JP2017048346A - Coating liquid for forming transparent film, method for producing coating liquid for forming transparent film, base material with transparent film and method for producing base material with transparent film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating liquid for forming a transparent film that hardly causes cracks after coating the base material.SOLUTION: The coating material for forming a transparent film is produced by dissolving or dispersing (A) an organic compound capable of forming a chelate with a metal alkoxide, (B) at least either one of a hexafunctional silane compound represented by the general formula (2) as given below and a hydrolyzed condensate thereof and (C) at least either one of a metal alkoxide represented by the general formula (3) as given below and a hydrolyzed condensate thereof in a mixed solvent including an organic solvent. The molar ratio (M1)/(M3) of the mol number (M1) of the component (A) to the mol number (M3) of the component (C) is in the range of not less than 0.25 to less than 2 and the molar ratio (M2)/(M3) of the mol number (M2) of the component (B) to the mol number (M3) of the component (C) is in the range of not less than 0.5 to not more than 8. (the general formulae (2) and (3) are as described in the specification.)SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to a coating solution for forming a transparent film, a method for producing a coating solution for forming a transparent film, a substrate with a transparent film, and a method for producing a substrate with a transparent film, which are used in the field of display elements such as touch panels.

  Conventionally, an ITO (Indium Tin Oxide) wiring pattern is visually recognized in a display element such as a touch panel, and there has been a problem that display properties are deteriorated. In view of this, a technique has been proposed in which the wiring pattern is not easily seen by index matching. For example, a technique for introducing a high refractive index thin film layer (IM layer) by sputtering or the like is known. On the other hand, there is a need to form an IM layer with a transparent film made of a relatively inexpensive and highly durable inorganic coating liquid material.

  Further, in a display element such as a touch panel, a metal wiring or the like is generally covered with a resin material coating. However, when the inorganic coating liquid material is coated on such a resin, cracks are likely to occur, and there is a problem that the display element may be defective in some cases.

  Moreover, the film used for a display element such as a touch panel is required to have hardness from the viewpoint of preventing scratches in the transport process, and also to have chemical resistance to an etching solution used when patterning a wiring such as metal. Furthermore, the coating film used for a display element such as a touch panel is required to be fired at 300 ° C. or lower because of the influence on the peripheral members.

  On the other hand, when a coating solution containing an acetylacetonate chelate compound, a silane compound, and a metal alkoxide other than silicon is used, it cures at a relatively low temperature by irradiation with ultraviolet rays during drying or after drying, and has excellent durability. It is known that a transparent ceramic film can be formed (see Patent Document 1). Moreover, when a coating solution containing a metal alkoxide exemplified by methyltrimethoxysilane (MTMS) or the like, a metal salt exemplified by aluminum nitrate nonahydrate, and a precipitation inhibitor is used, the pattern of the electrode is changed. It is known that it is possible to form a coating film that is suppressed from being noticeable, has high strength, and can prevent cracks even when applied on a resin (see Patent Document 2).

JP-A-2-48403 WO2012 / 099253

  On the other hand, the coating liquid disclosed in Patent Document 1 can provide a transparent film that cures at a relatively low temperature. However, for example, when the base is a resin, it is somewhat difficult to suppress the occurrence of cracks. . Further, the hardness and chemical resistance of the transparent film are not always sufficient. In addition, since the coating liquid disclosed in Patent Document 2 uses a metal alkoxide exemplified by MTMS having a non-bonding functional group, when baked at a low temperature, the degree of cross-linking of the coating becomes relatively low, and chemical resistance Sex is not enough.

  The present invention relates to a coating solution for forming a transparent film, which has sufficient hardness after being applied to a substrate, is resistant to cracking, and is excellent in chemical resistance, a method for producing a coating solution for forming a transparent film, and a substrate with a transparent film And a method for producing a substrate with a transparent coating.

As a result of intensive studies to solve the above problems, the present inventors,
It is sufficient to use a coating solution in which an organic compound capable of chelating with a metal alkoxide, a specific hexafunctional silane compound, and a metal alkoxide (excluding silicon alkoxide) are dissolved or dispersed in a mixed solvent composed of water and an organic solvent. It has been found that a transparent film having a high hardness, hardly cracking, and excellent in chemical resistance can be obtained. The present invention has been completed based on this finding.
That is, the present invention provides the following coating solution for forming a transparent coating, a method for producing a coating solution for forming a transparent coating, a substrate with a transparent coating, and a method for producing a substrate with a transparent coating.
In addition, the present invention provides a coating liquid for forming a transparent film that can form a transparent film having a high refractive index (refractive index: 1.3 to 2.3) without blending high refractive index particles in the coating liquid for forming a transparent film. It is to provide.

[1] An organic compound (A) capable of forming a chelate with a metal alkoxide, at least one of a hexafunctional silane compound represented by the following general formula (2) and a hydrolysis-condensation product thereof (B), and the following general formula At least one of the metal alkoxide represented by (3) and its hydrolysis condensate (C) is dissolved or dispersed in a mixed solvent containing water and an organic solvent, and the number of moles of the component A ( The molar ratio (M1) / (M3) of M1) to the number of moles of the C component (M3) is in the range of 0.25 or more and less than 2, the number of moles of the B component (M2) and the number of moles of the C component A coating liquid for forming a transparent film, wherein the molar ratio (M2) / (M3) of (M3) is in the range of 0.5 to 8.

（Ｒ^３は炭素数２〜６のアルキレン基である。Ｒ^４〜Ｒ^９は炭素数１から８までの非置換又は置換アルコキシ基、非置換又は置換アリールオキシ基、ビニルオキシ基、水酸基、水素原子、およびハロゲン原子のいずれかであり、同一であってもよく、異なっていてもよい。）
Ｍ（ＯＲ^１０）_ｎ （３）
（Ｍは、Ｂｅ、Ａｌ、Ｐ、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｆｅ、Ｎｉ、Ｚｎ、Ｇａ、Ｇｅ、Ａｓ、Ｓｅ、Ｙ、Ｚｒ、Ｎｂ、Ｉｎ、Ｓｎ、Ｓｂ、Ｔｅ、Ｈｆ、Ｔａ、Ｗ、Ｐｂ、Ｂ、Ｂｉ、Ｃｅ、およびＣｕから選ばれた１種の元素であり、Ｒ^１０は炭素数１から１０までの非置換又は置換アルキル基である。ｎはＭの原子価と同じ整数である。）

(R ³ is an alkylene group having 2 to 6 carbon atoms. R ^{4 to} R ⁹ are unsubstituted or substituted alkoxy groups having 1 to 8 carbon atoms, unsubstituted or substituted aryloxy groups, vinyloxy groups, hydroxyl groups, and hydrogen atoms. And a halogen atom, which may be the same or different.)
M (OR ¹⁰ ) _n (3)
(M is Be, Al, P, Sc, Ti, V, Cr, Fe, Ni, Zn, Ga, Ge, As, Se, Y, Zr, Nb, In, Sn, Sb, Te, Hf, Ta, One element selected from W, Pb, B, Bi, Ce, and Cu, R ¹⁰ is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, and n is the same as the valence of M (It is an integer.)

