WO2013176155A1 - Procédé de production d'une base conductrice à motifs, base conductrice à motifs produite par ledit procédé et écran tactile - Google Patents

Procédé de production d'une base conductrice à motifs, base conductrice à motifs produite par ledit procédé et écran tactile Download PDF

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WO2013176155A1
WO2013176155A1 PCT/JP2013/064148 JP2013064148W WO2013176155A1 WO 2013176155 A1 WO2013176155 A1 WO 2013176155A1 JP 2013064148 W JP2013064148 W JP 2013064148W WO 2013176155 A1 WO2013176155 A1 WO 2013176155A1
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conductive
layer
pattern
inorganic oxide
conductive layer
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PCT/JP2013/064148
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English (en)
Japanese (ja)
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真多淳二
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東レ株式会社
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Priority to CN201380026425.3A priority Critical patent/CN104321836A/zh
Priority to JP2013532768A priority patent/JPWO2013176155A1/ja
Priority to KR1020147029862A priority patent/KR20150016934A/ko
Publication of WO2013176155A1 publication Critical patent/WO2013176155A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/02—Local etching
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/30—Acidic compositions for etching other metallic material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/067—Etchants
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0108—Transparent
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/017—Glass ceramic coating, e.g. formed on inorganic substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0242—Shape of an individual particle
    • H05K2201/026—Nanotubes or nanowires
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/032—Materials
    • H05K2201/0323—Carbon
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/032—Materials
    • H05K2201/0326—Inorganic, non-metallic conductor, e.g. indium-tin oxide [ITO]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/032—Materials
    • H05K2201/0329—Intrinsically conductive polymer [ICP]; Semiconductive polymer

Definitions

  • the present invention at least a base material, an inorganic oxide layer and a conductive layer are formed in this order, and a resist is formed by bringing a conductive base material having a resist layer as a part of the outermost layer into contact with an aqueous solution containing fluoride ions.
  • the present invention relates to a method for producing a patterned conductive substrate in which the conductive layer is removed together with the inorganic oxide layer in a portion that is not present, a conductive substrate patterned by this production method, and a touch panel using the patterned conductive substrate It is.
  • Transparent conductive films are widely used in electronic display devices such as flat panel displays and touch panels.
  • the transparent conductive material is typified by tin-doped indium oxide (hereinafter referred to as ITO), and the demand and usage of ITO continue to increase.
  • ITO tin-doped indium oxide
  • indium is a rare metal, it replaces indium, or it is a novel that compensates for the disadvantages inherent in ITO transparent conductive films, such as weakness to bending and difficult to reduce costs due to vacuum film formation.
  • conductive materials carbon nanotubes (hereinafter referred to as CNT), conductive polymers, metal nanoparticles, metal nanowires, and the like have been actively developed. These new materials are of a type that can be applied under atmospheric pressure, and a method of applying a dispersion in which ITO is also made into fine particles has been developed. Therefore, there are high expectations for the development of new conductive materials.
  • a novel conductive material for example, it has been proposed to apply CNT or silver nanowire as a transparent conductive laminate to a touch panel (for example, see Patent Document 1). Moreover, applying a conductive polymer to electronic paper as a transparent conductive layer is proposed (for example, refer patent document 2). It has also been proposed to use ITO powder together with a binder resin (see, for example, Patent Document 3).
  • conductive films are used by forming a pattern like a line electrode.
  • the patterning method of the conductive film is important.
  • the conductive film is required to have a uniform surface resistance.
  • the light transmittance is also required to be uniform. For this reason, it is indispensable that the patterned conductive base material is formed by uniformly forming a conductive material on the entire surface of the base material and then removing unnecessary portions to form a pattern.
  • Patent Document 4 A method of patterning a CNT film applicable as a conductive film by dry etching has been proposed (for example, see Patent Document 4).
  • An etchant that improves the etching properties of an existing ITO conductive film has been proposed (see, for example, Patent Document 5).
  • etchants In addition to ITO and metal thin films, materials used for conductive films are diversifying, such as CNT, silver nanowires, and conductive polymers. In order to pattern them using a wet process, search for etchants each time. There was a need to develop or develop. Also, existing etchants for ITO and metal thin films are often strong acids, mixed acids, oxidizing or corrosive chemicals, and strong alkalis, and careful handling and handling equipment design was required. .
  • Patent Documents 1 to 3 It is possible to pattern the conductive film described in Patent Documents 1 to 3 using the dry etching process described in Patent Document 4 depending on the layer structure.
  • the general ITO wet etching process described in Patent Document 5 cannot be applied, and the difference in the etching process becomes a barrier to cost competitiveness when developing a new conductive film.
  • iron chloride used in the etchant of Patent Document 5 is a general chemical, but it is highly corrosive and can be used as an anti-corrosion measure for etching equipment, ancillary equipment such as rooms where the equipment is installed, and exhaust ducts. This included factors that would increase the cost of the equipment, such as being necessary. Even in Patent Document 6, hydrofluoric acid, which is dangerous to handle, was used.
  • an object of the present invention is to provide a novel method for patterning a conductive film, which is excellent in handleability and applicable to existing equipment.
  • a method for producing a patterned conductive substrate of the present invention has the following configuration. That is, A step of forming a resist layer on a part of the outermost layer of the conductive substrate in which at least the substrate, the inorganic oxide layer and the conductive layer are formed in this order; and contacting the conductive substrate with an aqueous solution containing fluoride ions, It is a manufacturing method of the patterned conductive base material including the process of patterning the said conductive layer by removing the said conductive layer with the said inorganic oxide layer in the part in which the resist is not formed.
  • the patterned conductive substrate of the present invention has the following configuration.
  • the conductive layer contains carbon nanotubes, and the conductive layer removed portion is a conductive base material patterned by the above manufacturing method in which the base material surface is exposed.
  • the touch panel of the present invention has the following configuration. That is, A touch panel using the patterned conductive substrate.
  • the aqueous solution containing fluoride ions is preferably an aqueous solution of at least one of alkali metal fluorides and fluoride ammonium salts.
  • the pH of the aqueous solution containing fluoride ions is preferably 1-7.
