JPS61193307A - Covered conductive thin film - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a conductive thin film coated with a curable resin composition.

(Prior art) Transparent electrode materials conventionally used for liquid crystal displays, photoelectric conversion elements, etc. include Nesa glass, which has a tin oxide film formed on the glass surface, and ITO glass, which has an indium oxide film formed on the glass surface. Are known. In addition, a transparent conductive thin film was formed on a plastic film instead of such a glass substrate. So-called transparent isoelectric film.

It is widely used because of its advantages such as thinness, light weight, combustibility, workability, impact resistance, and large area.

Conductive thin films such as tin oxide films and indium oxide films are extremely useful materials in the electronics and optoelectronics fields, and will continue to be used in liquid crystal displays in the future.

It is thought that it will be widely used in fields such as photoconductive elements, photoelectric conversion elements, electronic recording, and optical memory.As the application fields of conductive thin films expand in this way, the protection of conductive thin films and the Also for coating resins used for insulation purposes? IE characteristics are now required. For example, the resin coated on the conductive thin film of the transparent conductive film described above is required to have appropriate hardness, be transparent, and have excellent adhesiveness, flexibility, processability, etc. Also.

The resin that coats the conductive thin film formed on photoelectric conversion elements such as solar cells has translucency, weather resistance, processability, and external properties such as photoelectric conversion elements (e.g. amorphous silicon solar cells). For the purpose of protection from the environment, it is required to have excellent properties such as water resistance, humidity resistance, heat resistance, and thermal shock resistance.

In order to impart these properties, some of the present inventors have already proposed an epoxy compound (A) having two or more epoxy groups in the molecule as a method for coating a conductive thin film with a curable resin layer. We have proposed a coated conductive thin film formed 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. c.

(Problems to be Solved by the Invention) However, it has been found that this curable resin composition has a defect in that it does not necessarily maintain sufficient adhesion with the conductive thin film when immersed in boiling water. -O (Means for Solving the Problems) In view of this situation, the present inventors have developed a coating with a curable resin composition that has improved adhesiveness and is also excellent in water resistance, heat resistance, etc. As a result of extensive research in order to obtain a conductive thin film that has the following properties, we discovered that by adding a silane coupling agent to the curable resin composition.

The inventors have found a way to solve the above-mentioned defects and have arrived at the present invention.

That is, the present invention provides an epoxy compound (A) having two or more epoxy groups in five molecules on a conductive thin film.

Photopolymerizable compound (B) having a carboxyl group in the molecule
Alternatively, it is a coated conductive thin film obtained by coating and curing a curable resin composition containing 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 V equivalent is 100 to 4. 000. Preferably 100-1
,000.

A typical compound is bisphenol A.

Bispheno-/l/F, halogenated bisphenol A,
Bisphenol type epoxy resins which are diglycidyl ethers such as phenol novolak, novolac type epoxy resins which are polyglycidyl ethers such as cresol nopolak, polyglycidyl ethers of dihydric or higher polyhydric phenols, ethylene Glico/I/
, propylene glyco-7+/, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, trimethylo-A/7'o-han, and other polyglycidyl ethers of dihydric or higher polyhydric alcohols. be. These epoxy compounds can be used alone or in combination of two or more.

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

Among these epoxy compounds having at least two epoxy groups in the molecule, preferred epoxidized metals include:
Bisphenol type epoxy compound.

Examples include phenol novolac type polyepoxy compounds and cresol novolak type polyepoxy compounds.

Examples of the photopolymerizable compound (B) having one or more carboxyl groups in the molecule used in the present invention include (1)
Acrylic acid, methacrylic acid, itaconic acid, crotonic acid,
There are unsaturated carboxylic acid compounds such as fumaric acid and compounds represented by the following general formula (I).

R1.

