TW201020300A - Coating composition, method of antifouling treatment and antifouling substrate - Google Patents

Abstract

Provided are a coating composition with which an antifouling film having excellent antifouling properties, being transparent, and having durability sufficient for practical use can be formed at low cost; a method of antifouling treatment; and an antifouling substrate. The coating composition comprises a solvent, and dissolved therein, a compound represented by Formula 1 containing a perfluoroalkylene ether group in the molecular main chain and containing a hydrolyzable group containing a silicon atom in a side chain. The solvent is a mixed solvent of fluorinated solvents containing at least one of fluorinated hydrocarbon and fluorinated ether. The fluorinated solvents have a boiling point at 1 atm of 40 DEG C or higher and 70 DEG C or lower, and a difference between the highest and lowest boiling points of the mixed fluorinated solvents is within 25 DEG C.

Description

201020300 VI. [Technical Field] The present invention relates to a coating composition, an antifouling treatment method, and an antifouling substrate, and more particularly to a coating composition capable of imparting antifouling properties and prevention Pollution treatment method and mobile phone using the method for antifouling treatment. [Prior Art] 显示 The display surface of the mobile phone, the display surface of the LCD panel or the touch panel, the spectacle lens, etc. are attached to sebum, fingerprints, sweat, cosmetics, etc. due to human use. Therefore, there is a case where the antifouling treatment is performed as a surface treatment for making the stain less likely to adhere and the soiling is easy. * Antifouling treatment is a substance that is antifouling-coated on the surface of a substrate in the form of a film. Most of the raw materials of the film use a fluoroalkyl resin or a polyoxyl resin. The compound containing a perfluoropolyether group has a small surface energy and a soft molecular structure because it contains an ether bond, so that it is known to exhibit excellent antifouling properties. Sex Φ. When coating the film in the form of a film, in order to ensure the adhesion between the substrate and the film, it is generally used as a raw material by introducing a hydrolyzable group into the same compound. For example, Patent No. 3449070 is proposed by vacuum distillation. A method of coating a perfluoropolyether to modify decane in a film form. However, the vacuum evaporation method requires expensive production equipment' and has a problem of high production cost due to low productivity. Further, since the raw material which can be thinned by vacuum vapor deposition is limited to a molecular weight of about 5,000 or less, there is a problem that a long-chain raw material having high function cannot be utilized. 201020300 Therefore, wet coating methods such as dipping method and spray method which can be produced at low cost have attracted attention. However, in the past, the wet coating method dissolves the target compound in a soluble solvent and coats it on the surface of the substrate, but since the target compound contains a hydrolyzable group, the solution is exposed to the atmosphere, the atmosphere The water reacts with the compound to gel the solution, and the target compound is particleized. Further, in the immersion method, since the solution is exposed to the atmosphere for a long period of time, the solution is deteriorated, and the utilization efficiency of the raw material and the quality of the film are caused, and as a result, the production cost is increased. Further, in the dipping method, since the film formed by the principle is not deposited by a single layer of molecules, it is difficult to form a film which is practically durable enough. ^ The spray method avoids the deterioration of the solution by shortening the exposure time of the solution to the atmosphere. Moreover, since it is also highly productive and easy to be large-area, it can be called a method of mass production. However, the droplets are ejected from the nozzle to adhere to the surface of the substrate, and the wet diffusion is carried out to dry the solvent, so that the target compound is crystallized during the film formation, and the film is turbid. [Patent Document 1] Patent No. 3449070 [Disclosure] [Problems to be Solved by the Invention] The present invention has been made to solve the above problems, and an object of the present invention is to provide an excellent antifouling property at a low cost, which is transparent and practical. -6 - 201020300 A coating composition having an antifouling film having sufficient durability, an antifouling treatment method, and an antifouling substrate. [Means for Solving the Problem] The coating composition of the present invention is characterized in that a compound having a perfluoroalkyl ether group in a molecular main chain and a hydrolyzable group containing a ruthenium atom in a side chain is dissolved in a solvent. The composition of the composition. In the composition, the Φ characteristic of the solvent is a mixed solvent of a fluorine-based solvent containing at least one of a fluorinated hydrocarbon and a fluorinated ether, and the boiling point of the fluorine-based solvent at 4 atm is 4 〇 ° C or more and 7 (TC). In the following, the difference between the maximum enthalpy and the minimum enthalpy of the boiling point of the fluorine-based solvent to be mixed is within 25 ° C. In particular, the compound is characterized by a compound represented by the following formula (1): [Chemical 3]