  • the inorganic oxide layer is preferably a layer containing silica and / or alumina.
  • the conductive layer preferably contains carbon nanotubes.
  • the patterning method of the present invention is excellent in handleability and corrosion resistance, and can pattern a conductive film with high resolution using existing equipment.
  • a base material, an inorganic oxide layer and a conductive layer are formed in this order, and a resist is formed by bringing a conductive base material having a resist layer as a part of the outermost layer into contact with an aqueous solution containing fluoride ions.
  • This is a method for producing a patterned conductive substrate in which the conductive layer is removed together with the inorganic oxide layer in a portion that is not.
  • various required characteristics such as the performance as a conductive substrate, lamination processability, patternability, conductive characteristics after patterning, stability of optical characteristics and physical durability characteristics, etc. are balanced. Can be achieved.
  • patterning process stability can be obtained by specifically etching and patterning when the conductive substrate is in contact with an aqueous solution containing fluoride ions.
  • the substrate in the present invention includes polyethylene terephthalate (hereinafter referred to as PET), polyethylene naphthalate (hereinafter referred to as PEN), polycarbonate (hereinafter referred to as PC), polymethyl methacrylate (hereinafter referred to as PMMA), polyimide, polyphenylene sulfide (hereinafter referred to as PPS), Aramid, polypropylene (hereinafter referred to as PP), polyethylene (hereinafter referred to as PE), polylactic acid (hereinafter referred to as PLA), polyvinyl chloride (hereinafter referred to as PVC), alicyclic acrylic resin, cycloolefin, triacetylcellulose, and other polymers
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • PMMA polymethyl methacrylate
  • PPS polymethyl methacrylate
  • PPS polyimide
  • PPS polyphenylene sulfide
  • PE poly
  • These substrates may be a film having a thickness of 200 ⁇ m or less, or a thick film substrate having a thickness greater than that.
  • a metal substrate, metal foil, a glass substrate, a flexible thin film sheet-like glass base material etc. can be used as a base material.
  • glow discharge treatment, corona discharge treatment, plasma treatment, UV ozone treatment, flame treatment, acid cleaning treatment Further, surface treatment such as alkali cleaning treatment, and in addition to these, self-assembled monomolecular (SAM) layer treatment may be performed, and a resin layer may be provided separately.
  • SAM self-assembled monomolecular
  • the inorganic oxide constituting the inorganic oxide layer in the present invention silica, alumina, titania, zirconia and the like are used, and polysiloxane is also used.
  • a glass material mainly composed of silicon dioxide is also used, and boron oxide, phosphorus oxide, sodium oxide, magnesium oxide, calcium oxide and the like may be included as subcomponents.
  • CVD chemical vapor deposition
  • a coating solution containing an inorganic oxide or a precursor thereof and a solvent is applied to the substrate.
  • a wet process is preferably used in which an inorganic oxide layer is formed by coating on top and drying and heating.
  • a sol-gel method as a method of forming by a wet process.
  • An inorganic oxide layer can be obtained by applying a sol dispersion obtained by hydrolyzing a metal alkoxide or the like, followed by dehydration condensation after forming a coating film.
  • a metal alkoxide or a metal chelate compound may be mixed in the sol dispersion described above or used alone.
  • Tetraalkoxy such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxysilane are used as raw materials for forming the silica-based inorganic oxide layer.
  • Silanes methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane N-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane , Vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysi
  • These raw materials are used by being dissolved or dispersed in alcohol, water, or an organic solvent, and are used by appropriately mixing an acid catalyst or a base catalyst. Furthermore, the above-mentioned silane-based material is polymerized in advance in a molecular weight range that is soluble in a solvent, and the resulting polysiloxane is mixed with a solvent and an acid, applied and dried, and then subjected to a hydrolysis and polymerization reaction by heating. May be formed.
  • the inorganic oxide layer preferably contains silica fine particles, alumina fine particles, titania fine particles, zirconia fine particles, polymer fine particles and the like.
  • the particle diameter of these fine particles is preferably in the range of several nm to several ⁇ m.
  • the composition that is the main component of the inorganic oxide layer, the presence or absence of fine particles, and the type and content of fine particles when they are included are determined by the optical properties, conductive properties, physical properties, and process during layer coating. It can be selected in consideration of sex. For example, when the conductive layer is formed on the conductive layer, when the solvent of the coating solution is aqueous, the inorganic oxide layer contains hydrophilic fine particles to improve the wettability of the conductive coating solution. Further, it is possible to make the film thickness uniform, and in turn, make the conductivity uniform. Thus, the fine particles are useful for controlling the properties of the inorganic oxide layer.
  • the inorganic oxide layer contains fine particles, irregularities are formed on the surface of the inorganic oxide layer, and an insulating component such as a dispersant contained in the conductive layer coating liquid is selectively adsorbed. It is also possible. By carrying out like this, since an electroconductive component can be collected on a surface layer and the contact resistance of electroconductive parts can be reduced, an electroconductive characteristic can be improved. At this time, the conductive layer film obtained has a smaller amount of dispersant component than the composition in the coating solution, so that the re-solubility of the conductive layer in the dispersion medium can be reduced and laminated on the conductive layer by wet coating. In doing so, it is possible to prevent the elution of the components of the conductive layer.
  • Physical durability can also be controlled by changing the type of inorganic oxide, the type or content of particles. If the content of fine particles is increased, the sol-gel hydrolysis conditions are moderated, or the polysiloxane curing conditions are moderated to reduce the crosslink density of the inorganic oxide layer, a flexible material should be used for the substrate. When used, the bending durability can be improved. On the other hand, the hardness of the surface can be improved by reducing the amount of fine particles added and increasing the curing conditions.
  • the thickness of the inorganic oxide layer is preferably 1 nm to 10 ⁇ m, more preferably 10 nm to 500 nm. By being in this range, optical characteristics, physical strength characteristics, patterning properties, and the like can be improved in a balanced manner.
  • the inorganic oxide layer is formed by a coating process
  • any of dip coater, bar coater, gravure coater, die coater, spin coater, screen printing, ink jet coating and the like can be preferably used.
