TWI682010B - Coating liquid for forming film, method for manufacturing the same, and method for manufacturing base material with coating - Google Patents

Abstract

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

(Formulas (2) and (3) are as described in the description)

Description

Coating liquid for forming film, method for manufacturing the same, and method for manufacturing base material with coating

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

In detail, the present invention relates to a coating liquid that can form a transparent coating film excellent in both the hardness and the crack resistance despite being cured at a relatively low temperature.

Previously, a film was formed on the surface of the substrate in order to impart functions to the substrate such as glass or plastic. For example, in order to improve the scratch resistance of substrate surfaces such as glass, plastic sheets, plastic lenses, resin films, and front panels of display devices, a hard coating film is formed on the surface of the substrate. As such a hard coating film, an organic resin film and an inorganic film are known. Furthermore, it is also known that the organic resin film and the inorganic film are blended with inorganic particles such as resin particles or silica to further improve scratch resistance.

In addition, a transparent coating base material in which conductive particles are blended into a transparent coating to impart antistatic performance and electromagnetic wave shielding performance is also known. Furthermore, a high-refractive-index transparent film in which a high-refractive-index particle is blended in a transparent film, a low-refractive-index transparent film in which a low-refractive-index particle is blended in a transparent film to impart antireflection performance, and a coloring compound are also known Transparent coating of pigment particles, etc.

In addition, it is also known to use alkane to adjust the refractive index or dielectric constant of the base material. The oxide compound, or the coating liquid in which colloidal particles are blended, forms a coating for a touch panel by a sol-gel method. However, in this method, in order to harden the coating, it is necessary to heat at a temperature of about 500°C, and only substrates with high heat resistance can be used.

On the other hand, it is known that if a coating solution containing an acetone chelate compound, a silane compound, and a metal alkoxide other than silicon is used (during or after drying), it can be irradiated by ultraviolet rays. It is cured at a relatively low temperature to form a transparent ceramic film excellent in durability (for example, refer to Document 1 (Japanese Patent Laid-Open No. 2-48403)).

In addition, it is known to use a coating solution composed of a sol-gel film having a fine uneven surface layer to form a tetraalkoxy group added with a metal alkoxide stabilized with acetone. A mixture of sol A obtained by hydrolysis and dehydration condensation of silane, and sol B obtained by hydrolysis and dehydration condensation of alkyl trialkoxysilane with one functional group alkylated; isopropyl alcohol as the main component Solvent; and glycols mixed with these (for example, refer to Document 2 (Japanese Patent Laid-Open No. 2005-281132)).

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

In addition, Document 2 discloses that a sol obtained by hydrolyzing and dehydrating and condensing (hydrolyzing and condensing) trifunctional silane (for example, alkyltrialkoxysilane) is used to form a fine uneven surface layer. However, since it is difficult to form a coating with sufficient hardness at a low temperature, it is necessary to perform baking at a temperature of at least about 600°C. Therefore, a substrate with low heat resistance cannot be used.

An object of the present invention is to provide a coating solution for forming a coating that has sufficient hardness after application to a substrate and is less likely to crack.

The present inventors have made intensive studies to solve the above-mentioned problems, and found that if an organic compound that can form a chelate compound with a metal alkoxide, a trifunctional silane compound, or a metal alkoxide (wherein, except (Silica oxide) dissolving or dispersing in a mixed solvent composed of water and organic solvents, a coating with sufficient hardness and hard to crack can be obtained. The present invention was completed based on this knowledge.

That is, the coating solution for forming a film of the present invention is at least one of an organic compound (component A) capable of forming a chelate compound with a metal alkoxide, a silane compound with a trifunctionality or more, and its hydrolyzed condensate (component B ), and at least one of metal alkoxide and its hydrolyzed condensate (component C) is dissolved or dispersed in a mixed solvent containing water and an organic solvent. At this time, the molar ratio (M1) of component A (M1) to the molar number of component C (M3) (M1/M3) is more than 0.25 and less than 2.0, and the molar number of component B (M2) and C The molar ratio (M2/M3) of the molar number (M3) of the components is 0.1 or more and 9.0 or less. In addition, B component and C component are shown by following formula (2) and formula (3), respectively.

Further, derived from the ₂ SiO B component in terms of concentration (concentration C2) set in a range of 0.005 to 12% by mass, derived from the elements C MO _x component of M in terms of the concentration (concentration C3) 0.02 to 14.25 mass% The range (CT) of the concentration C2 and the concentration C3 is set to a range of 0.1 to 15% by mass. Thereby, the crack resistance of the coating can be improved.

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

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

Step 1: Blend organic solvent, water, silane compound (component B) with 3 or more functions, and hydrolysis catalyst to prepare preliminary solution 1

Step 2: The organic solvent, the organic compound (component A) that can form a chelate compound with the metal alkoxide, and the metal alkoxide (component C) are blended to prepare the preparation solution 2

Here, the blending amount of the component A is not less than 0.25 mol and less than 2.0 mol relative to 1 mol of the metal element of the component C.

Step 3: Blend the preparation solution 1, the preparation solution 2, and water, and stir at a temperature above 5°C and below 40°C

In addition, the B component and the C component are respectively represented by the following formula (2) and formula (3).

Furthermore, the base material with a coating of the present invention forms a coating on the base material using the coating solution of any of the above-mentioned configurations.

Furthermore, the method for manufacturing a coated substrate of the present invention includes: a coating step which applies the coating liquid of any of the above-mentioned configurations to the substrate; a drying step which applies the substrate to 80 after the coating step Heating above ℃ and below 150 ℃; irradiation step, which irradiates the coating film formed on the substrate with ultraviolet rays after the drying step; and heating step, which irradiates the coating film above 80 ℃ after the irradiation step and Heating below 300°C. Since the film can be formed in a process below 300°C, a film with both hardness and crack resistance can be produced on a substrate with low heat resistance.

If the present invention is applied, a transparent film with a high refractive index (refractive index of 1.3 to 2.3) can be formed even if high-refractive-index particles are not blended into the coating liquid.

Hereinafter, the coating liquid for forming a film of the present invention, the method for manufacturing the coating liquid, the base material for coating, and the method for manufacturing the base material for coating will be described.

[Coating solution for film formation]

The coating solution for film formation (hereinafter, referred to as "this coating solution") is an organic compound (component A) capable of forming a chelate compound with a metal alkoxide, and a trifunctional or more functional compound represented by formula (2) At least one of the silane compound and its hydrolyzed condensate (component B), and at least one of the metal alkoxide represented by formula (3) and its hydrolyzed condensate (component C) are dissolved or dispersed to include water and an organic solvent Made of mixed solvents.

(R ³ ) _(4-m) Si(R ⁴ ) _m (2)

(Here, m is at least one of 3 or 4; R ³ is any of unsubstituted or substituted alkyl having 1 to 8 carbons, unsubstituted or substituted aryl, and vinyl ; R ⁴ is any one of unsubstituted or substituted alkoxy groups having 1 to 8 carbon atoms, unsubstituted or substituted aryloxy groups, vinyloxy groups, hydroxyl groups, hydrogen atoms, and halogen atoms, which may be Same or different)

M(OR ⁵ ) _n (3)

(Here, M is selected from Be, Al, Sc, Ti, V, Cr, Fe, Ni, Zn, Ga, Ge, As, Se, Y, Zr, Nb, In, Sn, Sb, Te, Hf, One element in Ta, W, Pb, B, Bi, Ce, and Cu, R ⁵ is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms; n is the same number as the atomic value of M)

According to the above formula (2), when the component B has m=3, "at least one of a trifunctional silane compound and its hydrolyzed condensate (component B3)", and when m=4 "At least one of a 4-functional silane compound and its hydrolyzed condensate (component B4)". Furthermore, the present coating liquid contains at least one of the B3 component and the B4 component as the B component. In addition, the present coating liquid may contain a hydrolyzed condensate formed by hydrolytically condensing components B and C.

At this time, the molar ratio (M1) of component A (M1) and the molar ratio (M1/M3) of component C (M3) of component C need to be at least 0.25 and less than the range of 2.0. Furthermore, the molar ratio (M2) of component B (M2) and the molar ratio (M2/M3) of component C (M3) must be in the range of 0.1 or more and 9.0 or less. Here, in the case of hydrolyzing each component, the Mohr number (M1 to M3) also uses the value based on the structure before hydrolysis.

If the molar ratio (M1/M3) is 2.0 or more, the A component is located in the majority of the OR ⁵ part of the C component, and the reaction between the B component and the C component may be suppressed. Therefore, it is difficult to form -MO-Si- crosslinks during curing, and the hardness of the obtained coating may become insufficient. In addition, the amount of the A component remaining in the film increases, and electrical characteristics such as the surface resistance value of the film change with time, thereby reducing reliability. In addition, when the molar ratio (M1/M3) is less than 0.25, the component C reacts excessively, so the stability of the hydrolyzed condensate in the coating liquid becomes poor, and the life of the coating liquid is shortened. The crack resistance of the obtained coating may adversely affect it. In particular, the molar ratio (M1/M3) is preferably in the range of 0.5 or more and 1.0 or less.

When the molar ratio (M2/M3) is less than 0.1, the stability of the coating liquid is reduced and the life of the coating liquid is shortened. Therefore, there is a possibility that coating characteristics such as film thickness, refractive index, and hardness cannot be stably obtained. On the other hand, if the molar ratio (M2/M3) exceeds 9.0, when the coating film formed from the coating liquid is heated at a temperature of 300°C or lower, the hardness of the coating film becomes insufficient Yu.

