed that the mixture represented by the following formula (3d).

Step (3iii)
Next, 20 g of the compound (formula (3d)) obtained in the above step (3ii), 30 g of 1,3 trifluoromethylbenzene, 10 g of diethyl ether, and 6.0 g of bromotrimethylsilane were mixed, and reacted at 70 ° C. for 24 hours. I let it. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 21 g of a liquid product. The obtained mixture was measured by ¹ H-NMR, and it was confirmed that the mixture represented by the following formula (3e).

The ¹ H-NMR (TMS standard, ppm) data of the compound of the above formula (3e) (hereinafter, referred to as “compound 4”) is shown below.

Preparation of Surface Treatment Agent and Cured Coating The perfluorooxyalkylene group-containing polymer-modified phosphonic acid derivative compounds 1 to 4 obtained in Examples 1 to 3 were mixed with a fluorine-based solvent Novec7200 (manufactured by 3M) so that the concentration became 10% by mass. ) To give a treating agent. After the surface of the sapphire glass was subjected to the plasma treatment, each of the above surface treatment agents was applied by vacuum deposition under the following conditions and apparatus. After curing for 1 hour in an atmosphere of 80 ° C. and 80% humidity, the coating was cured at 150 ° C. for 3 hours to form a coating.

[Plasma treatment conditions]
-Equipment: Plasma dry cleaning equipment PDC210
Gas: _{O 2} gas 80cc, Ar gas 10cc
・ Output: 250W
・ Time: 30 seconds

[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
・ Evaporation temperature (attainable temperature of boat): 500 ° C
・ Evaporation distance: 20mm
・ Amount of treatment agent: 50mg
・ Evaporation amount: 50mg

  The surface treatment agents and the cured films of Comparative Examples 1 and 2 were prepared in the same manner as in the Examples except that the following Compounds 5 and 6 were used instead of Compounds 1 to 4, and evaluation tests were performed.

(Comparative Example 1) Compound 5

(Comparative Example 2) Compound 6

  The obtained cured film was evaluated by the above method.

  The evaluation results are shown in Table 1 (initial performance) and Table 2 (wear resistance).

  From Tables 1 and 2, the films formed from the perfluorooxyalkylene group-containing polymer-modified phosphonic acid derivatives of Examples 1 to 4 have high water / oil repellency, low dynamic friction coefficient, and low wiping properties of magic ink. It was excellent. On the other hand, in the coatings of Comparative Examples 1 and 2 formed from a compound having no phosphonic acid group or phosphonic acid ester group, the water and oil repellency and the dynamic friction coefficient were within the allowable range, but the wiping property of the magic ink was poor. It was bad. Furthermore, the coatings formed from the perfluorooxyalkylene group-containing polymer-modified phosphonic acid derivatives of Examples 1 to 4 have high water repellency, such as a water contact angle of 100 degrees or more and an oleic acid contact angle of 60 degrees or more even after rubbing with a cloth. It showed oil repellency. On the other hand, in the coating films of Comparative Examples 1 and 2 formed from compounds having no phosphonic acid group or phosphonic acid ester group, the water / oil repellency was significantly reduced. That is, the fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the present invention provides a cured film having excellent water / oil repellency, low dynamic friction, dirt wiping, abrasion resistance, and adhesion to a substrate. I knew I could do it.

  Note that the present invention is not limited to the above embodiment. The above embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and has the same effect. It is included in the technical range.

Claims (7)

A fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative represented by the following formula (1):

(In equation (1),
A is a monovalent fluorine-containing group whose terminal is a —CF ₃ group,
Rf ¹ 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} - fluoro oxyalkylene group represented by,
d is each independently 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 is 3 to 200, and the units shown in parentheses may be randomly bonded.
B is a single bond or a divalent linking group selected from the group consisting of the following formulas (4-1) to (4-8) ;
D is a carbon atom or a silicon atom,
E is each independently a single bond, an oxygen atom, or a diorganosiloxane group;
Q is a divalent linking group having silicon atoms at both ends selected from the group consisting of the following formulas (5-1) to (5-4) ;
X is each independently a hydrogen atom, an alkali metal atom, an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms, an aryl group, or J ₃ Si— (J is independently an unsubstituted or substituted An alkyl group or an aryl group.)
a and b are each independently an integer of 2 to 20; )

(In the formulas (4-1) to (4-8), h is an integer of 2 to 10, and R is each independently an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms or a C 6-10 alkyl group. An aryl group.)

(In formulas (5-1) to (5-4), i is an integer of 1 to 10, j is an integer of 1 to 100, and R is each independently an unsubstituted or substituted carbon number of 1 to 5. Is an alkyl group or an aryl group having 6 to 10 carbon atoms.) A is a perfluoroalkyl group having 1 to 6 carbon atoms,
B is a single bond or a divalent linking group selected from the group consisting of formulas (4-1), (4-2) and (4-3);
The fluorooxy according to claim 1, wherein Q is a divalent linking group having silicon atoms at both terminals selected from the group consisting of formulas (5-1), (5-2) and (5-4). An alkylene group-containing polymer-modified phosphonic acid derivative.

(In the formulas (4-1) to (4-3), h is an integer of 2 to 10.)

(In the formulas (5-1), (5-2) and (5-4), i is an integer of 1 to 10, j is an integer of 1 to 100, and R is each independently unsubstituted or substituted Is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.) The fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative according to claim 1 or 2 , wherein Rf ¹ is a divalent linear fluorooxyalkylene group represented by the following formula (3).

(In the formula (3), d is each independently an integer of 0 to 5, p = 1 to 80, q = 1 to 80, r = 0 to 10, s = 0 to 10, and p + q = 5 to 100. It is an integer that satisfies, p + q + r + s is 10 to 100, and each unit shown in parentheses may be randomly bonded.) Surface treatment agent containing at least one of the fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative according to any one of claims 1-3. A method for treating a surface of an article, comprising a step of treating the surface of the article with the surface treating agent according to claim 4 . A surface treatment method for an optical article, comprising a step of treating the surface of the optical article with the surface treatment agent according to claim 4 . A surface treatment method for a touch panel display, comprising a step of treating the surface of the touch panel display with the surface treatment agent according to claim 4 .