JPH10206905A - Uv-absorbing transparent conductive substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a transparent conductive substrate having excellent UV- shielding performance by forming a UV-absorbing layer between a transparent substrate and a transparent electrode and by forming the UV-absorbing layer by applying and hardening a component prepared by the reaction of an aminosilane compd. and a UV-absorbent having carboxyl groups in the molecule to produce amide bonds on the transparent substrate. SOLUTION: A transparent conductive substrate is obtd. by successively forming a transparent substrate 1, a UV-absorbing layer 2, an overcoat layer 3 and a transparent conductive film 4. Namely, the UV-absorbing layer 4 is formed between the transparent substrate 1 and the transparent conductive film 4, and the UV-absorbing layer 4 is formed by applying and hardening a component prepared by the reaction of at least an aminosilane compd. or its deriv. and a UV-absorbent having carboxyl groups in the molecule to produce amide bonds derived from the aminosilane compd. or its deriv. on the transparent substrate 1. Therefore, the transparent conductive substrate having both of high conductivity and excellent shielding effect against UV rays can be obtd. at a low cost.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent conductive substrate provided with a function of blocking ultraviolet rays, which is useful as various electric devices.

[0002]

2. Description of the Related Art An electric device using a liquid crystal or an electrochromic material is deteriorated by irradiation with ultraviolet rays. In order to prevent this, if an ultraviolet blocking layer is provided under the transparent conductive film, it does not affect the abrasion resistance of the glass constituting the device. However, the production of a transparent conductive film such as ITO requires a high degree of vacuum and a high temperature, and an ultraviolet absorbing layer containing an organic ultraviolet absorbing agent alone cannot withstand this condition, and the ultraviolet absorbing agent volatilizes. Performance could not be obtained. Therefore, for example, as disclosed in Japanese Patent Application Laid-Open No. 1-276120, attempts have been made to provide an ultraviolet absorbing layer on the outside of the device and cover the layer with another glass. However, the structure is complicated and the number of steps is increased. Further, in the case where a dichroic layer is provided as disclosed in JP-A-63-236016, there is a problem that the cost is high. When an ultraviolet absorbing layer made of a metal oxide is used as in Japanese Patent Application Laid-Open No. 62-148339, it is difficult to sufficiently cut the near ultraviolet region. SUMMARY OF THE INVENTION An object of the present invention is to provide a transparent conductive substrate having a relatively simple structure having excellent ultraviolet blocking ability at a low cost.

[0003]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the object, and as a result, have found a novel transparent conductive substrate having a specific ultraviolet absorbing layer. That is, according to the present invention, at least, a transparent conductive substrate composed of a transparent substrate and a transparent conductive film, having an ultraviolet absorbing layer containing an organic ultraviolet absorber between the transparent substrate and the transparent conductive film, The ultraviolet absorbing layer comprises at least (a) an aminosilane compound represented by the following general formula (1) or a derivative thereof (hereinafter, referred to as an aminosilane compound).
A component that is formed by reacting (b) a UV absorber having a carboxyl group in the molecule (hereinafter referred to as “component B”) to form an amide bond,
There is provided an ultraviolet-absorbing transparent conductive substrate, which is produced by applying and curing on a transparent substrate. Further, according to the present invention, there is provided an ultraviolet-absorbing transparent conductive substrate having an overcoat layer between the ultraviolet-absorbing layer and the transparent conductive film.

Embedded image In addition, each substituent of the general formula (1) will be described later.

[0004]

DETAILED DESCRIPTION OF THE INVENTION The ultraviolet absorbing transparent conductive substrate of the present invention has at least an ultraviolet absorbing layer between the transparent substrate and the transparent conductive film. As a preferred embodiment, an overcoat layer is provided between the ultraviolet absorbing layer and the transparent conductive film. The transparent substrate used in the present invention is not particularly limited, for example, colorless or colored glass, other than tempered glass is used,
A colorless or colored resin having transparency can be used.
Specific examples include polyethylene terephthalate, polyamide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylenesulfide, polycarbonate, polyimide, polymethylmethacrylate, polystyrene, and the like. Transparent in the present invention means having a visible light transmittance of usually 3% or more, preferably 10 to 100%. Further, the substrate in the present invention has a smooth surface at room temperature,
The surface may be flat or curved, or may be deformed by stress. The transparent conductive film used in the present invention is not particularly limited as long as it satisfies transparency, and examples thereof include a metal thin film of gold, silver or the like, and a conductive film made of a metal oxide. As the metal oxide, for example, ITO (In ₂ O ₃ —SnO ₂ ), tin oxide, zinc oxide, vanadium oxide and the like are used. The film thickness is usually 100 to 5000 angstroms, preferably 500 to 3000 angstroms. The surface resistance (resistivity) is appropriately selected depending on the use of the substrate of the present invention, and is usually 0.5 to 500 Ω / cm.
² , preferably ² to 50 Ω / cm ² . The method for forming the transparent conductive film is not particularly limited, and a known method is appropriately selected and used depending on the type of the metal or metal oxide used as the conductive layer. Usually, a vacuum deposition method, an ion plating method, or the like is used. Method, sputtering method or sol-gel method is used. In each case, the substrate temperature was 10
It is desirable to form within the range of 0 to 350 ° C.