If this coating liquid is used, UV treatment and low temperature (80~300℃) The following heat treatment can form a coating with sufficient hardness and scratch resistance. Therefore, a coating having sufficient hardness and scratch resistance can be formed even on a substrate with poor heat resistance, and a coating substrate with sufficient hardness and hard to crack can be obtained.

That is, according to the present invention, the high refractive index of the coating film (refractive index 1.3 to 2.3) can be achieved without blending high-refractive-index particles into the coating liquid. Therefore, it is possible to prevent the problem of the conventional coating liquid blended with high-refractive-index particles (the void caused by the high-activity fine particles surrounding the solvent and being thickened, resulting in a decrease in the density of the film, a decrease in hardness, Chemical resistance reduction, etc.).

In addition, the SiO ₂ conversion concentration (concentration C2) derived from the component B is preferably 0.005 to 12% by mass. If the concentration C2 is 0.005 mass% or more, the hydrolysis reaction can proceed smoothly, and the crack resistance of the coating can be sufficiently improved. In addition, if the concentration C2 is 12% by mass or less, the hydrolysis reaction does not proceed excessively, and a stable coating liquid can be obtained. It is particularly preferably 0.01 to 8% by mass.

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

If the concentration C3 is 0.02% by mass or more, the hydrolysis reaction proceeds smoothly, and the crack resistance of the coating becomes sufficiently high. In addition, if the concentration C3 is 14.25% by mass or less, the hydrolysis reaction does not proceed excessively, and a stable coating liquid is obtained. Especially preferred is 0.04 to 9.5% by mass.

Furthermore, the concentration CT of the total 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 with a sufficient thickness can be obtained under normal coating conditions, and the need to repeat coating to obtain a film with high hardness and crack resistance can also be reduced. If the concentration CT is 15% by mass or less, the thickness of the film obtained can be controlled under normal coating conditions, and the occurrence of cracks is easily suppressed. In addition, the stability of the coating solution becomes sufficient, Therefore, the increase in viscosity over time can be suppressed. Therefore, the film thickness, refractive index, hardness and other characteristics of the obtained coating are relatively stable. Furthermore, the concentration CT is more preferably 0.2 to 10% by mass.

In addition, when the coating liquid contains at least one of the trifunctional silane compound and its hydrolyzed condensate (component B3) as the component B, the pH of the coating liquid is preferably 4 to 8, and more preferably 4~7.5. If the blending liquid containing the B3 component is acidic, the trifunctional silane compound is easily precipitated in the form of an insoluble solid component, which is not preferable.

In addition, when the B component contained in the coating liquid is at least one of the trifunctional silane compound and its hydrolyzed condensate (component B3), that is, when only the B3 component is included as the B component, the mole number of the B component ( M2) The molar ratio (M2/M3) of the molar number (M3) of the component C must be in the range of 0.5 or more and 8.0 or less. If the molar ratio (M2/M3) is less than 0.5, the stability of the coating liquid is reduced and the life of the coating liquid is shortened. Therefore, there are cases where coating characteristics such as film thickness, refractive index, and hardness cannot be stably obtained. Furthermore, there is a possibility that the crack resistance may decrease. If the molar ratio (M2/M3) exceeds 8.0, the hardness of the obtained coating may become insufficient, and the crack resistance may decrease. Furthermore, the molar ratio (M2/M3) is more preferably 0.6 or more and 7.5 or less.

Similarly, when the coating solution 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% by mass, and more preferably 0.04 to 9.5% by mass . If the concentration C3 is 14% by mass or less, the hydrolysis reaction does not proceed excessively, and a stable coating liquid is obtained.

Next, the case where the coating liquid contains at least one of the trifunctional silane compound and its hydrolyzed condensate (component B3) and at least one of the tetrafunctional silane compound and its hydrolyzed condensate (component B4) will be described. The values of the molar number of component B3 (M _B3 ) and the molar ratio of component B4 (M _B4 ) (M _B4 /M _B3 ) are preferably 0.01 or more and 1 or less. If the molar ratio (M _B4 /M _B3 ) is 0.01 or more, the hardness of the film increases, and if it is 1 or less, it is difficult to cause a decrease in crack resistance. Furthermore, the molar ratio is more preferably 0.01 or more and 0.5 or less.

Here, when the B3 component or the B4 component is hydrolyzed, the mole number is also a value based on the structure before hydrolysis. Moreover, the hydrolyzed condensate of B3 component, B4 component, and C component part may also be included.

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 that can form a chelate compound with a metal alkoxide, and one organic compound may be used, or two or more kinds may be mixed and used. From the viewpoint of the effect as a chelating agent, it is particularly preferable to use acetone.

啉、4-羥基-1,5-萘啶、8-羥基-1,6-萘啶、8-羥基-1,7-萘啶、5-羥基喹

啉、8-羥基喹唑啉、2,2'-聯吡啶、2-(2'-噻吩基)吡啶、1,10-啡啉、2-甲基-1,10-啡啉、5-甲基-1,10-啡啉、2,9-二甲基-1,10-啡啉、4,7-二甲基-1,10-啡啉、5-氯-1,10-啡啉、6-溴-1,10-啡啉、5-硝基-1,10-啡啉、5-苯基-1,10-啡啉、4,7-二苯基-1,10-啡啉、丁二酮肟、丁二酮肟-O-甲酯、二甲基二硫代胺基甲酸、二乙基二硫代胺基甲酸、N-亞硝基苯基羥胺、1-亞硝基-2-萘酚、2-亞硝 基-1-萘酚、3-羥基黃酮、5-羥基黃酮、1-(2-吡啶基偶氮)-2-萘酚、4-(2-吡啶基偶氮)間苯二酚、2-(4'-二甲胺基苯基偶氮)吡啶、羊毛鉻黑A(Eriochrome Black A)、羊毛鉻黑T、羊毛鉻藍黑B、羊毛鉻藍黑R、酞錯合劑、烷醇胺、及羥基酸等。 In addition, as the component A, trifluoroacetone acetone, hexafluoroacetone acetone, benzoyl acetone, benzoyl trifluoroacetone, dibenzoyl methane, furan methyl acetone, trifluorofuran methyl Acetyl acetone, benzoyl furan methyl acetone, thiophene methyl acetone, trifluorothiophene methyl acetone, furan methyl thiophene methyl acetone, 8-hydroxyquinoline (oxine), 2-methyl-8-hydroxyquinoline , 4-methyl-8-hydroxyquinoline, 5-methyl-8-hydroxyquinoline, 6-methyl-8-hydroxyquinoline, 7-methyl-8-hydroxyquinoline, 8-hydroxyquinoline -5-sulfonic acid, 7-iodo-8-hydroxyquinoline-5-sulfonic acid, quinoline-2-carboxylic acid, quinoline-8-carboxylic acid, 8-hydroxyl

Porphyrin, 4-hydroxy-1,5-naphthyridine, 8-hydroxy-1,6-naphthyridine, 8-hydroxy-1,7-naphthyridine, 5-hydroxyquin

Porphyrin, 8-hydroxyquinazoline, 2,2'-bipyridine, 2-(2'-thienyl)pyridine, 1,10-morpholine, 2-methyl-1,10-morpholine, 5-methyl Yl-1,10-morpholine, 2,9-dimethyl-1,10-morpholine, 4,7-dimethyl-1,10-morpholine, 5-chloro-1,10-morpholine, 6-bromo-1,10-morpholine, 5-nitro-1,10-morpholine, 5-phenyl-1,10-morpholine, 4,7-diphenyl-1,10-morpholine, Butanedione oxime, butanedione oxime-O-methyl ester, dimethyldithiocarbamic acid, diethyldithiocarbamic acid, N-nitrosophenylhydroxylamine, 1-nitroso- 2-naphthol, 2-nitroso-1-naphthol, 3-hydroxyflavone, 5-hydroxyflavone, 1-(2-pyridylazo)-2-naphthol, 4-(2-pyridyl) (Nitrogen) resorcinol, 2-(4'-dimethylaminophenylazo) pyridine, wool chrome black A (Eriochrome Black A), wool chrome black T, wool chrome blue black B, wool chrome blue black R , Phthalic acid complexing agent, alkanolamine, and hydroxy acid, etc.

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

In 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 methyl, ethyl, isopropyl, phenyl, furyl, thienyl, trifluoromethyl, methoxy, and ethoxy. Particularly preferred are methyl, ethyl, and ethoxy. Regarding R ² , for example, methyl, ethyl, isopropyl, phenyl, furyl, thienyl, trifluoro, methoxy, and ethoxy groups can be exemplified as organic groups.

<component B>

By blending the B component (a silane compound with 3 or more functions), the hardness or crack resistance of the coating film (transparent coating) is improved. In particular, the trifunctional silane compound has a large volume of non-functional organic groups (unsubstituted or substituted alkyl groups having 1 to 8 carbon atoms, unsubstituted or substituted aryl groups, and vinyl groups), Therefore, the film is given flexibility, and the wettability between the film and the substrate (organic material) is improved. Therefore, the crack resistance is further improved. In addition, in the case where at least a part of the organic group is decomposed by ultraviolet irradiation in the film forming step, stress concentration can also be relieved, so this case also contributes to improving crack resistance.

