JP2017002094A - Fluorooxyalkylene group-containing polymer modified phosphonic acid derivative and surface treatment agent containing the derivative, article and optical article treated by the surface treatment agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound forming a coated film excellent in water repellent and oil repellent, low dynamic friction, wiping of stain, releasability, abrasion resistance and adhesion to a substrate, a surface treatment agent capable of maintaining performance over long time and having durability containing the same, an article and an optical article treated by the surface treatment agent.SOLUTION: There is provided a fluorooxyalkylene group-containing polymer modified phosphonic acid derivative represented by the formula (1), where A is a monovalent fluorine-containing group with terminal of a -CFgroup or the same group as a group connecting to Rf, B is H, an acyl group or a silyl group, Q is a bivalent connecting group having a silicon atom on both terminals, X is each independently H, an alkali metal atom, an unsubstituted/substituted C1 to 5 alkyl group, aryl group or a monovalent group expressed by JSi-, where J is each independently an unsubstituted/substituted C1 to 5 alkyl group or aryl group and a and b are each independently an integer of 2 to 20.SELECTED DRAWING: None

Description

  The present invention relates to a fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative and a surface treatment agent containing the derivative. Specifically, the article has excellent water and oil repellency and fingerprint wiping properties, and is treated with the surface treatment agent and optical It relates to goods.

  Generally, perfluorooxyalkylene group-containing compounds have characteristics such as water and oil repellency, chemical resistance, lubricity, releasability, and antifouling properties because their surface free energy is very small. Is widely used industrially for water and oil repellent and antifouling agents such as paper and textiles, lubricants for magnetic recording media, oil proofing agents for precision equipment, mold release agents, cosmetics, and protective films. .

  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 directly adhere to the substrate surface.

  On the other hand, a silane coupling agent is well known as a material for bonding a substrate surface such as glass or cloth and an organic compound, 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 (particularly a hydrolyzable silyl group) in one molecule. The hydrolyzable silyl group causes a self-condensation reaction with moisture in the air and forms a film. The coating becomes a strong coating having durability by chemically and / or physically bonding the hydrolyzable silyl group to the surface of glass or cloth.

  In Patent Document 1, a fluorooxyalkylene group-containing polymer-modified silane represented by the following formula (I) is proposed.

(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, each repeating unit And A and B are independently of each other an Rf ² group or a group represented by the following formula (II), and Rf ² is F, H, and a terminal is a —CF ₃ group or — Any one of monovalent fluorine-containing groups which are CF ₂ H groups, Q is a divalent organic group, Z contains a silalkylene structure or a silarylene structure, and does not contain a siloxane bond. 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, and c is an integer of 1 to 5. .)

  The glass treated with the fluorooxyalkylene group-containing silane has excellent dirt wiping properties and can provide a material with excellent adhesion, but it can be directly adhered to a surface other than glass or silicon dioxide (silica). It was difficult.

  Recently, in order to improve the appearance and visibility, there is an increasing demand for technology that makes it difficult to attach fingerprints to the display surface and the housing of electronic devices, and technology that makes it easier to remove dirt. Development of materials that can adhere to surfaces other than (silica) is also desired.

  In addition, as electronic devices change from stationary to portable, and the signal input method shifts from the button method to the touch panel method, the opportunity to directly touch the electronic device is increasing. The types of substrates that need to be easily wiped are diversifying. Examples of the substrate include metal oxides and resins other than glass. Further, the water / oil repellent layer coated on the surface of the touch panel display or wearable terminal preferably has a low coefficient of dynamic friction from the viewpoint of scratch resistance and fingerprint wiping. Therefore, development of a water / oil repellent layer having a low dynamic friction coefficient is also required. Furthermore, since these terminals often perform a dirt wiping operation, wear resistance is required.

JP 2013-1117012 A

  Accordingly, an object of the present invention is to contain a fluorooxyalkylene group that forms a film excellent in water and oil repellency, low dynamic friction, dirt wiping, mold release, abrasion resistance, and adhesion to a substrate. It is an object of the present invention to provide a polymer-modified phosphonic acid derivative, a surface treatment agent comprising the same and having durability capable of maintaining performance over a long period of time, an article treated with the surface treatment agent, and an optical article.