Rf^OCF2CF2 CF2-^-〇-(CF2

Η (1) wherein Rf represents a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, Y represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R1 represents a halogen atom selected from -OR3. a group of -OCOR3 groups, -OC(R3) = C(R4)2 groups, -ON = C(R3)2 groups and -ON = at least one group of C(R5)2 groups, and R3 represents an aliphatic hydrocarbon group or aroma a hydrocarbon group, R4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R5 represents a divalent aliphatic hydrocarbon group having 3 to 6 carbon atoms, q represents an integer of 1 to 50, m represents an integer of 〇~2, and r represents 1 An integer of ~10. 201020300 In addition, the fluorine-based solvent characterized by dissolving the compound represented by the formula (1) is 1,1,1,3,3-pentafluorobutyl, perfluorohexan, 1,1,1,2,2,3 , 3,4,5,5,5-undefluoro-4-(trifluoromethyl)pentane or methyl nonafluorobutyl ether.

The antifouling treatment method of the present invention is characterized in that the antifouling treatment method is performed by applying a coating on the surface of an inorganic substrate or an inorganic surface film formed on an inorganic or organic substrate, thereby performing an antifouling treatment. The coating layer on the surface of the inorganic substrate or the surface of the inorganic surface film is coated with the coating composition of the present invention by a spray coating method. H In particular, the above inorganic surface film is an inorganic surface film formed by coating a polyazirane solution by a spray method. The antifouling substrate of the present invention is an antifouling substrate having an antifouling layer on the surface of the substrate or the surface of the inorganic surface film formed on the substrate, wherein the antifouling layer is the present invention. The antifouling layer formed by the antifouling treatment method. In particular, the antifouling substrate is a mobile phone having an image display portion and having the antifouling layer formed on the surface of the image display portion. [Effect of the invention] The coating composition of the present invention is Since the compound represented by the formula (1) uses a plurality of mixed solvents having a specific structure and a boiling point as a solvent, it is possible to form a film which is excellent in antifouling property, is transparent, and has practically sufficient durability at a low cost. [Embodiment] -8 - 201020300 The compound containing a perfluoroalkyl ether group in the main chain of the present invention and containing a hydrolyzable group containing a ruthenium atom in the side chain can be used as a coating composition. Solute compound. The perfluoroalkylene ether group is represented by the following formula ο-1), and the hydrolyzable group containing a ruthenium atom is represented by the following formula (1-2): [Chemical 4] —^OCnFin+i^— (1 —1) 4CT 七Si-(Bf)3 (1-2) In the formula (1-1), η represents an integer of 1 to 5, and in the formula (1-2), m represents an integer of 〇~2, and R1 represents Hydrolyzable group. The frequency of occurrence of the ether bond in the perfluoroalkylene ether group is not particularly limited, and -(〇CF2)-, -(〇C2F4)-, -(OC3F6)-, -(〇C4F8)-, etc. may be used as The repeat unit is a perfluoroalkylene ether group formed by a combination of a single or a plurality of combinations. Further, the one end of the perfluoroalkylene ether group is preferably a CnF2n+1- group having η of 1 or more. The hydrolyzable group containing a ruthenium atom in the side chain is preferably a group which is decomposed by the action of water when forming a coating film in coating, and is represented by the above formula (1-2). R1 is exemplified by, for example, a halogen atom, a -R3 group, an -OCOR3 group, -oc(r3) = c(r4)2 group, -〇N = C(R3)2 group, -on=c(r5)2 group, and the like. . Here, R3 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R5 represents a divalent aliphatic hydrocarbon having a carbon number of 3 to 6 201020300. In the present invention, it is preferred that when a compound represented by the formula (1) is used as a solute, the chlorine atom, the -OCH3 group, and the -OC2H5 group in which the film is clouded can be further suppressed. A preferred example of the compound used in the above invention can be exemplified by the compound represented by the formula (1).

