JPH0752610B2 - Coated conductive thin film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a conductive thin film coated with a curable resin composition.

(Prior Art) As a transparent electrode material that has been conventionally used for liquid crystal displays, photoelectric conversion elements, and the like, a Nesa glass having a tin oxide-based coating formed on the surface of glass or an indium oxide-based coating has been formed.
ITO glass is well known. In addition, instead of such a glass substrate, a so-called transparent conductive film, which is a transparent conductive film formed on a plastic film, is a thin film, lighter weight, flexibility, processability, impact resistance, large area. It is widely used by making the most of its advantages.

The conductive thin film typified by such tin oxide-based coating and indium oxide-based coating is an extremely useful material in the fields of electronics and optoelectronics, and in the future, liquid crystal displays, photoconductive elements, photoelectric conversion elements,
It is considered to be widely used in fields such as electronic recording and optical memory.

As the field of application of the conductive thin film has expanded in this way, the coating resin used for the purpose of protecting and insulating the conductive thin film has also been required to have high properties. For example, with respect to the resin coated on the conductive thin film of the transparent conductive film described above, it is required to have appropriate hardness, be transparent and have excellent adhesiveness, flexibility, and processability, In addition, for a resin that coats a conductive thin film formed on a photoelectric conversion element such as a solar cell, translucency, weather resistance, processability, and photoelectric conversion element (for example, amorphous silicon solar cell), etc. For the purpose of protecting from the external environment, excellent properties such as water resistance, moisture resistance, heat resistance, and thermal shock resistance are required.

In order to impart these properties, as a method of coating a curable resin layer on a conductive thin film, some of the present inventors have already prepared an epoxy compound (A) having two or more epoxy groups in the molecule, We proposed a coated conductive thin film obtained by coating and curing a curable resin composition containing a photopolymerizable compound (B) having a carboxyl group in the molecule and another photopolymerizable compound (C) as essential components.

(Problems to be Solved by the Invention) However, it has been found that when the curable resin composition is immersed in boiling water, the adhesiveness to the conductive thin film is not always sufficiently retained.

(Means for Solving Problems) The inventors of the present invention have improved adhesiveness in view of such a situation, and have conductivity coated with a curable resin composition having excellent water resistance and heat resistance. As a result of intensive studies to obtain a thin film, they have found that the above-mentioned defects can be solved by adding a silane coupling agent to the curable resin composition, and have reached the present invention.

That is, the present invention provides an epoxy compound (A) having two or more epoxy groups in the molecule on a conductive thin film and a photopolymerizable compound represented by the general formula (I) having a carboxyl group in the molecule. A coated conductive thin film obtained by coating and curing a curable resin composition containing (B) or the compound (B), another photopolymerizable compound (C), and a silane coupling agent (D).

The epoxy compound (A) having at least two epoxy groups in the molecule used in the present invention is an epoxy compound having two or more epoxy groups in one molecule, and its epoxy equivalent is 100 to 4,000, preferably It is 100 to 1,000.

Representative compounds include bisphenol type epoxy resins which are diglycidyl ethers such as bisphenol A, bisphenol F and halogenated bisphenol A, and novolak type epoxies which are polyglycidyl ethers such as phenol novolac and cresol novolac. Polyglycidyl ethers of polyvalent phenols with a valence of 2 or more typified by resins, ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, etc. There are polyglycidyl ethers of the above polyhydric alcohols. These epoxy compounds can be used alone or in combination of two or more.

Further, an epoxy compound having one epoxy group in the molecule, such as allyl glycidyl ether and phenyl glycidyl ether, can be used in combination.

Among these epoxy compounds having at least two epoxy groups in the molecule, preferred epoxy compounds are:
Examples thereof include bisphenol type epoxy compounds, phenol novolak type polyepoxy compounds, and cresol novolak type polyepoxy compounds.

The photopolymerizable compound (B) having one or more carboxyl groups in the molecule used in the present invention is a compound represented by the following general formula (I).

