KR101368495B1 - Transparent electronde and conducting laminates - Google Patents

Abstract

The present invention includes a photosensitive resin layer in which carbon nanotubes are dispersed on a surface, thereby providing a transparent electrode having an easy and transparent electrode pattern and high electrical conductivity.

Description

Transparent Electrode and Conducting Laminates

The present invention relates to a transparent electrode and a conductive laminate, and relates to a transparent electrode including a photosensitive resin layer in which carbon nanotubes are dispersed on a surface thereof.

BACKGROUND OF THE INVENTION As computers, various home appliances and communication devices are digitized and rapidly upgraded, there is a desperate need for realization of large-screen and portable displays. In order to realize a portable, large-area flexible display, a display material of a material that can be folded like a newspaper is needed.

To this end, the electrode material for the display must exhibit a high transparency and a low resistance, as well as a high strength so as to be mechanically stable even when the device is bent or folded, and have a thermal expansion coefficient similar to that of the plastic substrate, Even at high temperatures, short circuit or change of sheet resistance should not be large.

Flexible displays allow the manufacture of displays of any shape, so not only portable display devices, but also garments that can change colors or patterns, clothing labels, billboards, price signs on product shelves, large-scale electric lighting devices, etc. Can be used.

In this regard, a transparent conductive thin film is widely used for devices that simultaneously require two purposes, namely, image sensor, solar cell, and various displays (PDP, LCD, flexible) Material.

Indium tin oxide (ITO) has been extensively studied as a transparent electrode for a flexible display. However, in order to manufacture a thin film of ITO, a vacuum process is basically required and thus not only an expensive process cost is required but also a flexible display device When it is bent or folded, its life is shortened due to breakage of the thin film.

In order to solve the above problems, the carbon nanotubes are chemically bonded to the polymer and then molded into a film, or the carbon nanotubes are coated on the conductive polymer layer by coating the purified carbon nanotubes or the carbon nanotubes chemically bonded to the polymer. Nanoscale is dispersed inside or on the coating layer, and metal nanoparticles such as gold and silver are mixed to minimize scattering of light in the visible region and improve conductivity, so that the transmittance in the visible region is 80% or more, and sheet resistance A transparent electrode having 100 Ω / □ or less has been developed (Korean Patent Publication No. 10-2005-001589). In this case, a solution of carbon nanotubes in a specific concentration was reacted with polyethylene terephthalate to prepare a solution of a high-concentration carbon nanotube polymer. Then, the solution was coated on a polyester film substrate and dried to prepare a transparent electrode.

However, the transparent electrode has a disadvantage in that the manufacturing process is complicated and expensive materials are used.

In addition, research into using a conductive polymer which is an organic material as a transparent electrode material is underway. In the case of an electrode manufactured using a conductive polymer, various existing polymer coating methods can be used, which greatly reduces the process cost and operation. That is, in manufacturing flexible displays and electric lighting devices, transparent electrodes made of conductive polymers such as polyacetylene, polypyrrole, polyaniline, polythiophene, etc. are much more flexible and brittle as well as process advantages over transparent indium tin oxide electrodes. This has the advantage that the life of the device can be extended in cases where less flexible electrodes are needed, especially in the manufacture of touch screens and the like. However, in general, the conductive properties of organic electrodes made of conductive polymers increase in proportion to the thickness of the electrodes. Since the conductive polymers absorb light in the visible region, the coating is thinly coated to increase the transmittance for use in displays. In this case, when the transmittance of the visible light region is increased, it is difficult to satisfy the sheet resistance required in the application field of the transparent electrode. In particular, in the case of using polythiophene (byteron P, Bayer Co., Ltd.) in which conductive polymer nanoparticles are dispersed in order to improve processability, even when using a mixed solvent to improve conductivity and coating property, the substrate is 50 nm thick. When spin coating on the substrate, there is a problem that it is difficult to obtain sheet resistance of 1 kΩ / □ or less.

In addition, most conventional organic electrode materials using carbon nanotubes are prepared by simply mixing carbon nanotubes and conductive polymers, and carbon nanotubes are formed in a conductive polymer matrix by a strong van der Waals force. Agglomerates heavily at Due to the agglomeration of the carbon nanotubes, despite the excellent conduction characteristics of the carbon nanotubes, in order to improve the conductivity by means of percolation, 1 to 10 wt% of carbon nanotubes must be mixed and aggregated at a micro scale. The carbon nanotubes were not suitable for use as transparent electrodes because they significantly reduced the transparency of the electrodes. Therefore, there is a demand for an organic transparent electrode material having excellent transparency and low sheet resistance even when a small amount of carbon nanotubes are used.

In one embodiment of the present invention to provide a transparent electrode that is easy to implement a circuit pattern.

In one embodiment of the present invention also to provide a transparent electrode excellent in light transmittance and electrical conductivity as a thin film.

In one embodiment of the present invention to provide a conductive laminate easy to implement a circuit pattern.

In one embodiment of the present invention also to provide a conductive laminate excellent in light transmittance and electrical conductivity as a thin film.

In one embodiment of the invention the carbon nanotubes exposed on the surface; And a carbon nanotube mixed layer having a photopolymerizable resin composition or a photodegradable resin composition mixed with a carbon nanotube, and a photosensitive resin layer having a photopolymerizable resin composition or a photodegradable resin composition.

In the transparent electrode according to the embodiment of the present invention, the carbon nanotubes and the carbon nanotube mixed layer exposed on the surface are formed on the photosensitive resin layer having the photopolymerizable resin composition or the photodegradable resin composition, carbon nanotubes, water and It may be formed by applying a carbon nanotube dispersion liquid containing an organic solvent. At this time, the organic solvent may be soluble in the photosensitive resin layer, water and the organic solvent may be included in a weight ratio of 5:95 to 95: 5.

In the transparent electrode according to an embodiment of the present invention, the photopolymerizable resin composition may include an alkali-soluble binder resin, a photopolymerizable compound and a photoinitiator.

In the transparent electrode according to another embodiment, the photodegradable resin composition may include an alkali-soluble binder resin, a positive photosensitive compound and a sensitivity enhancer.

In the transparent electrode according to an embodiment of the present invention, the carbon nanotubes in the carbon nanotube dispersion may be dispersed to 0.001 to 2.0% by weight.

In the transparent electrode according to an embodiment of the present invention, the photosensitive resin layer may have a thickness of 110nm to 110㎛.

In the transparent electrode according to the embodiment of the present invention, the carbon nanotube and the carbon nanotube mixed layer exposed on the surface may have a total thickness of 10 nm to 10 μm.

