JP2013008897A - Removal method of conductive film and conductive film remover - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive film remover and a removal method of a conductive film which can reduce corrosiveness load on an etching step facility and in which safety of an operator is excellent, versatility is high, and a color of an etching trace or the like does not change.SOLUTION: A removal method of a conductive film comprises the steps of: applying a conductive film remover whose pH is 6.0 to 8.0 at 20°C to at least a part of a base material with a conductive film; heat-treating the base material with the conductive film to which the conductive film remover was applied; and removing the conductive film from the heated-treated base material with the conductive film by cleaning the base material with a liquid. This removal method makes pH of the conductive film remover less than 6.0 or greater than 8.0 by volatilizing at least some components of the conductive film remover applied in the step of heat-treating the base material.

Description

  The present invention relates to a conductive film removing method and a conductive film remover.

    Transparent conductive films made of tin-doped indium oxide (ITO) are widely used in display panels such as liquid crystal displays, plasma displays, and electroluminescent (EL) displays, and electronic devices such as touch panels and solar cells.

  The conductive film including these transparent conductive films is used by forming a desired pattern, and a chemical etching method using a photoresist or an etching solution is generally used as a pattern forming method. (See Patent Document 1). However, since the etchant used in the chemical etching method is a strongly acidic solution such as sulfuric acid, nitric acid, phosphoric acid, and aqua regia, there are problems with corrosion of process equipment and worker safety (risk of chemical injury). It was.

  In addition, as a chemical etching method that does not use an acid, a method is known in which a water-soluble etching paste containing a base, a thickener, and a solvent is applied onto a substrate with a conductive film, and the conductive film is deteriorated and removed. . (Refer to Patent Document 2) This method has a feature that equipment corrosivity can be minimized because a base is used as an etching component of the conductive film and a paste-like etchant is directly applied. However, since the base is used as the etching component, the paste has a strong basicity, and there is a problem that the corrosiveness of the non-metallic part and the risk of chemical burns of the worker are high.

  Here, as a chemical etching method in which an acid and an alkali are added, an etching solution using oxalic acid and an alkali compound is known. However, although it contains an acid and an alkali, the etching solution shows strong acidity, and the above problem has not been solved.

  On the other hand, an etching solution containing iodine has been proposed as an etching solution for the neutral region. (See Patent Document 4) By using iodine as an etching component, the pH of the etching solution is maintained in a neutral region.

JP 2005-162893 A JP 2010-21137 A JP 2010-45253 A JP 2006-293141 A

  However, the etching solution of Patent Document 4 is not versatile because the metal that can be etched is limited to gold or a part of the platinum group metal because of its reactivity with iodine. In addition, iodine is easily adsorbed on the base material, and there is a problem that the etching mark is discolored.

  In view of the above-described problems of the prior art, the present invention reduces the corrosive load applied to the etching process equipment, and is excellent in the safety of the operator. An object is to provide a removal method and a conductive film remover.

  The present invention includes a step of applying a conductive film remover having a pH of 6.0 to 8.0 at 20 ° C. to at least a part of a substrate with a conductive film, and heating the substrate with a conductive film coated with the conductive film remover. And a step of removing the conductive film by washing using a liquid from the heat-treated substrate with the conductive film, and at least a part of the component of the conductive film removing agent applied in the heat treatment step is volatilized. Thus, the conductive film removing method is characterized in that the pH of the conductive film removing agent is less than 6.0 or greater than 8.0. Furthermore, the conductive film removing agent used in the present invention includes an acid and a base, a solvent and a resin having different vapor pressures as a single substance, and the resin is a cationic resin.

  That is, since the conductive film remover of the present invention has a pH of 6.0 to 8.0 at 20 ° C., it is neutral during handling, and even in the step of applying the conductive film remover during the etching operation. Since the pH of the conductive film removing agent is less than 6.0 or greater than 8.0 in the heat treatment process (for example, at 80 ° C. or higher), it becomes acidic or basic for the first time to obtain an etching effect. Is.

  According to the present invention, it is possible to reduce or eliminate the corrosion resistance equipment in the etching operation. Moreover, the risk of chemical burns for the handling operator can be reduced, and a conductive film removing agent that does not discolor the etching marks can be obtained in the conductive film to be removed.

Schematic which shows the state (before heat processing) which apply | coated the electrically conductive film removal agent to the base material with an electrically conductive film Schematic which shows the state which removed the electrically conductive film by the electrically conductive film removal method of this invention

  The conductive film removing method of the present invention includes a step of applying a conductive film remover having a pH of 6.0 to 8.0 at 20 ° C. on at least a part of a substrate with a conductive film, and a conductive film coated with a conductive film remover. At least one of the conductive film removers applied in the heat treatment step, the step of heat-treating the substrate with heat treatment, and the step of removing the conductive film from the heat-treated base material with conductive film by washing with a liquid. The conductive film removing method is characterized in that the pH of the conductive film removing agent is less than 6.0 or greater than 8.0 by volatilization of the components of the part.

  The conductive film removing method of the present invention uses a conductive film remover having a pH of 6.0 to 8.0 at 20 ° C., and the pH is within the above range until the heat treatment step. For example, in the step of applying the conductive film removing agent, the possibility of equipment corrosion due to acid (or base, which may be omitted) is extremely low, and no special equipment for acid resistance (or base) is required. . Furthermore, since no acid (or base) conductive film remover is used, the risk of chemical injury to the handling operator is lower than that of known methods, and it can be used easily.

  And since the said electrically conductive film removal agent contains the acid and base from which vapor pressure differs, in the process of heat processing, content of both components can be changed and pH of the said electrically conductive film removal agent is adjusted arbitrarily. can do. For example, when the removal component of the conductive film is an acid, a base having a higher vapor pressure than the acid is selected and added. Then, in the state before the heat treatment, the neutralization reaction is caused and the pH of the neutral region is maintained, but the conductive film removing agent is applied to at least a part on the substrate with the conductive film, and the heat treatment is performed. By doing so, the base evaporates earlier than the acid, the pH of the removal agent on the substrate changes to acidic, and an etching effect can be obtained.

  In the method for removing a conductive film of the present invention, the conductive film removing agent is applied to a portion to be removed of the substrate with a conductive film. In the present invention, the substrate with a conductive film can be removed even if it has an overcoat layer on the conductive film. Examples of the material for forming the overcoat layer include organic or inorganic polymer materials and organic-inorganic hybrid resins.

