JP3581390B2 - Coating solution for forming protective film - Google Patents

Description

[0001]
[Industrial applications]
The present invention relates to a novel coating liquid for forming a protective film, and more specifically, to form a protective film having excellent homogeneity and high hardness and low surface resistance, for example, a protective film for electric / electronic parts, particularly a liquid crystal display device. The present invention relates to a coating liquid for forming a protective film suitable for forming a protective film for an electrode.
[0002]
[Prior art]
Conventionally, a liquid crystal display element is formed by sequentially laminating a transparent electrode layer made of an inorganic material such as ITO and an alignment film made of an organic polymer material such as polyimide on a substrate made of a resin plate such as transparent glass or acrylic or PET. Substrates with laminated electrodes were arranged substantially in parallel at predetermined intervals, the periphery thereof was sealed with, for example, frit glass, an organic adhesive, or the like to form cells, and liquid crystal was sealed in the cells. . However, since the transparent electrode is made of a hard inorganic material such as ITO, there is a difference in the coefficient of thermal expansion from the orientation film made of an organic material, which causes cracks in the electrode when a liquid crystal display element is manufactured. I was Therefore, it has been proposed to interpose a protective film between the transparent electrode layer and the alignment film in order to solve the above-mentioned drawbacks, but this protective film is coated with, for example, a silanol compound-containing coating solution to increase the practical hardness. Exposure of the transparent electrode to a high temperature deteriorates the electrode and increases the resistance value. For example, the electrode is baked at a calcination temperature of 400 ° C. or higher to obtain a film containing silicon dioxide as a main component. The high firing temperature not only deteriorated the transparent electrode, but also had an adverse effect on a recently developed plastic liquid crystal display device using a resin such as acrylic or PET as a substrate. Therefore, there has been a demand for a coating liquid that can form a film at a low temperature and can form a protective film having high hardness. The present inventors as a coating solution to meet such demands have a formula (A) represented by the general formula Si (OR) ₄ ... (I) wherein R represents an alkyl group having 1 to 14 carbon atoms or a phenyl group. A hydrolysis reaction product of at least one compound, (B) a general formula R ¹ _n Si (OR) _4-n ... (II), wherein R ¹ is an acryloxypropyl group, a methacryloxypropyl group, a glycidyl group; A hydroxy group or a vinyl group, R represents an alkyl group or a phenyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 3). A coating solution for forming a protective film containing a fine-particle filler having a diameter of 5 to 200 nm has been proposed (Japanese Patent Application No. 5-247163). However, the protective film formed with the protective film forming coating solution has low conductivity, and cannot sufficiently remove static electricity generated by the rubbing treatment taken at the time of forming the alignment film. However, there is a disadvantage that a displayed image is uneven.
[0003]
[Problems to be solved by the invention]
Accordingly, the present inventors have conducted intensive studies to improve the conductivity of the above-mentioned protective film forming coating solution, and as a result, by further adding a specific metal nitrate to the protective film forming coating solution, the alignment film was charged. It has been found that the present invention can be prevented, and the present invention has been completed. That is,
[0004]
An object of the present invention is to provide a coating liquid for forming a protective film, which can be formed at a low temperature, has excellent homogeneity, has high hardness, and has a low surface resistance.
[0005]
[Means for Solving the Problems]
The present invention that achieves the above objects,
(A) General formula Si (OR) ₄ ... (I)
(Wherein, R represents an alkyl group having 1 to 14 carbon atoms or a phenyl group)
A hydrolysis reaction product of at least one compound represented by
(B) General formula R ¹ _n Si (OR) _4-n (II)
(Wherein, R ¹ represents an acryloxypropyl group, a methacryloxypropyl group, a glycidyloxypropyl group or a vinyl group, R represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and n represents an integer of 1 to 3) )
A hydrolysis reaction product of at least one compound represented by
(C) a fine-particle filler having an average particle size of 5 to 200 nm, and (D) a general formula M (NO ₃ ) _m (III)
(Wherein, M represents Al, In, Ni or Co, and m represents 2 or 3)
And a coating solution for forming a protective film containing each component of a metal nitrate represented by the formula: and the component (B) of the coating solution component for forming a protective film, wherein at least one compound represented by the general formula (II) is used The hydrolysis reaction product of the reaction product or the general formula R ² _n Si (OR) _4-n (IV)
(Wherein, R ² represents an acryloxypropyl group, a methacryloxypropyl group or a vinyl group, R represents an alkyl group or a phenyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 3)
The coating liquid for forming a protective film, which is a hydrolysis reaction product of a polymerization reaction product of at least one compound represented by the following and a polyfunctional acrylic monomer, or the coating liquid for forming a protective film, further comprises (E) a polyfunctional compound. The present invention relates to a coating liquid for forming a protective film containing a hydrophilic acrylic monomer.