(In the formula, R ₁ represents hydrogen or a methyl group, R ₂ and R ₃ each represent an aliphatic, aromatic, or alicyclic residue, A represents an ester bond, and m and n each represent 1 to 1). 3 represents a positive integer.) In the general formula (I), R ₂ has 2 to 10 carbon atoms 2
To a tetravalent hydrocarbon group or a hydroxyl group-containing hydrocarbon group, R ₃ is a divalent to tetravalent aliphatic polybasic acid residue having 2 to 10 carbon atoms, and 6 to 15 carbon atoms. A divalent to tetravalent aromatic polybasic acid residue or 6 to 6 carbon atoms
It is preferably a divalent to tetravalent alicyclic polybasic acid residue of 10.

Examples of the compound represented by the general formula (I) include the following compounds.

Examples of the compound of m = 1 and n = 1 include succinic acid mono (meth) acryloyloxyethyl ester (acryloyloxyethyl ester and methacryloyloxyethyl ester are shown. Others are abbreviated in the same manner), phthalic acid mono (meth). ) Acryloyloxyethyl ester, methyl tetrahydrophthalic acid mono (meth) acryloyloxyethyl ester, maleic acid mono (meth)
Acryloyloxyethyl ester, tetrahydrophthalic acid mono (meth) acryloyloxyethyl ester, hexahydrophthalic acid mono (meth) acryloyloxyethyl ester, endo-bicyclo (2.2.
1) -5-heptene-2,3-dicarboxylic acid mono (meth)
Acryloyloxyethyl ester, tetrahydrophthalic acid mono-2- (meth) acryloyloxy-1-
(Phenoxymethyl) ethyl ester, phthalic acid mono-
2-hydroxy-3- (meth) acryloyloxypropyl ester, succinic acid mono-2-hydroxy-3-
(Meth) acryloyloxypropyl ester and the like.

Examples of the compound with m = 1 and n = 2 include trimellitic acid mono-2- (meth) acryloyloxyethyl ester. Examples of the compound in which m = 1 and n = 3 include pyromellitic acid mono-2- (meth) acryloyloxyethyl ester.

Examples of the compound in which m = 2 and n = 1 include phthalic acid mono- [2,3-bis (meth) acryloyloxyisopropyl] ester and methyltetrahydrophthalic acid mono-
[2,3-Bis (meth) acryloyloxyisopropyl] ester, tetrahydrophthalic acid mono- [2,3-
Examples include bis (meth) acryloyloxyisopropyl] ester and succinic acid mono- [2,3-bis (meth) acryloyloxyisopropyl] ester.

Examples of the compound having m = 2 and n = 2 include trimellitic acid mono- [4,5-bis (meth) acryloyloxyneopentyl] ester and trimellitic acid mono- [3,4-
Bis (meth) acryloyloxyisobutyl] ester and the like.

Examples of the compound having m = 3 and n = 2 include trimellitic acid mono- [3,4,5-tris (meth) acryloyloxyneopentyl] ester.

Examples of the compound in which m = 3 and n = 3 include pyromellitic acid mono- [3,4,5-tris (meth) acryloyloxyneopentyl] ester.

The above-mentioned photopolymerizable compound (B) having a carboxyl group in the molecule is used alone or in combination of two or more kinds, or in combination with one or more kinds of many photopolymerizable compounds (C) described below. used.

The amount of the photopolymerizable compound (B) containing one or more carboxyl groups in the molecule in the photopolymerizable compound (B + C) used in the present invention is 10 to 100% by weight. If the blending amount is less than 10% by weight, the curability of the obtained resin composition is remarkably poor.

The photopolymerizable compound (C) used in the present invention is 1 in the molecule.
A photopolymerizable compound having one or more photopolymerizable double bonds.

Examples of the photopolymerizable compound having one photopolymerizable double bond in the molecule include (i) alkyl (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate and lauryl (meth) acrylate. Acrylates, hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, or polyoxyalkylene glycol mono (meth) acrylates such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate, Heterocycle-containing (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate, (ii) alkylene oxide adducts of bisphenol A such as ethylene oxide and propylene oxide adducts of bisphenol A (( A) acrylates, (iii) a diisocyanate compound and one or more alcoholic hydroxyl group-containing compounds are previously reacted to obtain a terminal isocyanate group-containing compound, which is further obtained by reacting an alcoholic hydroxyl group-containing (meth) acrylate Urethane-modified mono (meth) acrylates having one (meth) acryloyloxy group in the molecule, and (iv) compounds obtained by reacting a compound having one or more epoxy groups in the molecule with acrylic acid or methacrylic acid. Epoxy mono (meth) acrylates, and (v) oligoester mono (meth) obtained by reacting acrylic acid or methacrylic acid and a polyvalent carboxylic acid as a carboxylic acid component with a divalent or higher polyhydric alcohol as an alcohol component. There are acrylates.