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

Further, as the trifunctional silane compound, preferably, methyl trimethoxy silane (MTMS), methyl triethoxy silane (MTES), ethyl triethoxy silane (ETES), methyl triiso Propoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, octyltrimethoxysilane, octyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , Phenyltrimethoxysilane, phenyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, γ-(meth)acryloxypropyldimethoxy Silane, and γ-(meth)acryl propylpropyl diethoxy silane, etc. One of these may be used, or any two or more of them may be mixed and used. However, if R ³ becomes an excessively long chain, it may be difficult to obtain sufficient hardness. In addition, if R ^{3 is} different from each other, the hydrolysis rate is different and it becomes difficult to cause a uniform reaction. Therefore, it is preferable to use methyltrimethoxysilane (MTMS).

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

The 4-functional silane compound may be used alone or in combination.

<Component C>

As described above, the component C is at least one of the metal alkoxide represented by formula (3) and its hydrolyzed condensate. The metal element M of the component C is a metal element other than Si. Specifically, the metal element M is selected from Be, Al, Sc, Ti, V, Cr, Fe, Ni, Zn, Alkoxides of at least one element of Ga, Ge, As, Se, Y, Zr, Nb, In, Sn, Sb, Te, Hf, Ta, W, Pb, B, Bi, Ce and Cu. Particularly preferred are Ti, Al, and Zr.

Examples of the metal alkoxides as component C include aluminum trimethoxide, aluminum triethoxide, aluminum tripropoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, and aluminum tributoxide. , Aluminum tripentoxide, aluminum trihexanol, aluminum trioctoxide, aluminum tribenzyl alcohol, aluminum triphenol, aluminum trimethoxyethanol, aluminum trimethoxyethoxyethanol, aluminum trimethoxypropoxide, titanium tetramethoxide , Titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetramethoxyethoxide, titanium tetrabutoxide, zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetrapropoxide, zirconium tetraisopropoxide, tetramethoxy Zirconium ethoxide, zirconium tetrabutoxide, niobium pentaethanol, indium trimethoxide, indium triethanolate, indium tripropoxide, indium triisopropoxide, indium tributoxide, indium triisobutoxide, indium tributoxide , Indium triamyl alcohol, indium trihexanol, indium trioctyl alcohol, indium tribenzyl alcohol, indium triphenol, indium trimethoxyethanol, indium trimethoxyethoxyethanol, indium trimethoxypropanol, antimony trimethoxide , Antimony triethanol, antimony tripropanol, antimony triisopropanol, antimony tributanol, antimony triisobutanol, etc. One of these may be used alone, or any two or more of them may be mixed and used. From the viewpoint of an appropriate hydrolysis rate and easy availability, titanium tetraisopropoxide and zirconium tetrapropoxide are preferably used.

<Component D>

In this coating liquid, the catalyst for hydrolysis derived from the manufacturing process may remain at about 0.2% by mass. According to the application of the coating liquid, it is desirable to remove the catalyst for hydrolysis. In this case, for example, the catalyst for hydrolysis can be removed by ion exchange, neutralization, distillation, or the like. In the case of neutralization, the acid-neutralizing substance remains in the coating liquid. Hereinafter, the case of the neutralization process will be described in detail.

Component D is an acid-neutralizing substance added to set the pH of the coating solution to 4 to 8. When a trifunctional silane compound (component B3) is included as the above component B, B3 The components are hydrolyzed by an acid catalyst and other hydrolysis catalysts. In order to restore the blended liquid to neutrality, an acid neutralizing substance is added. If the blending liquid is in an acidic state, the trifunctional silane compound is easily precipitated in the form of 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 substance 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 kind of acid-neutralizing substance may be used, or any two or more kinds of acid-neutralizing substances may be mixed and used.

<Mixed solvent>

A mixed solvent of water and organic solvent is used in this coating solution. However, as the organic solvent, an organic compound (component A) that can form a chelate compound with the metal alkoxide of the above component (A) is excluded. As the mixing ratio of water and organic solvent, water/organic solvent (mass ratio) is preferably 20/80 to 0.1/99.9, more preferably 10/90 to 1/99. Regarding the organic solvent, the boiling point is preferably 120°C or higher. More preferably, it is 150°C or higher. Among them, the boiling point is preferably 300° C. or lower. In addition, the viscosity of the organic solvent at 20°C is preferably in the range of 1 to 400 mPa‧s, and more preferably in the range of 20 to 350 mPa‧s. In the case of mixing a plurality of organic solvents, the organic solvent having a boiling point of 120° C. or higher and a viscosity of 1 to 400 mPa‧s at 20° C. is preferably 50% by mass or more, and more preferably 60% by mass or more.

Examples of organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, diacetone alcohol, furan methanol, ethylene glycol, and hexanediol; esters such as methyl acetate and ethyl acetate; diethyl ether, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether and other ethers; acetone , And ketones such as methyl ethyl ketone.

In addition, in this coating liquid, arbitrary components can be added within a range that does not hinder its effect. For example, inorganic oxide fine particles, organic resin fine particles, organic polysiloxane resin fine particles, pigments, colorants, antistatic agents, and surfactants may also be added.

[Manufacturing method of this coating liquid]

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

Step 1: The organic solvent, water, component B (a silane compound with more than 3 functions represented by formula (2)) and a hydrolysis catalyst are blended to prepare the preparation solution 1

Here, when a 4-functional silane compound is used as the component B, the blending amount of the component B is in a range of 0.1 mol or more and 9.0 mol or less with respect to 1 mole of the metal element M of the C component in step 2 .

In addition, when the trifunctional silane compound is used as the component B, the blending amount of the component B is in the range of 0.5 mol or more and 8.0 mol or less with respect to 1 mole of the metal element M of the C component in step 2. Furthermore, the neutralization process was implemented, and the pH value of the preliminary solution 1 was adjusted to the range of 5-8.

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

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

Step 3: The preparation solution 1 obtained in step 1 and the preparation solution 2 obtained in step 2 and water are blended, and the stirring step is performed at a temperature of 5°C or higher and 40°C or lower

Hereinafter, the above steps will be described in detail.

<Step 1>

When the 4-functional silane compound is used as the component B, the 4-functional 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 4-functional silane compound and its hydrolyzed condensate is prepared and dispersed Solution prepared in mixed solvent (preparation solution 1). Alternatively, when the 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 then neutralized to set the pH value of the solution to 5~ The scope of 8. In the above manner, it is possible to obtain a preliminary liquid 1 in which at least one of the trifunctional silane compound and its hydrolyzed condensate is dispersed in a mixed solvent. Generally, in this step 1, water, a catalyst for hydrolysis, and component B are added to an organic solvent, and the mixture is stirred at 5 to 40° C. for 5 to 120 minutes to obtain a preliminary solution 1.

As the catalyst for hydrolysis, inorganic acids such as (a) 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, and (c) sulfonic acids such as methanesulfonic acid can be used. Acid and (d) acidic or weakly acidic inorganic salts and other catalysts. However, it is not limited to these. Also, 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% (SiO ₂ conversion, external ratio) relative to the trifunctional silane compound of component B or more.

The amount of water is preferably in the range of 0.5 to 10 mol (SiO ₂ conversion, external ratio) with respect to 1 mol of the trifunctional silane compound of component B or more. As long as it is within the range of this molar ratio, it is effective in effectively promoting the hydrolysis of the component B. Furthermore, the amount of water is more preferably in the range of 1-8 moles.

The amount of the component B in the preliminary solution 1 is not particularly limited as long as it can be hydrolyzed and condensed, and is preferably in the range of 0.01 to 8% by mass (in terms of SiO ₂ ).

In addition, when component B is a trifunctional silane compound, trifunctional After the hydrolyzed condensate of the silane compound, an acid-neutralizing substance is added in order to restore the admixture to neutrality. If the blending liquid containing the component B is in an acidic state, the trifunctional silane compound is likely to be precipitated as an insoluble solid component, which is not preferable. Here, it is recommended that the pH value of the trifunctional silane solution is preferably 5 to 8, more preferably the pH value is 6 to 7.5.

Furthermore, the acid-neutralizing substance (component D) is not necessary. Instead of adding acid-neutralizing substances, ion exchange resins can be used to remove the hydrolysis catalyst and set the pH to 5-8.

<Step 2>

In this step, component A and component C (metal alkoxide represented by formula (3)) are added to the organic solvent and stirred, thereby preparing metal alkoxide including metal alkoxide or its hydrolyzed condensate Material solution (preparation solution 2). The organic solvent, component A or component C is as described above.

In this step, the molar ratio (M1) of the component A (M1) to the molar number (M3) of the component C (M1/M3) is 0.25 or more and less than 2.0. In this step, the component A will coordinate with the alkoxy group of the component C. If the molar ratio (M1/M3) is 0.25 or more and less than 2.0, the chelation that is not with the component A will remain. The metal alkoxide whose coordination group is coordinated can control the reactivity of the C component. Furthermore, the molar ratio (M1/M3) is more preferably in the range of 0.5 or more and 1.0 or less.

In the case where the molar ratio (M1/M3) is 2.0 or more, the coordination of the metal alkoxide to the alkoxy group is excessively performed, so the stabilization of the metal alkoxide is too large, and the co-hydrolysis condensation with the component B It may cause an effect and become unsuitable for low-temperature curing (80 to 300°C) of the coating liquid for film formation.