  Examples of organic polymer materials include thermoplastic resins, thermosetting resins, cellulose resins, and photocurable resins. From the viewpoints of visible light permeability, substrate heat resistance, glass transition point, film hardness, and the like. Can be appropriately selected. Examples of the thermoplastic resin include acrylic resins such as polymethyl methacrylate and polystyrene, polyester resins such as polyethylene terephthalate, polycarbonate, and polylactic acid, ABS resins, polyethylene, polypropylene, and polystyrene. Examples of the thermosetting resin include phenol resin, melamine resin, alkyd resin, polyimide, epoxy resin, fluorine resin, and urethane resin. Examples of the cellulose resin include acetyl cellulose and triacetyl cellulose. Examples of the photocurable resin include, but are not limited to, resins containing various oligomers, monomers, and photopolymerization initiators.

  Examples of the inorganic material include silica sol, alumina sol, zirconia sol, titania sol, etc., a polymer obtained by hydrolyzing these inorganic materials by adding water or an acid catalyst, and dehydrating and condensing them, or already tetramer to pentamer. Examples thereof include a polymer obtained by further hydrolyzing and dehydrating and condensing a polymerized commercial solution. Examples of the organic-inorganic hybrid resin include those obtained by modifying a part of the inorganic material with an organic functional group and resins mainly composed of various coupling agents such as a silane coupling agent.

  When the substrate with a conductive film has an overcoat layer, the conductive film remover is applied on the portion of the overcoat layer to be removed. Examples of the coating method include screen printing method, dispenser method, stencil printing method, pad printing method, spray coating, ink jet method, micro gravure printing method, knife coating method, spin coating method, slit coating method, roll coating method, curtain Examples thereof include, but are not limited to, a coating method and a flow coating method. In order to further reduce the etching unevenness of the conductive film, it is preferable to apply the conductive film removing agent uniformly on the substrate. The coating thickness of the conductive film removing agent is appropriately determined depending on the material and thickness of the conductive film to be removed, the heating temperature and the heating time, but it may be applied so that the thickness after drying is 0.1 to 200 μm. Preferably, it is 2-200 micrometers. By setting the film thickness after drying within the above range, a necessary amount of the conductive film removing component is contained in the coating film, and the conductive film can be more uniformly removed in the plane. Moreover, since the sagging in the lateral direction can be suppressed during heating, a desired pattern can be obtained without any positional deviation of the coating film boundary line.

  Next, the base material with a conductive film coated with the conductive film removing agent is heat-treated. The heat treatment evaporates from the contained acid and base from the higher vapor pressure, so that the ratio of acid to base in the conductive film remover changes and the pH also deviates from the neutral region. At this time, if the vapor pressure of the contained base is higher than that of the acid, the base is evaporated by heat treatment, and the pH of the removal agent becomes lower than that in the neutral region. And the part to which the electrically conductive film removal agent was apply | coated is decomposed | disassembled, melt | dissolved or solubilized because pH of this removal agent will be 6.0 or less. When the base material with a conductive film has an overcoat layer, the overcoat layer and the conductive film are decomposed, dissolved or solubilized.

  The heat treatment temperature is not particularly limited as long as the base (or acid) contained for neutralizing the conductive film removing agent can be evaporated, but it is preferably 80 ° C. or higher. If the heat treatment temperature is 80 ° C. or more, the volatilization of the neutralizing component is promoted and the etching component (residual acid or base) is also activated, so that the portion where the conductive film removing agent is applied is decomposed. Lysis or solubilization can be processed in a short time.

  The heat treatment method can be appropriately selected depending on the purpose and application, and examples thereof include a hot plate, a hot air oven, an infrared oven, and microwave irradiation with a frequency of 300 megahertz to 3 terahertz, but are not limited thereto. .

  As described above, if the vapor pressure of the contained base is higher than that of the acid, the conductive film remover becomes acidic only after heat treatment, so that there is a possibility that an acid-resistant facility is necessary. In this case, since only the base material with the conductive film is in contact with the conductive film removing agent that has been changed to acidic, there is no risk of corrosion in the process equipment here, and no special acid-resistant equipment is required. There are many cases. In addition, the base evaporates first in the heat treatment, and a small amount of base is contained in the evaporation component. However, if the exhaust gas control device such as a scrubber is adjusted and a scrubber is installed, it can be handled with general equipment. Many.

  On the other hand, when the conductive film removing component is a base, the same effect as described above can be obtained by selecting and adding an acid having a higher vapor pressure than the base. The corrosivity due to the acid (or base) can be observed by a change in appearance and weight after a test material such as a metal piece, a plastic piece, or a rubber piece is immersed in the remover and a certain time has passed. Of the test materials, the reactivity with acid (or base) is high, and the presence of corrosiveness can be conveniently checked by using aluminum which is generally used in process equipment.

  Next, after the heat treatment, the conductive film removing agent and the decomposed / dissolved material of the conductive film are removed from the heat-treated substrate with the conductive film by using a liquid to obtain a desired conductive pattern. The liquid used in the cleaning step is preferably one in which the resin contained in the conductive film removing agent dissolves, specifically, an organic solvent such as acetone, methanol, tetrahydrofuran, an aqueous solution containing the organic solvent, sodium hydroxide, Examples include, but are not limited to, basic aqueous solutions containing ethanolamine, triethylamine, and the like. In the washing step, the liquid may be heated to 25 to 100 ° C. and used for washing on the substrate without residue.

  The conductive film removing method of the present invention will be described again with reference to the drawings. FIG. 1 is a schematic view showing a state (before heat treatment) in which a conductive film removing agent is applied to a substrate with a conductive film. FIG. 2 is a schematic view showing a state where the conductive film is removed by the conductive film removal method of the present invention.

  The conductive film removing method of the present invention includes a step of applying the conductive film removing agent 103 to at least a part of a substrate with a conductive film having a conductive film 102 on the substrate 101, and a conductive film coated with a conductive film removing agent. A step of heat-treating the substrate with attachment, and a step of removing the conductive film from the heat-treated substrate with conductive film by washing with a liquid. In FIG. 2, reference numeral 104 denotes a portion where the conductive film has been removed.

  In the method for removing a conductive film of the present invention, a conductive film removing agent is directly applied on a substrate and then heat-treated, whereby a neutralizing component evaporates from the removing agent, and an etching component is applied to the conductive film lower layer in a short time. The reaction proceeds promptly. Since the conductive film removing agent of the present invention has high penetrating power to the conductive film, it includes not only the transparent oxide conductive film but also whisker-like conductors, fibrous conductors, or particulate conductors that have been difficult in the past. A particularly excellent removal effect is also exhibited for the removal of the conductive film.