Examples of the photopolymerizable compound having two photopolymerizable double bonds in the molecule include (i) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and 1,4-butanediol di Alkylene glycol di (meth) acrylates such as (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) Polyoxyalkylene glycol di (meth) acrylates such as acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, (ii)
Di (meth) acrylates of alkylene oxide adducts of bisphenol A such as ethylene oxide and propylene oxide adducts of bisphenol A, (iii) obtained by previously reacting a diisocyanate compound with two or more alcoholic hydroxyl group-containing compounds Urethane-modified di (meth) acrylates having two (meth) acryloyloxy groups in the molecule obtained by further reacting a terminal isocyanate group-containing compound with an alcoholic hydroxyl group-containing (meth) acrylate, (iv) molecule Epoxy di (meth) obtained by reacting a compound having two or more epoxy groups with acrylic acid and / or methacrylic acid
Acrylates, (v) carboxylic acid components such as acrylic acid or methacrylic acid and polyhydric carboxylic acids, and oligoester di (meth) acrylates obtained by reacting two or more polyhydric alcohols as alcohol components.

Examples of the photopolymerizable compound having three or more photopolymerizable double bonds in the molecule include (i) trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, pentaerythritol tetra ( Poly (meth) acrylates of trivalent or more aliphatic polyhydric alcohols such as (meth) acrylates, (ii) terminal isocyanate group-containing compounds obtained by previously reacting a diisocyanate compound with three or more alcoholic hydroxyl group-containing compounds , Urethane-modified poly (meth) acrylates having 3 or more (meth) acryloyloxy groups in the molecule obtained by further reacting with an alcoholic hydroxyl group-containing (meth) acrylate, and (iii) 3 or more in the molecule. Acrylic acid or /
And epoxy poly (meth) acrylates obtained by reacting methacrylic acid.

Examples of the silane coupling agent (D) used in the present invention include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, trivinylethoxysilane and vinyltriacetoxysilane. , Γ-glycidoxypropyltrimethoxysilane,
Epoxysilanes such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, mercaptosilanes such as 2-mercaptoethyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, Methacryloyloxymethylsilanes such as methacryloylpropylmethyldichlorosilane and methacryloylpropyltris (methoxyethoxy) silane, halogenated silanes such as γ-chloropropyltrimethoxysilane and γ-chloropropyltriethoxysilane, γ-aminopropyltriethoxy Silane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ- (2-aminoethyl)
-Aminopropylmethyldimethoxysilane, γ- (N-
Allyl-2-aminoethyl) -aminopropyltrimethoxysilane, γ- (N-allyl) aminopropyltrimethoxysilane, γ- (N-phenyl) -aminopropyltrimethoxysilane, δ-aminobutylmethylmethoxysilane, γ -Aminopropyldimethylethoxysilane,
γ-aminopropylmethyldiethoxysilane, γ- (N,
N-diethyl) -aminopropyltrimethoxysilane,
p- (N, N-dimethyl) -aminophenyltriethoxysilane, γ- (N, N-dimethyl) -aminopropyltrimethoxysilane, p-aminophenyltrimethoxysilane, aminoethylaminomethylphenethyltriphenyl Examples thereof include aminosilanes such as methoxysilane, 1-trimethoxysilyl-2- (p-aminomethylphenyl) ethane, and bis [3- (triethoxysilyl) propyl] amine. In the present invention, epoxy silanes and mercapto silanes are particularly preferable.

The compounding ratio of the epoxy compound (A) used in the present invention and the above-mentioned photopolymerizable compound (B) having a carboxyl group in the molecule or a mixture of (B) and another photopolymerizable compound (C) is epoxy. Compound (A): Photopolymerizable compound [(B)
Or (B) + (C)] = 10:90 to 90:10 (weight ratio), preferably epoxy compound (A): photopolymerizable compound [(B) or (B) + (C)] ] = 20:80 ~ 80:20
(Weight ratio) range. When the compounding amount of the epoxy compound (A) is less than 10% by weight, the reaction between the photopolymerizable compound (B) having a carboxyl group in the molecule and the epoxy compound (A) is substantially too small and the adhesiveness, It is difficult to obtain a cured product with excellent heat resistance. Further, when the compounding amount of the epoxy compound (A) exceeds 90% by weight, the viscosity of the curable resin composition becomes high, the handling property is poor, and the advantage of the curing reaction by actinic rays, that is, the fast curing property is obtained. I can't make use of it.

