JP2010161013A - Method for manufacturing laminate having conductive resin pattern, and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a laminate equipped with a conductive resin pattern, which has an excellent conductive performance after etching and reliability. <P>SOLUTION: The method for manufacturing the laminate equipped with a conductive resin pattern includes in order a process (a) in which a transparent base body and a conductive laminate having a conductive resin composition layer provided on the transparent base body are prepared, a process (b) in which a resist pattern is formed on the conductive resin composition layer, a process (c) in which the conductive resin composition layer of a resist-pattern-non-formed part is removed by using an etching agent containing at least one selected from a group composed of cerium nitrate ammonium, sulphuric acid cerium ammonium, and hypochlorite, and a process (d) in which the resist pattern is removed by an aprotic organic solvent not containing nitrogen atom and/or a remover agent having nitrogen atoms in a chemical structure and moreover containing an organic solvent other than a primary, secondary amine compounds and a quaternary ammonium acid. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a laminate having a conductive resin pattern, and the laminate.

At present, ITO (indium tin oxide) containing indium (In) is mainly used as the transparent conductive film, but In is a rare element with a recoverable reserve of 3,000 tons. There is an expectation that the recoverable reserves will be used up around the year, and there is an urgent need to develop an alternative material for ITO that does not use In. The conductivity of the conductive polymer is remarkably improved, and the conductive polymer is promising as an alternative material for ITO.
This conductive polymer has the characteristics that it is conductive, light transmissive, light-emitting, flexible even after film formation, such as transparent conductive film, electrolytic capacitor, antistatic agent, battery, organic EL element, touch panel, etc. Application to the research has been studied, and some have been put into practical use.

By using a conductive polymer having higher conductivity and higher stability than the electrolytic solution of the electrolytic capacitor, it is possible to obtain an electrolytic capacitor with improved frequency characteristics and excellent heat resistance.
In addition, by forming a conductive polymer thinly on the surface of the polymer film, it is possible to prevent static electricity while maintaining transparency, so such products can be used as easy-to-use antistatic films and antistatic containers. Has been.

The conductive polymer can be used as a positive electrode of a secondary battery, and is used for a lithium polyaniline battery, a lithium ion polymer battery, or the like.
There is a polymer organic EL display using a conductive polymer for a light emitting layer, and a flexible display can be manufactured by using plastic instead of glass for a substrate. A conductive polymer can also be used for the hole transport layer. Organic EL displays, including polymer organic EL displays, are self-luminous displays, have a wide viewing angle, are easily thinned, and have excellent color reproducibility. In addition, the response speed is high because light is emitted by recombination of holes and electrons. Since the organic EL display has such excellent features, it is a promising display in the future. Since a conductive polymer is more flexible than ITO, a flexible display that can be folded using an organic EL and a conductive polymer as a transparent conductive film has also been developed.
In addition, electronic devices such as diodes and transistors can be manufactured using conductive polymers, and improvement in performance has been studied. By using conductive polymer as the counter electrode of titanium dioxide for dye-sensitized solar cells instead of platinum, research has been conducted with the aim of developing solar cells that are cheaper than silicon-based solar cells, which are currently mainstream. ing.
Thus, the conductive polymer is a useful material for the future electronics industry, and the patterning method of the conductive polymer is an important technique when using the conductive polymer.

  In Patent Document 1, a pattern is directly drawn by a screen printing method using a printing paste containing a solution or dispersion containing a functional polymer such as a conductive polymer and having a specific viscosity, and the solvent or dispersion in the paste It describes that an intended functional thin film pattern is formed by removing the medium.

  Furthermore, Patent Document 2 discloses a method of patterning a light emitting material as a functional material using an ink jet printing apparatus. In this method, a liquid luminescent material is applied onto a substrate by an ink jet apparatus and polymerized by heat treatment.

  In Patent Document 3, a reverse pattern of a target functional thin film is formed on a substrate with a radiation-sensitive resin composition, a conductive polymer is applied and dried thereon, and then the substrate is treated with a release agent. Thus, a method of forming a pattern by removing the reverse pattern together with the conductive polymer layer on the pattern is shown.

On the other hand, the photo-etching method widely used for patterning has an advantage that a simple film-forming method can be adopted because patterning is performed after forming a uniform film.
For example, Patent Document 4 discloses a method of patterning a conductive polymer by etching.

  Patent Document 5 discloses a transparent conductor comprising a base and a conductive layer containing conductive particles and a conductive polymer, and the conductive layer is provided on one surface of the base. ing.

Special table 2002-500408 gazette JP-A-10-153967 JP 2004-14215 A JP 2008-91487 A JP 2006-286418 A

In the method of forming a functional thin film pattern described in Patent Document 1, the resolution is not always sufficient, and there is a problem that it takes time and effort to adjust the printing paste to a specific viscosity.
Further, in the patterning method of the light emitting material described in Patent Document 2, it is necessary to form a dripping prevention wall in advance when applying the liquid light emitting material on the substrate. Furthermore, the viscosity and surface of the liquid light emitting material are required. It takes time to adjust the tension.
In the method described in Patent Document 3, the edge shape is not always appropriate, and it is difficult to maintain conductivity and maintain reliability after pattern formation.
Furthermore, in the method described in Patent Document 4, there is no description about the conductive performance of the conductive layer after the etching treatment, and it is unclear whether the patterned conductive layer has durability.
In Patent Document 5, generally, when a transparent conductor is used in a high-humidity environment or in a chemical substance atmosphere such as an organic solvent or organic gas, the electrical resistance value of the transparent conductor itself is increased. There is a description that the change with time increases.

  The objective of this invention is providing the manufacturing method of the laminated body which has the electroconductive performance after an etching, and the reliability which was excellent in the reliability. Furthermore, this invention aims at providing the laminated body obtained by the said manufacturing method.

The inventors of the present invention have completed the present invention as a result of intensive studies to achieve the above-mentioned problems. That is, the present invention is as listed below.
[1] (a) A step of preparing a conductive laminate having a transparent substrate and a conductive resin composition layer provided on at least one surface of the transparent substrate, (b) on the conductive resin composition layer Forming a resist pattern; (c) conducting the resist pattern non-formation part using an etching agent containing at least one selected from the group consisting of cerium ammonium nitrate, cerium ammonium sulfate, and hypochlorite A step of removing the conductive resin composition layer, and (d) an aprotic organic solvent containing no nitrogen atom, a resist pattern having a nitrogen atom in the chemical structure, and a primary amine compound, Removed with a release agent containing at least one organic solvent selected from the group consisting of organic solvents other than secondary amine compounds and organic quaternary ammonium salts A process for producing a laminate having a conductive resin pattern, characterized in that
[2] The method for producing a laminate according to [1], wherein the conductive resin composition includes a complex of poly (3,4-disubstituted thiophene) and a polyanion.
[3] A laminate obtained by the method according to [1] or [2],
[4] The laminate according to [3], wherein the total light transmittance is 80% or more and the surface resistivity is 2,000Ω / □ or less.
[5] The laminate according to [3] or [4], which has a surface resistivity of 2,000 Ω / □ or less after being allowed to stand for 240 hours in a thermal environment at 80 ° C.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the laminated body which has the conductive resin pattern which was excellent in the electroconductivity after etching, and reliability was able to be provided. Furthermore, according to this invention, the laminated body obtained by the said manufacturing method was able to be provided.
According to the present invention, compared to other patterning methods, the conductive resin composition has a small increase in surface resistance, and a conductive laminate excellent in conductivity can be supplied. In addition, the conductive laminate patterned by the present invention has a feature excellent in heat resistance.

