+

WO2014098157A1 - Procédé de formage de film, film conducteur et film isolant - Google Patents

Procédé de formage de film, film conducteur et film isolant Download PDF

Info

Publication number
WO2014098157A1
WO2014098157A1 PCT/JP2013/083982 JP2013083982W WO2014098157A1 WO 2014098157 A1 WO2014098157 A1 WO 2014098157A1 JP 2013083982 W JP2013083982 W JP 2013083982W WO 2014098157 A1 WO2014098157 A1 WO 2014098157A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
forming method
film
film forming
resin
Prior art date
Application number
PCT/JP2013/083982
Other languages
English (en)
Japanese (ja)
Inventor
浩志 松木
基実 松島
富明 大竹
Original Assignee
株式会社クラレ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社クラレ filed Critical 株式会社クラレ
Priority to JP2014553187A priority Critical patent/JPWO2014098157A1/ja
Publication of WO2014098157A1 publication Critical patent/WO2014098157A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • 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
    • H05K3/027—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 by irradiation, e.g. by photons, alpha or beta particles
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1142—Conversion of conductive material into insulating material or into dissolvable compound
    • 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
    • H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces

Definitions

  • the present invention relates to a transparent conductive film, for example.
  • a transparent conductive film substrate in which a transparent conductive film (for example, a transparent conductive film made of indium tin oxide (ITO) or the like) is provided on a transparent substrate is known.
  • This type of substrate is used for a display panel, for example.
  • a display panel for example.
  • it is used for a liquid crystal display.
  • plasma displays Used for organic EL displays.
  • organic EL displays Used for organic EL displays.
  • it is used for a touch panel.
  • solar cell In addition, it is used in various fields.
  • the transparent conductive film is formed in a desired pattern.
  • a chemical etching means (a photolithography means using a photoresist or an etchant) is generally employed.
  • the chemical etching method is a photoresist film forming process (applying a photoresist paint on the ITO film formed on the entire surface of the substrate) ⁇ photoresist film patterning process (exposure development forms the photoresist film into a predetermined pattern) ) ⁇ ITO film etching process (etching the ITO film using a predetermined pattern of photoresist film as a mask) ⁇ Photoresist film removing process is required. Therefore, the chemical etching method is cumbersome.
  • the chemical etching method has a problem of a decrease in etching accuracy due to swelling of the photoresist film in the solution.
  • the chemical etching method has problems in the handling of the etching solution and the waste solution treatment.
  • a laser ablation method has been proposed as a method for solving the above problems.
  • unnecessary portions are removed by directly irradiating a conductive film with a laser.
  • This method does not require a photoresist and enables highly accurate patterning.
  • the laser ablation method In the laser ablation method, applicable substrates are limited.
  • the laser ablation method has a high process cost. In the laser ablation method, the processing speed is slow. Therefore, the laser ablation method is not a method suitable for a mass production process.
  • Chemical etching techniques that do not require a photolithography process include “use of iron (III) chloride or iron (III) chloride hexahydrate as an etching component in a composition for etching an oxide surface”, “iron chloride” (III) or iron (III) chloride hexahydrate, in display technology (TFT), in photovoltaics, semiconductor technology, high performance electronics, mineralogy or glass industry, in OLED lighting, in the manufacture of OLED displays, and Use as an etching component in a composition in paste form for the manufacture of photodiodes and for the construction of ITO glass for flat panel screen applications (plasma displays) "" Composition for etching oxide layers " A) salt as an etching component Iron (III) or iron (III) chloride hexahydrate, b) solvent, c) optionally homogeneously dissolved organic thickener, d) optionally at least one inorganic acid and / or organic
  • etching medium for etching a transparent conductive layer of an oxide comprising phosphoric acid or a salt thereof or a phosphoric acid adduct or a mixture of phosphoric acid and a phosphate and / or a phosphoric acid adduct
  • Etching medium containing at least one etchant A method for etching a transparent conductive layer of oxide, characterized in that the etching medium is applied to a substrate to be etched by a printing process” It has been proposed (Japanese Patent Publication No. 2009-503825).
  • a transparent conductive film made of carbon nanotubes is known in addition to the transparent conductive film made of ITO.
  • the carbon nanotube is a tube-shaped material having a diameter of 1 ⁇ m or less.
  • An ideal carbon nanotube has a structure in which a carbon hexagonal mesh surface is parallel to the tube axis to form a tube.