The linear or branched perfluoroalkyl group having 1 to 16 carbon atoms represented by Rf is exemplified by a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group or the like. The alkyl group having 1 to 3 carbon atoms represented by Y is exemplified by methyl, ethyl and propyl 〇q, and represents an integer of 1 to 50, preferably 18 to 30, more preferably 22 to 2 6 , and m is shown as 0. ~2, preferably an integer of 0, and r represents an integer of 1 to 10, preferably 1 to 5. .

The fluorine compound represented by the formula (1) can be obtained by subjecting a commercially available perfluoropolyether to treatment with decane. This method is disclosed in, for example, Japanese Laid-Open Patent Publication No. Hei No. Hei. G The fluorine-based solvent containing at least one of a fluorinated hydrocarbon and a fluorinated ether which is a component of the mixed solvent used in the present invention has a boiling point of 40 t or more and 70 ° C or less at atmospheric pressure. Further, the difference between the maximum enthalpy and the minimum enthalpy of the boiling point of the fluorine-based solvent in the mixed solvent is within 25 ° C, preferably within 20 ° C. The preferred mixed solvent is a fluorine-based solvent 1 having a boiling point of 40 ° C or more and 70 ° C or less at a pressure of atmospheric pressure, and a fluorine-based solvent 2 having a boiling point difference of 20 ° C or less with respect to the boiling point of the solvent 1 Mixed solvent. When a coating agent obtained by dissolving two or more kinds of solvents of the above-mentioned boiling point conditions was spray-coated with -10-201020300, it was found that a film having a suppressed film thickness unevenness and a transparent film was obtained. When the coating is applied by a spray method using a solvent-like coating agent, the film is easily clouded, and the range of conditions for obtaining a transparent film (for example, 'the humidity and temperature of the atmosphere at the time of coating, etc.) is remarkably narrow. The result becomes a high-cost process. Further, the combination of a solvent having a boiling point difference of more than 25 t will impair the uniformity of the film thickness uniformity of the film. When the solvent having a boiling point higher than 70 ° C is used, the time until drying becomes longer, and when a low solvent having a boiling point of less than 40 ° C is used, the droplet of the coating composition sprayed from the spray gun before reaching the substrate That is, powdering, and a transparent film cannot be obtained. The mechanism is not clear, but the composition of the above solvent can suppress the unevenness of the film thickness and obtain a transparent film. The solvent used in the present invention is preferably selected from 1,1,1,3,3-pentafluorobutane (boiling point 40°) in consideration of effects on environmental damage, safety during production, and availability. C), perfluorohexane (boiling point 56. 〇, 1,1,1,2,2,3,3,4,5,5,5-O dec-fluoro_4_(trifluoromethyl)pentane ( a solvent having a boiling point of 56. 〇 'methyl nonafluorobutyl ether (boiling point 6 1 ° C) and a mixture of two or more solvents, especially two or more solvents having a difference in boiling point of 20 ° C or less Further, the mixing ratio of the mixed solvent is preferably 1% by weight or more, more preferably 2% by weight or more, based on the total amount of the mixed solvent. Further, the solvent can be mixed and adjusted in the above solvent. The coating composition of the present invention can be applied by spraying a substrate onto a substrate by a dipping method in which a substrate is immersed in a coating group -11 - 201020300. A wet process such as a spin coating method in which a coating composition is dropped while a substrate is rotated, and a solvent such as a coating composition is used for vacuum evaporation using a solvent for a coating composition. A conventional method such as a dry process is applied to the surface to form an antifouling layer. In the above, it is understood that the antifouling layer formed by the spray method is more excellent in abrasion resistance than those formed by other methods. From the viewpoint of utilization efficiency and productivity of the material, the spray method is also advantageous than other methods. Therefore, the optimum coating method is the spray method. @ The substrate forming the above antifouling layer can be exemplified by an inorganic substrate. Or an organic substrate 〇 an inorganic substrate is exemplified by glass, metal, ceramics, etc. Among these, a transparent or translucent glass, ceramic, etc. are preferable. 'The organic substrate is exemplified by plastic, rubber, elastomer, etc. Medium, "good for transparent or translucent plastic, preferably acrylic resin, polycarbonate resin, etc.

