KR20160117290A - Coating solution for forming film, method for producing the coating solution, and method for producing substrate with film - Google Patents

Abstract

The coating liquid for forming a transparent coating film of the present invention contains at least one (component B) of an organic compound capable of forming a chelate with a metal alkoxide (component A), a silane compound having three or more functions represented by formula (2) and a hydrolyzed condensate thereof, At least one of the metal alkoxide represented by the formula (3) and the hydrolyzed condensate thereof (component C) is dissolved or dispersed in a mixed solvent containing water and an organic solvent. At this time, the molar ratio (M1 / M3) of the molar number (M1) of the component A and the molar number (M3) of the component C is in the range of 0.25 or more and less than 2.0, and the molar number (M2) The molar ratio (M2 / M3) is in the range of 0.1 to 9.0.
(General formulas (2) and (3) are as described in the specification.)

Description

TECHNICAL FIELD [0001] The present invention relates to a coating liquid for forming a film, a method for producing the coating liquid, a method for producing the coated substrate,

The present invention relates to a coating liquid for forming a film.

More specifically, the present invention relates to a coating liquid capable of forming a transparent coating having excellent both hardness and crack resistance regardless of curing at a relatively low temperature.

Conventionally, a coating film is formed on the surface of a substrate to impart a function to a substrate such as glass or plastic. For example, a hard coat film is formed on the surface of a substrate to improve scratch resistance of the substrate surface such as glass, plastic sheet, plastic lens, resin film, and display front plate. As such a hard coat film, an organic resin film or an inorganic film is known. It is also known that resin particles or inorganic particles such as silica are incorporated into an organic resin film or an inorganic film to further improve scratch resistance.

In addition, a substrate having a transparent coating formed by blending conductive particles in a transparent coating film to impart an antistatic property and an electromagnetic shielding property is also known. Further, there are known high-refractive-index transparent coatings in which high-refractive-index particles are blended in the transparent coating, low-refractive-index transparent coatings in which low refractive index particles are blended in the transparent coating to impart antireflection properties, and transparent coatings in which colored pigment particles are blended.

It is also known to form a touch panel coating film by a gel-sol method using an alkoxide compound or a coating liquid in which colloidal particles are blended to adjust the refractive index and permittivity of the substrate. However, in this method, it is necessary to heat the film at about 500 DEG C in order to cure the film, so that only a substrate having high heat resistance can be used.

On the other hand, when a coating liquid containing an acetylacetonate chelate compound, a silane compound and a metal alkoxide other than silicon is used (cured at a relatively low temperature by irradiation with ultraviolet rays (after drying or after drying), transparent ceramics It is known that a film can be formed (see, for example, Document 1 (Japanese Patent Application Laid-Open No. 2-48403)).

In addition, a mixture of a sol A, in which hydrolysis and dehydration condensation of a tetraalkoxysilane to which a metal alkoxide stabilized with acetylacetone has been added, and a sol B in which hydrolysis and dehydration condensation of an alkyltrialkoxysilane in which one functional group is alkylated, It is known to form a sol-gel film having a fine uneven surface layer by using a coating solution comprising a solvent mainly composed of isopropyl alcohol and diols mixed therewith (see, for example, Japanese Patent Application Laid-Open -281132).

The coating liquid disclosed in Document 1 can provide a transparent coating film that is cured at a relatively low temperature. However, there is a problem that it is slightly difficult to suppress the occurrence of cracks when the base material is a resin, for example.

Also, in Document 2, it is disclosed that a fine uneven surface layer is formed by using a sol obtained by hydrolyzing and dehydrating and condensing (hydrolyzing and condensing) a trifunctional silane (for example, alkyltrialkoxysilane). However, since it is difficult to form a film having sufficient hardness at a low temperature, firing by at least about 600 캜 is required. Therefore, a substrate having low heat resistance could not be used.

An object of the present invention is to provide a coating liquid for forming a film which has sufficient hardness after being applied to a substrate and is hardly cracked.

DISCLOSURE OF THE INVENTION As a result of intensive studies to overcome the above problems, the present inventors have found that an organic compound capable of forming a chelate with a metal alkoxide, a silane compound having three or more functions and a metal alkoxide (excluding a silicon alkoxide) It has been found that a coating film having sufficient hardness and in which cracks are hard to occur can be obtained. The present invention has been completed on the basis of this finding.

That is, the coating liquid for forming a film of the present invention contains at least one (component B) of an organic compound capable of forming a chelate with a metal alkoxide (component A), a silane compound having three or more functionalities and a hydrolyzed condensate thereof, a metal alkoxide, At least one of the decomposition and condensation products (component C) is dissolved or dispersed in a mixed solvent containing water and an organic solvent. At this time, the molar ratio (M1 / M3) of the molar ratio (M1) of the component A to the molar number (M3) of the component C is 0.25 or more and less than 2.0, / M3) is not less than 0.1 and not more than 9.0. The B component and the C component are represented by the following equations (2) and (3), respectively.

(Concentration C ₂ ) derived from the B component is in the range of 0.005 to 12 mass%, and the MO _x reduced concentration (concentration C 3) of the element M derived from the C component is in the range of 0.02 to 14.25 mass% (CT) of the concentration C2 and the concentration C3 is set in the range of 0.1 to 15 mass%. This improves the crack resistance of the coating film.

When the component B is at least one of the trifunctional silane compound and the hydrolyzed condensate thereof, the molar ratio (M2 / M3) is set in the range of 0.5 to 8.0.

The method for producing a coating liquid of the present invention includes the following steps 1 to 3.

Step 1: A step of preparing the preliminary solution 1 by mixing an organic solvent, water, a silane compound having three or more functional groups (component B) and a hydrolysis catalyst

Step 2: A step of mixing the organic solvent with an organic compound capable of forming a chelate with the metal alkoxide (component A) and a metal alkoxide (component C) to prepare the preliminary solution 2

Here, the blending amount of the A component is in the range of 0.25 mol or more and less than 2.0 mol per 1 mol of the metal element of the C component.

Step 3: Step of mixing the preliminary liquid 1, the preliminary liquid 2, and water and stirring at 5 ° C or higher and 40 ° C or lower

The B component and the C component are represented by the following equations (2) and (3), respectively.

Further, the coated base material of the present invention has a coating formed on a base material using the coating liquid of any of the above-described constitutions.

A method for producing a coated substrate of the present invention comprises a coating step of applying a coating liquid of any of the above-described constitution to a substrate, a drying step of heating the substrate at a temperature of 80 ° C or higher and 150 ° C or lower after the coating step, An irradiating step of irradiating the coating film formed on the substrate with ultraviolet rays and a heating step of heating the coated film at 80 ° C or higher and 300 ° C or lower after the irradiation step. The film can be formed at a process temperature of 300 DEG C or less. Thus, it is possible to produce a coating film having both hardness and crack resistance on a substrate having low heat resistance.

By applying the present invention, a transparent coating film having a high refractive index (refractive index of 1.3 to 2.3) can be formed without adding high refractive index particles to the coating liquid.

Hereinafter, the coating liquid for forming a film, the method for producing a coating liquid, the substrate on which a film is formed, and the method for producing a substrate on which a film is formed will be described.

[Film forming liquid for coating]

The coating liquid for forming a film (hereinafter referred to as " the present coating liquid ") contains an organic compound capable of forming a chelate with a metal alkoxide (component A), a silane compound having three or more functional groups represented by formula (2) At least one (component C) of at least one of the components (component B) and the metal alkoxide represented by the formula (3) and the hydrolyzed condensate thereof is dissolved or dispersed in a mixed solvent containing water and an organic solvent.

(R ³ ) _(4-m) Si (R ⁴ ) _m (2)

(Wherein m is at least one of 3 and 4, and R ³ is any of an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted or substituted aryl group, and a vinyl group. R ⁴ is an unsubstituted or substituted alkoxy group having 1 to 8 carbon atoms, an unsubstituted or substituted aryloxy group, a vinyloxy group, a hydroxyl group, a hydrogen atom, or a halogen atom, and may be the same or different.)

M (OR &_lt; ⁵ &_gt;) _n (3)

(Where M is at least one element selected from the group consisting of Be, Al, Sc, Ti, V, Cr, Fe, Ni, Zn, Ga, Ge, As, Se, Y, Zr, Nb, In, Sn, Sb, Te, , Pb, B, Bi, Ce and Cu, and R ⁵ is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, and n is a number equal to the valence of M)

As can be seen from the above-described formula (2), the B component includes at least one of the trifunctional silane compound and the hydrolyzed condensate thereof (B3 component) when m = 3, , At least one of the tetrafunctional silane compound and the hydrolyzed condensate thereof (component B4) ". The present coating liquid contains at least one of the B3 component and the B4 component as the B component. The present coating liquid may contain a hydrolysis-condensation product in which a component B and a component C are produced by hydrolysis and condensation.

At this time, the molar ratio (M1 / M3) of the molar number (M1) of the component A to the molar number (M3) of the component C needs to be in the range of 0.25 or more and less than 2.0. The molar ratio (M2 / M3) of the molar number (M2) of the component B and the molar number (M3) of the component C needs to be in the range of 0.1 to 9.0. Here, even when each component is hydrolyzed, a value based on the structure before hydrolysis is used as the molar numbers (M1 to M3).