The aminosilane compound used as component A in the present invention is represented by the following general formula (1).

Embedded image In the general formula (1), R ¹ is an alkylene group having 1 to 10, preferably 1 to 5 carbon atoms, or a general formula-(CH ₂ )
_m- NH- [m is a divalent group represented by 1 ≦ m ≦ 4]. Specific examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group. Each R ² is the same or different, and includes a hydrogen atom, a hydroxyl group, a halogen atom such as chlorine and bromine,
An alkyl or alkoxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, or 6 to 10 carbon atoms, preferably 6 carbon atoms
To 8 aryl groups. However, at least one of all R ² is an alkoxy group or a hydroxyl group. Examples of the alkyl group of R ² include a methyl group, an ethyl group, a propyl group, and an i-propyl group, and examples of the aryl group include a phenyl group and a tolyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and an i-propoxy group. n is n ≧ 0, preferably 0
≤n≤3. Preferred examples of the aminosilane compound represented by the general formula (1) include 3-aminopropyltriethoxysilane, 3-aminopropyldiisopropylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrichlorosilane, -
Examples include aminopropyl polydimethylsiloxane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltris (methoxyethoxyethoxy) silane, and the like. In the present invention, a derivative of the aminosilane compound can be used as the component A,
Preferred examples of the derivative include a hydrolyzate of the above-mentioned suitable aminosilane compound. These aminosilane compounds or derivatives thereof can be produced by a known method. The ultraviolet absorber having a carboxyl group in the molecule used as the component B is a compound having one or two or more carboxyl groups in a side chain of the molecule, for example, a compound having a benzotriazole skeleton or a benzophenone skeleton. Can be As the compound having a benzotriazole skeleton, a compound represented by the following general formula (2) is preferably exemplified.

Embedded image In the general formula (2), R ³ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 10, preferably 1 to 6 carbon atoms. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, and a cyclohexyl group. The substitution position of R ³ is the 4-position or 5-position of the benzotriazole skeleton, and the halogen atom and the alkyl group are usually located at the 4-position. R in the formula
⁴ is a hydrogen atom or carbon number 1 to 10, preferably 1 to
6 represents an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group,
Examples thereof include a t-butyl group and a cyclohexyl group. R ⁵ in the formula represents an alkylene group having 1 to 10, preferably 1 to 3 carbon atoms or an alkylidene group. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group, and examples of the alkylidene group include ethylidene,
And a propylidene group. Examples of the compound represented by the general formula (2) include 3- (5-chloro-2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-benzenepropanoic acid, (2
H-benzotriazol-2-yl) -4-hydroxybenzeneethaneanoic acid, 3- (5-methyl-2H-benzotriazol-2-yl) -5- (1-methylethyl)-
Examples thereof include 4-hydroxybenzenepropanoic acid. Preferable examples of the compound having a benzophenone skeleton include benzophenone-based compounds represented by the following general formulas (3) to (6).

Embedded image

Embedded image

Embedded image

Embedded image In the general formulas (3) to (6), R ⁷ and R ⁸ are the same or different groups and are a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 10, preferably 1 to 6 carbon atoms. Is shown. n and m are integers in the range of 0 ≦ m ≦ 3 and 0 ≦ n ≦ 3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, and a cyclohexyl group.Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and an i-propoxy group. , Butoxy group and the like. Wherein R ⁶ is
And represents an alkylene group having 1 to 10, preferably 1 to 3 carbon atoms or an alkylidene group. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group, and examples of the alkylidene group include an ethylidene group and a propylidene group. Specific examples of such a compound having a benzophenone skeleton include 2-hydroxy-4
-Methoxybenzophenone-5-carboxylic acid, 2,2 '
-Dihydroxy-4-methoxybenzophenone-5-carboxylic acid, 4- (2-hydroxybenzoyl) -3-hydroxybenzenepropanoic acid and the like are preferred. The ultraviolet absorbent having a benzotriazole skeleton or a benzophenone skeleton can be produced by a known method. An amide bond derived from component A is formed in the reaction mixture obtained by reacting component A and component B described above, and this reaction is usually mainly dehydration. The amount of the amide bond generated by the reaction is not particularly limited,
Generally, it is preferable that an amide bond is formed in 10 mol% or more, preferably 50 mol% or more of all aminosilanes of the component A. The upper limit is usually 100 mol%, but the upper limit is 1 mol%.
Less than 00 mol% may be used.

When reacting component A with component B or after the reaction of both components, optional components can be further coexisted and added within a range not to impair the object of the present invention. One example of such an optional component is a silicone resin (hereinafter, referred to as “component C”).
The component C is preferably a reactive silicone resin, that is, a silicone resin having a functional group capable of reacting with the alkoxysilyl group moiety of the component A (usually a dehydration reaction and / or a dealcoholization reaction). As the functional group, an alkoxysilyl group, a silanol group or the like is preferable. Generally, such a reactive silicone resin can be easily synthesized by a partial hydrolysis reaction of alkoxysilane or chlorosilanes and a subsequent condensation reaction. As a commercially available product, pure silicone varnish (for example, trade name “XO793”)
1-clear ": manufactured by Okitsumo Co., Ltd., silicone resin (for example, trade name" SR2410 ": manufactured by Toray Dow Corning Silicone Co., Ltd.), acrylic-modified silicone resin (for example, trade name" Silacoat 1000 ": Chisso ( Co., Ltd.). Further, the silicone resin can be used in the form of a solution using various solvents as long as the object of the present invention is not impaired. The solvent is not particularly limited, but usually various hydrocarbon solvents, ketones, ethers, esters, ether / esters and the like are used. Further, a modified silicone resin may be used. Component C is allowed to coexist during or after the reaction of Component A and Component B.
It is particularly preferred to coexist with the reaction of component B. Other examples of the optional component include various epoxy silanes (hereinafter, referred to as “component D”), and preferably, epoxy silanes represented by the following general formulas (7) to (8) are used. .