[0006]
Among the matrix components (A), (B) and (E) constituting the coating liquid for forming a protective film of the present invention, the compound of the general formula (I) which forms the component (A) is specifically exemplified by tetra Methoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like can be mentioned.
[0007]
As the compound of the general formula (II) and the compound of the general formula (IV) forming the component (B) of the matrix component, specifically, monoacryloxypropyltrimethoxysilane, monomethacryloxypropyltrimethoxysilane, Monoglycidyloxypropyltrimethoxysilane, monovinyltrimethoxysilane, diacryloxypropyldimethoxysilane, dimethacryloxypropyldimethoxysilane, triacryloxypropylmonomethoxysilane, trimethacryloxypropylmonomethoxysilane, diglycidyloxypropyldimethoxysilane , Divinyldimethoxysilane, triglycidyloxypropylmonomethoxysilane, trivinylmonomethoxysilane, monoacryloxypropyltriethoxysilane, monomethacryloxypropyl Liethoxysilan, monoglycidyloxypropyltriethoxysilane, monovinyltriethoxysilane, diacryloxypropyldiethoxysilane, dimethacryloxypropyldiethoxysilane, diglycidyloxypropyldiethoxysilane, divinyldiethoxysilane, tria Acryloxypropylmonoethoxysilane, trimethacryloxypropyltrimonoethoxysilane, triglycidyloxypropylmonoethoxysilane, trivinylmonoethoxysilane, monoacryloxypropyltripropoxysilane, monomethacryloxypropyltripropoxysilane, monoglycidyloxy Propyl tripropoxy silane, monovinyl tripropoxy silane, diacryloxy propyl dipropoxy silane, dimethacryloxy propyl dipro Xysilane, diglycidyloxypropyldipropoxysilane, divinyldipropoxysilane, triacryloxypropylmonopropoxysilane, trimethacryloxypropyl monopropoxysilane, triglycidyloxypropyl monopropoxysilane, trivinylmonopropoxysilane, monoacryloxypropyl tri Butoxysilane, monomethacryloxypropyltributoxysilane, monoglycidyloxypropyltributoxysilane, monovinyltributoxysilane, diacryloxypropyldibutoxysilane, dimethacryloxypropyldibutoxysilane, diglycidyloxypropyldibutoxysilane, divinyl Dibutoxysilane, triacryloxypropylmonobutoxysilane, trimethacryloxypropylmonobutoxysilane, Liglycidyloxypropyl monobutoxy silane, trivinyl monobutoxy silane and the like can be mentioned.
[0008]
Further, as the polyfunctional acrylic monomer which is a polymerization component of the compound of the general formula (IV) and is contained as a matrix component, specifically, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol Erythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, hexa (methacryloxyethoxy) phosphazene, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate and the like. Can be The polyfunctional acrylic monomer forms a polymerization reaction product by a polymerization reaction with the compound of the general formula (IV). In the polymerization reaction, preferably, tert-butyl hydroperoxide, cumene hydroperoxide, 2,2′- Heat polymerization is preferably performed in the presence of a polymerization initiator such as azobisisobutyronitrile, benzoyl peroxide, and 2,2′-azobis (2,4-dimethylvaleronitrile). When used as a matrix component, it is preferably blended together with the polymerization initiator. The compounding amount of the polyfunctional acrylic monomer is selected in the range of 0.5 to 300 parts by weight per 100 parts by weight of the compound of the general formula (II) or the compound of the general formula (IV).