  • the inorganic oxide layer can be formed by a dry process such as a sputtering method or a CVD method.
  • a material having a volume resistivity of 10 ⁇ 6 to 10 8 ⁇ cm can be used for the conductive layer used in the present invention.
  • metals are classified as 10 ⁇ 6 to 10 ⁇ 3 ⁇ cm
  • semiconductors are classified as 10 ⁇ 3 to 10 8 ⁇ cm, and any of them can be used.
  • conductive fine particles or conductive fibrous materials are used for the conductive layer, they are mixed with a dispersant for dispersing them or used with a binder resin for forming a coating film. Sometimes. In that case, the mixture is referred to as a conductive layer.
  • the conductive layer used in the present invention include CNT, graphene, fullerene, fullerene whisker, carbon fine particle, metal fine particle, metal nanowire, conductive polymer, metal thin film, metal oxide thin film, metal oxide fine particle, metal There are oxide nanowires.
  • those capable of forming a conductive layer by coating are more preferable, and conductive formed using a CNT dispersion, graphene dispersion, metal colloid dispersion, metal nanowire dispersion, conductive polymer, metal oxide fine particle dispersion, or the like.
  • a layer is preferred.
  • CNT is preferred when used for transparent conductive applications.
  • CNTs are particularly preferable in that they have low surface reflection, excellent flexibility, high stability against environmental changes, and high reliability even when a micropattern is formed by forming a fine network of microfibers.
  • CNT includes single-wall CNT, two-wall CNT, three- to five-layer thin-wall CNT, multi-wall CNT, etc., but it is preferable to use this because double-wall CNT can achieve both higher transmittance and higher conductivity. .
  • the conductive layer of the present invention is preferably a thin film.
  • the thin film refers to a film having a thickness of 10 ⁇ m or less, and usually has a thickness of 100 nm or less.
  • the thickness can be determined according to the required sheet resistance, light transmittance, and the like.
  • the thickness is preferably 5 to 50 nm.
  • a protective layer can be provided on the outermost layer of the conductive substrate in the present invention.
  • the material used for the protective layer may be an inorganic oxide used for the base layer of the conductive layer, or a normal polymer, and needs the friction resistance, flex resistance, light resistance, hardness, etc. required for the substrate. It can be appropriately selected according to the characteristics.
  • the thickness of the protective layer is preferably about 10 nm to 5 ⁇ m, but is not limited thereto. When the contact resistance on the surface of the conductive layer is reduced as in the resistive touch panel, the protective layer thickness is preferably 10 to 100 nm, and thicker when used for a capacitive touch panel or electromagnetic shield. be able to.
  • FIG. 1 shows an example of a conductive substrate in the present invention.
  • An inorganic oxide layer 102, a conductive layer 103, and a protective layer 104 are provided over the substrate 101.
  • the conductive base material in which the base material, the inorganic oxide layer, and the conductive layer are formed in this order can be removed together with the inorganic oxide layer by contacting the strong acid aqueous solution or the strong alkaline aqueous solution.
  • the conductive base material in which the base material, the inorganic oxide layer, and the conductive layer are formed in this order can be removed together with the inorganic oxide layer by contacting the strong acid aqueous solution or the strong alkaline aqueous solution.
  • the inorganic oxide is easily attacked by the strong alkaline aqueous solution and the entire inorganic oxide layer is easily peeled off from the substrate, it is difficult to selectively remove it according to the resist pattern. Further, when immersed in an aqueous solution of strong acid, the conductive layer can be removed according to an approximate resist pattern, but poor removal and excessive removal are mixed, resulting in poor pattern precision.
  • the inorganic oxide layer is peeled off from the substrate by permeation of a strong acid, but the inorganic oxide layer itself is not decomposed and is therefore selectively removed by tearing along the resist pattern shape. Therefore, it becomes difficult to precisely control the pattern shape.
  • the inventors have found that the conductive layer can be removed according to the resist pattern provided on the outermost layer by bringing the conductive substrate as described above into contact with an aqueous solution containing fluoride ions. I found it.
  • the method for producing a patterned conductive substrate according to the present invention utilizes this wet etching method.
  • the method for producing a patterned conductive substrate of the present invention includes a step of forming a resist layer on a part of the outermost layer of the conductive substrate in which at least the substrate, the inorganic oxide layer, and the conductive layer are formed in this order; It is a method of patterning the conductive layer by bringing the conductive base material into contact with an aqueous solution containing fluoride ions and removing the conductive thin film layer where the resist is not formed together with the inorganic oxide layer.
  • the aqueous solution containing fluoride ions penetrates from the outermost layer into the inorganic oxide layer that is the base of the conductive layer, and the inorganic oxide layer is peeled off from the base material, so that the conductive layer is separated from the inorganic oxide layer. By being removed, patterning is performed. It is known that an aqueous solution containing fluoride ions is used for surface etching of a silicon substrate or quartz glass. The present inventors have found that an aqueous solution containing fluoride ions permeates the conductive layer and penetrates to the inorganic oxide layer which is the base layer, and have reached the present invention. Furthermore, the method of the present invention also has an effect that a desired pattern can be obtained without side etching due to penetration into the lower portion of the remaining resist portion.
  • FIG. 2 is a process diagram showing an example of a conductive layer pattern forming method in the present invention.
  • the conductive substrate an inorganic oxide layer 102, a conductive layer 103, and a protective layer 104 are provided on a substrate 101, and a resist 105 is provided on the outermost layer.
  • the conductive substrate is brought into contact with an aqueous solution containing fluoride ions. Accordingly, the protective layer 104, the conductive layer 103, and the inorganic oxide layer 102 are all peeled from the base material 101. Finally, if the resist 105 is removed, a patterned conductive substrate is obtained.