  Examples of the substrate to which the conductive film removing method of the present invention can be applied include thermoplastic resins such as polyethylene, polystyrene, polymethyl methacrylate, and polyvinyl chloride, polyesters such as polyethylene terephthalate, polyethylene 2,6 naphthalate, and polyparaffin. Examples thereof include phenylene sulfite, polyamide resin, polyimide resin, acrylic resin, urethane resin, alkyd resin, phenol resin, epoxy resin, silicone resin, polycarbonate resin, ABS resin, various glasses, and quartz. It may contain inorganic fillers such as silica and glass, and fine particles such as acrylic beads. The substrate may be subjected to various surface treatments such as plasma treatment, UV / ozone treatment, and the coating properties and permeability can be further improved. The shape of the substrate may be any shape such as a disk shape, a card shape, or a sheet shape.

  The conductive film removing method of the present invention preferably uses a conductive film remover containing a cationic resin. By containing the cationic resin, a conductive film removing agent having non-Newtonian fluidity can be obtained and can be easily applied to the substrate by a known method. Furthermore, by being a cationic resin, the conductive film removing agent can maintain high solubility even after the heating step, and can be easily washed with water, an aqueous solution of a basic aqueous solution or an organic solvent described later, Residues can be suppressed and in-plane uniformity can be further improved.

  Specific examples include, for example, polydialkylaminoethyl methacrylate, polydialkylaminoethyl acrylate, polydialkylaminoethyl methacrylamide, polydialkylaminoethyl acrylamide, polyepoxyamine, polyamidoamine, dicyandiamide-formalin condensate, polydimethyldiallylammonium chloride. , Guar hydroxypropyltrimonium chloride, polyamine polyamide epichlorohydrin, polyvinylamine, polyallylamine, polyacrylamine, polyquaternium-4, polyquaternium-6, polyquaternium-7, polyquaternium-9, polyquaternium-10, polyquaternium-11, polyquaternium-16, Polyquaternium-28, Polyquaternium-32, Polyqua Um -37, polyquaternium -39, polyquaternium -51, polyquaternium -52, polyquaternium -44, polyquaternium -46, polyquaternium -55, compounds such as polyquaternium -68 and the like modified products thereof. For example, polyquaternium-10 has a trimethylammonium group at the end of the side chain. Under acidic or basic conditions, the trimethylammonium group is cationized and exhibits high solubility due to the action of electrostatic repulsion. Moreover, dehydration polycondensation by heating hardly occurs, and high solubility is maintained even after heating. Therefore, after the heat treatment, the conductive film can be removed in a short time in the step of removing the conductive film by cleaning with a liquid.

  In the conductive film removing agent of the present invention, the content of the cationic resin is preferably 0.01 to 80% by weight in the components excluding the solvent. In order to keep the heating temperature required for removing the conductive film low and shorten the heating time, it is more preferable that the resin content in the conductive film removing agent is as small as possible within the range that maintains the non-Newtonian fluidity. The viscosity of the conductive film removing agent is preferably about 2 to 500 Pa · S (25 ° C.), and a uniform coating film can be easily formed by a screen printing method. The viscosity of the conductive film removing agent can be adjusted by, for example, the contents of the solvent and the resin.

  One embodiment of the conductive film removing agent of the present invention includes an acid and a base, a solvent and a resin having different vapor pressures as a single substance, has a pH of 6.0 to 8.0 at 20 ° C., and the resin is a cationic resin. is there. When the conductive film remover contains both an acid and a base, a neutralization reaction occurs, and the pH of the conductive film remover at 20 ° C. is maintained in a neutral region of 6.0 to 8.0. . That is, the amount of acid and base contained in the conductive film removing agent of the present invention is adjusted so that the pH is 6.0 to 8.0.

  The acid used for this electrically conductive film removal agent can be suitably selected with the kind of conductor. For example, monocarboxylic acids such as formic acid, acetic acid and propionic acid, dicarboxylic acids such as oxalic acid, succinic acid, tartaric acid and malonic acid, tricarboxylic acids such as citric acid and tricarballylic acid, alkylsulfonic acids such as methanesulfonic acid, benzene Phenyl sulfonic acid such as sulfonic acid, alkyl benzene sulfonic acid such as toluene sulfonic acid and dodecylbenzene sulfonic acid, sulfonic acid compound such as phenol sulfonic acid, nitrobenzene sulfonic acid, styrene sulfonic acid and polystyrene sulfonic acid, organic acid such as trifluoroacetic acid And a partially fluorinated derivative, and inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid. Two or more of these may be contained.

  Examples of the base contained in the conductive film removing agent include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide, beryllium hydroxide, and hydroxide. Alkali earth metal hydroxides such as magnesium and calcium hydroxide, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, n-hexylamine, cyclohexylamine, n-heptylamine , N-octylamine, n-nonylamine, monoalkylamines such as n-decylamine, dimethylamine, diethylamine, di-n-butylamine, di-n-isopropylamine, di-n-pentylamine, di-n-hexyl Amine, dicyclohexylamine, di Dialkylamines such as n-heptylamine, di-n-octylamine, di-n-nonylamine and di-n-decylamine, trialkylamines such as trimethylamine, triethylamine, tri-n-butylamine and tri-n-propylamine , Alkanolamines such as ethanolamine and diethanolamine, aromatic amines such as aniline, N-methylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine and 1-naphthylamine , Primary amines having a bridged alicyclic skeleton such as 1-adamantylamine, N-methyl-1-adamantylamine, urea, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4 4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2'-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4- Aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1 Diamine compounds such as-(4-aminophenyl) -1-methylethyl] benzene and 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, imidazole, benzimidazole, 4-methylimidazole Imidazoles such as 4-methyl-2-phenylimidazole and 2-phenylbenzimidazole, ethylene Imine, pyrrole, pyrazole, indole, isoindole, purine, carbazole, carboline, perimidine, phenothiazine, phenoxazine, pyrrolidine, pyrroline, imidazolidine, imidazoline, pyrazolidine, pyrazoline, piperazine, indoline, isoindoline, benzimidazole, 4-methyl Imidazole, 4-methyl-2-phenylimidazole, 2-phenylbenzimidazole, pyridine, picoline, lutidine, pyrazine, pyrimidine, pyridazine, piperidine, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] Nitrogen-containing compounds such as octane. Two or more of these may be contained.

  Furthermore, the base contained in the conductive film removing agent of the present invention is preferably one whose content can be controlled by heat treatment, and a nitrogen-containing compound having a vapor pressure as a simple compound is particularly preferred. For example, when the conductive film removing component is an acid, an amine compound having a higher vapor pressure than the acid is preferable. Specifically, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutyl Amine, n-hexylamine, cyclohexylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, ethanolamine, aniline, N-methylaniline, urea, ethylenediamine, tetramethylenediamine, imidazole, benzimidazole, ethyleneimine, pyrrole, pyrazole, indole Pyrrolidine, pyrroline, pyridine, pyrazine, pyrimidine, pyridazine, piperidine and the like.

