TW200804541A - Phosphoric ester containing coating fluid and antireflection coatings - Google Patents

Abstract

A coating fluid for film formation which is excellent in storage stability and can give a film exhibiting a high water contact angle and excellent dust wipe-off properties; films formed from the fluid; processes for production of both; and antireflection coatings made by using the fluid. A coating fluid for film formation which comprises (A) a polysiloxane having fluorinated organic groups as side chains and (B) a phosphoric ester having hydroxyl attached to the phosphorus atom; films formed from the fluid; and processes for production of both.

Description

[Technical Field] The present invention relates to a coating liquid for forming a film containing a polysiloxane and a phosphate compound, and a film formed therefrom, and a method for producing the same. Specifically, the coating liquid for forming a film containing a polyoxyalkylene having an organic group substituted with a fluorine atom in a side bond, and a phosphate compound having a hydroxyl group, and a film formed thereby, and a film Forming method. Further, Φ is applied to the anti-reflection application of the coating liquid for forming a film and the film formed thereby. [Prior Art] Conventionally, it has been known that when a film having a refractive index lower than the refractive index of the substrate is formed on the surface of the substrate, the reflectance of light reflected from the surface of the film is lowered. Therefore, the film having reduced light reflectance is displayed as a light-proof reflective film, and is suitable for use on various substrate surfaces. #, for example, an alcohol dispersion of MgF2 fine particles which is formed by reacting a magnesium salt, an alkoxymagnesium compound or the like as a source of Mg with a fluoride salt as a source of F, or added thereto for improving film strength A liquid such as tetraalkoxy decane is used as a coating liquid, coated on a glass substrate such as a Brownian tube, and then heat-treated at 1 Torr to 5 ° C to form a low refractive index on the substrate. A method of preventing an antireflection film (see Patent Document 1). Further, it is disclosed that a hydrolyzed polycondensate such as two or more kinds of tetraalkoxydecane, methyltrialkoxydecane or ethyltrialkoxydecane having a different average molecular weight is mixed with a solvent such as an alcohol to form a coating. When the liquid is formed into a film from the coating liquid, the method of mixing the ratio and the relative humidity is applied to the film to form a film, and then heating is performed on the glass substrate. A low-reflection glass having a film having a thickness of 1.21 to 1.40 and having a thickness of from 60 to 160 nm having micropits or concavities and convexities having a diameter of 50 to 200 nm (refer to Patent Document 2) is formed. Further, there is disclosed a low reflectance glass which is formed of glass, an underlayer film having a high refractive index formed on the surface thereof, and a film having a low refractive index φ formed on the surface of the underlayer film. (Refer to Patent Document 3). In this publication, the details of the method for forming the upper layer film include a fluorine-containing fluorenone compound having a polyfluorocarbon chain such as CF3(CF2)2C2H4Si(OCH3)3, and 5 to 90 weights thereof. % of a decane coupling agent such as Si(OCΗ3)4, which is hydrolyzed at room temperature in an alcohol solvent in the presence of a solvent such as acetic acid, and then pulverized to prepare a liquid of the cocondensate. The above-mentioned underlayer film is heated at 120 to 250 ° C to form a conformation method. Further, a reaction mixture containing a ruthenium compound represented by Si(OR) 4 in a specific ratio, CFHCFdndCHdUOR1), an alcohol represented by R2CH2OH, and oxalic acid is disclosed in the absence of water. Heating at 40 to 180 ° C to form a solution of polyoxyalkylene, and then coating a coating liquid containing the solution on the surface of the substrate, and thermally curing the coating film at 80 to 450 ° C to The surface of the material is densely grounded to form a film having a water contact angle of 1.28 to 1.38 and a water contact angle of 90 to 11 5 (refer to Patent Document 4), and a display element (especially a liquid crystal display element) which is antireflection treated by the above-described technique In the case of charging due to the influence of the use environment, the adhesion of dust-5-200804541 (3) is caused, and it becomes difficult to see an image. Further, since the adhered dust is often not easily rubbed off, a display element which can easily wipe off dust adhering to the antireflection film is required. Therefore, in the antireflection film ' particularly the antireflection layer on the outermost surface of the display element, it is strongly required to impart the function of suppressing the electrification to prevent the adhesion of dust and to easily wipe off the adhered dust (dust erasability). Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 208 898 OBJECTS OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The object of the present invention is to provide a coating liquid for forming a film which is excellent in storage stability, has a high water contact angle, and has excellent dust repellency, and is formed of the film formed therefrom. • Membrane' and its method of manufacture. Further, an object of the present invention is to use the coating liquid for coating film formation and the film formed therefrom for antireflection use. Means for Solving the Problems The inventors of the present invention have intensively studied in view of the above-described conditions, and have completed the present invention shown below. That is, the present invention has the following gist. A coating liquid for forming a film, comprising: (A) a component, that is, a polyoxyalkylene having an organic group substituted with a fluorine atom in a side chain; and (B) a component, that is, a phosphorus atom bond A phosphate compound having a hydroxyl group. (4) The coating liquid for forming a film according to the above-mentioned item 1, wherein the component (A) contains the alkoxydecane represented by the formula (1) and the alkoxydecane represented by the formula (2). Alkoxy decane, polycondensed by polycondensation, [Chemical 1]

Si(OR1)4 (1)

(R1 represents a hydrocarbon group having 1 to 5 carbon atoms), [Chemical 2] R2Si(OR3)3 (2) (R2 represents an organic group substituted by a fluorine atom, and R3 represents a hydrocarbon group having 1 to 5 carbon atoms) . The coating liquid for forming a film according to the above 2, wherein R2 is a perfluoroalkyl group in the formula (2). 4. The coating liquid for forming a film according to the above 2 or 3, wherein the component (a) is obtained by polycondensing an alkoxysilane represented by the formula (3). R4nSi(〇R5)4.n (3) (R represents an organic group which is not substituted by a fluorine atom, R5 represents a hydrocarbon group having from 〗 〖200804541 (5) carbon atoms, and η represents an integer of from 1 to 3). 5. The coating liquid for forming a film according to any one of the above 1 to 4, wherein the (Β) component is a phosphate compound represented by the formula (4). 〇P(〇H)m(OR6)3.m (4) (R6 represents an organic group having 1 to 20 carbon atoms, and m represents an integer of 1 or 2). 6. The coating liquid for forming a film according to the above 5, wherein R6 in the formula (4) is an organic group having 1 to 6 carbon atoms. The coating liquid for forming a film according to any one of the above-mentioned items 1 to 6, wherein the total amount of the ruthenium atoms of the (A) component is 1 至1 to 0.45 mol ( B) The phosphorus atom of the component. The coating liquid for forming a film according to any one of the above aspects, wherein the component (A) contains 60 to 95 mol% of the alkoxydecane represented by the formula (1) and 5 to 40. The polyoxyalkylene obtained by polycondensation of the alkoxydecane of the alkoxydecane represented by the formula (2). A coating film formed by using the coating liquid for forming a film according to any one of the above 1 to 8 above. An antireflection film formed by the coating liquid for forming a film according to any one of the above items 1 to 8. A coating film forming method according to any one of the above 1 to 8, which is applied to a substrate, dried at room temperature to 150 ° C, and then at room temperature. Hardening at 150 °C. 200804541 (6) The method for forming an anti-reflection film, which is applied to a substrate by a coating liquid for forming a film according to any one of the above 1 to 8, at room temperature to 150 ° After C is dried, it is hardened at room temperature to i 5 °C. An antireflection substrate comprising the film according to the above 9 or the antireflection film described in JP. An antireflection film comprising the film according to the above 9 or the antireflection film described in the above. A method for producing a coating liquid for forming a film, characterized by a peralkoxy group for obtaining a polyoxyalkylene having an organic group substituted with a fluorine atom in a side chain of the component (A). Within the decane, 60 to 95 mol% of the alkoxydecane represented by the formula (1) and 5 to 40 mol% of the alkoxydecane of the alkoxydecane represented by the formula (2), and For alkoxy groups of 1 mol of all alkoxy squalane, 0. 2 to 2 mol of oxalic acid is heated in an organic solvent at a liquid temperature of 50 to 180 ° C to obtain a polycondensation. a solution of a polyoxane, which is mixed with a phosphate compound having a hydroxyl group bonded to a phosphorus atom, [Chemical 5]