It is process drawing which shows the method of peeling the resist film directly formed on the conductive polymer. It is process drawing which shows the method of peeling the resist film formed through the other film | membrane on the conductive polymer.

The manufacturing method of the laminated body which has the conductive resin pattern of this invention prepares the conductive laminated body which has the (a) transparent base | substrate and the conductive resin composition layer provided in at least one surface of this transparent base | substrate. (B) a step of forming a resist pattern on the conductive resin composition layer, (c) containing at least one selected from the group consisting of cerium ammonium nitrate, cerium ammonium sulfate, and hypochlorite A step of removing the conductive resin composition layer in the resist pattern non-formation portion using an etching agent, and (d) an aprotic organic solvent containing no nitrogen atom, and nitrogen in the chemical structure And a small amount selected from the group consisting of organic solvents other than primary amine compounds, secondary amine compounds and organic quaternary ammonium salts. Removing the release agent containing Kutomo one organic solvent, a characterized in that it comprises in that order.
That is, the method for producing a laminate of the present invention includes (1) a conductive laminate, (2) a resist, (3) an etching agent, and (4) a resist pattern remover, and (5) a conductive resin pattern. This is a method for producing a laminate.
A detailed method will be described below.

(1) Conductive Laminate The conductive laminate used in the present invention has a transparent substrate and a conductive resin composition layer provided on at least one surface of the transparent substrate.
The transparent substrate is preferably a transparent resin substrate or a transparent glass substrate.
Here, “transparent” means that the total light transmittance is 80% or more. The total light transmittance of the substrate is preferably 85% or more, more preferably 90% or more, and further preferably 95% or more.

(Transparent resin substrate or transparent glass substrate)
In the present invention, the conductive resin composition layer is preferably provided on a transparent resin substrate or a transparent glass substrate.
The transparent resin substrate or transparent glass substrate used in the present invention is not particularly limited, and can be appropriately selected according to the purpose of use and application.
Examples of the transparent resin substrate include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polyethylene, polypropylene, poly-4-methylpentene, and cyclic polyolefin, as well as polystyrene, polyimide, polyacrylate, polymethacrylate (for example, polymethacrylate). Examples thereof include methyl acid (PMMA)).
Although there is no restriction | limiting in the shape of these transparent resin base | substrates, Since it is excellent in productivity by a roll to roll, it is preferable that it is a roll shape.
Examples of the transparent glass substrate include inorganic glasses such as soda lime glass, silicate glass, barium glass, phosphate glass, borate glass, fluoride glass, and quartz glass.

(Conductive resin composition layer)
The conductive resin composition layer used in the present invention is formed by forming a conductive resin composition containing a π-conjugated conductive polymer. As the π-conjugated conductive polymer, a known π-conjugated conductive polymer can be used. For example, the π-conjugated conductive polymer can be obtained by polymerizing one or more of the following monomers as monomers. Examples thereof include conductive polymers.
Examples of the monomer include pyrrole, N-methylpyrrole, N-ethylpyrrole, N-phenylpyrrole, N-naphthylpyrrole, N-methyl-3-methylpyrrole, N-methyl-3-ethylpyrrole, N-phenyl- 3-methylpyrrole, N-phenyl-3-ethylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-butylpyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-n-propoxypyrrole, 3- n-butoxypyrrole, 3-phenylpyrrole, 3-toluylpyrrole, 3-naphthylpyrrole, 3-phenoxypyrrole, 3-methylphenoxypyrrole, 3-aminopyrrole, 3-dimethylaminopyrrole, 3-diethylaminopyrrole, 3-diphenyl Aminopyrrole, 3-methylphenylaminopyrrole And pyrrole derivatives such as 3-phenylnaphthylaminopyrrole; aniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-methoxyaniline, m-methoxyaniline, p-methoxyaniline, o-ethoxyaniline , M-ethoxyaniline, p-ethoxyaniline, o-methylaniline, m-methylaniline, p-methylaniline, sulfonated aniline and other aniline derivatives; thiophene, 3-methylthiophene, 3-n-butylthiophene, 3- n-pentylthiophene, 3-n-hexylthiophene, 3-n-heptylthiophene, 3-n-octylthiophene, 3-n-nonylthiophene, 3-n-decylthiophene, 3-n-undecylthiophene, 3- n-dodecylthiophene, 3-methoxythiol Down, 3-naphthoxycarbonyl thiophene, thiophene derivatives, such as 3,4-ethylenedioxy thiophene. Among these, pyrrole, aniline, thiophene, and 3,4-ethylenedioxythiophene are preferable, and 3,4-ethylenedioxythiophene is more preferable. These monomers may be used independently and may use 2 or more types together.

In the present invention, a dopant can be used in combination for the purpose of increasing the electrical conductivity of the conductive polymer. The dopant may be either an acceptor or a donor. Halogens such as iodine and chlorine, Lewis acids such as BF ₃ and PF ₅ , proton acids such as nitric acid and sulfuric acid, poly anions (polymer type polyanions), transitions Examples include known metals, alkali metals, amino acids, nucleic acids, surfactants, dyes, chloranil, tetracyanoethylene, TCNQ, and the like. In the case of using polythiophenes, it is preferable to use a polyanion as a dopant, and it is particularly preferable to use polystyrene sulfonic acid.

In addition, conductive polymers are commercially available. As specific conductive polymers, polyaniline manufactured by Panipol and marketed under the trade name “Panipol” is known. It is a doped organic solvent soluble polyaniline. Polyaniline manufactured by Ormecon and marketed under the trade name “Ormecon” is a solvent-dispersed polyaniline using an organic acid as a dopant.
In addition, poly (3,3) manufactured by H.C. Starck and marketed under the trade name “CLEVIOS” (registered trademark) or “Callenfine” manufactured by Teijin DuPont Films, Inc. 4-ethylenedioxythiophene). “Karen Fine” uses polystyrene sulfonic acid as a dopant.
In addition, polypyrrole marketed under the trade name “ST Poly” from Achilles, sulfonated polyaniline marketed under the trade name “PETMAX” from Toyobo Co., Ltd., polyaniline marketed under the trade name “SCS-NEO” from Maruai Can also be used in the present invention.
Furthermore, the conductive polymer described in Chemistry 6 “Organic conductive polymer” in the 2001 patent distribution support chart as a patent distribution promotion business can also be used in the present invention.