The transparent electrode according to the preferred embodiment may have a light transmittance of 70% or more at 550 nm and a surface resistance of 5000 Ω / □ or less.

In one exemplary embodiment of the invention the carbon nanotubes exposed on the surface; And a carbon nanotube mixed layer having a photopolymerizable resin composition or a photodegradable resin composition mixed with the carbon nanotubes; a photosensitive resin layer having a photopolymerizable resin composition or a photodegradable resin composition; And it provides a conductive laminate comprising a substrate layer.

In the conductive laminate according to one embodiment of the present invention, the carbon nanotubes and the carbon nanotube mixed layer exposed on the surface are formed on the photosensitive resin layer having the photopolymerizable resin composition or the photodegradable resin composition. And it may be formed by applying a carbon nanotube dispersion containing an organic solvent. In this case, the organic solvent may be soluble in the photosensitive resin layer, and water and the organic solvent may be included in a weight ratio of 5:95 to 95: 5.

In the conductive laminate according to one embodiment of the present invention, the photopolymerizable resin composition may include an alkali-soluble binder resin, a photopolymerizable compound, and a photoinitiator.

In the conductive laminate according to another embodiment, the photodegradable resin composition may include an alkali-soluble binder resin, a positive photosensitive compound, and a sensitivity enhancer.

In the conductive laminate according to one embodiment of the present invention, the carbon nanotubes in the carbon nanotube dispersion may be dispersed to 0.001 to 2.0% by weight.

In the conductive laminate according to one embodiment of the present invention, the photosensitive resin layer may have a thickness of 110nm to 110㎛.

In the conductive laminate according to one embodiment of the present invention, the carbon nanotube and the carbon nanotube mixed layer exposed on the surface may have a total thickness of 10 nm to 10 μm.

The conductive laminate according to the preferred embodiment may have a light transmittance of 70% or more at 550 nm and a surface resistance of 5000 Ω / □ or less.

In the conductive laminate according to one embodiment of the present invention, the substrate layer may be a plastic film or a glass substrate.

According to one embodiment of the present invention, it is possible to provide a transparent electrode that is easy to form an electrode pattern, has a high electrical conductivity and has excellent transparency while forming an electrode layer with a thin film.

Hereinafter, the present invention will be described in detail.

The conductive laminate and the transparent electrode of the present invention are excellent in transparency and electrical conductivity, which may be a conductive layer formed on the base layer.

In this case, the substrate layer may be a plastic film or a glass substrate.

In particular, the transparent electrode may be formed of an electrode layer on a heat resistant and transparent substrate or an electrode layer obtained directly from the composition for forming an electrode.

The substrate constituting the film-shaped transparent electrode is not particularly limited as long as the film satisfies heat resistance and transparency. For example, the average linear expansion measured in the range of 50 to 250 ° C. by thermomechanical analysis based on the film thickness of 50 to 100 μm. It may be a polyimide film having a coefficient (CTE) of 35.0 ppm / ° C or less and a yellowness of 15 or less.

If the average coefficient of linear expansion (CTE) is greater than 35.0 ppm / ° C based on a film thickness of 50 to 100 μm, the difference in thermal expansion coefficient with the plastic substrate is increased, and a short circuit may occur when the device is overheated or at a high temperature. In addition, a yellowness of greater than 15 is not preferred as a transparent electrode because of the lack of transparency. In this case, the average linear expansion coefficient is obtained by measuring a strain according to a temperature rise within a predetermined temperature range, which may be measured using a thermomechanical analyzer.

In view of transparency, a colorless transparent plastic film, specifically a polyimide film having a yellow degree of 15 or less based on a film thickness of 50 to 100 mu m, may be preferable. Also, a polyimide film having an average transmittance of 85% or more at 380 to 780 nm can be used as a plastic film when the transmittance is measured using a UV spectrophotometer based on a film thickness of 50 to 100 μm. When such transparency is satisfied, it can be used as a transparent electronic paper and a plastic substrate for a liquid crystal display device. Moreover, the plastic film may be a polyimide film having a transmittance of at least 88% at 550 nm and a transmittance of at least 70% at 420 nm when the transmittance is measured by a UV spectrophotometer based on a film thickness of 50 to 100 μm.

In addition, the polyimide film has a L value of 90 or more, a value of 5 or less, and b value of 5 in terms of improving transparency to improve transparency, when the color coordinate is measured by UV spectrophotometer based on the film thickness of 50 to 100 μm. It may be the following polyimide film.

Such a polyimide film may be obtained by polymerizing an aromatic dianhydride and a diamine to obtain a polyamic acid, and then imidating it. Examples of the aromatic dianhydride include 2,2-bis (3,4-dicarboxy). Phenyl) hexafluoropropane dianhydride (6-FDA), 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dica At least one selected from carboxyl anhydride (TDA) and 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic anhydride) (HBDA) and pyromellitic dian One or more selected from hydride (PMDA), biphenyltetracarboxylic dianhydride (BPDA) and oxydiphthalic dianhydride (ODPA), but is not limited thereto.

Examples of the aromatic diamine include 2,2-bis [4- (4-aminophenoxy) -phenyl] propane (6HMDA), 2,2'-bis (trifluoromethyl) -4,4'- Biphenyl (2,2'-TFDB), 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (3,3'-TFDB), 4,4'-bis (3-aminophenoxy) diphenyl sulfone (DBSDA), bis (3-aminophenyl) sulfone (3DDS), bis (APB-133), 1,4-bis (4-aminophenoxy) benzene (APB-134), 2,2'-bis [3- (3-aminophenoxy) phenyl] hexafluoropropane ), Hexafluoropropane (4-BDAF), 2,2'-bis (3-aminophenyl) hexafluoropropane (3,3 ' But not limited to, at least one selected from the group consisting of 2,2'-bis (4-aminophenyl) hexafluoropropane (4,4'-6F) .

There is no particular limitation in the method for producing a polyimide film using such a monomer, and as one example thereof, the aromatic diamine and the aromatic dianhydride are polymerized under a first solvent to obtain a polyamic acid solution. After imidizing the mixed acid solution, the imidized solution was added to the second solvent, filtered and dried to obtain a solid content of the polyimide resin, and a polyimide solution obtained by dissolving the obtained polyimide resin solid content in the first solvent was formed into a film. It can form into a film through a process. In this case, the second solvent may have a lower polarity than the first solvent. Specifically, the first solvent may include m-crossover, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF) Amide (DMAc), dimethylsulfoxide (DMSO), acetone, and diethyl acetate, and the second solvent may be at least one selected from water, alcohols, ethers and ketones.