When the molar ratio (M1 / M3) is 2.0 or more, the A component is coordinated to most of the OR ⁵ parts in the C component, and the reaction between the B component and the C component may be inhibited. For this reason, crosslinking of -MO-Si- is not well formed at the time of curing, and there is a possibility that the hardness of the resulting film becomes insufficient. Further, the amount of the component A present in the coating film increases, and electrical characteristics such as the surface resistance value of the film change over time, thereby reducing reliability. When the molar ratio (M1 / M3) is less than 0.25, since the reaction of the component C becomes excessive, the stability of the hydrolyzed and condensed product in the coating liquid deteriorates and the service life of the coating solution becomes short. There is a risk of adverse effects. In particular, the molar ratio (M1 / M3) is preferably in the range of 0.5 to 1.0.

When the molar ratio (M2 / M3) is less than 0.1, the stability of the coating liquid deteriorates and the service life of the coating liquid is shortened. Therefore, there is a possibility that the film properties such as film thickness, refractive index, and hardness may not be stably obtained. On the other hand, when the molar ratio (M2 / M3) is more than 9.0, when the coating film formed from the coating liquid is heated at 300 DEG C or less, the hardness of the coating film may be insufficient.

When such a coating liquid is used, a film having sufficient hardness and scratch resistance can be formed by UV treatment and heat treatment at a low temperature (80 to 300 DEG C). As a result, it is possible to form a coating film having sufficient hardness and scratch resistance even for a substrate having poor heat resistance, and a substrate having sufficient hardness and a coating film which is not easily cracked can be obtained.

That is, according to the present invention, it is possible to realize a high refractive index (refractive index: 1.3 to 2.3) of the film without adding high refractive index particles to the coating liquid. For this reason, the problem of the coating liquid containing conventional high refractive index particles (voids formed by high-active fine particles gravitating toward the solvent, degradation of the denseness of the film due to high concentration of the solvent, deterioration of hardness, .

The SiO ₂ -converted concentration (concentration C ₂ ) derived from the component B is preferably 0.005 to 12 mass%. When the concentration C 2 is 0.005 mass% or more, the hydrolysis reaction progresses smoothly and the crack resistance of the coating film can be sufficiently increased. When the concentration C2 is 12 mass% or less, the hydrolysis reaction does not proceed excessively, and a stable coating liquid can be obtained. In particular, it is preferably 0.01 to 8% by mass.

The MO _x converted concentration (concentration C3) of the element M derived from the C component is preferably 0.02 to 14.25 mass%.

When the concentration C 3 is 0.02 mass% or more, the hydrolysis reaction progresses smoothly, and the crack resistance of the film becomes sufficiently high. If the concentration C 3 is 14.25 mass% or less, the hydrolysis reaction does not proceed as expected, and a stable coating liquid is obtained. In particular, it is preferably 0.04 to 9.5 mass%.

The total concentration CT of the concentration C2 and the concentration C3 is preferably 0.1 to 15% by mass. If the concentration CT is 0.1% by mass or more, a film having a sufficient thickness can be obtained even under ordinary coating conditions, and it is also unnecessary to repeatedly coat the film to obtain a film having high hardness and crack resistance. When the concentration CT is 15 mass% or less, the film thickness obtained under ordinary coating conditions can be controlled, and it is easy to suppress the occurrence of cracks. Further, since the stability of the coating liquid is sufficient, it is possible to suppress an increase in viscosity over time. Therefore, characteristics such as film thickness, refractive index, and hardness of the resulting film are stabilized. The concentration CT is more preferably 0.2 to 10% by mass.

When the coating liquid contains at least one of the trifunctional silane compound and the hydrolyzed condensate thereof (component B3) as component B, the pH of the coating liquid is preferably 4 to 8, more preferably 4 to 7.5 Suitable. If the blend liquid containing the B3 component is in an acidic state, the bifunctional silane compound tends to precipitate as an insoluble solid component, which is not preferable.

When the B component contained in the coating liquid is at least one of the trifunctional silane compound and the hydrolyzed condensate thereof (B3 component), that is, when only the B3 component is contained as the B component, the molar number of the B component (M2 ) And the number of moles of the component C (M3) should be in the range of 0.5 or more and 8.0 or less. When the molar ratio (M2 / M3) is less than 0.5, the stability of the coating liquid is lowered and the service life of the coating liquid is shortened. Therefore, film characteristics such as film thickness, refractive index, and hardness may not be stably obtained. Further, there is a possibility that the crack resistance is lowered. When the molar ratio (M2 / M3) is more than 8.0, the hardness of the obtained film becomes insufficient, and crack resistance is likely to decrease. The molar ratio (M2 / M3) is more preferably 0.6 or more and 7.5 or less.

Similarly, when the present coating liquid contains only the B3 component as the B component, the MO _x converted concentration (concentration C3) of the element M derived from the C component is preferably 0.02 to 14 mass%, more preferably 0.04 to 9.5 mass% More preferable. When the concentration C3 is 14 mass% or less, the hydrolysis reaction does not proceed excessively, and a stable coating liquid is obtained.

Next, a case where at least one of the trifunctional silane compound and the hydrolyzed condensate thereof (component B3) and at least one of the tetrafunctional silane compound and the hydrolyzed condensate thereof (component B4) are included in the coating liquid will be described. The value of the molar ratio (M _B4 / M _B3 ) of the molar number (M _B3 ) of the component _{B3 to} the mol number (M _B4 ) of the component _B4 is preferably 0.01 or more and 1 or less. When the molar ratio (M _B4 / M _B3 ) is 0.01 or more, the hardness of the film is improved. When the molar ratio is 1 or less, the crack resistance is not caused sufficiently. The molar ratio is particularly preferably 0.01 or more and 0.5 or less.

Here, even when the B3 component or the B4 component is hydrolyzed, the number of moles is a value based on the structure before hydrolysis. The hydrolysis-condensation product of the B3 component, the B4 component and the C component may be contained.

Hereinafter, each component contained in the coating liquid of the present invention will be described in detail.

<Component A>

The component A is an organic compound capable of forming a chelate with the metal alkoxide, and may be an organic compound or a mixture of two or more kinds thereof. It is particularly preferable to use acetylacetone in view of the effect as a chelating agent.

In addition to this, as the component A, at least one selected from the group consisting of trifluoroacetylacetone, hexafluoroacetylacetone, benzoyl acetone, benzoyltrifluoroacetone, dibenzoylmethane, furoyl acetone, trifluoro-chloroacetone, benzoyl furoyl methane, 4-methyloxine, 5-methyloxine, 6-methyloxine, 7-methyloxine, oxine-5-sulfonic acid, 7-iodooxine-5-sulfonic acid Hydroxyquinoline-2-carboxylic acid, quinoline-8-carboxylic acid, 8-hydroxycinoline, 4-hydroxy- 1,5-naphthyridine, 8- Hydroxyquinoline, hydroxy-1,7-naphthyridine, 5-hydroxyquinoxaline, 8-hydroxyquinazoline, 2,2'-bipyridine, 2- (2'-thienyl) pyridine, 1,10-phenanthroline Methyl-1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 4,7-dimethyl- Troline, 5-chlor-1, 10-phenanthroline, 6 -Bromo-1,10-phenanthroline, 5-nitro-1,10-phenanthroline, 5-phenyl-1,10-phenanthroline, 4,7- Dimethylglyoxime-o-methyl ester, dimethyldithiocarbamic acid, diethyldithiocarbamic acid, N-nitrosophenylhydroxylamine, 1-nitroso-2-naphthol, 2- 2-naphthol, 4- (2-pyridylazo) resorcin, 2- (4'-dimethylaminophenyl) Azo) pyridine, eriochrome black A, eriochrome black T, eriochrome blue black B, eriochrome blue black R, phthalaine complexone, alkanolamine, and hydroxy acid.

As the component A, a carbonyl compound having two or more carbonyl groups represented by the following formula (1) is particularly preferable.

In the formula (1), R ¹ is an organic group having 1 to 10 carbon atoms. R ² is an organic group having 1 to 10 carbon atoms or a hydroxyl group. Examples of R ¹ include a methyl group, an ethyl group, an isopropyl group, a phenyl group, a furyl group, a thienyl group, a trifluoromethyl group, a methoxy group and an ethoxy group. Particularly, a methyl group, an ethyl group, and an ethoxy group are preferable. As R ² , for example, methyl group, ethyl group, isopropyl group, phenyl group, furyl group, thienyl group, trifluoro group, methoxy group and ethoxy group can be exemplified as an organic group.

<Component B>

By compounding the B component (silane compound having three or more functional groups), the hardness and crack resistance of the coating film (transparent coating film) are improved. Particularly, since the trifunctional silane compound has a bulky organic functional group (an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted or substituted aryl group, and a vinyl group), flexibility is imparted to the film And the wettability of the coating film and the substrate (organic material) is improved. Therefore, the crack resistance is further improved. In addition, even when at least a part of the organic material is decomposed by ultraviolet irradiation in the film forming step, stress concentration is relaxed, which also contributes to improvement of crack resistance.

In R ³ and R ⁴ in the above-mentioned formula (2), examples of the unsubstituted alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, an isopropoxy group, and a butoxy group. Similarly, as the substituted alkoxy group, there can be mentioned a group obtained by substituting the hydrogen atom of the aforementioned unsubstituted alkoxy group with a methyl group, an ethyl group or the like. As the aryloxy group, phenoxy group, naphthyloxy group and the like can be given. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the trifunctional silane compounds include methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES), ethyltriethoxysilane (ETES), methyltriisopropoxysilane, ethyltrimethoxysilane, ethyl Triisopropoxysilane, octyltrimethoxysilane, octyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, trifluoromethyltrimethoxysilane , Trifluoromethyltriethoxysilane? - (meth) acryloxypropyldimethoxysilane,? - (meth) acryloxypropyldiethoxysilane, and the like. These may be used alone or in combination of two or more. However, when R ³ is too long, it may be difficult to obtain sufficient hardness. When R ³ is different from each other, a difference in the rate of hydrolysis occurs, and a homogeneous reaction hardly occurs. Therefore, it is preferable to use methyltrimethoxysilane (MTMS).

