TWI697529B - Film-forming coating liquid, manufacturing method of film-forming coating liquid and film-covered base material - Google Patents

Abstract

The coating liquid for film formation of the present invention is characterized in that it is an organic compound capable of forming a chelate with a metal alkoxide (component A), a hexafunctional silane compound represented by the following formula (2), and its hydrolysis condensation At least one of the substance (component B) and at least one of the metal alkoxide represented by the following formula (3) and its hydrolysis condensate (component C) are dissolved or dispersed in a mixed solvent containing an organic solvent The molar ratio (M1/M3) of the molar number of component A (M1) and the molar number of component C (M3) (M1/M3) is 0.25 or more and not within the range of 2, and the molar number of component B (M2) The molar ratio (M2/M3) between the molar number (M3) of the component C and the molar ratio is in the range of 0.5 or more and 8 or less.

(Equations (2) and (3) are as described in the manual)

Description

Coating liquid for film formation, method for producing coating liquid for film formation, and substrate with film

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

Conventionally, in display elements such as touch panels, there is a problem that ITO (Indium Tin Oxide) wiring patterns are recognized and displayability is reduced. Therefore, a technique has been proposed to make the wiring pattern difficult to see through index matching. For example, a technique of introducing a high refractive index thin film layer (IM layer) by sputtering or the like is known. On the other hand, there is also a need to form an IM layer by using a transparent film obtained from a relatively inexpensive and high-durability inorganic coating liquid material.

In addition, in display elements such as touch panels, metal wiring and the like are usually coated by coating a resin material. However, when an inorganic coating liquid material is applied to such a resin, there is a problem that cracks are easily generated, which may cause defects of the display element depending on the situation.

In addition, the coating used for display elements such as touch panels prevents damage during the transport step. From the point of view of injury, in addition to hardness, chemical resistance to etching solutions used to pattern wiring of metals and the like is also required. Furthermore, coatings used for display elements such as touch panels are also required to be fired at 300°C or lower due to the influence on peripheral components.

In contrast to this, 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, it can be relatively compared by irradiating ultraviolet rays during or after drying. It is cured at a low temperature to form a transparent ceramic film with excellent durability (refer to Document 1: Japanese Patent Application Laid-Open No. 2-48403). In addition, it is known that if a coating solution containing metal alkoxides such as methyltrimethoxysilane (MTMS), etc., and metal salts such as aluminum nitrate nonahydrate, and a precipitation inhibitor, etc., is used, the electrode The eye-catching pattern is suppressed, and it has high strength. Even when it is coated on the resin, it can form a coating film that can prevent the occurrence of cracks (refer to Document 2: WO2012/099253).

On the other hand, although the coating liquid disclosed in Document 1 can provide a transparent film that is cured at a relatively low temperature, it has the following problem: for example, when the base layer is resin, it is difficult to suppress the occurrence of cracks. In addition, the hardness or chemical resistance of the transparent film may not necessarily be sufficient. In addition, the coating solution disclosed in Document 2 uses the metal alkoxides exemplified by MTMS having non-bonding functional groups, so when firing at low temperature, the degree of crosslinking of the film becomes relatively low , Insufficient chemical resistance.

The object of the present invention is to provide a coating liquid for forming a film, a method for producing a coating liquid for forming a film, and a substrate with a film, which has sufficient hardness after being applied to a substrate and is difficult to generate cracks, and has excellent chemical resistance .

In order to solve the above-mentioned problems, the inventors have made painstaking research and found that if organic compounds that can form chelate with metal alkoxides, specific 6-functional silane compounds and metal alkoxides (but not silanoxides) are used A coating liquid that is dissolved or dispersed in a mixed solvent composed of water and an organic solvent can obtain a coating film that has sufficient hardness, is hard to crack, and has excellent chemical resistance. The present invention was completed based on this knowledge.

That is, the present invention provides the following coating liquid for film formation, a method for producing a coating liquid for film formation, and a substrate with a film.

In addition, the present invention provides a coating liquid for forming a film, which can form a film with a high refractive index (refractive index 1.3 to 2.3) without mixing high refractive index particles in the coating liquid for forming a film.

[1] A coating liquid for forming a film, which is an organic compound capable of forming a chelate with a metal alkoxide (component A), a 6-functional silane compound represented by the following formula (2) and its hydrolysis condensate At least one of (component B) and at least one of the metal alkoxide represented by the following formula (3) and its hydrolysis condensate (component C) is dissolved or dispersed in a mixed solvent containing water and an organic solvent The molar ratio (M1/M3) of the molar number of component A (M1) and the molar number of component C (M3) (M1/M3) is 0.25 or more and not within the range of 2, and the molar number of component B (M2) The molar ratio (M2/M3) between the molar number (M3) of the component C and the molar ratio is in the range of 0.5 or more and 8 or less.

(R ³ is an alkylene group with 2 to 6 carbons. R ⁴ to R ⁹ is an unsubstituted or substituted alkoxy group with a carbon number of 1 to 8, unsubstituted or substituted aryloxy, ethylene oxide Any of the group, the hydroxyl group, the hydrogen atom, and the halogen atom may be the same or different).

M(OR ¹⁰ ) _n (3)

(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, Ta, W , Pb, Bi, Ce, and Cu, R ¹⁰ is an unsubstituted or substituted alkyl group with 1 to 10 carbon atoms. N is an integer with the same valence as M).

[2] The coating liquid for film formation as in [1] above, in which the SiO ₂ conversion concentration derived from component B (concentration C2) is in the range of 0.005 to 12% by mass, derived from component C The converted concentration of MO _X (concentration C3) is in the range of 0.02-14% by mass, and the total of concentration C2 and concentration C3 (concentration CT) is in the range of 0.1-15% by mass.

[3] The coating liquid for forming a film as described in [1] or [2], which further contains at least one of the tetrafunctional silane compound represented by the following formula (4) and its hydrolysis condensate (component D), The molar ratio (M4/M2) of the molar number (M4) of the component D to the molar ratio (M2) of the component B is in the range of 0.01 or more and 0.5 or less.

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, both Can be the same or different).

[4] The coating liquid for film formation as in [3] above, in which the SiO ₂ conversion concentration derived from component B (concentration C2) is 0.005-12% by mass, and the MO derived from component C _X conversion concentration (concentration C3) is 0.02-14% by mass, SiO ₂ conversion concentration (concentration C4) derived from component D is 12% by mass or less, and the total of concentration C2, concentration C3, and concentration C4 (concentration CT) is 0.1 ~15% by mass.

[5] The coating liquid for forming a film as in any one of [1] to [4] above, 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.

[6] A method for manufacturing a coating liquid for film formation, which is the method for manufacturing a coating liquid for film formation in any one of [1] to [5] above, and implements the following preliminary steps 1, preliminary steps 2, and formal step.