[2] In the coating liquid for forming a transparent film, the SiO ₂ equivalent concentration (C2) derived from the B component is in the range of 0.005 to 12% by mass, and the MO _X equivalent concentration (C3 derived from the C component) ) Is in the range of 0.02 to 14% by mass, and the total (CT) of the C2 and C3 is in the range of 0.1 to 15% by mass. Coating liquid for forming.
[3] Furthermore, it contains at least one of the tetrafunctional silane compound represented by the following general formula (4) and its hydrolysis condensate (D), and the mole of the component D relative to the number of moles (M2) of the component B The coating for forming a transparent film according to [1] or [2] above, wherein the molar ratio (M4) / (M2) of the number (M4) is in the range of 0.01 to 0.5. liquid.
Si (R ¹¹ ) ₄ (4)
(R ¹¹ is any one 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, May be different.)

[4] In the coating liquid for forming a transparent film, the SiO ₂ equivalent concentration (C2) derived from the B component is 0.005 to 12% by mass, and the MO _X equivalent concentration (C3) derived from the C component is a 0.02 to 14 wt%, the SiO ₂ concentration in terms derived from the D component (C4) is 0 to 12 wt%, the C2, total (CT) is 0.1 of the C3 and the C4 The coating liquid for forming a transparent film as described in [3] above, which is 15% by mass.

[5] The transparency according to any one of [1] to [4] above, wherein the boiling point of the organic solvent is 120 ° C. or higher, and the viscosity at 20 ° C. is in the range of 1 to 400 mPa · s. Coating liquid for film formation.

[6] The method for producing a coating liquid for forming a transparent film according to any one of [1] to [5], wherein the following preliminary step 1, preliminary step 2, and this step are performed.
Preliminary step 1: a step of preparing a hexafunctional silane solution by blending the organic solvent, the water, the component B (hexafunctional silane compound represented by the general formula (2)), and a hydrolysis catalyst. (However, the blending amount of the B component is in the range of 0.5 mol or more and 8 mol or less with respect to 1 mol of the C component metal in the preliminary step 2.)
Preliminary step 2: a step of blending the organic solvent, the component A, and the component C (metal alkoxide represented by the general formula (3)) to prepare a metal alkoxide solution (however, the component A The blending amount is in the range of 0.25 mol or more and less than 2 mol with respect to 1 mol of the C component metal.
This step: Add the metal alkoxide solution obtained in the preliminary step 2 to the hexafunctional silane solution obtained in the preliminary step 1, then add water, and stir at a temperature of 5 ° C. to 40 ° C. Mixing process

[7] The production of the coating liquid for forming a transparent film as described in [6] above, wherein the weight average molecular weight (polystyrene conversion) of the component B after hydrolysis and condensation is in the range of 300 to 3000. Method.

[8] In the preliminary step 1, the component D in the above [3] (a tetrafunctional silane compound represented by the general formula (4)) is further added, and the component D relative to the number of moles (M2) of the component B The above-mentioned [6] or [7], wherein the molar ratio (M4) / (M2) of the number of moles (M4) is from 0.01 to 0.5. Manufacturing method of coating liquid.

[9] The method for producing a coating liquid for forming a transparent film according to the above [6] or [7], wherein in this step, co-hydrolysis and condensation reaction of the B component and the C component are performed. .

[10] The method for producing a coating liquid for forming a transparent film according to the above [8], wherein in the step, the B component, the C component, and the D component are cohydrolyzed and condensed. .

[11] A substrate with a transparent coating, which is obtained by applying the transparent coating-forming coating solution according to any one of [1] to [5] to a substrate.
[12] The transparent film-coated substrate according to [11], wherein the transparent film has an average film thickness of 20 nm to 200 nm.

[13] The method for producing a substrate with a transparent coating according to the above [11] or [12], wherein the following film forming process 1 to film forming process 4 are performed.
Film-forming process 1: A process of applying the coating liquid for forming a transparent film to a substrate Film-forming process 2: A process of heating and drying the substrate at 80 ° C. to 150 ° C. following the film-forming process 1 Step 3: Following the film forming step 2, a step of irradiating the coating film formed on the substrate with ultraviolet rays Film forming step 4: Following the film forming step 3, the coating formed on the substrate Heating the film at 80 ° C. or higher and 300 ° C. or lower

[14] The method for producing a substrate with a transparent coating according to [13], wherein the ultraviolet ray includes at least one of an ultraviolet ray having a wavelength of 254 nm and an ultraviolet ray having a wavelength of 365 nm.

According to the present invention, a coating solution for forming a transparent film that has sufficient hardness after being applied to a substrate, is resistant to cracking, and has excellent chemical resistance, a method for producing a coating solution for forming a transparent film, and a transparent film The base material and the manufacturing method of a base material with a transparent film can be provided.
More specifically, the coating liquid for forming a transparent film of the present invention exhibits sufficient hardness and scratch resistance by UV treatment and heat treatment at a relatively low temperature of 80 to 300 ° C., and has a high refractive index (refractive index of 1. A transparent film showing 3 to 2.3) can be formed.
According to the method for producing a substrate with a transparent film of the present invention, it is possible to form a transparent film exhibiting sufficient hardness and scratch resistance even for a substrate having poor heat resistance.
The substrate with a transparent coating of the present invention can be suitably used for an insulating film used between a transparent electrode substrate of a liquid crystal display device and an alignment film, a protective film on a transparent electrode of a touch panel, and the like.

  Below, one embodiment is described in detail about the manufacturing method of the coating liquid for transparent film formation of the present invention, the manufacturing method of the coating liquid for transparent film formation, the substrate with a transparent film, and the substrate with a transparent film.

[Transparent coating solution]
The coating solution for forming a transparent film in the present embodiment (hereinafter also simply referred to as “the present coating solution”) is represented by the organic compound (A) capable of chelating with a metal alkoxide and the general formula (2). At least one of the functional silane compound and its hydrolysis condensate (B), at least one of the metal alkoxide represented by the general formula (3) and its hydrolysis condensate (C), water and It is formed by dissolving or dispersing in a mixed solvent containing an organic solvent.

<A component>
The component A in the coating solution is an organic compound that can form a chelate with a metal alkoxide.
Examples of organic compounds capable of chelating with metal alkoxides include acetylacetone, trifluoroacetylacetone, hexafluoroacetylacetone, benzoylacetone, benzoyltrifluoroacetone, dibenzoylmethane, furoylacetone, trifluorofuroylacetone, benzoylfuroylmethane. , Thenoylacetone, trifluorothenoylacetone, furoylthenoylacetone, oxine, 2-methyloxine, 4-methyloxine, 5-methyloxine, 6-methyloxine, 7-methyloxine, oxine-5-sulfonic acid, 7 Iodooxin-5-sulfonic acid, quinoline-2-carboxylic acid, quinoline-8-carboxylic acid, 8-hydroxycinoline, 4-hydroxy-1,5-naphthyridine, 8-hydroxy- , 6-naphthyridine, 8-hydroxy-1,7-naphthyridine, 5-hydroxyquinoxaline, 8-hydroxyquinazoline, 2,2'-bipyridine, 2- (2'-thienyl) pyridine, 1,10-phenanthroline, 2- Methyl-1,10-phenanthroline, 5-methyl-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 4,7-dimethyl-1,10-phenanthroline, 5-chloro-1,10- Phenanthroline, 6-bromo-1,10-phenanthroline, 5-nitro-1,10-phenanthroline, 5-phenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, dimethylglyoxime, dimethylglycol Oxime-o-methyl ester, dimethyldithiocarbamine Diethyldithiocarbamic acid, N-nitrosophenylhydroxylamine, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 3-hydroxyflavone, 5-hydroxyflavone, 1- (2-pyridylazo) -2-naphthol, 4- (2-pyridylazo) resorcin, 2- (4'-dimethylaminophenylazo) pyridine, Eriochrome Black A, Eriochrome Black T, Eriochrome Blue Black B, Eriochrome Blue Black R, Phthalein Complexone, Alkanol Examples include amines and hydroxy acids.