  The combination of the acid and the base contained in the conductive film removing agent of the present invention can be applied as long as both vapor pressures are different, and is not particularly limited. The vapor pressure in the present invention can be measured by a static method or a boiling point method, and is a value of a saturated vapor pressure at room temperature.

  The conductive film removing agent of the present invention comprises an acid, a base, a solvent, and a resin having different vapor pressures as a single substance, but is dissolved and contained in the solvent even when the conductive film removal component is solid and has no vapor pressure. One component (acid or base) can be applied if it has a vapor pressure.

  In the conductive film removing agent of the present invention, the content of acids and bases having different vapor pressures as a single substance is not particularly limited as long as the pH is adjusted to 6.0 to 8.0, but the molecular weight of the compound It can be appropriately selected depending on the equilibrium constant of the acid or base, the material and film thickness of the conductive film to be removed, the heating temperature and the heating time. Especially, 1 to 80 weight% is preferable in the component except a solvent. Among them, the acid content is preferably 10 to 70% by weight, more preferably 20 to 70% by weight, in the components excluding the solvent. Moreover, 10 to 70 weight% is preferable in the component except a solvent, and, as for content of a base, 20 to 70 weight% is more preferable.

  The electrically conductive film removal agent of this invention contains a solvent. Specific examples of solvents include acetates such as ethyl acetate and butyl acetate, ketones such as acetone, acetophenone, ethyl methyl ketone, and methyl isobutyl ketone, aromatic hydrocarbons such as toluene, xylene, and benzyl alcohol, methanol, ethanol 1,2-propanediol, terpineol, acetyl terpineol, butyl carbitol, ethyl cellosolve, alcohols such as ethylene glycol, triethylene glycol, tetraethylene glycol, glycerol, ethylene glycol monoalkyl ethers such as triethylene glycol monobutyl ether , Ethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, ethylene glycol monoaryl ethers, polymers Ethylene glycol monoaryl ethers, propylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, ethylene carbonate, propylene carbonate, γ-butyrolactone, solvent naphtha, water, N-methylpyrrolidone, dimethyl Examples thereof include sulfoxide, hexamethylphosphoric triamide, dimethylethyleneurea, N, N′-dimethylpropyleneurea, and tetramethylurea. Two or more of these may be contained.

  In the conductive film removing agent of the present invention, the content of the solvent is preferably 1% by weight or more, more preferably 30% by weight or more, and more preferably 50% by weight or more in the conductive film removing agent. By making content of a solvent into 1 weight% or more, the fluidity | liquidity of a electrically conductive film removal agent can be improved and applicability | paintability can be improved more. On the other hand, 99.9 weight% or less is preferable and 95 weight% or less is more preferable. By setting the content of the solvent to 99.9% by weight or less, the fluidity during heating can be maintained in an appropriate range, and a desired pattern can be accurately maintained.

  The conductive film removing agent of the present invention contains a resin, and the resin is a cationic resin. Here, the cationic resin is as described above.

  The conductive film removing agent of the present invention includes inorganic fine particles such as titanium oxide, alumina, and silica, a thixotropic agent that can impart thixotropic properties, an antistatic agent, an antifoaming agent, a viscosity modifier, and light resistance depending on the purpose. Stabilizers, weathering agents, heat agents, antioxidants, rust inhibitors, slip agents, waxes, mold release agents, compatibilizers, dispersants, dispersion stabilizers, rheology control agents, and the like may be included.

  Furthermore, the conductive film removing agent of the present invention can contain nitrate or nitrite as an etching accelerator. When an acid is applied as an etching component, the reaction rate between the acid and the conductor may differ depending on the type of the acid. However, by including nitrate or nitrite, the acid and nitrate or nitrite may be reacted during heat treatment. Since nitrate reacts and nitric acid is generated in the system, dissolution of the conductor can be further promoted. For this reason, the conductive film can be removed by a short heat treatment. Examples of the nitrate include lithium nitrate, sodium nitrate, potassium nitrate, calcium nitrate, ammonium nitrate, magnesium nitrate, barium nitrate, and hydrates of these nitrates. Examples of the nitrite include sodium nitrite, potassium nitrite, calcium nitrite, silver nitrite, and barium nitrite. Two or more of these may be contained. Among these, in consideration of the reaction rate of nitric acid production, nitrate is preferable, and sodium nitrate or potassium nitrate is more preferable.

  Next, an example is given and demonstrated about the manufacturing method of the electrically conductive film removal agent of this invention. First, the resin is added to the solvent and dissolved with sufficient stirring. Stirring may be performed under heating conditions, and stirring is preferably performed at 50 to 80 ° C. for the purpose of increasing the dissolution rate. Next, an acid and a base having different vapor pressures as a single substance, and, if necessary, a leveling agent and the additive are added and stirred. The addition method and the addition order are not particularly limited. Stirring may be performed under heating conditions, and stirring is preferably performed at 50 to 80 ° C. for the purpose of increasing the dissolution rate of the additive.

  The conductive film removing agent of the present invention can remove a conductive film made of a metal, a carbon-based compound, a metal oxide, a conductive polymer, or the like by selecting an acid or base suitable for the material of the conductive film. . The metal belongs to the group IIA, IIIA, IVA, VA, VIA, VIIA, VIII, IB, IIB, IIIB, IVB or VB in the short periodic table of elements. Elements. Specifically, gold, platinum, silver, nickel, silicon, stainless steel, copper, brass, aluminum, gallium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, manganese, antimony, palladium, bismuth, technetium, Examples include rhenium, iron, osmium, cobalt, zinc, scandium, boron, gallium, indium, silicon, germanium, tellurium, tin, magnesium, and alloys containing these.

  Examples of the carbon-based compound include carbon nanohorn, carbon nanotube, carbon nanocoil, carbon whisker, fullerene, graphene and the like. Carbon nanotubes may be single-walled or multi-walled, and two or more types of CNTs having different numbers of layers may be used.

  Examples of the metal oxide include indium oxide or a compound in which at least one element selected from the group consisting of tin, zinc, tellurium, silver, zirconium, hafnium, and magnesium is doped, tin oxide, or tin oxide. Examples include compounds doped with antimony, zinc, fluorine, or the like, zinc oxide, or compounds in which zinc oxide is doped with an element such as aluminum, gallium, indium, boron, fluorine, or manganese.