  As a result of intensive studies to solve the above problems, the present inventors have found that the following compound having a fluorooxyalkylene group-containing polymer in the main chain structure and having a phosphonic acid group as a terminal group adheres to the metal oxide. After application, the present inventors have found that a water- and oil-repellent layer excellent in dirt wiping property and low dynamic friction property and excellent in wear resistance can be formed on a metal oxide, thereby completing the present invention.

  That is, the present invention provides the following fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative, a surface treatment agent containing the derivative, an article treated with the surface treatment agent, an optical article, and a touch panel display.

[1]
A fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative 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 - a and, d Each independently represents an integer of 0 to 5, p, q, r, s and t each independently represents an integer of 0 to 200, and p + q + r + s + t is 3 to 200, and each unit shown in parentheses May be bonded randomly, B is a hydrogen atom, acyl group or silyl group, Q is a divalent linking group having silicon atoms at both ends, and X is independently a hydrogen atom or an alkali metal atom. , Unsubstituted or substituted alkyl group having 1 to 5 carbon atoms, aryl group, or J ₃ Si— (J is independently an unsubstituted or substituted alkyl group or aryl group having 1 to 5 carbon atoms.), And a and b are each independently an integer of 2 to 20. )

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

(In Formula (3), d is an integer of 0-5 each independently, p = 1-80, q = 1-80, r = 0-10, s = 0-10, p + q = 5-100. (It is an integer satisfying, and p + q + r + s + t is 10 to 100, and each unit shown in parentheses may be combined randomly.)

[3]
The fluoro according to [1] or [2], wherein Q is a divalent linking group having a silicon atom at both ends, selected from the group consisting of the following formulas (4-1) to (4-4): An oxyalkylene group-containing polymer-modified phosphonic acid derivative.

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

[4]
[1] A surface treating agent comprising at least one of the fluorooxyalkylene group-containing polymer-modified phosphonic acid ester derivatives according to any one of [1] to [3].

[5]
Articles surface-treated with the surface treating agent according to [4].
[6]
Optical article surface-treated with the surface treating agent according to [4].
[7]
A touch panel display treated with the surface treatment agent according to [4].

  The fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the present invention is excellent in adhesion to a substrate, can give a film excellent in water and oil repellency, low dynamic friction, and dirt wiping, and has 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 - a and, d Each independently represents an integer of 0 to 5, p, q, r, s and t each independently represents an integer of 0 to 200, and p + q + r + s + t is 3 to 200, and each unit shown in parentheses May be bonded randomly, B is a hydrogen atom, acyl group or silyl group, Q is a divalent linking group having silicon atoms at both ends, and X is independently a hydrogen atom or an alkali metal atom. , Unsubstituted or substituted alkyl group having 1 to 5 carbon atoms, aryl group, or J ₃ Si— (J is independently an unsubstituted or substituted alkyl group or aryl group having 1 to 5 carbon atoms.), And a and b are each independently an integer of 2 to 20. )

The fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the present invention comprises a monovalent fluorooxyalkylene group or a divalent fluorooxyalkylene group-containing polymer residue (Rf ¹ ) and a phosphonic acid group (— (CH ₂ ) _a. -PO (OH) ₂ ) is a diorganosilylene group such as a dimethylsilylene group, a diethylsilylene group or a diphenylsilylene group, or a diorganopolysiloxane group such as a dimethylpolysiloxane group, a diethylpolysiloxane group or a diphenylpolysiloxane group. It has a structure bonded via a divalent linking group containing a phosphonic acid group at the end.

In the above formula (1), Rf ¹ is 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 combined at random. The total (p + q + r + s + t) of repeating units of the fluorooxyalkylene group is 3 to 200, preferably 10 to 150, and more preferably 15 to 80.
Specific examples of Rf ¹ containing the 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. The upper limit is the same as the upper limit of r, s, t.)

Among them, Rf ¹ is preferably a divalent linear fluorooxyalkylene group represented by the following formula (3) from the viewpoint of low dynamic friction, for applications where importance is attached to slipperiness such as a touch panel.

(In Formula (3), d is an integer of 0-5 each independently, p = 1-80, q = 1-80, r = 0-10, s = 0-10, p + q = 5-100. (It is an integer satisfying, and p + q + r + s + t is 10 to 100, and each unit shown in parentheses may be combined randomly.)