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

In the above 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. R ¹ is particularly preferably a methyl group, an ethyl group, or an ethoxy group.
Examples of the organic group in R ² include a methyl group, an ethyl group, an isopropyl group, a phenyl group, a furyl group, a thienyl group, a trifluoro group, a methoxy group, and an ethoxy group.
As the component A, one type may be used, or two or more types may be mixed and used, but acetylacetone is particularly preferable from the viewpoint of the effect as a chelating agent.

<B component>
The B component in the coating solution is at least one of a hexafunctional silane compound represented by the following general formula (2) and a hydrolysis-condensation product thereof. In the present coating solution, by adding the component B, the crack resistance of the coating film is improved, and the chemical resistance and the insulation are also improved.

Here, R ³ is an alkylene group having 2 to 6 carbon atoms. R ^{4 to} R ⁹ are any one 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 are the same. It may be different.
Examples of such hexafunctional silane compounds include 1,2-bis (triethoxysilyl) ethane ((C ₂ H ₅ O) ₃ —Si—C ₂ H ₄ —Si (OC ₂ H ₅ ) ₃ ), 1,2-bis (triethoxysilyl) propane, 1,2-bis (triethoxysilyl) butane, 1,2-bis (triethoxysilyl) pentane, 1,2-bis (triethoxysilyl) hexane, 2-bis (trimethoxysilyl) ethane, 1,2-bis (trimethoxysilyl) propane, 1,2-bis (trimethoxysilyl) butane, 1,2-bis (trimethoxysilyl) pentane, and 1,2 -Bis (trimethoxysilyl) hexane is preferred. These may use 1 type and may mix and use arbitrary 2 or more types. If R ³ is too long, it may be difficult to obtain sufficient hardness. Therefore, an alkylene group having 2 to 6 carbon atoms is preferable. In addition, when R ^{4 to} R ⁹ are different from each other, a difference in hydrolysis rate occurs, and a uniform reaction hardly occurs. Therefore, as the B _component, it is preferred to use _{(C 2 H 5 O) 3} -Si-C 2 H 4 -Si (OC 2 H 5) 3.
Moreover, it is preferable from a crack-resistant viewpoint that the weight average molecular weights (polystyrene conversion) of B component after hydrolysis condensation are the range of 300-3000. Here, the weight average molecular weight is determined by GPC (Gel Permeation Chromatography).

As described above, in this coating solution, the crack resistance of the coating film (transparent coating) is improved by blending the component B (hexafunctional silane compound). This is because the presence of the organic group (alkylene group) of the hexafunctional silane compound imparts flexibility to the transparent film and further improves the wettability with the substrate (organic material) on which the transparent film is formed. It can be said that. In addition, even when part or all of the organic group is decomposed by ultraviolet irradiation in the film forming process, the organic group works in a direction to relieve stress concentration, which can also be said to contribute to improvement of crack resistance. In addition, unlike a silane compound having a substituted alkyl group such as MTMS (methyltrimethoxysilane), chemical resistance is improved because it can be made dense without reducing the degree of crosslinking of the transparent film.
Furthermore, in the method for producing a coating liquid for forming a transparent film of the present invention, the B component (hexafunctional silane compound) is oligomerized (weight average molecular weight (polystyrene conversion) 300 to 3000) and then the C component (metal alkoxide and It is desirable to cohydrolyze and condense with at least one of the hydrolyzed condensates. The cohydrolyzed condensate thus obtained is dense and has excellent crack resistance.

<C component>
The C component in the coating solution is at least one of a metal alkoxide represented by the following general formula (3) and a hydrolysis condensate thereof.
M (OR ¹⁰ ) _n (3)
Here, R ¹⁰ is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms. M is a metal element and may be the same or different. n is the same integer as the valence of M.
Here, a metal element other than Si is selected as the metal element M. Specifically, the metal element M includes Be, Al, P, Sc, Ti, V, Cr, Fe, Ni, Zn, Ga, Ge, As, Se, Y, Zr, Nb, In, Sn, Sb, An alkoxide of at least one element selected from Te, Hf, Ta, W, Pb, B, Bi, Ce and Cu is used.

  Examples of the metal alkoxide as the C component include aluminum trimethoxide, aluminum triethoxide, aluminum tripropoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum tri-t-butoxide, aluminum Tripentyl oxide, aluminum trihexyl oxide, aluminum trioctyl oxide, aluminum tribenzyl oxide, aluminum triphenoxide, aluminum trimethoxy ethoxide, aluminum trimethoxy ethoxy ethoxide, aluminum trimethoxy propoxide, titanium tetramethoxide, titanium tetraethoxy , Titanium tetrapropoxide, titanium tetraisopropoxide Titanium tetramethoxyethoxide, titanium tetrabutoxide, zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetrapropoxide, zirconium tetraisopropoxide, zirconium tetramethoxyethoxide, zirconia butoxide, niobium pentaethoxide, indium trimethoxide, Indium triethoxide, indium tripropoxide, indium triisopropoxide, indium tri-n-butoxide, indium triisobutoxide, indium tri-t-butoxide, indium tripentyl oxide, indium trihexyl oxide, indium trioctyl oxide, indium trioctyl oxide Benzyl oxide, indium triphenoxide, indium trimethoxyethoxy , Indium trimethoxyethoxy ethoxide, indium trimethoxy propoxide, antimony trimethoxide, antimony triethoxide, antimony tripropoxide, antimony triisopropoxide, antimony tri-n-butoxide, antimony triisobutoxide and the like are preferable. It is done. These may be used alone or in admixture of two or more, but it is preferable to use titanium tetraisopropoxide from the viewpoint that the hydrolysis rate is appropriate and availability is easy.

<Mixed solvent>
As a mixed solvent in this coating solution, a mixed solvent of water and an organic solvent is used. At least one of the organic solvents to be mixed preferably has a boiling point of 120 ° C. or higher. However, the boiling point is preferably 300 ° C. or lower. 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.
Examples of the organic solvent include methanol, ethanol, isopropyl alcohol, butanol, diacetone alcohol, furfuryl alcohol, alcohols such as ethylene glycol and hexylene glycol, esters such as methyl acetate and ethyl acetate, diethyl ether, Preferred are ethers such as 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 ketones such as acetone and methyl ethyl ketone. Can be mentioned. These may use 1 type and may mix and use arbitrary 2 or more types.
In addition, as the said organic solvent in this coating liquid, the organic compound which can chelate with the said component (A) metal alkoxide is excluded.

<D component>
Moreover, you may further mix | blend at least any one among the tetrafunctional silane compound represented by following General formula (4), and its hydrolysis condensate as D component in this coating liquid.
Si (R ¹¹ ) ₄ (4)
Here, R ¹¹ is any one 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. Well, it can be different.
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, examples of the substituted alkoxy group include groups in which the hydrogen atom of the aforementioned unsubstituted alkoxy group is replaced with a methyl group, an ethyl group, or the like. Examples of the aryloxy group include a phenoxy group and a naphthyloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

By further blending component D, the hardness of the coating film can be further improved.
Examples of the D-functional tetrafunctional silane compound include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane tetrachlorosilane, and trimethoxysilane. As the component D, tetraethoxysilane is particularly preferable.
Only 1 type may be used for D component and it may mix and use 2 or more types arbitrarily.