Examples of the tetrafunctional silane compound include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetrachlorosilane and trimethoxysilane. In particular, tetraethoxysilane is preferred.

The tetrafunctional silane compound may be used singly or in combination of plural species.

<Component C>

As described above, the C component is at least one of the metal alkoxide represented by the formula (3) and the hydrolyzed condensate thereof. A metal element other than Si is selected as the metal element M of the C component. Specifically, the metal element M is at least one selected from the group consisting of Be, Al, Sc, Ti, V, Cr, Fe, Ni, Zn, Ga, Ge, As, Se, Y, Zr, Nb, In, Sn, , And an alkoxide of at least one element selected from Ta, W, Pb, B, Bi, Ce and Cu is used. In particular, Ti, Al and Zr are preferable.

As the metal alkoxide as the component C, at least one selected from the group consisting of aluminum trimethoxide, aluminum triethoxide, aluminum tripropoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, , Aluminum tripentyloxide, aluminum trihexyloxide, aluminum trioctyloxide, aluminum tribenzyloxide, aluminum triphenoxide, aluminum trimethoxyethoxide, aluminum trimethoxyethoxyethoxide, aluminum trimethoxypropoxy A titanium compound such as titanium tetraethoxide, titanium tetraethoxide, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetramethoxyethoxide, titanium tetrabutoxide, zirconium tetramethoxide, zirconium tetraethoxide, Zirconium tetrapropoxide, zirconium tetrapropoxide Zirconium butoxide, niobium pentaethoxide, indium trimethoxide, indium triethoxide, indium tribopropoxide, indium triisopropoxide, indium tributoxide, indium tributoxide, indium tributoxide, But are not limited to, tri-n-butoxide, indium triisobutoxide, indium tri-t-butoxide, indium tripentyl oxide, indium trihexyloxide, indium trioctyloxide, indium tribenzyloxide, An antimony trioxide, an antimony trioxide, an antimony trioxide, an antimony trioxide, an antimony trioxide, a side, indium trimethoxy ethoxy ethoxide, Tri-n-butoxide, and antimony triisobutoxide. These may be used alone or in admixture of any two or more species. However, titanium tetraisopropoxide and zirconium tetrapropoxide are preferably used from the viewpoints of a suitable hydrolysis rate and easy availability .

<Component D>

In the present coating liquid, about 0.2% by mass of the hydrolysis catalyst may remain after the production process. It is desired to remove the hydrolysis catalyst in accordance with the application of the coating liquid. In this case, for example, the hydrolysis catalyst is removed by ion exchange, neutralization, distillation or the like. In the case of neutralization, the acid neutralizing material remains in the coating liquid. Hereinafter, the case of the neutralization treatment will be described in detail.

Component D is an acid neutralizing material added to make the pH of the coating liquid 4 to 8. When the trifunctional silane compound (component B3) is contained as the above-described component B, the component B3 is hydrolyzed by a catalyst for hydrolysis such as an acid catalyst. An acid neutralizing material is added to return the mixture to neutral. If the compounding liquid is in an acidic state, the bifunctional silane compound tends to precipitate as an insoluble solid component, which is not preferable. The D component contained in the coating liquid is preferably 1% by mass or less.

The acid neutralizing material is preferably an amine compound from the viewpoint of mixing of metal impurities and solubility in an organic solvent. Examples of the amine compound include triethanolamine, diethanolamine, monoethanolamine, trimethylamine, ethylenediamine, piperidine, aniline and pyridine. One acid neutralizing material may be used, or arbitrary two or more acid neutralizing materials may be mixed and used.

<Mixed solvent>

As the coating liquid, a mixed solvent of water and an organic solvent is used. However, as the organic solvent, an organic compound capable of forming a chelate with the metal alkoxide (A) (component A) is excluded. The mixing ratio of water to the organic solvent is preferably 20/80 to 0.1 / 99.9, more preferably 10/90 to 1/99, in the water / organic solvent (mass ratio). The organic solvent preferably has a boiling point of 120 캜 or higher. More preferably at least 150 ° C. However, it is preferable that the boiling point is 300 占 폚 or less. The viscosity of the organic solvent at 20 캜 is preferably in the range of 1 to 400 mPa s, more preferably in the range of 20 to 350 mPa 쨌 s. When a plurality of organic solvents are mixed, the organic solvent having a boiling point of 120 ° C or higher and a viscosity at 20 ° C of 1 to 400 mPa · s is preferably 50 mass% or more, more preferably 60 mass% or more .

Examples of the organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, diacetone alcohol, furfuryl alcohol, ethylene glycol and hexylene glycol, esters such as acetic acid methyl ester and ethyl acetate ester, Ethers such as ethylene glycol monoethyl ether, glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol monopropyl ether, And ketones such as methyl ethyl ketone.

In addition, optional components may be added to the coating liquid within the range not hindering the effect. For example, inorganic oxide fine particles, organic resin fine particles, organopolysiloxane resin fine particles, pigments, coloring agents, antistatic agents and surfactants may be added.

[Method of producing the present coating liquid]

The manufacturing method of the present coating liquid includes the following steps 1, 2, and 3.

Step 1: A process of preparing a preliminary liquid 1 by mixing an organic solvent, water, a B component (a silane compound having three or more functional groups represented by formula (2)) and a hydrolysis catalyst

Here, when a tetrafunctional silane compound is used for the component B, the amount of the component B is in the range of 0.1 mol or more and 9.0 mol or less per mol of the metal element M of the component C in the step 2.

When the trifunctional silane compound is used for the component B, the amount of the component B is in the range of 0.5 mol or more to 8.0 mol or less per mol of the metal element M of the component C in the step 2. Further, the pH of the preliminary liquid 1 is adjusted to a range of 5 to 8 by neutralization treatment.

Step 2: A step of preparing a metal alkoxide solution (preliminary solution 2) by mixing an organic solvent, component A, and component C (metal alkoxide represented by formula (3))

Here, the A component is in a range of 0.25 mol or more and less than 2 mol per 1 mol of the metal element M of the C component.

Step 3: Step of mixing the preliminary liquid 1 obtained in Step 1, the preliminary liquid 2 obtained in Step 2 and water and stirring at a temperature of not lower than 5 ° C and not higher than 40 ° C

Each of the steps described above will be described in detail below.

&Lt; Step 1 &

When a tetrafunctional silane compound is used as the component B, the tetrafunctional silane compound is hydrolyzed and condensed in the presence of an organic solvent, water and a catalyst for hydrolysis, and at least one of the tetrafunctional silane compound and its hydrolyzed condensate is mixed A solution (preliminary solution 1) to be dispersed in a solvent is prepared. Alternatively, when a trifunctional silane compound is used as the component B, the trifunctional silane compound is hydrolyzed and condensed in the presence of an organic solvent, water and a catalyst for hydrolysis, and further neutralized to adjust the pH of the solution to 5 to 8 . In this way, the preliminary liquid 1 in which at least one of the trifunctional silane compound and its hydrolyzed condensate is dispersed in the mixed solvent is obtained. Usually, in this Step 1, water, a catalyst for hydrolysis and a component B are added to an organic solvent, and stirring is performed at 5 to 40 ° C for 5 to 120 minutes to obtain a preliminary liquid 1.

Examples of the catalyst for hydrolysis include (a) inorganic acids such as nitric acid, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and hydrogen fluoride, (b) carboxylic acids such as oxalic acid and maleic acid, (c) sulfonic acids such as methanesulfonic acid, And (d) an acidic or slightly acidic inorganic salt. However, the present invention is not limited thereto. A plurality of these catalysts may be arbitrarily mixed. The amount of the hydrolysis catalyst is preferably in the range of 0.001 to 1 mol% (converted to SiO ₂ , external ratio) relative to the trifunctional or higher functional group-B silane compound.

The amount of water is preferably in the range of 0.5 to 10 moles (in terms of SiO _{2, in} terms of SiO ₂ ) per 1 mol of the silane compound having three or more functional groups. This range of molar ratio is effective in effectively hydrolyzing the B component. The amount of water is more preferably in the range of 1 to 8 moles.

The amount of the component B in the preliminary liquid 1 is not particularly limited as long as the hydrolysis and condensation can proceed, but it is preferably in the range of 0.01 to 8 mass% (in terms of SiO ₂ ).

When the component B is a trifunctional silane compound, a hydrolysis-condensation product of a bifunctional silane compound is produced, and then an acid neutralizing substance is added in order to return the compounding solution to neutral. If the blend liquid containing the B component is in an acidic state, the bifunctional silane compound tends to precipitate as an insoluble solid component, which is not preferable. The pH of the trifunctional silane solution is preferably from 5 to 8, more preferably from 6 to 7.5.

In addition, the acid neutralizing material (component D) is not necessarily essential. The pH may be adjusted to 5 to 8 by removing the hydrolysis catalyst by using an ion exchange resin instead of adding the acid neutralizing material.

&Lt; Step 2 &

In this step, a metal alkoxide solution (preliminary solution 2) containing a metal alkoxide or a hydrolyzed condensate thereof is prepared by adding an A component and a C component (metal alkoxide represented by the formula (3)) to an organic solvent and stirring the mixture . The organic solvent, component A or component C is as described above.