Si(〇R1)4 (1) (R1 represents a hydrocarbon group having 1 to 5 carbon atoms), [6] (2) R2Si(OR3) 200804541 (7) (R2 represents an organic group substituted by a fluorine atom, R3 represents a nicotinic group having 1 to 5 carbon atoms). According to the coating liquid for forming a film of the present invention, it is possible to form a stable film which is excellent in storage stability, has a high water contact angle, is excellent in dust repellency, and does not change with time. Among them, a coating liquid for forming a film having a low reflectance is used as a coating liquid for forming an antireflection film, and a film formed therewith exhibits low reflectance, high antifouling property, and dust erasing property. Therefore, it is very useful as an anti-reflection film. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The present invention relates to a coating liquid for forming a film comprising a polyoxyalkylene having an organic group substituted with a fluorine atom in a Φ side chain of the component (A), and a hydroxyl group bonded to a phosphorus atom in the (B) component. a phosphate compound; and a film formed therefrom, and a method of producing the same. <(A) Component> The component (A) is a polyoxo having an organic group substituted with a fluorine atom in a side chain. In the present invention, the aforementioned side chain system mainly imparts a high water contact angle to the film, and as long as the antifouling property is exhibited thereby, the aforementioned side chain is not particularly limited by -10-200804541 (8). The organic group substituted by such a fluorine atom is an organic group in which a part or all of a hydrogen atom of an aliphatic group or an aromatic group is substituted with a fluorine atom. Specific examples of these are as follows. For example, a trifluoropropyl group, a tridecafluorooctyl group, a heptadecafluorodecyl group, a 'pentafluorophenylpropyl group, etc. are mentioned. Among these, a perfluoroalkyl group is preferred because it is easy to obtain a film having transparency. More preferred is a perfluorocarbon base having a carbon number of 3 to 15. Specific examples thereof include a trifluoropropyl group, a tridecafluorooctyl group, and a heptadecafluoroindenyl group. In the present invention, a plurality of polysiloxanes having a side chain as described above may be used. The method for obtaining a polyoxyalkylene having an organic group substituted with a fluorine atom in the side chain as described above is not particularly limited. In general, the alkoxydecane having an organic group in the side chain described above may be obtained by polycondensation of alkoxysilane having the other group. In particular, it is preferably obtained by polycondensation of an alkoxy decane containing an alkoxy decane represented by the formula (1) and an alkoxy decane represented by the formula (2). [Chemistry 7]