<Combination ratio of each component in the coating solution>
In this coating solution, it is necessary that the molar ratio (M1) / (M3) of the number of moles of component A (M1) to the number of moles of component C (M3) is in the range of 0.25 or more and less than 2. , Preferably in the range of 0.5 to 1 inclusive. Here, even when the A component and the C component are hydrolyzed, M1 and M2 are values based on the structure before hydrolysis.
When the molar ratio (M1) / (M3) is 2 or more, the A component is coordinated to most of ¹⁰ parts of the OR in the C component, and the reaction between the B component and the C component may be suppressed. For this reason, it is difficult to form a —MO—Si— crosslink during film curing, and the resulting transparent film may have insufficient hardness. In addition, the amount of the A component remaining in the transparent film increases, and electrical characteristics such as the surface resistance value of the film change over time, which may reduce reliability.
In addition, when the molar ratio (M1) / (M3) is less than 0.25, the progress of the reaction of the component C becomes excessive, so that the stability of the hydrolyzed condensate in the coating solution is deteriorated, and the coating solution life is increased. , The crack resistance of the transparent coating obtained may be adversely affected.

Further, SiO ₂ concentration in terms derived from the B component (C2) is preferably from 0.005 to 12 wt%, and more preferably from 0.01 to 8 wt%. When the concentration (C2) is 0.005% by mass or more, the hydrolysis reaction proceeds more smoothly, and the crack resistance can be sufficiently increased when a transparent film is formed. When the concentration (C2) is 12% by mass or less, the hydrolysis reaction does not proceed excessively, and a stable coating solution can be obtained.

The SiO ₂ equivalent concentration (C3) derived from the component C is preferably 0.02 to 14% by mass, and more preferably 0.04 to 9.5% by mass. When the concentration (C3) is 0.02% by mass or more, the hydrolysis reaction proceeds more smoothly, and the crack resistance can be sufficiently increased when a transparent film is formed. When the concentration (C3) is 14% by mass or less, the hydrolysis reaction does not proceed excessively, and a stable coating solution can be obtained.

The molar ratio (M2) / (M3) between the number of moles of the component B (M2) and the number of moles of the component C (M3) must be in the range of 0.5 to 8, and 0.6 It is preferable to be in the range of 7.5 or less. Here, even when the B component and the C component are hydrolyzed, (M2) and (M3) are values based on the structure before hydrolysis.
If the molar ratio (M2) / (M3) is less than 0.5, the stability of the coating solution is lowered and the life of the coating solution is shortened. The characteristics may not be obtained constantly, and the crack resistance may be reduced.
When the molar ratio (M2) / (M3) exceeds 8, the resulting transparent film has insufficient hardness, and the crack resistance may be lowered.

  In this coating solution, CT (total solid content concentration) which is the total value of C2 and C3 is preferably in the range of 0.1 to 15% by mass, and more preferably in the range of 0.2 to 10% by mass. preferable. When the total solid content (CT) is 0.1% by mass or more, the film thickness obtained under normal coating conditions can be sufficiently increased, and the film thickness for achieving the effects of the present invention can be obtained. The need for repeated application is also reduced. When the CT (total solid content concentration) is 15% by mass or less, the film thickness obtained under normal coating conditions can be controlled to an appropriate thickness, and the occurrence of cracks can be easily suppressed. In addition, since the stability of the coating solution is sufficient, an increase in viscosity with time can be suppressed, and characteristics such as the film thickness, refractive index, and hardness of the obtained transparent coating can be stably obtained.

The molar ratio (M4) / (M2) of the number of moles of component D (M4) to the number of moles of component B (M2) is preferably in the range of 0.01 to 1, more preferably 0. The range is from .01 to 0.5. When the molar ratio (M4) / (M2) is 0.01 or more, the hardness of the film is improved, and when it is 1 or less, crack resistance is hardly lowered.
Here, even when the B component and the D component are hydrolyzed, (M2) and (M4) are values based on the structure before hydrolysis.

In the present coating solution, a part of the B component and a part of the C component may be cohydrolyzed and condensed. That is, the present coating solution includes a part of the hexafunctional silane compound represented by the general formula (2) and the hydrolysis condensate thereof, the metal alkoxide represented by the general formula (3) and the hydrolysis condensate thereof. A co-hydrolysis condensate with a part of may be contained.
Further, when the coating solution further contains the component D, it is represented by the hexafunctional silane compound represented by the general formula (2) and a part of the hydrolysis condensate thereof, and the general formula (3). A co-hydrolysis condensate of a part of the metal alkoxide and the hydrolysis condensate thereof with a part of the tetrafunctional silane compound represented by the general formula (4) and the hydrolysis condensate thereof. Absent.

About 0.2% by mass of the catalyst for hydrolysis may remain in the coating solution due to the manufacturing process of the coating solution described later. A typical example of such a hydrolysis catalyst is nitric acid. Depending on the application of the coating solution, the hydrolysis catalyst can be removed as desired. Examples of such operations include ion exchange, neutralization, and distillation.
In addition, arbitrary components can be added to the coating liquid for forming a transparent film of the present invention as long as the effect is not impaired. Examples of such optional components include inorganic oxide fine particles, organic resin fine particles, organopolysiloxane resin fine particles, pigments, colorants, antistatic agents, and surfactants.

[Production method of this coating solution]
The manufacturing method of this coating liquid is characterized by including the following preliminary | backup process 1, preliminary | backup process 2, and this process.
Preliminary step 1: a step of preparing a hexafunctional silane solution by blending the organic solvent, the water, the component B (hexafunctional silane compound represented by the general formula (2)), and a hydrolysis catalyst ( However, the blending amount of the B component is in the range of 0.5 mol or more and 8 mol or less with respect to 1 mol of the C component metal in the preliminary step 2.)
(In the present application, the solution containing at least one of the hexafunctional silane compound and its hydrolysis condensate prepared in the preliminary step 1 is referred to as a “hexafunctional silane solution”.)
Preliminary step 2: a step of preparing a metal alkoxide solution by blending the organic solvent, the component A and the component C (metal alkoxide represented by the general formula (3)) (however, the component A is (The range is from 0.25 mol to less than 2 mol with respect to 1 mol of the C component metal.)
(In this application, the solution containing at least one of the metal alkoxide and its hydrolysis condensate prepared in the preliminary step 2 is referred to as “metal alkoxide solution”.)
This step: Add the metal alkoxide solution obtained in the preliminary step 2 to the hexafunctional silane solution obtained in the preliminary step 1, then add water, and stir at a temperature of 5 ° C. to 40 ° C. Mixing process

A preferable embodiment will be described in detail below for each of the steps described above.
<Preliminary process 1>
In the preliminary step 1, hydrolysis condensation is allowed to proceed with respect to the hexafunctional silane compound as the B component in the presence of water and a hydrolysis medium in an organic solvent, and the hydrolysis condensation product of the hexafunctional silane compound is dispersed in the mixed solvent. A hexafunctional silane solution is prepared.
As the hydrolysis catalyst, a conventionally known catalyst can be used. Examples thereof include (a) inorganic acids such as nitric acid, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and hydrogen fluoride; Examples thereof include, but are not limited to, acids, carboxylic acids such as maleic acid, (c) sulfonic acids such as methanesulfonic acid, and (d) acidic or weakly acidic inorganic salts. Moreover, you may use these catalysts in mixture of multiple types arbitrarily.
The amount of the hydrolysis catalyst is preferably in the range of 0.001 to 1 mol% (in terms of SiO ₂ , outer percentage) with respect to the B-functional hexafunctional silane compound.

