TW201708308A - Polymer-modified phosphonic acid derivative containing fluorinated oxyalkylene group, surface treatment agent comprising the same, article to be treated with the surface treatment agent, and optical article treated with the surface treatment agent capable of forming a coating film having water and oil repellency, low dynamic friction, detergency, mold releasability, abrasion resistance and excellent adhesion to a substrate - Google Patents

Abstract

The present invention provides a polymer-modified phosphonic acid derivative containing fluorinated oxyalkylene group characterized by the following formula (1), a surface treatment agent containing the derivative, an article treated with the surface treatment agent, and an optical article treated with the surface treatment agent. The compound is capable of forming a coating film having water and oil repellency, low dynamic friction, detergency, mold releasability, abrasion resistance and excellent adhesion to a substrate, and the surface treatment agent is capable of maintaining these excellent properties for a long period of time and durability.

Description

a polymer modified phosphonic acid derivative containing a fluorooxyalkylene group, a surface treating agent comprising the same, an article treated with the surface treating agent, and an optical article treated with the surface treating agent

The present invention relates to a fluorine-containing oxyalkylene-containing polymer-modified phosphonic acid derivative, a surface treatment agent containing the derivative, an article treated with the surface treatment agent, and an optical article treated with the surface treatment agent In particular, a polymer modified phosphonic acid derivative containing a fluorine-containing oxyalkylene group excellent in water repellency and fingerprint erasability, a surface treating agent containing the same, and a surface treating agent treated therewith An article and an optical article treated with the surface treatment agent.

In general, a compound containing a perfluorooxyalkylene group has characteristics such as water repellency, chemical resistance, lubricity, mold release property, and antifouling property because of its very small surface free energy, and its properties are used in the industry. In terms of production, it is widely used in water- and oil-repellent antifouling agents such as paper and fiber, lubricants for magnetic recording media, precision mechanical oil-repellent agents, mold release agents, cosmetic materials, and protective films.

However, its nature also means non-adhesiveness and non-adhesiveness to other substrates at the same time. Even if a compound containing a perfluorooxyalkylene group can be coated on the surface of a substrate, it is difficult to directly adhere the film to the surface of the substrate.

On the other hand, as a material for bonding a surface of a substrate such as glass or cloth to an organic compound, a decane coupling agent is widely known, and is widely used as a coating agent for various substrate surfaces. The decane coupling agent has an organic functional group and a reactive germyl group (particularly a hydrolyzable formyl group) in one molecule. The hydrolyzable formyl group undergoes a self-condensation reaction by moisture or the like in the air to form a film. The film is chemically and/or physically bonded to the surface of glass, cloth, etc. by its hydrolyzable formyl group to form a durable film having durability.

In the patent document (JP-A-2013-117012), a polymer-modified decane containing a fluorooxyalkylene group represented by the following formula I is proposed. [Chemical Formula I]

In Formula I, Rf ¹ is a divalent linear fluorooxyalkylene group having a repeating unit of 5 to 100-C _d F _2d O- (d is an integer of 1 to 6, and each repeating unit may also be used. For different). A and B are groups independently of each other, represented by Rf ² group or by the following formula II. Rf ² is any one of F, H and a monovalent fluorine-containing group having a -CF ₃ group or a -CF ₂ H group at the terminal. In the following formula II, Q is a divalent organic group, and Z is a 2- to 7-valent linking group having a polyalkylene structure or a polyarylene structure and having no siloxane structure, and R is a carbon atom. An alkyl group or a phenyl group having 1 to 4, X is a hydrolyzable group, a is an integer of 2 or 3, b is an integer of 1 to 6, and c is an integer of 1 to 5. [Chemical Formula II]

As a glass which has been treated with the fluorinated alkylene group-containing decane, it is possible to obtain a material excellent in detergency and adhesion, but it is difficult to directly form a surface other than glass and cerium oxide (alumina). Sticky.

Recently, in order to optimize the appearance and definition, the technology for attaching a fingerprint to a surface of a display and an outer casing of an electromechanical device, and the technique of easy decontamination have been increasing year by year. It is expected that the development of materials that can adhere to surfaces other than glass and cerium oxide (alumina) is expected.

As the electronic machine shifts from the fixed type to the mobile type and the signal input mode from the button mode to the touch panel mode, the number of substrates that are difficult to attach fingerprint processing or easy to decontaminate is required due to an increase in the chance of directly touching the electronic machine. Become diversified. Other than glass, the substrate may be a metal oxide or a resin. Further, the water-repellent oil layer coated on the surface of the touch panel display and the mobile terminal is expected to have a low dynamic friction coefficient from the viewpoint of preventing damage and erasing fingerprints. Therefore, it is also necessary to develop a water-repellent oil-repellent layer having a low dynamic friction coefficient. Further, these terminals also need to have wear resistance due to the large number of decontamination operations.

In view of the above problems, an object of the present invention is to provide a surface treatment agent having durability, an article treated with the surface treatment agent, and an optical article treated with the surface treatment agent, the surface treatment agent containing formation The film having excellent water-repellent property, low dynamic friction property, detergency, mold release property, abrasion resistance, and adhesion to a substrate contains a polymer-modified phosphonic acid derivative having a fluorooxyalkylene group.