(CH2=C-COO R2)-A(Rs3COO
H). ......(I) (In the formula, mR1 represents hydrogen or a methyl group, R2 and R8 each represent an aliphatic and aromatic ring group residue, A represents an ester bond, and 1m and n are Each represents a positive integer of 1 to 3.) In the general formula CI), R2 is preferably a divalent to tetravalent hydrocarbon group having 2 to 10 carbon atoms or a hydroxyl-based legged hydrogen group, R3 has 2 to 1 carbon atoms
Di- to tetravalent aliphatic polybasic acid residue which is O, carbon number 6
It is preferable that it is a di- to tetravalent aromatic polybasic acid residue having 15 to 15 valences or a di- to tetravalent alicyclic polybasic acid residue having 6 to IO carbon atoms.

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

m=1. Examples of the compound where n=1 include succinic acid mono(meth)acryloyloxyethyl ester (acryloyloxyethyl ester and methacryloyloxyethyl ester).

The rest will be abbreviated in the same way. ), phthalic acid mono(meth)acryloyloxyethyl ester, methyltetrahydrophthalic acid mono(meth)acryloyloxyethyl ester/
L/, 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-(phenoxymethy/I/)ethyl ester, phthalic acid mono-2-hydroxy-3-
Examples include (meth)acryloyloxypropyl ester and succinic acid mono 2'-hydroxy-3=(meth)acryloyloxypropyl ester.

Examples of compounds where mwl and n=2 include trimellitic acid mono-2-(meth)acryloyloxyethyl ester. Examples of the compound where m=l and n=3 include pyromellitic acid mono-2-(meth)acryloyloxyethyl ester.

m=2. The compound where n=1 is 1, for example, phthalate mono-[2,3-bis(meth)acryloyloxyisopropyl]ester, I+/, methyltetrahydrophthalate 7-C2,3-bis(meth)acryloyloxyisopropyl ]Ester, tetrahydrophthalic acid mono-
Examples include [2,3-bis(meth)acryloyloxyisopropyl]ester/L/, succinic acid mono-[2,3-bis(meth)acryloyloxyisopropyl]ester, and the like.

m=2. Examples of compounds where n=2 are 2, for example, trimellitic acid mono-(4,5-bis(meth)acryloyloxyneopentyl) ester, trimellitic acid heptano[3,
Examples include 4-bis(meth)acryloyloxypropyl ester.

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

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

Photopolymerizable compound (B) having a carboxyl group in the molecule
Among the above-mentioned compounds, (1) is particularly preferred. These photopolymerizable compounds (B) having a V group in the molecule are used alone, and two or more TFCs are used in combination,
Alternatively, it is used in combination with one or more of the other photopolymerizable compounds (C) described below.

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 resulting resin composition will be extremely poor.

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

Examples of photopolymerizable compounds having one photopolymerizable double bond in the molecule include (I) methyl (meth)acrylate, ethyl (meth)acrylate, lauri/L/(
Alkyl (meth)acrylates such as meth)acrylate, hydroxyalkyl/I/(meth)acrylates such as 2-hydroxyethyl (meth)acrylate, or polyethylene glycol mono(meth)acrylate, polypropylene glycol 7-(meth)acrylate Polyoxyalkylene glycol nanano (meth) such as
acrylates, heterocycle-containing (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate,
(1) mono(meth)acrylates of alkylene oxide adducts of bisphenol A, such as ethylene oxide and propylene oxide adducts of bispheno-1'vA; (fil) diisocyanate compounds and compounds containing one or more alcoholic hydroxyl groups; A urethane-modified mono(meth) having one (meth)acryloyloxy V group in the molecule obtained by further reacting a terminal isocyanate group-containing compound obtained by reacting in advance with an alcoholic hydroxyl group-containing (meth)acrylate. acrylates,
(IV) EBOKI V mono(meth)acrylates obtained by reacting acrylic acid or methacrylic acid with a compound having one or more epoxy groups in the molecule, and (V) acrylic acid or methacrylic acid as a carboxylic acid component and There are oligoester mono(meth)acrylates obtained by reacting a polyhydric carboxylic acid with a polyhydric alcohol having a valence of 2 or more as an alcohol component.