Embedded image

Embedded image In the general formulas (7) and (8), R ⁹ and R ^{11 each} independently represent an alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, or a compound of the formula —R—O—R′— (where R And R ′ each represent an alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms)
And each R ¹⁰ is independently a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group or an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, or 6 to 10 carbon atoms. Represents 6 to 8 aryl groups. However, at least one of all R ¹⁰ is an alkoxy group or a hydroxyl group. n represents an integer of n ≧ 0, preferably 0 ≦ n ≦ 3. As the alkylene group,
Preferable examples include a methylene group, a trimethylene group, and a tetramethylene group. As the alkyl group, a methyl group,
Preferable examples include an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
Methoxy, ethoxy, propoxy, butoxy,
Examples include a t-butoxy group, a pentyloxy group, and a hexyloxy group. Examples of the aryl group include a phenyl group and a tolyl group. Specific examples of component D include 3-
Glycidoxypropyltrimethoxysilane, dimethoxy
-3-glycidoxypropylmethylsilane, 2- (3,
4-epoxycyclohexylethyl) trimethoxysilane, dimethylethoxy-3-glycidoxypropylsilane, 1,3-bis (3-glycidoxypropyl) -1,
A suitable example is 3-dimethyl-1,3-dimethoxydisiloxane or a mixture thereof. Component D may be used after being hydrolyzed in advance. Further, the epoxy group can be used by ring-opening polymerization with an appropriate polymerization catalyst in advance. As the polymerization catalyst, a Lewis acid catalyst such as boron trifluoride diethyl ether complex, aluminum chloride, and diethyl zinc is preferable. The polymerization conditions for ring-opening polymerization of the epoxy group are not particularly limited, but are usually about -80 ° C to 130 ° C, preferably about -20 ° C to 80 ° C, and the reaction time depends on the reaction conditions, reaction mode, and the like. It can be appropriately selected and is usually about 10 minutes to 10 hours, preferably about 1 hour to 6 hours. The solvent used at this time is not particularly limited, for example,
Examples include aromatic hydrocarbon solvents such as toluene and xylene, and various ketones and esters. Component D is allowed to coexist during or after the reaction of components A and B, but is preferably added after the reaction of components A and B. However, in the case of using a component D in which the epoxy group of the component D has been subjected to ring-opening polymerization in advance, it is preferably added during the reaction of the components A and B. The other optional component is a polyether-modified polysiloxane (hereinafter, referred to as “component E”), and the component is preferably a polyether-modified polysiloxane represented by the following general formula (9).

Embedded image In the general formula (9), R ¹² , R ¹³ and R ¹⁴ each independently represent an alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and each R ¹⁵ independently represents a hydrogen atom, a hydroxyl group, or a halogen atom. It represents an atom, an alkyl group or an alkoxy group having 1 to 10, preferably 1 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms. At least one of R ¹⁵ is an alkoxy group or a hydroxyl group. m, n, p
Is m ≧ 0, preferably 0 ≦ m ≦ 100, n ≧ 0,
Preferably 0 ≦ n ≦ 10, p ≧ 0, preferably 0 ≦ p ≦
Indicates an integer of 10. Preferable examples of the alkylene group include a methylene group, a trimethylene group, and a tetramethylene group. Preferred examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. As the alkoxy group,
Methoxy, ethoxy, propoxy, butoxy,
Examples include a t-butoxy group, a pentyloxy group, and a hexyloxy group. As the aryl group, a phenyl group,
And a tolyl group. Specific examples of Component E include tetraethylene glycol-bis (triethoxysilylethyl) ether, polyethylene glycol-bis (triethoxysilylethyl) ether, polypropylene glycol-bis (triethoxysilylethyl) ether or mixtures thereof. Is done. Component E may be used after being hydrolyzed in advance. Component E is allowed to coexist during or after the reaction of components A and B, but is preferably added during the reaction of components A and B. When epoxysilanes of component D and polyether-modified polysiloxanes of component E are used as optional components, the ultraviolet absorbing film formed on the substrate has improved adhesion to the substrate without impairing heat resistance. In addition, there is an effect that the film is hardly cracked even if the film is thick.

As an optional component other than the above, an inorganic fine particle dispersion (hereinafter, referred to as “component F”) can be mentioned. The component F is not particularly limited, but a dispersion of fine particles of silica, alumina, titanium oxide, antimony oxide and the like is generally used. The particle diameter of the fine particles is about 1 to 100 nm, and water, methanol, xylene, methyl ethyl ketone and the like are commonly used as the dispersion medium. LUDOX for commercial products
Preferable examples include LS (manufactured by DuPont) and XBA-ST (manufactured by Nissan Chemical Industries, Ltd.). Component F is allowed to coexist during or after the reaction of components A and B, but is preferably added after the reaction of components A and B. By adding the component F, the surface hardness of the coating is improved, and the abrasion resistance, chemical resistance, and the like can be improved. Each of the above-mentioned optional components can be manufactured by a known method.