The compounding amount of the silane coupling agent (D) used in the present invention is such that the epoxy compound (A) and the photopolymerizable compound [(B)
Alternatively, it is 0.05 to 20% by weight, preferably 0.1 to 10% by weight, based on the total amount of (B) + (C)].

The method for curing the curable resin composition used in the present invention is as follows. First, a photopolymerizable compound (B) having a carboxyl group by irradiation with actinic rays or a mixture of (B) and another photopolymerizable compound (C) is used. Polymerization is carried out to obtain a carboxyl group-containing polymer, and then the epoxy compound (A) is reacted with the carboxyl group contained in the above polymer by heating to complete curing.

When using ultraviolet rays as actinic rays, it is necessary to add a photoinitiator. The photoinitiator is a compound that accelerates the photopolymerization reaction of a photopolymerizable compound, and includes, for example, ketals such as benzyldimethyl ketal, benzoin methyl ether, benzoin ethyl ether, benzoin-i-propyl ether, benzoin, α-methyl. Benzoins such as benzoin, anthraquinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone and 2-ethylanthraquinone, benzophenone, p-chlorobenzophenone, benzophenone such as p-dimethylaminobenzophenone , 2-hydroxy-2-methylpropionenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropionenone and other propiophenones, dibenzosuberone and other suberones, diphenyl Disulf De, tetramethyl thiuram Soo Ruff Id, sulfur-containing compounds such as thioxanthone, methylene blue, eosin, etc. dyes such as fluorescein and the like, are used in combination alone or two or more.

In the present invention, the content of the photoinitiator is 0.05 to 20% by weight, preferably 0.5 to 10% by weight based on the total amount of the epoxy compound (A) and the photopolymerizable compound (B or B + C).
% By weight.

In the present invention, the addition of a reaction accelerator is effective when it is necessary to accelerate the reaction between the epoxy group and the carboxyl group. Examples of the reaction accelerator include 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4.
-Imidazoles such as methylimidazole, tertiary amines such as benzyldimethylamine, triethanolamine, N, N-dimethylaminoethanol, N, N-diethylaminoethanol, N, N-dipropylaminoethanol, tridimethyl There are tertiary amine salts such as triacetate and tribenzoate of aminomethylphenol, which are used alone or in combination of two or more kinds.

In the present invention, the addition amount of these reaction accelerators is 0.05 to 5% by weight, preferably 0.1 to 5% by weight based on the total amount of the epoxy compound (A) and the photopolymerizable compound (B or B + C).
It is 3.5% by weight.

The curable resin composition used in the present invention is easily manufactured by stirring and mixing at room temperature or under heating if necessary. In order to prevent thermal polymerization during production and dark reaction during storage, hydroquinone, hydroquinone monomethyl ether, 1-butyl-catechol, p-benzoquinone, 2,5
It is desirable to add a known thermal polymerization inhibitor such as -t-butyl-hydroquinone or phenothiazine. The amount added is 0.001 to 0.1 with respect to the photopolymerizable compound used in the present invention.
% By weight, preferably 0.001 to 0.05% by weight.

In addition to the above-mentioned additives, various additives such as known colorants, surface smoothing agents, and defoaming agents may be added to the curable resin composition for conductive thin film coating used in the present invention, if necessary. it can.

The photopolymerization reaction conditions, the light intensity ^{20mW / cm 2 ~200mW / cm 2} , is preferred time 0.1 seconds to 15 minutes. The post heat treatment conditions are a temperature of 40 ° C to 250 ° C and a time of 120 minutes to 10
Seconds are preferred.

The curable resin composition for coating a conductive thin film used in the present invention is an applicator, a coater, a roller, using a usual coating method such as a spray up or a printing method, on the substrate i. After coating or printing an amount of several hundreds of micron, it is polymerized by ultraviolet rays and then completely cured by heat treatment.