Examples of photopolymerizable compounds having two photopolymerizable double bonds in the molecule include (1) ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, l,4-butanediol di Alkylene glycol di(meth)acrylates such as (meth)acrylate, neobentyl glycol di(meth)acrylate, 1,6-hexanethiol di(meth)acrylate.

Diethylene glycol di(meth)acrylate.

Triethylene glycol di(meth)acrylate.

Dipropylene glycol di(meth)acrylate.

Polyoxyalkylene glycol di(meth)acrylates such as polyethylene glycol di(meth)acrylate and polypropylene glyco-μ di(meth)acrylate; (key) bisphenols such as ethylene oxide and propylene oxide adducts of bisphenol A; A/
A terminal isocyanate group-containing compound obtained by reacting in advance di(meth)acrylates of alkylene oxide adducts, (lil) diisocyanate compounds, and two or more alcoholic hydroxyl group-containing compounds is further added with alcoholic hydroxyl group-containing (meth) ) Urethane-modified di(meth)acrylates having two (meth)acrylomorphic groups in the molecule obtained by reacting acrylates, (l
v) Epoxy di(meth)acrylates obtained by reacting acrylic acid or/and methacrylic acid with a compound having two or more epoxy groups in the molecule, (V) Acrylic acid or methacrylic acid and polyhydric acid as a carboxylic acid component Examples include oligoester di(meth)acrylates obtained by reacting a carboxylic acid with two or more polyhydric alcohols as alcohol components.

Examples of photopolymerizable compounds having three or more photopolymerizable double bonds in the molecule include (+) ) IJ methylolpropane tri(meth)acrylate.

Trimethylolethane tri(meth)acrylate.

Terminal isocyanate group obtained by reacting in advance a trivalent or higher aliphatic polyhydric alcohol alcohol acrylate such as pentaerythritol tetra(meth)acrylate, '(II) diisocyanate compound and a compound containing three or more alcoholic hydroxyl groups. Urethane-modified poly(meth)acrylates having three or more d-meth)acryloyloxy groups in the molecule obtained by reacting the containing compound with an alcoholic hydroxyl group-containing (meth)acrylate.

(There are epoxy poly(meth)acrylates obtained by reacting a compound having three or more epoxy groups in 10 molecules with acrylic acid and/or methacrylic acid.

Examples of the silane coupling agent (D) used in the present invention include vinyltrichlor Vlan, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltris(
Vinyl silanes such as β-methoxyV ethoxysilane, trivinylethoxysilane, vinyltriacetoxysilane, γ-glycidoxyVpropyltoglytoxysilane, β
- Epoxy V silanes such as (3,4-epoxycyclohexyne/L/)ethyltrimethoxy V silane, r-merca-
7”) Mercaptosilanes such as propyltrimethoxine or 2-mercaptoethyltriethoxysilane, 3
- methacryloyloxypropyltrimethoxy V run,
Methacryloyloxy silanes such as methacryloylpropylmethyldichlorosilane and methacryloylpropyltris(methoxyethoxy)silane, halogenated V-ranes such as γ-chloropropyltrimethoxysilane and γ-chloropropyltriethoxysilane, and γ-aminopropyltris(methoxyethoxy)silane. Ethoxysilane mr-(2-aminoethyl 1v)
-aminopropyltrimethoxysilane h r-(2-
(aminoethyl)-aminopropylmethyldimethoxysilane, γ-(N-allyl-2-aminoethyl)-aminopropyltrimethoxysilanebr-(N-allyl)aminopropyltrimethoxysilane, γ-(N-phenyl)-
Aminopropyltrimethoxysilane, δ-aminobutyldimethylmethoxy Vlan, γ-aminopropyldimethylethoxysilane, r-aminopropylmethyljethoxysilane% r -(N,N-diethyl 1v)-aminopropyltrimethoxysilane h p -(NlN-dimethy)V), -aminophenyltriethoxysilane 5r-(
NlN-dimethoxylv)-aminopropyltrimethoxysilane, p-aminophenyltrimethoxysilane.