  • Alkali metal fluorides such as lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), AlF 3 , BiF 3 , CaF 2 , CrF 2 , MgF 2 , PtF 2 , RhF 2 , ThF 4 , fluorides of metals other than alkali metals such as UF 4 , sodium hydrogen fluoride (NaHF 2 ), potassium hydrogen fluoride (KHF 2 ), ammonium fluoride (NH 4 F), ammonium hydrogen fluoride (NH 4 HF 2 ), N, N, N-trimethylmethane fluoride ((CH 3 ) 4 NF), benzyltrimethylammonium fluoride (C 6 H 5 CH 2 (CH 3 ) 3 NF), tetraethylammonium fluoride (M
  • Buffered hydrofluoric acid can also be used.
  • hardly soluble fluorides such as AlF 3 , BiF 3 , CaF 2 , CrF 2 , MgF 2 , PtF 2 , RhF 2 , ThF 4 , UF 4, etc. can be dissolved and used at high temperatures together with strong acids. .
  • These hydrates or a mixture of two or more of these may be used.
  • an ammonium salt of fluoride or an alkali metal fluoride is preferable.
  • ammonium fluoride, sodium fluoride, or potassium fluoride is preferably used. Two or more of these may be mixed, but it is more preferable to use one alone.
  • the production method of the present invention can be carried out using hydrofluoric acid, it is used only in a strictly controlled environment only when the concentration of hydrogen fluoride in water is 1% by mass or less. be able to.
  • Using an aqueous solution with a hydrogen fluoride concentration of several percent by mass or more increases the possibility of workers being exposed to hydrogen fluoride gas and reacts with calcium in the body to cause hypocalcemia. Rise. For this reason, when hydrofluoric acid is used, it is necessary to carry out it within a dedicated draft or chamber, and careful handling is required for handling.
  • acids and bases can be used.
  • acids include sulfuric acid, hydrochloric acid, nitric acid, oxalic acid, acetic acid, phosphoric acid, benzenesulfonic acid, and toluenesulfonic acid.
  • bases include sodium hydroxide and potassium hydroxide. Sodium carbonate, sodium hydrogen carbonate, tetramethylammonium hydroxide, 2-aminoethanol and the like are used. Of course, the acid and base used are not limited to these.
  • the pH of the aqueous solution containing fluoride ions is preferably in the range of 1 to 7, more preferably in the range of pH 1 to 6.
  • the conductive layer can be stably removed in a desired pattern with good reproducibility, and further, the concentration of fluoride ions required for removing the conductive layer can be reduced.
  • the processing time can be shortened.
  • the aqueous solution containing fluoride ions may further contain an organic solvent having affinity for water or a surfactant.
  • An organic solvent and a surfactant can be appropriately selected according to each purpose such as control of wettability to a conductive substrate, control of permeability to a conductive film, and suppression of bubbles in an etching tank.
  • the concentration of fluoride ions in the aqueous solution containing fluoride ions is determined according to the type of conductive layer of the conductive substrate, the thickness of each layer, and the tact time of the patterning equipment, and is 1 ⁇ 10 ⁇ 5 to 10 mol / L. A range is preferable. In view of solubility of fluoride ions in water and patterning properties of the conductive layer, 0.0001 to 0.1 mol / L is more preferable.
  • the concentration of acid or alkali contained in the aqueous solution containing fluoride ions is preferably 1/1000 to 1,000 times, more preferably 1/10 to 10 times the molar concentration of fluoride ions. is there. In terms of molar concentration, it is preferably 0.0001 to 0.1 mol / L. More preferably, patterning can be performed more stably using an acid than an alkali.
  • the temperature of the aqueous solution is preferably 25 to 80 ° C. Although it can be used outside this range, it is more preferably 30 to 60 ° C. in order to control with a heater higher than room temperature and to suppress the volatilization of moisture.
  • a method of immersing the conductive substrate in the aqueous solution a method of showering the aqueous solution on the conductive substrate, a method of passing the conductive substrate through the water flow by the aqueous solution, etc. Either method can be used.
  • After contacting the conductive substrate with the aqueous solution it is preferable to drain the water once and then wash with water.
  • any method such as dipping, showering or passing through a water stream can be used.
  • a screen printing resist or a photoresist can be used as a resist provided on a part of the outermost layer of the conductive base material.
  • a photoresist a dry film resist that is used by transferring a photoresist already formed into a sheet shape onto a substrate, or a coating type photoresist that is used by applying a resist solution with a spin coater or the like can be used. .
  • These resists can be used properly according to the required definition. It is preferable to use a screen printing resist if the accuracy is 100 ⁇ m or more, a dry film resist if the accuracy is 20 ⁇ m or more, and a coating type photoresist if the accuracy is 20 ⁇ m or less.
  • a development process using an alkaline aqueous solution is performed after exposure.
  • fluoride ions are dissolved in the alkaline aqueous solution, and the conductive layer is removed along with the development and removal of the photoresist. It is also possible to do.
  • the development of the photoresist is performed with a normal alkaline aqueous solution, and the conductive layer is removed with an aqueous solution containing fluoride ions.
  • the conductive layer removed portion of the conductive base material patterned by the above-described method is preferably exposed at the base material surface.
  • “the substrate surface is exposed” means that the inorganic oxide layer is almost completely removed and the substrate surface is not damaged.
  • the substrate surface can be easily and cleanly exposed.
  • the conditions are excessive, the surface of the base material is swollen, and conversely, if the conditions are weak, the conductive layer or the oxide layer remains and the base material surface is exposed cleanly. It is difficult to let In addition, problems such as an increase in haze value due to surface roughness also occur.
  • Patterning procedure A A coating type photoresist is spin-coated on the outermost layer of the conductive substrate and dried.
  • A-2 Ultraviolet rays are irradiated to a portion where the conductive layer is to be removed through a photomask to solubilize the photoresist with alkali.
  • A-3) A resist pattern is formed by alkali development and water washing.
  • A-4) After washing with water, drying and heat treatment are performed in an oven or hot plate at about 50 to 120 ° C.
  • (B-2) The portion where the conductive layer is to be obtained is irradiated with ultraviolet rays through a photomask, and the photoresist is photocured.
  • B-3) A resist pattern is formed by alkali development and water washing.
  • (B-4) Immerse in an aqueous solution containing fluoride ions.
  • (B-5) Unnecessary portions of the conductive layer are removed by shower water washing.