Preliminary step 1: Blending organic solvent, water, component B (hexafunctional silane compound represented by formula (2)), and hydrolysis catalyst to prepare a hexafunctional silane solution (wherein, the blending amount of component B is relative to 1 mol of C component metal in preliminary step 2 is in the range of 0.5 mol or more and 8 mol or less); Preliminary step 2: Blending organic solvent, component A, and component C (metal alkoxide represented by formula (3)) to prepare a metal alkoxide solution (wherein, the blending amount of component A is relative to component C 1 mol of metal, which is above 0.25 mol and less than the range of 2 mol); Formal step: Add the metal alkoxide solution obtained in the preliminary step 2 to the 6-functional silane solution obtained in the preliminary step 1, and then add water, stir and mix at a temperature above 5°C and below 40°C step

(R ³ is an alkylene group with 2 to 6 carbons. R ⁴ to R ⁹ is an unsubstituted or substituted alkoxy group with a carbon number of 1 to 8, unsubstituted or substituted aryloxy, ethylene oxide Any of the group, the hydroxyl group, the hydrogen atom, and the halogen atom may be the same or different).

M(OR ¹⁰ ) _n (3)

(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, Ta, W , Pb, Bi, Ce, and Cu. R ¹⁰ is an unsubstituted or substituted alkyl with 1 to 10 carbon atoms. n is an integer with the same valence of M).

[7] The method for producing a coating liquid for forming a film as described in [6] above, wherein the weight average molecular weight (in terms of polystyrene) of the component B after the hydrolysis and condensation is in the range of 300 or more and 3000 or less.

[8] The method for producing a coating liquid for forming a film as described in [6] or [7], wherein in the preliminary step 1, the component D in the above [3] (the tetrafunctional represented by the formula (4) is added Silane compound), and the molar ratio (M4/M2) of the molar number (M4) of the component D to the molar number (M2) of the component B is in the range of 0.01 to 0.5.

[9] The method for producing a coating liquid for forming a film as described in [6] or [7], in which the co-hydrolysis and condensation reaction of component B and component C are carried out in the main step.

[10] The method for producing a coating liquid for forming a film as in [8] above, in which the co-hydrolysis and condensation reactions of the B component, the C component, and the D component are carried out in the main step.

[11] A substrate with a film, which is obtained by applying the coating liquid for forming a film of any one of [1] to [5] above to a substrate.

[12] The substrate with a film as in [11] above, the average thickness of the film is 20 nm or more and 200 nm or less.

[13] The method for producing a substrate with a film as described in [11] or [12], characterized in that the following film-forming step 1 to film-forming step 4 are carried out.

Film formation step 1: The step of applying the coating liquid for film formation to the substrate

Film formation step 2: Following the film formation step 1, the step of heating and drying the substrate at a temperature above 80°C and below 150°C

Film-forming step 3: Following film-forming step 2, the step of irradiating the coating film formed on the substrate with ultraviolet rays

Film-forming step 4: Following film-forming step 3, the step of heating the coating film formed on the substrate at a temperature above 80°C and below 300°C

[14] The method for manufacturing a substrate with a film as described in [13] above, wherein the ultraviolet rays include at least one of ultraviolet rays with a wavelength of 254 nm and ultraviolet rays with a wavelength of 365 nm.

According to the present invention, it is possible to provide a coating liquid for forming a film, a method for producing a coating liquid for forming a film, and a base with a film, which have sufficient hardness after being applied to a substrate, are hard to crack, and are also excellent in chemical resistance. material.

In more detail, the coating liquid for forming a film of the present invention can form a coating solution that exhibits sufficient hardness and scratch resistance by UV treatment and heat treatment at a relatively low temperature of 80 to 300°C, and exhibits high Refractive index (refractive index 1.3~2.3) coating.

According to the method for producing a substrate with a film of the present invention, a film that exhibits sufficient hardness and scratch resistance even for a substrate with poor heat resistance can be formed.

The substrate with a film of the present invention can be suitably used for insulating films used between electrode substrates and alignment films of liquid crystal display devices, protective films on electrodes of touch panels, and the like.

Hereinafter, an embodiment of the coating liquid for film formation, the method for producing the coating liquid for film formation, the base material with a film, and the method for producing the base material with a film of the present invention will be described in detail.

〔Coating liquid for film formation〕

The coating liquid for film formation in this embodiment (hereinafter also simply referred to as "this coating liquid") is an organic compound capable of forming a chelate with a metal alkoxide (component A), represented by the above formula (2) At least one of the hexafunctional silane compound and its hydrolysis condensate (component B), and at least one of the metal alkoxide represented by the above formula (3) and its hydrolysis condensate (component C) is dissolved or dispersed It is made in a mixed solvent containing water and organic solvent.

<A component>

The A component in the coating solution is an organic compound capable of forming a chelate with metal alkoxide.

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、二甲基乙二肟、二甲基乙二肟-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、鉻黑A、鉻黑T、鉻藍黑B、鉻藍黑R、鄰甲酚酞絡合劑、烷醇胺、及羥酸等。 Examples of organic compounds capable of forming a chelate with metal alkoxides include: acetone, trifluoroacetone, hexafluoroacetone, benzylacetone, benzyltrifluoroacetone, and benzhydryl Methane, furanomethanyl acetone, trifluorofuranomethanoyl acetone, benzofuranmethanoyl acetone, thienyl acetone, trifluorothenyl acetone, furanoyl thienyl acetone, Ocine, 2-methyloxycine, 4-methyloxycine, 5-methyloxycine, 6-methyloxycine, 7-methyloxycine, Ocine-5-sulfonic acid, 7-iodooxycine Octane-5-sulfonic acid, quinoline-2-carboxylic acid, quinoline-8-carboxylic acid, 8-hydroxyl

Phytoline, 4-hydroxy-1,5-naphthyridine, 8-hydroxy-1,6-naphthyridine, 8-hydroxy-1,7-naphthyridine, 5-hydroxyquine

Morpholine, 8-hydroxyquinazoline, 2,2'-bipyridine, 2-(2'-thienyl)pyridine, 1,10-phenanthroline, 2-methyl-1,10-phenanthroline, 5-methyl Phenyl-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, dimethylglyoxime-o-methyl, 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 -Pyridylazo) resorcinol, 2-(4'-dimethylaminophenylazo)pyridine, chrome black A, chrome black T, chrome blue black B, chrome blue black R, o-cresolphthalein complex Mixture, alkanolamine, and hydroxy acid, etc.

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

In the above formula (1), R ¹ is an organic group with 1 to 10 carbon atoms. R ² is an organic group or hydroxyl group with 1 to 10 carbon atoms.

Examples of R ¹ include methyl, ethyl, isopropyl, phenyl, furyl, thienyl, trifluoromethyl, methoxy, and ethoxy. As R ¹ , methyl, ethyl, and ethoxy are particularly preferred.

In R ² , examples of the organic group include methyl, ethyl, isopropyl, phenyl, furyl, thienyl, trifluoro, methoxy, and ethoxy.

As the A component, one type may be used or two or more arbitrary types may be mixed and used, but from the viewpoint of the effect as a chelating agent, it is particularly preferable to use acetone.