The inventors have found that the phosphonic acid group can adhere to a large number of metal oxides in order to achieve the above objective. Further, it has been found that a treatment agent comprising a polymer having a fluorine-oxyalkylene group-containing polymer excellent in detergency and low dynamic friction property in the main chain structure and having a phosphonic acid group at a terminal group, which is a metal oxide The present invention can be completed by forming a water-repellent oil-repellent layer excellent in abrasion resistance.

That is, the present invention provides the following polymer-modified phosphonic acid derivative containing a fluorooxyalkylene group, a surface treating agent comprising the same, an article which has been treated with the surface treating agent, and having been subjected to the surface treatment An optical article that is treated with a dose and a touch panel display that has been treated with the surface treatment agent.

The technical means for solving the problems of the prior art is to provide a polymer modified phosphonic acid derivative containing a fluorooxyalkylene group, wherein: it is represented by the following formula 1, [Chemical Formula 1] In Formula 1, A is a monovalent fluorine-containing group having a terminal -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 -, d are independently 0~ The integers of 5, p, q, r, s, and t are each an integer of 0 to 200, respectively, and p+q+r+s+t is 3 to 200, and each unit represented by the parentheses may be randomly bonded, and Q ¹ is arbitrary. a divalent linking group having an alkylene structure at the terminal, Q ² is a divalent linking group having a halogen atom at both terminals, and X is independently a hydrogen atom, an alkali metal atom, an unsubstituted or substituted carbon atom a number of 1 to 5 alkyl groups, aryl groups or a monovalent group represented by J ₃ Si- (J is independently an unsubstituted or substituted alkyl group or aryl group having 1 to 5 carbon atoms), a is An integer from 2 to 20. [Chemical Formula 2]

In one embodiment of the present invention, there is provided a polymer modified phosphonic acid derivative containing a fluorooxyalkylene group, wherein: Rf ¹ is a divalent linear oxyfluoride represented by the following formula 3. Alkyl group, [Chemical Formula 3] -(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 -O(CF ₂ ) _d - In Equation 3, d is independently an integer from 0 to 5, and p = 1 to 80, q = 1 to 80, r = 0 to 10, s = 0 to 10, and p + q = 5 to 100. An integer, and p+q+r+s+t is 10~100, and each unit represented in parentheses can also be randomly bonded.

In one embodiment of the present invention, there is provided a polymer modified phosphonic acid derivative containing a fluorooxyalkylene group, wherein: Q ¹ is selected from the group consisting of the following formula 4-1 to formula 4-8 Valence linking group, [Chemical Formula 4-1~ 4-8] In Formula 4-1 to Formula 4-8, h is an integer of 2 to 10, and R is independently an unsubstituted or substituted alkyl group or aryl group having 1 to 5 carbon atoms.

In one embodiment of the present invention, there is provided a polymer modified phosphonic acid derivative containing a fluorooxyalkylene group, wherein: the Q ² is selected from the following formula 5-1 to formula 5-4; a divalent linking group having a deuterium atom at both ends, [Chemical Formula 5-1 to 5-4] In Formula 5-1 to Formula 5-4, i is an integer of 1 to 10, j is an integer of 1 to 100, and R is independently an unsubstituted or substituted alkyl group or aryl group having 1 to 5 carbon atoms. .

The present invention provides a surface treatment agent for solving the problems of the prior art, wherein: it contains at least one of the above-mentioned polymer modified phosphonic acid containing a fluorooxyalkylene group as described above. derivative.

The technical means employed by the present invention to solve the problems of the prior art provides an article in which it is surface-treated with the surface treating agent described above.

The technical means employed by the present invention to solve the problems of the prior art provides an optical article wherein it is surface treated with the surface treating agent described above.

The technical means employed by the present invention to solve the problems of the prior art provides a touch panel display in which it is surface-treated with a surface treating agent as described above.

A film obtained by curing a fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the present invention by a technical means employed in the present invention, which is adhered to by a phosphonic acid group via a linking group The surface of the metal oxide. The fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the present invention has a surface excellent in fingerprint erasability and low dynamic friction property because it has a polymer containing a fluorooxyalkylene group.

The fluoroalkylene oxide-containing polymer-modified phosphonic acid derivative of the present invention can provide a film excellent in adhesion to a substrate, water repellency, low dynamic friction, and stain release property, and can be effectively used for a long period of time. Used in a variety of coating applications.

The specific embodiments of the present invention will be further described by the following examples and the accompanying drawings.

Embodiments of the invention will be described below. This description is not intended to limit the embodiments of the invention, but is an embodiment of the invention.

The fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the present invention is represented by the following formula 1. [Chemical Formula 1]

In Formula 1, A is a monovalent fluorine-containing group having a terminal -CF ₃ group or a group represented by the following formula 2. 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 -. d is independently an integer of 0 to 5, and 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 represented by brackets. Each unit can also be randomly bonded. Q ¹ is a divalent linking group having an alkylene structure at any terminal, and Q ² is a divalent linking group having a deuterium atom at both terminals, and X is independently a hydrogen atom, an alkali metal atom, and an unsubstituted Or a substituted alkyl group having 1 to 5 carbon atoms, an aryl group or a group represented by J ₃ Si—(J is independently an unsubstituted or substituted alkyl group or aryl group having 1 to 5 carbon atoms) A valence group, a is an integer from 2 to 20. [Chemical Formula 2]

The fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the present invention has a structure in which a polymer residue (Rf ¹ ) containing a monovalent fluorooxyalkylene group or a divalent fluorooxyalkylene group is present. Via a divalent linking group containing a quinonealkyl structure or a fluorene arylene structure with a phosphonic acid group (-(CH ₂ ) _a -PO(OH) ₂ ) or a phosphonate group (-(CH ₂ ) _a -PO(OX) ₂ ) bonding.

