KR20140127161A - Fluorooxyalkylene group-containing polymer modified silane and surface treatment agent comprising said silane, and article treated with said surface treatment agent - Google Patents

Abstract

The present invention provides a fluorooxyalkylene group-containing polymer modified silane by which a water repellent and oil repellent layer has excellent heat resistance, a surface treating agent including the silane and/or a hydrolyzed and condensed product of the same, and an article having a surface treated through the surface treating agent, wherein the fluorooxyalkylene group-containing polymer modified silane is represented by Chemical Formula (1). (In Formula, Rf is a monovalent or bivalent straight-chain fluorooxyalkylene group-containing polymer residue; b is averagely 0 to 10; Z is independently a bi- to hexa-valent group which may have a siloxane bond; R is independently a C1 to 4 alkyl group or phenyl group; X is independently a hydrolyzing group; a is independently 2 or 3; y is independently an integer of 1 to 5 for each unit; α is an integer of 1 to 5; and β is 1 or 2.)

Description

TECHNICAL FIELD [0001] The present invention relates to a surface treatment agent containing a fluorooxyalkylene group-containing polymer modified silane and the silane, and a surface treated surface treated with the surface treatment agent. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] AGENT}

TECHNICAL FIELD The present invention relates to a fluoroalkylene group-containing polymer-modified silane, and more particularly to a fluorooxyalkylene group-containing polymer-modified silane which forms a film excellent in water- and oil-repellency and heat resistance, and a silane or partially hydrolyzed condensate thereof And an article treated with the surface treatment agent.

BACKGROUND ART [0002] In recent years, a touch panel of a screen has been accelerated including a display of a cellular phone. However, the touch panel is in a state in which the screen is exposed, and there is a lot of chance that a finger or a ball is directly attached to the touch panel, so that it is apt to be contaminated with sebum or the like. Therefore, a technique for making fingerprints hard to get on the surface of the display and a technique for making it easy to remove the dirt have been increasing year by year in order to improve the appearance and visibility, and development of a material capable of meeting these demands is desired . However, the conventional water-repellent oil-repellent layer has a high water-repellent and oil-repellent property and is excellent in polish wiping property, but has a problem that the antifouling performance is deteriorated during use. One of the causes of deterioration of the antifouling performance is heat resistance.

Generally, the perfluorooxyalkylene group-containing compound has water repellency and oil resistance, chemical resistance, lubricity, releasability and antifouling property because its surface free energy is very small. Utilizing this property, it is industrially widely used as a water-repellent oil-repellent antifouling agent for paper and fiber, a lubricant for a magnetic recording medium, an oil repellent for precision instruments, a release agent, a cosmetic, and a protective film. However, this property means that the film is non-tacky and non-tacky to other substrates at the same time, and it is difficult to adhere the film to the substrate even though the film can be applied to the surface of the substrate.

On the other hand, a silane coupling agent for bonding an organic compound to a substrate surface such as glass or cloth is well known and widely used as a coating agent for various substrate surfaces. The silane coupling agent has an organic functional group and a reactive silyl group (generally an alkoxysilyl group) in one molecule. An alkoxysilyl group causes a self condensation reaction by moisture or the like in the air to form a film. The coating film is chemically and physically bonded to the surface of the glass or metal by an alkoxysilyl group to form a strong coating having durability.

As a fluorine-containing polymer composition containing these, a fluorooxyalkylene group-containing polymer composition containing, as a main component, the following formula is proposed in Japanese Patent Application Laid-Open No. 2012-072272. The lens or the antireflection film treated with the perfluorooxyalkylene group-containing polymer modified silane is excellent in slipperiness, releasability and abrasion resistance but not in heat resistance.

(CF ₂ ) _d - (OC ₂ F ₄ ) _e (OCF ₂ ) _f -O (CF ₂ ) _d - wherein A is a monovalent fluorine-containing group having a terminal -CF ₃ group, R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolysable group, a is 2 or 3, b is an organic group having a valency of 2 to 8, Is an integer of 1 to 6, c is an integer of 1 to 5, a is 0 or 1, d is independently 0 or an integer of 1 to 5, e is an integer of 0 to 80, f is an integer of 0 to 80 An integer of e + f = 5 to 100, and the repeating unit may be bonded at random)

Japanese Patent Laid-Open Publication No. 2012-072272

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a fluorooxyalkylene group-containing polymer modified silane capable of forming a water-repellent oil repellent layer excellent in heat resistance, a surface treatment agent comprising the silane and / It is an object of the present invention to provide an article treated with the surface treatment agent.