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 following formula (2), and when A is a fluorine-containing group, 6 perfluoro groups are preferred, and —CF ₃ groups and —CF ₂ CF ₃ groups are more preferred.

  In said formula (1) and (2), a and b are the integers of 1-20, However, The integer of 2-10 is preferable.

In the above formula (1) and (2), Q is - (CH ₂₎ a- group and - (CH _{2) b} - is a linking group of the group, an unsubstituted or substituted divalent number from 2 to 40 carbons The organic group is preferably a diorganosilylene group such as a dimethylsilylene group, a diethylsilylene group or a diphenylsilylene group, a diorganopolysiloxane group such as a dimethylpolysiloxane group, a diethylpolysiloxane group or a diphenylpolysiloxane group. 1 type or 2 or more types of groups selected from the group which consists of.

  Here, as the unsubstituted or substituted divalent hydrocarbon group having 1 to 12 carbon atoms, methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group) ), An alkylene group such as a hexamethylene group and an octamethylene group, an arylene group such as a phenylene group, or a divalent group represented by a combination of two or more of these groups (such as an alkylene / arylene group). A part or all of the hydrogen atoms in the group may be substituted with halogen atoms such as fluorine, chlorine, bromine, iodine, etc. Among them, an unsubstituted or substituted alkyl group having 1 to 3 carbon atoms or a phenyl group may be used. preferable.

  For example, Q includes the following groups.

(In the formula, h is an integer of 1 to 10, i is an integer of 2 to 20, Me is a methyl group, and Ph is a phenyl group.)

  In the above formulas (1) and (2), B is a hydrogen atom, an acyl group or a silyl group. Examples of the acyl group include an acetyl group, an acetimidoyl group, a thioacetyl group, and a benzenesulfonyl group. Examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a triisopropylylsilyl group, a triphenylsilyl group, a tert-butyldimethylsilyl group, and a tert-butyldiphenylsilyl group. B is preferably a hydrogen atom or a trimethylsilyl group.

The fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the present invention is a compound represented by the above formula (1), and each X is independently a hydrogen atom, an alkali metal atom, an unsubstituted or substituted carbon atom having 1 to 5 carbon atoms. An alkyl group, an aryl group, or a monovalent group represented by J ₃ Si— (J is independently an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms or an aryl group), 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 excellent in adhesion to a substrate, water and oil repellency, low dynamic friction, releasability, dirt wiping, and abrasion resistance. Can be used effectively for a long time in various coating applications. Further, it is easy to wipe off dirt, and is suitable as a film for spectacle lenses, antireflection films, polarizing plates, TVs, touch panel displays, wearable terminals, tablet PCs, watches, mobile phones, ornaments, 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 in which a terminal unsaturated group is added to a terminal hydroxyl group of a perfluorooxyalkylene group-containing polymer is obtained by a known method.
Next, a fluorooxyalkylene group-containing polymer having two unsaturated bond groups and an organosilicon compound having two SiH bonds are added in a fluorine-based solvent, such as a chloroplatinic acid / vinylsiloxane complex. Under 40-120 ° C., preferably 60-100 ° C., for 1-72 hours, preferably 3-24 hours, after which the solvent and unreacted material are 80-150 ° C., preferably 90 ° C.-120 ° C. By distilling off under reduced pressure, a fluorooxyalkylene group-containing polymer having a SiH group at the end can be obtained. Next, the polymer and a phosphonic acid having an unsaturated bond group at the terminal are added in a fluorine-based solvent at 40 to 120 ° C., preferably 60 to 100 ° C. in the presence of an addition reaction catalyst such as a chloroplatinic acid / vinylsiloxane complex, It is aged for 1 to 72 hours, preferably 3 to 24 hours, and then the solvent and unreacted substances are distilled off under reduced pressure at 80 to 150 ° C., preferably 90 to 120 ° C. Acid esters can be obtained. Furthermore, a fluorooxyalkylene group-containing polymer-modified phosphonic acid can be obtained by hydrolyzing the ester. Hydrolysis can be performed by reacting with a large amount of water in the presence of an acid such as hydrochloric acid or sulfuric acid, and it is preferable to react for 3 hours or more in a reflux state. 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 having two unsaturated bond groups at the molecular chain terminal include those shown below.