The amount of water used is preferably in the range of 0.5 to 4 mol (in terms of SiO ₂ , outer percentage) with respect to 1 mol of the hexafunctional silane compound of component B. Within this molar ratio range, it is effective in that the hydrolysis of the B-functional hexafunctional silane compound is effectively advanced. The amount of water used is more preferably in the range of 1 to 3 mol.
The amount of the component B in the mixed solvent is not particularly limited as long as hydrolysis condensation can proceed, but a range of 0.01 to 8% by mass (in terms of SiO ₂ ) is preferable.
In the preliminary step 1, water, a catalyst for hydrolysis, and a component B (hexafunctional silane compound represented by the general formula (2)) are usually added to an organic solvent, and the mixture is stirred at 5 to 40 ° C. for 5 to 120 minutes. To prepare a hexafunctional silane solution.
In addition, when mix | blending D component further, it mix | blends in this preliminary process 1. A preferable blending amount is as described above.

<Preliminary process 2>
In the preliminary step 2, a component A and a component C (metal alkoxide represented by the general formula (3)) are added to an organic solvent and stirred to prepare a metal alkoxide solution containing the metal alkoxide and its hydrolysis condensate. . Preferred organic solvents are as described above. Moreover, as an example of A component and C component (metal alkoxide represented by General formula (3)), each above-mentioned compound can be mentioned suitably.
The molar ratio (M1) / (M3) of the number of moles of component A (M1) to the number of moles of component C (M3) in preliminary step 2 needs to be in the range of 0.25 or more and less than 2. In Preliminary Step 2, the A component is coordinated to the alkoxy group of the C component. If the molar ratio (M1) / (M3) is in the range of 0.25 or more and less than 2, the chelate coordinating group possessed by the A component. Since the metal alkoxide which is not coordinated to the remaining remains, it is preferable in terms of controlling the reactivity of the C component. The molar ratio (M1) / (M3) is more preferably in the range of 0.5 to 1.
When the molar ratio (M1) / (M3) is 2 or more, the coordination of the metal alkoxide to the alkoxy group proceeds excessively, so that the stabilization of the metal alkoxide becomes excessive, and the co-hydrolysis condensation with the hexafunctional silane or the like also occurs. It may be unsuitable for low-temperature curing (80 to 300 ° C.) of the coating liquid for forming a transparent film.
The MO _X equivalent concentration of the C component in the preliminary step 2 is preferably in the range of 0.04 to 9.5% by mass.
The metal alkoxide solution prepared in the preliminary step 2 contains a metal alkoxide coordinated with the component A and a hydrolysis condensate thereof.

[This process]
The metal alkoxide solution prepared in Preliminary Step 2 is added to the hexafunctional silane solution prepared in Preliminary Step 1, and then water is added, followed by stirring and mixing at 5 to 40 ° C. to prepare this coating solution.
Here, it is preferable that the molar ratio (M2) / (M3) satisfies the range of 0.5 to 8 in terms of the number of moles of component B (M2) and the number of moles of component C (M3). This is because when the molar ratio (M2) / (M3) is within this range, the cohydrolysis reaction proceeds smoothly.
The addition of water described above is preferable for obtaining a dense transparent film because the co-hydrolysis condensation reaction between the hydrolysis condensate of hexafunctional silane and the metal alkoxide and / or its hydrolysis condensate is promoted.

[Method for producing substrate with transparent coating]
The method for producing a substrate with a transparent coating according to this embodiment is characterized in that the following film forming process 1 to film forming process 4 are performed.
Film formation step 1: A step of applying this coating solution to a substrate Film formation step 2: A step of heating and drying the substrate at 80 ° C. or more and 150 ° C. or less following the film formation step 1 Film formation step 3: Following the film forming step 2, the step of irradiating the substrate with ultraviolet rays Film forming step 4: Following the film forming step 3, the step of heating the substrate at 80 ° C. or higher and 300 ° C. or lower

A preferred embodiment will be described in detail below for each of the film forming steps described above.
<Film formation process 1>
In the film-forming process 1, this coating liquid is apply | coated to a base material. As a coating method, conventionally known methods such as a dipping method, a spinner method, a bar coating method, a spray method, a roll coater method, a flexographic printing method, and a slit coating method can 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.

<Film formation process 2>
The temperature for heating and drying is not particularly limited as long as desired strength, hardness, scratch resistance and the like can be obtained without altering the base material, but a range of 80 to 150 ° C is preferable, and a range of 90 to 140 ° C is preferable. More preferred. Heating and drying are preferably performed for about 1 to 10 minutes.
There is no clear boundary between drying and heating, and drying and heating may be performed at a time as long as a transparent film having desired hardness, strength, and the like is obtained, and after drying, heating may be performed at a temperature higher than the drying temperature.
A conventionally known method can be adopted as a drying method or a heating method. Moreover, electromagnetic wave irradiation processing can also be used together.
When the drying temperature and the heating temperature are less than 80 ° C., sufficient film strength cannot be obtained due to residual solvent and insufficient cross-linking of —M—O—M— or —M—O—Si—. When the drying temperature exceeds 350 ° C., the organic group of the component B may be decomposed and the desired film characteristics may not be obtained.

<Film formation process 3>
In the film forming step 3, following the film forming step 2, the heat-dried transparent film is irradiated with ultraviolet rays (UV). For example, ultraviolet rays of 3,000 mJ / cm ² are irradiated using a 2 kw high-pressure mercury lamp. Due to the UV irradiation, the A component is desorbed in the heat-dried transparent film, and the transparent film is easily crosslinked in the film forming step 4. As the ultraviolet rays, at least one of ultraviolet rays with a wavelength of 254 nm and ultraviolet rays with a wavelength of 365 nm promotes the removal of residual solvent and the cross-linking of -MO-M- or -MO-Si-. From the viewpoint of In particular, it is more preferable that both ultraviolet rays having a wavelength of 254 nm and ultraviolet rays having a wavelength of 365 nm are included.

<Film formation process 4>
Subsequent to the film forming step 3, as the film forming step 4, the transparent film is heated in the range of 80 to 300 ° C. By this heating, the transparent film is sufficiently crosslinked. If the heating temperature is in the range of 80 to 300 ° C., for example, it is advantageous in terms of suppressing resistance change of the ITO wiring. The heating time is preferably 1 to 10 minutes.

[Base material with transparent film]
The base material with a transparent coating in this embodiment can suppress wiring appearance in a display element such as a touch panel, and has high pencil hardness, chemical resistance, and insulation. In addition, when the coating liquid for forming a transparent film in the present embodiment is used, the coating film is hardly cracked and can be cured at a relatively low temperature.
Here, the average film thickness (T) of the transparent film in the transparent film substrate obtained by the film forming step is preferably in the range of 20 to 200 nm, and more preferably in the range of 40 to 150 nm.
When the transparent film has an average film thickness (T) of 20 nm or more, the film thickness is sufficient, so that a portion where the film cannot be formed (coating unevenness) hardly occurs, and the effect of film formation can be sufficiently obtained. On the other hand, when the average film thickness (T) of the transparent coating is 200 nm or less, the occurrence of cracks can be sufficiently suppressed, and the strength and hardness of the film are sufficient.
The substrate with a transparent coating of the present invention can be suitably used for an insulating film used between an electrode substrate of a liquid crystal display device and an alignment film, a protective film on a transparent electrode of a touch panel, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.