The metal alkoxide solution obtained by this step contains the component A coordinated Metal alkoxide or its hydrolyzed condensate.

<Step 3>

Add the metal alkoxide solution (preparation solution 2) prepared in step 2 to the silane solution (preparation solution 1) prepared with more than 3 functions prepared in step 1, then add water and stir at 5~40°C. And this coating liquid was obtained.

From the viewpoint of crack resistance, before this step, the weight average molecular weight (in terms of polystyrene) of the component B contained in the preliminary solution 1, that is, the component B after hydrolysis and condensation is preferably in the range of 300 to 3000. Furthermore, the weight average molecular weight of component B is more preferably in the range of 500 to 1500. Here, the weight average molecular weight is determined by GPC.

Here, when the component B is a 4-functional silane compound, the molar ratio (M2/M3) of the molar number (M2) of the component B and the molar number (M3) of the component C is 0.1 or more and 9.0 or less, It is preferably in the range of 0.2 or more and 5.0 or less. In the case where the component B is a trifunctional silane compound, the molar ratio (M2/M3) of the component B (M2) to the molar number (M3) of the component C is 0.5 or more and 8 or less, preferably 0.6 to 7.5. The reason is that if the molar ratio (M2/M3) is within these ranges, the co-hydrolysis reaction will proceed smoothly.

By adding water, it is possible to promote the co-hydrolysis condensation reaction of at least one of trifunctional silane hydrolyzate and metal alkoxide, so it is preferable in terms of obtaining a dense coating.

Furthermore, when the component B contains a trifunctional silane compound, the pH value of the coating solution is preferably 4-8, more preferably 4-7.5.

[Manufacturing method of base material with coating]

The manufacturing method of the base material with coating includes: a coating step, which is to coat the coating liquid The cloth is applied to the substrate; the drying step is to dry the coating liquid on the substrate to form a coating film; and the curing step is to harden the coating film on the substrate to form a coating film substrate. The drying step and the hardening step will be described in further detail. The drying step is composed of a step of heating the coating liquid on the substrate at a temperature of 80° C. or higher and 150° C. or lower, and the curing step is a step of drying The subsequent step of irradiating the substrate with the coating film to ultraviolet rays and a heating step of heating at a temperature of 80° C. or more and 300° C. or less.

As the coating method for applying the coating liquid to the substrate, a dipping method, a spin coating method, a bar coating method, a spray method, a roll coating method, a flexographic printing method, and a slit coating method can be used Bufa and other previously known methods. Examples of the base material include sheets, films, and plates using materials such as glass, ITO film-treated substrates, polycarbonate, acrylic resin, PET, and TAC.

In the drying step, the heating temperature is not particularly limited as long as the required hardness, crack resistance, etc. can be obtained without deteriorating the base material, preferably in the range of 80 to 150°C, more preferably The range of 90~140℃. In addition, in the drying step, it is preferably heated for about 1 to 10 minutes.

In the drying step, as long as a coating with the required hardness, crack resistance, etc. is obtained, it can be dried and heated in one step operation, or it can be heated at a temperature higher than the drying temperature after drying . As the drying method or heating method, a previously known method can be used. In addition, electromagnetic wave irradiation treatment may be used together.

In the case where the heating temperature in the drying step does not reach 80°C, sufficient film strength cannot be obtained due to the residual solvent or insufficient crosslinking of -MOM- or -MO-Si-. If the heating and drying temperature exceeds 150 At ℃, the organic group of component B may be decomposed and the desired film characteristics may not be obtained.

In the irradiation step, the transparent film dried by the drying step is irradiated with ultraviolet rays (UV). For example, a 2kw high-pressure mercury lamp is used to irradiate 3,000mJ/cm ² of ultraviolet rays. By UV irradiation, desorption of component A occurs in the coating, and the coating becomes in a state of being easily crosslinked during the heating step.

After the irradiation step, the coating is heated in the range of 80 to 300°C. By this heating step, the transparent film becomes fully crosslinked. If the heating temperature is in the range of 80 to 300°C, for example, the resistance change of the ITO wiring can be suppressed. Furthermore, the heating time is preferably from 1 to 10 minutes.

[Substrates with coating]

The average film thickness (T) of the film obtained by the above film forming method is preferably 20 to 200 nm, more preferably 40 to 150 nm. If the average film thickness (T) of the coating is 20 nm or more, it is difficult to produce a portion where the film cannot be formed (uneven coating) because the film thickness is sufficient, and the effect of film formation can also be sufficiently obtained. On the other hand, if the average film thickness (T) is 200 nm or less, the occurrence of cracks can be sufficiently suppressed, and the hardness of the film becomes sufficient.

The coating of the present invention can be preferably 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.

Examples

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

[Example 1]

"Preparation of Coating Liquid for Forming Transparent Coating"

(step 1)

4507.86 g of hexanediol (made by Wako Pure Chemical Industries, Ltd.), 214.93 g of pure water, and 3.58 g of nitric acid with a concentration of 61% by mass were mixed and stirred for 5 minutes. Subsequently, 1243.78 g of ethyl silicate (product of Tama Chemical Co., Ltd.: SiO ₂ concentration 28.8% by mass) as a component B (4-functional silane compound) was added while stirring, and stirred for 30 minutes. In this way, the preliminary solution 1 having a solid content concentration of 6.0% by mass was obtained.

(Step 2)

Hexanediol (made by Wako Pure Chemical Industries, Ltd.) 297.97g, acetone as component A (made by Wako Pure Chemical Industries, Ltd.) 149.25g, tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Manufactured by Co., Ltd.: Organix TA-10, TiO ₂ concentration 28% by mass) 852.88g was mixed and stirred for 5 minutes. By this, the preliminary solution 2 having a solid content concentration of 6.0% by mass was obtained.

(Step 3)

While stirring, the preliminary liquid 2 was mixed into the preliminary liquid 1, and after stirring for 10 minutes, 49.75 g of pure water was added and stirred at 5° C. for 144 hours. After the stirring was completed, it was filtered with a 0.2 μm filter to remove aggregates and the like to prepare a coating liquid having a concentration CT of 6.0% by mass.

Table 1 shows the concentration, molar ratio, and the like of each component in the obtained coating liquid. In addition, in Table 1, the mole number of component A (organic compound that can form a chelate compound with metal alkoxide) is set to M1, and component B (silicon dioxide compound with more than 3 functions and its hydrolyzed condensate) At least one of them) is set to M2. In addition, as component B, when at least one of the trifunctional silica compound and its hydrolyzed condensate (component B3) coexists with at least one of the tetrafunctional silica compound and its hydrolyzed condensate (component B4), Let the number of moles of component B3 be M _B3 and the number of moles of component _B4 be M _B4 .

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

In the coating liquid, the SiO ₂ conversion concentration derived from the component B is defined as the concentration C2, the MO _x conversion concentration derived from the component C is defined as the concentration C3, and the total of the concentration C2 and the concentration C3 is defined as the concentration CT.

Regarding the coating liquid, the stability over time was evaluated by the following method. The results are shown in Table 1.

"Time Stability"

After the coating liquid was heated at 40°C for 72 hours, the viscosity was measured with an E-type viscometer (manufactured by Toki Industries Co., Ltd.: TV-25 type), and evaluated according to the following criteria.

◎: No change in viscosity

○: Visible viscosity increased slightly (less than 5mPa‧s)

×: Visible viscosity increased significantly (over 5mPa‧s)

"Evaluation of Substrates with Transparent Coating"

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

"Film Thickness"

The measurement was performed using a surface roughness measuring machine (manufactured by Tokyo Precision Co., Ltd.: Surfcom).

《Surface Resistance Value》

The surface resistance value is measured using a surface resistance measuring machine (Mitsubishi Chemical Analytech Co., Ltd.: Hiresta-UX MCP-HT800) for measurement.

"Pencil Hardness"

According to JIS-K-5600, a pencil hardness tester was used for the measurement. That is, a pencil is set at an angle of 45 degrees to the surface of the transparent film, a specific load is applied, and the film is stretched at a constant speed to observe the presence of scratches.

The transparent coating base material for evaluation of the film thickness, surface resistance value and pencil hardness was prepared by the following method.

The coating liquid obtained in Example 1 was applied on a glass substrate with an ITO film (manufactured by AGC Fabritech Co., Ltd., thickness: 1.1 mm) by a flexographic printing method. After drying at 90 ℃ 5 minutes and then irradiated at a wavelength of 365nm ultraviolet (3000mJ / cm ²⁾ with a wavelength of 254nm ultraviolet light (2000mJ / cm ^2), heated for 30 minutes at 230 deg.] C, to obtain a substrate with a transparent film.

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

"Full Light Transmission and Haze"

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

"Determination of Scratch Resistance"

The #0000 steel wool was brought into contact with the surface of the transparent film, and slid 10 times with a load of 2 kg/cm ² , the surface of the film was visually observed, and the scratch resistance was evaluated according to the following criteria.

Evaluation criteria:

No streak scars: ◎

Striated scars are slightly visible: ○

A large number of visible scars: △

The entire surface is scraped: ×

The base material with a transparent film for evaluation of total light transmittance, haze and scratch resistance was prepared by the following method.