<B component>

The B component in this coating liquid is the 6-functional silane compound represented by the following formula (2) and its water At least any one of decondensates. In this coating solution, by blending component B, the crack resistance of the coating film is improved, and the chemical resistance or insulation is also improved.

Here, R ³ is an alkylene group having 2 to 6 carbon atoms. In addition, R ⁴ to R ⁹ are 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 One can be the same or different.

As such a hexafunctional silane compound, for example, 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, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(trimethoxysilyl)propane, 1, 2-bis(trimethoxysilyl)butane, 1,2-bis(trimethoxysilyl)pentane, and 1,2-bis(trimethoxysilyl)hexane, etc. One of these may be used, or any two or more of them may be mixed and used. If R ³ is a long chain that is too long, it may be difficult to obtain sufficient hardness. Therefore, as the alkylene group, a carbon number of 2 or more and 6 or less is preferable. In addition, if R ⁴ to R ^{9 are} different from each other, the hydrolysis rate will be different, making it difficult to produce a uniform reaction. Therefore, as the B component, (C ₂ H ₅ O) ₃ -Si-C ₂ H ₄ -Si(OC ₂ H ₅ ) _{3 is} preferably used.

In addition, the weight average molecular weight (in terms of polystyrene) of the component B after the hydrolysis condensation is preferably in the range of 300 or more and 3000 or less from the viewpoint of crack resistance. Here, the weight average molecular weight is obtained by GPC (Gel Permeation Chromatography).

As described above, by blending component B (a hexafunctional silane compound) in this coating solution, the crack resistance of the coating film (film) is improved. It can be considered that the presence of the organic group (alkylene group) possessed by the 6-functional silane compound imparts flexibility to the film, thereby improving the wettability of the substrate (organic material) for film formation. In addition, even when the organic group is partially or completely decomposed by ultraviolet irradiation in the film forming step, it plays a role in alleviating stress concentration, so it is considered that it also contributes to the improvement of crack resistance. In addition, since it is different from silane compounds having substituted alkyl groups such as MTMS (methyltrimethoxysilane), it can achieve compactness without reducing the degree of crosslinking of the film, thereby improving chemical resistance.

Furthermore, in the method for producing the coating liquid for film formation of the present invention, it is preferable to oligomerize component B (hexafunctional silane compound) (weight average molecular weight (in terms of polystyrene) 300 or more and 3000 or less) and then The component C (at least one of the metal alkoxide and its hydrolysis condensate) undergoes co-hydrolysis condensation, and the co-hydrolysis condensate thus obtained is dense and has excellent crack resistance.

<C component>

The C component in this coating liquid is at least any one of the metal alkoxide represented by the following formula (3) and its hydrolysis condensate.

M(OR ¹⁰ ) _n (3)

Here, R ¹⁰ is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms. M series metal element. n is an integer with the same valence as M.

Here, as the metal element M, a metal element other than Si is selected. Specifically, the metal element M can be selected from Be, Al, Sc, Ti, V, Cr, Fe, Ni, Zn, Ga, Ge, As, Se, Y, Zr, Nb, In, Sn, Sb, Te , Hf, Ta, W, Pb, Bi, Ce and At least one element of Cu.

As the metal alkoxide of the component C, for example, aluminum trimethoxide, aluminum triethoxide, aluminum tripropoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, tri-trimethoxide Aluminum butoxide, aluminum tripentoxide, aluminum trihexanoxide, aluminum trioctoxide, aluminum tribenzyloxide, aluminum triphenoxide, aluminum trimethoxyethoxide, aluminum trimethoxyethoxyethoxide, aluminum trimethoxypropoxide , Titanium tetramethoxide, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetramethoxyethoxide, titanium tetrabutoxide, zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetrapropoxide, zirconium tetraisopropoxide , Zirconium tetramethoxyethoxide, zirconium butoxide, niobium pentaethoxide, indium trimethoxide, indium triethoxide, indium tripropoxide, indium triisopropoxide, indium tri-n-butoxide, indium triisobutoxide, third Indium tributoxide, indium tripentoxide, indium trihexanoxide, indium trioctoxide, indium tribenzyloxide, indium triphenyl oxide, indium trimethoxyethoxide, indium trimethoxyethoxyethoxide, trimethoxypropanol Indium, antimony trimethoxide, antimony triethoxide, antimony tripropoxide, antimony triisopropoxide, antimony tri-n-butoxide, and antimony triisobutoxide, etc. These may be used alone or in combination of any two or more of them, but from the viewpoint of proper hydrolysis rate and ease of acquisition, it is preferable to use titanium tetraisopropoxide.

<Mixed solvent>

As the mixed solvent in this coating liquid, a mixed solvent of water and organic solvent is used. At least one of the mixed organic solvents preferably has a boiling point of 120°C or higher. Among them, the boiling point is preferably 300°C or lower. Furthermore, the viscosity of the organic solvent at 20°C is preferably in the range of 1~400mPa‧s, more preferably in the range of 20~350mPa‧s.

As the organic solvent, for example, alcohols such as methanol, ethanol, isopropanol, butanol, diacetone alcohol, furanmethanol, ethylene glycol, and hexylene glycol; and esters such as methyl acetate and ethyl acetate can be mentioned. ; 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, etc. Ethers Acetone, methyl ethyl ketone and other ketones. One of these may be used, or any two or more of them may be mixed and used.

In addition, as this organic solvent in this coating liquid, the organic compound (A component) which can form a chelate compound with a metal alkoxide is excluded.

<D component>

In addition, in this coating liquid, as the D component, at least one of the tetrafunctional silane compound represented by the following formula (4) and its hydrolysis condensate may be further blended.

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 , Can be the same or 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, as a substituted alkoxy group, the group which substituted the hydrogen atom of an unsubstituted alkoxy group with a methyl group, an ethyl group, etc. can be mentioned. As an aryloxy group, a phenoxy group, a naphthoxy group, etc. are mentioned. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

By further blending component D, the hardness of the coating film can be further increased.

As the tetrafunctional silane compound of component D, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetrachlorosilane, and trimethoxysilane can be cited Base silane and so on. As the D component, tetraethoxysilane is particularly preferred.

D component may use only 1 type, and may mix and use 2 or more types arbitrarily.

<The blending ratio of each component in this coating solution>

In this coating liquid, the molar ratio (M1/M3) of the molar number of component A (M1) and the molar number of component C (M3) (M1/M3) must be 0.25 or more and not within the range of 2, preferably 0.5 or more And the range below 1. Here, even when the A component or the C component is hydrolyzed, M1 or M2 is a value based on the structure before hydrolysis.

If the molar ratio (M1/M3) is 2 or more, the A component will be located in most of the OR ¹⁰ part of the C component, and the reaction between the B component and the C component may be inhibited. Therefore, when the film hardens, It may become difficult to form -MO-Si- crosslinks, and the hardness of the obtained film may become insufficient. In addition, the amount of the A component remaining in the film may increase, and electrical characteristics such as the surface resistance of the film may change with time, and reliability may decrease.