  • B-6) The photoresist on the conductive layer is removed by dipping in an organic solvent or a strong alkaline aqueous solution.
  • (B-7) Wash with water, blow with air, and dry at 50 to 120 ° C.
  • drying / heating treatment (A-4) is performed as necessary.
  • the adhesion between the conductive layer and the inorganic oxide layer is reduced due to the permeation of the alkaline developer, the adhesion can be improved by performing this treatment, and the subsequent steps can be performed stably. .
  • the pattern shape of the conductive layer in the present invention is determined by the application. For example, a pattern that removes only the periphery of a rectangular conductive substrate, a pattern that forms a line electrode, a pattern that leaves a pseudo electrode between line electrodes, a pattern that provides a triangular or rhombus pad on the line electrode, etc.
  • the present invention is not limited to these, and various patterns can be formed.
  • the conductive substrate in the present invention can be used for transparent electrodes or line electrodes of touch panels, electronic paper, photovoltaic elements, organic EL elements, liquid crystal display elements, and the like.
  • a capacitive touch panel two conductive substrates are used.
  • An X electrode base material and a Y electrode base material are formed, both are bonded, and used by being laminated on the upper layer of a screen such as a liquid crystal display.
  • at least two conductive substrates are used for passive electronic paper.
  • the conductive film pattern forming method using the present invention will be specifically described based on examples.
  • the present invention is not limited to the following examples.
  • (1) Method of measuring pH of etchant The pH of the etchant was measured at 20 ° C. using a pH tester (Checker / HI90103, manufactured by Hanna Instruments Inc.).
  • (2) Method for evaluating pattern shape after patterning Evaluation of the substrate on which pattern formation was performed was performed using a microscope observation (manufactured by Keyence Co., Ltd., surface shape measurement microscope VF7500) with a magnification of 250 to 1,250 times. And the line width of the pattern was measured.
  • Alumina particles having a diameter of about 40 nm are added and dispersed in the solution described in the preparation example of the inorganic oxide layer 1, and an appropriate amount of this liquid is dropped on the base material, and applied using a wire bar # 8. It left still for 1 minute in a 80 degreeC drying machine, and formed the inorganic oxide layer 3 which contains an alumina particle which has silica as a main component.
  • the conductive layer of CNT was produced by the following operation.
  • a catalyst for CNT synthesis was prepared.
  • About 24.6 g of iron (III) ammonium citrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 6.2 kg of ion-exchanged water, and magnesium oxide (manufactured by Iwatani Chemical Industry Co., Ltd., MJ-) was dissolved in this solution.
  • About 1,000 g of 30) was added, vigorously stirred for 60 minutes with a stirrer, and the resulting suspension was introduced into a 10 L autoclave vessel.
  • 0.5 kg of ion exchange water was used as a washing solution, and both were added to the autoclave container.
  • the autoclave was sealed and heated to 160 ° C. and held for 6 hours.
  • the autoclave container was allowed to cool, the slurry-like cloudy substance was taken out from the container, excess water was filtered off by suction filtration, and a small amount of water contained in the filtered product was dried in a 120 ° C. drier.
  • the obtained solid content was refined in a mortar, and a sieve having a particle size in the range of 20 to 32 mesh was collected using a sieve to obtain a catalyst for CNT synthesis.
  • iron contained in this catalyst was 0.39 mass% from the EDX analysis result.
  • CNT was synthesized by chemical vapor deposition.
  • the catalyst 132g was introduced onto a quartz sintered plate at the center of a cylindrical reactor installed in the vertical direction. While heating the catalyst layer until the temperature in the reaction tube reaches about 860 ° C., nitrogen gas is supplied from the bottom of the reactor toward the top of the reactor using a mass flow controller at 16.5 L / min. Circulated to pass through. Thereafter, while supplying nitrogen gas, methane gas was further introduced at 0.78 L / min for 60 minutes using a mass flow controller, and the gas was passed through the catalyst body layer for reaction.
  • the contact time (W / F) obtained by dividing the mass of the solid catalyst body by the flow rate of methane at this time was 169 min ⁇ g / L, and the linear velocity of the gas containing methane was 6.55 cm / sec. While the introduction of methane gas was stopped and nitrogen gas was passed through 16.5 L / min, the quartz reaction tube was cooled to room temperature, and the catalyst-attached carbon nanotube composition on the quartz sintered plate was recovered.
  • the catalyst was removed.
  • 115 g of the catalyst-attached carbon nanotube composition was put in 2,000 mL of a 4.8N hydrochloric acid aqueous solution, and stirred for 1 hour to dissolve iron as a catalyst metal and MgO as its support.
  • the obtained black suspension was filtered, and the filtered product was again put into 400 mL of a 4.8N hydrochloric acid aqueous solution, stirred and filtered, and subjected to de-MgO treatment. This operation was repeated three times to obtain a carbon nanotube composition from which the catalyst was removed.
  • This carbon nanotube composition was put into concentrated nitric acid (manufactured by Wako Pure Chemical Industries, Ltd., grade 1, Assay 60-61 mass%) having a mass of about 300 times. Thereafter, the mixture was heated to reflux with stirring in an oil bath at about 140 ° C. for 25 hours. After heating to reflux, the nitric acid solution containing the carbon nanotube-containing composition was diluted with ion-exchanged water three times and suction filtered. After washing with ion-exchanged water until the suspension of the filtered material became neutral, the carbon nanotube composition in a wet state containing water was stored. When the carbon nanotube composition was observed with a high-resolution transmission electron microscope, the ratio of the double-walled carbon nanotubes was 90%.
  • Carbon nanotube-containing composition in the above wet state 25 mg in terms of dry mass
  • 5 g of sodium carboxymethylcellulose aqueous solution (Daicel Finechem Co., Ltd., Daicel 1140, weight average molecular weight 450,000, concentration 1% by mass, solid content 50 mg )
  • 6.7 g of zirconia beads (manufactured by Toray Industries, Inc., Treceram, bead size: 0.8 mm) was added to the container, and the pH was adjusted to 10 using a 28% by mass aqueous ammonia solution (manufactured by Kishida Chemical Co., Ltd.).