Meanwhile, in order to form an electrode layer having a uniform thickness in forming a metal film on the plastic film, the surface smoothness of the plastic film may be 2 μm or less, preferably 0.001 to 0.04 μm.

To form a conductive layer on the heat-resistant transparent film substrate, the conductive layer according to an embodiment of the present invention is a photopolymerizable resin composition or photodegradable resin composition mixed with carbon nanotubes and carbon nanotubes exposed on the surface It comprises a photosensitive resin layer comprising a carbon nanotube mixed layer.

1 is a cross-sectional view for better understanding thereof.

1, the photosensitive resin layer 3 is formed on the base material 4, and the photosensitive resin layer 3 becomes the photosensitive resin composition mixed with the carbon nanotube 1 and carbon nanotube exposed on the surface. A carbon nanotube mixed layer 2 is included.

In the description of the present invention, the photopolymerizable resin composition or the photodegradable resin composition will be understood as a photosensitive resin composition commonly referred to as a negative photoresist composition or a positive photoresist composition, and the composition thereof is not particularly limited.

For example, the photopolymerizable resin may include a composition containing an alkali-soluble binder resin, a photopolymerizable compound, and a photoinitiator. For example, the alkali-soluble binder polymer may be a copolymer of (meth) acrylic acid and (meth) acrylic acid ester or a conductive resin film. It may be an alkali-soluble polymer resin such as hydroxypropyl methylcellulose acetate phthalate to improve mechanical strength such as scratch resistance.

The copolymer of (meth) acrylic acid and (meth) acrylic acid ester can be obtained through copolymerization of two or more monomers selected from the following; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylic acid, methacrylic acid, 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxy propyl acrylate, 2-hydroxy propyl methacrylate, acrylamide, methacrylamide, styrene, α-methyl styrene and the like.

These copolymers preferably have an average molecular weight of 30,000 to 150,000, and a glass transition temperature of 20 to 150 ° C. in consideration of coating property, followability, and mechanical strength of the pattern itself after circuit formation. The content of such a binder polymer is usually preferably 20 to 80% by weight in the resin composition.

A photopolymerizable compound is a compound which initiates reaction by a photoinitiator, and has at least 2 terminal ethylene group, For example, 1, 6- hexanediol (meth) acrylate and 1, 4- cyclohexanediol- (meth) acrylate , Poly-propylene glycol- (meth) acrylate, poly-ethylene glycol- (meth) acrylate, 2-di- (p-hydroxy phenyl) -propane-di- (meth) acrylate, glycerol tri (meth) Acrylate, trimethol propane tri- (meth) acrylate, polyoxy propyl trimethol propane tri- (meth) acrylate, polyethylene (propylene) di (meth) acrylate containing bisphenol A groups and urethane groups Polyfunctional group (meth) acrylate etc. are mentioned.

It is usually preferable that the total content of the photopolymerizable compound is 1.0 to 50% by weight in terms of solids content in the resin composition.

Photoinitiators are substances that initiate chain reactions with photopolymerizable compounds by UV and other radiation, for example anthraquinone derivatives, such as 2-methyl anthraquinone, 2-ethyl anthraquinone, benzoin derivatives, benzo Phosphorus methyl ether, benzophenone, phenanthrene quinone, and 4,4 'bis- (dimethylamino) benzophenone. In addition to this, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholi Nopropan-1-one, 2-benzyl-2-dimethylamino-1- [4-morpholinophenyl] butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1- [4- (2-hydroxymethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one, 2,4-diethyl Thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxycyxanthone, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4 '-Methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzo , 2-isoamyl 4-dimethylaminobenzoate, 2,2-diethoxyacetophenone, benzyl ketone dimethylacetal, benzyl ketone β-methoxy diethyl acetal, 1-phenyl-1,2-propyldioxime-o , o '-(2-carbonyl) ethoxyether, methyl o-benzoylbenzoate, bis [4-dimethylaminophenyl) ketone, 4,4'-bis (diethylamino) benzophenone, 4,4'- Dichlorobenzophenone, benzyl, benzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-butoxybenzoin, isobutoxybenzoin, tert-butoxybenzoin, p-dimethylaminoacetophenone , p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, dibenzosuberon, α, α-dichloro- And a compound selected from 4-phenoxycetophenone and pentyl 4-dimethylaminobenzoate.

The content of the photoinitiator is usually preferably 2 to 10% by weight in the resin composition.

On the other hand, the photodegradable resin composition is not particularly limited, and examples thereof include a composition containing an alkali-soluble binder resin, a positive photosensitive compound, and a sensitivity enhancer. Here, the alkali-soluble binder resin is not particularly limited, but may include a thermosetting novolak resin, which is a condensation product of phenol and aldehyde, and most preferably may include a cresol novolak resin.

Novolak resins are obtained by polycondensation of phenol alone or in combination with aldehydes and acidic catalysts.

Although it does not specifically limit as phenols, Phenol, o-cresol, m-cresol, p-cresol, 2, 3- xylenol, 2, 5- xylenol, 3, 4- xylenol, 3, 5- character Monovalent such as ethylene, 2,3,5-trimethylphenol-xyleneol, 4-t-butyl phenol, 2-t-butyl phenol, 3-t-butyl phenol, 4-methyl-2-t-butyl phenol Phenols; And 2-naphthol, 1,3-dihydroxy naphthalene, 1,7-dihydroxy naphthalene, 1,5-dihydroxy naphthalene, resorcinol, pyrocatechol, hydroquinone, bisphenol A, phloroglucinol, Polyhydric phenols, such as a pyrogallol, etc. are mentioned, It can be used individually or in combination of 2 or more types. In particular, a combination of m-cresol and p-cresol is preferable.

Examples of the aldehydes include, but are not particularly limited to, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α- or β-phenyl propylaldehyde, o-, m- or p-hydroxy benzaldehyde. And glutaraldehyde, terephthalaldehyde and the like, and can be used alone or in combination of two or more thereof.

It is preferable that cresol novolak resin is a weight average molecular weight (when measured by GPC method) 2,000-30,000.

In addition, since the physical properties such as the photoresist rate and the residual film ratio vary depending on the content ratio of meta / para cresol, the cresol novolak resin used in the present invention has a meta / para cresol content ratio of 4: 6 to 6: 6 by weight. It is preferable to mix in the ratio of 4.