(2) R2Si(OR3) -11 - 200804541 (9) R1 in the formula (1) represents a hydrocarbon group, and since the carbon number is less, the reactivity is higher, so the carbon number is preferably from 1 to 5. The saturated hydrocarbon group is more preferably a methyl group, an ethyl group, a propyl group or a butyl group. Specific examples of such a tetraalkoxy decane include tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, and tetrabutoxy decane, which are easily available from commercially available products. In the present invention, at least one of the alkoxydecanes represented by the formula (1) can be used, and a plurality of kinds can be used as needed. The alkoxydecane represented by the formula (2) is an alkoxydecane having an organic group substituted with a fluorine atom in the side chain. Therefore, the alkoxysilane is a person who imparts water repellency to the coating film. Here, R2 in the formula (2) represents the above-mentioned organic group substituted by a fluorine atom, but the number of fluorine atoms which the organic group has is not particularly limited. Further, R3 in the formula (2) represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group or a butyl group. Among the alkoxydecanes represented by the formula (2), R2 is preferably a perfluoroalkyl alkoxydecane, and R2 is more preferably an organosiloxane of the organic group represented by the formula (5). . CF3(CF2)kCH2CH2 (5) In the formula (5), k represents an integer of 〇 to 12. -12- (10) 200804541 Specific examples of the alkoxydecane having an organic group represented by the formula (5) include trifluoropropyltrimethoxydecane and a trifluoropropyltriethoxy group. Heptafluorodecyltrimethoxydecane, tridecafluorooctyltriethoxyphthalate, heptafluorodecyltrimethoxydecane, heptadecafluorodecyltriethoxydecane, and the like. It is particularly preferable that k is an integer of 2 to 12 because the anti-reflection film has good fingerprint erasability. In the present invention, at least one of the alkoxysilanes represented by the formula (2) may be used, and a plurality of kinds may be used as needed. Further, the polyoxyalkylene (A) may be carried out from the alkoxydecane represented by the formula (1) and the formula (2), and the alkoxydecane represented by the formula (3) and/or the formula (6) other than the above. Polycondensation is the result. In this case, in addition to the alkoxysilanes represented by the formulas (1) and (2), the decyl oxide sand represented by the formula (3) and the alkoxy decane represented by the formula (6) may be used singly. Either of them can also use both. R4nSi(OR5)4-n (3) In the formula (3), R4 represents an organic group which is not substituted by a fluorine atom, and R5 represents a hydrocarbon group having 1 to 5 carbon atoms, and n is not 1 to 3 The integer. (6) (6) (R70)3SiR8Si(0R7)3 -13- (11) (11)200804541 In the formula (6), R7 represents a hydrocarbon group having 1 to 5 carbon atoms, and R8 represents 1 to 20 An organic chain of carbon atoms. The alkoxydecane of the formula (3) has an organic group in which R4 is not substituted with a fluorine atom and an alkoxydecane having 1, 2 or 3 alkoxy groups. R5 in the formula (3) is a hydrocarbon group each having 1 to 5 carbon atoms. When η is 1, 2, it is usually the case that R5 is the same, but in the present invention, R5 may be the same or different. R4 in the formula (3) is an organic group having 1 to 20 carbon atoms, preferably an organic group having 1 to 15 carbon atoms. When η is 2 or 3, usually R4 is the same, but in the present invention, R4 may be the same or different. Specific examples of the alkoxydecane represented by the formula (3) are shown below, but are not limited thereto. Methyl trimethoxy decane, methyl triethoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, propyl trimethoxy decane, propyl triethoxy decane, butyl Trimethoxy decane, butyl triethoxy decane, pentyl trimethoxy decane, pentyl triethoxy decane, heptyl trimethoxy decane, heptyl triethoxy decane, octyl trimethoxy decane, Octyltriethoxydecane, dodecyltrimethoxydecane,dodecyltriethoxydecane,hexadecyltrimethoxydecane,hexadecyltriethoxydecane,octadecyltrimethoxydecane, Octadecyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, 3-isocyanate propyl trimethoxy Decane, 3-isocyanatepropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, γ-glycidoxypropyltrimethoxy Decane, γ-glycidoxypropyltriethoxydecane, γ-mercaptopropyltrimethoxydecane-14- 200804541 (12) Γ-mercaptopropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-propenyloxypropyltriethoxydecane, γ-methylpropenyloxypropyltrimethyl Oxygen sand yard, γ-methylpropenyl methoxypropyl triethoxy decane, γ-ureidopropyl trimethoxy decane, γ·ureidopropyl triethoxy decane and dimethyl di Dioxane " decane and the like such as methoxy decane or dimethyldiethoxy decane. R5 in the formula (3) is a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated φ and a hydrocarbon group having 1 to 4 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 3 carbon atoms. In the present invention, a plurality of types of hospital oxygen chopping represented by the formula (3) can be used as needed. Further, the alkoxydecane system R7 of the formula (6) is a hydrocarbon group having 1 to 5 carbon atoms, preferably a saturated hydrocarbon group having 1 to 4 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 3 carbon atoms. In the present invention, a plurality of alkoxydecanes represented by the formula (6) can be used as needed. In general, R7 is the same in many cases, but in the present invention, R7 may be the same or different. R8 is an organic chain having 1 to 20 carbon atoms, and is not particularly limited in structure, and may have a cyclic structure or a branched structure such as a double bond or a triple bond or a phenyl group. Further, a hetero atom such as nitrogen, oxygen or fluorine may be contained. In order to make the water repellency of the film formed by the present invention more excellent, among the alkoxy decanes represented by the formula (6), it is preferred to use a formula (7) in which a part of R8 contains a perfluoroalkyl chain. The alkoxy decane of the organic chain. -15- (13) (13) 200804541 -CH2CH2(CF2)pCH2CH2- (7) In the formula (7), p represents an integer of 1 to 12. Specific examples of the alkoxydecane having an organic chain-like structure of a perfluoroalkyl chain represented by the formula (7), which is one of R8 in the formula (6), may be 1,6-bis(trimethoxy). Base alkyl ethyl) dodecafluorohexane, 1,6-bis(triethoxydecylethyl)dodecafluorohexane, and the like. The component (A) used in the present invention usually has an alkoxydecane represented by the formula (1) and the formula (2), and the alkoxydecane represented by the formula (3) and the formula (6) may be optionally used. Either or both of them are obtained by polycondensation, and the ratio of the alkoxydecane used is not particularly limited as long as it is in a homogeneous solution state in a solvent. When the alkoxydecane represented by the formula (2) is 5 mol% or more in the total amount of the alkoxydecane used to obtain the component (A), the contact angle of water can be easily obtained as 8 0. The above film is preferably used, and if it is 40 mol% or less, the formation of a gel or impurities can be suppressed, and a homogeneous solution of the component (A) can be easily obtained, which is preferable. On the other hand, the amount of the alkoxydecane of the formula (1) is preferably from 6 mol% to 95 mol% in the total amount of all the alkoxydecane used to obtain the component (A). . In the case of using only the alkoxydecane represented by the formula (3), the total amount of the alkoxydecane used for obtaining the component (A) is preferably from 0 mol% to 35 mol%. Further, in the case of using only the alkoxydecane represented by the formula (6), it is preferable to use a molar amount of from 20 to 20 moles in the total amount of the alkoxysilane used for the composition of the compound (1) to (A). %. Further, in the case of using the alkoxy fluorene•16-200804541 (14) alkane represented by the formula (3) and the formula (6), the alkoxydecane represented by the formula (3) and the formula (6) The total amount of the alkoxydecane used to obtain the component (A) is 0 to 35 mol%, and the ratio of the alkoxydecane represented by the formula (6) is used for In the total amount of the hospitality of the component (A), it is preferably 0 to 15 mol%. The method for condensing the polyoxane of the component (A) used in the present invention is not particularly limited. For example, a method of hydrolyzing and condensing an alkoxydecane in an alcohol or a diol φ solvent can be mentioned. In this case, the hydrolysis/condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, it is theoretically possible to add 0.5 to 5 moles of water of all alkoxy groups in the alkoxysilane, but usually an excess of water is added in excess of 0.5 times mole. In the present invention, the amount of water used in the above reaction can be appropriately selected as desired, but is usually 0.1 to 2.5 times moles of all alkoxy groups in the alkoxydecane. Further, in general, for the purpose of promoting the condensation reaction, an acid such as hydrochloric acid, Φ sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid or maleic acid; a base such as ammonia, methylamine, ethylamine, ethanolamine or triethylamine; or hydrochloric acid; A metal salt such as sulfuric acid or nitric acid is used as a catalyst. In this case, the amount of the catalyst used for the reaction is preferably from about 0.001 to about 0.05 moles of all alkoxy groups in the alkoxydecane. Further, by heating a solution in which an alkoxysilane is dissolved, the hydrolysis/condensation reaction is generally further promoted. In this case, the heating temperature and the heating time may be appropriately selected as desired, and it is preferred that the reaction system be 50 to 180 ° C. in a closed container or under reflux without causing evaporation or evaporation of the liquid. Dozens to tens of hours. For example, a method of heating at 50 ° C, stirring at -17-200804541 (15) for 24 hours, or heating under reflux, stirring for 8 hours, or the like can be mentioned. Further, as another method, for example, a method of heating a mixture of alkoxysilane, a solvent and oxalic acid can be mentioned. Specifically, a method in which oxalic acid is previously added to an alcohol to form an alcohol solution of oxalic acid, and the solution and alkoxysilane are mixed and heated. At this time, the amount of oxalic acid is generally 0.2 to 2 moles for the total oxo-oxyl group of 1 mole of alkoxydecane. The heating in the method can be carried out at a liquid temperature of 50 to 180 ° C, preferably in a manner that does not cause evaporation of the liquid #, volatilization, etc., for example, in a closed vessel or under reflux for several tens of minutes to several tens hour. In the above respective methods, when a plurality of alkoxydecanes are used, a plurality of alkoxydecanes may be mixed in advance, or a plurality of alkoxydecane may be added in order. When the alkoxy decane is polycondensed by the above-mentioned method, the total amount of the argon atoms of the alkoxy decane to be charged is converted into a concentration of SiO 2 (hereinafter referred to as a concentration of SiO 2 ) of generally 20% by mass or less. By selecting an arbitrary concentration within such a concentration range, gel formation can be suppressed, and a homogeneous polyoxane solution can be obtained. The solvent used in the polycondensation of the alkoxydecane is capable of dissolving the alkoxydecane represented by the formula (1) and the formula (2) and optionally the alkane represented by the formula (3) and the formula (6). The oxane can be used without particular limitation. In general, in order to form an alcohol by a polycondensation reaction of an alkoxydecane, an alcohol or an organic solvent having good compatibility with an alcohol is used. Specific examples of such an organic solvent include alcohols such as methanol, ethanol, propanol, and butanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl-18-200804541 (16) ether, and An ether such as ethylene glycol monomethyl ether or diethylene glycol monoethyl ether; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone. In the present invention, a plurality of the above organic solvents may be mixed. <(B) Component> The component (B) used in the present invention is a phosphate compound having a hydroxyl group. 〇# In order to exhibit the excellent dust rubbing property of the effect of the present invention, it is preferred to have one or two molecules in one molecule. The phosphate compound bonded to the hydroxyl group of the phosphorus atom is preferably a phosphate compound represented by the formula (4). OP(OH)m(OR6)3.m (4)