Examples include aminosilanes such as aminoethylaminomethyl-phenethyltrimethoxysilane, 1-trimethoxysilyl-2-(p-aminomethylphenylene/I/) ethale, and bis[3-(triethoxysilyl/I/)propyl ether. . In the present invention, in particular, epoxysilanes,
Mercapto-silanes are preferred.

Epoxy compound (A) used in the present invention and photopolymerizable compound (B) having carboxy V/l/group in the molecule described above
Or, the blending ratio of the mixture of (B) and other photopolymerizable compound (C) is epoxy compound (A):photopolymerizable compound C (
B) 1 * C (B) + (C) ], = l O:
The range is 90 to 90; 10 (weight ratio), preferably epoxy compound (A) bipolymerizable compound [(B) or (B) + (C)) = 20: 80 to 80:
20 (weight ratio). If the 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) will be substantially too small, resulting in poor adhesiveness. It is difficult to obtain a cured product with excellent heat resistance. It was.

If the amount of the epoxy compound (A) exceeds 90% by weight, the curable resin composition will not have high viscosity, will lack ease of handling, and will not have the advantage of curing reaction with actinic rays, that is, fast curing. I can't do it.

The blending amount of the silane coupling agent (D) used in the present invention is determined by mixing the epoxy compound (A) and the photopolymerizable compound [(B)
Mataka (B) + (C)) ,! : 0 for the total amount.
05-20% by weight, preferably 0.1-10% by weight.

The method for curing the curable resin composition used in the present invention is to first cure the photopolymerizable compound (B) having a cyclocarboxylic V group or (B) and another photopolymerizable compound (C
) is polymerized to form a carboxyl group-containing polymer, and then the jepoxy compound (A) is reacted with the carboxyl group contained in the polymer by heating to completely cure it.

When using ultraviolet rays as active light, it is necessary to add a photoinitiator. A photoinitiator is a compound that promotes the photopolymerization reaction of a photopolymerizable compound.

For example, ketals such as benzyl dimethyl ketal, benzoin methyl ether, benzoin ethyl ether,
Benzoin-i-propyl ether.

Benzoins such as benzoin and α-methylbenzoin, anthraquinones such as 10-anthraquinone, l-chloroanthraquinone, 2-chloroanthraquinone, and 2-ethylanthraquinone, benzophenone, p-
Benzophenones such as chlorbenzophenone and p-dimethylaminobenzophenone; propiophenones such as 2-hydroxy-2-methylpropiophenone and 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropiophenone; Examples include suberones such as dibenzosuberonate, sulfur-containing compounds such as diphenyl disulfide, tetramethylthiuram disulfide, and thioxanthone, and pigments such as methylene blue, niosin, and fluorescein.

They may be used alone or in combination of two or more.

In the present invention, the blending amount of this photoinitiator is 0.05 to 20% by weight, preferably 0.05 to 20% by weight based on the total amount of the epoxy compound (A) and the photopolymerizable compound (B or B+C).
．． It is 5 to 10% by weight.

In the present invention, when it is necessary to promote the reaction between an epoxy group and a carboxyl group, it is effective to add a reaction promoter. Examples of reaction accelerators include 2-methylimidazole, 2-ethylimidazo-A/, 2-ethyl-
Imidazoles such as 4-methylimidazole, benzyldimethylamine, triethanolamine, N, N
Tertiary amines such as -dimethylaminoethanol, N,N-diethylaminoethanol/L', NlN-dipropylaminoethanol, tertiary amines such as triacetate and tribenzoate of tridimethylaminomethylphenol, etc. Reeds can be used alone or in combination of two or more.

In the present invention, the amount of these reaction accelerators added is 0.05 to 5% by weight, preferably 0.05% to 5% by weight based on the total amount of the epoxy compound (A) and the photopolymerizable compound (B or B+C).
．． It is 1 to 3.5% by weight.