The molar ratio (M1 / M3) of the mole number (M1) of the A component to the mole number (M3) of the C component in this step is in the range of 0.25 or more and less than 2.0. In this process, the component A is coordinated to the alkoxy group of the component C, but if the molar ratio (M1 / M3) is in the range of 0.25 or more and less than 2.0, the metal alkoxide which is not coordinated to the chelating component of the component A is present. Can be controlled. The molar ratio (M1 / M3) is more preferably 0.5 or more and 1.0 or less.

When the molar ratio (M1 / M3) is 2.0 or more, the coordination of the metal alkoxide with the alkoxy group is excessively advanced, so that the stabilization of the metal alkoxide becomes excessive and also affects the cohydrolysis and condensation with the component B, There is a fear that it may not be suitable for low-temperature curing (80 to 300 ° C).

The metal alkoxide solution obtained by this process contains a metal alkoxide for the component A and a hydrolysis-condensation product thereof.

&Lt; Step 3 >

The metal alkoxide solution (preliminary solution 2) prepared in Step 2 was added to the silane solution (preliminary solution 1) having three or more functions prepared in Step 1, followed by addition of water and stirring at 5 to 40 캜, .

Prior to this step, the weight average molecular weight (in terms of polystyrene) of the B component contained in the preliminary liquid 1, that is, the B component after the hydrolysis and condensation is preferably in the range of 300 to 3000 from the viewpoint of crack resistance. The weight average molecular weight of the component B is more preferably in the range of 500 to 1,500. Here, the weight average molecular weight is obtained by GPC.

When the B component is a tetrafunctional silane compound, the molar ratio (M2 / M3) of the molar number (M2) of the B component to the mol number (M3) of the C component is 0.1 to 9.0, preferably 0.2 to 5.0 . When the B component is a trifunctional silane compound, the molar ratio (M2 / M3) of the mole number (M2) of the B component to the mole number (M3) of the C component is in the range of 0.5 to 8, preferably 0.6 to 7.5 desirable. When the molar ratio (M2 / M3) falls within these ranges, the cohydrolysis reaction proceeds smoothly.

Addition of water promotes the co-hydrolysis and condensation reaction of at least one of the hydrolysis-condensation product of the silane with three or more functional groups and the metal alkoxide, so that it is preferable to obtain a dense coating film.

When the component B contains a trifunctional silane compound, the pH of the present coating liquid is preferably 4 to 8, more preferably 4 to 7.5.

[Process for producing a film-coated substrate]

A method of producing a coated substrate includes a coating step of applying the coating liquid to a substrate, a drying step of drying the coating liquid on the substrate to form a coating film, and a curing step of curing the coated film on the substrate to form a coated substrate . The drying step and the curing step will be described in more detail. The drying step is a step of heating the coating liquid on the substrate at a temperature of 80 ° C or more and 150 ° C or less, a curing step is a step of irradiating ultraviolet rays And a heating step of heating at 80 DEG C or higher and 300 DEG C or lower.

As a coating method of applying the present coating liquid to a substrate, conventionally known methods such as a dipping method, a spinner method, a bar coating method, a spraying method, a roll coater method, a flexographic printing method, and a slit coating method may be employed. Examples of the substrate include glass, a substrate treated with an ITO film, a sheet, a film, and a panel using materials such as polycarbonate, acrylic resin, PET, and TAC.

In the drying step, the heating temperature is not particularly limited as long as desired hardness and crack resistance can be obtained without deteriorating the substrate, but is preferably in the range of 80 to 150 ° C, more preferably in the range of 90 to 140 ° C. In the drying step, it is preferable to heat for 1 to 10 minutes.

In the drying step, if a film having desired hardness, crack resistance, etc. is obtained, drying and heating may be carried out in a single operation, or it may be heated at a temperature higher than the drying temperature after drying. As the drying method and the heating method, conventionally known methods can be employed. In addition, an electromagnetic wave irradiation process may be used in combination.

When the heating temperature in the drying step is less than 80 캜, sufficient film strength can not be obtained due to residual solvent, insufficient cross-linking of -MOM- or -MO-Si-, , The organic group of the component B may be decomposed, and desired film characteristics may not be obtained.

In the irradiation step, ultraviolet rays (UV) are applied to the transparent coating film which is dried by the drying step. For example, an ultraviolet ray of 3,000 mJ / cm 2 is irradiated using a high-pressure mercury lamp of 2 kw. By the UV irradiation, the component A is desorbed in the coating film, and the coating film is in a state where it is easily crosslinked in the heating process.

After the irradiation step, the film is heated in the range of 80 to 300 占 폚. By this heating step, the transparent coating film is in a state in which the crosslinking proceeds sufficiently. When the heating temperature is in the range of 80 to 300 占 폚, for example, the resistance change of the ITO wiring can be suppressed. The heating time is preferably 1 to 10 minutes.

[Substrate formed with film]

The average film thickness (T) of the film obtained by the above-described film forming method is preferably 20 to 200 nm, more preferably 40 to 150 nm. When the average film thickness (T) of the coating film is 20 nm or more, the film thickness is sufficient and the portion (coating unevenness) which can not be formed is not easily generated, and the film forming effect is sufficiently obtained. On the other hand, when the average film thickness T is 200 nm or less, occurrence of cracks can be sufficiently suppressed, and the film hardness can be sufficiently obtained.

The coating film according to the present invention can be suitably used for an insulating film used between an electrode substrate and an alignment film of a liquid crystal display device, a protective film on a transparent electrode of a touch panel, and the like.

Example

Hereinafter, examples of the coating liquid for forming a transparent coating film will be specifically described. This coating liquid can be applied to a protective film on a transparent electrode of a touch panel or the like. But the present invention is not limited to these examples.

[Example 1]

<< Preparation of coating liquid for forming a transparent film >>

(Step 1)

4507.86 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 214.93 g of pure water and 3.58 g of nitric acid at a concentration of 61% by mass were mixed and stirred for 5 minutes. Next, while stirring, 1243.78 g of ethyl silicate (SiO ₂ concentration: 28.8 mass%, manufactured by Tama Chemical Co., Ltd.) was added as component B (tetrafunctional silane compound) and stirred for 30 minutes. Thus, a preliminary liquid 1 having a solid concentration of 6.0% by mass is obtained.

(Step 2)

297.97 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 149.25 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as component A, and 480 g of tetraisopropyl titanate (manufactured by Matsumoto Fine Chemicals Co., : ORGATIX TA-10, TiO ₂ concentration 28% by mass) were mixed and stirred for 5 minutes. Thus, a preliminary liquid 2 having a solid concentration of 6.0% by mass is obtained.

(Step 3)

The preliminary liquid 2 was mixed with the preliminary liquid 1 while stirring, and after stirring for 10 minutes, 49.75 g of pure water was added and stirred at 5 캜 for 144 hours. After completion of the stirring, filtration is performed with a filter of 0.2 mu m to remove the aggregates and the like to prepare a coating liquid having a concentration CT of 6.0% by mass.

The concentrations, molar ratios, and the like of each component in the obtained coating liquid are shown in Table 1. The number of moles of component A (organic compound capable of forming a chelate with the metal alkoxide) in Table 1 is denoted by M1, and the number of moles of component B (at least one of the trifunctional or more functional silica compound and its hydrolyzed condensate) is M2. When at least one (B3 component) of the trifunctional silica compound and its hydrolyzed condensation product and at least one of the tetrafunctional silica compound and its hydrolyzed condensation product are present as the component B, the number of moles of the component B3 Let the number of moles of M _B3 and B4 components be M _B4 .

The number of moles of at least one of the metal alkoxide represented by the formula (3) and the hydrolyzed condensate thereof (component C) is M3.

In the coating liquid, the SiO ₂ -converted concentration derived from the B component is referred to as a concentration C ₂ , and the MO _x -converted concentration derived from the C component is referred to as a concentration C 3, and the sum of the concentration C 2 and the concentration C 3 is referred to as a concentration CT.

The time lapse stability of the coating liquid is evaluated by the following method. The results are shown in Table 1.

<< Time Stability >>

After heating the coating liquid at 40 占 폚 for 72 hours, viscosity was measured with an E-type viscometer (TV-25 type, manufactured by TOKI INDUSTRIAL CO., LTD.) And evaluated according to the following criteria.

◎: Viscosity is not changed

○: Increase in viscosity slightly (less than 5 mPa · s)

X: a clear increase in viscosity is observed (at least 5 mPa · s)

&Lt; Evaluation of substrate on which a transparent coating is formed &gt;

The film thickness, the surface resistance value and the pencil hardness of the base material having the transparent coating film are measured by the following method. The results are shown in Table 1.

<< Thickness >>

The surface roughness is measured with a surface roughness tester (Surfcomm manufactured by Tokyo Precision Co., Ltd.).

<< Surface resistance value >>

The surface resistance value is measured with a surface resistance meter (Hiresta-UX MCP-HT800, manufactured by Mitsubishi Chemical Corporation).

<< Pencil hardness >>

And measured by a pencil hardness tester in accordance with JIS-K-5600. That is, a pencil was set at an angle of 45 degrees with respect to the surface of the transparent coating, and a predetermined weight was loaded and drawn at a constant speed, and the presence or absence of a scratch was observed.

The substrate having the transparent film for evaluation of film thickness, surface resistance value and pencil hardness is prepared by the following method.