R6 in the formula (4) is an organic group having 1 to 20 carbon atoms, and may have a cyclic structure or a branched structure such as a double bond or a triple bond or a phenyl group. Further, a hetero atom such as nitrogen or oxygen may be contained. When the carbon number of R6 is 21 or more, the compatibility with the polyoxyalkylene (A) is insufficient, and the storage stability of the coating liquid cannot be sufficiently obtained. Therefore, an organic group having 1 to 20 carbon atoms is preferable. When the film of the present invention is used for the antireflection film, it is more preferably a carbon number of 1 to 10 because the increase in reflectance can be suppressed, and particularly preferably a carbon number of 1 to 6, because the reflectance hardly rises. -19- (17) (17) 200804541 In the formula (4), m is an integer of 1 or 2, but when m is 0, the compound of the formula (4) is a phosphate compound having no hydroxyl group, and it is difficult to obtain the present invention. The antistatic effect of the effect. On the other hand, when m is 3, the compound of the formula (4) represents phosphoric acid, and since the affinity with the polyoxyalkylene (A) is insufficient, the formed film becomes unstable and whitens over time. Therefore, the compound having the dust-repelling property of maintaining the stability and antistatic property of the film and exhibiting the effects of the present invention is a phosphate compound having a hydroxyl group and an alkyl ester moiety in which m is 1 or 2. The more the number of hydroxyl groups is, the stronger the antistatic effect is. In particular, when m is 2, the effect of the invention can be achieved in a small amount, which is preferable. Specific examples of such a phosphate compound are exemplified below, but are not limited thereto. For example, methyl phosphate (alias methyl phosphate, monoester: diester = 50:50 (% by mass) mixture), ethyl phosphate (alias ethyl phosphate, monoester: diester = 3 7:63 (quality) %) mixture), isopropyl phosphate (alias isopropyl phosphate, monoester: diester = 30:70 (% by mass) mixture), di-n-butyl phosphate (monoester: diester = 3 6:64 ( Mass %) mixture), di-n-butyl phosphate (diester isolated crystal), phenyl phosphate (alias monophenyl phosphate, monoester isolate), diphenyl phosphate (alias diphenyl phosphate, diester segregation) (product), 2-ethylhexyl phosphate (alias 2-ethylhexyl phosphate, monoester: diester = 40:60 (% by mass) mixture), mono-n-dodecyl phosphate (alias phosphate mono-n-dodecyl) Ester, monoester segregation crystal), n-tridecyl phosphate (alias n-tridecyl phosphate, monoester diester mixture), 1-aminopropyl phosphate (alias mono-aminopropyl phosphate), single Ester isolation crystal), 1-amino-2-methylpropyl phosphate (alias phosphate 1-amino-2 _methylpropyl-20- 200804541 (18) phosphate, monoester isolate), ethylene phosphate , Bing Xixi 3_ phosphate ester group, phosphoric acid group, 3-methyl-Bing Xixi C class. The component (B) in the present invention is not particularly limited as long as it has good compatibility with the component (A), and a plurality of these may be used. The content of the component (B) is preferably such that the phosphorus atom of the component (B) is 〇〇1 mol or more, more preferably 0.1, in terms of the total amount of the ruthenium atoms in the (a) component. More than Mo Er, especially good for 〇.15 Moule. If Φ is less than 0.01 mol, it is difficult to obtain good dust erasability of the effect of the present invention. On the other hand, if it exceeds 0.45 mol, it is particularly difficult to improve the effect of rubbing rubbing, and therefore it is preferably 〇45 5 or less. When used for an antireflection film, it is preferably 0.4 m or less, and particularly preferably 0.25 m or less. < (C) Solvents The coating liquid for forming a film of the present invention is usually a solution Φ in which the components (A), (B), and other components to be used, which are used as needed, are dissolved in a solvent. Therefore, the solvent (C) used in the present invention is not particularly limited as long as it can uniformly dissolve the component (A), the component (B), and other components to be described later. Usually it is an organic solvent. Specific examples of such a glutinous agent include alcohols such as methanol, ethanol, propanol, butanol, and diacetone; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Glycols such as ethylene glycol, propylene glycol, hexanediol, etc.; ethyl alcohol monomethyl ether 'ethylene diethyl ether, ethylene glycol monobutyl ether, ethyl carbitol, butyl carbitol, two Ethylene glycol monomethyl ether, propylene glycol monomethyl-21 - (19) (19) 200804541 Ether, propylene glycol monobutyl ether, tetrahydrofuran and other ethers; esters of methyl acetate, ethyl acetate, ethyl lactate, etc. Classes, etc. In the present invention, a plurality of solvents can also be used. <Other components> In the present invention, other components other than the components (A) and (B) may be contained as long as the effects of the present invention are not impaired, for example, inorganic fine particles, dips, leveling agents, surface modification A component such as a granule or a surfactant. Examples of the inorganic fine particles include metal oxide fine particles, metal double oxide fine particles, and magnesium fluoride fine particles. Examples of the metal oxide include vermiculite, alumina, titania, chromium oxide, tin oxide, zinc oxide, and the like, and metal oxides such as ITO, ruthenium, AZO, and zinc ruthenate. Further, hollow vermiculite particles or porous vermiculite particles or the like can be exemplified. Such inorganic fine particles may be any of a powder and a colloidal solution, but the colloidal solution is preferred because of ease of handling. The colloidal solution may be a dispersion of the inorganic fine particle powder in a dispersion medium, or may be a commercially available colloidal solution. In the present invention, by containing inorganic fine particles, the surface shape or other functions of the formed hardened film can be imparted. The inorganic fine particles are preferably those having an average particle diameter of 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm. When the average particle diameter of the inorganic fine particles exceeds 0.2 μm, the transparency of the cured film formed by the prepared coating liquid is lowered. -22-200804541 (20) As a dispersion medium of the inorganic fine particles, water and organic solvent are dissolved at 1 ° as a colloidal solution, and from the viewpoint of the stability of the coating liquid for forming a film, pH or pKa is preferable. The organic solvent used for the dispersion medium of the colloidal solution is adjusted to 2 to 1 〇, preferably 3 to 7 °, and alcohols such as methanol, ethanol, propanol, and butanol; glycols such as ethylene glycol; a ketone such as methyl ethyl ketone or methyl isobutyl ketone; an aromatic hydrocarbon such as toluene or xylene; dimethylformamide, dimethylacetamide, and N-methyl 11 D is a guanamine such as φ ketone; an ester such as ethyl acetate, butyl acetate or butyrolactone; an ether such as ethylene glycol monopropyl ether, tetrahydrofuran or 1,4-dioxane. Among these, alcohols and ketones are preferred. These organic solvents may be used singly or in combination of two or more kinds as a dispersion medium. Further, the "leveling agent, surface modifier, surfactant, etc." can be used by a conventional one, and a commercial product is particularly preferable because it is easy to obtain. <Coating Liquid for Film Formation> The method for preparing the coating liquid for forming a film of the present invention is not particularly limited. The (Α) component and the (Β) component can be in a uniform solution state. Usually, the '(Α) component is obtained in a solution state because it is polycondensed in a solvent. Therefore, a solution containing a (Α) component (hereinafter referred to as a solution of a (Α) component) is used as it is, and a method of mixing with a (Β) component is simple. Further, if necessary, the solution of the (Α) component may be concentrated by adding solvent or substituted with another solvent, and then mixed with the (Β) component. Further, after mixing the (与) component solution and the (Β) component, a solvent may be added. Further, the (Β) component may be dissolved in the (C) solvent and then mixed with the solution of the (Α) component. -23- (21) (21) 200804541 The concentration of Si〇2 in the coating liquid for forming a film is preferably from 0.5 to 15% by mass, more preferably from 5 to 6% by mass. When the Si〇2 conversion concentration is lower than 〇.5 mass%, it is difficult to obtain a desired film thickness in one application, and if it is higher than 15% by mass, the storage stability of the solution tends to be insufficient. The solvent to be used for dilution or replacement may be the same solvent as that used in the above-mentioned polycondensation of the above alkoxydecane, or may be another solvent. The solvent is not particularly limited as long as it does not impair the compatibility between the component (A) and the component (B), and may be arbitrarily selected from one or more of them. The method of mixing the other components may be carried out simultaneously with the components (A) and (B), or after the mixing of the components (A) and (B), and is not particularly limited. In the present invention, a specific example of the coating liquid for forming a film 〇[1] coating liquid for film formation, which contains the component (A) and the total amount of the ruthenium atom of the (A) component for 1 mol. In terms of quantity, the phosphorus atom of the component (B) is from 0.01 to 0.45 mol. [2] The coating liquid for forming a film, which contains the above [1] and the inorganic fine particle 〇 [3] coating liquid for forming a film, which contains the above [1] or [2] and a coating material, a leveling agent, and a surface. At least one selected from the group consisting of a modifier and a surfactant. <Formation of Coating Film> The coating liquid for forming a film of the present invention can be applied onto a substrate, and the heat-24 - (22) 200804541 is cured to obtain a desired film. The coating method can be carried out by a conventional or well-known method. For example, dip coating, flow coating, spin coating, offset printing, inkjet coating, spray coating, bar coating, gravure coating, roll coating, and blade coating may be employed. Method, air knife coating method, air knife coating method, wire coating method, reverse coating method, transfer roll coating method, micro-groove roll coating method, kiss roll coating method, casting coating Method, slit hole coating method, curtain coating method, port mode coating method, and the like. # At this time, the substrate to be used may be, for example, a conventional or well-known substrate such as plastic, glass, or ceramic. Examples of the plastic include polycarbonate, poly(meth)acrylate, polyether maple, polyarylate, polyurethane, polyfluorene, polyether, polyetherketone, trimethylpentene, and polyolefin. A plate or a film of polyethylene terephthalate, (meth)acrylonitrile, triacetyl cellulose, diacetyl cellulose, cellulose acetate butyrate or the like. The coating film formed on the substrate may be thermally cured at room temperature to 450 ° C, preferably at a temperature of 40 to 45 ° C, or before, at room temperature # to 150 ° ° In the temperature range of C, it is preferably in a temperature range of from 1 〇 ° C to 150 ° C to be thermally hardened after drying. At this time, the time required for drying is preferably from 10 seconds to 10 minutes. The time required for the heat hardening can be appropriately selected depending on the characteristics of the film desired, but it is usually from 1 hour to 1 day. When a low hardening temperature is selected, the hardening time becomes long, and it is easy to obtain a film having sufficient scratch resistance, in particular, the substrate is a TAC (triethylene cellulose) film or a PET (polyester) film. For the organic substrate, consider the heat resistance of the substrate. -25-200804541 (23) The curing temperature is room temperature to 15 (TC, preferably the temperature is 10 ° C to 150 ° C. At this time, the drying step is used. Preferably, it is preferably from room temperature to 15 (temperature range of TC) at a temperature of 1 (TC to 150 ° C in a temperature range of 10 seconds to 10 minutes. The thus obtained invention is The film is characterized by a water contact angle system of 80° or more, and is excellent in rubbing property. Further, in the film formed by the present invention, the low reflectance is particularly suitable as a low refractive Φ layer for antireflection use. When the film of the present invention is used for antireflection, on a substrate having a refractive index higher than that of the film of the present invention, for example, on a surface of a usual glass or TAC (triethylene cellulose) film. Forming the film of the present invention' can easily convert the substrate into a film A substrate having a light-reflecting ability. In this case, the film of the present invention is effective even when a single film which is a surface of the substrate is used, and a film is formed on the lower film having a high refractive index, and is effectively used as an anti-reflection layer. φ Here, the relationship between the thickness of the film and the wavelength of light, the thickness d (nm) of the film having the refractive index a, and the wavelength λ (ηπι) of the light which is desired to reduce the reflectance by the film are described. In the meantime, a relational expression of d = (2b-1)λ/4& (wherein b represents an integer of 1 or more) is known. Therefore, by determining the thickness of the film by this formula, it is possible to easily prevent the desired Reflection of light of a wavelength. As a specific example, for a light having a wavelength of 550 nm, a film having a refractive index of 1.3 2 is formed, and in order to prevent reflected light from the surface of the glass, these numbers are substituted into λ and a in the above formula, The optimum film thickness is calculated. In this case, b can be substituted with an arbitrary positive integer. For example, 1 is substituted into b to obtain a film thickness of -26-(24) (24) 200804541 of 1 0 4 nm, and 2 is substituted. The film thickness obtained by b is 3 1 2 nm. The thickness can be easily imparted to the antireflection ability. The thickness of the film formed on the substrate can be adjusted according to the film thickness at the time of coating, but it can be easily adjusted by adjusting the concentration of the coating solution in terms of SiO 2 conversion. The film of the present invention is characterized by water repellency (antifouling property) and good dust repellency, and has low reflectance. Therefore, it can be applied to a glass-made Bronze tube, television, computer, car navigation. A display such as a portable telephone, a mirror with a glass surface, a glass display box, etc., which is intended to prevent reflection of light, in particular, a liquid crystal display, a plasma display, a projection display, an EL display, an SED, an FET, A polarizing plate such as a CRT or an antireflection film used in the front panel. EXAMPLES Hereinafter, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited by the examples. The abbreviations in the embodiment are explained. TEOS: Tetraethoxydecane UPS: γ-ureidopropyltriethoxydecane MAS: γ-Methyl propylene methoxypropyltrimethoxydecane MPS : γ-mercaptopropyltrimethoxydecane GPS: Γ-glycidoxypropyltrimethoxydecane APS: 3-aminopropyltriethoxydecane F3:trifluoropropyltrimethoxydecane-27- 200804541 (25) F13: trifluorooctyltrimethyl Oxydecane F17: heptadecafluorotrimethoxydecane F12: 1,6-bis(trimethoxydecylethyl)dodecafluorohexane