(2) Resist As the resist used in the present invention, a general-purpose photoresist or dry film resist can be used.
There are two types of photoresists: a positive type in which the UV-irradiated part dissolves in the developer, and a negative type in which the UV-irradiated part becomes insoluble in the developer. The width (line) is used for etching in the order of several μm to several tens of μm. The positive type liquid resist preferably contains a naphthoquinone diazide compound and a novolac resin. More preferably, the novolac resin is a cresol novolac resin.
The negative type includes a dry film resist in addition to a liquid resist, and a PDP (Plasma Display Panel) or the like is used for etching in the display with a line width of the order of several tens of μm.
Both positive and negative type resists can be used in the present invention, and may be selected from the definition and usability of the target pattern.

(3) Etching agent The etching agent for conductive polymers used for patterning of the electrically conductive film of this invention contains the at least 1 compound selected from the group which consists of cerium ammonium nitrate, cerium ammonium sulfate, and hypochlorous acid. In the present invention, the conductive polymer etching agent is preferably selected from the group consisting of the following (etching agent A) to (etching agent C).
(Etching agent A)
Etching agent containing cerium ammonium nitrate (NH ₄ ) ₂ Ce (NO ₃ ) ₆ (etching agent B)
Etching agent containing cerium ammonium sulfate (NH ₄ ) ₄ Ce (SO ₄ ) ₄ (etching agent C)
Etchant that is hypochlorite aqueous solution

Each of the etching agents shown in (Etching Agent A) to (Etching Agent C) will be described.
(Etching Agent A): Etching Agent Containing (NH ₄ ) ₂ Ce (NO ₃ ) _{6 In the} present invention, the first etching agent (etching agent A) is cerium ammonium nitrate ((NH ₄ ) ₂ Ce (NO ₃ ) _{Contains 6} ). It is preferable to contain more than 0.5 wt% and not more than 70 wt% (NH ₄ ) ₂ Ce (NO ₃ ) ₆ .
In the present invention, the solvent for the etching agent is not particularly limited as long as it is a medium that can dissolve the cerium salt and does not affect the etching process, but is preferably water. It is also preferable to use a mixture of water and an inorganic acid as a solvent.

In the present invention, when (NH ₄ ) ₂ Ce (NO ₃ ) ₆ is used, the addition amount is preferably more than 0.5%, more preferably 1.0% by weight or more, from the processing ability of the etching agent. Although the treatment speed increases with the concentration, it is preferably 70% by weight or less, more preferably 40% by weight or less, and still more preferably 2.0-30% by weight (in the present invention, “2. “0 to 30% by weight” is also referred to as “2.0 to 30% by weight. The same shall apply hereinafter.), Particularly preferably 5.0 to 15% by weight. In the present invention, in the etching agent (etching agent A) using (NH ₄ ) ₂ Ce (NO ₃ ) ₆ , it is preferable that the concentration is in the above range because the etching processing ability is excellent.

In the etching agent (etching agent A) using (NH ₄ ) ₂ Ce (NO ₃ ) ₆ , a stabilizer can be used to prevent decomposition of the etching agent. Is preferable. The stabilizer is preferably HNO ₃ or HClO ₄ .
When HNO ₃ is used as the stabilizer, the concentration is preferably more than 0.1% by weight, more preferably 70% by weight or less, and more preferably 1.0 to 60% by weight. Preferably, it is 5 to 50 weight%, More preferably, it is 10 to 20 weight%. Further, when HClO ₄ is used as the stabilizer, its concentration is preferably more than 0.1% by weight, preferably 60% by weight or less, and 1.0 to 50% by weight. Is more preferable, and it is further more preferable that it is 5 to 40 weight%. Sulfuric acid is not preferable as a stabilizer because it makes the (NH ₄ ) ₂ Ce (NO ₃ ) ₆ etching agent cloudy. In the etching agent using (NH ₄ ) ₂ Ce (NO ₃ ) ₆ , it is preferable that the stabilizer has a concentration in the above range since the stability of the etching agent is improved.

(Etching Agent B): Etching Agent Containing (NH ₄ ) ₄ Ce (SO ₄ ) _{4 In the} present invention, as the solvent for the second etching agent (etching agent B), the cerium salt can be dissolved and etching treatment is performed. The medium is not particularly limited as long as it does not affect the water, but water is preferable. It is also preferable to use a mixture of water and an inorganic acid as a solvent.

In the present invention, the content of (NH ₄ ) ₄ Ce (SO ₄ ) ₄ is preferably an addition amount exceeding 0.5% by weight, more preferably 1.0% by weight or more from the processing ability of the etching agent. In addition, the treatment speed increases with the concentration, but it is preferably 30% by weight or less, more preferably 25% by weight or less, still more preferably 2.0 to 25% by weight, and particularly preferably 5% from the viewpoint of solubility. ~ 15%. In the present invention, it is preferable that (NH ₄ ) ₄ Ce (SO ₄ ) ₄ contained in the etching agent (etching agent B) is in the above range because the etching processing ability is excellent.

In the second etching agent (etching agent B), a stabilizer can be used to prevent decomposition of the etching agent, and the etching agent is preferably blended with a stabilizer. As the stabilizer, H ₂ SO ₄ is preferable.
When H ₂ SO ₄ is used as the stabilizer, the concentration is preferably more than 1.0% by weight, preferably 40% by weight or less, and 2.0 to 30% by weight. Is more preferable, and it is further more preferable that it is 3 to 20 weight%. Nitric acid is not preferable as a stabilizer because it makes the second etching agent (etching agent B) containing (NH ₄ ) ₄ Ce (SO ₄ ) ₄ cloudy. In the second etching agent (etching agent B), it is preferable that the stabilizer has a concentration in the above range because the stability of the etching agent is improved.

(Etching agent C): Etching agent which is hypochlorite aqueous solution In the present invention, the third etching agent (etching agent C) uses an aqueous solution of hypochlorite, and as the salt, An alkali metal salt or an alkaline earth metal salt can be exemplified, and an alkali metal salt is preferable. As the alkali metal salt, a sodium salt or a potassium salt is preferable, and a sodium salt is more preferable. As the alkaline earth metal salt, a calcium salt is preferable.
In the present invention, the solvent for the third etching agent (etching agent C) is not particularly limited as long as it is a medium that does not affect the etching process, but is preferably water.

Hypochlorite is produced by absorbing chlorine in an alkali metal hydroxide or alkaline earth metal hydroxide, so that the aqueous solution is strongly alkaline due to the influence of unreacted alkali metal hydroxide or alkaline earth metal hydroxide. Indicates. Since the conductive polymer etching agent exhibiting strong alkalinity in this manner adversely affects the resist, the pH of the third etching agent (etching agent C) is preferably more than 3 and less than 8, and pH 4 to More preferably, it is 7.5, it is further more preferable that it is pH 4.5-7, Especially preferably, pH is 5-6.
It is preferable that the pH of the etching agent is less than 8 because the influence on the resist is small. Moreover, when the pH is 3 or more, the decrease in effective chlorine concentration due to the generation of chlorine gas is suppressed, the time required for etching is short, and there are few obstacles to the etching apparatus and the equipment in the vicinity of the etching apparatus due to the generated chlorine gas. Therefore, it is preferable. Further, the pH of the etching agent is preferably 4.0 or more because it hardly generates chlorine gas, and the pH of 4.5 or more is particularly preferable because chlorine gas is not generated.