In the above formula 1, Rf ¹ is represented by -(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 -

Wherein d is independently an integer of 0 to 5, and 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 represented by the parenthesis may be absent. Rule bonding. The total number of repeating units of the fluorooxyalkylene group (p+q+r+s+t) is from 3 to 200, preferably from 10 to 150, more preferably from 15 to 80.

The Rf ¹ containing the above repeating unit can be specifically exemplified as follows. Wherein, ^{d, of} the above-described d are the same, ^{p, is} of the p-identical, ^q, with ^the above-described q ^{same, r,, s,, t} , integer of 1 or more, respectively, the upper limit of the above r, s The upper limit of t is the same.

In particular, Rf ¹ is preferably used in a field where slidability is important for a touch panel or the like from the viewpoint of low dynamic friction properties of the divalent linear oxyalkylene oxide group represented by the following formula 3. [Chemical Formula 3] -(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 -O(CF ₂ ) _d -

In Equation 3, d is independently an integer of 0 to 5, and satisfies p=1 to 80, q=1 to 80, r=0 to 10, s=0 to 10, and p+q=5 to 100. An integer, and p+q+r+s+t is 10~100, and each unit represented in parentheses can also be randomly bonded.

In the above formula 1, A is a monovalent fluorine-containing group having a terminal -CF ₃ group, or a group represented by the following formula 2, and in the case where A is a fluorine-containing group, it is preferably a carbon number of 1 a perfluoro group of ~6, more preferably a -CF ₃ group or a -CF ₂ CF ₃ group. [Chemical Formula 2]

In the above formulas 1 and 2, a is an integer of 2 to 20, and preferably an integer of 3 to 10.

In the above formulas 1 and 2, Q ¹ is a divalent linking group having an alkylene structure at any terminal, and Q ² is a divalent linking group having a deuterium atom at both terminals, and X is independently a hydrogen atom, an alkali metal atom, an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms, an aryl group or an alkyl group having 1 to 5 carbon atoms which are unsubstituted or substituted by J ₃ Si—(J independently The monovalent group represented by the group or the aryl group may be a group obtained by substituting a part of hydrogen atoms or all hydrogen atoms of these groups with a halogen atom such as fluorine, chlorine, bromine or iodine. Further, examples of the alkali metal include sodium and potassium.

For example, the following groups are exemplified as Q ¹ . 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.

Further, examples of Q ² include the following groups. In the formula, i is an integer of 1 to 10, and Me is a methyl group.

As a combination of Q ¹ and Q ^2, for example, it may include the following groups. In the formula, h is an integer of 2 to 10, i is an integer of 1 to 10, and Me is a methyl group.

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

The fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the present invention is particularly excellent in adhesion to a metal oxide. Although the adhesion mechanism of the phosphonic acid group or phosphonate group to the surface of the metal oxide is not clear, it is considered that the phosphonic acid group or the phosphonate group is chemically bonded to the surface of the metal oxide or the phosphonic acid group or the phosphonic acid. The ester group is adsorbed on the surface of the metal oxide to form a film. Therefore, it is considered that if a polymer modified phosphonic acid derivative containing a fluorooxyalkylene group is coated on the surface of a metal oxide, the oxyalkylene oxide is easily oriented to the outermost surface, and the phosphonic acid group or the phosphonic acid is preferred. The ester group is easily oriented on the side of the metal oxide, thereby providing a film excellent in water repellency, low dynamic friction, mold release property, and stain release property.

Therefore, the fluorooxyalkylene group-containing polymer modified phosphonic acid derivative of the present invention can form adhesion to a substrate, water repellency, low dynamic friction, mold release property, stain release property, and abrasion resistance. A cured film excellent in damage properties, and can be used effectively in various coating fields for a long time. In addition, since it is easy to decontaminate, it is suitable as a film for an ophthalmic lens, an antireflection film, a polarizing plate, a TV, a touch panel display, a mobile phone, a clock, a portable terminal, an ornament, and a precision mold.

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 obtained by adding an unsaturated group to a hydroxyl group at the terminal of a polymer containing a perfluorooxyalkylene group is obtained by a conventional method. As this method, for example, the following compound can be obtained by reacting allyl bromide in the presence of a base such as tetrabutylammonium hydrogen sulfate and sodium hydroxide, followed by treatment with hydrochloric acid. Where p1/q1=1.0, the average of p1+q1 is average=45

Further, by subjecting the above-mentioned compound containing a perfluorooxyalkylene to a quinone or a arylene compound having a SiH bond at both terminals, for example, 1,4-bis(dimethylformamido)benzene The reaction is then carried out with diethyl allylphosphonate to give the following compound. The addition reaction may be carried out under conventional reaction conditions, or may be carried out in the presence of an addition reaction catalyst such as a platinum compound.

Further, by reacting the above-mentioned perfluorooxyalkylene group-containing polymer with trimethylformamidine bromide and trimethylformamidine iodide, the following polymer can be obtained. The addition reaction may be carried out under conventional reaction conditions, and the reaction may be carried out by stirring only for three days at room temperature.