The curable resin composition used in the present invention can be easily produced by stirring and mixing at room temperature or under heating if necessary. To prevent thermal polymerization during manufacturing and dark reactions during storage,
hydroquinone, hydroquinone monomethyl ether,
l-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 from 0.001 to the photopolymerizable compound used in the present invention.
0.1% by weight, preferably 0.001-0.05
Weight%.

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

Photopolymerization reaction conditions include light intensity of 20 mW/CTA~
At 20077JW/ltA, time 0.1 seconds to 1
5 minutes is preferred. In addition, the post-heating treatment conditions include a temperature of 40
1 hour 120 minutes to 10 seconds at 250°C to 250°C is preferred.

An applicator, coater, and roller for the curable resin composition for coating a conductive film used in the present invention.

After coating or printing a thickness of several microns to several hundred microns on a base material, that is, a conductive thin film, using a conventional coating method such as spray-up or printing method, the film is subjected to multiple polymerization using ultraviolet rays, followed by heat treatment. Completely cure.

The conductive thin film used in the present invention generally has a specific resistance of 10
For example, gold has a conductivity of -30 m or less.

Metals such as palladium, aluminum and platinum; metal compounds such as silicon, gallium oxide, gallium arsenic, gallium aluminum oxide; semiconductors such as indium oxide, tin oxide, titanium oxide, zirconium oxide, and copper iodide. For example, printing method, spray method, coating method, CVD method,
It is a thin film formed on a base material by a sputtering method, an ion plating method, a vapor deposition method, etc.

The form of the conductive thin film may be a single layer film or a multilayer film consisting of a combination of titanium oxide/silver/titanium oxide, for example.

Substrates on which these thin films are formed include polyethylene terephthalate film, polypropylene film, polycarbonate film, polyimide film, plastic films such as polyphenylene sulfide, amorphous silicon, single crystal silicon, polycrystalline silicon, etc. Examples include semiconductors, woven fabrics, glass, ceramics, and metals such as iron, stainless steel, and aluminum.

The light source used for ultraviolet irradiation is sunlight.

Chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, carbon arc lamps, xenon lamps, metal halide lamps, etc. are used. A photoinitiator is not necessarily required when irradiating with an electron beam.

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

(Function) After the curable resin composition used in the present invention is coated on a conductive thin film, it is irradiated with actinic rays to form a photopolymerizable compound (B) or (B) having a carboxyl group and other photopolymerizable compounds. The mixture with the chemical compound (C) is polymerized to become a carboxyl group-containing substance, and then, by heating, the jepoxy compound (A) and the carboxyl group contained in the polymer react with each other to obtain a completely cured coating. The silane coupling agent contained in the curable resin composition improves the adhesion at the interface between the conductive thin film and the cured film.

(Examples) Examples will be given below to specifically explain the present invention, but the present invention is not limited to these Examples in any way.

Performance evaluation of the cured coatings in Examples was carried out by the following method: 1) IF property: Measured by a cross-cellophane tape peel test immediately after curing.

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

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

Example 1 Bispheno-A/A type epoxy resin Ebico)
tool (manufactured by Yuka Shell Chemical Co., Ltd.) 100 parts by weight, 42 parts by weight of phthalic acid monoacroyloxyethyl ester, methyltetrahydrophthalic acid monoacroyloxyethyl ester/L/18 parts by weight, and Hinatrahydrofurfurylmeth Pour 6 parts by weight of 1 acrylic into a container, and
The mixture was stirred and mixed at ℃ to obtain a transparent resin composition (I). To 100 parts by weight of the obtained resin composition (I), 1 part by weight of 2-hydroxy-2-methylpropiophenone as a photoinitiator, 0.5 part by weight of N,N-diethylaminoethanol and silane as a curing accelerator. 1 part by weight of γ-glycidoxypropyl trimethoxy V run was added as a system coupling agent and mixed with stirring at room temperature to obtain a curable resin composition (A) for coating a conductive thin film.