[0008] Regardless of whether or not the optional components coexist, by reacting the components A and B, a reaction mixture containing a desired amount of an amide bond can be obtained. The reaction conditions for this reaction can be appropriately selected as long as an amide bond derived from component A is generated. Usually, component A and component B are mixed, and if desired, optional components are mixed in a solvent. Later, in the presence of a solvent,
At room temperature to 350 ° C, preferably at 60 to 250 ° C,
The reaction is generally performed for 5 minutes to 50 hours, preferably 10 minutes to 15 hours. This reaction operation can be performed repeatedly. The solvent used for the reaction is not particularly limited as long as the object of the present invention is not impaired. For example, aromatic solvents such as toluene and xylene, ketone solvents such as cyclohexanone, and mixtures thereof can be used. The solvent may or may not be removed after the reaction. In the above reaction, the ratio of the components A and B used is not particularly limited, but the amount of the component B is usually 5 to 90% by mass, preferably 10 to 80% by mass relative to the total amount of the components A and B. It can be arbitrarily selected in the range of mass%. The reaction mixture thus obtained can be coated on a transparent substrate by adding the above-mentioned optional components to the reaction mixture as necessary.
Any additive can be added to this coating liquid as long as the object of the present invention is not impaired. Examples of such additives include an antioxidant, a quencher or a radical scavenger, or an inorganic or organic acid such as hydrochloric acid, sulfuric acid, or acetic acid, a boron trifluoride / diethyl ether complex, or sodium hexafluoroantimonate. Lewis acids, potassium hydroxide, sodium hydroxide, triethylamine, bases such as aniline, dibutyltin dilaurate, as exemplified by organic metals such as titanium tetraisopropoxide,
A catalyst having a curing promoting action (usually preferably 0.1 to 5.0% by mass based on the ultraviolet absorbing material), toluene, xylene, ethanol, isopropanol, dimethylformamide, cyclohexanone, 1-
Solvents such as methoxy-2-acetoxypropane and various thinners can be exemplified. The amount of the silicone resin, which is an optional component, is not particularly limited, but is preferably 5 to 300 parts by mass, and more preferably 20 to 150 parts by mass, based on 100 parts by mass of the components A and B in total. The amount of the epoxysilane used is not particularly limited, either, but is preferably 10 to 500 parts by mass, and more preferably 100 to 400 parts by mass, based on 100 parts by mass of the components A and B in total. Also, the amount of the polyether-modified polysiloxane is not particularly limited, but is preferably 10 parts by mass based on 100 parts by mass of the components A and B in total.
-500 parts by mass, preferably 100-400 parts by mass. The amount of colloidal silica to be used is not particularly limited either, but is preferably 5 to 400 parts by mass, more preferably 10 to 200 parts by mass, per 100 parts by mass of the total of components A and B.

The ultraviolet absorbing layer according to the present invention can be obtained by applying a coating solution containing the above reaction mixture on a substrate and curing it. The application method is not particularly limited, and a known method can be appropriately employed. For example, spin coating, spray coating, dip coating, cast coating, blade coating, flow coating, and the like can be appropriately adopted according to the purpose. The coating film is usually from room temperature to 250 ° C.
Preferably, it can be cured at about 40 ° C to 200 ° C. Even without using the catalyst, usually from room temperature to 350 ° C,
Preferably, it can be cured by heating at 60 ° C to 250 ° C. The time required for curing depends on the curing temperature, but is usually about 10 minutes to 5 hours. The thickness of the ultraviolet absorbing layer formed on the transparent substrate is not particularly limited and may be appropriately selected, but is usually 0.5 to 50 μm.
It is used within a range of about m. When the thickness is less than 0.5 μm, it may be difficult to obtain a sufficient ultraviolet ray blocking ability.
If it is more than μm, it may be difficult to apply without causing cracks.