The transparent or translucent substrate is mostly used for a display unit such as a mobile phone or a display G, and is particularly required to form a substrate of an antifouling layer. The shape of the substrate is preferably a film or a sheet. However, it is not particularly limited, and if it is a flat surface or a smooth curved surface, it can be used as a substrate for forming an antifouling layer. Further, other surface treatment such as a hard coat layer, an anti-reflective coating layer, or an anti-glare coating layer may be applied to the substrate in advance. An inorganic surface film is preferably provided on the surface of the inorganic substrate or the organic substrate. In particular, it is preferred to provide an inorganic surface film on the surface of the organic substrate. By setting the inorganic surface film on -12-201020300, the adhesion of the anti-fouling layer can be improved. As for the inorganic surface film, the thickness of the semiconductor film, the oxide film, the nitride film, the oxynitride film, etc., which is required to meet the requirements of the product, is preferably formed to ensure the adhesion of the antifouling coating layer, which is 0·01~ The range of 1 μιη, more preferably 0.05. However, when an inorganic film other than the anti-fouling property is required, the film thickness may be appropriately set. φ The inorganic surface film is formed on the surface of the substrate by a conventional forming method such as a spray coating method or a CVD method. When the antifouling layer of the compound represented by the formula (1) is formed, the azane solution is applied by a spray coating method and dried to obtain a practically sufficient abrasion resistance. Further, in terms of production cost, since the method of coating the polyazirane solution by the spray method is also excellent as in other methods, the inorganic method is formed. The φ polyazane solution is prepared by blending the type of the substrate with the type of the substrate, the film thickness, and the spray strip. Further, the spray coating of the polyfluorene carrier gas is preferably a gas which does not contain moisture as much as possible, and it is most appropriate to use nitrogen gas. Further, if the dry 'alkyl-based inorganic film is placed in a high-humidity atmosphere as needed, or by conversion, the conversion to cerium oxide can be promoted. The antifouling substrate of the present invention is a metal film selected from the display of a mobile phone or the display surface of a touch panel, an eyeglass lens or the like. Insulin surface film minimum required -0.2 μιη range to be in this range, sol method, splashing knows the use of polythene machine surface film can be obtained, the production of the view into the inorganic surface film surface film is better for sale, concentration, dissolution The above-mentioned defense is carried out on the surface of the substrate such as the surface of the substrate after the drying of the polypyrene nitrogen applied light or thermal energy surface, the liquid crystal panel with sebum, the fingerprint-13-201020300, the sweat, the cosmetics, etc. Stainer. Hereinafter, an example of a mobile phone in which an antifouling layer is formed using the coating composition of the present invention will be described with reference to the drawings. 1 and 2 are diagrams showing an example of a mobile phone. Fig. 1 shows the entire mobile phone, which is various operation keys 1 used for a call or the like, various information related to the telephone (telephone number, radio wave state, battery residual amount, etc.) or screen display device 2 of the screen display portion, microphone 3, speaker 4 Composition. The screen display device 2 is specifically exemplified by a liquid crystal display @ (LCD) or an organic electroluminescence display (organic EL display). Figure 2 shows a section AA' of Figure 1. The screen display device 2 is disposed inside the casing 5 of the mobile phone, and the transmission window member 6 is disposed on the screen display device 2. The window member 6 is generally a resin having a good light transmittance, and the material may be acrylic or polycarbonate. In the