When imparting long-term durability to the water-repellent oil-repellent layer covering the surface of a touch panel display or the like, heat resistance is required. The present inventors first proposed a fluorooxyalkylene group-containing polymer composition containing, as a main component, a fluorooxyalkylene group-containing polymer having hydrolyzable groups at both terminals, as described above (JP-A-2012-072272 : Patent Document 1), the film formed from the composition has insufficient heat resistance.

A polymer having a fluoroxyalkylene structure in its main chain and containing a hydrolyzable group at one end or both ends of the molecular chain is firmly adhered to the base material when used as a surface treatment agent and is excellent in abrasion resistance by a cloth or the like , A linking group of a fluoroxyalkylene group and an alkoxysilyl group, for example, an ether bond of -CF ₂ CH ₂ -O-CH ₂ -, is poor in heat resistance.

Accordingly, the present inventors have intensively studied in order to solve the above-mentioned problems. As a result, they have found that the fluoroxyalkylene group-containing polymer modified with -CF (CF ₃ ) -CON (CH ₃ ) -Ph- (Ph is a phenylene group) Silane-containing surface treatment agent can form a water-repellent oil-repellent layer excellent in heat resistance, and has accomplished the present invention.

Accordingly, the present invention provides a surface treating agent comprising the following fluorooxyalkylene group-containing polymer-modified silane and the silane and / or a partially hydrolyzed condensate thereof, and an article surface-treated with the surface treatment agent.

[1] A fluorooxyalkylene group-containing polymer-modified silane represented by the following formula (1).

(Wherein Rf is a monovalent or divalent straight-chain fluorooxyalkylene group-containing polymer residue, b is an average of 0 to 10, Z is a 2 to 6-valent group which may have a siloxane bond, R Is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydrolysable group, a is independently 2 or 3, y is independently an integer of 1 to 5, and a is an integer of 1 to 5 , beta is 1 or 2)

[2] The fluorooxyalkylene group-containing polymer modified silane according to [1], wherein? In the above formula (1) is 1 and the Rf group is a group represented by the following formula (2).

(Wherein p, q, r and s are each an integer of 0 to 200, p + q + r + s = 3 to 200, and each repeating unit may be bonded at random)

[3] The fluorooxyalkylene group-containing polymer modified silane according to [1], wherein? In the above formula (1) is 2 and the Rf group is a group represented by the following formula (3).

(Wherein p, q, r and s are each an integer of 0 to 200, p + q + r + s = 3 to 200, and each repeating unit may be bonded at random)

[4] The positive resist composition according to the above [1], wherein Z is a group in which the diorganosilylene group and the diorganosilylene group are bonded to each other through an alkylene group, a linear, branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms or a group wherein the siloxane moiety and diorgano silyl alkylene group, which is bonded via an alkylene group, of Rf molecular weight branched perfluoropolyether portion _{- (CF (CF 3) CF} 2 O) b - is greater than the molecular weight, The fluorooxyalkylene group-containing polymer modified silane according to any one of [1] to [3].

[5] The method according to any one of [1] to [5], wherein the hydrolyzable group X in the formula (1) is an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, A fluoroalkylene group-containing polymer modified silane according to any one of [1] to [4].

[6] A surface treatment agent comprising the fluorooxyalkylene group-containing polymer-modified silane and / or the partially hydrolyzed condensation product of the fluoroalkylene group-containing polymer-modified silane according to any one of [1] to [5].

[7] An article treated with the surface treatment agent according to [6].

[8] An optical article treated with the surface treatment agent according to [6].

[9] A touch panel treated with the surface treatment agent according to [6].

[10] An antireflection film treated with the surface treatment agent according to [6].

[11] A SiO _2- treated glass treated with the surface treatment agent according to [6].

[12] A tempered glass treated with the surface treatment agent according to [6].

[13] A quartz substrate treated with the surface treatment agent according to [6].

The coating film formed from the fluorooxyalkylene group-containing polymer modified silane of the present invention has high water and oil repellency. By treating with the surface treatment agent containing the fluorooxyalkylene group-containing polymer-modified silane and / or partial hydrolyzed condensate thereof of the present invention, it is possible to impart excellent water and oil repellency to various articles, to exhibit high resistance to heat, The antifouling performance can be maintained.