The coating liquid obtained in Example 1 is applied onto a glass substrate (1.1 mm in thickness, manufactured by AGC Fabric Tech Co., Ltd.) on which an ITO film is formed by the flexographic printing method. (3000 mJ / cm 2) at a wavelength of 365 nm and ultraviolet light (2000 mJ / cm 2) at a wavelength of 254 nm and then heated at 230 캜 for 30 minutes to obtain a substrate having a transparent coating film .

The total light transmittance, haze, and scratch resistance of a substrate having a transparent coating film are measured by the following method. The results are shown in Table 1.

<< Total light transmittance and haze >>

The total light transmittance and haze are measured by a haze meter (manufactured by Suga Test Instruments Co., Ltd.).

<< Measurement of scratch resistance >>

# 0000 Steel wool was placed on the surface of the transparent coating and slid ten times at a load of 2 kg / cm 2, and the surface of the film was visually observed, and scratch resistance was evaluated according to the following criteria.

Evaluation standard :

No scratches on stripe: ◎

Scratched slightly on stripes: ○

There are many scratches on stripes: △

The entire surface is shaved: ×

A substrate having a transparent coating film for evaluating total light transmittance, haze and scratch resistance is prepared by the following method.

The coating liquid obtained in Example 1 was applied onto a glass substrate (manufactured by AGC Fabric Tech Co., Ltd., thickness 1.1 mm) on which a silica film was formed by the flexographic printing method. (3000 mJ / cm 2) at a wavelength of 365 nm and ultraviolet light (2000 mJ / cm 2) at a wavelength of 254 nm and then heated at 230 캜 for 30 minutes to obtain a substrate having a transparent coating film .

With respect to the base material having the transparent coating film, the refractive index is measured by the following method. The results are shown in Table 1.

<< Refractive index >>

And measured with a spectroscopic ellipsometer (manufactured by SOPRA Corporation: ES4G, @ 550 nm).

The substrate on which the transparent coating film for evaluation of refractive index is formed is prepared by the following method.

The coating liquid obtained in Example 1 is applied on a 6-inch silicon wafer (manufactured by Matsuzaki Co., Ltd., thickness: 0.625 mm) by flexographic printing. (3000 mJ / cm 2) at a wavelength of 365 nm and ultraviolet light (2000 mJ / cm 2) at a wavelength of 254 nm and then heated at 230 캜 for 30 minutes to obtain a substrate having a transparent coating film .

With respect to the substrate having the transparent coating film, the crack resistance was measured by the following method. The results are shown in Table 1.

<< Crack resistance of coating film >>

The surface of the coated film was visually observed, and crack resistance was evaluated based on the following criteria.

◎: Cracks are not seen in the coated surface

○: Some cracks are visible at the edge

X: Cracks occur in the coated surface

The substrate on which the transparent film for evaluating the crack resistance of the coated film is formed is prepared by the following method.

An acrylic resin layer having a thickness of 2 mu m was formed on a glass substrate (manufactured by AGC Fabric Tech Co., Ltd., thickness 1.1 mm) on which a silica film was formed. The acrylic resin layer was applied using a bar coater (No. 4), dried at 80 ° C for 2 minutes, and irradiated with ultraviolet light (300 mJ / cm 2) at a wavelength of 365 nm. The coating liquid obtained in Example 1 was applied onto a glass substrate having the acrylic resin layer formed thereon by flexographic printing, dried at 90 DEG C for 5 minutes, irradiated with ultraviolet light (wavelength 365 nm) of 3000 mJ / Thereafter, the substrate was heated at 230 캜 for 30 minutes to obtain a substrate having a transparent coating film.

[Example 2]

<< Preparation of coating liquid for forming a transparent film >>

In the same manner as in Example 1 except that 255.917 g of hexyleneglycol (manufactured by Wako Pure Chemical Industries, Ltd.) and 568.05 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) were used, the concentration CT was 6.0 % &Lt; / RTI &gt;

The concentrations, molar ratios, and the like of each component in the obtained coating liquid are shown in Table 1.

&Lt; Evaluation of substrate on which a transparent coating is formed &gt;

Measurement and evaluation were carried out in the same manner as in Example 1 except that this coating liquid was used. The results are shown in Table 1.

[Example 3]

<< Preparation of coating liquid for forming a transparent film >>

In the same manner as in Example 1 except that 3052.48 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) and 74.74 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) were used, the concentration CT was 6.0 % &Lt; / RTI &gt;

The concentrations, molar ratios, and the like of each component in the obtained coating liquid are shown in Table 1.

&Lt; Evaluation of substrate on which a transparent coating is formed &gt;

Measurement and evaluation were carried out in the same manner as in Example 1 except that this coating liquid was used. The results are shown in Table 1.

[Example 4]

<< Preparation of coating liquid for forming a transparent film >>

(Step 1)

6536.14 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 311.64 g of pure water and 5.19 g of 61% by mass nitric acid were mixed and stirred for 5 minutes. Next, 1803.48 g of ethyl silicate (SiO ₂ concentration: 28.8% by mass, manufactured by Tama Chemical Co., Ltd.) as a B component (tetrafunctional silane compound) was added with stirring and stirred for 30 minutes to obtain a preliminary liquid 1 .

(Step 2)

, 967.76 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 48.58 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as the component A, tetraisopropyl titanate (manufactured by Matsumoto Fine Chemicals Co., : ORGATIX TA-10, TiO ₂ concentration: 28% by mass), and stirred for 5 minutes to prepare a pre-solution 2 having a solid content concentration of 6.0% by mass.

(Step 3)

The preliminary liquid 2 was mixed with the preliminary liquid 1 while stirring, and after stirring for 10 minutes, 49.75 g of pure water was added and stirred at 5 캜 for 144 hours. After completion of the stirring, filtration is carried out with a filter of 0.2 mu m to remove the aggregates and the like to prepare a coating liquid having a concentration CT of 6.0% by mass.

The concentrations, molar ratios, and the like of each component in the obtained coating liquid are shown in Table 1.

&Lt; Evaluation of substrate on which a transparent coating is formed &gt;

Measurement and evaluation were carried out in the same manner as in Example 1 except that this coating liquid was used. The results are shown in Table 1.

[Example 5]

<< Preparation of coating liquid for forming a transparent film >>

(Step 1)

1126.97 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 53.73 g of pure water and 0.90 g of 61 mass% of nitric acid were mixed and stirred for 5 minutes. Next, while stirring, 310.95 g of ethyl silicate (a 28.8 mass% concentration of SiO ₂ , manufactured by Tama Chemical Co., Ltd.) was added as a component B (tetrafunctional silane compound) and stirred for 30 minutes to obtain a preliminary solution having a solid content concentration of 6.0% 1 is prepared.

(Step 2)

6327.69 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 317.66 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as component A, and 460 g of tetraisopropyl titanate (manufactured by Matsumoto Fine Chemicals Co., : ORGATIX TA-10, TiO ₂ concentration: 28% by mass) were mixed and stirred for 5 minutes to prepare a preliminary liquid 2 having a solid content concentration of 6.0% by mass.

(Step 3)

The preliminary liquid 2 was mixed with the preliminary liquid 1 while stirring, and after stirring for 10 minutes, 49.75 g of pure water was added and stirred at 5 캜 for 144 hours. After completion of the stirring, filtration is carried out with a filter of 0.2 mu m to remove the aggregates and the like to prepare a coating liquid having a concentration CT of 6.0% by mass. The concentrations, molar ratios, and the like of each component in the obtained coating liquid are shown in Table 1.

&Lt; Evaluation of substrate on which a transparent coating is formed &gt;

Measurement and evaluation were carried out in the same manner as in Example 1 except that this coating liquid was used. The results are shown in Table 1.

[Example 6]

<< Preparation of coating liquid for forming a transparent film >>

(Step 1)

5239.00 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 107.46 g of pure water and 1.79 g of 61% by mass of nitric acid were mixed and stirred for 5 minutes. Subsequently, 621.89 g of ethyl silicate (SiO ₂ concentration: 28.8% by mass, manufactured by Tama Chemical Co., Ltd.) was added as a component B (tetrafunctional silane compound) with stirring and stirred for 30 minutes to obtain a preliminary solution having a solid content concentration of 6.0% 1 is prepared.

(Step 2)

3478.92 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 74.74 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as the component A, and 60 g of tetraisopropyl titanate (manufactured by Matsumoto Fine Chemicals Co., : ORGATIX TA-10, TiO ₂ concentration 28% by mass) were mixed and stirred for 5 minutes to prepare a pre-solution 2 having a solid content concentration of 6.0% by mass.

(Step 3)

The preliminary liquid 2 was mixed with the preliminary liquid 1 while stirring, and after stirring for 10 minutes, 49.75 g of pure water was added and stirred at 5 캜 for 144 hours. After completion of the stirring, filtration is carried out with a filter of 0.2 mu m to remove the aggregates and the like to prepare a coating liquid having a concentration CT of 6.0% by mass. The concentrations, molar ratios, and the like of each component in the obtained coating liquid are shown in Table 1.

&Lt; Evaluation of substrate on which a transparent coating is formed &gt;

The measurement and evaluation were carried out in the same manner as in Example 1 except that the heating conditions after the ultraviolet irradiation were 120 占 폚 for 30 minutes. The results are shown in Table 1.

[Example 7]

<< Preparation of coating liquid for forming a transparent film >>

(Step 1)

3776.72 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 322.39 g of pure water and 5.37 g of nitric acid at a concentration of 61% by mass were mixed and stirred for 5 minutes. Next, 1865.67 g of ethyl silicate (SiO ₂ concentration: 28.8% by mass, manufactured by Tama Chemical Co., Ltd.) as a B component (tetrafunctional silane compound) was added with stirring and stirred for 30 minutes to obtain a preliminary solution having a solid content concentration of 9.0% 1 is prepared.