[0010] The ultraviolet absorbing transparent conductive substrate according to the present invention may be provided with an overcoat layer adjacent to the ultraviolet absorbing layer and the transparent conductive film. This overcoat layer forming material is not particularly limited, but is usually formed of a resin having excellent heat resistance, specifically, polyimide, polyamide, polycarbonate, polyarylate, polyether sulfone, melamine resin, Phenol resin, epoxy resin, silicone resin such as silicone varnish, urea resin and the like are used. Of these, silicone resin overcoat agents are most suitable. These may be used in combination. Glass fillers and inorganic powders may be used in combination. As the inorganic powder, usually Zn
Fine particles such as O, TiO ₂ , CeO ₂ and silica are used. Examples of the silicone resin overcoating agent include a silicone resin in which inorganic fine particles such as colloidal silica are dispersed, and a partial hydrolysis product and a partial polycondensation product of silanes such as alkoxysilane and chlorosilane. Specifically, Tosgard 510 is commercially available
(Manufactured by Toshiba Silicone), polysilazane (manufactured by Tonen) such as APZ7703, APZ7705 (manufactured by Nippon Unicar), NL110 and NL710. It is also known that a partial hydrolysis product of epoxysilane is excellent in abrasion resistance and the like as an overcoat agent. The method for forming the overcoat layer is not particularly limited and a known method may be appropriately selected, but is usually obtained by applying a solution of a resin constituting the overcoat layer or a solution of a precursor. . After application, necessary processing is performed depending on the properties of each resin, and an overcoat layer is obtained. The overcoat layer can also be provided by a method of attaching a film made of the above resin. By the way, when a silicone varnish is used, a catalyst such as dibutyltin dilaurate is added thereto, and after coating, 100 to 20
By heating and curing at about 0 ° C for about 5 minutes to 2 hours,
An overcoat layer of 20 μm can be obtained. Also, when using an acrylic-melamine resin precursor,
By heating and curing at 130 to 190 ° C. for about 5 minutes to 2 hours after application, an overcoat layer of 10 to 100 μm can be obtained. When a photocurable acrylic resin precursor or the like is used, an overcoat layer having a thickness of 1 to 10 μm can be usually obtained within 5 minutes by applying the composition and then placing it under irradiation with a high-pressure mercury lamp. A known method is used as a coating method. For example, spin coating, spray coating, cast coating, blade coating, dip coating and the like can be used. In addition, by applying a light surface modification or a primer treatment to the ultraviolet absorbing layer before forming the overcoat layer, it is possible to improve the wettability of the overcoat material and the adhesion of the overcoat layer to the ultraviolet absorbing layer.

A preferred configuration of the transparent conductive substrate of the present invention is as follows.
It has a specific ultraviolet absorbing layer between the transparent substrate and the transparent conductive film, and has an overcoat layer between the ultraviolet absorbing layer and the transparent conductive film. The simplest example is shown in FIG.
1, a transparent substrate 1, an ultraviolet absorbing layer 2, an overcoat layer 3, and a transparent conductive film 4 are sequentially provided. Further, as shown in FIG. 2, one or more intermediate layers 5 can be provided between the transparent substrate 1 and the ultraviolet absorbing layer 2. Although the function of the intermediate layer 5 is not particularly limited, for example, in order to suppress the deterioration of the organic ultraviolet absorbent due to far ultraviolet rays, Z
In order to provide an ultraviolet absorbing layer containing an inorganic oxide such as nO, CeO ₂ or TiO ₂ , or to improve the adhesion between the transparent substrate 1 and the ultraviolet absorbing layer 2, a silane coupling agent, a surfactant or the like is used. And an intermediate layer containing: Further, as shown in FIG. 3, one or more intermediate layers 6 may be provided between the ultraviolet absorbing layer 2 and the overcoat layer 3. The function of the mid layer 6 is not particularly limited,
For example, for the purpose of improving the adhesion between the ultraviolet absorbing layer 2 and the overcoat layer 3, an intermediate layer containing a silane coupling agent, a surfactant, or the like can be used. Furthermore,
As shown in FIG. 4, one or more intermediate layers 5 and 6 may be provided between the transparent substrate 1 and the ultraviolet absorbing layer 2 and between the ultraviolet absorbing layer 2 and the overcoat layer 3, respectively. The functions of the intermediate layers 5 and 6 are not particularly limited, but the same functions as those described in FIGS. 2 and 3 can be provided. In the transparent conductive substrate of the present invention, the laminated structure may be provided not only on one side of the substrate but also on both sides of the substrate.

[0012]

The transparent conductive substrate of the present invention has both high conductivity and excellent ultraviolet blocking effect. In particular, by appropriately selecting an ultraviolet absorbing layer, a wavelength of 400 nm or less can be very clearly cut off. Also,
The effect of the overcoat layer provided between the transparent conductive film and the ultraviolet absorbing layer makes it possible to easily form the transparent conductive film, and to protect an electric device manufactured using the same from ultraviolet light. It is possible.
Further, by chemically bonding the ultraviolet absorbent to the polymer, a stable ultraviolet absorbing layer can be obtained when the transparent conductive film is formed, and a transparent conductive substrate having the ultraviolet absorbing layer can be easily obtained. Furthermore, since the transparent conductive substrate of the present invention has such features, it can be used for various applications, for example, used for an electrochromic device for dimming or display or a liquid crystal device for display. And can exhibit excellent effects. As described above, the present invention has been described in detail. As the preferred embodiments of the ultraviolet absorbing transparent conductive substrate of the present invention, the following embodiments are mentioned. 1. The ultraviolet-absorbing layer-forming coating component comprises, in the presence of the silicone resin, (a) an aminosilane compound represented by the general formula (1) or a derivative thereof, and (b) ultraviolet light having a carboxylic acid residue in the molecule. An ultraviolet-absorbing transparent conductive substrate according to the present invention, comprising a reaction mixture obtained by reacting an absorbent. 2. The ultraviolet absorbing layer-forming coating component is obtained by reacting (a) the aminosilane compound represented by the general formula (1) or a derivative thereof with (b) the ultraviolet absorbing agent having a carboxylic acid residue in the molecule. The ultraviolet-absorbing transparent conductive substrate of the present invention, which is obtained by further adding the epoxysilane to the amide bond-containing reaction mixture obtained. 3. The ultraviolet absorbing layer-forming coating component is obtained by reacting (a) the aminosilane compound represented by the general formula (1) or a derivative thereof with (b) the ultraviolet absorbing agent having a carboxylic acid residue in the molecule. The ultraviolet-absorbing transparent conductive substrate of the present invention, which is obtained by further adding colloidal silica to the resulting amide bond-containing reaction mixture.