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

(Wherein Rf is a monovalent or divalent straight-chain fluorooxyalkylene group-containing polymer residue, b is an average of 0 to 10, Z is a 2 to 6-valent group which may have a siloxane bond, R Is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydrolysable group, a is independently 2 or 3, y is independently an integer of 1 to 5, and a is an integer of 1 to 5 , beta is 1 or 2)

The fluorooxyalkylene group-containing polymer modified silane of the present invention is obtained by reacting a monovalent or divalent straight chain fluorooxyalkylene group-containing polymer residue (Rf) with a hydrolyzable silyl group (-Si (R) _{3- a} (X) _a ) is bonded through a linking group -CF (CF ₃ ) -CON (CH ₃ ) -Ph- (Ph is a phenylene group, hereinafter the same), and the fluoroxyalkylene group the hydrolyzable silyl-containing polymer such as a residue (Rf) and an alkoxysilyl group group _{(-Si (R) 3-a} (X) a) , ether bond or -CF ₂ -CONH- bond, -CF ₂ -CONPh-CH ₂ - It is superior in heat resistance compared to the case where it is connected through bonding or the like.

As Rf containing the repeating unit, when b is 1, a monovalent fluorooxyalkylene group represented by the following formula (2) is preferable.

(Wherein p, q, r and s each represent an integer of 0 to 200, preferably 10 to 100, and p + q + r + s = 3 to 200, preferably 10 to 100, May be combined at random)

As Rf containing the repeating unit, when b is 2, a divalent fluorooxyalkylene group represented by the following formula (3) is preferable.

(Wherein p, q, r and s each represent an integer of 0 to 200, preferably 10 to 100, and p + q + r + s = 3 to 200, preferably 10 to 100, May be combined at random)

Specific examples of Rf include the following.

(Wherein each repeating unit may be bonded at random)

Further, Rf polyether part by the molecular weight of Rf branched-chain perfluoroalkyl group as _{- (CF (CF 3) CF} 2 O) b - than the molecular weight of the (b, on average, that it is preferred that 0 to 10, 2 to 6) The larger one is preferable in terms of slidability. The above molecular weight can be obtained as polystyrene reduced number average molecular weight by gel permeation chromatography (GPC) analysis.

In the above formula (1), Z is a

(-C _y H _2y -Si (R) _3-a (X)) containing a hydrolyzable silyl group such as an Rf group and an alkoxysilyl group having a structure represented by the formula (b is 0 to 10 on average) _a) having a, is from 2 to 6 optionally having a siloxane bond, and preferably 2 to 4-valent linking group, it is preferred that the heat-resistant, such as an ether bond which do not have a bad connector. By having a siloxane bond in the molecule, a coating excellent in abrasion resistance and scratch resistance can be provided. Preferable examples of Z include a group in which the diorganosilylene group and the diorganosilylene group are bonded to each other through an alkylene group and the number of silicon atoms is 2 to 10, preferably 2 to 9, particularly 2 to 6, Or a cyclic organopolysiloxane residue, a group in which the siloxane residue and the diorganosilylene group are bonded through an alkylene group, for example, the following groups.

In the above formula (1), X is a hydrolyzable group which may be different from each other. Examples of such X include alkoxy groups of 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy and butoxy, alkoxyalkoxy groups of 2 to 10 carbon atoms such as methoxymethoxy and methoxyethoxy, An alkenyloxy group having 2 to 10 carbon atoms such as an isopropenyloxy group, an acyloxy group having 1 to 10 carbon atoms, and a halogen group such as a chloro group, a bromo group and an iodo group. Of these, a methoxy group, an ethoxy group, an isopropenoxy group and a chloro group are suitable.

In the above formula (1), R is an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group or a butyl group, or a phenyl group. a is 2 or 3, and 3 is preferred from the viewpoints of reactivity and adhesion to a substrate. and y is an integer of 1 to 5, preferably 1 to 3.

Also,? Is an integer of 1 to 5, preferably 1 to 3.

Examples of the fluoroalkylene group-containing polymer-modified silane represented by the above formula (1) include those represented by the following formulas. In each formula, the number of repeating units (or degree of polymerization) of each repeating unit constituting the fluoroalkylene group may be any number satisfying the above-mentioned formulas (2) and (3).

As the method for producing the fluorooxyalkylene group-containing polymer-modified silane represented by the above formula (1) wherein? Is 1, for example, the following method can be mentioned.