The conductive thin film used in the present invention generally has a specific resistance of 10 ^−3.
Having conductivity of Ω · cm or less, for example, gold, palladium,
Metals such as aluminum and platinum, silicon, gallium
Metal compounds such as phosphorus, gallium / arsenic, gallium / aluminum / phosphorus, and semiconductors such as indium oxide, tin oxide, titanium oxide, zirconium oxide, and copper iodide are 50
It is a thin film formed on a base material by a printing method, a spraying method, a coating method, a CVD method, a sputtering method, an ion plating method, a vapor deposition method or the like in a thickness of 0 angstrom to several microns.

The form of the conductive thin film may be a single-layer film or a multi-layer film in which each of them is combined such as titanium oxide / silver / titanium oxide.

As a substrate formed on the surface of these thin films, polyethylene terephthalate film, polypropylene film, polycarbonate film, polyimide film, plastic film such as polyphenylene sulfide, amorphous silicon, single crystal silicon,
Examples thereof include semiconductors such as polycrystalline silicon, woven cloth, glass, ceramics, metals such as iron, stainless steel, and aluminum.

Light sources used for UV irradiation include sunlight, chemical lamps, low pressure mercury lamps, high pressure mercury lamps, carbon arc lamps,
Xenon lamps and metal halide lamps are used. A photoinitiator is not always necessary when irradiating with an electron beam.

As the heat source used for the heat treatment, a known heating method such as an infrared heater, hot air heating, or high frequency heating is used.

(Operation) The curable resin composition used in the present invention is coated on a conductive thin film and then irradiated with an actinic ray to form a photopolymerizable compound (B) having a carboxyl group (B) or (B) and another photopolymerized compound. The mixture with the polymerizable compound (C) is polymerized to form a carboxyl group-containing material, and then the epoxy compound (A) reacts with the carboxyl group contained in the polymer by heating to obtain a completely cured coating film. The silane coupling agent contained in the curable resin composition improves the adhesiveness at the interface between the conductive thin film and the cured coating.

(Examples) Examples will be given below to specifically describe the present invention, but the present invention is not limited to these examples.

The performance of the cured coatings in the examples was evaluated by the following method.

1) Adhesiveness: Immediately after curing, it was measured by a scoring-cellophane tape peeling test.

2) Water resistance: Measured by a change in appearance after immersion in boiling water for 120 minutes and a scoring-cellophane tape peeling test.

3) Heat resistance: Measured by appearance change after heating in air at 200 ° C. for 120 minutes and by a scoring-cellophane tape peeling test.

Example 1. Epicoat 1001 which is a bisphenol A type epoxy resin
(Yukaka Shell Chemical Co., Ltd.) 100 parts by weight, phthalic acid monoacryloyloxyethyl ester 42 parts by weight, methyl tetrahydrophthalic acid monoacryloyloxyethyl ester 18
Parts by weight and 76 parts by weight of tetrahydrofurfuryl methacrylate were placed in a container and mixed with stirring at 80 ° C. to obtain a transparent resin composition (I). Obtained resin composition (I) 100
1 part by weight of 2-hydroxy-2-methylpropiophenone as a photoinitiator and N, N as a curing accelerator with respect to parts by weight.
-0.5 parts by weight of diethylaminoethanol and 1 part by weight of γ-glycidoxypropyltrimethoxysilane as a silane coupling agent were mixed and stirred at room temperature to obtain a curable resin composition (A) for coating a conductive thin film.

Then, a pin-type amorphous silicon layer was formed on a stainless steel substrate (width 0.1 mm, width 40 mm, length 60 mm), and ITO conductive thin film layer with width 10 mm and length 15 mm was further formed on it. The curable resin composition (A) for coating the conductive thin film obtained on the conductive thin film of the photoelectric conversion element and on the amorphous silicon is printed to a thickness of about 30 μm using a polyester mesh screen printing plate of 180 mesh and 50 mW. It was irradiated with ultraviolet rays of / cm ² for 30 seconds and then heated at 200 ° C. for 20 minutes to obtain a cured film. The performance of the obtained cured film is the first
Shown in the table.