[0009]
The matrix component and each organic compound forming the matrix component are preferably used after being dissolved in an organic solvent. Then, the compound of the above general formula (I), the compound of the general formula (II), the intermolecular reactant thereof, and the polymerization reaction product of the compound of the general formula (IV) and the polyfunctional acrylic monomer dissolved in the organic solvent Is used in the range of 0.05 to 9 mol, preferably 0.1 to 5 mol, of the compound of the general formula (II) or the compound of the general formula (IV) per 1 mol of the compound of the general formula (I). It is selected, individually or mixed, and subjected to a hydrolysis reaction in the presence of water, preferably in the presence of an acid catalyst such as hydrochloric acid, nitric acid, phosphoric acid and the like. The amount of water used in the hydrolysis reaction is in the range of 2 to 10 moles, preferably 3 to 8 moles, based on the total moles of the respective compounds. The amount of the acid catalyst used is preferably in the range of 0.001 to 1% by weight based on all the compounds.
[0010]
Specific examples of the organic solvent include monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, and octylene glycol. Polyhydric alcohols, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol dimethyl ether, ethylene Glycol diethyl ether, diethylene glycol monomethyl ether Ethers such as ter, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether And fatty acids such as acetic acid and propionic acid, and esters such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, methyl propionate and ethyl propionate.
[0011]
The finely divided filler having an average particle size of 5 to 200 nm, which constitutes the component (C) of the coating liquid for forming a protective film of the present invention, is preferably non-conductive and inorganic, and more specifically, colloidal silica. (Commercial products: Snowtex manufactured by Nissan Chemical Co., OSCAL manufactured by Kasei Kagaku Kogyo Co., Ltd., Adelite AT manufactured by Asahi Denka Kogyo Co., Ltd., silica doll manufactured by Nippon Chemical Industry Co., Ltd.) Aerosil), titania fine particles (Idemitsu Titania manufactured by Idemitsu Kosan Co., Ltd., Taipaque manufactured by Ishihara Sangyo Co., Ltd.), colloidal alumina (commercial product: Snowtex AS manufactured by Nissan Chemical Co., Ltd.) and the like. One or two or more of these may be used in combination, and a dispersant may be used in order to achieve uniform dispersion in the compounding. The hardness of the protective film and the adhesion to the alignment film are improved by blending the fine particulate filler. It is preferable that the compounding amount of the fine particulate filler is 2 to 90% by weight based on the total solid content in the coating solution. If the compounding amount is less than 2% by weight, a coating film having high hardness is obtained. When the amount exceeds 90% by weight, the adhesion of the coating film is deteriorated.
[0012]
Further, specific examples of the metal nitrate salt of the general formula (III) added as a surface resistance lowering component of the protective film include aluminum nitrate, indium nitrate, nickel nitrate, and cobalt nitrate. The amount of the metal nitrate compounded varies depending on the type of the component constituting the matrix of the coating liquid for forming a protective film and the type of the fine particulate filler, and is not particularly limited. It is preferable that the amount is less than 8% by weight. If the amount is less than 8% by weight, a protective film having a practical surface resistance value is not formed, and the amount is less than 50% by weight. Exceeding this is not preferred because the hardness decreases.
[0013]
The following preparation methods are employed for blending the components (A) to (E). That is, (a) a method of preparing a solution containing all components other than the components (C) and (D) first, then blending the components (C) and (D), and (b) a matrix component (C) and (D) are added at the time of the production of the components (A) and (B), and then the other components are blended in an arbitrary order. After dissolving in a solvent, adding a polymerization initiator, and heating and polymerizing to obtain an intermolecular reactant, the compound of the general formula (I), the components (C) and (D) are added thereto, and the presence of a catalyst is preferable. (D) a compound of the general formula (IV) and a polyfunctional acrylic monomer, preferably after adding a polymerization initiator, and heat-polymerizing the same; The compound, component (C) and component (D) are added, and water is added, preferably in the presence of a catalyst. Additionally hydrolyzing preparation method, in this case, if necessary, the general formula ^{_{R 3 n Si (OR) 4}} -n ... (V) ( wherein, ^{R 3} is glycidyl Giro propyl group, R represents 1 to 4 carbon atoms To 4 alkyl groups or phenyl groups, and n represents an integer of 1 to 3). (E) A preparation method in which the component (E) is further added to the coating liquid for forming a protective film prepared by the above preparation method.