  Furthermore, the structure which protected the hydroxyl group of the said structure with the silyl group or the acyl group can be illustrated. Silylation or acylation may be carried out by a known method. For example, a trimethylsilyl group can be introduced by stirring trimethylsilane in the presence of tris (pentafluorophenyl) borane at room temperature (25 ° C.). For example, protection of the acetyl group can be introduced by stirring acetic anhydride at 60 ° C. for 24 hours in the presence of triethylamine and pyridine.

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

  The surface treating agent of the present invention is mainly composed of the fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the present invention.

  The surface treating agent of the present invention may be a mixture of a type having a phosphonic acid group at one end and a type having a phosphonic acid group at both ends. A type having a phosphonic acid group at one end has higher water and oil repellency, a lower dynamic friction coefficient, and excellent wear resistance than a type having a phosphonic acid group at both ends. On the other hand, the type having a phosphonic acid group at both ends is superior to the type having a phosphonic acid group at one end in that the surface can be modified even by thin film coating. Therefore, it is preferable to use as a surface treatment agent by mixing a type having a phosphonic acid group at one end and a type having a phosphonic acid group at both ends in accordance with the application.

  The surface treatment agent of the present invention may contain a non-functional fluorooxyalkylene group-containing polymer, preferably 5 to 120 parts by mass, preferably 100 parts by mass of the one-end hydrolyzable polymer and the both-end hydrolyzable polymer, The inclusion of 10 to 60 parts by mass is advantageous in achieving both a low dynamic friction coefficient and durability.

  The surface treatment agent is preferably applied after being dissolved in a suitable solvent. Such solvents include fluorine-modified aliphatic hydrocarbon solvents (pentafluorobutane, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorocyclohexane, perfluoro1,3-dimethylcyclohexane, etc.), fluorine-modified aromatics Group 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.), hydrocarbon solvents (petroleum benzine, Ral spirits, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ether solvents (tetrahydrofuran, diethyl ether, etc.), ester solvents (ethyl acetate, etc.), alcohol solvents (isopropyl alcohol, etc.) ). Among these, fluorine-modified solvents are preferable in terms of solubility, wettability, and the like. Methyl perfluorobutyl ether, ethyl perfluorobutyl ether, methoxyperfluoroeptene, decafluoropentane, pentafluorobutane, perfluorohexane Hexafluorometaxylene is more preferable, and ethyl perfluorobutyl ether, decafluoropentane, pentafluorobutane, and perfluorohexane are particularly preferable.

  Two or more of these solvents may be mixed. The optimum concentration of the fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative dissolved in the solvent varies depending on the treatment method, but is 0.01 to 50% by mass, particularly 0.03. It is preferably ˜25% by mass.

  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 curing temperature varies depending on the curing method, but is preferably in the range from 80 ° C to 200 ° C. The curing humidity is preferably performed under humidification in order to accelerate the reaction.

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

  The substrate to be treated with the surface treatment agent is not particularly limited, and may be of various materials such as paper, cloth, metal and oxide thereof, glass, plastic, ceramic, quartz, sapphire, sapphire, metal oxide It is preferable that these are imparted with water and oil repellency, low dynamic friction 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 to be 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 displays, organic EL displays, plasma displays, touch panel displays, medical equipment such as eyeglass lenses, camera lenses, lens filters, sunglasses, stomach cameras, photocopiers, protective films, antireflection films An optical article such as Since the surface treatment agent of the present invention can prevent fingerprints and sebum from adhering to the article and easily wipe off dirt, touch panel displays such as eyeglass lenses, smartphones, PCs, smart watches, etc., and transportation equipment It is useful as a water and oil repellent layer for instrument panels.

  Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the following examples.

  The test methods used in Examples and Comparative Examples are as follows.

[Evaluation method of water and oil repellency]
Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), the water contact angle of the cured coating and the contact angle with respect to oleic acid were measured at 25 ° C. and humidity of 40%. The water contact angle was measured 1 second after a 2 μl droplet was deposited on the sample surface. The oleic acid contact angle was measured 1 second after a 4 μl droplet was deposited on the sample surface.