In the present invention, it is preferable to add an acid in order to bring the pH of the etching agent C within the above range. As the acid to be added, both inorganic acids and organic acids can be used.
Specifically, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, citric acid and the like can be preferably exemplified, and among these, sulfuric acid and nitric acid are more preferable.
In the present invention, the pH of the etching agent can be measured using a commercially available pH meter.

In the present invention, the third etching agent (etching agent C) preferably has an effective chlorine concentration of hypochlorous acid of 0.06% by weight or more. It is preferable that the effective chlorine concentration of the etching agent is 0.06% by weight or more because good etching processing ability can be obtained.
The effective chlorine concentration is more preferably 0.1% by weight or more, still more preferably 0.2% by weight or more, preferably 3% by weight or less, more preferably 2% by weight or less, More preferably, it is 1% by weight or less. In the present invention, it is preferable that the effective chlorine concentration of the third etching agent (etching agent C) is within this range because the conductive polymer can be etched efficiently.

In the present invention, the effective chlorine concentration is preferably measured by a titration method with Na ₂ SO ₃ . That is, W grams of a sample to be measured are collected and made up to 250 ml with ion exchange water. 10 ml of this sample solution is collected, and 10 ml of a 10% aqueous solution of potassium iodide is added. Then, 10 ml of acetic acid (1: 2) is added to make the pH acidic, and titration is performed with a 0.1 normal concentration sodium thiosulfate aqueous solution (soluble starch is added to facilitate determination of the end point during the titration). The effective chlorine concentration is determined from the titration amount of 0.1 normal concentration Na ₂ SO ₃ and the sample collection amount W and the following equation.
Effective chlorine concentration (wt%) =
0.003546 × (Na ₂ SO ₃ titer: ml) × 100 / W / (10/250)

(4) Stripping agent In the present invention, the stripping agent for removing the resist pattern has a resist pattern stripping ability, and (a) an aprotic organic solvent containing no nitrogen atom (aprotic organic solvent) (A)) and (b) an organic solvent having a nitrogen atom in the chemical structure and other than the primary amine compound, secondary amine compound and quaternary ammonium salt (organic solvent (b)) It is necessary to contain at least one organic solvent selected from the group consisting of, more preferably the aprotic organic solvent (a) and / or the organic solvent (b) as a main component, More preferably, the main component is the aprotic organic solvent (a) or the organic solvent (b).
That is, the present invention contains at least one organic solvent selected from the group consisting of an aprotic organic solvent (a) and an organic solvent (b), and contains two or more aprotic organic solvents (a) or 2 A seed or more organic solvent (b) may be used, or the aprotic organic solvent (a) and the organic solvent (b) may be used in combination.
Hereinafter, the aprotic organic solvent (a) and the organic solvent (b) will be described in detail.

(A) Aprotic organic solvent containing no nitrogen atom In the present invention, the aprotic organic solvent (a) is selected from the group consisting of dialkyl sulfones, dialkyl sulfoxides, alkylene carbonates, and alkyl lactones. An aprotic organic solvent which does not contain a nitrogen atom selected from the three choices is preferable.
In the present invention, an aprotic organic solvent means an organic solvent having a remarkably low ability to donate protons. In contrast, a protic organic solvent is a solvent that dissociates itself and generates protons, such as water, alcohols such as methanol and ethanol, carboxylic acids such as acetic acid, phenol, and liquid ammonia. is there.

In the present invention, the aprotic organic solvent (a) preferably contains an oxygen atom and / or a sulfur atom in the chemical structure and does not contain a nitrogen atom.
Such aprotic organic solvents (a) include dialkyl sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide, dialkyl sulfones such as dimethyl sulfone, alkylene carbonates such as ethylene carbonate and propylene carbonate, γ-butyrolactone, δ-valerolactone, A solvent selected from the group consisting of alkyl lactones such as ε-caprolactone is preferred. These aprotic organic solvents (a) may be used alone or in admixture of two or more.
The dialkyl sulfoxides and the dialkyl sulfones may form a ring by combining two alkyl groups. For example, the dialkyl sulfones includes sulfolanes.

In the dialkyl sulfones, the two alkyl groups preferably have 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and 1 or 2 carbon atoms (methyl group or ethyl group). Further preferred. Two alkyl groups may be the same or different. The two alkyl groups may be bonded to form a ring, and sulfolanes can be exemplified. The said sulfolane means a substituted or unsubstituted sulfolane, and a C1-C6 alkyl group can be illustrated as said substituent. The substituent is preferably an alkyl group having 1 to 4 carbon atoms. The substituent can be substituted with any carbon atom, and the number of substitutions is not limited. Examples of the sulfolanes include sulfolane and tetramethylsulfolane.
In the dialkyl sulfoxides, the two alkyl groups preferably have 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and 1 or 2 carbon atoms (methyl group or ethyl group). Further preferred. Two alkyl groups may be the same or different.
In the alkylene carbonates, the alkylene group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and specific examples include an ethylene group, a propylene group, and a butylene group. .
The alkyl lactones preferably have 3 to 6 carbon atoms, more preferably 4 to 6 carbon atoms, and in view of availability, the carbon number is further 4 or 6 (butyrolactone or caprolactone). preferable.

  The aprotic organic solvent (a) is preferably selected from the group consisting of dialkyl sulfoxides, alkylene carbonates, and alkyl lactones because of its relatively low boiling point, good drying properties, high safety, and ease of handling. At least one aprotic organic solvent, more preferably at least one aprotic organic solvent selected from the group consisting of dimethyl sulfoxide, ethylene carbonate, propylene carbonate, and γ-butyrolactone, and more preferably Is at least one aprotic organic solvent selected from dimethyl sulfoxide, ethylene carbonate, and γ-butyrolactone, particularly preferably γ-butyrolactone.

In the present invention, another aprotic organic solvent containing an oxygen atom and / or a sulfur atom in the chemical structure and not containing a nitrogen atom can be used in combination.
Examples of the aprotic organic solvent include ethers such as tetrahydrofuran, dimethyl ether, diethyl ether, ethyl vinyl ether, and ethylene glycol dimethyl ether, but have a low boiling point, high volatility, strong odor, flammability, and storage. It is difficult to handle because it is easy to produce peroxides and there is a danger of explosion. Furthermore, it tends to permeate the interface between the base material and the conductive polymer and may reduce the adhesion. Therefore, in the present invention, the content of ethers in the release agent is preferably 30% by weight or less, more preferably 10% by weight or less, and further preferably 3% by weight or less of the entire release agent. Preferably it is not contained.