In addition, when the molar ratio (M1/M3) is less than 0.25, the reaction of component C becomes excessive, so the stability of the hydrolyzed condensate in the coating solution deteriorates and the life of the coating solution is shortened. It may have a bad influence on the crack resistance of the obtained film.

In addition, the SiO ₂ conversion concentration (concentration C2) derived from the B component is preferably 0.005 to 12% by mass, more preferably 0.01 to 8% by mass. If the concentration C2 is 0.005 mass% or more, the hydrolysis reaction proceeds more smoothly, and when the film is formed, the crack resistance 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.

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

The SiO ₂ conversion concentration (concentration C4) derived from the D component is preferably 0.0001 to 12% by mass, more preferably 0.0005 to 9.5% by mass. If the concentration C4 is 0.0001% by mass or more, the hardness of the film is improved, and if it is 12% by mass or less, it is less likely to cause a decrease in crack resistance, which is more preferable.

The molar ratio (M2/M3) of the molar number of component B (M2) and the molar number of component C (M3) (M2/M3) must be in the range of 0.5 or more and 8 or less, preferably 0.6 or more and 7.5 or less. Here, even when the component B or component C is hydrolyzed, (M2) or (M3) is a value based on the structure before hydrolysis.

If the molar ratio (M2/M3) is less than 0.5, the stability of the coating liquid will decrease, and the life of the coating liquid will be shortened. Therefore, the film thickness, refractive index, and hardness of the obtained film may not be fixedly obtained. Furthermore, there is a possibility that the crack resistance may decrease.

If the molar ratio (M2/M3) exceeds 8, the hardness of the obtained film becomes insufficient, and the crack resistance may still decrease.

In the present coating liquid, the concentration CT (total solid content concentration), which is the total value of the concentration C2 and the concentration 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. If the concentration CT is 0.1% by mass or more, the film thickness obtained under normal coating conditions can be sufficiently thickened, and the need for repeated coating to obtain the film thickness for expressing the effects of the present invention is also reduced. If the concentration CT is 15% by mass or less, the film thickness obtained under normal coating conditions can be controlled to an appropriate thickness, which can easily suppress the occurrence of cracks. In addition, since the stability of the coating solution is also sufficient, the increase in viscosity over time can be suppressed, and the film thickness, refractive index, and hardness of the obtained film can be stably obtained.

The molar number of component D (M4) relative to the molar number of component B (M2) The value of the ear ratio (M4/M2) is preferably in the range of 0.01 or more and 1 or less, and more preferably in the range of 0.01 or more and 0.5 or less. If the molar ratio (M4/M2) is 0.01 or more, the hardness of the film is improved and it is preferable, and if it is 1 or less, it is difficult to cause a decrease in crack resistance, which is preferable.

Here, even when the component B or component D is hydrolyzed, (M2) or (M4) is a value based on the structure before hydrolysis.

In this coating liquid, a part of the B component and a part of the C component may also undergo co-hydrolysis and condensation. That is, the coating solution may also contain a part of the 6-functional silane compound represented by formula (2) and part of its hydrolysis condensate, and a part of the metal alkoxide represented by formula (3) and part of its hydrolysis condensate. Things.

In addition, when the coating solution further contains component D, it may also contain a part of the hexafunctional silane compound represented by formula (2) and its hydrolysis condensate, and the metal alkoxide represented by formula (3) and its hydrolysis A part of the condensate, and a co-hydrolysis condensate of a part of the 4-functional silane compound represented by the formula (4) and a part of the hydrolysis condensate thereof.

In this coating liquid, about 0.2% by mass of the hydrolysis catalyst may remain due to the following production steps of this coating liquid. As such a hydrolysis catalyst, nitric acid etc. are mentioned typically. According to the application of the coating liquid, the hydrolysis catalyst can be removed as needed. Examples of such operations include ion exchange, neutralization, and distillation.

Furthermore, in the coating liquid for film formation of this invention, arbitrary components can be added in the range which does not inhibit the effect. Examples of such optional components include inorganic oxide microparticles, organic resin microparticles, organopolysiloxane resin microparticles, pigments, coloring materials, antistatic agents, and surfactants.

The film obtained from the coating liquid for film formation of the present invention has a view of visibility In terms of point, it is preferably transparent.

[Method of manufacturing this coating liquid]

The manufacturing method of the coating liquid is characterized by including the following preliminary steps 1, preliminary steps 2, and formal steps.

Preliminary step 1: Blending organic solvent, water, component B (hexafunctional silane compound represented by formula (2)), and hydrolysis catalyst to prepare a hexafunctional silane solution (wherein, the blending amount of component B is relative to 1 mol of C component metal in preliminary step 2 is in the range of 0.5 mol or more and 8 mol)

(In this application, the solution containing at least one of the 6-functional silane compound and its hydrolysis condensate prepared by the preliminary step 1 is called "6-functional silane solution")

Preliminary step 2: Blending organic solvent, component A, and component C (metal alkoxide represented by formula (3)) to prepare a metal alkoxide solution (wherein component A is relative to the metal element M of component C 1 mol, which is more than 0.25 mol and not within the range of 2 mol)

(In this application, the solution containing at least one of the metal alkoxide and its hydrolysis condensate prepared by the preliminary step 2 is referred to as the "metal alkoxide solution")

Formal step: Add the metal alkoxide solution obtained in the preliminary step 2 to the 6-functional silane solution obtained in the preliminary step 1, and then add water, stir and mix at a temperature above 5°C and below 40°C step

Regarding the above steps, the preferred implementation aspects are described in detail below.

<Preliminary Step 1>

In preliminary step 1, in an organic solvent, in the presence of water and a hydrolysis medium, the hexafunctional silane compound as component B is hydrolyzed and condensed to prepare water of the hexafunctional silane compound The decondensate is dispersed in a mixed solvent to form a 6-functional silane solution.

As the hydrolysis catalyst, conventionally known catalysts can be used. Examples of this include (a) inorganic acids such as nitric acid, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and hydrogen fluoride, and (b) oxalic acid and maleic acid. Such as carboxylic acids, (c) sulfonic acids such as methanesulfonic acid, and (d) acidic or weakly acidic inorganic salts, etc., but are not limited to these. Moreover, it is also possible to arbitrarily mix and use plural kinds of these catalysts.

The amount of the hydrolysis catalyst is preferably within the range of 0.001 to 1 mol% in terms of an additional ratio relative to the 6-functional silane compound of component B (in terms of SiO ₂ ).

The amount of water used is preferably in the range of 0.5-4 mol relative to 1 mol (calculated as SiO ₂ ) of the 6-functional silane compound of component B, in addition to the ratio. If it is in the range of the molar ratio, it is more effective in effectively promoting the hydrolysis of the hexafunctional silane compound of the B component. Furthermore, the amount of water used is more preferably in the range of 1 to 3 moles.

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

In preliminary step 1, usually add water, hydrolysis catalyst and component B (hexafunctional silane compound represented by formula (2)) to an organic solvent, and stir at 5-40°C for 5 to 120 minutes to prepare hexafunctional silane Solution.