MeOH: methanol IPA: isopropanol (2-propanol) 'n-BuOH: n-butyl alcohol (1-butanol) PG: propylene glycol φ PA: phosphoric acid

MePA: methyl phosphate (alias methyl phosphate, monoester: diester = 50:50 (% by mass) mixture)

EtPA: Ethyl phosphate (alias ethyl phosphate, monoester: diester = 3 7:63 (% by mass) mixture) IPPA: isopropyl phosphate (alias isopropyl phosphate, monoester: diester = 30: 70 (% by mass) mixture)

PhPA: phenyl phosphate (alias monophenyl phosphate, monoester isolate) • EhPA: 2-ethylhexyl phosphate (alias 2-ethylhexyl phosphate, monoester: diester = 4 0:60 (quality %)mixture)

DdP A: mono-n-dodecyl phosphate (alias mono-n-dodecyl phosphate, monoester-isolated crystal) Butane MePA: trimethyl phosphate (alias trimethyl phosphate, triester isolate) The following synthesis examples are shown below. In the assay. [Residual alkoxydecane monomer assay] -28- 200804541 (26) Determination of residual alkoxydecane in a solution of polyoxane (A) by gas chromatography (hereinafter referred to as GC) body. The GC measurement was carried out under the following conditions using Shimadzu GC-14B manufactured by Shimadzu Corporation. Column · Capillary column CBPl-W25- 100 (25mmx0.53mm (D χίμπι) Column temperature · Start temperature is 50 °C, heat up at 15 °C / min, reach temperature 290 °C (3 minutes) ).