Further, by hydrolyzing the above-mentioned polymer containing a perfluoroalkylene group with water, the following polymer can be obtained.

Further, the present invention provides a surface treatment agent containing at least one or more of the fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the present invention. The surface treating agent of the present invention may also be a type in which a terminal having a phosphonic acid group or a phosphonate group is mixed with a type having a phosphonic acid group or a phosphonate group at both terminals. If the type having a phosphonic acid group or a phosphonate group at one end is compared with a type having a phosphonic acid group or a phosphonate group at both terminals, a dialing type having a phosphonic acid group or a phosphonate group at one end is used. It has higher oiliness, lower dynamic friction coefficient and better wear resistance. The type having a phosphonic acid group or a phosphonate group at both ends can be surface-modified even if it is a coating film. Therefore, it is preferred to use a type having a phosphonic acid group or a phosphonate group at one end and a type having a phosphonic acid group or a phosphonate group at both terminals as a surface treating agent depending on the use.

Further, the surface treatment agent of the present invention may also include a polymer containing a non-functional fluorooxyalkylene group. The amount of use of the one terminal hydrolyzable polymer and the two terminal hydrolyzable polymer is preferably from 5 to 120 parts by mass, preferably from 10 to 60 parts by mass, in terms of a low dynamic friction coefficient and durability.

Further, the surface treatment agent of the present invention is preferably coated after dissolving it in a suitable solvent. As such a solvent, a fluorine-modified aliphatic hydrocarbon solvent (pentafluorobutane, decafluoropentane, perfluorohexane, perfluoroheptane, methoxyperfluoroheptene, perfluorooctane, Perfluorocyclohexane, perfluoro1,3-dimethylcyclohexane, etc.), fluorine-modified aromatic hydrocarbon solvent (hexafluorometa-xylene, m-xylene hexafluoride, trifluorotoluene, 1,3) -trifluoromethylbenzene, etc., fluorine-modified ether solvent (methyl perfluoropropyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc., fluorine Modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (petroleum, mineral alcohol, toluene, xylene, etc.), ketone solvents (acetone, methyl b) An ketone, a methyl isobutyl ketone or the like), an ether solvent (such as tetrahydrofuran or diethyl ether), an ester solvent (such as ethyl acetate), or an alcohol solvent (such as isopropyl alcohol). Among these, from the viewpoint of solubility, wettability, and the like, a solvent which has been modified with fluorine is preferable. More preferably, it is methyl perfluorobutylether, ethyl perfluorobutylether, methoxy perfluoroheptene, decafluoropentane, pentafluorobutane, perfluorohexane, hexafluoro-m-xylene, and especially preferably B. Perfluorobutyl ether and decafluoropentane, pentafluorobutane, perfluorohexane.

The above solvents may be mixed in two or more kinds. 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 preferably 0.01 to 50% by mass, particularly preferably 0.03%. 25 mass percent.

The surface treatment agent can be applied to the substrate according to a conventional method such as a wet coating method (brushing, dipping, spraying, inkjet) or a vapor deposition method. Further, although the curing temperature varies depending on the curing method, it is preferably in the range of 80 ° C to 200 ° C. As the curing humidity, it is preferred to carry out the reaction under humidification from the viewpoint of promoting the reaction.

Further, the film 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 above surface treatment agent is not particularly limited, and examples thereof include various materials such as paper, cloth, metal, and oxides thereof, glass, plastic, ceramics, quartz, and sapphire. Among them, sapphire and metal oxide are preferable. These materials can be given water and oil repellency, low dynamic friction and antifouling properties.

The surface of the substrate can also be subjected to hard coating treatment and anti-reflection treatment. In the case of poor adhesion, as a bottom layer, it can be treated by a metal oxide layer (Ti0 ₂ , AI ₂ O ₃ , Zr0 ₂ , Ta ₂ 0 ₅ , ITO, AgO, and CuO, etc.), vacuum plasma Conventional treatment methods such as treatment, atmospheric pressure plasma treatment, in vitro treatment, UV treatment, VUV (vacuum ultraviolet treatment), alkali treatment, acid treatment, etc., improve adhesion.

As articles treated with the surface treatment agent of the present invention, it can be cited for use in a car navigation system, a car audio, a tablet computer, a smart phone, a wearable terminal, a mobile phone, a digital camera, a digital camera, a PDA, and a portable audio player. Medical devices such as liquid crystal displays, organic EL displays, plasma displays, touch panel displays and ophthalmic lenses, camera lenses, photographic filters, sunglasses, gastroscopes, etc. for machines, game consoles, various operation panels, electronic bulletins, etc. Optical articles such as photocopiers, protective films, anti-reflective films, etc. The surface treatment agent of the present invention can prevent fingerprints and sebum from adhering to the article, and is easy to wipe off dirt, especially as a touch panel display for optical glasses, smart phones, PCs, smart watches, and the like. The water-repellent layer of the board is useful.

[Examples]

The present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited by the following examples.

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

[Evaluation method of water and oil repellency]

The water contact angle of the cured film and the contact angle with oleic acid were measured under the conditions of a temperature of 25 ° C and a humidity of 40% using a contact angle meter (DropMaster manufactured by Japan Concord Interface Science Co., Ltd.). Here, after 2 μl of the droplet was dropped on the surface of the sample, the water contact angle was measured after 1 second. After 4 μl of the droplet was dropped on the surface of the sample, the oleic acid contact angle was measured after 1 second.