  Examples of the conductive polymer include polythiophene, polyaniline, poly (2-ethylhexyloxy-5-methoxy-1,4-phenylvinylene), and the like.

  The conductive film removing agent of the present invention can be applied to a conductive film including a whisker-like conductor, a fibrous conductor, and a particulate conductor of the conductor in addition to the vapor-deposited film and the coating film of the conductor. The surface shape of the conductive film is not limited.

  Hereinafter, the conductive film removing agent and the conductive film removing method of the present invention will be specifically described based on examples. However, the present invention is not limited to the following examples.

(1) Method for measuring pH of conductive film removing agent (before and after heat treatment)
The pH of the conductive film removing agent before the heat treatment was directly measured at 20 ° C. using a pH meter (“SevenGO pH SG2”, manufactured by METTLER TOLEDO). The pH of the electrically conductive film removing agent after the heat treatment was obtained by collecting 1 g of the electrically conductive film removing agent immediately after the heat treatment, stirring it in 1 mL of pure water (extracting the etching components), and measuring the pH of the aqueous solution using a pH meter. And measured at 20 ° C.

(2) Corrosion test The weight of the metal aluminum piece (length 1 cm x width 1 cm) contained in the conductive film remover was measured, immersed in the remover, and allowed to stand at 25 ° C for 1 week. Thereafter, the aluminum piece was taken out, washed with water and lightly dried, and then the weight was measured. After immersion in the removal agent, if there was no surface change such as rust and the weight change was less than ± 3%, it was evaluated as “Good” (no corrosiveness). On the other hand, when rust or the like was generated on the aluminum surface after immersion in the remover, or when the weight change was 3% or more, the evaluation was x (corrosive).

(3) Appearance Evaluation Method of Conductive Film Removal Surface On the substrate with conductive film described in each Example / Comparative Example, the conductive film with a frame-like pattern having an outer frame of 10 cm × 10 cm and an inner frame of 9 × 9 cm and a line width of 1 cm. The remover was applied by a known method so that the film thickness after drying was 1.0 μm, and then placed in an infrared oven and heat-treated under the conditions shown in Table 1. After heat treatment, take it out of the oven, let it cool to room temperature, and then check that the dry film thickness is the specified thickness using a stylus-type film thickness meter ("Surfcom", manufactured by Tokyo Seimitsu Co., Ltd.) did. Moreover, pH measurement of the electrically conductive film removal agent after heat processing was implemented. Then, it wash | cleaned on the conditions as described in each Example and a comparative example, and removed the electrically conductive film removal agent and decomposition product which have adhered to the base material. The substrate was drained with compressed air, then placed in an infrared oven and dried at 80 ° C. for 1 minute to obtain a substrate with a conductive film on which the conductive film was patterned. The patterned substrate with the conductive film was observed with an optical microscope (Nikon Corporation ECLIPSE-L200, magnification 500 times), and the outer frame was 10 cm × 10 cm in a spot shape having an outer periphery of 0.01 mm or more and / or The presence or absence of dot-like residues was evaluated.

(4) Evaluation method of conductive film removal line width Film thickness after drying the conductive film remover using the sus # 500 mesh on the base material with the conductive film described in Examples 1 to 14 and Comparative Examples 1 to 3. Was screen-printed so as to be 1.0 μm. The print pattern was a straight line having a line length of 5 cm and a line width of 30 μm, 50 μm, 100 μm, and 500 μm. After applying the conductive film remover, heat treatment is performed under the conditions shown in Table 1, taken out from the oven, allowed to cool to room temperature, and then the stylus type film thickness meter ("Surfcom" “Measured by Tokyo Seimitsu) and confirmed. The film was washed with pure water at 25 ° C. for 1 minute to remove the conductive film remover and decomposition products adhering to the substrate. The substrate was drained with compressed air and then dried in an infrared oven at 80 ° C. for 1 minute to obtain a substrate with a conductive film on which the conductive film was patterned. Next, a 1 cm portion was cut from both ends of the etching line to obtain a 3 cm × 10 cm base material with a conductive film partitioned by the etching line. Then, apply the insulation resistance meter (EA709DA-1 manufactured by Sanwa Denki Keiki Co., Ltd.) to the right and left sides of the etching line, and set the minimum line width of the pattern showing a resistance of 10 MΩ or more when DC 25V is applied. The conductive film removal line width was used. When the conductive film removal line width is 500 μm or less, it can be said that a high-definition pattern can be formed.

(5) Evaluation Method of Line Linearity (Waviness) at Etching Boundary Area A frame-like conductive film removal line formed by the method described in (1) above is an optical microscope (Nikon Corporation ECLIPSE-L200, magnification 500 times). ). The width of the removal line was measured every 100 μm, and the standard deviation (σ) was calculated from a total of 20 points. When the standard deviation is 5 or less, it can be said that a high-definition pattern can be formed.

Example 1
Add 100 g of N-methylpyrrolidone and 10 g of pure water to a container, mix, and add 5 g of Polyquaternium-11 (manufactured by Osaka Organic Chemical Industry Co., Ltd., HC-Polymer 2L) to an oil bath at 60 ° C. The mixture was stirred for 30 minutes while heating. Next, after removing the container from the oil bath and allowing to cool to room temperature, 0.5 g of a leveling agent (fluorine-based surfactant F-477 manufactured by DIC Corporation) and sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd., concentration 98) %) 4 g was added and stirred for 15 minutes. Next, 2.5 g of ethylenediamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added while cooling the vessel with ice, and the mixture was stirred for 15 minutes. The resulting solution was filtered through a membrane filter (Omnipore membrane PTFE manufactured by Millipore Corporation, nominal 0.45 μm diameter) to obtain a conductive film remover. It was 7.2 when pH measurement of the obtained electrically conductive film removal agent was implemented by the method of said (1) description. When the corrosivity test was evaluated by the method described in (2) above, no occurrence of rust was confirmed on the surface of the metal aluminum, and the weight change was less than 3%.

  Next, an ITO transparent conductive film (manufactured by Toray Film Processing Co., Ltd., high beam, thickness 125 μm PET film, transmittance at 550 nm is 88%, surface resistance is 200Ω / □) is cut into a size of 21 × 15 cm, The conductive film remover is applied in a frame pattern described in (3) above by screen printing using sus # 200 mesh on the film, and the conductive film is patterned by the method described in (3). A substrate with a film was obtained. Washing was performed with pure water at 25 ° C. for 1 minute. It was pH1.0 when the pH measurement of the electrically conductive film removal agent after heat processing was implemented. When the appearance of the conductive film removal surface was evaluated, no residue was observed and the appearance was good. The conductive film removed portion was applied with a direct current of 25 V using an insulation resistance meter (EA709DA-1 manufactured by Sanwa Denki Keiki Co., Ltd.) and measured at intervals of 1 cm. As a result, the insulation resistance was 40 MΩ or more. It was 100 micrometers when the electrically conductive film removal line width was evaluated by the method of said (4) description. When the line linearity (waviness) at the etching boundary was evaluated by the method described in (5) above, the standard deviation (σ) was 10 or less.