The coating liquid obtained in Example 1 was applied onto a glass substrate with a silicon dioxide film (manufactured by AGC Fabritech Co., Ltd., thickness: 1.1 mm) by a flexographic printing method. After drying at 90 ℃ 5 minutes and then irradiated at a wavelength of 365nm ultraviolet (3000mJ / cm ²⁾ with a wavelength of 254nm ultraviolet light (2000mJ / cm ^2), heated for 30 minutes at 230 deg.] C, to obtain a substrate with a transparent film.

Regarding the base material with a transparent coating, the refractive index was measured by the following method. The results are shown in Table 1.

"Refractive Index"

The measurement was performed using a spectroscopic ellipsometer (manufactured by SOPRA Corporation: ES4G, @550nm).

The base material with a transparent film for evaluation of the refractive index was prepared by the following method.

The coating liquid obtained in Example 1 was applied to a 6-inch silicon wafer (made by Matsuzaki Manufacturing Co., Ltd., thickness: 0.625 mm) by a flexographic printing method. After drying at 90 ℃ 5 minutes and then irradiated at a wavelength of 365nm ultraviolet (3000mJ / cm ²⁾ with a wavelength of 254nm ultraviolet light (2000mJ / cm ^2), heated for 30 minutes at 230 deg.] C, to obtain a substrate with a transparent film.

For the substrate with a transparent coating, the crack resistance was measured by the following method. Will result 示于表1。 Shown in Table 1.

"Crack Resistance of Coating Film"

The surface of the coating film was visually observed and evaluated for crack resistance according to the following criteria.

◎: No cracks in the coated surface

○: Cracks are slightly visible at the edge

×: Cracks occurred in the coated surface

The transparent coating base material for evaluation of the crack resistance of the coating film was prepared by the following method.

An acrylic resin layer with a thickness of 2 μm was formed on a glass substrate with a silicon dioxide film (manufactured by AGC Fabritech Co., Ltd., thickness: 1.1 mm). The acrylic resin layer was applied using a bar coater (No. 4), followed by drying at 80°C for 2 minutes, and then irradiated with ultraviolet light (300 mJ/cm ² ) at a wavelength of 365 nm. The coating liquid obtained in Example 1 was applied to a glass substrate with an acrylic resin layer by a flexographic printing method, dried at 90°C for 5 minutes, and then irradiated with ultraviolet light (wavelength 365 nm) of 3000 mJ/cm ² Then, it heated at 230 degreeC for 30 minutes, and obtained the base material with a transparent film.

[Example 2]

"Preparation of Coating Liquid for Forming Transparent Coating"

In Step 2, 255.917 g of hexanediol (made by Wako Pure Chemical Industries, Ltd.) and 568.05 g of acetone (made by Wako Pure Chemical Industries, Ltd.) were used, except that the concentration was prepared in the same manner as in Example 1. CT is 6.0% by mass of coating liquid.

Table 1 shows the concentration, molar ratio, etc. of the components of the obtained coating liquid.

"Evaluation of Substrates with Transparent Coating"

The measurement and evaluation were performed in the same manner as in Example 1, except that the coating liquid was used. The results are shown in Table 1.

[Example 3]

"Preparation of Coating Liquid for Forming Transparent Coating"

In Step 2, the concentration was prepared in the same manner as in Example 1, except that hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 3054.48 g and acetone (manufactured by Wako Pure Chemical Industries, Ltd.) 74.74 g were used. CT is 6.0% by mass of coating liquid.

Table 1 shows the concentration, molar ratio, etc. of the components of the obtained coating liquid.

"Evaluation of Substrates with Transparent Coating"

The measurement and evaluation were performed in the same manner as in Example 1, except that the coating liquid was used. The results are shown in Table 1.

[Example 4]

"Preparation of Coating Liquid for Forming Transparent Coating"

(step 1)

6536.14 g of hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.), 311.64 g of pure water, and 5.19 g of nitric acid with a concentration of 61% by mass were mixed and stirred for 5 minutes. Then, while stirring, 1803.48 g of ethyl silicate (produced by Tama Chemical Co., Ltd.: SiO ₂ concentration 28.8% by mass) as a component B (4-functional silane compound) was added, and stirred for 30 minutes to prepare a solid content concentration of 6.0% %的prep液1.

(Step 2)

Hexanediol (Wako Pure Chemical Industries, Ltd.) 967.76g, component A acetone (Wako Pure Chemical Industries, Ltd.) 48.58g, C component tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) Manufactured by Co., Ltd.: Organix TA-10, TiO ₂ concentration 28% by mass) 277.19 g were mixed and stirred for 5 minutes to prepare a preparative solution 2 with a solid content concentration of 6.0% by mass.

(Step 3)

While stirring, the preliminary liquid 2 was mixed into the preliminary liquid 1, and after stirring for 10 minutes, 49.75 g of pure water was added and stirred at 5° C. for 144 hours. After the stirring was completed, it was filtered with a 0.2 μm filter to remove aggregates and the like, and a coating liquid having a concentration CT of 6.0% by mass was prepared.

Table 1 shows the concentration, molar ratio, etc. of the components of the obtained coating liquid.

"Evaluation of Substrates with Transparent Coating"

The measurement and evaluation were performed in the same manner as in Example 1, except that the coating liquid was used. The results are shown in Table 1.

[Example 5]

"Preparation of Coating Liquid for Forming Transparent Coating"

(step 1)

1126.97 g of hexanediol (made by Wako Pure Chemical Industries, Ltd.), 53.73 g of pure water, and 0.90 g of nitric acid with a concentration of 61% by mass were mixed and stirred for 5 minutes. Subsequently, 310.95 g of ethyl silicate (product of Tama Chemical Co., Ltd.: SiO ₂ concentration 28.8% by mass) as a component B (4-functional silane compound) was added while stirring, and stirred for 30 minutes to prepare a solid content concentration of 6.0 Preparative solution of mass% 1.

(Step 2)

Hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 6,237.69 g, acetone as component A (manufactured by Wako Pure Chemical Industries, Ltd.) 317.66 g, and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Co., Ltd. manufacture: Organix TA-10, TiO ₂ concentration 28% by mass) 1812.37 g are mixed and stirred for 5 minutes to prepare a preparative solution 2 with a solid content concentration of 6.0% by mass.

(Step 3)

While stirring, the preliminary liquid 2 was mixed into the preliminary liquid 1, and after stirring for 10 minutes, 49.75 g of pure water was added and stirred at 5° C. for 144 hours. After the stirring was completed, it was filtered with a 0.2 μm filter to remove aggregates and the like, and a coating liquid having a concentration CT of 6.0% by mass was prepared. Table 1 shows the concentration, molar ratio, and the like of each component in the obtained coating liquid.

"Evaluation of Substrates with Transparent Coating"

The measurement and evaluation were performed in the same manner as in Example 1, except that the coating liquid was used. The results are shown in Table 1.

[Example 6]

"Preparation of Coating Liquid for Forming Transparent Coating"

(step 1)

5235.00 g of hexanediol (made by Wako Pure Chemical Industries, Ltd.), 107.46 g of pure water, and 1.79 g of nitric acid with a concentration of 61% by mass were mixed and stirred for 5 minutes. Then, while stirring, 621.89 g of ethyl silicate (made by Tama Chemical Co., Ltd.: SiO ₂ concentration 28.8% by mass) as component B (4-functional silane compound) was added, and stirred for 30 minutes to prepare a solid content concentration 6.0% by mass of preparation solution 1.

(Step 2)

3,478.92 g of hexanediol (Wako Pure Chemical Industries, Ltd.), 74.74 g of acetone (product of Wako Pure Chemical Industries, Ltd.) as component A, and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Co., Ltd. manufacture: Organix TA-10, TiO ₂ concentration 28% by mass) 426.44g was mixed and stirred for 5 minutes to prepare a preparative solution 2 with a solid content concentration of 6.0% by mass.

(Step 3)

While stirring, the preliminary liquid 2 was mixed into the preliminary liquid 1, and after stirring for 10 minutes, 49.75 g of pure water was added and stirred at 5° C. for 144 hours. After the stirring was completed, it was filtered with a 0.2 μm filter to remove aggregates and the like, and a coating liquid having a concentration CT of 6.0% by mass was prepared. Table 1 shows the concentration, molar ratio, etc. of the components of the obtained coating liquid.

"Evaluation of Substrates with Transparent Coating"

Except that the heating conditions after ultraviolet irradiation were 120° C. and 30 minutes, measurement and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

[Example 7]

"Preparation of Coating Liquid for Forming Transparent Coating"

(step 1)

3776.72 g of hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.), 322.39 g of pure water, and 5.37 g of nitric acid with a concentration of 61% by mass were mixed and stirred for 5 minutes. Next, 1865.67 g of ethyl silicate (made by Tama Chemical Co., Ltd.: SiO ₂ concentration 28.8% by mass) as component B (4-functional silane compound) was added while stirring, and stirred for 30 minutes to prepare a solid content concentration 9.0% by mass of preparation solution 1.

(Step 2)

Hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 2476.55 g, acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) 224.23 g as component A, and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Co., Ltd. manufacture: Organix TA-10, TiO ₂ concentration 28% by mass) 1279.32 g was mixed and stirred for 5 minutes to prepare a preparative solution 2 having a solid content concentration of 9.0% by mass.

(Step 3)

While stirring, the preliminary liquid 2 was mixed into the preliminary liquid 1, and after stirring for 10 minutes, 49.75 g of pure water was added and stirred at 5° C. for 144 hours. After the stirring was completed, filtration was performed with a 0.2 μm filter to remove aggregates and the like, and a coating liquid having a concentration CT of 9.0% by mass was prepared. Table 1 shows the concentration, molar ratio, etc. of the components of the obtained coating liquid.