(Perfluorooxyalkylene group-containing polymer having an acid fluoride group (-C (= O) -F) at one end of the molecular chain, one or more of cesium fluoride and a solvent, , Preferably at 60 占 폚 for 20 to 120 minutes, preferably 30 minutes, and then aged at 20 to 60 占 폚, preferably at 25 占 폚, for 2 to 48 hours, preferably 16 hours. As the solvent, ether solvents such as monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran and dioxane can be used. Subsequently, after cooling to -25 to -40 캜, preferably -38 캜, perfluoro olefin is added and aged for 1 to 10 hours, preferably 3 hours, further adding hexafluoropropylene oxide to obtain 1 To 10 hours, preferably 3 hours. At this time, the polyether _{(-CF (CF 3) CF 2} O) b with branched perfluoro- length) depends on the feed rate of propylene oxide hexafluorophosphate. As the perfluoroolefin, for example, tetrafluoroethylene, hexafluoropropylene, octafluorobutene, octafluoroisobutene, decafluoroisopentene, dodecafluoroisobutene, and the like can be used. Thereafter, trimethylchlorosilane mixed with heptane is added and mixed at 20 to 60 캜, preferably 25 캜 for 30 minutes to 3 hours, preferably 1 hour. Instead of heptane, hydrocarbon solvents such as pentane, hexane, octane, nonane and decane may be used. In place of trimethylchlorosilane, for example, triethylchlorosilane, butyldimethylchlorosilane, Propyl chlorosilane, triphenyl chlorosilane and the like can be used. After the obtained mixture is filtered, the organic solvent layer and the fluorine compound layer are separated, and the residual solvent is distilled off under reduced pressure to obtain an acid fluoride group (-C (= O)) at one end of the molecular chain, -F) can be obtained. For example, as a perfluorooxyalkylene group-containing polymer

, A perfluorooxyalkylene group-containing polymer having the following structure is obtained.

Then, the compound obtained in the above step and the compound

Methyl- [3- (vinyldimethylsilyl)] aniline represented by the general formula (1) in an amount of 1 to 3 equivalents, preferably 1.2 equivalents, based on the acid fluoride is mixed with triethylamine at 40 to 80 캜, Is reacted at 60 DEG C for 30 minutes to 5 hours, preferably 2 hours. At this time, for example, tertiary amines such as tripropylamine, tributylamine, tripentylamine and diethylisopropylamine can be used instead of triethylamine. Thereafter, the solution is neutralized with calcium carbonate and the solvent is distilled off to obtain a fluorooxyalkylene group-containing polymer having aliphatic unsaturated bonds at one end of the molecular chain shown below. At this time, for example, an alkali metal such as sodium carbonate or magnesium carbonate or a carbonate of an alkaline earth metal may be used instead of calcium carbonate.

Then, the compound obtained in the above step is dissolved in a solvent, for example, 1,3-bistrifluoromethylbenzene, and a hydrolyzable group such as an alkoxy group, such as trimethoxysilane, Two or three silane compounds are aged in the presence of a toluene solution of a chloroplatinic acid / vinyl siloxane complex at 40 to 120 ° C, preferably 80 ° C for 1 to 24 hours, preferably 4 hours. Thereafter, the solvent and the unreacted material are distilled off under reduced pressure, for example, to obtain the objective compound represented by the following formula.

As the method for producing the fluorooxyalkylene group-containing polymer-modified silane represented by the above formula (1) wherein? Is 2, for example, the following method can be mentioned.

A perfluorooxyalkylene group-containing polymer having acid fluoride groups (-C (= O) -F) at both ends of the molecular chain is mixed with one or more of cesium fluoride and a solvent, , Preferably at 60 占 폚 for 20 to 120 minutes, preferably 30 minutes, and then aged at 20 to 60 占 폚, preferably at 25 占 폚, for 2 to 48 hours, preferably 16 hours. As the solvent, ether solvents such as monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran and dioxane can be used. Subsequently, after cooling to -25 to -40 캜, preferably -38 캜, perfluoro olefin is added and aged for 1 to 10 hours, preferably 3 hours, further adding hexafluoropropylene oxide to obtain 1 To 10 hours, preferably 3 hours. At this time, the polyether _{(-CF (CF 3) CF 2} O) b with branched perfluoro- length) depends on the feed rate of propylene oxide hexafluorophosphate. As the perfluoroolefin, for example, tetrafluoroethylene, hexafluoropropylene, octafluorobutene, octafluoroisobutene, decafluoroisopentene, dodecafluoroisobutene, and the like can be used. Thereafter, trimethylchlorosilane mixed with heptane is added and mixed at 20 to 60 캜, preferably 25 캜 for 30 minutes to 3 hours, preferably 1 hour. Instead of heptane, hydrocarbon solvents such as pentane, hexane, octane, nonane and decane may be used. In place of trimethylchlorosilane, for example, triethylchlorosilane, butyldimethylchlorosilane, Propyl chlorosilane, triphenyl chlorosilane and the like can be used. After the obtained mixture is filtered, the organic solvent layer and the fluorine compound layer are separated, and the residual solvent is distilled off under reduced pressure to obtain an acid fluoride group (-C (= O)) at both ends of the molecular chain, -F) can be obtained. For example, as a perfluorooxyalkylene group-containing polymer

, A perfluorooxyalkylene group-containing polymer having the following structure is obtained.