present invention, the inorganic surface film 6a and the antifouling layer 6b formed of the compound represented by the formula (1) are sequentially disposed on the transmission window member 6. The transparent inorganic surface film 6a is formed on the transmission window member 6 by sputtering. As the material of the inorganic surface film 6a, a polyazane-based inorganic film can be used. Further, the surface antifouling layer 6b can be formed by applying and drying a compound represented by the formula (J) as a coating composition for a solute by a spray coating method. Examples The substrate after the antifouling treatment was evaluated by the following method. Explain the evaluation project and evaluation method. -14 * 201020300 (Evaluation 1) Appearance The evaluation sample was visually observed under a illuminance of 500 lumens or more in a dark room to determine whether the film was cloudy or uneven. (Evaluation 2) Sebum adhesion The evaluation sample was pressed against the cheek to visually observe the adhesion state of sebum. The evaluation criteria were such that the state of adhesion of the untreated green sheet glass was not good, and it was good that the sebum adhesion state was significantly smaller than this. (Evaluation 3) Sebum-removing property The evaluation sample of the following (Evaluation 4) was gently rubbed back and forth 10 times with a non-woven fabric made of cellulose (BencoTE, manufactured by Asahi Kasei Corporation), and the residue was visually observed. The evaluation criteria were set to be good for those who had almost no sebum remaining, and those with obvious residuals were bad. Φ (Evaluation 4) Abrasion resistance The photocopying paper (SUPER-WHITE manufactured by ASKUL) was pressed against the sample at a load of 9_8 N/cm2, and slid back and forth to measure the contact angle of the sliding portion with respect to water, and the contact angle was determined to be less than 90. The number of slides until °. The test was carried out three or more times and the average enthalpy was evaluated. Further, if the abrasion resistance of about 50,000 times is carried out by the test method, it is considered to have practical wear resistance. In addition, the film thickness described in the following examples and comparative examples was measured on a Si (10 0) substrate formed simultaneously with the evaluation sample by a film thickness meter (polarization analyzer) (DHA-FR manufactured by Gully Optical Co., Ltd.). The film. Further, the contact angle was measured by measuring the contact angle of the surface of the sample with water by a contact angle meter (DM1 00 manufactured by Kyowa Interface Science Co., Ltd.) of -15-201020300. Example 1 1 part by weight of a compound represented by the following formula (2) was dissolved in 4 parts by weight of perfluorohexane (boiling point 56. 〇 and 195 parts by weight of 1,1,1,3,3-pentafluoro A composition obtained by mixing butane (a boiling point of 40 Å in a mixed solvent) is applied as a coating composition. The coating composition is applied onto a glass substrate (glass-coated glass S1225 manufactured by AS-ONE Co., Ltd.) by a spray method. And dried at 5 (TC for 30 minutes. The film thickness of the formed antifouling layer was 8.4 nm, and the contact angle was 116. The appearance of the film was not uneven and was transparent, and sebum adhesion and sebum removal were also good. The wear resistance was 95,763 times. The results are shown in Table 1. [Chemical 5] C3F7"(〇CF2CF2 CF七•Η (2) rl-10

In the formula (2), the repeating number of the repeating unit having a trimethoxydecane in the side chain of 1-10 is a mixture of the repeating numbers of 1 to 10. Example 2 Preparing 1 part by weight of the above formula (2) The compound is dissolved in 4 parts by weight of perfluorohexane (boiling point 56 ° C) and 195 parts by weight of 1,1,1,2,2,3,3,4,5,5,5- A group of 201020300, which is a mixture of monofluoro-(trifluoromethyl)pentane (boiling point of 56 ° C), is used as a coating composition. The coating composition is applied to a glass substrate by a spray method. (glass-coated glass S 1 225 manufactured by AS-A) was dried at 50 ° C for 30 minutes. The film thickness of the formed anti-fouling layer was 9.2 nm, and the contact angle was 115 °. The appearance of the film was not uneven. It was transparent, sebum adhesion and sebum removal were also good, and the abrasion resistance was 8,8,140 times. The results are shown in Table 1 〇φ Example 3 Preparation of 1 part by weight of the compound represented by the above formula (2) A composition obtained by dissolving in a mixed solvent of 4 parts by weight of perfluorohexane (boiling point 56t) and 195 parts by weight of methyl nonafluorobutyl ether (boiling point 611) as a coating group