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

[Magic ink wiping properties]
Using the film produced above, oil-based magic (“Hi-Mackey” manufactured by Zebra Co., Ltd.) is applied to the treated surface, and the wiping performance of magic ink after wiping under the following conditions with a rubbing tester (manufactured by Shinto Kagaku) Was visually evaluated using the following indices.
Test environment conditions: 25 ° C, humidity 40%
Wiping material: A tissue paper (Elmore manufactured by Kami Shoji Co., Ltd.) fixed to the tip of the tester that comes into contact with the sample.
Travel distance (one way) 20mm
Movement speed 1800mm / min
Contact area: 10mm x 30mm
Load: 500g
A: It can be wiped off easily and completely by a reciprocating wiping operation.
○: A small amount of ink remains in the reciprocating wiping operation.
Δ: About half of the wiping operation is performed once.
X: It cannot wipe off at all.

[Abrasion resistance test]
Using a reciprocating abrasion tester (HEIDON 30S manufactured by Shinto Kagaku Co., Ltd.), the abrasion resistance test of the cured coating was performed under the following conditions.
Evaluation environmental conditions: 25 ° C, humidity 40%
Rubbing material: 8 sheets of nonwoven fabric were stacked and fixed on the tip (10 mm × 30 mm) of the tester that was in contact with the sample.
Load: 500g
Rubbing distance (one way): 40mm
Rubbing speed: 4,800 mm / min
Number of round trips: 1000 round trips

Example 1
Step (1i)
In a reaction vessel, 150 g of tetrahydrofuran and 300 g of 1,3-bistrifluoromethylbenzene were mixed, and 160 ml of 0.7 M allylmagnesium bromide was optimized. Subsequently, 300 g of the compound represented by the following formula (1a) was slowly optimized and then heated at 60 ° C. for 4 hours.

  After the heating, the solution was cooled to room temperature, and the solution was optimized in 300 g of 1.2 M hydrochloric acid aqueous solution to stop the reaction. The lower fluorine compound layer was recovered by a liquid separation operation and then washed with acetone. After washing, the lower fluorine compound was recovered again, and the solvent and unreacted substances were distilled off to obtain 290 g of the following formula (1b).

Step (1ii)
Next, 20 g of the compound (formula (1b)) obtained in the above step (1i), 30 g of 1,3-trifluoromethylbenzene, 7.6 g of 1,2-bis (dimethylsilyl) ethane, 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 aged 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 confirmed to be the following formula (1c).

Step (1iii)
Next, 20 g of the compound (formula (1c)) obtained in the above step (1ii), 30 g of 1,3-trifluoromethylbenzene, 3.4 g of allylphosphonesanediethyl, toluene solution of chloroplatinic acid / vinylsiloxane complex 0 0.005 g (containing 1.25 × 10 ⁻⁹ mol as a simple substance of Pt) was mixed and aged at 90 ° C. for 48 hours. 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 confirmed to be the following formula (1d).

Step (1iv)
Next, 20 g of the compound (formula (1d)) obtained in the above step (1iii), 30 g of 1,3-trifluoromethylbenzene, 10 g of diethyl ether, and 2.9 g of bromotrimethylsilane are mixed and mixed at 70 ° C. for 24 hours. Aged. 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 confirmed to be the following formula (1e).

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

Step (1v)
Next, 20 g of the compound 1 of the above formula (1e) was optimized to a solution in which 100 g of water and 50 g of acetone were mixed, 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 17 g of a liquid product. It was confirmed by ¹ H-NMR that the obtained mixture was the following formula (1f).

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

Example 2
20 g of the compound obtained by Example 1 (formula (1d)), 30 g of 1,3-trifluoromethylbenzene, 10 g of diethyl ether and 3.250 g of bromotrimethylsilane were mixed and aged at 70 ° C. for 24 hours. 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 confirmed to be the following formula (2e).

In the formula (2e), X is CH ₂ CH ₃ or Si (CH ₃ ) ₃ .
_{CH 2 CH 3: Si (CH} 3) 3 = 59:41
(P / q = 0.9, p + q≈45)

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

Example 3
Step (3i)
20 g of the compound (formula (1b)) obtained in Example 1, 30 g of 1,3-trifluoromethylbenzene, 30 g of 1,4-bis (dimethylsilyl) benzene, toluene solution of chloroplatinic acid / vinylsiloxane complex 005 g (containing 1.25 × 10 ⁻⁹ mol as a simple substance of Pt) was mixed and aged at 80 ° C. for 5 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 21 g of a liquid product. The obtained compound was measured by ¹ H-NMR and 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, 4.0 g of allyl phosphonesanediethyl, toluene solution of chloroplatinic acid / vinylsiloxane complex 0 0.005 g (containing 1.25 × 10 ⁻⁹ mol as a simple substance of Pt) was mixed and aged at 90 ° C. for 48 hours. 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 confirmed to be 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 2.90 g of bromotrimethylsilane are mixed and aged at 70 ° C. for 24 hours. I let you. 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 confirmed to be the following formula (3e).