  • the tubes may be multiplexed.
  • Carbon nanotubes exhibit metallic or semiconducting properties depending on how the hexagonal network made of carbon is connected and the thickness of the tube. For this reason, carbon nanotubes are expected as functional materials. However, depending on the configuration and manufacturing method of the carbon nanotube, the thickness and direction are random.
  • the substrate is washed with a solvent that does not dissolve the binder.
  • a pattern is formed in which only the portion where the binder exists (to which the binder has been applied) remains.
  • a photoresist material can also be used instead of the binder. That is, a photoresist-containing paint is applied to the carbon nanotube film. Thereby, the photoresist is impregnated in the network of carbon nanotubes. Thereafter, a predetermined pattern is formed using photolithography.
  • the method of patterning after forming the carbon nanotube film on the entire surface of the substrate is complicated.
  • a pre-patterned carbon nanotube film is directly applied and formed on a substrate by an application method such as screen printing, inkjet, or gravure printing.
  • an application method such as screen printing, inkjet, or gravure printing.
  • the carbon nanotube dispersion generally contains a dispersant such as a surfactant.
  • the carbon nanotube dispersion has a relatively low viscosity. In order to obtain ink physical properties suitable for the coating method, it is necessary to add a material for adjusting the viscosity and surface tension to the carbon nanotube dispersion. In this case, the dispersibility of the carbon nanotubes may be deteriorated.
  • the conductive film removing agent is applied to at least a part of the base material with a conductive film having a conductive film containing a whisker-like conductor, a fibrous conductor (for example, carbon nanotube) or a particulate conductor on the base material.
  • a conductive film removal method including a process, a process of heat treatment at 80 ° C. or higher, and a process of removing the conductive film by cleaning with a liquid.
  • the conductive film in the portion where the conductive film remover is applied is decomposed, dissolved or solubilized, and has an overcoat layer. It is said that the overcoat layer and the conductive film are decomposed, dissolved or solubilized.
  • the carbon nanotube is exposed on the side surface (vertical wall surface) of the pattern formed by the technique using the conductive film remover of Patent Document 5. This is because even if an overcoat layer is provided on the upper surface of the carbon nanotube layer, the carbon nanotube layer and the overcoat layer are removed by the conductive film removing agent. That is, there is a carbon nanotube surface that is not covered with the overcoat layer. For this reason, a decrease in durability (for example, dropping of carbon nanotubes, change in physical properties due to moisture, etc.) can be considered.
  • Patent Document 5 requires a heating step of heating the conductive film remover applied in a predetermined pattern to 80 ° C. or higher. Therefore, workability is poor. Furthermore, the substrate is required to have a heat resistance of 80 ° C. or higher. This reduces the degree of freedom in substrate selection.
  • the present invention aims to solve the above problems.
  • the problem to be solved by the present invention is to provide a conductive (or insulating) film having high resolution and excellent durability by a simple method.
  • An overcoat layer was provided on a conductive film (for example, a conductive film formed by applying conductive carbon nanotubes).
  • a resin layer having a predetermined pattern for shielding (shielding) ultraviolet rays was provided on the overcoat layer.
  • Ultraviolet rays were irradiated using the resin layer as a mask.
  • ultraviolet rays were irradiated in an atmosphere containing oxygen.
  • the pattern thus formed had high pattern accuracy.
  • the durability of the conductive film (insulating film) was excellent.
  • pattern formation was simple.
  • the conductive film having a predetermined pattern is an insulating film having a predetermined pattern when viewed from the opposite standpoint.
  • the present invention has been achieved based on the above findings.
  • the present invention A method of forming a film with a predetermined pattern in which the conductive carbon layer in the ultraviolet irradiation region is modified to be insulative, and the conductive carbon layer in the non-ultraviolet irradiation region retains conductivity, A step of providing a conductive carbon layer; A step of providing an overcoat layer on the conductive carbon layer; A step in which a resin layer having a predetermined pattern is provided in close contact with the overcoat layer;
  • the present invention proposes a method for forming a film, comprising: a step of irradiating the conductive carbon layer with ultraviolet rays in a region having no oxygen in an atmosphere containing oxygen.