— adult. This coating composition was applied onto a glass substrate (glass-coated glass S 1 225 manufactured by AS-ONE - Co., Ltd.) by a spray method, and dried at 50 ° C for 30 minutes. The film thickness of the formed antifouling layer was 8.8 nm, and the contact angle was 116°. The outer layer of the film was not uneven and was transparent, and the sebum adhesion property and sebum removal property were also good. φ has an abrasion resistance of 92,598 times. The results are shown in Table 1. Example 4 A polyazide solution (AQUAMICA NL120A-05 manufactured by AZ Electronic Materials Co., Ltd.) was applied onto a hard-coated acrylic substrate (ACRYLITE MR-200 manufactured by Mitsubishi Rayon Co., Ltd.) by a spray method at atmospheric atmosphere. A film of polydecazane (film thickness 93 inn) was formed in the atmosphere for a day and night. Subsequently, the coating composition used in Example 2 was applied by a spray method under the same conditions as in Example 2. The anti-fouling layer has a film thickness of 8.5 ηηη and a contact angle of 1 17°. • 17- 201020300 The appearance of the film is not uniform and transparent, and the sebum adhesion and sebum removal properties are also good. The wear resistance is 6 6,0 3 1 times. Comparative Example 1 A composition obtained by dissolving 1 part by weight of the compound represented by the above formula (2) in 199 parts by weight of perfluorohexane (boiling point: 56 ° C) was prepared as a coating composition. This coating composition was applied onto a glass substrate (glass-coated si 22 5 manufactured by AS-ONE Co., Ltd.) by a spray method under the same conditions as in Example 1. The appearance of the film was obviously cloudy. Since the appearance of the film was poor, the evaluation of sebum adhesion, sebum removal property, and abrasion resistance was terminated. Comparative Example 2 1 part by weight of the compound represented by the above formula (2) was dissolved in 4 parts by weight of perfluorohexane (boiling point 56 t) and 195 parts by weight of Novec HFE 7200 (boiling point 76 ° C) manufactured by Asahi Glass Co., Ltd. The composition obtained in the mixed solvent is used as a coating composition. This coating composition was applied onto a glass substrate (glass-coated glass S1225 manufactured by AS-A) under the same conditions as in Example 1 by a spray coating method. Although the appearance of the film is transparent, a circular pattern (non-uniform) which is visually identifiable occurs. Since the appearance of the film was poor, the evaluation of sebum adhesion, sebum removal, and abrasion resistance was terminated. Comparative Example 3 1 part by weight of a compound represented by the above formula (2) was dissolved in 4 parts by weight of perfluorohexane (boiling point: 56 ° C) and 195 parts by weight of FLUORINERT manufactured by Sumitomo 3M -18-201020300 A mixed solvent of FC - 4 0 (boiling point 15 5 ° C) was used as a coating composition. This coating composition was applied onto a glass substrate (glass-loaded glass S 1 225 manufactured by AS-A) under the same conditions as in Example 1 by a spray method. Although the appearance of the film is transparent, unevenness of the amorphous shape (anamorphic shape) which is visually recognizable occurs. Since the appearance of the film was poor, the evaluation of sebum adhesion, sebum removal, and abrasion resistance was terminated. φ Comparative Example 4 The coating composition used in Example 2 was directly applied onto the hard coated acrylic substrate used in Example 4 by a spray method. The anti-fouling layer had a film thickness of 9.9 nm and a