When the content of the meta cresol in the cresol novolak resin exceeds the above range, the photoresist rate is increased while the residual film rate is drastically lowered. When the content of the para cresol exceeds the above range, the photosensitivity is slowed.

The cresol novolac resin may be used alone as cresol novolac resin having a content ratio of meta / para cresol of 4: 6 to 6: 4 by weight as described above, but more preferably mixed resins having different molecular weights may be used. have.

In this case, cresol novolak resin (iii) weight average molecular weight (when measured by GPC method) is 8,000-30,000 cresol novolak resin and (ii) weight average molecular weight (when measured by GPC method) 2,000 It is preferable to mix-use the cresol novolak resin of -8,000 at the weight ratio of 7: 3-9: 1.

Here, the term 'weight average molecular weight' is defined in terms of polystyrene equivalents, as determined by gel permeation chromatography (GPC). In the present invention, if the weight average molecular weight of the novolak resin is less than 2,000, the photoresist resin film may have a large thickness reduction in the non-exposed part after development, whereas if it exceeds 30,000, the development speed is lowered and the sensitivity is reduced. The novolak resin of the present invention can achieve the most preferable effect when the resin obtained after removing the low molecular weight component from the reaction product has a weight average molecular weight (2,000 to 30,000) in the above-described range. In removing the low molecular weight component from the novolak resin, it is convenient to use techniques including fractional precipitation, fractional dissolution, tube chromatography, and the like. Thereby, the performance of a photoresist resin film can be improved, especially scumming, heat resistance, etc. can be improved.

Novolak resins as alkali-soluble resins provide an image that is soluble in an aqueous alkali solution without increase in volume and can provide high resistance to plasma etching when used as a mask during etching.

One example of the positive photosensitive compound of the present invention is a diazide compound, which also acts as a dissolution inhibitor that reduces the solubility of alkali in the novolak resin. However, when the compound is irradiated with light, the compound is converted into an alkali-soluble material, which increases the alkali solubility of the novolak resin. Thus, due to the change in solubility due to light irradiation, the photosensitive compound is particularly useful in positive dry film photoresist.

The diazide compound which is a photosensitive compound can be synthesize | combined by esterification reaction of a polyhydroxy compound and a quinone diazide sulfonic acid compound. The esterification reaction for obtaining the photosensitive compound is carried out by dioxane, acetone, tetrahydrofuran, methylethylketone, N-methylpyrrolidine, chloroform, trichloroethane, trichloro and the polyhydroxy compound and the quinonediazide sulfonic acid compound. Dissolved in a solvent such as ethylene or dichloroethane, and condensed by dropwise addition of a basic catalyst such as sodium hydroxide, sodium carbonate, sodium bicarbonate, triethylamine, N-methylmorpholine, N-methylpiperazine or 4-dimethylaminopyridine The obtained product is washed, purified and dried. It is possible to selectively esterify only specific isomers and the esterification ratio (average esterification rate) is not particularly limited, but the diazide sulfonic acid compound for the OH group of the polyhydroxy compound is 20 to 100%, preferably 60 to 90 Range of%. Too low an esterification ratio results in deterioration of pattern shape or resolution, and too high an ester degradation.

As the quinone diazide sulfonic acid compound, for example, 1,2-benzoquinone diazide-4-sulfonic acid, 1,2-naphthoquinone diazide-4-sulfonic acid, 1,2-benzoquinone diazide-5-sulfonic acid and 1, O-quinone diazide sulfonic acid compounds, such as 2-naphthoquinone diazide-5-sulfonic acid, other quinone diazide sulfonic acid derivatives, etc. are mentioned. The diazide photosensitive compound is preferably 1,2-benzoquinone diazide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2-naphthoquinone diazide-5- At least one of sulfonic acid chlorides.

The quinonediazide sulfonic acid compounds themselves have a function as a dissolution inhibitor which lowers the solubility of the novolak resin in alkali. However, it decomposes in order to produce alkali-soluble resins upon exposure, thereby having the property of promoting dissolution of the novolak resin in alkali.

Examples of the polyhydroxy compound include trihydroxy benzophenones such as 2,3,4-trihydroxybenzophenone, 2,2 ', 3-trihydroxybenzophenone, and 2,3,4'-trihydroxy benzophenone. ; Tetrahydroxybenzophenones such as 2,3,4,4-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone and 2,3,4,5-tetrahydroxybenzophenone ; Pentahydroxybenzophenones such as 2,2 ', 3,4,4'-pentahydroxybenzophenone and 2,2', 3,4,5-pentahydroxybenzophenone; Hexahydroxybenzophenones such as 2,3,3 ', 4,4', 5'-hexahydroxybenzophenone and 2,2,3,3 ', 4,5'-hexahydroxybenzophenone; Gallic acid alkyl esters; And oxyflavanes.

The diazide compound which is a photosensitive compound used in the present invention is preferably 2,3,4,4-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-sulfonate, 2,3,4-tri Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate and (1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxy Phenyl) ethyl] benzene) -1,2-naphthoquinonediazide-5-sulfonate. In addition, diazide photosensitive compounds prepared by reacting diazide compounds such as polyhydroxy benzophenone, 1,2-naphthoquinone diazide, and 2-diazo-1-naphthol-5-sulfonic acid can also be used. .

As for the diazide compound which is such a photosensitive compound, Light Sensitive Systems, Kosar, J .; See John Wiley & Sons, New York, 1965, chapter 7.

Such photosensitive compound (photosensitive agent) used in the photodegradable resin composition is selected from substituted naphthoquinone diazide type photosensitive agents which are generally applied as a positive photoresist resin composition. 2,797,213; 3,106,465; 3,106,465; 3,148,983; 3,201,329; 3,785,825, 3,802,885 and the like.

The diazide compound, which is the photosensitive compound, may be used alone or in combination of two or more parts by weight based on 100 parts by weight of the alkali-soluble resin. If it is less than 30 parts by weight, it is not developed in the developer and the residual ratio of the photoresist film is considerably low. If it exceeds 80 parts by weight, it is not economical and the solubility in the solvent may be low.

The photosensitive compound diazide-based compound can be used to control the photosensitive speed of the positive photoresist resin film of the present invention, for example, a method of controlling the amount of the photosensitive compound and 2,3,4-trihydroxy There is a method of controlling the ester reactivity of a polyhydroxy compound such as benzophenone with a quinonediazide sulfonic acid compound such as 2-diazo-1-naphthol-5-sulfonic acid.