Next, the compound obtained in the above step and the compound of the following formula

Methylvinyl- [3- (vinyldimethylsilyl)] aniline represented by the following general formula (1) in an amount of 2 to 6 equivalents, preferably 2.4 equivalents, based on the acid fluoride is mixed with triethylamine at 40 to 80 캜, Is reacted at 60 DEG C for 30 minutes to 5 hours, preferably 2 hours. At this time, for example, tertiary amines such as tripropylamine, tributylamine, tripentylamine and diethylisopropylamine can be used instead of triethylamine. Thereafter, the solution is neutralized with calcium carbonate and the solvent is distilled off to obtain a fluorooxyalkylene group-containing polymer having aliphatic unsaturated bonds at both ends of the molecular chain shown below. At this time, for example, an alkali metal such as sodium carbonate or magnesium carbonate or a carbonate of an alkaline earth metal may be used instead of calcium carbonate.

Then, the compound obtained in the above step is dissolved in a solvent, for example, 1,3-bistrifluoromethylbenzene, and a hydrolyzable group such as an alkoxy group, such as trimethoxysilane, Two or three silane compounds are aged in the presence of a toluene solution of a chloroplatinic acid / vinyl siloxane complex at 40 to 120 ° C, preferably 80 ° C for 1 to 24 hours, preferably 4 hours. Thereafter, the solvent and the unreacted material are distilled off under reduced pressure, for example, to obtain the objective compound represented by the following formula.

The present invention also provides a surface treatment agent containing the fluoroalkylene group-containing polymer-modified silane. The surface treatment agent may include a partial hydrolyzed condensate obtained by partially hydrolyzing and condensing the terminal hydrolysable group of the fluoroalkylene group-containing polymer-modified silane by a known method.

As the surface treatment agent, a hydrolysis and condensation catalyst such as an organic tin compound (dibutyltin dimethoxide, dibutyl tin dilaurate etc.), an organic titanium compound (tetra n-butyl titanate etc.), an organic acid , Methane sulfonic acid, fluorine-modified carboxylic acid, etc.), inorganic acid (hydrochloric acid, sulfuric acid, etc.). Among these, acetic acid, tetra n-butyl titanate, dibutyl tin dilaurate and fluorine-modified carboxylic acid are particularly preferable.

The addition amount of the hydrolysis and condensation catalyst is a catalytic amount, and is usually 0.01 to 5 parts by mass, particularly 0.1 to 1 part by mass based on 100 parts by mass of the fluorooxyalkylene group-containing polymer-modified silane and / or the partial hydrolysis condensation product thereof.

The surface treatment agent may include a suitable solvent. Examples of such a solvent include fluorine-modified aliphatic hydrocarbon solvents such as perfluoroheptane and perfluorooctane, fluorine-modified aromatic hydrocarbon solvents such as 1,3-trifluoromethylbenzene, fluorine-modified ether solvents such as methylperfluoro (Perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbon solvents (e.g., methyl ethyl ketone, methyl ethyl ketone, methyl tert-butyl methyl ether, butyl tertiary butyl ether, perfluorobutyl ether, perfluoro Petroleum benzine, toluene, xylene and the like) and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone and the like). Of these solvents, fluorine-modified solvents are preferred in terms of solubility and wettability. Particularly preferred are m-xylene hexafluoride, perfluoro (2-butyltetrahydrofuran), perfluorotributylamine, Butyl ether is preferred.

The solvent may be a mixture of two or more kinds thereof, and it is preferable to uniformly dissolve the fluorooxyalkylene group-containing polymer-modified silane and the partial hydrolysis-condensation product thereof. The optimum concentration of the fluorooxyalkylene group-containing polymer-modified silane dissolved in the solvent differs depending on the treatment method and is preferably an amount that can be easily weighed. In the case of direct coating, however, the solvent and the fluorooxyalkylene group- 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass, based on 100 parts by mass of the total of the total amount of the fluorine-containing polymer (and its partially hydrolyzed condensate) And the partially hydrolyzed condensate thereof) is preferably 1 to 100 parts by mass, particularly preferably 3 to 30 parts by mass.