[Dynamic friction coefficient]

The dynamic friction coefficient with respect to BEMCOT (manufactured by Asahi Kasei Corporation, Japan) was measured under the following conditions using a surface tester (HEIDON 14FW manufactured by Shinto Scientific Co., Ltd.).

Contact area: 10mm × 30mm

Load: 100g

[marker ink erasability]

Using the film produced as described above, an oil-based marker ink ("Hi-Mckee" manufactured by ZEBRA Co., Ltd.) was applied to the treated surface, and the film was wiped under the following conditions by using a friction tester (manufactured by Nippon Shinko Scientific Co., Ltd.). The erasability of the marker ink was visually evaluated using the following indicators.

Experimental environmental conditions: temperature 25 ° C, humidity 40%

Erase material: A paper towel (Ellemoi manufactured by Kami Trading Co., Ltd.) was attached to the front end of the measuring instrument in contact with the test material.

Moving distance: (one way) 20mm

Movement speed: 1800mm/min

Contact area: 10mm × 30mm

Load: 500g

◎: It is simply and completely erased after a reciprocating erase operation.

○: A little ink remains after a reciprocating erase operation.

△: About half of the ink remains after one reciprocating erasing operation.

×: The ink was not erased at all.

[Abrasion resistance test]

The abrasion resistance test of the cured film was carried out under the following conditions using a reciprocating wear tester (HEIDON 30S manufactured by Shinto Scientific Co., Ltd.).

Experimental environmental conditions: temperature 25 ° C, humidity 40%

Friction material: 8 sheets of the nonwoven fabric were superposed and fixed to the front end portion (10 mm × 30 mm) of the measuring instrument in contact with the test material.

Load: 500g

Friction distance: (one way) 40mm

Friction speed: 4800mm/min

Number of reciprocations: 500 reciprocations

Example 1

A mixture consisting of 60% of the following formula (1a), 38% of the formula (1b), and 2% of the formula (1c) was used. This mixture was produced by partially fluorinating a perfluorooxy compound having a carboxylic acid group at both ends (FOMBLIN ZDIAC4000 manufactured by Solvay Solexis Co., Ltd.) using fluorine gas. Separation was carried out by adsorbing an acid adsorbent with a polymer having a carboxylic acid, and the content (molar %, the same hereinafter) of each polymer was determined by ¹⁹ F-NMR. [Chemical Formula 1a~1c]

Process (1i)

In the reaction vessel, a mixture of 600 g of the above formula (1a) 60%, the above formula (1b) 38%, and the above formula (1c) 12% was dissolved in 5.4 kg of a fluorine-based solvent (manufactured by PF5060 3M Co., Ltd.). . Next, 1.2 kg of an anion exchange resin B20-HG (manufactured by ORGANO Co., Ltd.) was added, and the mixture was stirred at 20 ° C for 3 hours to adsorb the components of the formula 1a and the formula 1b on the anion exchange resin. Then, after washing the anion exchange resin with PF5060, 6 kg of PF5060 was mixed with the resin, 0.1N hydrochloric acid was added in an appropriate amount, and the mixture was stirred at 20 ° C for 2 hours. After stirring, it was allowed to stand for 30 minutes to be divided into two layers. That is, the lower layer is a fluorine layer, and the upper layer is a mixed layer of hydrochloric acid and a resin. The fluorine layer was extracted, and PF5060 was distilled off to obtain 87 g of a liquid product. The obtained mixture was measured by ¹⁹ F-NMR to obtain the above formula 1a.

Process (1ii)

50 g of the compound (formula 1a) obtained in the above reaction was dissolved in a mixed solvent of 40 g of 1,3-(trifluoromethyl)benzene and 10 g of tetrahydrofuran, and then 30 g of bis(2-methoxyl) was added dropwise. A solution of sodium ethoxy)aluminum hydride in 40% toluene. After stirring at room temperature for 3 hours, an appropriate amount of hydrochloric acid was added, followed by thorough stirring and washing with water. Further, the lower layer was taken out, and the solvent was distilled off to obtain 42 g of a liquid product. The obtained mixture was measured by ¹⁹ F-NMR and ¹ H-NMR to confirm that it was represented by the following formula 1d. [Chemical Formula 1d]

Process (1iii)

40 g of the compound (formula 1d) obtained in the above process (1ii) and 3.5 g of allyl bromide and 0.4 g of tetrabutylammonium hydrogen sulfate and 5.2 g of a 30% aqueous sodium hydroxide solution were added dropwise to the reaction. After the vessel was stirred at 60 ° C for 3 hours. Then, PF5060 (a fluorine-based solvent manufactured by 3M Company) and hydrochloric acid were added in an appropriate amount, and the mixture was stirred, and then sufficiently washed with water. Further, the lower layer was taken out, and the solvent was distilled off to obtain 35 g of a liquid product. The obtained mixture was measured by ¹ H-NMR to confirm that it was represented by the following formula 1e. [Chemical Formula 1e]

Process (1iv)