Sample injection amount: 1 μ L φ Injection temperature: 240 ° C Detector temperature: 290 ° C Carrier gas: nitrogen (flow rate 30 mL / min) Detection method: FID method [Synthesis Example 1] 4-reaction flask with reflux tube Inside, 32.54 g of MeOH was charged, and 18 gram of oxalic acid was added little by little with stirring to prepare a solution of oxalic acid in MeOH. Next, the oxalic acid-methanol solution was heated and refluxed, and then 24.73 g of 1^〇11'17.71 g of D.8, 7.02 g was dropped. A mixture of 13. After the completion of the dropwise addition, the reaction was continued under reflux for 5 hours, and then left to cool to prepare a solution (P1) of the polyoxane (A). The solution (P 1 ) of the polyoxane (A) was determined by GC. As a result, no alkoxydecane monoammonium was detected. [Synthesis Examples 2 to 11] With the composition shown in Table 1, by the same method as in Synthesis Example 1, -29-(27) (27) 200804541 was obtained.

To the solution of polyoxane (A) (P2 to PI 1). At this time, in the same manner as in Synthesis Example 1, a plurality of alkoxysilanes (hereinafter referred to as monomers) were mixed in advance and used. The solution (P2 to P 1 1 ) of the obtained polyoxane (A) was separately measured by GC, and as a result, no monomer was detected. •30- (28)200804541 [Table 1]

Solution of polyoxyalkylene (A) alkoxy decane (g) (mole) MeOH (g) oxalic acid-methanol solution oxalic acid (g) MeOH (g) Synthesis Example 1 P1 TEOS F13 17.71 7.02 24.73 18.00 32.54 0.085 0.015 Synthesis Example 2 P2 TEOS F13 UPS 16.77 7.02 1.29 25.08 18.00 31.84 0.0805 0.015 0.0045 Synthesis Example 3 P3 TEOS FI 3 UPS 19.06 1.87 1.29 22.22 18.00 37.56 0.0915 0.004 0.0045 Synthesis Example 4 P4 TEOS F13 UPS 16.25 8.19 L29 25.73 18.00 30.54 0.078 0.0175 0.0045 Synthesis Example 5 P5 TEOS F3 UPS 15.73 4.36 1.29 21.38 18.00 39.24 0.0755 0.02 0.0045 Synthesis Example 6 P6 TEOS F17 UPS 17.81 5.68 1.29 24.78 18.00 32.44 0.0855 0.01 0.0045 Synthesis Example 7 P7 TEOS F13 MAS 16.77 7.02 1.12 24.91 18.00 32.18 0.0805 0.015 0.0045 Synthesis Example 8 P8 TEOS F13 MPS 16.77 7.02 0.88 24.67 18.00 32.66 0.0805 0.015 0.0045 Synthesis Example 9 P9 TEOS F13 GPS 16.77 7.02 1.06 24.85 18.00 32.30 0.0805 0.015 0.0045 Synthesis Example 10 P10 TEOS F1 3 APS GPS 13.85 9.36 1.00 2.12 26.33 18.00 29.34 0.0665 0.02 0.0045 0.009 Synthesis Example 11 P11 TEOS F13 F12 UPS 9.08 3.12 3.99 0.86 17.05 12.00 53.89 0.0437 0.0067 0.0067 0.003 -31 - (29) 200804541 [Synthesis Example 12] In a 4-neck reaction flask, 28.8 3 g of MeOH was charged, and 27.91 g of TEOS, 1.70 g of F1 3, and 1.98 g of UPS were added little by little with stirring to prepare a mixture of a plurality of alkoxydecane compounds. e Ο Η solution. Next, after mixing the mixed solution at room temperature, a mixture of 14.42 g of MeOH, 15.01 g of water, and 0.15 g of oxalic acid was added dropwise. After the completion of the dropwise addition, heating was started, and after continuing the reaction for 1 hour from the reflux, the mixture was cooled to prepare a solution (P 12) of the polyoxane (A). The solution (P 12) of the polyoxyalkylene (A) was measured by GC, and as a result, no monomer was detected. Table 2] Solution of polyoxyalkylene (A) alkoxy decane-MeOH solution water oxalic acid-MeOH solution alkoxy decane (g) (mole) MeOH (g) water (g) oxalic acid (g) MeOH ( g) TEOS F13 UPS Synthesis Example 12 P12 27.91 11.70 1.98 28.83 15.01 0.15 14.42 0.134 0.025 0.0075

[Examples 1 to 20] The phosphoric acid compound (B) and the solvent were mixed in a solution of polysiloxane (A) in the composition shown in Table 3 to prepare a coating liquid for forming a film. Using the coating liquid, the storage stability and the film evaluation described below were carried out. [Comparative Examples 1 to 8] In the composition shown in Table 3, the solution was mixed in a solution of the polyethoxylate (A) -32- (30) (30) 200804541

To prepare a coating solution. Using the coating liquid, the storage stability and the film evaluation described below were carried out in the same manner as in the examples. However, in Comparative Example 6, a coating liquid obtained by substituting PA for the phosphate compound (B) in the example was used, and in Comparative Example 7, the coating liquid of TMePA was used for evaluation. -33- (31)200804541 [Table 3]