Example 2
Except that the acid added to the conductive film remover was changed to 10 g of phosphoric acid and the addition amount of ethylenediamine was changed to 9.2 g, the same operation as in Example 1 was performed to obtain a base material with a conductive film in which the conductive film was patterned. It was. The pH of the obtained conductive film remover was measured in the same manner as in Example 1 and found to be 7.0. Moreover, when pH measurement of the electrically conductive film removal agent after heat processing was implemented, it was pH1.6. When the corrosivity test was evaluated in the same manner as in Example 1, the occurrence of rust was not confirmed on the surface of the metal aluminum, and the weight change was less than 3%. When the appearance of the conductive film removal surface was evaluated in the same manner as in Example 1, no residue was observed and the appearance was good. When the insulation resistance of the conductive film removed portion was measured in the same manner as in Example 1, it was 40 MΩ or more. When the conductive film removal line width was evaluated in the same manner as in Example 1, it was 100 μm. Further, when the line linearity (waviness) at the etching boundary portion was evaluated in the same manner as in Example 1, the standard deviation (σ) was 5 or less.

Example 3
The conductive film was patterned by performing the same operation as in Example 1 except that 6.5 g of pyridine was added to the conductive film remover, the heat treatment was changed to 100 ° C. for 5 minutes, and 5 g of sodium nitrate was further added. A substrate with a conductive film was obtained. The pH of the obtained conductive film remover was measured in the same manner as in Example 1 and found to be 7.0. Moreover, when pH measurement of the electrically conductive film removal agent after heat processing was implemented, it was pH1.0. When the corrosivity test was evaluated in the same manner as in Example 1, the occurrence of rust was not confirmed on the surface of the metal aluminum, and the weight change was less than 3%. When the appearance of the conductive film removal surface was evaluated in the same manner as in Example 1, no residue was observed and the appearance was good. When the insulation resistance of the conductive film removed portion was measured in the same manner as in Example 1, it was 40 MΩ or more. When the conductive film removal line width was evaluated in the same manner as in Example 1, it was 50 μm. Further, when the line linearity (swell) at the etching boundary portion was evaluated in the same manner as in Example 1, the standard deviation (σ) was 10 or less.

Example 4
A substrate with a conductive film in which the conductive film is partially patterned by performing the same operation as in Example 1, except that the resin and the leveling agent are not added to the conductive film remover, and the remover is applied by an inkjet method. Got. It was 7.2 when pH of the obtained electrically conductive film removal agent was measured similarly to Example 1. FIG. Moreover, when pH measurement of the electrically conductive film removal agent after heat processing was implemented, it was pH1.0. When the corrosivity test was evaluated in the same manner as in Example 1, the occurrence of rust was not confirmed on the surface of the metal aluminum, and the weight change was less than 3%. When the appearance of the conductive film removal surface was evaluated in the same manner as in Example 1, 10 or more residues having an outer periphery of 1.5 mm or more were observed. When the insulation resistance of the conductive film removed portion was measured in the same manner as in Example 1, it was 40 MΩ or more. The conductive film removal line width was evaluated in the same manner as in Example 1. However, part of the coating line was observed and line etching was not possible.

Example 5
The conductive layer of the substrate with a conductive film to be coated is a substrate with a conductive film in which a thin film of double-walled carbon nanotubes (DWCNT) is formed on a PET substrate (transmittance at 550 nm is 88%, surface resistance is 860 Ω / □ The acid added to the conductive film removing agent is changed to 10 g of p-toluenesulfonic acid monohydrate, the base to be added is 5 g of pyridine, the heat treatment time is changed to 3 minutes, and 5 g of sodium nitrate is added. Except having done, operation similar to Example 1 was performed and the base material with the electrically conductive film by which the electrically conductive film was patterned was obtained. It was 6.8 when pH of the obtained electrically conductive film removal agent was measured similarly to Example 1. FIG. Moreover, when pH measurement of the electrically conductive film removal agent after heat processing was implemented, it was pH1.1. When the corrosivity test was evaluated in the same manner as in Example 1, the occurrence of rust was not confirmed on the surface of the metal aluminum, and the weight change was less than 3%. When the appearance of the conductive film removal surface was evaluated in the same manner as in Example 1, no residue was observed and the appearance was good. When the insulation resistance of the conductive film removed portion was measured in the same manner as in Example 1, it was 40 MΩ or more. When the conductive film removal line width was evaluated in the same manner as in Example 1, it was 50 μm. Further, when the line linearity (waviness) at the etching boundary portion was evaluated in the same manner as in Example 1, the standard deviation (σ) was 5 or less.

Example 6
The same procedure as in Example 5 was performed, except that the acid added to the conductive film remover was 4 g of phenolsulfonic acid, the base was 1.4 g of propylamine, the heat treatment time was changed to 3 minutes, and 5 g of potassium nitrate was further added. The base material with the electrically conductive film by which the electrically conductive film was patterned was obtained. It was 7.4 when pH of the obtained electrically conductive film removal agent was measured similarly to Example 1. FIG. Moreover, when pH measurement of the electrically conductive film removal agent after heat processing was implemented, it was pH1.1. When the corrosivity test was evaluated in the same manner as in Example 1, the occurrence of rust was not confirmed on the surface of the metal aluminum, and the weight change was less than 3%. When the appearance of the conductive film removal surface was evaluated in the same manner as in Example 1, no residue was observed and the appearance was good. When the insulation resistance of the conductive film removed portion was measured in the same manner as in Example 1, it was 40 MΩ or more. When the conductive film removal line width was evaluated in the same manner as in Example 1, it was 50 μm. Further, when the line linearity (waviness) at the etching boundary portion was evaluated in the same manner as in Example 1, the standard deviation (σ) was 5 or less.