"Evaluation of Substrates with Transparent Coating"

Except that the heating conditions after ultraviolet irradiation were 280° C. for 30 minutes, measurement and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1.

[Example 8]

"Preparation of Coating Liquid for Forming Transparent Coating"

(step 1)

Hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 3681.42g, pure water 175.52g, and nitric acid 2.93g having a concentration of 61% by mass were mixed and stirred for 5 minutes. Then, while stirring, 1015.75 g of ethyl silicate (product of Tama Chemical Co., Ltd.: SiO ₂ concentration 28.8% by mass) as component B (4-functional silane compound) was added, and stirred for 30 minutes to prepare a solid content concentration 6.0% by mass of preparation solution 1.

(Step 2)

Hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 3416.09g, acetone as component A (manufactured by Wako Pure Chemical Industries, Ltd.) 218.93.g, n-propyl zirconate as component C (Matsumoto Fine Chemical Co., Ltd.) Orgatix ZA-45, ZrO ₂ concentration 21.2% by mass) 1439.61g was mixed and stirred for 5 minutes to prepare a preparation solution 2 with a solid content concentration of 6.0% by mass.

(Step 3)

While stirring, the preliminary solution 2 was mixed into the preliminary solution 1, and after stirring for 10 minutes, 49.23 g of pure water was added and stirred at 5° C. for 144 hours. After the stirring was completed, it was filtered with a 0.2 μm filter to remove aggregates and the like, and a coating liquid having a concentration CT of 6.0% by mass was prepared. Table 1 shows the concentration, molar ratio, etc. of the components of the obtained coating liquid.

"Evaluation of Substrates with Transparent Coating"

The measurement and evaluation were performed in the same manner as in Example 1, except that the coating liquid was used. The results are shown in Table 1.

[Example 9]

"Preparation of Coating Liquid for Forming Transparent Coating"

(step 1)

713.22g of KBM-13 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.: SiO ₂ concentration 44.1% by mass) as a component B (trifunctional silane compound) and Solmix AP-11 (manufactured by Japan Alcohol Trading Co., Ltd.) 1875.40g were mixed, And stir for 30 minutes. Then, while stirring, 570.50 g of nitric acid with a concentration of 0.1% by mass was added sequentially over 30 minutes, and stirred for 30 minutes. The pH value at this time is 2.0. On one side, 5.06 g of triethanolamine (manufactured by Lin Chun Pharmaceutical Co., Ltd.) was added while stirring, and the mixture was stirred for 10 minutes to prepare a preliminary liquid 1-1 having a solid content concentration of 10.0% by mass. The pH at this time is 7.1.

Then, in 2109.45 g of hexanediol (made by Wako Pure Chemical Industries, Ltd.), the preliminary liquid 1-1 was 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)

Hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 3,498.84g, acetone as component A (manufactured by Wako Pure Chemical Industries, Ltd.) 175.65g, tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Manufactured by Co., Ltd.: Organix TA-10, TiO ₂ concentration 28% by mass) 1002.13g was mixed and stirred for 5 minutes to prepare a preparative solution 2 with a solid content concentration of 6.0% by mass.

(Step 3)

While stirring, the preparation solution 2 was mixed into the preparation solution 1, and after stirring for 10 minutes, 49.75 g of pure water was added and stirred at 25° C. for 30 minutes. After the stirring was completed, it was filtered with a 0.2 μm filter to remove aggregates and the like, and a coating liquid having a concentration CT of 6.0% by mass was prepared. The results are shown in Table 1.

"Evaluation of Substrates with Transparent Coating"

The measurement and evaluation were performed in the same manner as in Example 1, except that the coating liquid was used. The results are shown in Table 1.

[Example 10]

"Preparation of Coating Liquid for Forming Transparent Coating"

Except for the following preliminary steps, a coating liquid was prepared in the same manner as in Example 1. Table 1 shows the concentration, molar ratio, etc. of the components of the obtained coating liquid.

(step 1)

1009.27g of KBM-13 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.: SiO ₂ concentration 44.1% by mass) as a component B (trifunctional silane compound) and 26.53.86g of Solmix AP-11 (manufactured by Japan Alcohol Trading Co., Ltd.) were mixed, And stir for 30 minutes. Then, while stirring, 807.32 g of nitric acid with a concentration of 0.1% by mass was added sequentially over 30 minutes and stirred for 30 minutes. The pH at this time is 2.1. On one side, 7.16 g of triethanolamine (manufactured by Linchun Pharmaceutical Co., Ltd.) was added while stirring, and stirred for 10 minutes to prepare a preliminary liquid 1-1 having a solid content concentration of 9.9% by mass. At this time, the pH value was 7.2.

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

(Step 2)

Hexanediol (Wako Pure Chemical Industries, Ltd.) 1861.08g, A component acetone (Wako Pure Chemical Industries, Ltd.) 93.43g, C component tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) Manufactured by Co., Ltd.: Organix TA-10, TiO ₂ concentration 28% by mass) 533.05g was mixed and stirred for 5 minutes to prepare a preparation solution 2 with a solid content concentration of 6.0% by mass.

"Evaluation of Substrates with Transparent Coating"

The measurement and evaluation were performed in the same manner as in Example 1, except that the coating liquid was used. The results are shown in Table 1.

[Example 11]

The transparent quilt was prepared in the same manner as in Example 1 except for the following steps Coating liquid for film formation.

Table 1 shows the concentration, molar ratio, etc. of the components of the obtained coating liquid.

(step 1)

1143.84 g of KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.: SiO ₂ concentration 44.1% by mass) and 3007.71 g of Solmix AP-11 (manufactured by Japan Alcohol Trading Co., Ltd.) as a component B (trifunctional silane compound), And stir for 30 minutes. Then, while stirring, 914.96 g of nitric acid with a concentration of 0.1% by mass was added sequentially over 30 minutes, and stirred for 30 minutes. The pH at this time is 2.1. Triethanolamine (manufactured by Linchun Pharmaceutical Co., Ltd.) 8.11 g was added to one side while stirring, 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 is 7.1.

Next, to 3383.08 g of hexanediol (Wako Pure Chemical Industries, Ltd.), the preparation liquid 1-1 was added while stirring, and the mixture was stirred for 30 minutes to prepare a preparation liquid 1 having a solid content concentration of 6.0% by mass.

(Step 2)

Hexanediol (made by Wako Pure Chemical Industries, Ltd.) 1116.65g, acetone as component A (made by Wako Pure Chemical Industries, Ltd.) 56.06g, tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Manufactured by Co., Ltd.: Organix TA-10, TiO ₂ concentration 28% by mass) 319.83g was mixed and stirred for 5 minutes to prepare a preparative solution 2 with a solid content concentration of 6.0% by mass.

"Evaluation of Substrates with Transparent Coating"

The measurement and evaluation were performed in the same manner as in Example 1, except that the coating liquid was used. The results are shown in Table 1.

[Example 12]

"Preparation of Coating Liquid for Forming Transparent Coating"

Except for the following steps, a coating liquid was prepared in the same manner as in Example 1.

Table 1 shows the concentration, molar ratio, etc. of the components of the obtained coating liquid.

(step 1)

403.71 g of KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.: SiO ₂ concentration 44.1% by mass) as a component B (trifunctional silane compound) and 1061.55 g of Solmix AP-11 (manufactured by Japan Alcohol Trading Co., Ltd.) were mixed, And stir for 30 minutes. Then, while stirring, 322.92 g of nitric acid with a concentration of 0.1% by mass was added sequentially over 30 minutes, and stirred for 30 minutes. The pH value at this time is 2.0. Triethanolamine (manufactured by Linchun Pharmaceutical Co., Ltd.) 2.86 g was added to one side while stirring, 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 is 7.0.

Then, to 1194.03 g of hexanediol (Wako Pure Chemical Industries, Ltd.), the preliminary liquid 1-1 was 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)

Hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 5211.04g, acetone as component A (manufactured by Wako Pure Chemical Industries, Ltd.) 261.60g, tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Manufactured by Co., Ltd.: Organix TA-10, TiO ₂ concentration 28% by mass) 1492.54 g was mixed and stirred for 5 minutes to prepare a preparative solution 2 with a solid content concentration of 6.0% by mass.

"Evaluation of Substrates with Transparent Coating"

The measurement and evaluation were performed in the same manner as in Example 1, except that the coating liquid was used. The results are shown in Table 1.

[Example 13]

"Preparation of Coating Liquid for Forming Transparent Coating"

Except for the following steps, a coating liquid was prepared in the same manner as in Example 1.

Table 1 shows the concentration, molar ratio, etc. of the components of the obtained coating liquid.

(step 1)

484.25 g of KBM-13 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.: SiO ₂ concentration 44.1% by mass) as a B3 component (trifunctional silane compound) 484.25 g and 1273.85 g of Solmix AP-11 (manufactured by Japan Alcohol Trading Co., Ltd.) were mixed, Stir for 30 minutes. Then, while stirring, 387.51 g of nitric acid with a concentration of 0.1% by mass was added sequentially over 30 minutes, and stirred for 30 minutes. The pH value at this time is 2.0. Triethanolamine (manufactured by Linchun Pharmaceutical Co., Ltd.) 3.44 g was added while stirring on one side, and stirred for 10 minutes to prepare a preliminary liquid 1-1 having a solid content concentration of 9.9% by mass. At this time, the pH value was 6.9.