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

  Furthermore, samples with different main chain number average molecular weights were prepared by supercritical purification of the compound 4. In addition, the number average molecular weight of the compound 4 was 4,380 by 19F-NMR.

  20 g of compound 4 was put in a 25 mL high pressure vessel and heated to 70 ° C. Thereafter, by introducing liquefied carbon dioxide gas, the pressure of the high-pressure vessel was increased to 15 MPa, and the supercritical state was maintained for 30 minutes. Carbon dioxide was flowed at 2 ml / min for 2 minutes, and the sample that flowed out was collected. When this operation was performed from 10 MPa to 22 MPa, the samples (compounds 5 to 12) shown in Table 1 could be collected.

Step (3iv)
Next, 20 g of the above compound 4 was optimized to a solution in which 100 g of water and 50 g of acetone were mixed, 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 17 g of a liquid product. The obtained mixture was confirmed by ¹ H-NMR to be the following formula (3f).

¹ H-NMR (TMS standard, ppm) data of the compound of the above formula (3f) (hereinafter referred to as “compound 13”) are shown below.

  Furthermore, samples having different main chain number average molecular weights were prepared by supercritical purification of the compound 13. In addition, the number average molecular weight of the compound 13 was 4,230 by 19F-NMR.

  20 g of compound 13 was put in a 25 mL high pressure vessel and heated to 70 ° C. Thereafter, by introducing liquefied carbon dioxide gas, the pressure of the high-pressure vessel was increased to 15 MPa, and the supercritical state was maintained for 30 minutes. Carbon dioxide was flowed at 2 ml / min for 2 minutes, and the sample that flowed out was collected. When this operation was performed from 10 MPa to 22 MPa, samples (compounds 14 to 20) shown in Table 2 could be collected.

Example 4
Step (4i)
In a reaction vessel, 150 g of tetrahydrofuran and 300 g of 1,3-bistrifluoromethylbenzene were mixed, and 160 ml of 0.8 M allylmagnesium bromide was optimized. Subsequently, 300 g of the compound represented by the following formula (4a) was slowly optimized and then heated at 60 ° C. for 4 hours.

  After the heating, the solution was cooled to room temperature, and the solution was optimized in 300 g of 1.2 M hydrochloric acid aqueous solution to stop the reaction. The lower fluorine compound layer was recovered by a liquid separation operation and then washed with acetone. After washing, the lower layer fluorine compound was recovered again, and the solvent and unreacted substances were distilled off to obtain 295 g of the following formula (4b).

Step (4ii)
Next, 20 g of the compound (formula (4b)) obtained in the step (4i), 30 g of 1,3-trifluoromethylbenzene, 11.0 g of 1,2-bis (dimethylsilyl) ethane, 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 aged 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 confirmed to be the following formula (4c).

Step (4iii)
Next, 20 g of the compound (formula (4c)) obtained in the above step (4ii), 30 g of 1,3 trifluoromethylbenzene, 4.76 g of allylphosphonesanediethyl, and a toluene solution of a chloroplatinic acid / vinylsiloxane complex, 0.8 g. 005 g (containing 1.25 × 10 ⁻⁹ mol as Pt alone) was mixed and aged at 90 ° C. for 48 hours. 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 confirmed to be the following formula (4d).

Step (4iv)
Next, 20 g of the compound (formula (4d)) obtained in the above step (4iii), 30 g of 1,3 trifluoromethylbenzene, 10 g of diethyl ether and 5.0 g of bromotrimethylsilane are mixed and aged at 70 ° C. for 24 hours. I let you. 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 confirmed to be the following formula (4e).

¹ H-NMR (TMS standard, ppm) data of the compound of the above formula (4e) (hereinafter referred to as “compound 21”) are shown below.