Next, 20 g of the compound (formula 1e) obtained in the above process (1iii) and 30 g of 1,3-trifluoromethylbenzene and 3.8 g of 1,2-bis(dimethylformamido) were added. Ethane and 0.005 g of a toluene solution of chloroplatinic acid/vinyloxirane complex (containing 1.25 × 10 ^-9 mol as a Pt unit) were mixed and aged at 80 ° C for 3 hours. Then, the solvent and the unreacted material were distilled off under reduced pressure to obtain 19 g of a liquid product. The obtained mixture was measured by ¹ H-NMR to confirm that it was represented by the following formula 1f. [Chemical Formula 1f]

Process (1v)

Next, 19 g of the compound (formula 1f) obtained in the above process (1iv) and 30 g of 1,3-trifluoromethylbenzene and 1.7 g of diethyl allylphosphonate and 0.005 g of chlorine were used. A toluene solution of a platinum acid/vinyl siloxane complex (containing 1.25 × 10 ^-9 moles as a Pt unit) was mixed and aged at 90 ° C for 48 hours. Then, the solvent and the unreacted material were distilled off under reduced pressure to obtain 20 g of a liquid product. The obtained mixture was measured by ¹ H-NMR to confirm that it was represented by the following formula 1g. [Chemical Formula 1g]

Craft (1vi)

Next, 20 g of the compound (formula 1g) obtained in the above process (1v) and 30 g of 1,3-trifluoromethylbenzene and 10 g of diethyl ether and 1.45 g of trimethylbromodecane were subjected. Mix and mature at 70 ° C for 24 hours. Then, the solvent and the unreacted material were distilled off under reduced pressure to obtain 21 g of a liquid product. The obtained mixture was measured by ¹ H-NMR to confirm that it was represented by the following formula 1h. [Chemical Formula 1h]

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

Craft (1vii)

Next, 20 g of the compound 1 obtained in the above process (1vi) was dropwise added to a solution in which 100 g of water and 50 g of acetone were mixed, and the mixture was stirred at 20 ° C for 3 hours and allowed to stand for 1 hour. Then, 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 measured by ¹ H-NMR to confirm that it was represented by the following formula 1i. [Chemical Formula 1i]

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

Example 2

20 g of the compound (formula 1g) obtained in the above Example 1 and 30 g of 1,3-trifluoromethylbenzene and 10 g of diethyl ether and 1.725 g of trimethylbromodecane were mixed at 70 Matured at °C for 24 hours. Then, the solvent and the unreacted product were distilled off under reduced pressure to obtain 20 g of a liquid product. The obtained mixture was measured by ¹ H-NMR to confirm that it was represented by the following formula 2h. [Chemical Formula 2h] In Formula 2h, X is CH ₂ CH ₃ or Si(CH ₃ ) ₃ . Wherein CH ₂ CH ₃ :Si(CH ₃ ) ₃ =61:39, p/q=0.9, p+q≒45.

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

Example 3

Process (3i)

20 g of the compound (Formula 1e) obtained in Example 1 and 30 g of 1,3-trifluoromethylbenzene and 15 g of 1,4-bis(dimethylformamido)benzene and 0.005 g of chlorine A toluene solution of a platinum acid/vinyl siloxane complex (containing 1.25 × 10 ^-9 mol as a Pt unit) was mixed, and aged at 80 ° C for 5 hours. Then, the solvent and the unreacted material were distilled off under reduced pressure to obtain 21 g of a liquid product. The obtained compound was measured by ¹ H-NMR to confirm that it was represented by the following formula 3f. [Chemical Formula 3f]

Process (3ii)

Next, 20 g of the compound (formula 3f) obtained in the above process (3i) and 30 g of 1,3-trifluoromethylbenzene and 2.0 g of diethyl allylphosphonate and 0.005 g of chlorine were used. A toluene solution of a platinum acid/vinyl siloxane complex (containing 1.25 × 10 ^-9 moles as a Pt unit) was mixed and aged at 90 ° C for 48 hours. Then, the solvent and the unreacted material were distilled off under reduced pressure to obtain 20 g of a liquid product. The obtained mixture was measured by ¹ H-NMR to confirm that it was represented by the following formula 3g. [Chemical Formula 3g]

Process (3iii)

Next, 20 g of the compound (formula 3g) obtained in the above process (3ii) and 30 g of 1,3-trifluoromethylbenzene and 10 g of diethyl ether and 1.45 g of trimethylbromodecane were subjected. Mix and mature at 70 ° C for 24 hours. Then, the solvent and the unreacted material were distilled off under reduced pressure to obtain 21 g of a liquid product. The obtained mixture was measured by ¹ H-NMR to confirm that it was represented by the following formula 3h. [Chemical Formula 3h]

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

Further, the above compound 4 was supercritically purified to prepare a sample having a different number average molecular weight of the main chain. Further, the number average molecular weight of the compound 4 was 4520 as measured by ¹⁹ F-NMR.

20 g of compound 4 was charged into a 25 mL high pressure vessel and allowed to warm to 70 °C. Then, the pressure of the high pressure vessel was raised to 15 MPa by introducing liquid carbon dioxide, and maintained in a supercritical state for 30 minutes. Carbon dioxide was allowed to flow at a flow rate of 2 ml/min for 2 minutes, and the sample that had flowed out was recovered. This operation was carried out from 10 MPa to 22 MPa, and the samples (Compounds 5 to 13) shown in Table 1 were collected. 【Table 1】

Process (3iv)

Next, 20 g of the compound 4 obtained in the above process (3iii) was dropwise added to a solution in which 100 g of water and 50 g of acetone were mixed, and the mixture was stirred at 20 ° C for 3 hours and allowed to stand for 1 hour. Then, 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 measured by ¹ H-NMR to confirm that it was represented by the following formula 3i. [Chemical Formula 3i]

The data of ¹ H-NMR (TMS standard, ppm) of the compound of the above formula 3i (hereinafter referred to as "compound 14") is shown below.