Next, in 270.06 g of hexanediol (made by Wako Pure Chemical Industries, Ltd.), 60.90 g of pure water and 1.01 g of nitric acid with a concentration of 61% by mass were mixed and stirred for 5 minutes. Subsequently, 352.40 g of ethyl silicate (manufactured by Tama Chemical Co., Ltd.: SiO ₂ concentration 28.8% by mass) as a B4 component (4-functional silane compound) was added while stirring, and stirred for 30 minutes. Furthermore, the preliminary liquid 1-1 was added while stirring, and stirred for 30 minutes to prepare the preliminary liquid 1 having a solid content concentration of 6.0% by mass.

(Step 2)

Hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 3,498.84g, acetone as component A (manufactured by Wako Pure Chemical Industries, Ltd.) 175.65g, tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Manufactured by Co., Ltd.: Organix TA-10, TiO ₂ concentration 28% by mass) 1002.13g was mixed and stirred for 5 minutes to prepare a preparative solution 2 with a solid content concentration of 6.0% by mass.

"Evaluation of Substrates with Transparent Coating"

The measurement and evaluation were performed in the same manner as in Example 1, except that the coating liquid was used. The results are shown in Table 1.

[Comparative Example 1]

"Preparation of Coating Liquid for Forming Transparent Coating"

4507.86 g of hexanediol (made by Wako Pure Chemical Industries, Ltd.), 214.93 g of pure water, and 3.58 g of nitric acid with a concentration of 61% by mass were mixed and stirred for 5 minutes. Subsequently, 1243.78 g of ethyl silicate (made by Tama Chemical Co., Ltd.: SiO ₂ concentration 28.8% by mass) as a component B (4-functional silane compound) was added while stirring, and stirred for 30 minutes to prepare a solid content concentration 6.0% by mass of 4-functional silane compound solution.

2527.95 g of hexylene glycol (Wako Pure Chemical Industries, Ltd.), 16.4 mass% titanium acetonate based on TiO ₂ concentration (Matsumoto Fine Chemical Co., Ltd.: Organatix TC-100, TiO ₂ concentration 16.4%) 238.81 g was mixed and stirred for 5 minutes to prepare a metal alkoxide solution having a solid content concentration of 6.0% by mass.

Then, while stirring, the metal alkoxide solution was mixed into the 4-functional silane compound solution, and after stirring for 10 minutes, 49.75 g of pure water was added, and the mixture was stirred at 5°C for 144 hours Time. After the stirring was completed, filtration was performed with a 0.2 μm filter to remove aggregates and the like, and a coating liquid for forming a transparent film having a concentration CT of 6.0% by mass was prepared.

Table 2 shows the concentration, molar ratio, etc. of the components of the obtained coating liquid.

"Evaluation of Substrates with Transparent Coating"

Using this coating liquid, measurement and evaluation were performed in the same manner as in Example 1, except that the heating conditions after ultraviolet irradiation were 350° C. for 30 minutes. The results are shown in Table 2.

[Comparative Example 2]

"Evaluation of Substrates with Transparent Coating"

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

[Comparative Example 3]

"Evaluation of Substrates with Transparent Coating"

In Comparative Example 1, measurement and evaluation were performed in the same manner as in Example 1, except that the coating liquid was used and the heating conditions after ultraviolet irradiation were 120°C and 30 minutes. The results are shown in Table 2.

[Comparative Example 4]

"Preparation of Coating Liquid for Forming Transparent Coating"

(step 1)

4507.86 g of hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.), 214.93 g of pure water, and 3.58 g of nitric acid with a concentration of 61% by mass were mixed and stirred for 5 minutes. Subsequently, 1243.78 g of ethyl silicate (made by Tama Chemical Co., Ltd.: SiO ₂ concentration 28.8% by mass) as a component B (4-functional silane compound) was added while stirring, and stirred for 30 minutes to prepare a solid content concentration 6.0% by mass of preparation solution 1.

(Step 2)

1931.33g of hexylene glycol (Wako Pure Chemical Industries, Ltd.), 1195.89g of acetone as a component (made by Wako Pure Chemical Industries, Ltd.), tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as a C component Manufactured by Co., Ltd.: Organix TA-10, TiO ₂ concentration 28% by mass) 852.88g was mixed and stirred for 5 minutes to prepare a preparative solution 2 with a solid content concentration of 6.0% by mass.

(Step 3)

While stirring, the preliminary liquid 2 was mixed into the preliminary liquid 1, and after stirring for 10 minutes, 49.75 g of pure water was added and stirred at 5° C. for 144 hours. After the stirring was completed, filtration was performed with a 0.2 μm filter to remove aggregates and the like, and a coating liquid for forming a transparent film having a concentration CT of 6.0% by mass was prepared.

Table 2 shows the concentration, molar ratio, etc. of the components of the obtained coating liquid.

"Evaluation of Substrates with Transparent Coating"

The measurement and evaluation were performed in the same manner as in Example 1, except that the coating liquid was used. The results are shown in Table 2.

[Comparative Example 5]

"Preparation of Coating Liquid for Forming Transparent Coating"

(step 1)

4507.86 g of hexanediol (made by Wako Pure Chemical Industries, Ltd.), 214.93 g of pure water, and 3.58 g of nitric acid with a concentration of 61% by mass were mixed and stirred for 5 minutes. Subsequently, 1243.78 g of ethyl silicate (product of Tama Chemical Co., Ltd.: SiO ₂ concentration 28.8% by mass) as a component B (4-functional silane compound) was added while stirring, and stirred for 30 minutes to prepare a solid content concentration of 6.0 Preparative solution of mass% 1.

(Step 2)

3067.43g of hexanediol (Wako Pure Chemical Industries, Ltd.), 59.79g of acetone as a component (made by Wako Pure Chemical Industries, Ltd.), tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as a component C Manufactured by Co., Ltd.: Organix TA-10, TiO ₂ concentration 28% by mass) 852.88g was mixed and stirred for 5 minutes to prepare a preparative solution 2 with a solid content concentration of 6.0% by mass.

(Step 3)

While stirring, the preparation solution 2 was mixed into the preparation solution 1. After stirring for 10 minutes, 49.75 g of pure water was added and stirred at 5° C. for 144 hours. However, gelation was observed during the stirring without carrying a transparent film base Material production and evaluation.

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

[Comparative Example 6]

"Preparation of Coating Liquid for Forming Transparent Coating"

Except for the following steps, a coating liquid was prepared in the same manner as in Example 1.

Table 2 shows the concentration, molar ratio, etc. of the components of the obtained coating liquid.

(step 1)

1184.22g of KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.: SiO ₂ concentration 44.1% by mass) and Solmix AP-11 (manufactured by Japan Alcohol Trading Co., Ltd.) 3131.87g as a component B (trifunctional silane compound) were mixed, And stir for 30 minutes. Then, while stirring, 947.25 g of nitric acid with a concentration of 0.1% by mass was added sequentially over 30 minutes, and stirred for 30 minutes. The pH value at this time is 2.0. Triethanolamine (manufactured by Linchun Pharmaceutical Industry Co., Ltd.) 8.40 g was added to one side while stirring, 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 is 7.0.

To 3502.49 g of hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.), the above prepared liquid 1-1 was added while stirring, and stirred for 30 minutes to prepare a prepared liquid 1 having a solid content concentration of 6.0% by mass.

(Step 2)

Hexanediol (Wako Pure Chemical Industries, Ltd.) 893.32g, A component acetone (Wako Pure Chemical Industries, Ltd.) 44.85g, C component tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) Manufactured by Co., Ltd.: Organix TA-10, TiO ₂ concentration 28% by mass) 255.86g was mixed and stirred for 5 minutes to prepare a preparative solution 2 with a solid content concentration of 6.0% by mass.

"Evaluation of Substrates with Transparent Coating"

The measurement and evaluation were performed in the same manner as in Example 1, except that the coating liquid was used. The results are shown in Table 2.

[Comparative Example 7]

"Preparation of Coating Liquid for Forming Transparent Coating"

The coating was prepared in the same manner as in Example 1 except for the following steps liquid.

Table 2 shows the concentration, molar ratio, etc. of the components of the obtained coating liquid.

(step 1)

67.28 g of KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.: SiO ₂ concentration 44.1% by mass) as a component B (trifunctional silane compound) and 176.92 g of Solmix AP-11 (manufactured by Japan Alcohol Trading Co., Ltd.) were mixed, And stir for 30 minutes. Then, while stirring, 53.82 g of nitric acid with a concentration of 0.1% by mass was added sequentially over 30 minutes, and stirred for 30 minutes. The pH at this time is 2.1. On one side, 0.48 g of triethanolamine (manufactured by Linchun Pharmaceutical Co., Ltd.) was added while 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 is 7.1.

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

(Step 2)

Hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 7072.12g, acetone as component A (manufactured by Wako Pure Chemical Industries, Ltd.) 355.03g, and tetraisopropyl titanate as component C (Matsumoto Fine Chemical Co., Ltd.) Co., Ltd.: Orgatix TA-10, TiO ₂ concentration 28% by mass) 2025.59g was mixed and stirred for 5 minutes to prepare a preparation solution 2 with a solid content concentration of 6.0% by mass.