(Step 2)

2476.55 g of hexyleneglycol (manufactured by Wako Pure Chemical Industries, Ltd.), 224.23 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as component A and 2 g of tetraisopropyl titanate (manufactured by Matsumoto Fine Chemicals Co., : ORGATIX TA-10, TiO ₂ concentration: 28% by mass), and the mixture was stirred for 5 minutes to prepare a pre-solution 2 having a solid content concentration of 9.0% by mass.

(Step 3)

The preliminary liquid 2 was mixed with the preliminary liquid 1 while stirring, and after stirring for 10 minutes, 49.75 g of pure water was added and stirred at 5 캜 for 144 hours. After completion of the stirring, filtration is performed with a filter of 0.2 mu m to remove the aggregates and the like to prepare a coating liquid having a concentration CT of 9.0 mass%. The concentrations, molar ratios, and the like of each component in the obtained coating liquid are shown in Table 1.

&Lt; Evaluation of substrate on which a transparent coating is formed &gt;

The measurement and evaluation were carried out in the same manner as in Example 1 except that the heating conditions after the ultraviolet irradiation were 280 占 폚 and 30 minutes. The results are shown in Table 1.

[Example 8]

<< Preparation of coating liquid for forming a transparent film >>

(Step 1)

3681.42 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 175.52 g of pure water and 2.93 g of nitric acid at a concentration of 61% by mass were mixed and stirred for 5 minutes. Next, 1015.75 g of ethyl silicate (SiO ₂ concentration: 28.8% by mass, manufactured by Tama Chemical Co., Ltd.) as a B component (tetrafunctional silane compound) was added with stirring and stirred for 30 minutes to obtain a preliminary solution having a solid content concentration of 6.0% 1 is prepared.

(Step 2)

3416.09 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 218.93 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as component A, and 0.2 g of n-propyl zirconate (manufactured by Matsumoto Fine Chemicals Co., : Orgatics ZA-45, ZrO ₂ concentration: 21.2% by mass) were mixed and stirred for 5 minutes to prepare a preliminary liquid 2 having a solid content concentration of 6.0% by mass.

(Step 3)

The preliminary liquid 2 was mixed with the preliminary liquid 1 while stirring, and after stirring for 10 minutes, 49.23 g of pure water was added and stirred at 5 캜 for 144 hours. After completion of the stirring, filtration is carried out with a filter of 0.2 mu m to remove the aggregates and the like to prepare a coating liquid having a concentration CT of 6.0% by mass. The concentrations, molar ratios, and the like of each component in the obtained coating liquid are shown in Table 1.

&Lt; Evaluation of substrate on which a transparent coating is formed &gt;

Measurement and evaluation were carried out in the same manner as in Example 1 except that this coating liquid was used. The results are shown in Table 1.

[Example 9]

<< Preparation of coating liquid for forming a transparent film >>

(Step 1)

713.22 g of KBM-13 (Shin-Etsu Chemical Co., Ltd., concentration of SiO ₂ : 44.1% by mass) as a B component (trifunctional silane compound) and 1875.40 g of Solmics AP-11 (manufactured by Nippon Alcohol Sales Co., Stir for 30 minutes. Then, while stirring, 570.50 g of nitric acid with a concentration of 0.1% by mass was continuously added over 30 minutes, and the mixture was stirred for 30 minutes. The pH at this time was 2.0. While stirring, 5.06 g of triethanolamine (Hayashi Junyaku Kogyo K.K.) was added and stirred for 10 minutes to prepare a pre-solution 1-1 having a solid content concentration of 10.0% by mass. The pH at this time was 7.1.

Next, the preliminary liquid 1-1 was added to 2109.45 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) with stirring, and the mixture was stirred for 30 minutes to prepare a preliminary liquid 1 having a solid content concentration of 6.0% by mass.

(Step 2)

, 3498.84 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 175.65 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as the component A, and tetraisopropyl titanate (manufactured by Matsumoto Fine Chemicals Co., : ORGATIX TA-10, TiO ₂ concentration: 28% by mass) were mixed and stirred for 5 minutes to prepare a pre-solution 2 having a solid content concentration of 6.0% by mass.

(Step 3)

The preliminary liquid 2 was mixed with the preliminary liquid 1 while stirring, and the mixture was stirred for 10 minutes. Then, 49.75 g of pure water was added and stirred at 25 캜 for 30 minutes. After completion of the stirring, filtration is performed with a filter of 0.2 mu m to remove the aggregates and the like to prepare a coating liquid having a concentration CT of 6.0% by mass. The results are shown in Table 1.

&Lt; Evaluation of substrate on which a transparent coating is formed &gt;

Measurement and evaluation were carried out in the same manner as in Example 1 except that this coating liquid was used. The results are shown in Table 1.

[Example 10]

<< Preparation of coating liquid for forming a transparent film >>

A coating liquid is prepared in the same manner as in Example 1 except for the following preliminary process.

The concentrations, molar ratios, and the like of each component in the obtained coating liquid are shown in Table 1.

(Step 1)

1009.27 g of KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd .: SiO ₂ concentration: 44.1% by mass) as a B component (trifunctional silane compound) and 2653.86 g of Solmics AP-11 (manufactured by Nippon Alcohol Sales Co., Stir for 30 minutes. Then, while stirring, 807.32 g of nitric acid with a concentration of 0.1% by mass was continuously added over 30 minutes, and the mixture was stirred for 30 minutes. The pH at this time was 2.1. While stirring, 7.16 g of triethanolamine (Hayashi Junyaku Kogyo K.K.) was added and stirred for 10 minutes to prepare a preliminary liquid 1-1 having a solid content concentration of 9.9% by mass. The pH at this time was 7.2.

Next, the preliminary liquid 1-1 was added to 2985.07 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) with stirring, and the mixture was stirred for 30 minutes to prepare a preliminary liquid 1-2 having a solid content concentration of 6.0% by mass.

(Step 2)

1861.08 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 93.43 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as the component A, and tetraisopropyl titanate (manufactured by Matsumoto Fine Chemicals Co., : Orgatic TA-10, TiO ₂ concentration: 28% by mass) were mixed and stirred for 5 minutes to prepare a pre-solution 2 having a solid content concentration of 6.0% by mass.

&Lt; Evaluation of substrate on which a transparent coating is formed &gt;

Measurement and evaluation were carried out in the same manner as in Example 1 except that this coating liquid was used. The results are shown in Table 1.

[Example 11]

A coating liquid for forming a transparent coating film was prepared in the same manner as in Example 1 except for the following steps.

The concentrations, molar ratios, and the like of each component in the obtained coating liquid are shown in Table 1.

(Step 1)

1143.84 g of KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd .: SiO ₂ concentration 44.1% by mass) as a B component (trifunctional silane compound) and 3007.71 g of Solmics AP-11 (manufactured by Nippon Alcohol Sales Co., Ltd.) Stir for 30 minutes. Next, while stirring, 914.96 g of nitric acid at a concentration of 0.1% by mass was continuously added over 30 minutes, and the mixture was stirred for 30 minutes. The pH at this time was 2.1. 8.11 g of triethanolamine (Hayashi Junyaku Kogyo Co., Ltd.) was added with stirring, and the mixture was stirred for 10 minutes to prepare a preliminary liquid 1-1 having a solid content concentration of 9.9% by mass. The pH at this time was 7.1.

Then, 3383.08 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) was added with the preliminary liquid 1-1 while stirring and stirred for 30 minutes to prepare a preliminary liquid 1 having a solid content concentration of 6.0% by mass.

(Step 2)

1116.65 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 56.06 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as component A, and 50 g of tetraisopropyl titanate (manufactured by Matsumoto Fine Chemicals Co., : ORGATIX TA-10, TiO ₂ concentration: 28% by mass) were mixed and stirred for 5 minutes to prepare a preliminary liquid 2 having a solid content concentration of 6.0% by mass.

&Lt; Evaluation of substrate on which a transparent coating is formed &gt;

Measurement and evaluation were carried out in the same manner as in Example 1 except that this coating liquid was used. The results are shown in Table 1.

[Example 12]

<< Preparation of coating liquid for forming a transparent film >>

A coating liquid is prepared in the same manner as in Example 1 except for the following steps.

The concentrations, molar ratios, and the like of each component in the obtained coating liquid are shown in Table 1.

(Step 1)

403.71 g of KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd .: SiO ₂ concentration: 44.1% by mass) as a B component (trifunctional silane compound) and 1061.55 g of Solmics AP-11 (manufactured by Nippon Alcohol Sales Co., Stir for 30 minutes. Next, while stirring, 322.92 g of nitric acid with a concentration of 0.1% by mass was added over a period of 30 minutes, and the mixture was stirred for 30 minutes. The pH at this time was 2.0. While stirring, 2.86 g of triethanolamine (Hayashi Junyaku Kogyo K.K.) was added and stirred for 10 minutes to prepare a preliminary liquid 1-1 having a solid content concentration of 9.9% by mass. The pH at this time was 7.0.

Next, 1194.03 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) was added with the preliminary liquid 1-1 while stirring and stirred for 30 minutes to prepare a preliminary liquid 1 having a solid content concentration of 6.0% by mass.