Further, the above compound 14 was supercritically purified to prepare a sample having a different number average molecular weight of the main chain. Further, the number average molecular weight of the compound 14 was 4,130 as measured by ¹⁹ F-NMR.

20 g of compound 14 was placed in a 25 mL high pressure vessel and the temperature was raised to 70 °C. Then, the pressure of the high pressure vessel was raised to 15 MPa by introducing liquid carbon dioxide, and maintained in a supercritical state for 30 minutes. Carbon dioxide was allowed to flow at a flow rate of 2 ml/min for 2 minutes, and the sample that had flowed out was recovered. This operation was carried out from 10 MPa to 22 MPa, and the samples (compounds 15 to 22) shown in Table 2 were collected. 【Table 2】

Example 4

Process (4i)

In a reaction vessel, a perfluorooxy compound having a carboxylic acid group at both ends (FOMBLIN ZDIAC4000 manufactured by Solvay Solexis Co., Ltd.) was dissolved in a mixed solvent of 40 g of 1,3-trifluoromethylbenzene and 10 g of tetrahydrofuran, and then dropped. 60 g of a 40% toluene solution of sodium bis(2-methoxyethoxy)aluminum hydride was added. After stirring at room temperature for 3 hours, an appropriate amount of hydrochloric acid was added, followed by thorough stirring and washing with water. Further, the lower layer was taken out, and the solvent was distilled off to obtain 41 g of a liquid product. The obtained mixture was measured by ¹⁹ F-NMR and ¹ H-NMR to confirm that it was represented by the following formula 4d. [Chemical Formula 4d]

Process (4ii)

40 g of the compound (formula 4d) obtained in the above process (4i) and 7.0 g of allyl bromide and 0.6 g of tetrabutylammonium hydrogen sulfate and 10.0 g of a 30% aqueous sodium hydroxide solution were added dropwise to the reaction. After the container, it was further stirred at 60 ° C for 3 hours. Then, PF5060 (a fluorine-based solvent manufactured by 3M Company) and hydrochloric acid were added in an appropriate amount, and the mixture was stirred, and then sufficiently washed with water. Further, the lower layer was taken out, and the solvent was distilled off to obtain 35 g of a liquid product. The obtained mixture was measured by ¹ H-NMR to confirm that it was represented by the following formula 4e. [Chemical Formula 4e]

Process (4iii)

Next, 20 g of the compound (formula 4e) obtained in the above process (4ii) and 30 g of 1,3-trifluoromethylbenzene and 7.0 g of 1,2-bis(dimethylformamidinyl) Ethane and 0.010 g of a chloroplatinic acid/vinyloxirane complex in a toluene solution (containing 2.5 × 10 ^-9 mol as a Pt unit) were mixed, and aged at 80 ° C for 3 hours. Then, the solvent and the unreacted material were distilled off under reduced pressure to obtain 18 g of a liquid product. The obtained compound was measured by ¹ H-NMR to confirm that it was represented by the following formula 4f. [Chemical Formula 4f]

Craft (4iv)

Next, 18 g of the compound (formula 4f) obtained in the above process (4iii) and 30 g of 1,3-trifluoromethylbenzene and 3.5 g of diethyl allylphosphonate and 0.005 g of chlorine were used. A toluene solution of a platinum acid/vinyl siloxane complex (containing 1.25 × 10 ^-9 moles as a Pt unit) was mixed and aged at 90 ° C for 48 hours. Then, the solvent and the unreacted material were distilled off under reduced pressure to obtain 21 g of a liquid product. The obtained mixture was measured by ¹ H-NMR to confirm that it was represented by the following formula 4g. [Chemical Formula 4g]

Craft (4v)

Next, 20 g of the compound (formula 4g) obtained in the above process (4iv) and 30 g of 1,3-trifluoromethylbenzene and 10 g of diethyl ether and 2.9 g of trimethylbromodecane were subjected. Mix and mature at 70 ° C for 24 hours. Then, the solvent and the unreacted material were distilled off under reduced pressure to obtain 21 g of a liquid product. The obtained mixture was measured by ¹ H-NMR to confirm that it was represented by the following formula 4h. [Chemical Formula 4h]

The data of ¹ H-NMR (TMS standard, ppm) of the compound of the above formula 4h (hereinafter referred to as "compound 23") is shown below.

Craft (4vi)

Next, 20 g of the compound (formula 4h) obtained in the above process (4v) was dropwise added to a solution in which 100 g of water and 50 g of acetone were mixed, and the mixture was stirred at 20 ° C for 3 hours and allowed to stand for 1 hour. Then, 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 measured by ¹ H-NMR to confirm that it was represented by the following formula 4i. [Chemical Formula 4i]

The data of ¹ H-NMR (TMS standard, ppm) of the compound of the above formula 4i (hereinafter referred to as "compound 24") is shown below.