[0014]
In each of the above-mentioned preparation methods, the compounding ratio of the compound of the general formula (I) and the compound of the general formula (II) or the compound of the general formula (IV) is expressed by the formula (II) per mole of the compound of the general formula (I) Or a compound of the general formula (IV) is selected in the range of 0.05 to 9 mol, preferably 0.1 to 5 mol. If the amount is less than 0.05 mol, uniformity and desired hardness of the film cannot be obtained, and if it exceeds 9 mol, it is difficult to uniformly form the coating liquid.
[0015]
In order to adjust the concentration of the coating solution prepared above, for example, a diluting solvent or the like for decreasing the concentration can be blended. As the diluting solvent, specifically, monohydric alcohols, polyhydric alcohols, ethers such as polyhydric alcohol ethers, acetic acid, fatty acids such as propionic acid, acetone, methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, Examples include ketones such as dibutyl ketone, and esters such as methyl acetate, ethyl acetate, butyl acetate, propyl acetate, isobutyl acetate, and isoamyl acetate.
[0016]
The coating liquid for forming a protective film prepared as described above was applied to the electrode surface formed on the substrate by a method such as dipping, spinner, spray, roll coater, or flexographic printing, and then formed. The coating is dried under heating and / or reduced pressure or under ventilation, and then cured at 120 to 400 ° C., preferably 140 to 300 ° C. to form a protective film.
[0017]
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
[0018]
【Example】
Example 1
One mole of tetramethoxysilane and one mole of monomethacryloxypropyltrimethoxysilane were dissolved in 175 g of butyl alcohol. Next, 126 g of pure water and 0.02 g of concentrated hydrochloric acid were added, and the mixture was stirred at room temperature for about 6 hours. To 70 g (solid content: 12 g) of the solution thus obtained, 228 g of Snowtex (trade name, colloidal silica manufactured by Nissan Chemical Industries, Ltd.) having a particle size of 10 to 20 nm as solid content, 800 g of isopropyl alcohol, and propylene glycol monopropyl were used. 395 g of ether was added, 197 g of aluminum nitrate was further added, and the mixture was dissolved and mixed to prepare a coating solution.
[0019]
This coating solution was applied on a 6-inch glass substrate by a spinner and baked at 200 ° C. for 1 hour to form a 100-nm-thick protective film. This protective film had no cracks and was excellent in homogeneity. The pencil hardness was measured and found to be 9H. The surface resistance of the protective film was measured using Hiresta IPMCP-HT260 (manufactured by Mitsubishi Yuka Co., Ltd.) and found to be 3 × 10 ¹¹ Ω / □.
[0020]
Example 2
One mole of tetraethoxysilane, 0.5 mole of monoacryloxypropyltrimethoxysilane and 0.5 mole of monovinyltrimethoxysilane were dissolved in 170 g of isopropyl alcohol. Next, 190 g of pure water and 0.02 g of concentrated nitric acid were added, and the mixture was stirred at room temperature for 6 hours. To the solution (solid content: 120 g) thus obtained, 6.35 g of Hypressica FQ (trade name, silica fine particles manufactured by Ube Nitto Kasei Co., Ltd.) having a particle size of 100 nm, 200 g of isopropyl alcohol, and 303.5 g of ethylene glycol monomethyl ether were added. 140 g of xylene glycol was added, and 400 g of aluminum nitrate was further added and dissolved and mixed to prepare a coating solution.
[0021]
Using this coating solution, a 100 nm-thick protective film was formed in the same manner as in Example 1 except that baking was performed at 180 ° C. for 2 hours. This protective film was excellent in homogeneity and had a pencil hardness of 8H. The surface resistance of the protective film was 8 × 10 ⁹ Ω / □.