[0013]

EXAMPLES The present invention will be described below with reference to examples of the present invention, but the present invention is not limited thereto.

EXAMPLE 1 Synthesis of UV absorber containing carboxylic acid residue 225 g (0.46 mol) of 3- (5-chloro-2H-)
Benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-benzenepropanoic acid octyl ester (TINUVIN 109, trade name, C)
iba-Geigy) was dissolved in 700 ml of acetone, 600 ml of a 2N aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 24 hours. After 650 ml of 2N hydrochloric acid was added to make the solution acidic, the insolubilized product was separated by filtration and washed with distilled water until the filtrate became neutral. The product is dried in vacuo and recrystallized from toluene to give 3- (5-chloro-2H-benzotriazol-2-yl) -5-.
(1,1-Dimethylethyl) -4-hydroxy-benzenepropanoic acid [Compound I] was obtained. Preparation of UV-Absorptive Coating Solution 3 g of 3-aminopropyltriethoxysilane was dissolved in 35 g of xylene, and the compound I was heated at 80 ° C.
Was gradually added. After the addition was completed, the temperature was raised to 130 ° C. and refluxed for 3 hours. After allowing to cool, 16 g of 3-glycidoxypropyltrimethoxysilane was added, and this was used as an ultraviolet absorbing coating solution. When the obtained coating solution was analyzed by ¹³ C-NMR, a carbonyl peak (about 173 ppm) derived from an amide bond was observed, and it was confirmed that an amide bond derived from aminosilanes as a raw material was present. Production of UV-absorbing transparent plate The above-mentioned UV-absorbing coating solution is spray-coated on a glass substrate, left at room temperature for 20 minutes, and then heated at 200 ° C. for 20 minutes to produce an ultraviolet-absorbing glass having a UV-absorbing coating with a thickness of about 17 μm did. Further, a silicone resin (APZ-7705, manufactured by Nippon Unicar) is spray-coated on the ultraviolet absorbing layer, and dried at 100 ° C. for 20 minutes to obtain a thickness of about 2 μm.
A μm protective film was provided. Production of UV-absorbing transparent conductive substrate ITO is sputtered on the UV-absorbing glass at a substrate temperature of 250 ° C. to form a transparent conductive film having a thickness of about 3300 angstroms and a resistance of 7.5 Ω / cm ² , and has a function of blocking ultraviolet rays. A transparent conductive substrate was obtained. FIG. 5 shows the spectral transmittance of this transparent conductive substrate.

Example 2 Preparation of UV-Absorptive Coating Solution 3 g of 3-aminopropyltriethoxysilane was dissolved in 40 g of xylene and heated to 60 ° C. while 5 g of Example 1 was used.
Was slowly added. After the addition, 130
C., and refluxed for 3 hours to obtain a solution-type ultraviolet absorbing coating solution. When the obtained solution was analyzed by ¹³ C-NMR, a carbonyl peak (about 173 ppm) derived from an amide bond was observed, and it was confirmed that an amide bond derived from aminosilanes as a raw material was present. Production of UV-absorbing transparent plate The above coating solution was spray-coated on a glass substrate,
After standing for 0 minutes, the mixture was heated at 130 ° C. for 30 minutes to produce an ultraviolet absorbing glass having an ultraviolet absorbing coating having a thickness of about 10 μm.
Further, a silicone resin (APZ-7705, manufactured by Nippon Unicar) was spray-coated on the ultraviolet absorbing layer and dried at 100 ° C. for 20 minutes to provide a protective film having a thickness of about 2 μm. When the UV-visible absorption spectrum of this UV-absorbing glass was measured, a glass substrate completely blocking UV light was obtained as in Example 1. Production of UV-absorbing transparent conductive substrate ITO is sputtered on the UV-absorbing glass at a substrate temperature of 250 ° C. to form a transparent conductive film having a thickness of about 3300 angstroms and a resistance of 7.5 Ω / cm ² , and has a function of blocking ultraviolet rays. A transparent conductive substrate was obtained. Also in this case, almost no change was observed as in Example 1, as compared with the spectrum before sputtering.

Example 3 Preparation of Ultraviolet Absorbing Coating Solution 17.7 g of silicone varnish (XO-7931-Clear, manufactured by Okitsumo) and 3 g of 3-aminopropyltriethoxysilane were dissolved in 35 g of xylene, and heated to 80 ° C. 5 g of compound I was added slowly. After completion of addition, 1
The temperature was raised to 30 ° C., and the mixture was refluxed for 3 hours to obtain a solution-like ultraviolet absorbing coating solution. Production of UV-absorbing transparent plate The UV-absorbing coating solution is spray-coated on a glass substrate, left at room temperature for 20 minutes, and then heated at 200 ° C. for 20 minutes to obtain a UV-absorbing glass having a UV absorbing film having a thickness of about 17 μm. Produced. When a cross-cut test was performed on this ultraviolet absorbing glass, 50% peeling was observed. The pencil hardness was 2H. Further, a silicone resin (APZ-7705, manufactured by Nippon Unicar) is spray-coated on the ultraviolet absorbing layer, and dried at 100 ° C. for 20 minutes to obtain a thickness of about 2 μm.
A μm protective film was provided. Production of UV-absorbing transparent conductive substrate ITO is sputtered on the UV-absorbing glass at a substrate temperature of 250 ° C. to form a transparent conductive film having a thickness of about 3300 angstroms and a resistance of 7.5 Ω / cm ² , and has a function of blocking ultraviolet rays. A transparent conductive substrate was obtained. FIG. 6 shows the spectral transmittance of this transparent conductive substrate.