Furthermore, when the component D is further blended, blending is performed in this preliminary step 1. The preferred blending amount is as described above.

<Preliminary Step 2>

In the preliminary step 2, the A component and the C component (metal alkoxide represented by formula (3)) are added to the organic solvent, and a metal alkoxide solution containing the metal alkoxide or its hydrolysis condensate is prepared by stirring . The preferred organic solvent is as described above. Also, as a component of A or C For example, the above-mentioned compounds can be suitably cited.

The molar ratio (M1/M3) of the molar number of component A (M1) to the molar number (M3) of component C in the preliminary step 2 must be 0.25 or more and not within the range of 2. In preliminary step 2, component A is assigned to the alkoxy group of component C, but as long as the molar ratio (M1/M3) is 0.25 or more and less than the range of 2, it is not assigned to the chelate of component A Since the metal alkoxide of the ligand remains, it is preferable in terms of controlling 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 or less.

When the molar ratio (M1/M3) is 2 or more, due to the excessive coordination of the alkoxy group of the metal alkoxide, the stabilization of the metal alkoxide becomes too high. Co-hydrolysis and condensation of functional silanes etc. may affect it and may become unsuitable for low-temperature curing (80-300°C) of coating liquids for film formation.

The MO _X converted concentration of component C in the preliminary step 2 is preferably in the range of 0.04 to 9.5% by mass.

The metal alkoxide solution prepared by the preliminary step 2 contains a metal alkoxide coordinated with component A or a hydrolysis condensate thereof.

[Official steps]

Add the metal alkoxide solution prepared in the preliminary step 2 to the 6-functional silane solution prepared in the preliminary step 1, and then add water, stir and mix at 5-40°C to prepare the coating solution.

Here, the molar number (M2) of the component B and the molar number (M3) of the component C preferably satisfy the range of the molar ratio (M2/M3) of 0.5 or more and 8 or less. The reason is that if the molar ratio (M2/M3) is in this range, the cohydrolysis reaction proceeds smoothly.

By the addition of the above water, the co-hydrolysis condensation reaction of the hydrolysis condensate of the hexafunctional silane and the metal alkoxide and/or the hydrolysis condensate thereof can be promoted, so a dense film can be obtained, which is preferable.

〔Method of manufacturing substrate with film〕

The method of manufacturing a substrate with a film of this embodiment is characterized in that the following film-forming step 1 to film-forming step 4 are carried out.

Film formation step 1: The step of applying the coating liquid to the substrate

Film-forming step 2: Following the above-mentioned film-forming step 1, the step of heating and drying the substrate at a temperature above 80°C and below 150°C

Film forming step 3: Following the above film forming step 2, the step of irradiating the substrate with ultraviolet rays

Film-forming step 4: Following the above-mentioned film-forming step 3, the step of heating the above-mentioned substrate at a temperature above 80°C and below 300°C

Regarding the above-mentioned film forming steps, preferred implementation aspects are described in detail below.

<Film forming step 1>

In the film formation step 1, the coating liquid is applied to the substrate. As the coating method, conventionally known methods such as 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. Examples of the above-mentioned substrate include glass, a substrate processed with an ITO film, and a sheet, film, and panel using materials such as polycarbonate, acrylic resin, PET, and TAC.

<Film forming step 2>

The heating and drying temperature is not particularly limited as long as the required strength, hardness, scratch resistance, etc. are obtained without deteriorating the substrate, and it is preferably in the range of 80 to 150°C, more preferably 90 The range of ~140℃. Moreover, it is preferable that heating and drying last about 1-10 minutes.

There is no clear boundary between drying and heating. As long as a film with required hardness and strength can be obtained, drying and heating can be performed in a short time, or heating can be performed at a temperature higher than the drying temperature after drying.

As the drying method or heating method, a conventionally known method can be used. In addition, electromagnetic wave irradiation treatment may be used in combination.

When the drying temperature and heating temperature are less than 80°C, sufficient film strength cannot be obtained due to residual solvent or insufficient cross-linking of -MOM- or -MO-Si-. If the heating and drying temperature exceeds 350°C, there will be The organic base of component B is decomposed, and the target film characteristics cannot be obtained.

<Film forming step 3>

In the film forming step 3, following the film forming step 2, the heat-dried film is irradiated with ultraviolet (UV). For example, use a 2kw high-pressure mercury lamp to irradiate 3,000mJ/cm ² of ultraviolet rays. By UV irradiation, the A component is desorbed in the heated and dried film, and the film becomes easily crosslinked in the film formation step 4. As ultraviolet rays, from the viewpoint of removing residual solvent or promoting cross-linking of -MOM- or -MO-Si-, it is preferable to include at least one of ultraviolet rays with a wavelength of 254 nm and ultraviolet rays with a wavelength of 365 nm. In particular, it is more preferable to include both ultraviolet rays with a wavelength of 254 nm and ultraviolet rays with a wavelength of 365 nm.

<Film forming step 4>

Following the film formation step 3, as the film formation step 4, the film is heated in the range of 80 to 300°C. By this heating, the film becomes a state in which crosslinking proceeds sufficiently. If the heating temperature is in the range of 80 to 300°C, it is advantageous, for example, in terms of suppressing the resistance change of the ITO wiring. Furthermore, the heating time is preferably set to 1 to 10 minutes.

〔Substrate with film〕

The substrate with a film in this embodiment is used in display elements such as touch panels, which can suppress wiring visibility, and has high pencil hardness, chemical resistance, and insulation. In addition, if the coating liquid for forming a film in this embodiment is used, there is almost no occurrence of cracks in the coating film, and it can be cured at a relatively low temperature.

Here, the average film thickness (T) of the film in the film base material obtained by the above-mentioned film forming step is preferably in the range of 20 to 200 nm, more preferably in the range of 40 to 150 nm.

If the average film thickness (T) of the film is 20 nm or more, the film thickness is sufficient, and therefore it is difficult to produce a portion where the film cannot be formed (uneven coating), and the effect after film formation can be sufficiently obtained. On the other hand, if the average film thickness (T) of the film is 200 nm or less, the generation of cracks can be sufficiently suppressed, and the strength and hardness of the film also become sufficient.

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

[Example]

The following examples are used to describe the coating liquid for forming a transparent film and the substrate with the film, but the present invention is not limited by these examples.

[Example 1]

The steps for producing the coating liquid for film formation and the substrate with the film are as follows. Table 1 shows the types and amounts of each component blended.

(Preliminary Step 1)

4,673.08 g of hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.), 214.07 g of pure water, and 3.57 g of nitric acid with a concentration of 60% by mass were mixed and stirred for 5 minutes. Next, while stirring, 1055.55 g of 1,2-bis(triethoxysilyl)ethane (manufactured by YAMANAKA HUTECH (Co., Ltd.): SiO ₂ concentration 33.8% by mass), which is a hexafunctional silane compound of component B, is added, The mixture was stirred for 30 minutes to prepare a preparation solution 1-1 with a solid content concentration of 6.0% by mass.