The surface treatment agent of the present invention can be applied to a substrate by a known method such as brush coating, dipping, spraying, or vapor deposition treatment. The heating method during the deposition process may be any of a resistance heating method and an electron beam heating method, and is not particularly limited. The curing temperature differs depending on the curing method, but is preferably in the range of 20 to 200 占 폚 when applied by brush application or dipping, for example. As the curing humidity, it is preferable to conduct under humidification in accelerating the reaction. The thickness of the cured coating film is appropriately selected according to the kind of the substrate, but is usually 0.1 to 20 nm, particularly 10 to 20 nm.

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

Examples of the article to be treated with the surface treatment agent of the present invention include a car navigation system, a cellular phone, a digital camera, a digital video camera, a PDA, a portable audio player, a car audio, a game device, a spectacle lens, ), Optical equipment such as a camera, a copying machine, a PC, a liquid crystal display, an organic EL display, a plasma display, a touch panel display, a protective film, and an antireflection film. The surface treatment agent of the present invention is useful as a water-repellent and oil-repellent layer of a touch panel display, an antireflection film, and the like, because it can prevent the fingerprints and sebum from adhering to the article and further can prevent scratches.

In addition, the surface treatment agent of the present invention can be used for antifouling coatings for hygiene products such as bathtubs and sinks, antifouling coatings for window glass or reinforced glass for automobiles, trains and aircrafts, headlamp covers, Anti-fouling coatings for construction materials, anti-fouling coatings for telephone boxes, anti-graffiti coatings for paper boxes and anti-graffiti coatings, anti-fingerprint coatings for artwork, anti-fingerprint coatings for compact discs and DVDs, mold release agents or paint additives, A fluidity modifier of an inorganic filler or a lubricity improver such as a dispersant, a modifier, a tape or a film.

[Example]

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

[Example 1]

(I) < / RTI >

Represented by Formula 100g (1.6 × 10 ^-2 mol) and then a solution of 7.2g of cesium fluoride, tetraethylene glycol dimethyl ether 44g, 14g mono ethylene glycol dimethyl ether and heated at 60 ℃ 30 minutes and at room temperature for 16 hours Respectively. Subsequently, after cooling to -38 占 폚, 29 g of hexafluoropropylene was fed for 22 minutes, aged for 3 hours, further fed with 16 g of hexafluoropropylene oxide in 54 minutes, and aged for 3 hours. Thereafter, 12 g of trimethylchlorosilane mixed with 30 g of heptane was added, and the mixture was stirred at room temperature for 1 hour. The organic solvent layer and the fluorine compound layer are separated from each other after filtration of the obtained mixture, and the remaining solvent is distilled off under reduced pressure,

To obtain 106 g of a perfluorooxyalkylene group-containing polymer represented by the following formula.

Next, 145 g (2.3 x 10 ^-2 mol) of the product represented by the formula (II) obtained in the above step,

(2.8 x 10 ^-2 mol) of a compound represented by the following formula was added to the flask, and 2.8 g of triethylamine was added thereto, followed by reaction at 60 ° C for 4 hours. Thereafter, the solution was neutralized with calcium carbonate, and the solvent was distilled off. The resulting product was mixed with 145 g of a fluorine-based inactive solvent PF5060 (manufactured by Sumitomo 3M Limited), 1.5 g of an alkali adsorbent Kyoward 700 SL (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and the mixture was stirred at room temperature for 1 hour. Thereafter, Kyowaru 700SL was removed by filtration, and the solvent was distilled off. Subsequently, the remaining low-boiling point component was removed by a molecular distillation apparatus, and 93 g of PF5060 and 0.93 g of Kyoward 500SH (manufactured by Kyowa Chemical Co., Ltd.) as an acid adsorbent were added and stirred at room temperature for 1 hour. After removal of Kyowaad 500SH by filtration, the solvent was distilled off to obtain a compound represented by the following formula (IV)

86 g of a fluorooxyalkylene group-containing polymer having an unsaturated bond at the terminal thereof was obtained.

Then, 40 g (7.2 x 10 ^-3 mol) of the compound represented by the formula (IV) obtained in the above step, 20 g of 1,3-bistrifluoromethylbenzene, 1.1 g (8.7 x 10 ^-3 mol) of trimethoxysilane, And 2.0 × 10 ^-2 g of a toluene solution of chloroplatinic acid / vinyl siloxane complex (containing 5.3 × 10 ^-7 mol as a unit of Pt) were mixed and aged at 80 ° C. for 4 hours. Thereafter, the solvent and the unreacted material were distilled off under reduced pressure. Subsequently, the remaining high boiling point component was removed by a molecular distillation apparatus to obtain 18 g of a liquid product.

The obtained compound was confirmed to be a structure of the following formula (V) by NMR.