  • This container was shaken for 2 hours using a vibration mill to obtain a carbon nanotube paste.
  • Ion exchange water was added to the carbon nanotube paste to dilute the carbon nanotube concentration to 0.15% by mass, and the aqueous solution was adjusted to pH 10 by adding 28% by mass aqueous ammonia again to 10 g of the diluted solution.
  • the aqueous solution was ice-cooled and kept at 10 ° C. or lower, and dispersion treatment was performed for 1.5 minutes at an output of 20 W using an ultrasonic homogenizer.
  • the obtained liquid was centrifuged at 10,000 G for 15 minutes with a high-speed centrifuge to obtain 9 g of a carbon nanotube dispersion.
  • a carbon nanotube layer was formed. Ion exchange water is added to the carbon nanotube dispersion to adjust to 0.04% by mass, dropped onto the substrate with the inorganic oxide layer, and coated using a wire bar # 8 at 80 ° C. The carbon nanotube conductive layer 1 was formed by allowing it to stand for 1 minute.
  • Example of preparation of sol-gel silica protective layer 40 g of n-butyl silicate and 20 g of ethanol were placed in a 100 mL plastic container and stirred for 30 minutes, 10 g of 0.1N hydrochloric acid aqueous solution was added, stirred for 2 hours, and allowed to stand at 4 ° C. for 12 hours.
  • a protective layer solution was prepared by diluting with a mixed solution of isopropyl alcohol and methyl ethyl ketone so that the solid concentration was 0.1% by mass. This liquid was applied onto the conductive layer using a wire bar # 8 and dried in a 125 ° C. dryer for 1 minute to form a protective layer.
  • L / S resolution evaluation pattern shape A pattern in which 5 to 10 straight lines having the same line width (L) and space width (S) were arranged in parallel was formed.
  • L / S scales are 200 ⁇ m / 200 ⁇ m, 150 ⁇ m / 150 ⁇ m, 100 ⁇ m / 100 ⁇ m, 50 ⁇ m / 50 ⁇ m, 40 ⁇ m / 40 ⁇ m, 30 ⁇ m / 30 ⁇ m, 25 ⁇ m / 25 ⁇ m, 20 ⁇ m / 20 ⁇ m, 15 ⁇ m / 15 ⁇ m, 10 ⁇ m / 10 ⁇ m, 6 ⁇ m / 6 ⁇ m. It was.
  • a dry film resist (manufactured by Asahi Kasei E-Materials Co., Ltd., SUNFORT / AQ209A) is placed on the surface of the conductive substrate with an inorganic oxide layer, passed through a hot roll press set at 105 ° C., and the dry film resist is laminated. did. This was cut to a size of 4 cm square, exposed to 80 mJ / cm 2 through the photomask having the above-mentioned L / S resolution evaluation pattern, and immersed in an aqueous solution of 1% by mass of sodium carbonate to obtain a resist pattern.
  • the dry film resist is a photo-curing type
  • a photomask having a shape that exposes the pattern forming portion and shields the development removed portion is used.
  • [Formation example of coating type positive resist pattern] A conductive substrate with an inorganic oxide layer is cut into 4 cm square, and a positive photoresist (Rohm and Haas Co., Ltd., LC100) is dropped on this surface, and a spin coater (Mikasa Co., Ltd., Spin The coating was carried out with a coater 1H-D3) at 1,000 rpm for 30 seconds, and allowed to stand for 30 minutes on a hot plate set at 100 ° C. for drying.
  • TMAH tetramethylammonium hydride
  • Example 1 An inorganic oxide layer 1 mainly composed of silica and a carbon nanotube conductive layer 1 are formed in this order on a PET film (Toray Industries, Inc., U46, thickness 125 ⁇ m) via a sol-gel method. A conductive substrate with an object underlayer was obtained. A resist pattern corresponding to the L / S resolution evaluation pattern was formed on this conductive substrate in accordance with the above-mentioned [Dry Film Resist Pattern Formation Example]. Here, the conductive substrate was placed on a hot plate and dried after development at 100 ° C. for 3 minutes. Next, an etchant having a concentration of 0.1% by mass of sulfuric acid and 0.1% by mass of ammonium fluoride was prepared. The pH of this etchant was 2.5.
  • the conductive substrate was immersed in an etchant heated to 40 ° C. for 60 seconds, immersed in pure water for 5 seconds, and washed with shower water using a sprayer.
  • the resist was peeled off by immersing in methyl cellosolve acetate (hereinafter referred to as MCA) for 60 seconds, immersed in pure water and washed with water.
  • MCA methyl cellosolve acetate
  • the risk level of the etchant was in the range at pH 2.5, the volatility was small, and the acute toxicity was small, so the risk level was I.
  • a protective layer using an inorganic oxide layer 1, a carbon nanotube conductive layer 1, and an inorganic oxide layer 1 is formed in this order on a PET film (Toray Industries, Inc., U46, thickness 125 ⁇ m). A conductive substrate with a base layer was obtained.
  • a resist pattern corresponding to the L / S resolution evaluation pattern was formed on this conductive substrate in accordance with the above-mentioned [Dry Film Resist Pattern Formation Example].
  • the conductive substrate was placed on a hot plate and dried after development at 100 ° C. for 3 minutes.
  • an etchant having a concentration of 1% by mass of sulfuric acid and 0.1% by mass of ammonium fluoride was prepared.
  • the pH of this etchant was 1.8.
  • the conductive substrate was immersed in an etchant heated to 40 ° C. for 60 seconds, immersed in pure water for 5 seconds, and washed with shower water using a sprayer.
  • the resist was peeled off by immersing in MCA for 60 seconds, immersed in pure water and washed with water.
  • the risk level of the etchant was in the range at pH 1.8, the volatility was small, and the acute toxicity was small, so the risk level was I.
  • Example 3 The same operation as in Example 2 was performed except that the inorganic oxide layer was changed to the inorganic oxide layer 2 formed from the polysilicate raw material.
  • Example 4 When the surface form of the conductive layer removal portion was observed with a laser microscope VK9710 manufactured by Keyence Corporation, it was the same form as the PET film surface substrate, and peeling occurred at the interface between the inorganic oxide layer and the PET film surface. I understood.