Preparation of surface treatment agent and cured film

The perfluorooxyalkylene-containing polymer-modified phosphonic acid derivative obtained in each of Examples 1 to 4 was dissolved in a fluorine-based solvent Novec 7200 (manufactured by 3M Company) in such a manner as to have a concentration of 10% by weight. The treatment agent. After the surface of the sapphire glass was subjected to a plasma treatment, a vacuum vapor deposition coating layer using each of the above surface treatment agents was carried out under the following conditions and using the apparatus described below. After curing for 1 hour in an environment of a temperature of 80 ° C and a humidity of 80%, it was further cured at 150 ° C for 3 hours to form a film.

[conditions for plasma treatment]

Device: plasma dry cleaning device PDC210

Gas: 80cc oxygen, 10cc argon

Output power: 2500W

Time: 30 seconds

[Vacuum evaporation coating conditions and coating device]

Measuring device: small vacuum evaporation device VPC-250F

Pressure: 2.0×10 ^-3 Pa~3.0×10 ^-2 Pa

Evaporation temperature (temperature to reach the porcelain boat): 500 ° C

Evaporation distance: 20mm

Processing agent loading: 50mg

Evaporation amount: 50mg

Comparative example

The surface treatment agent and the cured film of Comparative Examples 1 to 3 were prepared in the same manner as in the Example except that the following compounds 25 to 27 were used instead of the compound 1 and the compound 2, and an evaluation test was carried out. (Comparative Example 1) Compound 25 (Comparative Example 2) Compound 26 (Comparative Example 3) Compound 27

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). 【table 3】 【Table 4】

As is apparent from Tables 3 and 4, the film formed by modifying the phosphonic acid derivative of the perfluoroalkylene group-containing polymer of the examples has high water repellency, low dynamic friction coefficient, and erasing of the marker ink. Excellent sex. On the other hand, in the comparative example which does not have a phosphonic acid group or a phosphonate group, although the water-repellent oil-repellent property and the dynamic friction coefficient are within the allowable range, the marking pen ink is inferior in erasability. Further, the film formed of the perfluorooxyalkylene-containing polymer-modified phosphonic acid derivative of the example exhibits a water contact angle of 100 degrees or more and an oleic acid contact angle of 60 degrees even after rubbing with a cloth. Above the high water and oil repellency. On the other hand, in the comparative example which does not have a phosphonic acid group or a phosphonate group, the water repellency is drastically reduced. That is, the fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative of the present invention can provide a coating excellent in water repellency, low dynamic friction, stain release property, abrasion resistance, and adhesion to a substrate. .

The above description and description are only illustrative of the preferred embodiments of the present invention, and those of ordinary skill in the art can make other modifications in accordance with the scope of the invention as defined below and the description above, but such modifications should still be It is within the scope of the invention to the invention of the invention.

no

Claims (8)

A polymer modified phosphonic acid derivative containing a fluorooxyalkylene group, wherein: represented by the following formula 1, [Chemical Formula 1] Wherein in Formula 1, A is a monovalent fluorine-containing group having a terminal -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 (O CF(CF ₃ )CF ₂ ) _t -O(CF ₂ ) _d -, d are independently an integer of 0 to 5, p, q, r, s , t are each independently an integer of 0 to 200, and p + q + r + s + t is from 3 to 200, and each unit in parentheses indicated may be randomly bonded, Q ¹ is in the a divalent linking group having an alkylene structure at any terminal, Q ² is a divalent linking group having a halogen atom at both terminals, and X is independently a hydrogen atom, an alkali metal atom, an unsubstituted or substituted carbon An alkyl group having 1 to 5 atoms, an aryl group or a monovalent group represented by J ₃ Si- (J is independently an unsubstituted or substituted alkyl group or aryl group having 1 to 5 carbon atoms), a It is an integer from 2 to 20. [Chemical Formula 2] The fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative according to claim ¹ , wherein the Rf ¹ is a divalent linear fluorooxyalkylene group represented by the following formula 3, Chemical Formula 3] -(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 -O(CF ₂ ) _d - In the formula 3, d is independently an integer of 0 to 5, and an integer of p=1 to 80, q=1 to 80, r=0 to 10, s=0 to 10, and p+q=5 to 100, And p+q+r+s+t is 10~100, and each unit represented in parentheses can also be randomly bonded. The fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative according to claim ¹ , wherein the Q ¹ is a divalent linking group selected from the following formula 4-1 to formula 4-8; Group, [Chemical Formula 4-1~4-8] In the formula 4-1 to formula 4-8, h is an integer of 2 to 10, and R is independently an unsubstituted or substituted alkyl group or aryl group having 1 to 5 carbon atoms. The fluorooxyalkylene group-containing polymer-modified phosphonic acid derivative according to claim ¹ , wherein the Q ² is selected from the group consisting of the following formulas 5-1 to 5-4 and has a fluorene at both ends. a divalent linking group of an atom, [Chemical Formula 5-1~5-4] In the formula 5-1 to formula 5-4, i is an integer of 1 to 10, j is an integer of 1 to 100, and R is independently an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms or Aryl. A surface treatment agent containing at least one polymer modified phosphonic acid derivative containing a fluorooxyalkylene group as described in any one of Claims 1 to 4. An article which has been surface treated with a surface treating agent as claimed in claim 5. An optical article which is surface-treated with a surface treating agent as claimed in claim 5. A touch panel display that is surface-treated with a surface treatment agent as claimed in claim 5.