Example 4 Preparation of UV Absorbing Coating Solution 17.7 g of silicone varnish (XO-7931-Clear, manufactured by Okitsumo) and 3 g of 3-aminopropyltriethoxysilane were dissolved in 35 g of xylene, and heated to 80 ° C. 5 g of compound I was added slowly. After completion of addition, 1
The temperature was raised to 30 ° C. and refluxed for 3 hours. After cooling, 16 g of 3-glycidoxypropyltrimethoxysilane was added to obtain an ultraviolet absorbing coating solution. Production of UV-absorbing transparent plate The UV-absorbing coating solution is spray-coated on a glass substrate, left at room temperature for 20 minutes, and then heated at 200 ° C. for 20 minutes to obtain a UV-absorbing glass having a UV absorbing film having a thickness of about 17 μm. Produced. As in Example 3, no peeling was observed in the grid test. Furthermore, on this ultraviolet absorption layer,
Spray-coated silicone resin (APZ-7705, manufactured by Nippon Unicar), dried at 100 ° C for 20 minutes,
A protective film having a thickness of about 2 μm was provided. Production of UV-absorbing transparent conductive substrate ITO is sputtered on the UV-absorbing glass at a substrate temperature of 250 ° C. to form a transparent conductive film having a thickness of about 3300 angstroms and a resistance of 7.5 Ω / cm ² , and has a function of blocking ultraviolet rays. A transparent conductive substrate was obtained. FIG. 7 shows the spectral transmittance of this transparent conductive substrate.

Example 5 Preparation of UV Absorbing Coating Solution 17.7 g of silicone varnish (XO-7931-Clear, manufactured by Okitsumo) and 3 g of 3-aminopropyltriethoxysilane were dissolved in 35 g of xylene and heated to 80 ° C. 5 g of compound I was added slowly. After completion of addition, 1
The temperature was raised to 30 ° C. and refluxed for 3 hours. After cooling, 16 g of 3-glycidoxypropyltrimethoxysilane and 8 g of a colloidal silica dispersion (manufactured by Nissan Chemical Industries, MIBK-ST) were added to obtain an ultraviolet absorbing coating solution. Production of UV-absorbing transparent plate The UV-absorbing coating solution is spray-coated on a glass substrate, left at room temperature for 20 minutes, and then heated at 200 ° C. for 20 minutes to obtain a UV-absorbing glass having a UV absorbing film having a thickness of about 17 μm. Produced. The pencil hardness was 4H. Production of UV-absorbing transparent conductive substrate ITO is sputtered on the UV-absorbing glass at a substrate temperature of 250 ° C. to form a transparent conductive film having a thickness of about 3300 angstroms and a resistance of 7.5 Ω / cm ² , and has a function of blocking ultraviolet rays. A transparent conductive substrate was obtained. FIG. 8 shows the spectral transmittance of this transparent conductive substrate.

EXAMPLE 6 Polymerization of Epoxysilane 200 g of 3-glycidoxypropyltrimethoxysilane
Was dissolved in 75 g of xylene, 4 ml of boron trifluoride / diethyl ether complex was gradually added at room temperature, and the mixture was stirred for 4 hours to carry out ring-opening polymerization of an epoxy group. The molecular weight of the obtained polymer was Mw = 3300 (in terms of polystyrene). Preparation of UV Absorbing Coating Solution 17.7 g of silicone varnish (XO-7931-Clear, manufactured by Okitsumo) and 3 g of 3-aminopropyltriethoxysilane are dissolved in 29 g of xylene, and 5 g of compound I is gradually heated to 80 ° C. Was added. After completion of addition, 1
The temperature was raised to 30 ° C. and refluxed for 3 hours. After cooling, 22 g of the above epoxysilane polymer solution was added to obtain an ultraviolet absorbing material. Production of UV-absorbing transparent plate The above-mentioned solution-type UV-absorbing material was used as a coating solution, spray-coated on a glass substrate, allowed to stand at room temperature for 20 minutes, and then heated at 150 ° C. for 30 minutes to absorb ultraviolet rays having a thickness of about 15 μm. A glass substrate having a layer was prepared. Pencil hardness is 6H
Met. Further, a silicone resin (APZ-7705, manufactured by Nippon Unicar) is spray-coated on the ultraviolet absorbing layer, dried at 100 ° C. for 20 minutes, and has a thickness of about 2 μm.
m protective films were provided. Production of UV-absorbing transparent conductive substrate ITO is sputtered on the UV-absorbing glass at a substrate temperature of 250 ° C. to form a transparent conductive film having a thickness of about 3300 angstroms and a resistance of 7.5 Ω / cm ² , and has a function of blocking ultraviolet rays. A transparent conductive substrate was obtained. FIG. 9 shows the spectral transmittance of this transparent conductive substrate.