(B) an organic solvent having a nitrogen atom in the chemical structure and other than the primary amine compound, the secondary amine compound, and the organic quaternary ammonium salt, wherein a primary amine compound and Is a compound in which one of the hydrogen atoms of ammonia (NH ₃ ) is substituted with a hydrocarbon residue, and a secondary amine compound is a carbon atom of two hydrogen atoms of ammonia (NH ₃ ). It is a compound substituted with a hydrogen residue. Further, the quaternary ammonium salt is an ionic compound in which all four hydrogen atoms attached to the nitrogen atom of the ammonium salt (NH ₄ X) are substituted with hydrocarbon residues.
In the present invention, the organic solvent (b) is preferably a tertiary amine compound or an amide compound. In the present invention, the amide compound only needs to have a partial structure of —C═O—NR ^a — and includes a urea compound. Here, R ^a represents a hydrogen atom or a monovalent substituent.
Among these, the organic solvent (b) is preferably an amide compound.

  Examples of the organic solvent (b) include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, N-alkenylpyrrolidones, N, N-dimethylformamide, N, N-dimethyl. Examples thereof include dialkylcarboxamides such as acetamide and N, N-diethylacetamide, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, hexamethylphosphoric triamide, triethanolamine and the like.

The alkylpyrrolidones preferably have 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 to 2 carbon atoms (methyl group or ethyl group). The alkenylpyrrolidone preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, and still more preferably a vinyl group or an allyl group.
The dialkylcarboxamides are preferably represented by the following formula (1).
R ¹ — (C═O) —NR ² R ³ (1)
In the formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group having 6 to 10 carbon atoms. R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and further preferably a hydrogen atom or a methyl group.
In the formula (1), R ² and R ³ each independently represent an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.

  From the viewpoint of ease of handling and safety, it is preferably at least one organic solvent selected from the group consisting of N-alkylpyrrolidone and dialkylcarboxamide, more preferably N-methylpyrrolidone, dimethylformamide and dimethylacetamide. At least one organic solvent selected from the group consisting of: These organic solvents (b) may be used alone or in admixture of two or more.

When the organic solvent (b) is a primary amine compound, a secondary amine compound and / or an organic quaternary ammonium salt, the organic solvent increases the surface resistance value of the conductive polymer and deteriorates the conductivity. (B) is preferably an organic solvent that is not a primary amine compound, a secondary amine compound, or an organic quaternary ammonium salt. In particular, the release agent preferably does not contain monoethanolamine and tetramethylammonium hydroxide.
The primary amine compound, secondary amine compound and organic quaternary ammonium salt are preferably not contained as a whole release agent, and the primary amine compound, secondary amine compound and organic quaternary ammonium salt The content is preferably 5% by weight or less of the entire release agent, more preferably 3% by weight or less, and still more preferably not contained.

In the present invention, the aprotic organic solvent (a) or the organic solvent (b) can be used alone, or the aprotic organic solvent (a) and the organic solvent (b) can be used in combination.
The mixture of the aprotic organic solvent (a) and the organic solvent (b) has good releasability of the resist film from the conductive polymer and does not increase the surface resistance of the conductive polymer, that is, deteriorates the conductivity. And the adhesion between the substrate and the conductive polymer is not deteriorated.
The ratio of the aprotic organic solvent (a) to the organic solvent (b) is preferably (a) / (b) = 99/1 to 10/90 (weight ratio), and (a) / (b) = 70. / 30-20 / 80 (weight ratio) is more preferable.

In the present invention, in addition to the aprotic organic solvent (a) and the organic solvent (b), other compounds can be added to the release agent as long as the release characteristics are not deteriorated. Examples of such compounds include alcohols such as methanol, ethanol, ethylene glycol, and glycerin, alkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether. Examples thereof include glycol ethers having a flash point of 21 ° C. or higher, water and the like.
The components other than the aprotic organic solvent (a) and / or the organic solvent (b) are preferably 0 to 50% by weight based on the total weight of the release agent. More preferably, it is 0-30 weight%, More preferably, it is 0-10 weight%, Especially preferably, it is 0-5 weight%, Most preferably, it is 0-3 weight%.

(5) Method for producing a laminate having a conductive resin pattern In the present invention, a method for producing a laminate having a conductive resin pattern includes:
(A) preparing a conductive laminate having a conductive resin composition layer;
(B) forming a resist pattern on the conductive resin composition layer;
(C) removing the conductive resin composition layer of the resist pattern non-formation part using an etching agent; and
(D) a step of removing the resist pattern with a release agent;
In this order.
Hereinafter, each process is explained in full detail.

(Step a) Step of preparing a conductive laminate having a conductive resin composition layer The step of forming a conductive resin composition layer on a transparent substrate includes a conductive resin composition and a conductive resin composition to be used. What is necessary is just to select suitably with the electroconductive polymer compound to perform. For example, when poly (3,4-ethylenedioxythiophene) is used as the conductive polymer, it is dispersed in water, coated with a solution of the conductive polymer on a transparent substrate, dried and conductive. A polymer thin film (conductive resin composition layer) is formed.
The dopant can be added by a known method. Either a method of forming a conductive polymer film in advance and then introducing a dopant later, or a method of introducing a dopant when forming a conductive polymer film can be used.
The thickness of the conductive resin composition layer is preferably 1 nm or more and 10 μm or less, more preferably 5 nm or more and 1,000 nm or less, further preferably 10 nm or more and 500 nm or less, and particularly preferably 10 nm or more and 300 nm or less. It is.

(Step b) Step of forming a resist pattern on the conductive resin composition layer In Step (b), a resist pattern is formed on the conductive resin composition layer on the conductive laminate. The resist pattern preferably includes a step of forming a resist film and a step of selectively exposing the resist film using ultraviolet rays and developing the resist film with a developer, and more preferably include the above steps in this order.

The step of forming a resist film on the conductive resin composition layer is preferably a step of forming a resist film by coating a resist solution on the conductive resin composition layer and performing baking.
Next, it is preferable to include a step of irradiating the resist film with ultraviolet rays through a predetermined photomask, exposing the resist film in a predetermined pattern, and developing with a developer.

In the present invention, the resist pattern forming method is not limited to this. Other resist pattern formation methods include a method in which a resist layer forming material is ejected by ink jet and cured to form a resist pattern. After forming a resist film, a pattern is formed by irradiating the pattern with a laser. The method of doing etc. can be illustrated.
In addition, after pattern formation, you may perform a post-baking process further.

(Step c) Step of removing the conductive resin composition layer in the resist pattern non-formation portion using an etching agent In (Step c), the resist film in which the pattern is formed is used as a kind of mask to form the resist pattern non-formation portion. The conductive resin composition layer is etched to form a conductive resin pattern.
The step of removing the conductive resin composition layer in the resist pattern non-formed part using the etching agent can be used by either the dipping method or the spray method.
The spray nozzle used in the spray method is preferably a gun cone nozzle. The pressure at which the etching agent is sprayed is preferably 0.01 MPa or more because the time required for etching can be shortened by increasing the pressure. When the spraying pressure is increased, the conductive laminate is destroyed or it is difficult to fix the conductive laminate, so 0.5 MPa or less is preferable. More preferably, it is 0.05 MPa or more and 0.4 MPa or less, More preferably, it is 0.1 MPa or more and 0.3 MPa or less, Especially preferably, it is 0.15 MPa or more and 0.25 MPa or less.