The photosensitive compound diazide compound reduces the solubility of the alkali-soluble resin in the aqueous alkali solution developer about 100 times before exposure, but changes to a carboxylic acid form after exposure to become soluble in the aqueous alkali solution, compared to the non-exposure photodegradable resin composition. Solubility is increased by about 1000 to 1500 times.

A sensitivity enhancer is used to improve the sensitivity of the photodegradable resin layer. The sensitivity enhancer is a polyhydroxy compound having 2 to 7 phenolic hydroxyl groups and having a weight average molecular weight of less than 1,000 relative to polystyrene. Preferred examples include 2,3,4-trihydroxybenzophenone, 2,3,4,4-tetrahydroxybenzophenone, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [ It is preferable that it is 1 or more types chosen from 1, 1-bis (4-hydroxyphenyl) ethyl] benzene.

The polyhydroxy compound used as the sensitivity enhancer is preferably used 3 to 15 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the sensitivity enhancer is less than 3 parts by weight, the photosensitivity effect is insignificant, and resolution, sensitivity, etc. are insufficient, and when the sensitivity enhancer is more than 15 parts by weight, the sensitivity may be high, resulting in a narrow window process margin.

The photopolymerizable composition or the photodegradable composition described above is mixed with a certain amount of solvent to prepare a photosensitive resin composition. For example, the mixture may be applied to the heat-resistant transparent base film at a thickness of 100 nm to 100 μm, but the thickness of the photosensitive resin composition is not particularly limited as long as the light transmittance is not impaired to 70% or less.

The method for forming the photosensitive resin layer on the base film is a composition that is mixed with the solvent by a coating method such as a roller, a roll coater, a meyer rod, a gravure, a spray, a spin coater, and the like, which is generally used, onto the support film. It is performed by coating on and drying to volatilize the solvent in the composition. You may heat-harden the apply | coated composition as needed.

An example of a method for forming a carbon nanotube mixed layer made of a photosensitive resin in which carbon nanotubes and carbon nanotubes exposed on the surface are mixed on the surface of the photosensitive resin layer may include carbon nanotubes, water, and an organic solvent. And a method of applying the carbon nanotube dispersion onto the formed photosensitive resin layer and then drying.

The carbon nanotubes included in the carbon nanotube dispersion are not particularly limited, and may be single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes (DWCNTs), multi-walled carbon nanotubes (MWCNTs), and the like.

In consideration of the dispersibility, the carbon nanotubes are dispersed in the organic solvent with a dispersant as necessary and then dispersed by ultrasonication to obtain a uniformly dispersed carbon nanotube dispersion solution. The method of dispersing carbon nanotubes is not particularly limited, and examples thereof include ultrasonic dispersion, triple roll dispersion, homogenizer or kneader, mill blender, ball mill, and physical dispersion. And methods for using additives such as dispersants and emulsifiers in order to properly disperse the carbon nanotubes (CNT).

In this case, the organic solvent may be soluble to the above-mentioned photosensitive resin layer. Thus, when the carbon nanotube dispersion is prepared by including a predetermined amount of the soluble organic solvent in the photosensitive resin layer and then coated on the photosensitive resin layer, As the surface of the layer is finely melted, a part of the carbon nanotubes may penetrate into the photosensitive resin layer and be firmly combined with the resin layer.

Accordingly, the photosensitive resin layer 3 including the carbon nanotubes 1 exposed on the surface and the carbon nanotube mixed layer 2 having the photosensitive resin composition mixed with the carbon nanotubes can be obtained.

However, if a carbon nanotube dispersion containing an organic solvent soluble to the photosensitive resin layer is applied onto the photosensitive resin layer, the photosensitive resin layer may be dissolved and the resin layer may be non-uniform. It may be desirable to mix insoluble water with respect to the photosensitive resin layer, and more particularly, when the photosensitive resin layer is a thin film, wherein the water and the organic solvent may be preferably mixed at a weight ratio of 5:95 to 95: 5. have. More preferably it is mixed in a weight ratio of 90:20 to 40:60.

In addition, the carbon nanotube content in the carbon nanotube dispersion may be 0.001 to 2.0% by weight in terms of forming a conductive layer having excellent electrical conductivity without inhibiting transparency.

The method of applying the dispersion in which the carbon nanotubes are dispersed on the photosensitive resin layer is not particularly limited and it is preferable to use a casting method such as spray coating (Spray or FOG Coating), but the present invention is not limited thereto. In particular, it is preferable to be careful not to apply a physical force on the photosensitive resin layer in the process of apply | coating.

The carbon nanotube dispersion is coated on the photosensitive resin layer in consideration of light transmittance and conductivity, and then dried in consideration of the boiling point of the water and organic solvent used to mix the carbon nanotubes (1) and carbon nanotubes exposed on the surface. The photosensitive resin layer 3 which has the carbon nanotube mixed layer 2 which becomes the prepared photosensitive resin composition can be formed. At this time, since the solid content of the carbon nanotube dispersion is very low, the thickness of the photosensitive resin layer does not change significantly when the coating is made in consideration of light transmittance and conductivity. Penetration inside can be confirmed by electron scanning microscope. In addition, carbon nanotubes are entangled with each other and can exhibit excellent conductivity and can transmit water.

The carbon nanotube dispersion coated on the surface of the photosensitive resin layer is dried by allowing the contained organic solvent to finely dissolve the surface layer of the photosensitive resin layer so that a portion of the carbon nanotubes are mixed with the photosensitive resin composition and dried. Allow the strata to be firmly bound. However, since most of the carbon nanotubes are not mixed with the photosensitive resin layer and are exposed on the surface, they may exhibit excellent conductivity. In this case, the carbon nanotubes and the carbon nanotube mixed layer exposed on the surface may be advantageous in that light transmittance of 10 nm to 10 μm and excellent conductivity and electrode pattern developability of the electrode layer may be easily obtained.

The thickness of the entire photosensitive resin layer 3 including the same may be 110 nm to 110 um.

The transparent electrode thus obtained may be used as an electrode, or on the other hand, it may be used by forming a circuit pattern. The method of forming a circuit pattern includes, for example, carbon nanotubes and carbon nanotubes exposed on a surface thereof. In the case of including a photosensitive resin layer of a photopolymerizable resin composition including a carbon nanotube mixed layer having a mixed photopolymerizable resin composition, it is exposed to develop a desired electrode pattern and then developed to remove unexposed portions. An electrode pattern can be formed. As the unexposed photosensitive resin layer is washed away in the development process, the carbon nanotube mixed layer existing by being mixed with the surface of the photosensitive resin layer or the photosensitive resin may also be washed out to obtain an electrode pattern including the carbon nanotube mixed layer.