[Example 1]
Each process for manufacturing the coating liquid for transparent film formation and the base material with a transparent film is as follows. Table 1 shows the types and amounts of each component to be blended.
(Preliminary process 1)
4673.08 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 214.07 g of pure water and 3.57 g of nitric acid having a concentration of 60% by mass were mixed and stirred for 5 minutes. Next, 1055.55 g of 1,2-bis (triethoxysilyl) ethane (manufactured by Yamanaka Futec Co., Ltd .: SiO ₂ concentration of 33.8% by mass) was added as a B-functional hexafunctional silane compound while stirring. The mixture was stirred for a minute to prepare a preliminary liquid 1-1 having a solid content concentration of 6.0% by mass.

(Preliminary process 2)
2966.06 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 148.66 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as the carbonyl group-containing organic compound of the A component, and ORGATIX TA as the metal alkoxide of the C component 849.47 g of -10 (manufactured by Matsumoto Fine Chemical Co., Ltd .: TiO2 concentration 28 mass%) was mixed and stirred for 5 minutes to prepare Preliminary Solution 2-1 having a solid content concentration of 6.0 mass%.

(This process)
Preliminary liquid 2-1 was mixed with preparatory liquid 1-1 while stirring and stirred for 10 minutes, and then 49.55 g of pure water was added and stirred at 5 ° C. for 144 hours. After completion of the stirring, filtration was performed with a 0.2 μm filter to remove aggregates and the like, and a coating liquid for forming a transparent film (1) having a total solid content concentration of 6.0% by mass was prepared.

(Manufacture of substrate with transparent film (1))
The coating liquid for forming a transparent film (1) is applied onto a glass substrate with ITO film (manufactured by AGC Fabricec Co., Ltd., thickness: 1.1 mm) by flexographic printing, and dried at 90 ° C. for 5 minutes. to, after irradiation with wavelength 365nm UV ultraviolet (3000 mJ / cm ²⁾ to the wavelength 254 nm (2000 mJ / cm ^2), a transparent film-coated substrate was heated at 230 ° C. 30 minutes (1-1) was prepared.
About the obtained base material with a transparent film (1-1), the film thickness, pencil hardness, surface resistance, and chemical resistance were measured by the following methods. The results are shown in Table 1.
Separately, a 2 μm acrylic resin layer was formed on a glass substrate with a silica film (manufactured by AGC Fabricec Co., Ltd., thickness: 1.1 mm). The acrylic resin layer was applied using a bar coater (No. 3), then dried at 90 ° C. for 5 minutes, and then heated at 230 ° C. for 30 minutes. The coating liquid for forming a transparent film (1) is applied onto the glass substrate with an acrylic resin layer by flexographic printing, dried at 90 ° C. for 5 minutes, and then irradiated with 3000 mJ / cm ² ultraviolet rays (wavelength 365 nm). Then, it heated at 230 degreeC for 30 minutes, and prepared the base material (1-2) with a transparent film.
About the obtained base material with a transparent film (1-2), the crack resistance was measured with the following method. The results are shown in Table 1.
Separately, the coating liquid for forming a transparent film (1) is applied on a 6-inch silicon wafer (manufactured by Matsuzaki Seisakusho Co., Ltd., thickness: 0.625 mm) by flexographic printing, dried at 90 ° C. for 5 minutes, and then After irradiating ultraviolet rays (wavelength 365 nm) of 3000 mJ / cm ^2, the substrate with transparent coating (1-3) was prepared by heating at 230 ° C. for 30 minutes.
About the obtained base material with a transparent film (1-3), the refractive index was measured with the following method. The results are shown in Table 1.

[Example 2]
Except for the following preliminary steps, a transparent coating-forming coating solution (2) was prepared in the same manner as in Example 1, and substrates (2-1) to (2-3) with transparent coating were produced. Thereafter, evaluation was performed in the same manner as in Example 1.
(Preliminary process 1)
5141.36 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 267.58 g of pure water and 4.46 g of nitric acid having a concentration of 60% by mass were mixed and stirred for 5 minutes. Next, 1311.94 g of 1,2-bis (triethoxysilyl) ethane (manufactured by Yamanaka Futec Co., Ltd .: SiO ₂ concentration of 33.8% by mass) was added as a B-functional hexafunctional silane compound while stirring, Preliminary liquid 1-2 having a solid content concentration of 6.0% by mass was prepared by stirring for 5 minutes.

(Preliminary process 2)
1853.78 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 92.91 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as the carbonyl group-containing organic compound of component A, ORGATIX TA as the metal alkoxide of component C 530.92 g of -10 (manufactured by Matsumoto Fine Chemical Co., Ltd .: TiO2 concentration 28 mass%) was mixed and stirred for 5 minutes to prepare a preliminary liquid 2-2 having a solid content concentration of 6.0 mass%.

Example 3
Except for the following preliminary steps, a transparent coating-forming coating solution (3) was prepared in the same manner as in Example 1, and substrates (3-1) to (3-3) with transparent coating were produced. Thereafter, evaluation was performed in the same manner as in Example 1.
(Preliminary process 1)
6620.20 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 303.26 g of pure water and 5.05 g of nitric acid having a concentration of 60% by mass were mixed and stirred for 5 minutes. Next, 1495.36 g of 1,2-bis (triethoxysilyl) ethane (manufactured by Yamanaka Futec Co., Ltd .: SiO ₂ concentration of 33.8% by mass) was added as a B-functional hexafunctional silane compound while stirring. Preliminary liquid 1-3 having a solid content concentration of 6.0% by mass was prepared by stirring for a minute.

(Preliminary process 2)
1112.27 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 55.75 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as the carbonyl group-containing organic compound of the A component, and ORGATIX TA as the metal alkoxide of the C component 318.55 g of -10 (manufactured by Matsumoto Fine Chemical Co., Ltd .: TiO2 concentration 28% by mass) was mixed and stirred for 5 minutes to prepare Preliminary Solution 2-3 having a solid content concentration of 6.0% by mass.

Example 4
Except for the following preliminary steps, a transparent coating-forming coating solution (4) was prepared in the same manner as in Example 1, and substrates (4-1) to (4-3) with transparent coating were produced. Thereafter, evaluation was performed in the same manner as in Example 1.
(Preliminary process 1)
2336.54 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 107.03 g of pure water, and 1.78 g of nitric acid having a concentration of 60% by mass were mixed and stirred for 5 minutes. Next, 527.78 g of 1,2-bis (triethoxysilyl) ethane (manufactured by Yamanaka Futec Co., Ltd .: SiO ₂ concentration of 33.8% by mass) was added as a B-functional hexafunctional silane compound while stirring. Preliminary liquid 1-4 having a solid content concentration of 6.0% by mass was prepared by stirring for a minute.

(Preliminary process 2)
5190.60 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 260.15 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as the carbonyl group-containing organic compound of the A component, and ORGATIX TA as the metal alkoxide of the C component 1486.57g of -10 (Matsumoto Fine Chemical Co., Ltd. product: TiO2 density | concentration 28 mass%) was mixed, and it stirred for 5 minutes, and prepared the preliminary | backup liquid 2-4 with a solid content density | concentration of 6.0 mass%.