Example 7
A base material with a conductive film in which the conductive film is patterned is the same as in Example 5 except that 7.6 g of the base added to the conductive film remover is changed to 7.6 g of 4-methylpicoline and the resin is polyquaternium-10. Obtained. It was 6.8 when pH of the obtained electrically conductive film removal agent was measured similarly to Example 1. FIG. Moreover, when pH measurement of the electrically conductive film removal agent after heat processing was implemented, it was pH1.0. When the corrosivity test was evaluated in the same manner as in Example 1, the occurrence of rust was not confirmed on the surface of the metal aluminum, and the weight change was less than 3%. When the appearance of the conductive film removal surface was evaluated in the same manner as in Example 1, no residue was observed and the appearance was good. When the insulation resistance of the conductive film removed portion was measured in the same manner as in Example 1, it was 40 MΩ or more. When the conductive film removal line width was evaluated in the same manner as in Example 1, it was 100 μm. Further, when the line linearity (swell) at the etching boundary portion was evaluated in the same manner as in Example 1, the standard deviation (σ) was 10 or less.

Example 8
The base added to the conductive film removing agent is 5 g of 2-ethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.), the resin is 3 g of hydroxyethyl cellulose (manufactured by Daicel Chemical Industries, Ltd.), and the leveling agent is F-555 (DIC Corporation). ) Fluorine-based surfactant), except that the conductive layer of the substrate with a conductive film to be applied was changed to a graphene film formed by using the method described in The Journal of Physical Chemistry B, 2006, 110, p8535-8539. The same operation as in Example 1 was performed to obtain a base material with a conductive film in which the conductive film was patterned. It was 6.8 when pH of the obtained electrically conductive film removal agent was measured similarly to Example 1. FIG. Moreover, when pH measurement of the electrically conductive film removal agent after heat processing was implemented, it was pH1.0. When the corrosivity test was evaluated in the same manner as in Example 1, the occurrence of rust was not confirmed on the surface of the metal aluminum, and the weight change was less than 3%. When the appearance of the conductive film removal surface was evaluated in the same manner as in Example 1, no residue was observed and the appearance was good. When the insulation resistance of the conductive film removed portion was measured in the same manner as in Example 1, it was 40 MΩ or more. When the conductive film removal line width was evaluated in the same manner as in Example 1, it was 50 μm. Further, when the line linearity (waviness) at the etching boundary portion was evaluated in the same manner as in Example 1, the standard deviation (σ) was 5 or less.

Example 9
The same procedure as in Example 8 was performed except that the base added to the conductive film removing agent was changed to 6.5 g of pyridine, the resin was changed to polyquaternium-10, the heat treatment time was 3 minutes, and 5 g of sodium nitrate was further added. A substrate with a conductive film patterned was obtained. It was 6.7 when pH of the obtained electrically conductive film removal agent was measured similarly to Example 1. FIG. Moreover, when pH measurement of the electrically conductive film removal agent after heat processing was implemented, it was pH1.0. When the corrosivity test was evaluated in the same manner as in Example 1, the occurrence of rust was not confirmed on the surface of the metal aluminum, and the weight change was less than 3%. When the appearance of the conductive film removal surface was evaluated in the same manner as in Example 1, no residue was observed and the appearance was good. When the insulation resistance of the conductive film removed portion was measured in the same manner as in Example 1, it was 40 MΩ or more. When the conductive film removal line width was evaluated in the same manner as in Example 1, it was 100 μm. Further, when the line linearity (swell) at the etching boundary portion was evaluated in the same manner as in Example 1, the standard deviation (σ) was 10 or less.

Example 10
The silver nanowire synthesized by using the method described in Chemistry of Materials 2002 Volume 14 p4736-7455 to the conductive film of the substrate with a conductive film, 4 g of acid added to the conductive film remover, 4-base The same operation as in Example 1 was carried out except that 15 g of methylpicoline, 5 g of polyquaternium-10 and the leveling agent were changed to 0.5 g of F-555, and a conductive film-coated substrate having a patterned conductive film was obtained. . It was 7.5 when pH of the obtained electrically conductive film removal agent was measured similarly to Example 1. FIG. Moreover, when pH measurement of the electrically conductive film removal agent after heat processing was implemented, it was pH1.1. When the corrosivity test was evaluated in the same manner as in Example 1, the occurrence of rust was not confirmed on the surface of the metal aluminum, and the weight change was less than 3%. When the appearance of the conductive film removal surface was evaluated in the same manner as in Example 1, no residue was observed and the appearance was good. When the insulation resistance of the conductive film removed portion was measured in the same manner as in Example 1, it was 40 MΩ or more. When the conductive film removal line width was evaluated in the same manner as in Example 1, it was 200 μm. Further, when the line linearity (swell) at the etching boundary portion was evaluated in the same manner as in Example 1, the standard deviation (σ) was 10 or less.

Example 11
The same procedure as in Example 10 was performed except that 7.6 g of 4-methylpicoline added to the conductive film removing agent, heat treatment was changed to 100 ° C. for 3 minutes, and 5 g of sodium nitrate was further added. A patterned base material with a conductive film was obtained. It was 7.2 when pH of the obtained electrically conductive film removal agent was measured similarly to Example 1. FIG. Moreover, when pH measurement of the electrically conductive film removal agent after heat processing was implemented, it was pH1.0. When the corrosivity test was evaluated in the same manner as in Example 1, the occurrence of rust was not confirmed on the surface of the metal aluminum, and the weight change was less than 3%. When the appearance of the conductive film removal surface was evaluated in the same manner as in Example 1, no residue was observed and the appearance was good. When the insulation resistance of the conductive film removed portion was measured in the same manner as in Example 1, it was 40 MΩ or more. When the conductive film removal line width was evaluated in the same manner as in Example 1, it was 100 μm. Further, when the line linearity (swell) at the etching boundary portion was evaluated in the same manner as in Example 1, the standard deviation (σ) was 10 or less.

Example 12
The same operation as in Example 10 was performed except that the acid added to the conductive film removing agent was changed to 10 g of p-toluenesulfonic acid monohydrate, the base was changed to 4.9 g of 4-methylpicoline, and 5 g of sodium nitrate was further added. It performed and obtained the base material with the electrically conductive film by which the electrically conductive film was patterned. The pH of the obtained conductive film remover was measured in the same manner as in Example 1 and found to be 7.0. Moreover, when pH measurement of the electrically conductive film removal agent after heat processing was implemented, it was pH1.1. When the corrosivity test was evaluated in the same manner as in Example 1, the occurrence of rust was not confirmed on the surface of the metal aluminum, and the weight change was less than 3%. When the appearance of the conductive film removal surface was evaluated in the same manner as in Example 1, no residue was observed and the appearance was good. When the insulation resistance of the conductive film removed portion was measured in the same manner as in Example 1, it was 40 MΩ or more. When the conductive film removal line width was evaluated in the same manner as in Example 1, it was 50 μm. Further, when the line linearity (waviness) at the etching boundary portion was evaluated in the same manner as in Example 1, the standard deviation (σ) was 5 or less.