(Preliminary Step 2)

Hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 2966.06 g, acetone acetone (manufactured by Wako Pure Chemical Industries, Ltd.) as component A, which is a carbonyl group-containing organic compound, and 148.66 g, as component C metal alkane 849.47 g of ORGATIX TA-10 of oxide (manufactured by Matsumoto Fine Chemical Co., Ltd.: 28% by mass TiO ₂ ) was mixed and stirred for 5 minutes to prepare a preparation solution 2-1 with a solid content concentration of 6.0% by mass.

(Official steps)

While stirring, the preparation liquid 2-1 was mixed with the preparation liquid 1-1, and after stirring for 10 minutes, 49.55 g of pure water was added, and the mixture was 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 to prepare a coating solution (1) for film formation with a total solid content concentration of 6.0% by mass.

(Manufacturing of base material (1) with film)

The coating solution for film formation (1) was coated on a glass substrate with ITO film (manufactured by AGC Fabritech (Co., Ltd.), thickness: 1.1mm) by a flexible printing method, dried at 90°C for 5 minutes, and the irradiation wavelength was 365nm. After the ultraviolet light (3000mJ/cm ² ) and the ultraviolet light (2000mJ/cm ² ) with a wavelength of 254nm (2000mJ/cm ² ), heat at 230°C for 30 minutes to prepare a substrate (1-1) with a film.

With respect to the obtained substrate (1-1) with a film, the film thickness, pencil hardness, surface resistance, and chemical resistance were measured by the following methods. The results are shown in Table 1.

In addition, a 2 μm acrylic resin layer was formed on a glass substrate with a silicon oxide film (manufactured by AGC Fabritech Co., Ltd., thickness: 1.1 mm). The acrylic resin layer was applied using a bar coater (No. 3), followed by drying at 90°C for 5 minutes, and then heating at 230°C for 30 minutes. The coating solution for film formation (1) was coated on the glass substrate with acrylic resin layer by a flexible printing method, dried at 90°C for 5 minutes, and then irradiated with 3000mJ/cm ² of ultraviolet rays (wavelength 365nm) at 230°C Heat for 30 minutes to prepare a substrate (1-2) with a film.

Regarding the obtained substrate (1-2) with a film, the crack resistance was measured by the following method. The results are shown in Table 1.

In addition, the coating solution for film formation (1) was coated on a 6-inch silicon wafer (manufactured by Matsuzaki Manufacturing Co., Ltd., thickness: 0.625 mm) by a flexible printing method, dried at 90°C for 5 minutes, and then irradiated After 3000mJ/cm ² of ultraviolet (wavelength: 365nm), heat at 230°C for 30 minutes to prepare a substrate (1-3) with a film.

Regarding the obtained substrate (1-3) with a film, the refractive index was measured by the following method. The results are shown in Table 1.

[Example 2]

Except for the following preliminary steps, in the same manner as in Example 1, a coating liquid (2) for forming a film was prepared, and further substrates (2-1) to (2-3) with a film were manufactured. After that, evaluation was performed in the same manner as in Example 1.

(Preliminary Step 1)

5,841.36 g of hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.), 267.58 g of pure water, and 4.46 g of nitric acid with a concentration of 60% by mass were mixed and stirred for 5 minutes. Next, while stirring, 1,2-bis(triethoxysilyl)ethane (manufactured by YAMANAKA HUTECH (Co., Ltd.): SiO ₂ concentration 33.8% by mass), which is the 6-functional silane compound of component B, was added 1319.44 g , Stirred for 30 minutes to prepare a preparation solution 1-2 with a solid content of 6.0% by mass.

(Preliminary Step 2)

Hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 1853.78 g, acetone acetone (manufactured by Wako Pure Chemical Industries, Ltd.) as component A, which is a carbonyl-containing organic compound, 92.91 g, and metal alkane as component C 530.92 g of ORGATIX TA-10 (manufactured by Matsumoto Fine Chemical Co., Ltd.: 28% by mass of TiO ₂ ) of oxide was mixed and stirred for 5 minutes to prepare preparation 2-2 with a solid content of 6.0% by mass.

[Example 3]

Except for the following preliminary steps, in the same manner as in Example 1, a coating liquid (3) for forming a film was prepared, and further substrates (3-1) to (3-3) with a film were prepared. After that, evaluation was performed in the same manner as in Example 1.

(Preliminary Step 1)

Hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.), 6620.20 g, 303.26 g of pure water, and 5.05 g of nitric acid with a concentration of 60% by mass were mixed and stirred for 5 minutes. Next, while stirring, 1,2-bis(triethoxysilyl)ethane (manufactured by YAMANAKA HUTECH (Co., Ltd.): SiO ₂ concentration 33.8% by mass), which is a 6-functional silane compound of component B, was added 1495.36 g , Stirred for 30 minutes to prepare preparations 1-3 with a solid content concentration of 6.0% by mass.

(Preliminary Step 2)

Hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 1112.27 g, acetone acetone (manufactured by Wako Pure Chemical Industries, Ltd.) as component A, which is a carbonyl group-containing organic compound, 55.75 g, and metal alkane as component C 318.55 g of ORGATIX TA-10 (manufactured by Matsumoto Fine Chemical Co., Ltd.: TiO ₂ concentration 28% by mass) of oxide was mixed and stirred for 5 minutes to prepare a preparation solution 2-3 with a solid content concentration of 6.0% by mass.

[Example 4]

Except for the following preliminary steps, in the same manner as in Example 1, a coating liquid (4) for forming a film was prepared, and further substrates (4-1) to (4-3) with a film were manufactured. After that, evaluation was performed in the same manner as in Example 1.

(Preliminary Step 1)

Hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 2336.54 g, pure water 107.03 g, and 1.78 g of nitric acid with a concentration of 60% by mass were mixed, and stirred for 5 minutes. Next, while stirring, 527.78 g of 1,2-bis(triethoxysilyl)ethane (manufactured by YAMANAKA HUTECH (Co., Ltd.): SiO ₂ concentration 33.8% by mass), which is a hexafunctional silane compound of component B, was added , Stirred for 30 minutes to prepare preparations 1-4 with a solid content concentration of 6.0% by mass.

(Preliminary Step 2)

Hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 5190.60 g, acetone acetone (manufactured by Wako Pure Chemical Industries, Ltd.) as component A, a carbonyl-containing organic compound, 260.15 g, and metal alkane as component C 1486.57 g of oxide ORGATIX TA-10 (manufactured by Matsumoto Fine Chemical Co., Ltd.: 28% by mass TiO ₂ ) was mixed and stirred for 5 minutes to prepare a preparation solution 2-4 with a solid content concentration of 6.0% by mass.

[Example 5]

Except for the following preliminary steps, in the same manner as in Example 1, a coating liquid (5) for forming a film was prepared, and further substrates (5-1) to (5-3) with a film were manufactured. After that, evaluation was performed in the same manner as in Example 1.