"Evaluation of Substrates with Transparent Coating"

The measurement and evaluation were performed in the same manner as in Example 1, except that the coating liquid was used. The results are shown in Table 2.

[Comparative Example 8]

"Preparation of Coating Liquid for Forming Transparent Coating"

Except for the following steps, a coating liquid was prepared in the same manner as in Example 1.

Table 2 shows the concentration, molar ratio, etc. of the components of the obtained coating liquid.

(step 1)

134.57 g of KBM-13 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.: SiO ₂ concentration 44.1% by mass) as a B3 component (trifunctional silane compound) and 135.85 g of Solmix AP-11 (manufactured by Japan Alcohol Trading Co., Ltd.) were mixed, And stir for 30 minutes. Then, while stirring, 107.64 g of nitric acid with a concentration of 0.1% by mass was added sequentially over 30 minutes, and stirred for 30 minutes. The pH value at this time is 2.0. On one side, 0.95 g of triethanolamine (manufactured by Linchun Pharmaceutical Co., Ltd.) was added while 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. At this time, the pH value was 6.9.

In 1524.98 g of hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.), 53.73 g of pure water and 0.90 g of nitric acid with a concentration of 61% by mass were mixed and stirred for 5 minutes. Subsequently, 310.95 g of ethyl silicate (produced by Tama Chemical Co., Ltd.: SiO ₂ concentration 28.8% by mass) as a B4 component (4-functional silane compound) was added while stirring, and stirred for 30 minutes. Furthermore, the above-mentioned preparatory liquid 1-1 was added while stirring, and stirred for 30 minutes to prepare preparatory liquid 1 having a solid content concentration of 6.0% by mass.

(Step 2)

3621.25g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as component A 2242.29g, and tetraisopropyl titanate (Matsumoto Fine Chemical Co., Ltd.) as component C Manufactured by Co., Ltd.: Organix TA-10, TiO ₂ concentration 28% by mass) 1591.15 g was mixed and stirred for 5 minutes to prepare a preparative solution 2 with a solid content concentration of 6.0% by mass.

"Evaluation of Substrates with Transparent Coating"

The measurement and evaluation were performed in the same manner as in Example 1, except that the coating liquid was used. The results are shown in Table 2.

In addition, the pH values of the coating solutions for forming transparent films prepared in Examples 9 to 13 and Comparative Examples 6 to 8 using the component B (at least one of trifunctional silane compounds and their hydrolyzed condensates) are 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 is understood from Examples 1 to 13 that the transparent coating base material produced using the coating liquid of the present invention is excellent in pencil hardness, scratch resistance, and crack resistance.

On the other hand, the transparent coating base material using the coating liquids of Comparative Examples 1 to 8 cannot satisfy both hardness and crack resistance.

Claims (10)

A coating liquid for forming a transparent film, which is an organic compound (component A) that can form a chelate compound with a metal alkoxide, a trifunctional silane compound represented by the following formula (2) and its hydrolysis condensation At least one of the substances (component B), and at least one of the metal alkoxide represented by the following formula (3) and its hydrolyzed condensate (component C) are dissolved or dispersed in a mixed solvent containing water and an organic solvent The author is characterized in that the molar ratio (M1) of the above component A (M1) to the molar number (M3) of the above component C (M1/M3) is more than 0.25 and less than 2.0, and the above component B The molar ratio (M2) of the molar number (M2) to the molar number (M3) of the above component C (M2/M3) is 0.1 or more and 9.0 or less, the boiling point of the organic solvent is 120°C or more, and the viscosity at 20°C is 1~400mPa‧s, (R ³ ) _(4-m) Si(R ⁴ ) _m (2)(m is at least one of 3 or 4; R ³ is unsubstituted or carbon number 1 to 8) Any one of substituted alkyl, unsubstituted or substituted aryl, and vinyl; R ⁴ is an unsubstituted or substituted alkoxy, unsubstituted, or substituted having 1 to 8 carbon atoms Aryloxy group, vinyloxy group, hydroxyl group, hydrogen atom, and halogen atom, which may be the same or different) M (OR ⁵ ) _n (3) (M is selected from Be, Al, Sc, Ti, Among V, Cr, Fe, Ni, Zn, Ga, Ge, As, Se, Y, Zr, Nb, In, Sn, Sb, Te, Hf, Ta, W, Pb, B, Bi, Ce, and Cu 1 element; R ⁵ is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms; n is the same number as the atomic valence of M). A coating liquid for forming a transparent film, which is an organic compound (component A) that can form a chelate compound with a metal alkoxide, a trifunctional silane compound represented by the following formula (2) and its hydrolysis condensation At least one of the substances (component B), and at least one of the metal alkoxide represented by the following formula (3) and its hydrolyzed condensate (component C) are dissolved or dispersed in a mixed solvent containing water and an organic solvent The author is characterized in that the molar ratio (M1) of the above component A (M1) to the molar number (M3) of the above component C (M1/M3) is more than 0.25 and less than 2.0, and the above component B The molar ratio (M2/M3) of the molar number (M2) and the molar number (M3) of the above component C is 0.1 or more and 9.0 or less, and the SiO ₂ conversion concentration (concentration C2) derived from the above component B is 0.005 to In the range of 12% by mass, the MO _x conversion concentration (concentration C3) of the element M derived from the above C component is in the range of 0.02 to 14.25% by mass, and the total of the above concentration C2 and the above concentration C3 (concentration CT) is 0.1 to 15 mass % Range, (R ³ ) _(4-m) Si(R ⁴ ) _m (2) (m is at least one of 3 or 4; R ³ is an unsubstituted or substituted alkane with a carbon number of 1 to 8 Either of a group, 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 , Any of vinyloxy, hydroxyl, hydrogen, and halogen atoms, which may be the same or different) M(OR ⁵ ) _n (3) (M is selected from Be, Al, Sc, Ti, V, Cr, One element of Fe, Ni, Zn, Ga, Ge, As, Se, Y, Zr, Nb, In, Sn, Sb, Te, Hf, Ta, W, Pb, B, Bi, Ce, and Cu; R ⁵ is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms; n is the same number as the valence of M). If the coating liquid for forming a transparent film according to item 1 or 2 of the patent application, wherein the component B is at least one of a trifunctional silane compound and its hydrolyzed condensate, the mole number (M2) of the component B The molar ratio (M2/M3) to the molar number (M3) of the above C component is in the range of 0.5 to 8.0. For example, the coating liquid for forming a transparent film according to item 1 or 2 of the patent application range, where the coating liquid contains at least one of a trifunctional silane compound and its hydrolyzed condensate, the pH of the coating liquid is 4~8. A method for manufacturing a coating liquid for forming a transparent film, which implements the following steps: Step 1: an organic solvent, water, a trifunctional silane compound (component B) represented by formula (2) or more, and a hydrolysis catalyst are carried out The step of blending and preparing the preparation solution 1; Step 2: The organic solvent, the organic compound (component A) that can form a chelate compound with the metal alkoxide, and the metal alkoxide (C) represented by the formula (3) Ingredients) for blending, and the step of preparing the preliminary solution 2 (wherein the blending amount of the above-mentioned component A relative to the element M1 of the above-mentioned component C is more than 0.25 mol and less than 2.0 mol); Step 3 : Blending the above preparation solution 1, the above preparation solution 2, and water, and stirring at a temperature between 5°C and 40°C; (R ³ ) _(4-m) Si(R ⁴ ) _m ( 2) (m is at least one of 3 or 4; R ³ is any of unsubstituted or substituted alkyl groups having 1 to 8 carbon atoms, unsubstituted or substituted aryl groups, and vinyl groups; R ⁴ is any of unsubstituted or substituted alkoxy groups having 1 to 8 carbon atoms, unsubstituted or substituted aryloxy groups, vinyloxy groups, hydroxyl groups, hydrogen atoms, and halogen atoms, which may be the same ^May be different) M(OR ⁵ ) _n (3)(M is selected from Be, Al, Sc, Ti, V, Cr, Fe, Ni, Zn, Ga, Ge, As, Se, Y, Zr, Nb, One element in In, Sn, Sb, Te, Hf, Ta, W, Pb, B, Bi, Ce, and Cu, R ⁵ is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, n It is the same as the valence of M). For example, the method for manufacturing a coating liquid for forming a coating film according to item 5 of the patent application, wherein, when the above-mentioned component B is a trifunctional silane compound, the pH value of the preparation solution 1 obtained in the above step 1 is 5 to 8. range. The method for manufacturing a coating liquid for forming a coating according to item 5 of the patent application range, wherein the weight average molecular weight (in terms of polystyrene) of the component B contained in the preliminary liquid 1 is 300 or more and 3000 or less. A method for manufacturing a substrate with a coating, comprising: a coating step, which is to apply the coating liquid according to any one of items 1 to 4 of the patent application scope to the substrate; The drying step is to dry the coating liquid on the substrate to form a coating film after the coating step; and the curing step is to harden the coating film to form a coating film. A method for manufacturing a substrate with a coating film as claimed in item 8 of the patent application range, wherein in the drying step, the coating liquid is heated at 80°C or higher and 150°C or lower. The method for manufacturing a substrate with a coating film as claimed in item 8 of the patent scope includes: in the curing step, the coating film formed on the substrate is irradiated with ultraviolet rays at a temperature of 80°C or more and 300°C or less Steps of heating.