  • the present invention A method of forming a film with a predetermined pattern in which the conductive carbon layer in the ultraviolet irradiation region is modified to be insulative, and the conductive carbon layer in the non-ultraviolet irradiation region retains conductivity, A step of providing a conductive carbon layer; A step of providing an overcoat layer on the conductive carbon layer; A step in which a resin layer having a predetermined pattern is provided in close contact with the overcoat layer; In an atmosphere having oxygen, the step of irradiating the conductive carbon layer with ultraviolet rays corresponding to the location where the resin layer is absent; And a step of removing the resin layer after the ultraviolet irradiation.
  • the present invention is the film forming method, wherein the overcoat layer is preferably composed of a composition containing at least one selected from the group of hydrolyzable hydrolyzable organosilanes.
  • a film forming method is proposed.
  • the present invention proposes the film forming method, wherein the overcoat layer preferably has a thickness of 1 nm to 1 ⁇ m.
  • the present invention proposes the film forming method, wherein the resin layer having the predetermined pattern is preferably made of a resin that does not transmit ultraviolet rays, and is provided by a printing unit.
  • the present invention proposes the film forming method, wherein the ultraviolet ray is an ultraviolet ray having a wavelength in the range of 10 to 400 nm.
  • the present invention proposes the film forming method, wherein the ultraviolet ray is preferably an ultraviolet ray having a wavelength in the range of 150 to 180 nm.
  • the present invention proposes a film forming method as described above, wherein the cumulative amount of irradiated ultraviolet light is preferably 50 to 500,000 mJ / cm 2 .
  • the present invention proposes the film forming method, wherein the cumulative amount of irradiation with ultraviolet rays is preferably 500 to 30000 mJ / cm 2 .
  • the present invention proposes the film forming method, wherein the atmosphere containing oxygen has an oxygen pressure of preferably 101 to 21273 Pa.
  • the present invention proposes the film forming method, wherein the atmosphere containing oxygen has an oxygen pressure of preferably 1013 to 10130 Pa.
  • the present invention proposes the film forming method, wherein the conductive carbon layer is preferably composed of graphene.
  • the present invention proposes the film forming method, wherein the conductive carbon layer is preferably composed of carbon nanotubes.
  • the present invention proposes the above film forming method, wherein the conductive carbon layer is preferably composed of acid-treated single-walled carbon nanotubes.
  • the present invention proposes a conductive film formed by the film forming method.
  • the present invention proposes an insulating film formed by the film forming method.
  • a conductive (or insulating) film with high resolution can be easily obtained.
  • the first aspect of the present invention is a film forming method.
  • the method is, for example, a method of forming a conductive film having a predetermined pattern. Alternatively, it is a method of forming an insulating film having a predetermined pattern.
  • the method is a method of forming a transparent conductive film having a predetermined pattern. Alternatively, a transparent insulating film having a predetermined pattern is formed.
  • the method is a film formation method of a predetermined pattern in which the conductive carbon layer in the ultraviolet irradiation region is modified to be insulative and the conductive carbon layer in the non-ultraviolet irradiation region retains conductivity.
  • the above-described method is an insulating film forming method, particularly if the portion modified to be insulating is taken up.
  • the above method is a method for forming a conductive film, particularly if the conductive part is taken up.
  • the method includes the step of providing a conductive carbon layer.
  • conductive carbon for example, conductive graphene (conductive carbon nanotube)
  • a conductive carbon layer is provided on the substrate.
  • CVD chemical vapor deposition method
  • PVD physical vapor deposition method
  • the method includes a step of providing an overcoat layer on the conductive carbon layer.
  • an overcoat paint is applied on the conductive carbon layer.
  • This coating forms an overcoat layer.
  • the method includes a step in which a resin layer (a resin layer made of a material that does not transmit ultraviolet rays) is provided on the overcoat layer.
  • the overcoat layer and the resin layer are in close contact.
  • Adhesion means that a special force is required for peeling. That is, [bonding strength (peel strength) between the overcoat layer and the resin layer]> 0.
  • peeling strength peeling strength between the overcoat layer and the resin layer
  • oxygen active oxygen
  • the resin layer has a predetermined pattern.
  • the resin layer is provided at a location corresponding to a location (pattern) where the conductive carbon layer maintains conductivity.
  • the resin layer is not provided at a location corresponding to a location (pattern) where the conductive carbon layer loses conductivity and becomes insulating. That is, the resin layer having the predetermined pattern functions as a mask for forming a conductive film (insulating film) having a predetermined pattern.
  • Various resins can be used as the resin that does not transmit ultraviolet rays.
  • a resist material, a photocurable resin, a thermosetting resin, a thermoplastic resin, and the like can be given.