  • the risk level of the etchant was in the range at pH 1.8, the volatility was small, and the acute toxicity was small, so the risk level was I.
  • Example 4 The same operation as in Example 3 was performed except that the photoresist was changed to the above-described coating type positive resist.
  • the risk level of the etchant was in the range at pH 1.8, the volatility was small, and the acute toxicity was small, so the risk level was I.
  • the surface form of the conductive layer removal portion was observed with a laser microscope VK9710 manufactured by Keyence Corporation, it was the same form as the PET film surface substrate, and peeling occurred at the interface between the inorganic oxide layer and the PET film surface. I understood.
  • Example 5 The same operation as in Example 4 was performed except that soda lime glass having a thickness of 1.1 mm was used as the base material and a protective layer was not provided.
  • the risk level of the etchant was in the range at pH 1.8, the volatility was small, and the acute toxicity was small, so the risk level was I.
  • Example 6 The same operation as in Example 4 was performed except that soda lime glass having a thickness of 1.1 mm was used as the base material.
  • the risk level of the etchant was in the range at pH 1.8, the volatility was small, and the acute toxicity was small, so the risk level was I.
  • Example 7 The same operation as in Example 3 was performed except that a polyimide film (manufactured by Toray DuPont, Kapton 100V) was used as the base material.
  • the risk level of the etchant was in the range at pH 1.8, the volatility was small, and the acute toxicity was small, so the risk level was I.
  • Example 8 The same operation as in Example 3 was performed except that the inorganic oxide layer was changed to the inorganic oxide layer 3 described above.
  • the risk level of the etchant was in the range at pH 1.8, the volatility was small, and the acute toxicity was small, so the risk level was I.
  • Example 9 The same operation as in Example 4 was performed except that the conductive layer was changed to the antimony-doped tin oxide conductive layer 2 and the protective layer was not provided.
  • the risk level of the etchant was in the range at pH 1.8, the volatility was small, and the acute toxicity was small, so the risk level was I.
  • the risk level of the etchant was in the range at pH 1.8, the volatility was small, and the acute toxicity was small, so the risk level was I.
  • Example 11 The same operation as in Example 4 was performed except that the conductive layer was changed to the conductive polymer conductive layer 4 and the protective layer was not provided.
  • the risk level of the etchant was in the range at pH 1.8, the volatility was small, and the acute toxicity was small, so the risk level was I.
  • Example 12 The same operation as in Example 4 was performed except that the conductive layer was changed to the silver nanocolloid conductive layer 5 and the protective layer was not provided.
  • the risk level of the etchant was in the range at pH 1.8, the volatility was small, and the acute toxicity was small, so the risk level was I.
  • An etchant having a concentration of 1% by mass of sulfuric acid and 0.1% by mass of sodium fluoride was prepared, and the same operation as in Example 4 was performed except that this etchant was used.
  • the pH of this etchant was 1.8.
  • the risk level of the etchant was in the range at pH 1.8, the volatility was small, and the acute toxicity was small, so the risk level was I.
  • An etchant having a concentration of 1% by mass of toluenesulfonic acid and 0.1% by mass of potassium fluoride was prepared, and the same operation as in Example 4 was performed except that this etchant was used.
  • the pH of this etchant was 1.5.
  • the risk level of the etchant was in the range at pH 1.5, the volatility was small, and the acute toxicity was small, so the risk level was I.
  • Example 15 The same operation as in Example 4 was performed except that an etchant having a concentration of 1% by mass of ammonium fluoride was prepared, this etchant was used, the etchant liquid temperature was 50 ° C., and the etching time was 180 seconds. It was.
  • the pH of this etchant was 6.5.
  • the etchant risk level was in the range at pH 6.5, the volatility was low, and the acute toxicity was low, so the risk level was I.
  • Example 16 Prepared an etchant with a concentration of 0.1% by weight of sodium carbonate and 1% by weight of ammonium fluoride. This etchant was used except that the etchant temperature was 60 ° C. and the etching time was 180 seconds. The same operation as in Example 4 was performed. The pH of this etchant was 11.
  • the risk level of the etchant was in the range at pH 11, the volatility was small, and the acute toxicity was small, so the risk level was I.
  • Example 17 The same operation as in Example 3 was performed except that acetone was used instead of MCA for stripping the resist.
  • the risk level of the etchant was in the range at pH 1.8, the volatility was small, and the acute toxicity was small, so the risk level was I.
  • Example 18 The same operation as in Example 3 was performed except that a 1% by weight aqueous solution of sodium hydroxide was used instead of MCA for stripping the resist.
  • the risk level of the etchant was in the range at pH 1.8, the volatility was small, and the acute toxicity was small, so the risk level was I.
  • Example 1 The same operation as in Example 3 was performed except that the inorganic oxide layer was not provided, the protective layer was not provided, the etchant liquid temperature was 50 ° C., and the etching time was 600 seconds. The conductive layer was not etched, and an L / S resolution evaluation pattern could not be obtained. The risk level of the etchant was in the range at pH 1.8, the volatility was small, and the acute toxicity was small, so the risk level was I.
  • Example 2 The same operation as in Example 3 was performed except that the inorganic oxide layer was not provided, the etchant liquid temperature was 50 ° C., and the etching time was 600 seconds.
  • the conductive layer was not etched, and an L / S resolution evaluation pattern could not be obtained.
  • the risk level of the etchant was in the range at pH 1.8, the volatility was small, and the acute toxicity was small, so the risk level was I.
  • Comparative Example 3 The same operation as in Example 3 was performed, except that the inorganic oxide layer was not provided, the etchant was changed to 60% by mass sulfuric acid, the liquid temperature was 50 ° C., and the etching time was 600 seconds. The pH of this etchant was 1.
  • the conductive layer was not etched, and an L / S resolution evaluation pattern could not be obtained. In addition, due to the high concentration of sulfuric acid, careful handling was required.
  • the risk level of the etchant was out of range at pH 1, the volatility was small, and the acute toxicity was small, so the risk level was II.