[0022]
Example 3
Adoleit AT (trade name, trade name: 1 g of tetraethoxysilane, 0.1 mol of monoglycidoxypropyltriethoxysilane and 0.2 mol of dimethacryloxypropyldimethoxysilane) and 90 g of ethylene glycol monoethyl ether having a particle size of 10 to 20 nm 60 g of colloidal silica (Asahi Denka Kogyo Co., Ltd.) as solid content and 18 g of Snowtex AS (trade name, colloidal alumina manufactured by Nissan Chemical Co., Ltd.) having a particle size of 10 to 20 nm as solid content and 287 g of aluminum nitrate were further added, and further purified water 88 g and 0.01 g of phosphoric acid were added, and the mixture was stirred at room temperature for 24 hours. A coating solution was prepared by adding 200 g of dipropylene glycol monomethyl ether, 200 g of methyl alcohol, 280 g of isobutyl alcohol and 200 g of hexylene glycol to the solution (solid content: 195 g) thus obtained, and mixing.
[0023]
Using this coating solution, a 180-nm-thick protective film was formed in the same manner as in Example 1 except that baking was performed at 160 ° C. for 2 hours. This protective film was excellent in homogeneity and had a pencil hardness of 9H. The surface resistance of the protective film was 4 × 10 ¹⁰ Ω / □.
[0024]
Example 4
0.3 mol of tetramethoxysilane and 1 mol of monoglycidoxypropyltriethoxysilane were dissolved in 100 g of methyl alcohol. Next, 76 g of pure water and 0.01 g of concentrated hydrochloric acid were added, and the mixture was stirred at room temperature for 6 hours. 33 g of Idemitsu titania (trade name, titania fine particles manufactured by Idemitsu Kosan Co., Ltd.) having a particle diameter of 17 nm, 300 g of isopropyl alcohol, 200 g of dipropylene glycol, and 200 g of octylene glycol were added to the solution (solid content: 78 g) thus obtained. A coating solution was prepared by adding 50 g and 73 g of isobutyl alcohol, further adding 200 g of nickel nitrate and dissolving and mixing.
[0025]
Using this coating solution, a 200 nm-thick protective film was formed in the same manner as in Example 1 except that baking was performed at 160 ° C. for 2 hours. This protective film was excellent in homogeneity and had a pencil hardness of 9H. The surface resistance of the protective film was 5 × 10 ⁹ Ω / □.
[0026]
Example 5
A coating solution was prepared by adding 6 g of dipentaerythritol hexaacrylate to the coating solution prepared in Example 1.
[0027]
Using this coating solution, a protective film having a thickness of 120 nm was formed in the same manner as in Example 1 except that baking was performed at 200 ° C. for 2 hours. This protective film was excellent in homogeneity and had a pencil hardness of 9H. The surface resistance of the protective film was 5 × 10 ¹¹ Ω / □.
[0028]
Example 6
A coating solution was prepared in the same manner as in Example 1, except that 400 g of cobalt nitrate was used instead of 197 g of aluminum nitrate and 1233 g of isopropyl alcohol was used instead of 800 g of isopropyl alcohol.
[0029]
Using this coating solution, a protective film having a thickness of 150 nm was formed in the same manner as in Example 1. This protective film was excellent in homogeneity and had a pencil hardness of 9H. The surface resistance of the protective film was 4 × 10 ¹⁰ Ω / □.
[0030]
Example 7
A coating solution was prepared in the same manner as in Example 1 except that 400 g of indium nitrate was used instead of 197 g of aluminum nitrate.
[0031]
Using this coating solution, a protective film having a thickness of 150 nm was formed in the same manner as in Example 1. This protective film was excellent in homogeneity and had a pencil hardness of 9H. The surface resistance of the protective film was 4 × 10 ¹⁰ Ω / □.