contact angle of 116°. The appearance of the film was not uniform and was 'transparent, and the sebum adhesion property and sebum removal property were also good. However, the wear resistance is as low as 7,379 times. Comparative Example 5 φ The solute of the coating composition used in Example 2 was formed into a film on the glass substrate used in Example 2 by a vacuum deposition method. The background pressure of the vacuum evaporation was about 10_3 P a, and the solute of the coating composition placed in the glass crucible was heated from room temperature to 500 ° C in 30 minutes. The film thickness of the formed film was 7.2 nm, and the contact angle was 1 17°. The appearance of the film was not uniform and was transparent _, and sebum adhesion and sebum removal were also good. However, the abrasion resistance was 42,217 times, which was lower than that of Example 2. Comparative Example 6 -19-201020300 The coating composition used in Example 2 was formed into a film on the glass substrate used in Example 2 by a dipping method. The impregnation method was immersed at room temperature for 24 hours and pulled at a rate of 10 mm/sec. The formed film thickness was 5 nm or less and could not be measured. In addition, the contact angle was 117°. The appearance of the film was not uniform and was transparent, and the sebum adhesion property and sebum removal property were also good. However, the wear resistance is as low as 4,700 times. A SiO 2 film (film thickness: 10 nm) was formed by sputtering on the hard-coated acrylic substrate used in Example 4. The sputtering was performed with an ion beam, the background pressure was about 10_3 Pa, and the fused silica target was irradiated with an Ar ion beam of 700 eV. Subsequently, the coating-coating agent used in Example 2 was applied by a spray coating method. The film thickness of the antifouling layer was 8.9 nm, and the contact angle was 1 15 . . Outside the film. The view is not uneven and transparent, and sebum adhesion and sebum removal are also good. However, the abrasion resistance was 20,558 times, which was lower than that of Example 4. The results of the respective examples and comparative examples are summarized in Table 1. Further, in Table 1, φ 'solvent A represents perfluorohexane (boiling point 56. 〇, solvent b represents 丨, ;! pentafluorobutane (boiling point 40. 〇, solvent C is fluoro-(difluoromethyl)pentane) (Boiling point 56 ° C), solvent D is methyl nonafluorobutyl ether (boiling point 61 ° C), solvent E is N〇vecHFE7200 ( 'boiling point 76C)' solvent F manufactured by Asahi Glass Co., Ltd. FLUORINERT 1 manufactured by Sumitomo 3M ^-4 0 (boiling point 155° (:). -20- 201020300 [Table i] Coating composition substrate inorganic surface film coating method evaluation result solute solvent 1 solvent 2 appearance sebum adhesion sebum removal wear resistance (次) Example 1 Formula (2) AB Glass 4nr 喷 Spraying method is good and good 95,763 Example 2 Formula (2) AC glass Μ Spraying method is good and good 88, 140 Example 3 Formula (2) AD glass m Spraying cloth Good and good method 92,598 Example 4 Formula (2) AC Acrylic polyfluoride nitrogen spray method Good and good 66,031 Comparative example 1 Formula (2) A fte y»\\ Glass sister <n, N Spraying white turbidity _ _ Comparative Example 2 Formula (2) AE Glass 4E Spraying method Circular unevenness - - - Comparative Example 3 Formula (2) AF Glass Μ y\\\ Disproportionate unevenness in the spray method - - - Comparative Example 4 Formula (2) AC Acrylic acid 喷 Spraying method is good and good 7,379 Comparative Example 5 Formula (2) AC glass crucible Vacuum evaporation method is good and good 42,217 Comparative Example 式 Formula (2) A c Glass 4nr No immersion method Good good Good 4,701 Comparative Example 7 Formula (2) A c Acrylic acid sputtered SiO 2 Spraying method is good and good 20,558 [Probability of industrial use] φ By the coating of the present invention The cloth composition and the surface treatment method can form an antifouling film which is excellent in antifouling property and transparent, and which is practically durable enough at low cost, and can be used in a mobile phone, a display device, etc. ' [Simple description of the drawing] Fig. 1 is an external view showing an embodiment of a mobile phone according to the present invention. Fig. 2 is a schematic view showing a section AA' of Fig. 1. -21 - 201020300 [Description of main component symbols] 1: Operation key 2: Screen Display device 3: microphone (speaking port) 4: speaker (receiving port) 5: frame 6: transmission window member 6a: inorganic surface film @ 6b: antifouling layer-22-