  • Comparative Example 4 The same operation as in Example 3 was performed, except that the inorganic oxide layer was not provided, the etchant was changed to 3% by mass sodium hydroxide, the liquid temperature was 50 ° C., and the etching time was 600 seconds. The pH of this etchant was 14. Although the conductive layer was partially etched, an L / S resolution evaluation pattern could not be obtained. In addition, since the etchant was a strong alkaline aqueous solution, careful handling was required.
  • the risk level of the etchant was out of range at pH 14, the volatility was small, and the acute toxicity was small, so the risk level was II.
  • Comparative Example 5 An operation similar to that of Example 3 was performed except that an aqueous solution of 1% by mass of sulfuric acid was prepared, this solution was used as an etchant, and the etching time was 90 seconds. The pH of this aqueous solution was 1. Although the conductive layer was partially etched, an L / S resolution evaluation pattern could not be obtained.
  • the risk level of the etchant was in the range at pH 1.8, the volatility was small, and the acute toxicity was small, so the risk level was I.
  • Example 9 The same operation as in Example 3 was performed except that a 2.4% by mass aqueous solution of TMAH was prepared and this solution was used as an etchant.
  • the pH of this aqueous solution was 13.8.
  • the etchant was a strong alkaline aqueous solution, careful handling was required.
  • the risk level of the etchant was out of range at pH 13.8, the volatility was small, and the acute toxicity was small, so the risk level was II.
  • Example 10 An aqueous solution containing 3% by mass of sodium hydroxide was prepared, this solution was used as an etchant, and the same operation as in Example 3 was performed except that the etching time was 30 seconds.
  • the pH of this aqueous solution was 14.
  • the conductive layer was completely peeled off by shower water washing after etching, and a conductive pattern could not be obtained.
  • the etchant was a strong alkaline aqueous solution, careful handling was required.
  • the risk level of the etchant was out of range at pH 14, the volatility was small, and the acute toxicity was small, so the risk level was II.
  • Example 11 A mixed liquid of 36% by mass hydrochloric acid and 40% by mass ferric chloride was prepared, and the same operation as in Example 3 was performed except that this liquid was used as an etchant.
  • the pH of this aqueous solution was 0.5. Only a part of the conductive layer was removed, resulting in poor etching. Moreover, since the pH of the etchant was less than 1, careful handling was required, and volatile gas with high oxidizability was generated, so the surrounding equipment was corroded.
  • the risk level of the etchant was out of range at pH 0.5, the volatility was high, and the acute toxicity was low, so the risk level was III.
  • Tables 1 and 2 show the production conditions of the examples and comparative examples and Table 3 shows the evaluation results.
  • (Comparative Example 13) A protective layer using an inorganic oxide layer 2, a carbon nanotube conductive layer 1, and an inorganic oxide layer 1 is formed in this order on a PET film (Toray Industries, Inc., U46, thickness 125 ⁇ m). A conductive substrate with a base layer was obtained. Ten linear patterns having a width of the conductive removal portion of 20 ⁇ m were formed on the conductive surface of the conductive substrate by a laser etching method using an ultraviolet laser. When the conductive layer-removed portion of this space was observed with a laser microscope VK9710 manufactured by Keyence Corporation, it was confirmed that the PET film surface was removed.
  • Example 19 The substrate for the X electrode and the substrate for the Y electrode were patterned by the method of Example 3. When a drive circuit for a capacitive touch panel is attached to a panel on which these conductive substrates are bonded and the surface is pressed with a finger, the circuit recognizes the pressed point and can operate as a capacitive touch panel. It could be confirmed.

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Abstract

L'invention concerne un procédé de production d'une base conductrice à motifs, qui comprend : une étape de formation d'une couche d'agent photorésistant sur une partie de la couche la plus extérieure d'une base conductrice, au moins une base, une couche d'oxyde inorganique et une couche conductrice étant formées de manière séquentielle dans cet ordre ; et une étape de formation de motifs sur la couche conductrice par amenée de la base conductrice en contact avec une solution aqueuse contenant des ions fluorure, ce qui permet d'éliminer la couche conductrice conjointement avec la couche d'oxyde inorganique dans des parties dans lesquelles l'agent photorésistant n'est pas formé. L'invention concerne un nouveau procédé de formation de motifs sur un film conducteur, qui présente une excellente aptitude à la manipulation et pour lequel un équipement existant peut être utilisé.
PCT/JP2013/064148 2012-05-24 2013-05-22 Procédé de production d'une base conductrice à motifs, base conductrice à motifs produite par ledit procédé et écran tactile WO2013176155A1 (fr)

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CN201380026425.3A CN104321836A (zh) 2012-05-24 2013-05-22 经图案化的导电基材的制造方法、通过该方法而进行了图案化的导电基材及触控面板
JP2013532768A JPWO2013176155A1 (ja) 2012-05-24 2013-05-22 パターニングされた導電基材の製造方法、これによってパターニングされた導電基材およびタッチパネル
KR1020147029862A KR20150016934A (ko) 2012-05-24 2013-05-22 패터닝된 도전 기재의 제조 방법, 이에 의해 패터닝된 도전 기재 및 터치 패널

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WO2015083610A1 (fr) * 2013-12-04 2015-06-11 東レ株式会社 Stratifié électroconducteur transparent et panneau tactile l'utilisant
KR20150107319A (ko) * 2014-03-14 2015-09-23 주식회사 아모센스 터치 스크린 패널용 센서의 제조 방법 및 터치 스크린 패널용 센서
KR20150107320A (ko) * 2014-03-14 2015-09-23 주식회사 아모센스 터치 스크린 패널용 커버 필름 및 이를 포함하는 터치 스크린 패널
JP2016072370A (ja) * 2014-09-29 2016-05-09 東洋アルミニウム株式会社 回路基板の製造方法

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CN106661335B (zh) 2014-05-14 2020-11-27 三菱化学株式会社 导电性组合物、抗静电膜、层叠体及其制造方法以及光掩膜的制造方法
CN105887086A (zh) * 2016-06-07 2016-08-24 共青城超群科技协同创新股份有限公司 锚型三维立体蚀刻方法
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