Example 2. Epicoat 1001, a bisphenol A type epoxy resin
(Yukaka Shell Chemical Co., Ltd.) 90 parts by weight, succinic acid monoacryloyloxyethyl ester 43 parts by weight and tetrahydrofurfuryl methacrylator 51 parts by weight were charged into a container and stirred and mixed at 80 ° C. to give a transparent resin composition. (II) was obtained.
2-Hydroxy-2-methylpropiophenone 1 as a photoinitiator was added to 100 parts by weight of the obtained resin composition (II).
Parts by weight, 0.5 part by weight of N, N-diethylaminoethanol as a curing accelerator, and γ as a silane coupling agent.
1 part by weight of mercaptopropyltrimethoxysilane was mixed and mixed with stirring at room temperature to obtain a curable resin composition (B) for coating a conductive thin film.

Then, a cured film was obtained in the same manner as in Example 1. The performance of the obtained cured film is shown in Table 1.

Example 3. Epicoat 1001, a bisphenol A type epoxy resin
(Yukaka Shell Chemical Co., Ltd.) 100 parts by weight, phthalic acid monoacryloyloxyethyl ester 42 parts by weight, methyl tetrahydrophthalic acid monoacryloyloxyethyl ester 18
Parts by weight and tetrahydrofurfuryl acrylate 60
Part by weight was placed in a stirring vessel and mixed by stirring at 80 ° C. to obtain a transparent resin composition (III). Obtained resin composition (III) 10
2-hydroxy-2- as a photoinitiator with respect to 0 part by weight
1 part by weight of methyl propiophenone, N as a curing accelerator,
0.5 parts by weight of N-diethylaminoethanol and 1 part by weight of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as a silane coupling agent were mixed and mixed with stirring at room temperature to prepare a curable resin composition for conductive thin film coating ( C) was obtained.

Then, a cured film was obtained in the same manner as in Example 1. The performance of the obtained cured film is shown in Table 1.

Comparative Example 1. A cured film was obtained in the same manner as in Example 1 except that γ-glycidoxypropyltrimethoxysilane was not added. The performance of the obtained cured film is shown in Table 1.

Comparative Example 2. A cured film was obtained in the same manner as in Example 2 except that γ-mercaptopropyltrimethoxysilane was not added. The performance of the obtained cured film is shown in Table 1.

Comparative Example 3. A cured film was obtained in the same manner as in Example 3 except that β- (34-epoxycyclohexyl) ethyltrimethoxysilane was not added. The performance of the obtained cured film is shown in Table 1.

(Effects of the Invention) The effects of the present invention are as follows.

1) In the present invention, by using a silane coupling agent, the adhesiveness between the conductive thin film and the effect type resin composition,
In particular, the adhesiveness when immersed in boiling water can be significantly improved.

2) Since the curable resin composition is coated and cured on the conductive thin film, the conductive thin film surface is protected and there is no risk of damage. Moreover, since it is shielded from the outside air, it is not affected by moisture or the like, and a highly reliable liquid crystal display element, photoconductive element, photoelectric conversion element, or the like can be obtained.

3) Since the curable resin composition of the present invention can freely adjust the viscosity, the coating thickness on the conductive thin film can be freely adjusted,
This can reinforce the mechanical strength.

4) The curable resin composition of the present invention can be cured by irradiating it with an actinic ray for a short time and heating it at a relatively low temperature for a short time. Therefore, it is possible to reduce the manufacturing time and the manufacturing cost. .

5) Since there is no need for long-term high-temperature heating unlike conventional thermosetting resins, the selection range of substrate materials is wide.

6) Since the curable resin composition is solvent-free, a vaporizing solvent treatment device is not necessary, and a precise pattern can be formed on the conductive thin film with good reproducibility, for example, by a method such as a screen printing method.

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Claims (1)

[Claims] 1. An epoxy compound (A) having two or more epoxy groups in a molecule on a conductive thin film, and a photopolymerizable compound (A) having a carboxyl group in a molecule and represented by the general formula (I): B) or a mixture of the compound (B) with another photopolymerizable compound (C), and a silane coupling agent (D)
A coated conductive thin film obtained by coating and curing a curable resin composition containing. (In the formula, R ₁ represents hydrogen or a methyl group, R ₂ and R ₃ each represent an aliphatic, aromatic, or alicyclic residue, A represents an ester bond, and m and n each represent 1 to 1). Indicates a positive number of 3.)