Claims (1)

201020300 VII. Patent application scope: 1. A coating composition containing a perfluoroalkyl ether group in a molecular main chain, and a compound containing a hydrolyzable group containing a ruthenium atom in a side chain is dissolved in a solvent. The coating composition is characterized in that the solvent is a mixed solvent of a fluorine-based solvent containing at least one of a fluorinated hydrocarbon and a fluorinated ether, and the fluorine-based solvent has a boiling point of 40 ° C at 1 atm. Above 70 ° C, the difference between the maximum enthalpy and the minimum enthalpy of the boiling point φ of the fluorine-based solvent in the mixed solvent is 25. (2) The coating composition according to the first aspect of the invention, wherein the perfluoro-extension-based ether group is represented by the following formula (1-1): the hydrolyzable group containing the sand atom is represented by the following formula (1) - 2 ) means: [Chemical 1] - (〇C〇Fin+1 (i-i) Bu (R)3 0-2) ❹ (where η is an integer from 1 to 5, m is 〇~2 The formula of the coating of the second aspect of the invention, wherein the compound is a compound represented by the following formula (1): [Chemical 2] Rf-(〇CF2CF2 CF ,-^-〇-(CF2 heart ί— (1) -23- 201020300 (wherein Rf represents a linear or branched perfluoroalkyl group having a carbon number of 1 to 16 'Y represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R1 represents a halogen atom selected from - OR3 group, -OCOR3 group '-oc(r3)=c(r4)2 group, -on=c(r3)2 group and at least one group of -on=c(r5)2 group, R3 represents an aliphatic hydrocarbon group or An aromatic hydrocarbon group, R4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R5 represents a divalent aliphatic hydrocarbon group having 3 to 6 carbon atoms, q represents an integer of 1 to 50, m represents an integer of 0 to 2, and r represents An integer from 1 to 1). 4. The coating composition according to claim 3, wherein the above R1 is at least one selected from the group consisting of a chlorine atom, an -OCH3 group, and an -OC2H5 group. 5. The coating composition according to claim 1, wherein the fluorine-based solvent is 1,1,1,3,3-pentafluorobutane, perfluorohexane, 1,1,1,2, 2,3,3,4,5,5,5- · undecafluoro-4-(trifluoromethyl)pentane or methyl nonafluorobutyl ether. 6. Apply as coated in item 1 of the patent application a composition for cloth, wherein the mixed solvent is selected from the group consisting of 1,1,1,3,3-pentafluorobutane, perfluorohexane, 1,1,1,2,2,3,3,4,5, A mixed solvent of two fluorine-based solvents of 5,5-undefluoro-4-(trifluoromethyl)pentane and methyl nonafluorobutane@yl ether. 7. An antifouling treatment method which is an antifouling treatment method which performs an antifouling treatment by applying a coating on a surface of an inorganic substrate or an inorganic surface film formed on an inorganic or organic substrate, It is characterized in that the coating layer on the surface of the inorganic substrate or the surface of the inorganic surface film is coated by coating with a coating composition of the first application of the patent application. 8. The antifouling treatment method according to item 7 of the patent application, wherein the -24-201020300 inorganic surface film is an inorganic surface film formed by spraying a polyxazane solution by a spray method. An antifouling substrate which is an antifouling substrate having an antifouling layer on a surface of a substrate or an inorganic surface film formed on the substrate, wherein the antifouling layer is applied by Anti-fouling treatment formed by the anti-fouling treatment of Article 7 of the patent scope. 1 〇 — 防 防 防 防 防 防 防 防 防 防 防 防 防 前述 前述 前述 防 前述 前述 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防Anti-staining mobile phone. ❹ -25-