Next, a pin-type amorphous silicon layer is formed on a stainless steel substrate (thickness o, i m) with a width of 40 Ig and a length of 60 ff, and an ITO conductive layer with a width of 10 and a length of 15 m is formed on it. Curable resin m-acid (A) for coating conductive thin film obtained on conductive thin film of photoelectric conversion element with thin film layer formed and on amorphous silicon
Print to a thickness of approximately 30 μm using a T-180 mesh polyester screen printing plate.

Irradiated with 50 mW/- ultraviolet rays for 30 seconds, then 200 mW/-
A cured film was obtained by heating at ℃ for 20 minutes. The performance of the obtained cured film is shown in Table 1.

Example 2 Bispheno-A/A type epoxy resin Epicor)
1001 (manufactured by Yuka Vell Chemical Co., Ltd.) 90 parts by weight.

43 parts by weight of succinic acid monoacryloyloxyethyl ester and 5 parts by weight of tetrahydrofurfuryl methacrylate
1 part by weight was charged into a container and stirred and mixed at 80°C to obtain a transparent resin composition (II). Obtained resin composition (n)
2-hydroxy- as a photoinitiator per 100 parts by weight
1 part by weight of 2-methylpropiophenone, 10.5 parts by weight of N,N-diethylaminoethano-/L as a curing accelerator, and 1 part by weight of r-mercaptopropyltrimethoxysilane as a silane coupling agent were mixed at room temperature. The mixture was stirred and mixed to obtain a curable resin composition (B) for coating a conductive thin film.

A cured film was then obtained in the same manner as in Example 1.

The performance of the obtained 7'c cured film is shown in Table 1.

Example 3 Bisphenol A type epoxy resin Epicor) 1
001 (manufactured by Yuka Shell Chemical Co., Ltd.) 100 parts by weight.

42 parts by weight of phthalic acid monoacryloyloxyethyl ester, 18 parts by weight of methyltetrahydrophthalic acid monoacryloyloxyethyl ester) and 60 parts by weight of tetrahydrofurfuryl acrylate were placed in a stirring vessel,
The mixture was stirred and mixed at 80° C. to obtain a transparent resin composition (ff[). For 100 parts by weight of the obtained resin composition (nt),
2-Hydroxy-2-methylpropiophenone 1 [i parts] as photoinitiator.

N,N-diethylaminoethanol-yv as a curing accelerator
Parts of O,Sit and 1 part by weight of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane as a silane coupling agent were mixed with stirring at room temperature to form a curable resin composition for coating a conductive thin film ( After obtaining C), 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 no silane was added. The performance of the obtained cured film is shown in Table 1 and is 7'C.

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.

(Effect of the invention) The effects of the present invention include the following points.

l) In the present invention, by using a silane coupling agent, the adhesion between the conductive thin film and the curable resin composition, especially when immersed in boiling water, can be significantly improved. .

2) Since the curable resin composition is coated on the conductive thin film and cured, the surface of the conductive thin film is protected and there is no risk of damage. In addition, since it is isolated from the outside air, it is not affected by the harmful effects of humidity, making it highly reliable liquid crystal display elements, photoconductive elements,
Photoelectric conversion elements and the like can be obtained.

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

4) The curable resin composition of the present invention can be cured by short-time irradiation with actinic rays and heating at a relatively low temperature for a short time, thereby shortening manufacturing time and reducing manufacturing costs. I can do it.

5) Unlike conventional thermosetting resins, it does not require long-term heating at low temperature, so there is a wide range of substrate materials to choose from.

6) Since the curable resin composition is solvent-free, there is no need for a processing device for vaporized solvents, and precise patterns can be formed on conductive thin films with good reproducibility using techniques such as screen printing. .

Claims (1)

[Claims] An epoxy compound (A) having two or more epoxy groups in the molecule, a photopolymerizable compound (B) having a carboxyl group in the molecule, or the compound (B) and another photopolymerizable compound on the conductive thin film. A coated conductive thin film obtained by coating and curing a curable resin composition containing a mixture with (C) and a silane coupling agent (D).