As another example, in the case of including a photosensitive resin layer having a photodegradable resin composition including a carbon nanotube mixed layer comprising a carbon nanotube and a carbon nanotube mixed with a carbon nanotube exposed on a surface thereof, An electrode pattern may be formed by exposing and developing the electrode pattern to remove the exposed portion. As the photosensitive resin layer exposed in the development process is washed away, the carbon nanotube mixed layer existing on the photosensitive resin layer is also washed out to obtain an electrode pattern including the carbon nanotube mixed layer.

Although the transparent electrode of the present invention includes a photosensitive resin layer including a carbon nanotube mixed layer of carbon nanotubes exposed on the surface and a photosensitive resin composition in which carbon nanotubes are mixed, in consideration of light transmittance and conductivity Since the carbon nanotube mixed layer is formed, light may be transmitted to the photosensitive resin layer during exposure, so that the photosensitive resin layer may be exposed. However, the carbon nanotube mixed layer may cause the inhibition of light transmission and thus slightly increase the exposure dose. There may be.

The above-described photopolymerizable resin composition or photodegradable resin composition is not intended to limit the present invention, and those skilled in the art can modify the present invention as various compounds in a range that does not modify the technical spirit of the present invention. Of course it is.

The transparent electrode film obtained as described above can easily implement an electrode pattern and improve electrical conductivity without impairing the transmittance of incident light, thereby realizing a bright image.

The transparent electrode film according to an embodiment of the present invention may have a surface resistance of 5000 Ω / □ or less to be useful as an electrode, and have a light transmittance of 70% or more at a wavelength of 550 nm.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to the following examples. However, the present invention is not limited to these examples.

<Production of Polyimide Film>

Production Example 1

First, the precursor solution for forming the polyimide film which is an example of an organic insulating film is manufactured. This process consists of 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (2,2'-TFDB), biphenyltetracarboxylic dianhydride (BPDA) and 2, By condensing 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6-FDA) in dimethylacetamide by a well-known method, the polyimide precursor solution which is an example of the precursor solution of an organic insulating film (solid content 20%) was obtained. This reaction procedure is shown in the following reaction formula (1).

Thereafter, 300 g of the polyimide precursor solution was added with 2 to 4 equivalents of acetic anhydride (Acet oxide) and pyridine (Pyridine) as a chemical curing agent, according to a known process. After heating the polyamic acid solution at a temperature in the range of 20 to 180 ° C. at a rate of 1 to 10 ° C./min for 2 to 10 hours, the polyamic acid solution is partially imidized and partially cured by partially imidizing (partially A solution containing cured) intermediate was prepared.

The following Reaction Scheme 2 shows a process of obtaining a polyimide film by heating a polyimide precursor. In the embodiment of the present invention, the precursor solution is not completely imidized to form a polyimide, but only a predetermined proportion of the precursor is imidized I would like to use one.

More specifically, the polyimide precursor solution is heated and stirred under predetermined conditions to dehydrate and close the ring between the hydrogen atom and the carboxyl group of the amide group of the polyimide precursor, as shown in the following formula (1). Similarly, the form B of the intermediate portion and the form C of the imide portion are generated by the reaction. Also, in the molecular chain, a form A (polyimide precursor part) in which dehydration does not occur completely exists.

That is, the molecular chain in which the polyimide precursor is partially imidized has a structure of a form A (polyimide precursor), a form B (intermediate part) and a form C (imide part) as shown in the following chemical formula 1 .

Therefore, 30 g of the imidized solution containing the above structures is put into 300 g of water and precipitated. The precipitated solids are filtered and pulverized to fine powder, dried in a vacuum drying oven at 80 to 100 ° C for 2 to 6 hours To obtain about 8 g of resin solid powder. The polyimide precursor part of the [Form A] was converted into [Form B] or [Form C] by passing through the above steps. The resin solid content was dissolved in 32 g of DMAc or DMF as a polymerization solvent to prepare a 20 wt% polyimide solution . This was heated for 2 to 8 hours while raising the temperature at a rate of 1 to 10 占 폚 / min in a temperature range of 40 to 400 占 폚 to obtain a polyimide film having thicknesses of 50 占 퐉 and 100 占 퐉.

The state of partially imidized polyimide precursor is represented by the reaction formula 3 as shown in the reaction formula 3.

For example, under the above conditions, about 45 to 50% of the precursor is imidized and cured. The imidization rate at which a part of the precursor is imidized can be easily controlled by changing the heating temperature, time, etc., and is preferably about 30 to 90%.

In the step of imidizing a part of the polyimide precursor, water is generated when the polyimide precursor is dehydrated and closed and imidized, and this water causes hydrolysis of the amide of the polyimide precursor, cleavage of molecular chains, or the like. In order to reduce the stability, the azeotropic reaction using toluene, xylene, or the like is added during heating of the polyimide precursor solution or removed through volatilization of the above-mentioned dehydrating agent.

Next, an example of a step of manufacturing a coating liquid will be described. First, a uniform coating liquid is prepared in the ratio of 100 weight part of solutions and 20-30 weight part of polyimide precursors to the solvent which used the partially hardened intermediate at the time of manufacture of a polyimide precursor.

Next, the resin solution is cast on a film-coated plate for film or film such as glass or stainless steel using spin coating or a doctor blade, and then the film having a thickness of 50 μm through the above-mentioned high temperature drying process. Was formed. At this time, the formed film was formed with the same refractive index on the entire surface of the film because only one side was not stretched based on the vertical / horizontal axis of the film.

Production Example 2

N, N-dimethylacetamide (DMAc) (34.1904 g) was charged into a 100 ml 3-neck round bottom flask equipped with a stirrer, a nitrogen inlet, a dropping funnel, a temperature controller and a condenser, After lowering the temperature to 0 占 폚, 4.1051 g (0.01 mol) of 6-HMDA was dissolved and the solution was maintained at 0 占 폚. To this, 4.4425 g (0.01 mol) of 6-FDA was added and stirred for 1 hour to completely dissolve 6-FDA. At this time, the solid content was 20 wt%, and then the solution was left at room temperature and stirred for 8 hours. At this time, a polyamic acid solution having a solution viscosity of 2400 cps at 23 占 폚 was obtained.

After completion of the reaction, the polyamic acid solution obtained was cast to a thickness of 500 μm to 1000 μm using a doctor blade on a glass plate, and then dried in a vacuum oven for 1 hour at 40 ° C. and 2 hours at 60 ° C. for self-support. After obtaining a film (Self standing film) in a high-temperature furnace oven at a heating rate of 5 ℃ / min 3 hours at 80 ℃, 1 hour at 100 ℃, 1 hour at 200 ℃, 30 minutes at 300 ℃ to a thickness of 50㎛ A polyimide film was obtained.