The liquid temperature of the etching agent when using the etching agent is preferably 10 to 70 ° C, and more preferably 20 to 60 ° C. In the present invention, it is preferable that the etching agent has a liquid temperature in the above-mentioned range because the etching processing ability is excellent.
In the present invention, the etching time when using the etching agent is preferably 0.2 to 30 minutes, more preferably 0.3 to 25 minutes, and further preferably 0.4 to 15 minutes. In the present invention, it is preferable that the etching time is in the above range since the damage to the conductive laminate and the like in the etching process is small.

  In the present invention, the concentration of the etching agent can be controlled by controlling the oxidation-reduction potential, pH, electrical conductivity, specific gravity, etc., or a combination thereof.

(Step d) Step of removing resist pattern with release agent (peeling step)
Finally, in (Step d), the resist pattern on the conductive resin composition layer is removed with a release agent to obtain a conductive resin pattern. The conductive resin pattern is a pattern formed from a conductive resin composition layer.
In the (step d) (peeling step), it is necessary to bring the conductive laminate (hereinafter referred to as a test substrate) after patterning the conductive resin composition layer into contact with the stripping agent. Examples of such a peeling step include a method of placing a test substrate in a container containing a release agent, and a method of spraying the release agent on the test substrate.
In the method of placing the test substrate in the container, the release agent is preferably used so that the resist layer on the test substrate is completely immersed.
The contact between the test substrate and the release agent is necessary at least until the resist film completely peels from the conductive resin composition layer, and it is economical from the size of the apparatus to be within 5 minutes at the maximum, It is preferably selected within 3 minutes, more preferably within 2 minutes, particularly preferably between 10 seconds and 1 minute.
In addition, since these processing times can be shortened also by stirring a peeling agent, methods, such as immersion rocking | fluctuation, a liquid circulation, an ultrasonic wave, can be used besides the said spraying.

In the peeling step, it is preferable to control the temperature of the peeling agent. In order to shorten the peeling time and prevent peeling residue, the peeling temperature is preferably 5 ° C. or higher. In order to prevent deterioration of the conductivity of the conductive resin pattern after peeling, that is, increase in surface resistance, the peeling temperature is 60 ° C. It is preferable that it is below ℃. The temperature of the release agent is more preferably 5 ° C. or more and 50 ° C. or less, further preferably 10 ° C. or more and 40 ° C. or less, and particularly preferably 10 ° C. or more and 30 ° C. or less.
After completion of the peeling treatment, the test substrate is pulled up, washed with distilled water or an organic solvent as necessary, and dried.

After the peeling step, it is preferable to have a cleaning step of pulling up the test substrate and cleaning with a cleaning liquid such as water or an organic solvent.
The cleaning liquid used for cleaning is preferably water, a lower alcohol, or a mixture thereof. In the present invention, the lower alcohol is an alcohol having an alkyl group having 1 to 4 carbon atoms which may be branched. Specifically, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol. , Tert-butanol. These lower alcohols may be used as a mixture, and other relatively low-boiling alcohols such as n-hexanol and cyclohexanol may be mixed within a range that does not deteriorate the detergency. A preferred cleaning solution is ion-exchanged water, methanol and / or ethanol, or a mixture thereof.

  In the present invention, the washing step time is preferably 30 seconds to 5 minutes. When the cleaning process time is 30 seconds or longer, sufficient cleaning properties can be obtained, and when the cleaning process time is 5 minutes or shorter, the detachment of the conductive resin from the substrate can be suppressed. It is preferable to set the time of the cleaning step within the above range because the yield of the laminate having the conductive resin pattern is good.

  In the cleaning step, it is preferable to control the temperature of the cleaning liquid. In order to shorten the cleaning time and prevent cleaning residue, the cleaning temperature is preferably 5 ° C. or higher. In order to prevent deterioration of the conductivity of the conductive resin pattern after cleaning, that is, increase in surface resistance, the cleaning temperature is 60 ° C. It is preferable that it is below ℃. The temperature of the cleaning liquid is preferably 5 ° C. or higher and 50 ° C. or lower, more preferably 10 ° C. or higher and 40 ° C. or lower, and further preferably 10 ° C. or higher and 30 ° C. or lower.

  In this invention, it is preferable to perform at least one of a peeling process and a washing | cleaning process at the temperature of 5 to 60 degreeC, and it is more preferable to perform both a peeling process and a washing | cleaning process at the temperature of 5 to 60 degreeC.

  Moreover, in this invention, it is preferable to perform a drying process after a washing | cleaning process. The drying step can be appropriately selected from known methods.

This will be described in detail below with reference to the drawings. In the following drawings, the same reference numeral indicates the same object.
FIG. 1 is a process diagram showing a method for peeling a resist pattern directly formed on a conductive resin composition layer.
In FIG. 1A, the conductive resin composition layer 10 is formed on the transparent substrate 20. Next, a resist film 30 is formed on the conductive resin composition layer 10 (FIG. 1B). The resist film 30 is exposed through the mask pattern 40 (FIG. 1C) and developed in a pattern-like manner (FIG. 1D). In FIG. 1, a positive resist is used as the resist film 30, and the exposed portion becomes soluble. The light source used for exposure is not particularly limited, but ultraviolet rays can be preferably used.
Next, the conductive resin composition layer 10 is etched (FIG. 1 (e)), and the resist film 30 on the conductive resin composition layer 10 is further peeled off (FIG. 1 (f)). In the present invention, the release agent and the release method can be suitably used as the release agent for the resist film 30 on the conductive resin composition layer 10 shown in FIG. 1 (f) and the release method for the resist film.

FIG. 2 is a process diagram showing a method for peeling a resist film formed on another layer of the conductive resin composition layer.
In FIG. 2A, the conductive resin composition layer 10 and the other film 50 are formed on the substrate 20 in this order. Next, a resist film 30 is formed on the other film 50 (FIG. 2B), and the resist film 30 is exposed through the mask pattern 40 as in FIG. 1C (FIG. 2C). )). The resist film 30 is developed like a pattern (FIG. 2D), and then the other film 50 is etched (FIG. 2E). Finally, the resist film 30 formed on the conductive resin composition layer 10 is peeled off through another film 50. At this stage, the release agent is in contact with the conductive resin composition layer 10, so that the conductive resin composition An increase in surface resistance can be prevented without impairing the conductivity of the physical layer 10 (FIG. 2 (f)).
As shown in FIG. 2 (f), the laminate manufacturing method of the present invention includes a conductive resin via a resist film 30 provided on the conductive resin composition layer 10 via another film 50. It can also be used for the production of a laminate having a pattern.
Here, the other film is not particularly limited, for example, a wiring metal (aluminum, copper, silver, molybdenum, titanium, tantalum, chromium) such as an LCD or an organic EL, a reflective material of external light used for a reflective LCD ( Silver).