[Example 2]

Example 1 represented by the formula (IV) obtained in the compound 40g (5.3 × 10 ^-3 mol) of 1,3-trifluoroacetate was dissolved in 10g methyl benzene, toluene solution of 2.0 × 10 of chloroplatinic acid / vinyl siloxane complex ^{- 2} g (containing 5.3 x 10 < ^-7 > mol as the Pt group) and 1.8 g of 1- [1- or 2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane (1.1 x 10 ^-2 mol) was added dropwise, and the mixture was aged at 80 ° C for 4 hours. The solvent and the unreacted material were distilled off under reduced pressure. Subsequently, the remaining high boiling point component was removed by a molecular distillation apparatus, whereby 25 g of a liquid product was obtained.

The compound obtained in Example 2 was confirmed to be a structure of the following formula (VI) by NMR.

[Example 3]

6.4 g (2.7 x 10 ^-2 mol) of tetramethylcyclotetrasiloxane (cyclic siloxane H4) and 40 g (5.3 x 10 ^-3 mol) of the compound represented by the formula (IV) obtained in Example 1 were dissolved in 1,3- And the mixture was heated to 90 占 폚. Thereafter, 2.0 × 10 ^-2 g of a toluene solution of a chloroplatinic acid / vinylsiloxane complex (containing 5.0 × 10 ^-7 mol as a unit of Pt) was added dropwise and aged at 90 ° C. for 3 hours. The solvent and the unreacted material were distilled off under reduced pressure Respectively. The obtained product was mixed with 20 g of a fluorine-based inert solvent PF5060 (manufactured by Sumitomo 3M Limited), 0.80 g of activated charcoal Shirasagi AS (manufactured by Nippon Enbilo Chemicals Co., Ltd.) was added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the Shirasagi AS was removed by filtration, and the solvent was distilled off to obtain 38 g of a liquid product represented by the following formula (VII).

Then, 38 g (5.3 x 10 ^-3 mol) of the product represented by the formula (VII) obtained in the above step was dissolved in 21 g of 1,3-trifluoromethylbenzene, 3.6 g of vinyltrimethoxysilane (VMS) × 10 ^-2 mol) and added dropwise to contain 5.0 × 10 ^-7 mol as a toluene solution of 2.0 × 10 ^-2 g (Pt groups of chloroplatinic acid / vinyl siloxane complex), and from 80 ℃ aging 4 hours, the solvent and unreacted The reaction product was distilled off under reduced pressure. Subsequently, the remaining high boiling point component was removed by a molecular distillation apparatus, whereby 19 g of a liquid product was obtained.

The compound obtained in Example 3 was confirmed to be a structure of the following formula (VIII) by NMR.

[Example 4]

35 g (5.5 × 10 ^-3 mol) of the product represented by the formula (VII) obtained in Example 3 was dissolved in 18 g of 1,3-trifluoromethylbenzene, 4.5 g of allyltrimethoxysilane (ATMS) 10 ^-2 mol) and added dropwise to contain 5.0 × 10 ^-7 mol as a toluene solution of 2.0 × 10 ^-2 g (Pt groups of chloroplatinic acid / vinyl siloxane complex), 2 hours aging at 80 ℃, solvent and unreacted Was distilled off under reduced pressure. Subsequently, the remaining high boiling point component was removed by a molecular distillation apparatus to obtain 17 g of a liquid product.

The compound obtained in Example 4 was confirmed to have a structure of the following formula (IX) by NMR.

[Example 5]

In the same manner as in Example 1, the amount of hexafluoropropylene oxide added was changed to 32 g, and 27 g of a product represented by the following formula (X) was obtained through the same reaction process. The total amount of the intermediate obtained in each step was used as a raw material for the next step.

[Comparative Examples 1 and 2]

The compounds of Comparative Examples 1 and 2 are shown below.

Comparative Example 1:

Comparative Example 2:

Preparation of surface treatment agent and formation of cured film

The surface-treating agent was prepared by dissolving the fluorooxyalkylene group-containing polymer-modified silane of Examples 1 to 5 and Comparative Examples 1 and 2 in Novec 7200 (manufactured by 3M) to a concentration of 20% by mass. On glass (manufactured by Corning gorilla (Gorilla)) by the SiO ₂ 10nm treatment on the outermost surface of each of the surface treatment agent and 10mg vacuum evaporation (treatment conditions Pressure: 2.0 × 10 ^-2 Pa, a heating temperature: 700 ℃), 80 ℃ , And a humidity of 80% for 12 hours to form a cured film having a film thickness of 15 nm.

The obtained cured film was evaluated by the following method.