Production Example 3

2.9233 g (0.01 mol) of APB-133 was dissolved in 29.4632 g of N, N-dimethylacetamide (DMAc) in Production Example 2, 4.4425 g (0.01 mol) of 6-FDA was added thereto and stirred for 1 hour 6-FDA was completely dissolved. At this time, the solid content was 20 wt%, and then the solution was left at room temperature and stirred for 8 hours. At this time, a polyamic acid solution having a solution viscosity of 1200 cps at 23 占 폚 was obtained.

Then, a polyimide film was produced in the same manner as in Production Example 2 above.

Physical properties of the polyimide films obtained from Preparation Examples 1 to 3 were measured as follows, and are shown in Table 1 below.

(1) Transmission and color coordinates

The visible light transmittance of the prepared film was measured using a UV spectrometer (Varian, Cary100).

The color coordinates of the prepared film were measured according to the ASTM E 1347-06 standard by using a UV spectrometer (Varian, Cary100), and the illuminant was measured based on the measured value by CIE D65.

(2) Yellowness

Yellowness was measured according to ASTM E313 standard.

(3) Coefficient of linear expansion (CTE)

TMA (TA Instrument, Inc., Q400) was used to measure the average coefficient of linear expansion at 50-250 ° C. according to TMA-Method.

division thickness
(탆) Coefficient of linear expansion
(ppm / DEG C) Yellowness Permeability Color coordinates 380 nm
~ 780 nm 551 nm
~ 780 nm 550 nm 500 nm 420 nm L a b Manufacturing example One 50 21.6 2.46 86.9 90.5 89.8 89.3 84.6 96.22 -0.27 1.03 2 50 46 1.59 87.6 90.0 89.7 89.2 85.4 95.85 -0.12 0.99 3 50 46.0 6.46 83.8 88.8 87.2 84.8 73.2 94.6 0.59 5.09

Examples 1 to 6

On each of the polyimide films obtained from Preparation Examples 1 to 3, a photopolymerizable composition having a composition as shown in Table 2 was then applied as a thin film by a method selected according to the coating thickness from the spray method and the gravure coating method and dried at 80 ° C. To form a photosensitive resin layer.

Meanwhile, a carbon nanotube dispersion including carbon nanotubes, water, and an organic solvent was prepared as follows in Table 2; Distilled water was used as the water, and isopropyl alcohol was used as the organic solvent, and at least one selected from PVP (Polyvinylpyrrolidone) or Nafion- was added as a dispersant, and carbon nanotubes were added. Dispersing for a time to prepare a carbon nanotube dispersion.

The carbon nanotube dispersion thus obtained is applied at least once in consideration of light transmittance and conductivity by a spray coating method, and dried at 80 ° C. to form carbon nanotubes and carbon nanotubes having a photosensitive resin mixed on the surface thereof. A transparent electrode including a photosensitive resin layer having a nanotube mixed layer was prepared.

Polyimide film Photosensitive resin composition
(Content: wt% based on solid content) CNT dispersion (content: wt%) thickness
() Alkali Soluble Binder Resin Photopolymerizable compound Photoinitiator CNT Dispersant water Organic solvent Example 1 Production Example 1 One 49 49 2 0.1 0.1 90 9.8 Example 2 Production Example 2 2.5 49 49 2 0.5 0.5 85 14 Example 3 Production Example 3 2.5 49 49 2 0.5 0.5 85 14 Example 4 Production Example 1 10 49 49 2 0.5 0.5 60 39 Example 5 Production Example 1 50 49 49 2 0.05 0.05 49.9 50 Example 6 Production Example 1 50 49 49 2 1.5 0.75 9 90

(week)

CNT: SPH1128, manufactured by Unidym, Single-wall carbon nanotube

Alkali Soluble Binder Resin: Hydroxypropyl Methylcellulose Acetate Phthalate

Photopolymerizable compound: PU-280, Miwon Corporation and HX-220, Nippon Gunpowder 40: 60 wt% mixture

Photoinitiator: 50:50 wt% mixture of benzophenone and 4,4-bis (diethylamino) benzophenone

Organic Solvent: Isopropyl Alcohol

Example 7

Cresol novolac resins as alkali-soluble resins; 34 parts by weight of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride as a photosensitive compound based on 100 parts by weight of the alkali-soluble resin; 15 parts by weight of hexamethoxymethylmelamine as the thermosetting resin; 165.5 parts by weight of methyl ethyl ketone and 55 parts by weight of diethylene glycol monoethyl ether acetate as solvents; 2 parts by weight of isocyanate compound; A solution comprising 3.6 parts by weight of 2,3,4-trihydroxybenzophenone as a sensitivity enhancer was prepared. The prepared solution was filtered through a 0.2 μm Millipore Teflon filter to remove foreign substances and insoluble substances. The resulting solution was applied from the gravure coating method on each polyimide film obtained in Production Example 1 above and dried at 80 ° C. to form a 5 μm thick photosensitive resin layer.

Meanwhile, a carbon nanotube dispersion including carbon nanotubes, water, and an organic solvent was prepared as follows in Table 3; Carbon nanotube dispersion obtained by mixing distilled water and methyl ethyl ketone in a 50:50 weight ratio, adding PVP (Polyvinylpyrrolidone) as a dispersant to completely dissolve it, adding carbon nanotubes, and dispersing it for 2 hours with ultrasonic wave of 200 W 40 kHz. Prepared. At this time, PVP and carbon nanotubes were 0.25% by weight and 0.5% by weight with respect to the dispersion, respectively.

The carbon nanotube dispersion thus obtained was coated with a thin film by a spray coating method and dried at 100 ° C. to prepare a transparent electrode including a photosensitive resin layer having a carbon nanotube mixed layer formed on the surface thereof.

Experimental Example 1

The transparent electrode films obtained in Examples 1 to 7 were evaluated as follows, and the results are shown in Table 3 below.