(6) Performance of Laminate Having Conductive Resin Pattern The conductive resin pattern patterned by the method of the present invention is not only simply patterned, but also excellent in maintaining light transmittance, conductivity, and conductivity after a heat test. Thus, the laminate (conductive laminate) of the present invention is excellent in total light transmittance, surface resistivity, and surface resistivity after a heat test.

(Total light transmittance)
The total light transmittance of the laminate including the conductive resin pattern and the substrate is preferably 80% or more, and more preferably 84% or more.
The total light transmittance is a measure of transparency. When the total light transmittance is 80% or more, it is excellent in transparency and can be applied to materials that require transparency, such as display applications. Visibility is improved by increasing the amount of transmitted light, and therefore, particularly in display applications, it is preferable because the performance can be exhibited satisfactorily even if the light emission intensity level of a backlight or the like is not high, and the life of the display is extended.
Moreover, it is preferable to select a conductive resin composition etc. suitably so that a total light transmittance may become in the said range. Further, the above-described etching agent and release agent are preferable because a decrease in transmittance of the laminate is small and a laminate with high transmittance can be obtained.

(Surface resistivity)
The surface resistivity of the laminate including the conductive resin pattern and the substrate immediately after patterning is preferably 2,000 Ω / □ or less, more preferably 1,500 Ω / □ or less, and further preferably 1,300 Ω / □ or less. Preferably, 1,200Ω / □ or less is particularly preferable, and 10Ω / □ to 1,100Ω / □ is most preferable.
When the surface resistivity is within the above range, current can flow smoothly when used as a transparent electrode such as a liquid crystal pixel electrode, and circuit design is facilitated. Is preferable because conduction at the time of pressing is easily achieved. It is also preferable to select a conductive resin composition or the like as appropriate so that the surface resistivity is within the above range. In addition, the above-described etching agent and release agent are preferable since the increase in the surface resistivity of the laminate is small and a laminate having a low surface resistivity can be obtained.

(Surface resistivity after heat test)
The surface resistivity of the laminate including the conductive resin pattern and the substrate after the heat resistance test is preferably 10Ω / □ to 2,000Ω / □. Here, the heat resistance test is allowed to stand for 240 hours in a thermal environment of 80 ° C.
When the surface resistivity is 2,000 Ω / □ or less, the surface resistivity is appropriate, and when used as a base material for a touch panel, the conductivity does not decrease even when a load is applied, and malfunctions may occur. It is preferable because there are few. Moreover, when using as transparent electrodes, such as an organic electroluminescent element and an inorganic electroluminescent lamp, since predetermined electroconductivity can be obtained, it is preferable. On the other hand, it is preferable that the surface resistivity is 10Ω / □ or more because the amount of the conductive resin used can be suppressed, and as a result, the manufacturing cost of the laminate becomes low and the economy is excellent. Further, it is preferable that the surface resistivity is 10Ω / □ or more because the film thickness of the transparent conductive thin film can be reduced and the total light transmittance can be reduced.
In addition, the said surface resistivity can be measured based on JISK7150 etc., for example, and can also be measured easily using a commercially available surface resistivity meter.

(Patterning line width)
In the present invention, the method of patterning the conductive resin composition layer is suitable for patterning a fine line width. Specifically, it is preferably 1,000 μm or less, more preferably 500 μm or less, further preferably 100 μm or less, and further preferably 30 μm or less.
Since the exposure apparatus becomes expensive, it is preferable that the limit line width for patterning is 1 μm or more.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to such examples.

[Example 1]
(Preparation of conductive resin composition)
In 1,887 parts of an aqueous solution containing 20.8 parts of polystyrene sulfonic acid, 49 parts of a 1% iron (III) sulfate aqueous solution, 8.8 parts of 3,4-ethylenedioxythiophene, and 117 parts of 10 9% aqueous peroxodisulfate solution was added. The reaction mixture was stirred at 18 ° C. for 23 hours. Then, 154 parts of cation exchange resin and 232 parts of anion exchange resin were added to the reaction mixture and stirred for 2 hours, after which the ion exchange resin was filtered off and desalted poly (3,4-ethylene An aqueous dispersion (2,041 parts: solid content 1.32%) of a complex of dioxythiophene) and polystyrene sulfonic acid was obtained (hereinafter referred to as an aqueous dispersion (A)).

  To 10.4 parts of the aqueous dispersion (A), 3.0 parts of a polyester resin aqueous dispersion (manufactured by Nagase ChemteX Corporation: Gabsen ES-210), 1.0 part of a melamine-based crosslinking agent (Sumitomo) Chemical Co., Ltd .: Sumitex Resin M-3), 20 parts of N-methylformamide, a small amount of surfactant, a small amount of leveling agent, an appropriate amount of water, and denatured ethanol are added and stirred for 1 hour, and then added to 400 mesh SUS. And filtered to obtain a conductive resin composition.

A blue plate round glass (JIS-R3202) was used as a transparent glass substrate, and the above conductive resin composition was applied at 700 rpm for 30 seconds using a Mikasa coater manufactured by Mikasa Co., Ltd. And dried for 15 minutes to obtain a conductive laminate.
Next, a resist containing a naphthoquinonediazide compound and a cresol novolak resin (TRP-43, manufactured by Toagosei Co., Ltd.) is coated as a positive photoresist using a spin coater, and prebaked at 90 ° C. for 15 minutes to form a film. A resist layer having a thickness of 1 μm was formed.
In the center of the test substrate with a resist layer, a 50 mm square photomask is placed and exposed at 100 mJ / cm ² using an exposure apparatus (manufactured by Hitech Co., Ltd.), 0.5 wt% potassium hydroxide The resist pattern was formed by developing with (KOH) aqueous solution, washing with water, and drying.

Conductive resin composition for 1 minute at 30 ° C. using a resist pattern as a mask and an etchant that is a mixture of 10 wt% cerium ammonium nitrate and 10 wt% nitric acid on a test substrate with a resist pattern The physical layer was etched and washed with water to form a pattern of the conductive resin composition.
Finally, the resist pattern on the conductive resin composition is stripped by putting 700 ml of γ-butyrolactone as a stripping agent in a 1 liter beaker and dipping for 1 minute at 10 ° C. while stirring with a stirring blade at 400 rpm. did. Thereafter, 700 ml of ion-exchanged water as a cleaning solution was placed in a 1 liter beaker and immersed for 1 minute at 10 ° C. while stirring with a stirring blade at 400 rpm. The washed substrate was dried with cold air.
As a result, one test substrate A having a conductive polymer patterned in a 50 mm square at the center of the test substrate was obtained.
The test board A was subjected to the following measurements and tests.

<Total light transmittance measurement>
The total light transmittance including the glass substrate was measured with a haze meter (manufactured by Suga Test Instruments Co., Ltd., Haze Computer HGM-2B) with respect to a 50 mm square conductive resin pattern portion present in the center of the test substrate. The total light transmittance was measured according to JIS K7150.