(Preliminary Step 1)

4612.00 g of hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.), 214.07 g of pure water, and 3.57 g of nitric acid with a concentration of 60% by mass were mixed, and stirred for 5 minutes. Next, while stirring, 703.7g of 1,2-bis(triethoxysilyl)ethane (manufactured by YAMANAKA HUTECH (Co., Ltd.): SiO ₂ concentration 33.8% by mass), which is a 6-functional silane compound of component B, is added , And 412.94g of ethyl silicate (manufactured by Tama Chemical Co., Ltd.: SiO ₂ concentration 28.8% by mass) as a tetrafunctional silane compound of D component, stirred for 30 minutes to prepare a preparation solution with a solid content concentration of 6.0% by mass 1-5.

(Preliminary Step 2)

Hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 2966.06 g, acetone acetone (manufactured by Wako Pure Chemical Industries, Ltd.) as component A, which is a carbonyl group-containing organic compound, and 148.66 g, as component C metal alkane 849.47 g of ORGATIX TA-10 (manufactured by Matsumoto Fine Chemical Co., Ltd.: 28% by mass of TiO ₂ ) of oxide was mixed and stirred for 5 minutes to prepare preparation 2-5 with a solid content of 6.0% by mass.

[Example 6]

Except for the following preliminary steps, in the same manner as in Example 1, a coating liquid (6) for forming a film was prepared, and further substrates with a film (6-1) to (6-3) were manufactured.

After that, evaluation was performed in the same manner as in Example 1.

(Preliminary Step 1)

4612.00 g of hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.), 214.07 g of pure water, and 3.57 g of nitric acid with a concentration of 60% by mass were mixed, and stirred for 5 minutes. Next, while stirring, 1,2-bis(triethoxysilyl)ethane (manufactured by YAMANAKA HUTECH (Co., Ltd.): SiO ₂ concentration 33.8% by mass), which is a 6-functional silane compound of component B, was added 703.7 g And 352.89g of methyltrimethoxysilane as a trifunctional silane compound (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-13, SiO ₂ concentration 33.7 mass%), stirred for 30 minutes, and prepared solid content concentration 6.0 mass % Of preparation solution 1-6.

(Preliminary Step 2)

Hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 2966.06 g, acetone acetone (manufactured by Wako Pure Chemical Industries, Ltd.) as component A, which is a carbonyl group-containing organic compound, and 148.66 g, as component C metal alkane 849.47 g of ORGATIX TA-10 (manufactured by Matsumoto Fine Chemical Co., Ltd.: 28% by mass of TiO ₂ ) of oxide was mixed and stirred for 5 minutes to prepare preparation 2-6 with a solid content of 6.0% by mass.

[Comparative Example 1]

Except for the following preliminary steps, in the same manner as in Example 1, a coating liquid (7) for forming a film was prepared, and further substrates with a film (7-1) to (7-3) were manufactured. After that, evaluation was performed in the same manner as in Example 1.

(Preliminary Step 1)

6737.03 g of hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.), 308.61 g of pure water, and 5.14 g of nitric acid with a concentration of 60% by mass were mixed, and stirred for 5 minutes. Next, while stirring, 1521.75g of 1,2-bis(triethoxysilyl)ethane (manufactured by YAMANAKA HUTECH (Co., Ltd.): SiO ₂ concentration 33.8% by mass), which is a 6-functional silane compound of component B, is added , Stirred for 30 minutes to prepare preparation 1-7 with a solid content concentration of 6.0% by mass.

(Preliminary Step 2)

1001.04 g of hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.), 50.17 g of acetone acetone (manufactured by Wako Pure Chemical Industries, Ltd.) as the carbonyl-containing organic compound as component A, and metal alkane as component C 286.70 g of ORGATIX TA-10 of oxide (manufactured by Matsumoto Fine Chemical Co., Ltd.: 28% by mass TiO ₂ ) was mixed and stirred for 5 minutes to prepare preparation 2-7 with a solid content concentration of 6.0% by mass.

[Comparative Example 2]

Except for the following preliminary steps, in the same manner as in Example 1, a coating liquid (8) for forming a film was prepared, and further substrates with a film (8-1) to (8-3) were manufactured. After that, evaluation was performed in the same manner as in Example 1.

(Preliminary Step 1)

Hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.), 1,791.35 g, 82.06 g of pure water, and 1.37 g of nitric acid with a concentration of 60% by mass were mixed and stirred for 5 minutes. Next, while stirring, 404.63g of 1,2-bis(triethoxysilyl)ethane (manufactured by YAMANAKA HUTECH (Co., Ltd.): SiO ₂ concentration 33.8% by mass), which is a 6-functional silane compound of component B, was added. , Stir for 30 minutes to prepare preparation solution 1-8 with a solid content concentration of 6.0% by mass.

(Preliminary Step 2)

Hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 5709.66 g, acetone acetone (manufactured by Wako Pure Chemical Industries, Ltd.) as component A, which is a carbonyl-containing organic compound, 286.16 g, and metal alkane as component C 1635.22 g of oxide ORGATIX TA-10 (manufactured by Matsumoto Fine Chemical Co., Ltd.: 28 mass% TiO ₂ concentration) was mixed and stirred for 5 minutes to prepare preparation 2-8 with a solid content concentration of 6.0 mass%.

[Comparative Example 3]

Except for the following preliminary steps, in the same manner as in Example 1, a coating liquid (9) for forming a film was prepared, and further substrates with a film (9-1) to (9-3) were manufactured. After that, the same as in Example 1 Make an evaluation.

(Preliminary Step 1)

Hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 4669.95 g, 214.07 g of pure water, and 3.57 g of nitric acid with a concentration of 60% by mass were mixed and stirred for 5 minutes. Next, while stirring, 1055.68 g of ethyl silicate (manufactured by Tama Chemical Co., Ltd.: SiO ₂ concentration 28.8% by mass) as a silane compound was added and stirred for 30 minutes to prepare a preparation solution with a solid content concentration of 6.0% by mass 1-9.

(Preliminary Step 2)

Hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 2966.06 g, acetone acetone (manufactured by Wako Pure Chemical Industries, Ltd.) as component A, which is a carbonyl group-containing organic compound, and 148.66 g, as component C metal alkane 849.47 g of ORGATIX TA-10 (manufactured by Matsumoto Fine Chemical Co., Ltd.: 28% by mass TiO ₂ ) of oxide was mixed and stirred for 5 minutes to prepare preparation 2-9 with a solid content concentration of 6.0% by mass.

[Evaluation items, evaluation methods]

The following evaluations were performed on the substrate with a film obtained in each Example and each Comparative Example. Moreover, regarding the coating liquid for film formation, the stability with time was evaluated as follows. The results are shown in Table 1.

(1) Film thickness

The measurement was performed with a surface roughness measuring machine (manufactured by Tokyo Seiki Co., Ltd.: SURFCOM).

(2) Surface resistance value

The surface resistance value is measured by a surface resistance measuring machine (Mitsubishi Chemical ANALYTECH (Stock Company) Co., Ltd.) manufactured: Hiresta UXMCP-HT800) for measurement.