[0032]
Example 8
1 mol of monomethacryloxypropyltrimethoxysilane, 400 g of propylene glycol monomethyl ether and 180 g of propylene glycol monomethyl ether acetate were added to a 2-liter three-necked flask equipped with a reflux condenser, a thermometer, and a dropping funnel. , And a solution prepared by dissolving 2.5 g of 2,2'-azobisbutyronitrile in 90 g of ethylene glycol monoethyl ether was added dropwise with stirring, and the mixture was maintained at 80 ° C for 1 hour, and further maintained at 110 ° C for 1 hour. After holding, the mixture was cooled to room temperature. Next, 1 mol of tetramethoxysilane was dissolved in the obtained reaction solution, 126 g of pure water and 0.02 g of concentrated hydrochloric acid were added, and the mixture was stirred at room temperature for 24 hours. To 100 g (solid content: 10 g) of the solution thus obtained, 90 g of Snowtex (trade name, colloidal silica manufactured by Nissan Chemical Industries, Ltd.) having a particle size of 10 to 20 nm, 474 g of isopropyl alcohol, and 474 g of propylene glycol monopropyl were used. 300 g of ether was added, 485 g of aluminum nitrate was further added, and the mixture was dissolved and mixed to prepare a coating solution.
[0033]
Using this coating solution, a protective film having a thickness of 120 nm was formed in the same manner as in Example 1 except that baking was performed at 250 ° C. for 1 hour. This protective film was excellent in homogeneity and had a pencil hardness of 9H. The surface resistance of the protective film was 7 × 10 ¹⁰ Ω / □.
[0034]
Comparative Example 1
A coating solution was prepared in the same manner as in Example 1 except that aluminum nitrate was not used.
[0035]
Using this coating solution, a protective film having a thickness of 100 nm was formed in the same manner as in Example 1 except that baking was performed at 200 ° C. for 2 hours. This protective film was excellent in homogeneity, but had a surface resistance of 1 × 10 ¹⁴ Ω / □.
[0036]
【The invention's effect】
The coating solution for forming a protective film of the present invention has excellent homogeneity and can form a protective film having high hardness, has low surface resistance, and can easily remove static electricity charged on an alignment film during rubbing. This is a coating liquid for forming a film. Moreover, since the protective film formed using the protective film forming coating solution can have practical hardness even at a relatively low firing temperature, the electrodes of the liquid crystal display element and the plastic substrate do not deteriorate.

Claims (4)

(A) General formula Si (OR) ₄ ... (I)
(Wherein, R represents an alkyl group having 1 to 14 carbon atoms or a phenyl group)
A hydrolysis reaction product of at least one compound represented by
(B) General formula R ¹ _n Si (OR) _4-n (II)
(Wherein, R ¹ represents an acryloxypropyl group, a methacryloxypropyl group, a glycidyloxypropyl group or a vinyl group, R represents an alkyl group or a phenyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 3)
A hydrolysis reaction product of at least one compound represented by
(C) a fine-particle filler having an average particle size of 5 to 200 nm, and (D) a general formula M (NO ₃ ) _m (III)
(Wherein, M represents Al, In, Ni or Co, and m represents 2 or 3)
A metal nitrate represented by the formula:
A coating liquid for forming a protective film, comprising: (A) General formula
Si (OR) ₄ ... (I)
(Wherein, R represents an alkyl group having 1 to 14 carbon atoms or a phenyl group)
A hydrolysis reaction product of at least one compound represented by
(B) General formula
R ¹ _n Si (OR) _4-n (II)
(Wherein, R ¹ represents an acryloxypropyl group, a methacryloxypropyl group, a glycidyloxypropyl group or a vinyl group, R represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and n represents an integer of 1 to 3) )
A hydrolysis reaction product of an intermolecular reactant of at least one compound represented by
(C) a fine particulate filler having an average particle size of 5 to 200 nm, and
(D) General formula
M (NO ₃ ) _m ... (III)
(Wherein, M represents Al, In, Ni or Co, and m represents 2 or 3)
A metal nitrate represented by the formula:
A coating liquid for forming a protective film, comprising: 2. The coating solution for forming a protective film according to claim 1, wherein the component (B) has a general formula R ² _n Si (OR) _4-n (IV)
(Wherein, R ² represents an acryloxypropyl group, a methacryloxypropyl group or a vinyl group, R represents an alkyl group or a phenyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 3)
A coating liquid for forming a protective film, which is a hydrolysis reaction product of a polymerization reaction product of at least one compound represented by the following formula and a polyfunctional acrylic monomer. 3. A coating solution for forming a protective film, wherein the coating solution for forming a protective film according to claim 1 or 2 further comprises (E) a polyfunctional acrylic monomer.