Example 5
Except for the following preliminary steps, a coating liquid for forming a transparent film (5) was prepared in the same manner as in Example 1, and substrates with transparent film (5-1) to (5-3) were produced. Thereafter, evaluation was performed in the same manner as in Example 1.
(Preliminary process 1)
461.200 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 214.07 g of pure water and 3.57 g of nitric acid having a concentration of 60% by mass were mixed and stirred for 5 minutes. Next, 703.7 g of 1,2-bis (triethoxysilyl) ethane (manufactured by Yamanaka Futec Co., Ltd .: SiO ₂ concentration of 33.8% by mass) as a B component hexafunctional silane compound while stirring, Add 412.94 g of ethyl silicate (manufactured by Tama Chemical Co., Ltd .: SiO2 concentration 28.8 mass%) as a tetrafunctional silane compound, and stir for 30 minutes to prepare a preliminary liquid 1-5 having a solid content concentration of 6.0 mass%. Prepared.

(Preliminary process 2)
2966.06 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 148.66 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as the carbonyl group-containing organic compound of the A component, and ORGATIX TA as the metal alkoxide of the C component 849.47 g of -10 (manufactured by Matsumoto Fine Chemical Co., Ltd .: TiO2 concentration 28% by mass) was mixed and stirred for 5 minutes to prepare a preliminary liquid 2-5 having a solid content concentration of 6.0% by mass.

Example 6
Except for the following preliminary steps, a transparent coating-forming coating solution (6) was prepared in the same manner as in Example 1, and substrates (6-1) to (6-3) with transparent coating were produced.
Thereafter, evaluation was performed in the same manner as in Example 1.
(Preliminary process 1)
461.200 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 214.07 g of pure water and 3.57 g of nitric acid having a concentration of 60% by mass were mixed and stirred for 5 minutes. Next, 703.7 g of 1,2-bis (triethoxysilyl) ethane (manufactured by Yamanaka Futec Co., Ltd .: SiO ₂ concentration 33.8% by mass) as a B-functional hexafunctional silane compound with stirring and trifunctional silane As a compound, 352.89 g of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-13, SiO2 concentration of 33.7% by mass) was added, stirred for 30 minutes, and a preliminary solution having a solid content concentration of 6.0% by mass. 1-6 was prepared.

(Preliminary process 2)
2966.06 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 148.66 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as the carbonyl group-containing organic compound of the A component, and ORGATIX TA as the metal alkoxide of the C component 849.47 g of -10 (Matsumoto Fine Chemical Co., Ltd .: TiO2 concentration 28% by mass) was mixed and stirred for 5 minutes to prepare Preliminary Solution 2-6 having a solid content concentration of 6.0% by mass.

[Comparative Example 1]
Except for the following preliminary steps, a transparent coating-forming coating solution (7) was prepared in the same manner as in Example 1, and substrates with transparent coating (7-1) to (7-3) were produced. Thereafter, evaluation was performed in the same manner as in Example 1.
(Preliminary process 1)
6737.03 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 308.61 g of pure water and 5.14 g of nitric acid having a concentration of 60% by mass were mixed and stirred for 5 minutes. Next, 1521.75 g of 1,2-bis (triethoxysilyl) ethane (manufactured by Yamanaka Futec Co., Ltd .: SiO ₂ concentration of 33.8% by mass) was added as a B-functional hexafunctional silane compound while stirring, Preliminary liquid 1-7 having a solid content concentration of 6.0% by mass was prepared by stirring for 5 minutes.

(Preliminary process 2)
1001.04 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 50.17 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as the carbonyl group-containing organic compound of the A component, and ORGATIX TA as the metal alkoxide of the C component 286.70 g of -10 (manufactured by Matsumoto Fine Chemical Co., Ltd .: TiO2 concentration 28% by mass) was mixed and stirred for 5 minutes to prepare Preliminary Solution 2-7 having a solid content concentration of 6.0% by mass.

[Comparative Example 2]
Except for the following preliminary steps, a transparent coating-forming coating solution (8) was prepared in the same manner as in Example 1, and substrates (8-1) to (8-3) with transparent coating were produced. Thereafter, evaluation was performed in the same manner as in Example 1.
(Preliminary process 1)
1799.35 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 82.06 g of pure water and 1.37 g of nitric acid having a concentration of 60% by mass were mixed and stirred for 5 minutes. Next, 404.63 g of 1,2-bis (triethoxysilyl) ethane (manufactured by Yamanaka Futec Co., Ltd .: SiO ₂ concentration of 33.8% by mass) was added as a B-functional hexafunctional silane compound while stirring. Preliminary liquid 1-8 having a solid content concentration of 6.0% by mass was prepared by stirring for a minute.

(Preliminary process 2)
5709.66 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 286.16 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as the carbonyl group-containing organic compound of the A component, and ORGATIX TA as the metal alkoxide of the C component 1635.22 g of -10 (Matsumoto Fine Chemical Co., Ltd .: TiO2 concentration 28% by mass) was mixed and stirred for 5 minutes to prepare Preliminary Solution 2-8 having a solid content concentration of 6.0% by mass.

[Comparative Example 3]
Except for the following preliminary steps, a coating liquid for forming a transparent film (9) was prepared in the same manner as in Example 1, and substrates with transparent film (9-1) to (9-3) were produced. Thereafter, evaluation was performed in the same manner as in Example 1.
(Preliminary process 1)
4669.95 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 214.07 g of pure water and 3.57 g of nitric acid having a concentration of 60% by mass were mixed and stirred for 5 minutes. Next, 1055.68 g of ethyl silicate (manufactured by Tama Chemical Co., Ltd .: SiO2 concentration of 28.8% by mass) was added as a silane compound while stirring, and the mixture was stirred for 30 minutes and a preliminary solution having a solid content of 6.0% by mass. 1-9 was prepared.

(Preliminary process 2)
2966.06 g of hexylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 148.66 g of acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd.) as the carbonyl group-containing organic compound of the A component, and ORGATIX TA as the metal alkoxide of the C component 849.47 g of -10 (Matsumoto Fine Chemical Co., Ltd .: TiO2 concentration 28% by mass) was mixed and stirred for 5 minutes to prepare Preliminary Solution 2-9 having a solid content concentration of 6.0% by mass.

[Evaluation Item / Evaluation Method]
The following evaluation was performed with respect to the base material with a transparent film obtained by each Example and each comparative example. Further, the temporal stability of the coating solution for forming a transparent film was also evaluated as follows. The results are shown in Table 1.
(1) Film thickness It measured with the surface roughness measuring machine (Tokyo Seimitsu Co., Ltd. product: Surfcom).
(2) Surface resistance value The surface resistance value was measured with a surface resistance measuring device (manufactured by Mitsubishi Chemical Analytech Co., Ltd .: Hiresta UX MCP-HT800).

(3) Crack resistance of coating film The surface of the coating film was visually observed, and crack resistance was evaluated according to the following criteria.
◎: No cracks are observed in the coating surface ○: Slight cracks are observed in the edge portion ×: Cracks are generated in the coating surface

(4) Pencil hardness It measured with the pencil hardness tester according to JIS-K-5600. That is, a pencil was set at an angle of 45 degrees with respect to the transparent coating surface, and a predetermined load was applied and pulled at a constant speed, and the presence or absence of scratches was observed.
(5) Refractive index The refractive index was measured with a spectroscopic ellipsometer (manufactured by SOPRA, Inc .: ES4G, @ 550 nm).