Polyoxane (A) solution (g) Phosphate compound (B) (g) Solvent P/Si Mobi ratio PG (g) n-BuOH (g) IPA (g) Example 1 P1 33.33 PhPA 0.87 7.00 10.00 48.80 0.15 Example 2 P2 33.33 MePA 0.60 7.00 10.00 49.07 0.15 Example 3 P2 33.33 IPPPA 0.85 7.00 10.00 48.82 0.15 Example 4 P2 33.33 PhPA 0.12 7.00 10.00 49.55 0.02 Example 5 P2 33.33 PhPA 0.58 7.00 10.00 49.09 0.10 Example 6 P2 33.33 PhPA 0.87 7.00 10.00 48.80 0.15 Example 7 P2 33.33 EhPA 1.42 7.00 10.00 48.25 0.15 Example 8 P2 33.33 DdPA 1.33 7.00 10.00 48.34 0.15 Example 9 P3 33.33 PhPA 0.87 7.00 10.00 48.80 0.15 Example 10 P4 33.33 PhPA 0.87 7.00 10.00 48.80 0.15 Example 11 P5 33.33 PhPA 0.87 7.00 10.00 48.80 0.15 Example 12 P6 33.33 PhPA 0.87 7.00 10.00 48.80 0.15 Example 13 P7 33.33 PhPA 0.87 7.00 10.00 48.80 0.15 Example 14 P8 33.33 PhPA 0.87 7.00 10.00 48.80 0.15 Example 15 P9 33.33 PhPA 0·87 7.00 10.00 48.80 0.15 Example 16 ΡΙ0 3.33 PhPA 0.87 7.00 10.00 48.80 0.15 Example Π P12 2 0.00 PhPA 0.87 7.00 10.00 62.13 0.15 Example 18 P2 33.33 EtPA 0.96 7.00 10.00 48.71 0.20 Example 19 P2 33.33 EtPA 1.92 700 10.00 47.75 0.40 Example 20 P11 50.00 PhPA 0.87 7.00 10.00 32.13 0.15 Comparative Example 1 P1 33.33 - 7.00 10.00 49.67 - Comparative Example 2 P2 33.33 - 7.00 10.00 49.67 - Comparative Example 3 P5 33.33 - 7.00 10.00 49.67 - Comparative Example 4 P6 33.33 - 7.00 10.00 49.67 - Comparative Example 5 P12 20.00 - 7.00 10.00 63.00 - Comparative Example 6 P2 33.33 PA 0.49 7.00 10.00 49.18 0.15 Comparative Example 7 P2 33.33 TMePA 0.70 7.00 10.00 48.97 0.15 Comparative Example 8 P11 50.00 - 7.00 10.00 33.00 - -34- 200804541 (32) The P/Si molar ratio in Table 3 indicates the phosphorus atom of the phosphate compound (B). The molar ratio of the ruthenium atom of polyoxyalkylene (A). <Preservation stability> The coating liquid for forming a film prepared by the composition of Table 3 was allowed to stand at room temperature for one month, and then had a pore diameter of 4545 μm (DxL: 1 8 x 22 mm of non-aqueous polytetrafluoroethylene). Ethylene filter (Kuromatodisk 1 3 N, manufactured by Kuraboki Co., Ltd.) was filtered to 100 cc, and the filter was used as the 〇, and the clog was used as the x. The storage stability of the coating liquid is shown in Table 4. [Evaluation of the film] The coating liquid for forming a film to be formed was applied to the triethylenesulfide cellulose (hereinafter referred to as TAC) to which the treatment shown below was carried out using a wire rod (No. 3). On the film (film thickness 80 μm, reflectance at a wavelength of 550 nm, 4.5%) to form a coating film. Then, it was allowed to stand at room temperature for 1 minute, and dried at a temperature of 1 ° C for 5 minutes using a clean oven. Then, it was hardened at a temperature of 40 ° C for 3 days. The TAC film used at this time was a TAC film (film thickness 80 μm) made of Nippon Paper Co., Ltd., which was hard-coated at 40 ° C, and then immersed in 5 After being treated with alkali for 3 minutes in a mass% potassium hydroxide (KOH) aqueous solution, it is washed with pure water and then connected. It was immersed in a 5% mass% sulfuric acid (H2S04) aqueous solution at room temperature for 30 seconds, and finally washed with pure water, and then dried in an oven at a temperature of 70 ° (for 1 hour) to form a film. , water contact angle, magic eraser, fingerprint erasability, haze (HAZE), transmittance, reflectivity, -35 _ (33) (33) 200804541 surface resistance, frictional charge index, dust Evaluation of the erasability. The evaluation methods are as follows, and the evaluation results are shown in Tables 4 and 5. [Water Contact Angle] The automatic contact angle measuring device FACE (CA-W type) manufactured by Kyowa Interface Science Co., Ltd. was used. The liquid method is measured at an average of 5 points. At this time, in the environment of 2 3 t: and relative humidity of 50%, water droplets of 3 · 0 μ 1 of pure water are generated at the tip of the needle, and dripped onto the surface of the film to measure the contact. [Singular pen erasing property] After writing on the film surface with a black singular pen (manufactured by Magic Ink Co., Ltd. 0 00 0 - Τ 1), dry it and then wipe it with toilet paper. Visually evaluate the rubbing off according to the following criteria. Degree: 〇: The ink can be completely wiped off. △: Most of the ink It is rubbed off, but the traces remain. X: The ink itself remains and can hardly be wiped off. [Fingerprint erasability] After the fingerprint is attached to the film surface, wipe it with a toilet paper. 'According to the following criteria, visually evaluate the degree of rubbing off. 〇: The fingerprint and oil can be completely wiped off. △: The oil can be wiped off, but the fingerprint remains. X: The fingerprint and oil can not be erased. -36- (34) 200804541 [Haze and Transmittance] Use Tokyo The electric color company made 8? £ (: 1 eight [11 8 2 ug%] £11 ding (: -1 800 Η to measure. [Reflectance] The surface of the film on the opposite side of the coated surface (inside) was rubbed with a sandpaper, and after applying a black paint to the cage, the UV reflectance in the spectrophotometer UV-3 100PC manufactured by Shimadzu Corporation was attached. The measuring device MPC-3100 was measured in the wavelength range of 400-800 nm. The measurement wavelength was 550 nm and the incident angle was 5. Reflectivity. [Surface Resistance] The surface resistance 値 was measured using a digital insulation meter d S Μ - 8 1 0 3 manufactured by East Asia D K K. At this time, the sample was placed in an environment of 23 ° C and a relative humidity of 50% for 3 hours. Reference [friction band voltage] The bell-spinning friction band voltage measuring device EST-8 manufactured by Chung Textile Engineering Co., Ltd., which is a wool cloth (for gauze jIS L 0803), which is used as a rubbing cloth, is used at 23 ° C, relative humidity 5 After the sample placed in the 0% environment for 3 hours or more was rubbed by the film surface for 10 times, the surface band voltage 6 of 60 seconds was measured. The thus obtained triboelectric charging index IFC (integral enthalpy with voltage-time curve) was used to evaluate the chargeability of the film (the smaller the charge, the less charged, the better the dust rubbing property). This evaluation method is based on JIS L 1 094. -37- (35) (35) 200804541 [Dust-erasing property] On the surface of the film, the toilet paper is torn off, and the paper dust is adhered to the film surface, and then wiped with a toilet paper, and the rubbing is visually evaluated according to the following criteria. The extent of it. 〇: 70% or more of the adhered 麈 before wiping is removed △ ·· 4 to 70% of the dust attached before wiping is removed X: Almost wiped off

-38- (36) 200804541 Table 4] Example to preserve the stability water contact angle (degrees) Singular pen erasing fingerprint erasing property Example 1 〇 > 100 〇〇 Example 2 〇 > 100 〇〇 Example 3 〇 > 100 〇〇 Example 4 〇 > 100 〇〇 Example 5 〇 > 100 〇〇 Example 6 〇 > 100 〇〇 Example 7 〇 > 100 〇〇 Example 8 〇 > 100 〇〇Example 9 〇>100 〇〇Example 10 〇>100 〇〇Example 11 〇>80 〇〇Example 12 〇>100 〇〇Example 13 〇>100 〇〇Example 14 〇>100 〇〇Example 15 〇>100 〇〇Example 16 〇>100 〇〇Example 17 〇>100 〇〇Example 18 〇>100 〇〇Example 19 〇>100 〇 Example 20 〇 > 100 〇〇 Comparative Example 1 〇 > 100 〇〇 Comparative Example 2 〇 > 100 〇〇 Comparative Example 3 〇 > 80 〇〇 Comparative Example 4 〇 > 100 〇〇 Comparative Example 5 〇 >100 〇〇Comparative Example 6 〇>100 〇〇Comparative Example 7 〇>100 〇〇Comparative Example 8 〇&gt ;100 〇 〇 -39- (37)200804541 [Table 5]