Example 7 Preparation of UV Absorbing Coating Solution 3 g of 3-aminopropyltriethoxysilane and Example 6
11 g of the epoxysilane polymer solution was dissolved in 32 g of xylene, and 5 g of Compound I was gradually added while heating to 80 ° C. After the addition was completed, the temperature was raised to 130 ° C. and refluxed for 3 hours to obtain an ultraviolet absorbing material. Production of UV-absorbing transparent plate The above-mentioned solution-type UV-absorbing material was used as a coating solution, spray-coated on a glass substrate, allowed to stand at room temperature for 20 minutes, and then heated at 150 ° C. for 30 minutes to absorb ultraviolet rays having a thickness of about 15 μm. A glass substrate having a layer was prepared. Pencil hardness is 5H
Met. Further, a silicone resin (APZ-7705, manufactured by Nippon Unicar) is spray-coated on the ultraviolet absorbing layer, dried at 100 ° C. for 20 minutes, and has a thickness of about 2 μm.
m protective films were provided. Production of UV-absorbing transparent conductive substrate ITO is sputtered on the UV-absorbing glass at a substrate temperature of 250 ° C. to form a transparent conductive film having a thickness of about 3300 angstroms and a resistance of 7.5 Ω / cm ² , and has a function of blocking ultraviolet rays. A transparent conductive substrate was obtained. FIG. 10 shows the spectral transmittance of this transparent conductive substrate.

Comparative Example 1 A ZnO ultrafine particle dispersion coating material (UV-S-400, manufactured by Resino Color Industrial Co., Ltd.) was applied on a glass substrate by dip coating, and cured by heating at 200 ° C. for 20 minutes to form a coating having a thickness of about 2 μm. An ultraviolet absorbing layer was produced. On top of this, polyether sulfone (VICTRE, manufactured by ICI)
X'PES 4100P) was spin-coated with a methylene chloride solution to prepare a polymer layer having a thickness of about 2 µm. Further, an ultraviolet absorbing layer having a thickness of about 15 μm was prepared using the silicone varnish of Example 2. A polyimide varnish (manufactured by Nissan Chemical Industries, RN-812) was spin-coated on the ultraviolet absorbing layer thus obtained.
After the solvent was dried on a hot plate at 60 ° C., it was heated and cured in an oven at 200 ° C. for 30 minutes to obtain a protective layer having a thickness of about 2 μm. Further, ITO was sputtered thereon at a substrate temperature of 250 ° C. or less, and
A transparent conductive substrate having 050 angstroms and a surface resistance of 9.5 Ω / cm ² and capable of blocking ultraviolet rays from a transparent conductive film was obtained.
FIG. 11 shows the spectral transmittance of this transparent conductive substrate.

[Brief description of the drawings]

FIG. 1 is a structural explanatory view of a transparent conductive substrate of the present invention.

FIG. 2 is a structural explanatory view of another transparent conductive substrate of the present invention.

FIG. 3 is an explanatory view of the structure of another transparent conductive substrate of the present invention.

FIG. 4 is a diagram illustrating the structure of another transparent conductive substrate according to the present invention.

FIG. 5 is a graph showing the spectral transmittance of Example 1.

FIG. 6 is a graph showing the spectral transmittance of Example 3.

FIG. 7 is a graph showing the spectral transmittance of Example 4.

FIG. 8 is a graph showing the spectral transmittance of Example 5.

FIG. 9 is a graph showing the spectral transmittance of Example 6.

FIG. 10 is a graph showing the spectral transmittance of Example 7.

FIG. 11 is a graph showing the spectral transmittance of Comparative Example 2.

[Explanation of symbols]

 1: transparent substrate 2: ultraviolet absorbing layer 3: protective layer 4: transparent conductive film 5: intermediate layer 6: intermediate layer

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Yoshinori Nishikiya 8 Chidori-cho, Naka-ku, Yokohama, Japan Central Research Laboratory of Petroleum Corporation

Claims (2)

[Claims] 1. A transparent conductive substrate comprising at least a transparent substrate and a transparent conductive film, comprising an ultraviolet absorbing layer between the transparent substrate and the transparent conductive film, wherein the ultraviolet absorbing layer comprises at least (a) An aminosilane compound represented by the general formula (1) or a derivative thereof; (Wherein, R ¹ represents an alkylene group having 1 to 10 carbon atoms, or a divalent group represented by the general formula — (CH ₂ ) _m —NH— [m is an integer of 1 ≦ m ≦ 4], Each R ² is the same or different and represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, provided that at least one of all R ² is One represents an alkoxy group or a hydroxyl group, and n represents n ≧ 0.
Indicates an integer. (B) A component produced by reacting with an ultraviolet absorber having a carboxyl group in the molecule to form an amide bond derived from the aminosilane compound or a derivative thereof on a transparent substrate and curing the component. An ultraviolet absorbing transparent conductive transparent substrate, characterized in that: 2. The ultraviolet absorbing transparent conductive substrate according to claim 1, further comprising an overcoat layer between the ultraviolet absorbing layer and the transparent conductive film.