(6) Chemical resistance Each substrate with transparent coating is immersed for 5 minutes in a mixed solution of phosphoric acid / nitric acid / acetic acid / water (mass ratio: 80/5/5/10) heated to 40 ° C. and washed with pure water. did. Thereafter, the substrate with the transparent coating was immersed in a mixed solution of diethylene glycol monobutyl ether / 2-aminoethanol (mass ratio: 70/30) heated to 60 ° C. for 5 minutes, and the state of the coating film after washing with pure water was visually observed. And observed with an optical microscope, and the chemical resistance was evaluated according to the following criteria.
○: No change is observed in the coating film ×: Peeling or cracking of the coating film occurs (7) Stability of coating solution over time After heating the coating solution at 40 ° C. for 72 hours, an E-type viscometer The viscosity was measured with Sangyo Co., Ltd. (TV-25 type), and evaluated according to the following criteria.
A: No change in viscosity is observed
○: Slight increase in viscosity is observed (less than 5 mPa · s)
X: Clear increase in viscosity is observed (5 mPa · s or more)

〔Evaluation results〕
As shown in Table 1, from Examples 1 to 6, the substrate with a transparent coating produced using the coating solution for forming a transparent coating of the present invention has all of surface hardness, crack resistance, and chemical resistance. It turns out that it is excellent.
On the other hand, from Comparative Examples 1 to 3, the use of the coating liquid for forming a transparent film that does not have the configuration of the present invention cannot satisfy all of the surface hardness, crack resistance, and chemical resistance.

Claims (14)

An organic compound (A) capable of chelating with a metal alkoxide;
At least one (B) of a hexafunctional silane compound represented by the following general formula (2) and a hydrolysis-condensation product thereof;
At least one of the metal alkoxide represented by the following general formula (3) and its hydrolysis condensate (C),
Dissolved or dispersed in a mixed solvent containing water and an organic solvent,
The molar ratio (M1) / (M3) of the number of moles of the component A (M1) and the number of moles of the component C (M3) is in the range of 0.25 or more and less than 2.
The coating for forming a transparent film, wherein the molar ratio (M2) / (M3) of the number of moles of the component B (M2) and the number of moles of the component C (M3) is in the range of 0.5 to 8 liquid.

(R ³ is an alkylene group having 2 to 6 carbon atoms. R ^{4 to} R ⁹ are unsubstituted or substituted alkoxy groups having 1 to 8 carbon atoms, unsubstituted or substituted aryloxy groups, vinyloxy groups, hydroxyl groups, and hydrogen atoms. And a halogen atom, which may be the same or different.)
M (OR ¹⁰ ) _n (3)
(M is Be, Al, P, Sc, Ti, V, Cr, Fe, Ni, Zn, Ga, Ge, As, Se, Y, Zr, Nb, In, Sn, Sb, Te, Hf, Ta, One element selected from W, Pb, B, Bi, Ce, and Cu, R ¹⁰ is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, and n is the same as the valence of M (It is an integer.) In the coating liquid for forming the transparent film,
The SiO ₂ equivalent concentration (C2) derived from the B component is in the range of 0.005 to 12% by mass,
The MO _X equivalent concentration (C3) derived from the C component is in the range of 0.02 to 14% by mass,
The coating liquid for forming a transparent film according to claim 1, wherein the total (CT) of C2 and C3 is in the range of 0.1 to 15% by mass. Furthermore, it contains at least one (D) of a tetrafunctional silane compound represented by the following general formula (4) and its hydrolysis condensate,
The molar ratio (M4) / (M2) of the number of moles of the component D (M4) to the number of moles of the component B (M2) is in the range of 0.01 to 0.5. Claim | item 1 or the coating liquid for transparent film formation of Claim 2.
Si (R ¹¹ ) ₄ (4)
(R ¹¹ is any one 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, May be different.) In the coating liquid for forming the transparent film,
The SiO ₂ concentration in terms (C2) derived from the B component is 0.005 to 12 wt%,
The MO _X equivalent concentration (C3) derived from the C component is 0.02 to 14% by mass,
The SiO ₂ equivalent concentration (C4) derived from the component D is 0 to 12% by mass,
4. The coating liquid for forming a transparent film according to claim 3, wherein a total (CT) of the C2, the C3, and the C4 is 0.1 to 15% by mass. The boiling point of the organic solvent is 120 ° C. or higher,
The coating liquid for forming a transparent film according to any one of claims 1 to 4, wherein the viscosity at 20 ° C is in the range of 1 to 400 mPa · s. The following preliminary process 1, preliminary process 2, and this process are implemented, The manufacturing method of the coating liquid for transparent film formation in any one of Claim 1-5 characterized by the above-mentioned.
Preliminary step 1: a step of preparing a hexafunctional silane solution by blending the organic solvent, the water, the component B (hexafunctional silane compound represented by the general formula (2)), and a hydrolysis catalyst. (However, the blending amount of the B component is in the range of 0.5 mol or more and 8 mol or less with respect to 1 mol of the C component metal in the preliminary step 2.)
Preliminary step 2: a step of blending the organic solvent, the component A, and the component C (metal alkoxide represented by the general formula (3)) to prepare a metal alkoxide solution (however, the component A The blending amount is in the range of 0.25 mol or more and less than 2 mol with respect to 1 mol of the C component metal.)
This step: Add the metal alkoxide solution obtained in the preliminary step 2 to the hexafunctional silane solution obtained in the preliminary step 1, then add water, and stir at a temperature of 5 ° C. to 40 ° C. Mixing process The method for producing a coating liquid for forming a transparent film according to claim 6, wherein the weight average molecular weight (in terms of polystyrene) of the component B after hydrolysis and condensation is in the range of 300 to 3,000. In the preliminary step 1, component D in claim 3 (tetrafunctional silane compound represented by the general formula (4)) is further added,
The molar ratio (M4) / (M2) of the number of moles of the component D (M4) to the number of moles of the component B (M2) is in the range of 0.01 to 0.5. The manufacturing method of the coating liquid for transparent film formation of Claim 6 or Claim 7. In the said process, co-hydrolysis and condensation reaction of the said B component and the said C component are performed. The manufacturing method of the coating liquid for transparent film formation of Claim 6 or Claim 7 characterized by the above-mentioned. In the said process, the co-hydrolysis and condensation reaction of the said B component, the said C component, and the said D component are performed. The manufacturing method of the coating liquid for transparent film formation of Claim 8 characterized by the above-mentioned. A substrate with a transparent coating, which is obtained by applying the coating liquid for forming a transparent coating according to any one of claims 1 to 5 to a substrate. The average film thickness of the said transparent film is 20 nm or more and 200 nm or less. The base material with a transparent film of Claim 11 characterized by the above-mentioned. 13. The method for producing a substrate with a transparent coating according to claim 11 or 12, wherein the following film forming process 1 to film forming process 4 are carried out.
Film-forming process 1: A process of applying the coating liquid for forming a transparent film to a substrate Film-forming process 2: A process of heating and drying the substrate at 80 ° C. to 150 ° C. following the film-forming process 1 Step 3: Following the film forming step 2, a step of irradiating the coating film formed on the substrate with ultraviolet rays Film forming step 4: Following the film forming step 3, the coating formed on the substrate Heating the film at 80 ° C. or higher and 300 ° C. or lower The method for producing a substrate with a transparent coating according to claim 13, wherein the ultraviolet ray includes at least one of an ultraviolet ray having a wavelength of 254 nm and an ultraviolet ray having a wavelength of 365 nm.