(3) Crack resistance of coating film

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

◎: No cracks are seen in the coating surface

○: A small amount of cracks are seen at the edge

×: Cracks occur in the coated surface

(4) Pencil hardness

It is measured with a pencil hardness tester in accordance with JIS-K-5600. That is, the pencil is set at an angle of 45 degrees with respect to the surface of the film, a specific load is applied, and it is stretched at a fixed speed to observe whether there is damage.

(5) Refractive index

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

(6) Chemical resistance

Dip each substrate with a film in a mixed solution of phosphoric acid/nitric acid/acetic acid/water (mass ratio: 80/5/5/10) heated to 40°C for 5 minutes, and rinse with pure water. After that, the substrate with the film was immersed in a mixture of diethylene glycol monobutyl ether/2-aminoethanol (mass ratio: 70/30) heated to 60°C for 5 minutes, and observed by visual inspection and an optical microscope The state of the coated film after washing with pure water is evaluated for chemical resistance according to the following criteria.

○: No change in coating film

×: peeling or cracking of the coating film

(7) Stability of the coating liquid over time

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

◎: No change in viscosity

○: A slight increase in viscosity is visible (less than 5mPa‧s)

×: A clear increase in viscosity is visible (above 5mPa‧s)

〔Evaluation results〕

As shown in Table 1, it can be seen from Examples 1 to 6 that the substrate with a film produced using the coating liquid for film formation of the present invention has excellent surface hardness, crack resistance, and chemical resistance.

On the other hand, it is known from Comparative Examples 1 to 3 that if a coating liquid for forming a film that does not have the structure of the present invention is used, all of surface hardness, crack resistance, and chemical resistance cannot be satisfied.

Claims (9)

A coating liquid for forming a film, which combines at least one of an organic compound capable of forming a chelate with a metal alkoxide (component A), a hexafunctional silane compound represented by the following formula (2), and its hydrolysis condensate (Component B), and at least one of the metal alkoxide represented by the following formula (3) and its hydrolysis condensate (Component C) dissolved or dispersed in a mixed solvent containing water and an organic solvent The coating liquid is characterized in that the molar ratio (M1/M3) of the molar number (M1) of the component A and the molar number (M3) of the component C is 0.25 or more and not within the range of 2, and the component B The molar ratio (M2/M3) of the molar number (M2) and the molar number (M3) of the above component C is in the range of 0.5 or more and 8 or less,

(R ³ is an alkylene group with 2 to 6 carbons; R ⁴ to R ⁹ is an unsubstituted or substituted alkoxy group with a carbon number of 1 to 8, unsubstituted or substituted aryloxy, ethylene oxide Any of groups, hydroxyl groups, hydrogen atoms, and halogen atoms may be the same or different) M(OR ¹⁰ ) _n (3) (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, Ta, W, Pb, Bi, Ce, and Cu; R ¹⁰ series An unsubstituted or substituted alkyl group having 1 to 10 carbon atoms; n is an integer with the same valence as M). For example, the coating liquid for film formation in the first item of the scope of patent application, wherein the SiO ₂ conversion concentration (concentration C2) derived from the above B component is in the range of 0.005 to 12 mass%, and the MO _X conversion concentration derived from the above C component ( The concentration C3) is in the range of 0.02-14% by mass, and the sum of the above-mentioned concentration C2 and the above-mentioned concentration C3 (concentration CT) is in the range of 0.1-15% by mass. For example, the coating liquid for forming a film of the first item in the scope of the patent application, which further contains at least one of the tetrafunctional silane compound represented by the following formula (4) and its hydrolysis condensate (component D), the above-mentioned component D The molar ratio (M4/M2) of the ear number (M4) relative to the molar number (M2) of the B component above is 0.01 or more and 1 or less, Si(R ¹¹ ) ₄ (4) (R ¹¹ series 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 may be the same or Can be different). For example, the coating liquid for coating film formation in the third item of the scope of patent application, wherein the SiO ₂ conversion concentration (concentration C2) derived from the above B component is 0.005 to 12 mass%, and the MO _X conversion concentration derived from the above C component (concentration C3) ) Is 0.02-14% by mass, the SiO ₂ conversion concentration derived from the above D component (concentration C4) is 12% by mass or less, and the total of the above concentration C2, the above concentration C3, and the above concentration C4 (concentration CT) is 0.1 to 15 quality%. For example, the coating liquid for film formation in the first item of the scope of patent application, wherein the above organic solvent is The boiling point is above 120℃, and the viscosity at 20℃ is in the range of 1~400mPa‧s. A method for manufacturing a coating liquid for film formation is the method for manufacturing a coating liquid for film formation in any one of the 1 to 5 patents, and implements the following preliminary steps 1, preliminary steps 2, and formal steps: preparation Step 1: Blending organic solvent, water, hexafunctional silane compound (component B) represented by formula (2), and hydrolysis catalyst to prepare a hexafunctional silane solution (wherein, the blending amount of the above component B is relative to The element M 1 mol of component C in the preliminary step 2 is within the range of 0.5 mol or more and 8 mol or less); preliminary step 2: blending organic solvent, component A, and metal alkane represented by formula (3) Oxide (component C), a step of preparing a metal alkoxide solution (wherein, the blending amount of the above component A relative to the element M of the above component C is 1 mol, which is 0.25 mol or more and less than 2 mol ); Formal step: Add the above-mentioned metal alkoxide solution obtained by the above-mentioned preliminary step 2 to the above-mentioned 6-functional silane solution obtained by the above-mentioned preliminary step 1, and then add water at a temperature above 5°C and below 40°C Step of stirring and mixing at temperature;

(R ³ is an alkylene group with 2 to 6 carbons; R ⁴ to R ⁹ is an unsubstituted or substituted alkoxy group with a carbon number of 1 to 8, unsubstituted or substituted aryloxy, ethylene oxide Any of radicals, hydroxyl groups, hydrogen atoms, and halogen atoms may be the same or different) M(OR ¹⁰ ) _n (3) (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, Ta, W, Pb, Bi, Ce, and Cu; R ¹⁰ series Unsubstituted or substituted alkyl having 1 to 10 carbon atoms; n is an integer with the same valence of M). For example, the method for producing a coating liquid for forming a film in the scope of the patent application, wherein the weight average molecular weight (in terms of polystyrene) of the B component after hydrolysis and condensation is in the range of 300 or more and 3000 or less. The method for producing a coating liquid for forming a coating film in the scope of the patent application, wherein, in the above preliminary step 1, the tetrafunctional silane compound (component D) represented by formula (4) is further added, and the component D is The molar ratio (M4/M2) of the ear number (M4) to the molar number (M2) of the above B component is 0.01 or more and 0.5 or less. Si(R ¹¹ ) ₄ (4) (R ¹¹ is the carbon number Any one of 1 to 8 unsubstituted or substituted alkoxy, unsubstituted or substituted aryloxy, vinyloxy, hydroxyl, hydrogen atom, and halogen atom, which may be the same or different ). A substrate with a film, which is formed by applying the coating liquid for forming a film of any one of the scope of the patent application to the substrate.