(1) In order to confirm the pattern formation state, in Examples 1 to 6, a negative photomask for circuit evaluation was used on the transparent conductive resin film, and the thickness of the resin film using Perkin-Elmer 0B7120 (parallel light exposure machine). According to the irradiation with ultraviolet light at an exposure amount of 10 to 40mJ and left for 20 minutes. Thereafter, a circuit was formed by developing in a spray spray method with a 1.0 wt% aqueous solution of sodium carbonate, and a pattern forming state was confirmed through a magnifying glass, whereby the electrode layer 6 was observed at an exposed portion. If it was observed that the conductive resin film had been removed (5), it was good. If it was observed that the electrode layer did not form a circuit in the exposed portion, or it was observed that the conductive resin film in the non-exposed portion was not removed, it was evaluated as defective.

In Example 7, after the pre-baking of the transparent electrode film, a positive photomask for circuit evaluation was used on the transparent conductive resin film, and Perkin-Elmer 0B7120 (parallel light exposure machine) was used to After irradiating with ultraviolet light at an exposure dose of 30mJ, it was left for 20 minutes. After that, development was carried out using a 2.38% TMAH (tetramethylammonium hydroxide) aqueous solution under the conditions of spray injection, and after 15 minutes at 130 ° C., a circuit was formed by post-bake and the pattern formation state was confirmed through a magnifying glass. If the electrode layer 6 is observed in the non-exposed part and the conductive resin film in the exposed part is observed (5), it is good. It is observed that the electrode layer does not form a circuit in the non-exposed part, or the conductive resin film in the exposed part is observed. When it was observed that it was not removed, it was evaluated as bad.

(2) Optical characteristics

With no circuit formed on the manufactured transparent electrode film Visible light transmittance was measured using a UV Spectrophotometer (Konika Minolta, CM-3700d).

(3) Surface resistance

The surface resistance of the prepared transparent electrode film on the conductive resin film without a circuit was measured. The surface resistance was measured by using an ohmmeter (CMT-SR 2000N (Advanced Instrument Teshnology; AIT, 4-Point Probe System, Measuring range: 10 10 ^-3 to 10 × 10 ⁵ )) 10 times to obtain an average value.

Surface resistance
(Ω / □) Permeability
(550 nm,%) Pattern formation state Example 1 3,215 82 Good Example 2 2,568 83 Good Example 3 2,726 81 Good Example 4 821 80 Very good Example 5 254 77 Good Example 6 623 77 Good Example 7 325 65 Very good

From the results of Table 3, carbon nanotubes exposed on the surface; In the case of a conductive laminate including a photosensitive resin layer including a carbon nanotube mixed layer made of a photosensitive resin mixed with carbon nanotubes, the conductive layer has excellent conductivity and light transmittance, and an electrode pattern is easily formed by a photolithography method. It can be seen that the formation state is good. In particular, it can be seen that the conductive laminate is useful as a transparent electrode.

1 is a cross-sectional view of a conductive resin laminate obtained by one embodiment of the present invention.

2 is a cross-sectional view of a conductive resin laminate in which the electrode pattern is formed by an embodiment of the present invention.

<Detailed Description of Major Symbols in Drawing>

1-carbon nanotubes exposed on the surface

2-carbon nanotube mixed layer having a photosensitive resin composition mixed with carbon nanotubes

3-photosensitive resin layer 4-base material

5-portion of photosensitive resin layer removed after development

6-photosensitive resin layer part which formed the electrode layer

Claims (21)

Carbon nanotubes exposed on the surface; And a carbon nanotube mixed layer having a photopolymerizable resin composition or a photodegradable resin composition mixed with the carbon nanotubes; and a photosensitive resin layer having a photopolymerizable resin composition or a photodegradable resin composition. The carbon nanotube and the carbon nanotube mixed layer exposed on the surface of the carbon nanotube, water and an organic solvent comprising a carbon nanotube, water and an organic solvent on a photosensitive resin layer of a photopolymerizable resin composition or a photodegradable resin composition. Transparent electrode formed by applying a tube dispersion. The transparent electrode according to claim 2, wherein the organic solvent is soluble in the photosensitive resin layer. The transparent electrode of claim 2 or 3, wherein water and an organic solvent are included in a weight ratio of 5:95 to 95: 5. The transparent electrode of claim 1, wherein the photopolymerizable resin composition comprises an alkali-soluble binder resin, a photopolymerizable compound, and a photoinitiator. The transparent electrode of claim 1, wherein the photodegradable resin composition comprises an alkali-soluble binder resin, a positive photosensitive compound, and a sensitivity enhancer. The transparent electrode of claim 2, wherein the carbon nanotubes are dispersed in an amount of 0.001 to 2.0% by weight. The transparent electrode of claim 1, wherein the photosensitive resin layer has a thickness of 110 nm to 110 μm. The transparent electrode of claim 1, wherein the carbon nanotubes and the carbon nanotube mixed layer exposed on the surface have a total thickness of 10 nm to 10 μm. The transparent electrode according to claim 1, wherein the light transmittance is 70% or more at 550 nm and the surface resistance is 5000 Ω / □ or less. Carbon nanotubes exposed on the surface; And a carbon nanotube mixed layer having a photopolymerizable resin composition or a photodegradable resin composition mixed with the carbon nanotubes; a photosensitive resin layer having a photopolymerizable resin composition or a photodegradable resin composition; And A conductive laminate comprising a substrate layer. The carbon nanotube and the carbon nanotube mixed layer exposed on the surface of the carbon nanotube, water and an organic solvent containing carbon nanotubes, water and an organic solvent on the photosensitive resin layer having a photopolymerizable resin composition or a photodegradable resin composition. A conductive laminate formed by applying a tube dispersion. The conductive laminate according to claim 12, wherein the organic solvent is soluble in the photosensitive resin layer. The conductive laminate according to claim 12 or 13, wherein water and an organic solvent are included in a weight ratio of 5:95 to 95: 5. The conductive laminate according to claim 11, wherein the photopolymerizable resin composition comprises an alkali-soluble binder resin, a photopolymerizable compound and a photoinitiator. The conductive laminate according to claim 11, wherein the photodegradable resin composition comprises an alkali-soluble binder resin, a positive photosensitive compound, and a sensitivity enhancer. The conductive laminate of claim 12, wherein the carbon nanotubes in the carbon nanotube dispersion are dispersed in an amount of 0.001 to 2.0 wt%. The conductive laminate according to claim 11, wherein the photosensitive resin layer has a thickness of 110 nm to 110 μm. The conductive laminate of claim 11, wherein the carbon nanotubes and the carbon nanotube mixed layer exposed on the surface have a total thickness of 10 nm to 10 μm. The conductive laminate according to claim 11, wherein the light transmittance is 70% or more at 550 nm and the surface resistance is 5000 Ω / square or less. The conductive laminate of claim 11, wherein the substrate layer is a plastic film or a glass substrate.

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