<Heat resistance test>
The surface resistance of a 50 mm square conductive resin pattern present in the center of the test substrate was measured with a surface resistance meter (Diainstrument Co., Ltd., Lorester GP MCP-T600) to obtain the surface resistivity immediately after patterning. Next, after performing a heat resistance test for 240 hours at 80 ° C. in a drying furnace on the test substrate, the surface resistivity was measured with a surface resistance meter to obtain the surface resistivity after the heat resistance test.
These results are shown in Table 1.

[Example 2]
The same operation as in Example 1 was performed except that the resist stripping solution was changed to 50% by weight of γ-butyrolactone and 50% by weight of N-methyl-2-pyrrolidone, and the results are shown in Table 1.

[Example 3]
The type of the glass substrate is defined by JIS-R3202, and the coating method of the conductive resin composition is No. The same operation as in Example 1 was performed except that the conductive resin composition was applied with a wire bar of 8 and dried with a blow dryer at 130 ° C. for 15 minutes, and the results are shown in Table 1. .

[Example 4]
The type of the glass substrate is defined by JIS-R3202, and the coating method of the conductive resin composition is No. The same operation as in Example 2 was performed except that the conductive resin composition was applied with a wire bar of 8 and dried for 15 minutes with a blow dryer at 130 ° C., and the results are shown in Table 1. .

[Example 5]
The type of the glass substrate is determined by Corning # 1737, and the coating method of the conductive resin composition is No. 1. The same operation as in Example 1 was performed except that the conductive resin composition was applied with a wire bar of 8 and dried with a blow dryer at 130 ° C. for 15 minutes, and the results are shown in Table 1. .

[Example 6]
The type of the glass substrate is determined by Corning # 1737, and the coating method of the conductive resin composition is No. 1. The same operation as in Example 2 was performed except that the conductive resin composition was applied with a wire bar of 8 and dried for 15 minutes with a blow dryer at 130 ° C., and the results are shown in Table 1. .

[Comparative Example 1]
The same measurement and test as in Example 1 were performed except that the patterning method was lift-off processing under the conditions according to Japanese Patent Application Laid-Open No. 2004-14215, and the results are shown in Table 1.
That is, as the positive radiation sensitive resin composition layer, 29.6 parts by weight of cresol novolac resin (mixture of m-form and p-form) and 7.4 parts by weight of 2,3,4,4′-tetrahydroxy A mixture of benzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 0.1 part by weight of a fluorosurfactant and 63.0 parts by weight of propylene glycol monomethyl ether acetate was obtained. The coating was performed on the substrate using a spin coater at 2500 rpm for 30 seconds, and heated and dried at 90 ° C. for 2 minutes on a hot plate.
A photomask was placed on the substrate on which the positive radiation-sensitive resin composition layer was formed, and contact exposure was performed using an exposure machine PLA-501F manufactured by Canon Inc. at an exposure amount of 150 mJ / cm ² . Next, this is immersed in a developer at 23 ° C. (2.38 wt% tetramethylammonium hydroxide aqueous solution) for 1 minute to dissolve and remove the exposed portion, and washed with water, so that a positive radiation sensitive resin composition is obtained. A predetermined pattern of objects was formed.
Next, the conductive resin composition is applied to the surface of the substrate having a pattern formed of the positive radiation-sensitive resin composition using a spin coater at 700 rpm for 8 seconds, and then on a hot plate. It was heated and dried at 115 ° C. for 5 minutes.
Finally, the substrate was immersed in a 23 ° C. release agent (release agent N-321 (primary amine aqueous solution) manufactured by Nagase ChemteX Corporation) for 1 minute to dissolve the radiation-sensitive resin composition of the pattern, This was washed with water to obtain a pattern.

[Example 7]
A polyethylene terephthalate film (thickness: 188 μm) was used as a transparent substrate, and the same conductive resin composition as in Example 1 was applied with a wet film thickness of 10 μm by a gravure coating method, and dried at 130 ° C. for 1 minute. Then, the electroconductive laminated body was obtained by performing an aging process at 90 degreeC for 24 hours.
Otherwise, two test substrates B having a conductive resin pattern patterned in the center of the test substrate in a 50 mm square were obtained by the same operation as in Example 1.
The same measurement and test as in Example 1 were performed on the two test substrates B, and the results are shown in Table 2.

[Example 8]
The same operation as in Example 7 was performed except that n-methylpyrrolidone was used as the resist stripping solution, and the results are shown in Table 2.

[Comparative Example 2]
The same operation as in Example 7 was performed except that the resist stripping solution was monoethanolamine, and the results are shown in Table 2. Since the surface resistance after patterning exceeded 2,000Ω / □, the heat resistance test was not performed.

[Example 9]
The same operation as in Example 7 was performed except that the etching agent was adjusted to 6% by weight of cerium ammonium sulfate and 6% by weight of sulfuric acid, and the results are shown in Table 3.

[Example 10]
An etchant of sodium hypochlorite (manufactured by Toagosei Co., Ltd., Aronkurin ^R LB10) except that as available chlorine with sulfuric acid has to those adjusted to pH5.6 with 0.54 wt% Same as Example 7 The operation was performed and the results are shown in Table 3.

[Example 11]
The same operation as in Example 7 was performed except that the photomask had a minimum line width of 2 μm (L / S = 2/20).
When the line width of the conductive film after patterning was measured with a microscope (Laser surface shape observation microscope VF-7510 manufactured by Keyence Corporation), the line width that could be patterned was 4 μm (L / S = 4/20). The measured value was 3.9 μm.

  According to the present invention, a conductive laminate having a patterned conductive film that is flexible, has a total light transmittance and low surface resistance, and has excellent heat resistance can be obtained. This conductive laminate promotes the practical use of flexible displays such as touch panels and organic EL.

DESCRIPTION OF SYMBOLS 10 Conductive resin composition layer 20 Transparent base | substrate 30 Resist film 40 Mask pattern 50 Other films

Claims (5)

(A) preparing a conductive laminate having a transparent substrate and a conductive resin composition layer provided on at least one surface of the transparent substrate;
(B) forming a resist pattern on the conductive resin composition layer;
(C) removing the conductive resin composition layer in the resist pattern non-forming portion using an etching agent containing at least one selected from the group consisting of cerium ammonium nitrate, cerium ammonium sulfate, and hypochlorite And the process of
(D) a resist pattern having an aprotic organic solvent containing no nitrogen atom, a nitrogen atom in the chemical structure, and other than primary amine compound, secondary amine compound and organic quaternary ammonium salt And a step of removing with a release agent containing at least one organic solvent selected from the group consisting of organic solvents in this order. A method for producing a laminate having a conductive resin pattern.   The manufacturing method of the laminated body of Claim 1 in which the said conductive resin composition contains the composite_body | complex of poly (3,4-disubstituted thiophene) and a polyanion.   A laminate obtained by the method according to claim 1.   The laminate according to claim 3, wherein the total light transmittance is 80% or more and the surface resistivity is 2,000Ω / □ or less.   The laminate according to claim 3 or 4, wherein the surface resistivity after being allowed to stand for 240 hours in a thermal environment of 80 ° C is 2,000 Ω / □ or less.

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