Step (4v)
Next, 20 g of the compound (formula (4e)) obtained in the above step (4iv) was optimized to a solution in which 100 g of water and 50 g of acetone were mixed, 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 18 g of a liquid product. The obtained mixture was confirmed by ¹ H-NMR to be the following formula (4f).

¹ H-NMR (TMS standard, ppm) data of the compound of the above formula (4f) (hereinafter referred to as “compound 22”) are shown below.

Preparation of surface treatment agent and cured coating The perfluorooxyalkylene group-containing polymer-modified phosphonic acid derivative obtained in Examples 1 to 4 was dissolved in a fluorine-based solvent Novec7200 (manufactured by 3M) so as to have a concentration of 10% by mass. Thus, a treatment agent was obtained. After plasma treatment of the surface of the sapphire glass, each of the above surface treatment agents was vacuum-deposited by 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.

[Plasma treatment conditions]
-Equipment: Plasma dry cleaning equipment PDC210
・ Gas: O2 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
・ Vapor deposition temperature (attainment temperature of boat): 500 ℃
・ Vapor deposition distance: 20mm
・ Processing agent charge: 50mg
・ Deposition amount: 50mg

  The surface treatment agents and cured coatings of Comparative Examples 1 to 3 were prepared in the same manner as in Examples except that the following compounds 23 to 25 were used instead of the compounds 1 and 2, and evaluation tests were performed.

Comparative Example 1 Compound 23

Comparative Example 2 Compound 24

Comparative Example 3 Compound 25

  The obtained cured film was evaluated by the following method.

  The evaluation results are shown in Table 3 (initial performance) and Table 4 (wear resistance).

  From Tables 3 and 4, the film formed from the perfluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the example showed high water and oil repellency, low dynamic friction coefficient, and excellent wiping performance of magic ink. . On the other hand, in the comparative example having no phosphonic acid group or phosphonic acid ester group, the water and oil repellency and the dynamic friction coefficient were within the allowable ranges, but the wiping property of the magic ink was poor. Furthermore, the film formed from the perfluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the examples has a high water and oil 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. Indicated. On the other hand, in the comparative example having no phosphonic acid group or phosphonic acid ester group, the water / oil repellency was greatly reduced. That is, the fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the present invention provides a cured film excellent in water / oil repellency, low dynamic friction, dirt wiping, abrasion resistance, and adhesion to a substrate. it can.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. It is contained in the technical range.

Claims (7)

A fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative 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 - a and, d Each independently represents an integer of 0 to 5, p, q, r, s and t each independently represents an integer of 0 to 200, and p + q + r + s + t is 3 to 200, and each unit shown in parentheses May be bonded randomly, B is a hydrogen atom, acyl group or silyl group, Q is a divalent linking group having silicon atoms at both ends, and X is independently a hydrogen atom or an alkali metal atom. , Unsubstituted or substituted alkyl group having 1 to 5 carbon atoms, aryl group, or J ₃ Si— (J is independently an unsubstituted or substituted alkyl group or aryl group having 1 to 5 carbon atoms.), And a and b are each independently an integer of 2 to 20. )

Divalent fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative according to claim 1 is a straight-chain fluorooxyalkylene group represented by Rf ¹ is represented by the following formula (3).
(In Formula (3), d is an integer of 0-5 each independently, p = 1-80, q = 1-80, r = 0-10, s = 0-10, p + q = 5-100. (It is an integer satisfying, and p + q + r + s + t is 10 to 100, and each unit shown in parentheses may be combined randomly.)
The fluorooxyalkylene according to claim 1 or 2, wherein Q is a divalent linking group having a silicon atom at both ends, selected from the group consisting of the following formulas (4-1) to (4-4). Group-containing polymer-modified phosphonic acid derivative.
(In Formulas (4-1) to (4-4), h is an integer of 1 to 10, i is an integer of 1 to 100, and R is independently an unsubstituted or substituted carbon number of 1 to 5. An alkyl group or an aryl group.)   The surface treating agent containing at least 1 sort (s) or more of the fluorooxyalkylene group containing polymer modified phosphonic acid ester derivative of any one of Claims 1-3.   An article surface-treated with the surface treatment agent according to claim 4.   An optical article surface-treated with the surface treatment agent according to claim 4.   A touch panel display treated with the surface treatment agent according to claim 4.