(Step 2)

, 5211.04 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 261.60 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as component A, and 50 g of tetraisopropyl titanate (manufactured by Matsumoto Fine Chemicals Co., : ORGATIX TA-10, TiO ₂ concentration: 28% by mass) were mixed and stirred for 5 minutes to prepare a pre-solution 2 having a solid content concentration of 6.0% by mass.

&Lt; Evaluation of substrate on which a transparent coating is formed &gt;

Measurement and evaluation were carried out in the same manner as in Example 1 except that this coating liquid was used. The results are shown in Table 1.

[Example 13]

<< Preparation of coating liquid for forming a transparent film >>

A coating liquid is prepared in the same manner as in Example 1 except for the following steps.

The concentrations, molar ratios, and the like of each component in the obtained coating liquid are shown in Table 1.

(Step 1)

484.25 g of KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd., concentration of SiO ₂ : 44.1% by mass) as a B3 component (trifunctional silane compound) and 1273.85 g of Solmics AP-11 (manufactured by Nippon Alcohol Sales Co., And the mixture was stirred for 30 minutes. Then, while stirring, 387.51 g of nitric acid with a concentration of 0.1% by mass was continuously added over 30 minutes, and the mixture was stirred for 30 minutes. The pH at this time was 2.0. While stirring, 3.44 g of triethanolamine (Hayashi Junyaku Kogyo Co., Ltd.) was added and stirred for 10 minutes to prepare a preliminary liquid 1-1 having a solid content concentration of 9.9% by mass. The pH at this time was 6.9.

Next, 60.90 g of pure water and 1.01 g of nitric acid at a concentration of 61% by mass were mixed with 2710.06 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred for 5 minutes. Next, while stirring, 352.40 g of ethyl silicate (SiO ₂ concentration: 28.8% by mass, manufactured by Tama Chemical Co., Ltd.) as a B4 component (tetrafunctional silane compound) was added and stirred for 30 minutes. The preliminary liquid 1-1 was further added while stirring and stirred for 30 minutes to prepare a preliminary liquid 1 having a solid content concentration of 6.0% by mass.

(Step 2)

, 3498.84 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 175.65 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as the component A, and tetraisopropyl titanate (manufactured by Matsumoto Fine Chemicals Co., : ORGATIX TA-10, TiO ₂ concentration: 28% by mass) were mixed and stirred for 5 minutes to prepare a pre-solution 2 having a solid content concentration of 6.0% by mass.

&Lt; Evaluation of substrate on which a transparent coating is formed &gt;

Measurement and evaluation were carried out in the same manner as in Example 1 except that this coating liquid was used. The results are shown in Table 1.

[Comparative Example 1]

<< Preparation of coating liquid for forming a transparent film >>

4507.86 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 214.93 g of pure water and 3.58 g of nitric acid at a concentration of 61% by mass were mixed and stirred for 5 minutes. Next, 1243.78 g of ethyl silicate (SiO ₂ concentration: 28.8% by mass, manufactured by Tama Chemical Co., Ltd.) was added as a component B (tetrafunctional silane compound) with stirring and stirred for 30 minutes to obtain a tetrafunctional A silane compound solution is prepared.

Hexylene glycol (Wako Junya ku Co., Ltd. Preparation) 2527.95 g, titanium acetylacetonate in 16.4% by mass as TiO ₂ concentration (Matsumoto Fine Chemical Co., manufactured by Organo ticks TC-100, TiO ₂ concentration of 16.4% by mass) 238.81 g were mixed and stirred for 5 minutes to prepare a metal alkoxide solution having a solid content concentration of 6.0% by mass.

Next, while stirring, the metal alkoxide solution was mixed with the tetrafunctional silane compound solution, stirred for 10 minutes, 49.75 g of pure water was added, and stirred at 5 캜 for 144 hours. After completion of the stirring, filtration is performed with a filter of 0.2 mu m to remove the aggregates and the like to prepare a coating liquid for forming a transparent coating film having a concentration CT of 6.0% by mass.

Table 2 shows the concentrations, the molar ratios, and the like of each component in the obtained coating liquid.

&Lt; Evaluation of substrate on which a transparent coating is formed &gt;

Measurement and evaluation were carried out in the same manner as in Example 1 except that this coating liquid was used and the heating conditions after irradiation with ultraviolet light were 350 占 폚 for 30 minutes. The results are shown in Table 2.

[Comparative Example 2]

&Lt; Evaluation of substrate on which a transparent coating is formed &gt;

In Comparative Example 1, measurement and evaluation were carried out in the same manner as in Example 1, except that this coating liquid was used and the heating conditions after irradiation with ultraviolet rays were 200 占 폚 for 30 minutes. The results are shown in Table 2.

[Comparative Example 3]

&Lt; Evaluation of substrate on which a transparent coating is formed &gt;

In Comparative Example 1, measurement and evaluation were carried out in the same manner as in Example 1, except that this coating liquid was used and the heating conditions after irradiation with ultraviolet rays were 120 占 폚 for 30 minutes. The results are shown in Table 2.

[Comparative Example 4]

<< Preparation of coating liquid for forming a transparent film >>

(Step 1)

4507.86 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 214.93 g of pure water and 3.58 g of nitric acid at a concentration of 61% by mass were mixed and stirred for 5 minutes. Next, while stirring, 1243.78 g of ethyl silicate (SiO ₂ concentration: 28.8% by mass, manufactured by Tama Chemical Co., Ltd.) was added as the component B (tetrafunctional silane compound) and stirred for 30 minutes to obtain a preliminary solution having a solid content concentration of 6.0% 1 is prepared.

(Step 2)

1931.33 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 1195.89 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as component A and 10.0 g of tetraisopropyl titanate (manufactured by Matsumoto Fine Chemicals Co., : ORGATIX TA-10, TiO ₂ concentration 28% by mass) were mixed and stirred for 5 minutes to prepare a pre-solution 2 having a solid content concentration of 6.0% by mass.

(Step 3)

The preliminary liquid 2 was mixed with the preliminary liquid 1 while stirring, and after stirring for 10 minutes, 49.75 g of pure water was added and stirred at 5 캜 for 144 hours. After the completion of the stirring, filtration is carried out with a filter of 0.2 mu m to remove aggregates and the like to prepare a coating liquid for forming a transparent coating film having a concentration CT of 6.0% by mass.

Table 2 shows the concentrations, the molar ratios, and the like of each component in the obtained coating liquid.

&Lt; Evaluation of substrate on which a transparent coating is formed &gt;

Measurement and evaluation were carried out in the same manner as in Example 1 except that this coating liquid was used. The results are shown in Table 2.

[Comparative Example 5]

<< Preparation of coating liquid for forming a transparent film >>

(Step 1)

4507.86 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 214.93 g of pure water and 3.58 g of nitric acid at a concentration of 61% by mass were mixed and stirred for 5 minutes. Then, 1243.78 g of ethyl silicate (SiO ₂ concentration: 28.8% by mass, manufactured by Tama Chemical Co., Ltd.) was added as a component B (tetrafunctional silane compound) with stirring and stirred for 30 minutes to obtain a preliminary liquid 1 .

(Step 2)

, 3067.43 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 59.79 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as component A, and 50 g of tetraisopropyl titanate (manufactured by Matsumoto Fine Chemicals Co., : ORGATIX TA-10, TiO ₂ concentration 28% by mass) were mixed and stirred for 5 minutes to prepare a pre-solution 2 having a solid content concentration of 6.0% by mass.

(Step 3)

While the preliminary liquid 2 was mixed with the preliminary liquid 1 and stirred for 10 minutes, 49.75 g of pure water was added and stirred at 5 占 폚 for 144 hours. Since gelation was observed during stirring, the preparation and evaluation of the substrate I did not do it.

Table 2 shows the concentrations, the molar ratios, and the like of each component in the obtained coating liquid (including the gel).

[Comparative Example 6]

<< Preparation of coating liquid for forming a transparent film >>

A coating liquid is prepared in the same manner as in Example 1 except for the following steps.

Table 2 shows the concentrations, the molar ratios, and the like of each component in the obtained coating liquid.

(Step 1)

1184.22 g of KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd .: SiO ₂ concentration: 44.1% by mass) as a B component (trifunctional silane compound) and 3113.87 g of Solmics AP-11 (manufactured by Nippon Alcohol Sales Co., Stir for 30 minutes. Next, while stirring, 947.25 g of nitric acid at a concentration of 0.1% by mass was continuously added over 30 minutes, and the mixture was stirred for 30 minutes. The pH at this time was 2.0. 8.40 g of triethanolamine (Hayashi Junyaku Kogyo K.K.) was added with stirring, and the mixture was stirred for 10 minutes to prepare a preliminary liquid 1-1 having a solid content concentration of 9.9% by mass. The pH at this time was 7.0.

The preliminary liquid 1-1 is added to 3502.49 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) with stirring, and the mixture is stirred for 30 minutes to prepare a preliminary liquid 1 having a solid content concentration of 6.0% by mass.

(Step 2)

, 893.32 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 44.85 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as component A, and 50 g of tetraisopropyl titanate (manufactured by Matsumoto Fine Chemicals Co., : ORGATIX TA-10, TiO ₂ concentration: 28% by mass) were mixed and stirred for 5 minutes to prepare a pre-solution 2 having a solid content concentration of 6.0% by mass.

&Lt; Evaluation of substrate on which a transparent coating is formed &gt;

Measurement and evaluation were carried out in the same manner as in Example 1 except that this coating liquid was used. The results are shown in Table 2.

[Comparative Example 7]

<< Preparation of coating liquid for forming a transparent film >>

A coating liquid is prepared in the same manner as in Example 1 except for the following steps.