Example 13
10 g of acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) as an acid to be added to the conductive film removing agent on copper whiskers formed by using the method described in Japanese Patent Application Laid-Open No. 2002-266007 as a conductive layer of a substrate with a conductive film. The base material with the electrically conductive film in which the electrically conductive film was patterned was obtained by performing the same operation as in Example 10 except that the base was changed to 13 g of pyridine and the heat treatment temperature was changed to 100 ° C. The pH of the obtained conductive film remover was measured in the same manner as in Example 1 and found to be 7.0. Moreover, it was pH 2.9 when pH measurement of the electrically conductive film removal agent after heat processing was implemented. When the corrosivity test was evaluated in the same manner as in Example 1, the occurrence of rust was not confirmed on the surface of the metal aluminum, and the weight change was less than 3%. When the appearance of the conductive film removal surface was evaluated in the same manner as in Example 1, no residue was observed and the appearance was good. When the insulation resistance of the conductive film removed portion was measured in the same manner as in Example 1, it was 40 MΩ or more. When the conductive film removal line width was evaluated in the same manner as in Example 1, it was 100 μm. Further, when the line linearity (swell) at the etching boundary portion was evaluated in the same manner as in Example 1, the standard deviation (σ) was 10 or less.

Example 14
To the copper nanowires formed by using the method described in Japanese Patent Application Publication No. 2002-266007, a conductive layer of a substrate with a conductive film is further added with 5 g of sodium nitrate to the conductive film remover, and the heat treatment time is 3 minutes. Except having changed, operation similar to Example 13 was performed and the base material with the electrically conductive film by which the electrically conductive film was patterned was obtained. It was 7.4 when pH of the obtained electrically conductive film removal agent was measured similarly to Example 1. FIG. Moreover, when pH measurement of the electrically conductive film removal agent after heat processing was implemented, it was pH1.8. When the corrosivity test was evaluated in the same manner as in Example 1, the occurrence of rust was not confirmed on the surface of the metal aluminum, and the weight change was less than 3%. When the appearance of the conductive film removal surface was evaluated in the same manner as in Example 1, no residue was observed and the appearance was good. When the insulation resistance of the conductive film removed portion was measured in the same manner as in Example 1, it was 40 MΩ or more. When the conductive film removal line width was evaluated in the same manner as in Example 1, it was 50 μm. Further, when the line linearity (waviness) at the etching boundary portion was evaluated in the same manner as in Example 1, the standard deviation (σ) was 5 or less.

Comparative Example 1
Except not adding a base to an electrically conductive film removal agent, operation similar to Example 4 was performed and the base material with an electrically conductive film by which the electrically conductive film was partially patterned was obtained. It was 1.0 when pH of the electrically conductive film removal agent was measured similarly to Example 1. FIG. Moreover, when pH measurement of the electrically conductive film removal agent after heat processing was implemented, it was pH1.0. When the corrosivity test was evaluated in the same manner as in Example 1, the occurrence of rust was confirmed on the surface of the metal aluminum, and the weight was also reduced by 20%. When the appearance of the conductive film removal surface was evaluated in the same manner as in Example 1, 10 or more residues having an outer periphery of 1.5 mm or more were observed. When the insulation resistance of the conductive film removed portion was measured in the same manner as in Example 1, it was 40 MΩ or more.

Comparative Example 2
The same operation as in Example 4 was performed except that acid and sodium nitrate were not added to the conductive film removing agent, the base was changed to 5 g of sodium hydroxide, and the heat treatment time was changed to 10 minutes. However, the base material with a conductive film in which the conductive film was patterned could not be obtained. It was 14.0 when pH of the electrically conductive film removal agent was measured similarly to Example 1. FIG. Moreover, it was pH 14.0 when pH measurement of the electrically conductive film removal agent after heat processing was implemented. When the corrosivity test was evaluated in the same manner as in Example 1, the surface of the metal aluminum was corroded and the weight was reduced by 10%. When the appearance of the conductive film removal surface was evaluated in the same manner as in Example 1, 10 or more residues having an outer periphery of 1.5 mm or more were observed. When the insulation resistance of the conductive film removed portion was measured in the same manner as in Example 1, it was only 1000Ω.

Comparative Example 3
The same operation as in Example 9 was performed except that 5 g of sodium nitrate was added without adding acid and base to the conductive film remover. However, the base material with the electrically conductive film by which the electrically conductive film was patterned was not obtained. It was 6.9 when pH of the electrically conductive film removal agent was measured similarly to Example 1. FIG. Moreover, it was 6.9 when pH measurement of the electrically conductive film removal agent after heat processing was implemented. When the corrosivity test was evaluated in the same manner as in Example 1, the surface of the metal aluminum was not changed, and no change in weight was confirmed. When the appearance of the conductive film removal surface was evaluated in the same manner as in Example 1, 10 or more residues having an outer periphery of 1.5 mm or more were observed. When the insulation resistance of the conductive film removed portion was measured in the same manner as in Example 1, it was only 500Ω.

  Hereinafter, Tables 1 and 2 show the creation conditions and evaluation results of Examples and Comparative Examples.

DESCRIPTION OF SYMBOLS 101 Base material 102 Conductive film 103 Conductive film removal agent 104 The part from which the conductive film was removed

Claims (7)

A step of applying a conductive film remover having a pH of 6.0 to 8.0 at 20 ° C. to at least a part of the substrate with a conductive film, a step of heat-treating the substrate with a conductive film coated with the conductive film remover, And a method of removing the conductive film by cleaning with a liquid from the heat-treated conductive film-attached base material, wherein at least a component of the conductive film removing agent applied in the heat treatment step The conductive film removing method is characterized in that the volatilization of the conductive film remover causes the pH of the conductive film removing agent to be less than 6.0 or greater than 8.0. The conductive film removal method according to claim 1, wherein the pH of the conductive film removing agent is less than 6.0 in the heat treatment step. The electrically conductive film removal method of Claim 1 or 2 whose heat processing temperature is 80 degreeC or more. The electrically conductive film removal method in any one of Claims 1-3 using the electrically conductive film removal agent containing cationic resin. A conductive film removing agent comprising an acid, a base, a solvent, and a resin having different vapor pressures as a simple substance, having a pH of 6.0 to 8.0 at 20 ° C, and the resin being a cationic resin. The conductive film removing agent according to claim 5, wherein the base is a nitrogen-containing compound. 7. The conductive film removing agent according to claim 6, wherein the nitrogen-containing compound is an amine compound having a vapor pressure higher than that of acid.

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