[Evaluation of water repellency and oil repellency]

The contact angle (water repellency) of the cured coating to water and the contact angle (oil repellency) to oleic acid were measured using DropMaster (manufactured by Kyowa Chemical Co., Ltd.) using the glass produced above. Respectively. The results are shown in Table 1.

[Evaluation of sliding property (dynamic friction coefficient)] [

Using the glass produced above, the coefficient of dynamic friction of the cured coating was measured using a contact angle drop master (manufactured by Kyowa Chemical Co., Ltd.). The results are shown in Table 1.

[Evaluation of heat resistance]

The glass prepared above was heated to 200 캜 and 250 캜 and cooled to room temperature. Thereafter, steel wool (BONSTAR # 0000) was worn using a reciprocating abrasion tester HEIDON 30S manufactured by Shinto Chemical Co., Ltd. to evaluate the water and oil repellency as shown above. The above operation was performed until the contact angle (water repellency) of the cured coating film against water was 100 DEG or less. The results are shown in Tables 2 and 3.

Measuring conditions:

Load 1 kg / cm ²

Friction speed ㆍ Distance 3,600mm / min ㆍ 20mm

Evaluation environment 25 캜, 50% RH

From the above results, Comparative Example 1 having an ether bond at the linking group is inferior in heat resistance. In addition, Comparative Example 2 having a branched chain perfluoropolyether at the end group had heat resistance but was poor in slidability. On the other hand, the examples having a -CF (CF ₃ ) -CON (CH ₃ ) -Ph- bond in the connecting group and a straight chain perfluoropolyether in the terminal group were excellent both in heat resistance and slipperiness. As described above, the surface treatment agent of the Examples is excellent in water repellency and oil repellency, slipperiness, and heat resistance, and can maintain the characteristics of the film even in an environment where it is heated excessively.

The fluorooxyalkylene group-containing polymer modified silane of the present invention can provide a cured film excellent in water and oil repellency and heat resistance. Therefore, the surface treating agent containing the fluoroalkylene group-containing polymer-modified silane and / or the partially hydrolyzed condensate thereof of the present invention has excellent heat resistance even in a high temperature environment when applied to a touch panel display, an antireflection film and the like And it is possible to give long term durability.

Claims (13)

A fluorooxyalkylene group-containing polymer-modified silane represented by the following formula (1).

(Wherein Rf is a monovalent or divalent straight-chain fluorooxyalkylene group-containing polymer residue, b is an average of 0 to 10, Z is a 2 to 6-valent group which may have a siloxane bond, R Is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydrolysable group, a is independently 2 or 3, y is independently an integer of 1 to 5, and a is an integer of 1 to 5 , beta is 1 or 2) The fluoroalkylene group-containing polymer modified silane according to claim 1, wherein the? In the formula (1) is 1 and the Rf group is a group represented by the following formula (2).

(Wherein p, q, r and s are each an integer of 0 to 200, p + q + r + s = 3 to 200, and each repeating unit may be bonded at random) The fluoroalkylene group-containing polymer modified silane according to claim 1, wherein the? In the formula (1) is 2 and the Rf group is a group represented by the following formula (3).

(Wherein p, q, r and s are each an integer of 0 to 200, p + q + r + s = 3 to 200, and each repeating unit may be bonded at random) 4. The compound according to any one of claims 1 to 3, wherein Z is a group in which the diorganosilylene group and the diorganosilylene group are bonded to each other through an alkylene group, a group in which 2 to 10 silicon atoms Branched or cyclic organopolysiloxane residue or a group in which the siloxane residue and the diorganosilylene group are bonded through an alkylene group and the molecular weight of Rf is a branched chain perfluoropolyether moiety - (CF (CF ₃ ) CF ₂ O) _b - is a fluoroalkylene group-containing polymer modified silane. The positive resist composition according to any one of claims 1 to 3, wherein the hydrolyzable group X of the formula (1) is an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms , An alkenyloxy group having 2 to 10 carbon atoms, and a halogen group. A surface treatment agent containing the fluorooxyalkylene group-containing polymer modified silane and / or the partial hydrolyzed condensate of the fluoroalkylene group-containing polymer modified silane according to any one of claims 1 to 3. An article treated with the surface treatment agent according to claim 6. An optical article treated with the surface treatment agent according to claim 6. A touch panel treated with the surface treatment agent according to claim 6. An antireflection film treated with the surface treatment agent according to claim 6. A SiO _2- treated glass treated with the surface treatment agent according to claim 6. A tempered glass treated with the surface treatment agent according to claim 6. A quartz substrate treated with the surface treatment agent according to claim 6.