Example Haze transmittance (%) Reflectance (%) Surface resistance (Ω / □) Frictional charge index IFC (kV / min) After 1 week after the dust-off film formation, Example 1 0.2 0.2 94.7 1.4 1011 0.01 〇 Example 2 0.2 0.2 95.0 1.5 1012 0.08 〇 Example 3 0.2 0.2 94.4 1.5 1012 0.12 〇 Example 4 0.2 0.2 94.7 1.4 1013 0.20 〇 Example 5 0.2 0.2 94.5 L5 1012 0.02 〇 Example 6 0.2 0.2 94.6 1.5 1011 0.00 〇 Example 7 0.2 0.2 94.0 L8 1013 0.05 〇 Example 8 0.2 0.2 93.0 1.7 1012 0.05 〇 Example 9 0.2 0.2 93.7 2.0 1010 0.00 〇 Example 10 0.2 0.2 94.5 1.4 1012 0.00 〇 Example 11 0.2 0.2 93.5 2.2 1010 0.00 〇 Example 12 0.2 0.2 94.2 1.7 1011 0.00 〇 Example 13 0.2 0.2 94.0 1.7 1010 0.00 〇 Example 14 0.2 0.2 94.2 1.7 1011 0.00 〇 Example 15 0.2 0.2 94.3 1.5 1010 0.00 〇 Example 16 0.2 0.2 93.4 1.8 1011 0.01 〇 Example 17 0.2 0.2 94.6 1.7 1012 0.01 〇 Example 18 0, 2 0.2 94.7 1.7 1011 0.02 〇 Example 19 0.2 0.2 94.4 1.8 1010 0.01 〇 Example 20 0.2 0.2 94 .1 1.9 1012 0.04 〇Comparative Example 1 0.2 0.2 95.0 1.3 1015 1.00 X Comparative Example 2 0.2 0.2 94.8 1.4 1015 0.60 X Comparative Example 3 0.2 0.2 94.1 1.9 1014 0.30 X Comparative Example 4 0.2 0.2 94.7 1.5 1015 0.48 X Comparative Example 5 0.2 0.2 94.9 1.6 1015 2.99 X Comparative Example 6 0.4 0.8 94.2 1.4 1〇10 0.00 〇Comparative Example 7 0.2 0.2 94.5 1.9 1015 0.55 X Comparative Example 8 0.2 0.2 94.3 1.8 1015 0.62 X -40- (38) (38) 200804541 In Examples 1 to 20, a film having a high water contact angle and good rubbing property was obtained, but in Comparative Examples 1 to 5, Comparative Example 7, and Comparative Example 8, dust rubbing property was inferior. Further, in Comparative Example 6, the water contact angle was high and the dust rubbing property was good as in the example. However, the haze after one week passed increased, and the stable film of Examples 1 to 20 could not be obtained. . Industrial Applicability The coating liquid for forming a film of the present invention can form a stable film which is excellent in storage stability, has a high water contact angle, is excellent in dust repellency, and does not change with time. Among them, those exhibiting low reflectance are suitable as coating liquids for forming antireflection films, and the film formed by them is very useful as an antireflection film. Therefore, it is very suitable as an antireflection film used for a display element such as a plasma display device including a liquid crystal display element. Moreover, the entire contents of the specification, the scope of the patent application, and the abstract of the Japanese Patent Application No. 2000-101, filed on Apr. 13, 2006, are hereby incorporated by reference. Incorporated by the disclosure of the specification.

Claims (1)

200804541 (1) Patent Application No. 1. A coating liquid for forming a film, which comprises: (A) a component, that is, a polyoxyalkylene having an organic group substituted with a fluorine atom in a side chain; B) The component 'is a phosphate compound having a hydroxyl group bonded to a phosphorus atom. *2. The coating liquid for forming a film according to the first aspect of the invention, wherein the component (A) contains the alkoxydecane represented by the formula (1) and the alkoxydecane represented by the formula (2). Alkoxy decane, polycondensed by polycondensation [Chemical] Si(〇R1)4 (1) (R1 represents a hydrocarbon group having 1 to 5 carbon atoms), [Chemical 2] Φ R2Si ( OR3)3 (2) (R2 represents an organic group substituted by a fluorine atom, and R3 represents a hydrocarbon group having 1 to 5 carbon atoms). 3. The coating liquid for forming a film according to the second aspect of the invention, wherein R2 is a perfluoroalkyl group in the formula (2). 4. The coating liquid for forming a film according to the second or third aspect of the invention, wherein the component (A) further polycondenses the alkoxysilane represented by the formula (3) to obtain a polyoxane. • 42- (2) 200804541 [3] (3) R4nSi(〇R5)4.n (R4 represents an organic group substituted without a wearing atom, and R5 represents a hydrocarbon group having 1 to 5 carbon atoms' η represents 1 An integer to 3). 5. The coating liquid for forming a film according to any one of the above-mentioned claims, wherein the component (B) is a phosphate compound represented by the formula (4), and is an OP(OH)m ( 〇R6)3.m (4) (R6 represents an organic group having 1 to 20 carbon atoms, and m represents an integer of 1 or 2). 6. The coating liquid for forming a film according to the fifth aspect of the invention, wherein R6 in the formula (4) is an organic group having 1 to 6 carbon atoms. The coating liquid for film formation according to any one of claims 1 to 6, wherein the total amount of the ruthenium atom of the (1) component of the (A) component is 〇_〇1 to 0.45 The phosphorus atom of the component (B) of the ear. The coating liquid for forming a film according to any one of claims 2 to 7, wherein the component (A) contains 60 to 95 mol% of the alkoxydecane represented by the formula (1) and 5 to 40 mol% of a polyoxyalkylene obtained by polycondensation of an alkoxydecane of an alkoxydecane represented by the formula (2). 9. A film formed by using a coating liquid for forming a film according to any one of claims 1 to 8. An anti-reflection film is formed by using a coating liquid for forming a film according to any one of the above-mentioned claims 1 to 8 - 43- (3) 200804541. And a coating liquid for forming a film according to any one of the first to eighth aspects of the invention, which is applied to a substrate and dried at room temperature to 150 ° C. Hardening is allowed from room temperature to 150 °C. (2) A method for forming an anti-reflection film, which is applied to a substrate by a coating liquid for forming a film according to any one of claims 1 to 8, at room temperature to 150° After C is dried, it is hardened at room temperature to 150 °C. Φ 1 3 . An antireflection substrate having the film of claim 9 or the antireflection film of claim 1 of the patent application. An antireflection film comprising the film of claim 9 or the antireflection film of the first aspect of the patent application. A method for producing a coating liquid for forming a film, characterized by containing 60 to 95 mol% of the alkoxydecane represented by the formula (1) and 5 to 40 mol% of the formula (2) The alkoxydecane of the alkoxydecane represented, and the alkoxy group of all alkoxydecanes of 1 mole, 0.2 to 2 moles of oxalic acid φ, in an organic solvent, at 50 to 1 The liquid temperature of 80 ° C is heated to carry out polycondensation to obtain a solution of polyoxyalkylene to be mixed with a phosphate compound having a hydroxyl group bonded to the phosphorus atom, [Chemical 5] Si(〇R1)4 (1 (R1 Table 7K has a hydrocarbon group of 1 to 5 carbon atoms), [Chem. 6] (2) R2Si(OR3) -44- 200804541 (4) (R2 represents an organic group substituted by a fluorine atom, and R3 represents 1 a hydrocarbon group of up to 5 carbon atoms). -45- 200804541 Ming said that there is no simple: the number is the map of the map element on behalf of the map: the table pattern represents the book without a set of one or two. If the case has a chemical formula, please reveal the chemical formula that best shows the characteristics of the invention. : (1) (2) SUOR1)* R2Si(OR3); -3-