Table 2 shows the concentrations, the molar ratios, and the like of each component in the obtained coating liquid.

(Step 1)

67.28 g of KBM-13 (Shin-Etsu Chemical Co., Ltd., concentration of SiO ₂ : 44.1 mass%) and 176.92 g of Solmics AP-11 (manufactured by Nippon Alcohol Sales Co., Ltd.) as a B component (trifunctional silane compound) Stir for 30 minutes. Then, while stirring, 53.82 g of nitric acid at a concentration of 0.1% by mass was continuously added over 30 minutes, and the mixture was stirred for 30 minutes. The pH at this time was 2.1. While stirring, 0.48 g of triethanolamine (Hayashi Junyaku Kogyo Co., Ltd.) was added and stirred for 10 minutes to prepare a preliminary liquid 1-1 having a solid content concentration of 9.9% by mass. The pH at this time was 7.1.

To the 199.00 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), the preliminary liquid 1-1 is added with stirring and stirred for 30 minutes to prepare a preliminary liquid 1 having a solid content concentration of 6.0% by mass.

(Step 2)

, 7072.12 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 355.03 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as component A, and 60 g of tetraisopropyl titanate (manufactured by Matsumoto Fine Chemicals Co., : ORGATIX TA-10, TiO ₂ concentration: 28% by mass) were mixed and stirred for 5 minutes to prepare a pre-solution 2 having a solid content concentration of 6.0% by mass.

&Lt; Evaluation of substrate on which a transparent coating is formed &gt;

Measurement and evaluation were carried out in the same manner as in Example 1 except that this coating liquid was used. The results are shown in Table 2.

[Comparative Example 8]

<< Preparation of coating liquid for forming a transparent film >>

A coating liquid is prepared in the same manner as in Example 1 except for the following steps.

Table 2 shows the concentrations, the molar ratios, and the like of each component in the obtained coating liquid.

(Step 1)

134.57 g of KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd., concentration of SiO ₂ : 44.1% by mass) as a B3 component (trifunctional silane compound) and 353.85 g of Solmics AP-11 (manufactured by Nippon Alcohol Sales Co., Stir for 30 minutes. Next, while stirring, 107.64 g of nitric acid at a concentration of 0.1% by mass was continuously added over 30 minutes, and the mixture was stirred for 30 minutes. The pH at this time was 2.0. While stirring, 0.95 g of triethanolamine (Hayashi Junyaku Kogyo K.K.) was added and stirred for 10 minutes to prepare a preliminary liquid 1-1 having a solid content concentration of 9.9% by mass. The pH at this time was 6.9.

To 1524.98 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 53.73 g of pure water and 0.90 g of nitric acid at a concentration of 61% by mass were mixed and stirred for 5 minutes. Next, while stirring, 310.95 g of ethyl silicate (tetrachlorosilane compound) as a B4 component (manufactured by Tama Chemical Co., Ltd .: SiO ₂ concentration 28.8 mass%) was added and stirred for 30 minutes. The preliminary liquid 1-1 is further added while stirring and stirred for 30 minutes to prepare a preliminary liquid 1 having a solid content concentration of 6.0% by mass.

(Step 2)

3621.25 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 2242.29 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as component A, and 2 g of tetraisopropyl titanate (manufactured by Matsumoto Fine Chemicals Co., : ORGATIX TA-10, TiO ₂ concentration 28% by mass) were mixed and stirred for 5 minutes to prepare a pre-solution 2 having a solid content concentration of 6.0% by mass.

&Lt; Evaluation of substrate on which a transparent coating is formed &gt;

Measurement and evaluation were carried out in the same manner as in Example 1 except that this coating liquid was used. The results are shown in Table 1.

The pH of the coating liquid for forming each of the transparent films prepared in Examples 9 to 13 and Comparative Examples 6 to 8 using the component B (at least one of the trifunctional silane compound and its hydrolyzed condensate) was as follows.

Example 9 (pH 5.0)

Example 10 (pH 5.5)

Example 11 (pH 6.0)

Example 12 (pH 4.5)

Example 13 (pH 4.0)

Comparative Example 6 (pH 6.0)

Comparative Example 7 (pH 4.0)

Comparative Example 8 (pH 3.3)

〔Evaluation results〕

As shown in Table 1, it can be seen from Examples 1 to 13 that the substrate having a transparent coating formed using the coating liquid of the present invention has excellent pencil hardness, scratch resistance and crack resistance.

On the other hand, in the substrate having the transparent coating formed using the coating liquids of Comparative Examples 1 to 8, neither hardness nor crack resistance could be satisfied.

Claims (11)

An organic compound capable of forming a chelate with the metal alkoxide (component A)
(B component) of a silane compound having three or more functional groups represented by the following formula (2) and a hydrolyzed condensate thereof,
At least one of the metal alkoxide represented by the following formula (3) and the hydrolyzed condensate thereof (component C)
As a coating liquid dissolved or dispersed in a mixed solvent containing water and an organic solvent,
Wherein the molar ratio (M1 / M3) of the molar number (M1) of the A component to the molar number (M3) of the C component is 0.25 or more and less than 2.0,
Wherein the molar ratio (M2 / M3) of the molar number (M2) of the B component to the mol number (M3) of the C component is 0.1 or more and 9.0 or less.
(R ³ ) _(4-m) Si (R ⁴ ) _m (2)
(m is at least one of 3 and 4, and R ³ is any of an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted or substituted aryl group, and a vinyl group. R ⁴ is an unsubstituted or substituted alkoxy group having 1 to 8 carbon atoms, an unsubstituted or substituted aryloxy group, a vinyloxy group, a hydroxyl group, a hydrogen atom, or a halogen atom, and may be the same or different.)
M (OR &_lt; ⁵ &_gt;) _n (3)
(M is at least one element selected from the group consisting of Be, Al, Sc, Ti, V, Cr, Fe, Ni, Zn, Ga, Ge, As, Se, Y, Zr, Nb, In, Sn, Sb, Te, Hf, , B, Bi, Ce and Cu, R ⁵ is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, and n is a number equal to the valence of M) The method according to claim 1,
The SiO ₂ -converted concentration (concentration C ₂ ) derived from the component B is in the range of 0.005 to 12 mass%
Wherein MO _x of the element M is derived from the component C in terms of the concentration (concentration C3) is in the range of 0.02 to 14.25% by weight,
Wherein the total (concentration CT) of the concentration C2 and the concentration C3 is in the range of 0.1 to 15 mass%. The method according to claim 1,
(M2 / M3) of the molar number (M2) of the B component to the mol number (M3) of the C component is in the range of 0.5 to 8.0 when the B component is at least one of the trifunctional silane compound and the hydrolyzed condensate thereof By weight of the coating liquid. The method according to claim 1,
Wherein the coating liquid has a pH of 4 to 8 when the coating liquid contains at least one of a trifunctional silane compound and a hydrolyzed condensate thereof. The method according to claim 1,
The organic solvent contained in the coating liquid has a boiling point of 120 캜 or higher
And a viscosity at 20 占 폚 is in a range of 1 to 400 mPa 占 퐏. A method for producing a coating liquid for forming a film, comprising the steps of:
Step 1: A step of mixing an organic solvent, water, a silane compound having three or more functional groups represented by formula (2) (component B) and a hydrolysis catalyst to prepare a preliminary liquid 1
Step 2: A step of mixing an organic solvent, an organic compound capable of forming a chelate with the metal alkoxide (component A) and a metal alkoxide (component C) represented by the formula (3) to prepare a preliminary solution 2 Is in the range of from 0.25 mol or more to less than 2.0 mol based on M1 mol of the element of the component C)
Step 3: Step of mixing the preliminary liquid 1, the preliminary liquid 2, and water and stirring at a temperature of 5 ° C or higher and 40 ° C or lower
(R ³ ) _(4-m) Si (R ⁴ ) _m (2)
(m is at least one of 3 and 4, and R ³ is any of an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms, an unsubstituted or substituted aryl group, and a vinyl group. R ⁴ is any of an unsubstituted or substituted alkoxy group having 1 to 8 carbon atoms, an unsubstituted or substituted aryloxy group, a vinyloxy group, a hydroxyl group, a hydrogen atom, and a halogen atom, and may be the same or different.)
M (OR &_lt; ⁵ &_gt;) _n (3)
(M is at least one element selected from the group consisting of Be, Al, Sc, Ti, V, Cr, Fe, Ni, Zn, Ga, Ge, As, Se, Y, Zr, Nb, In, Sn, Sb, Te, Hf, , B, Bi, Ce and Cu, and R ⁵ is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, and n is the same number as the valence of M) The method according to claim 6,
Wherein the pH of the preliminary solution 1 obtained in the step 1 is in the range of 5 to 8 when the component B is a trifunctional silane compound. The method according to claim 6,
Wherein the B component contained in the preliminary liquid (1) has a weight average molecular weight (in terms of polystyrene) of 300 or more and 3000 or less. A coating method comprising: a coating step of applying the coating liquid according to any one of claims 1 to 5 to a substrate;
A drying step of drying the coating liquid on the substrate to form a coating film after the coating step,
And a curing step of curing the coating film to form a coating film. 10. The method of claim 9,
Wherein the coating liquid is heated at 80 DEG C or more and 150 DEG C or less in the drying step. 10. The method of claim 9,
Irradiating ultraviolet rays onto the coating film formed on the substrate in the curing step, and heating the coated film at 80 DEG C or more and 300 DEG C or less.