  • the resin layer having the predetermined pattern is formed by printing means such as screen printing. Alternatively, it is formed using a photolithography technique. Of course, it is not limited to this.
  • the method includes a step of irradiating with ultraviolet rays in an oxygen-containing atmosphere after the resin layer having the predetermined pattern is provided. In this irradiation step, the conductive carbon in the lower position where the resin layer exists is not irradiated with ultraviolet rays. The conductive carbon in the lower position where the resin layer does not exist is irradiated with ultraviolet rays. Ultraviolet rays are irradiated to the portions that should be insulated.
  • the ultraviolet non-irradiated region is a region where electrical conductivity should be ensured.
  • the ultraviolet irradiation region is a region where conductivity should be lost.
  • ultraviolet irradiation is performed. Adhesion between the overcoat layer and the mask was improved by using the resin layer (resin mask). Thereby, it is difficult for the ultraviolet rays to reach a portion where the ultraviolet rays are masked or a portion where the activated oxygen due to the ultraviolet irradiation is masked. As a result, the pattern accuracy of the conductive film (insulating film) is increased. A film with a high resolution pattern was obtained.
  • the overcoat layer is preferably composed of a composition containing at least one selected from the group of hydrolyzable organosilane hydrolysates.
  • the ultraviolet rays are preferably ultraviolet rays having a wavelength in the range of 10 to 400 nm. More preferred is ultraviolet light having a wavelength in the range of 150 to 260 nm. Particularly preferred is ultraviolet light having a wavelength in the range of 150 to 180 nm.
  • the atmosphere containing oxygen preferably has an oxygen pressure (oxygen partial pressure in the case of a mixed gas) of 101 to 21273 Pa. More preferably, the oxygen pressure is 507-20260 Pa. Particularly preferably, the oxygen pressure is 1013 to 10130 Pa.
  • the conductive carbon layer is made of graphene, for example.
  • the conductive carbon layer is composed of, for example, carbon nanotubes.
  • the conductive carbon layer (carbon nanotube layer) is composed of single-walled carbon nanotubes, for example.
  • the conductive carbon layer (carbon nanotube layer) is composed of, for example, single-walled carbon nanotubes subjected to acid treatment.
  • the carbon nanotube is preferably a carbon nanotube of G (intensity at a Raman peak common to graphite substances appearing near 1590 cm ⁇ 1 ) / D (intensity at a Raman peak due to defects appearing near 1350 cm ⁇ 1 ) ⁇ 10 .
  • the upper limit value of G / D is about 150, for example.
  • the second aspect of the present invention is a conductive film.
  • the film is a conductive film formed by the film forming method.
  • the third aspect of the present invention is an insulating film.
  • the film is an insulating film formed by the film forming method.
  • FIG. 1 is a schematic cross-sectional view showing the layer structure before ultraviolet irradiation
  • FIG. 2 is a schematic cross-sectional view showing the layer structure after ultraviolet irradiation
  • FIG. 3 is a plan view of a resin layer (mask) provided on the overcoat layer. is there.
  • the transparent conductive carbon layer 1 is a transparent conductive carbon layer.
  • the transparent conductive carbon layer 1 is made of graphene, for example.
  • the transparent conductive carbon layer 1 was made of carbon nanotubes, for example.
  • the transparent conductive carbon layer 1 was composed of, for example, single-walled carbon nanotubes.
  • the transparent conductive carbon layer 1 is composed of, for example, single-walled carbon nanotubes that have been subjected to acid treatment.
  • Examples of the carbon nanotubes (CNT) constituting the transparent conductive carbon layer 1 include single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes.
  • Single-walled carbon nanotubes are preferred.
  • single-walled carbon nanotubes having a G / D of 10 or more (for example, 20 to 60) are preferable.
  • CNTs having a diameter of 0.3 to 100 nm are preferable.
  • CNT having a diameter of 0.3 to 2 nm is preferable.
  • CNTs having a length of 0.1 to 100 ⁇ m are preferred.
  • CNTs having a length of 0.1 to 5 ⁇ m are preferable.
  • the CNTs in the transparent conductive carbon layer 1 are intertwined with each other, for example.
  • the single-walled carbon nanotube may be a single-walled carbon nanotube obtained by any manufacturing method.
  • single-walled carbon nanotubes obtained by a production method such as arc discharge, chemical vapor deposition, or laser evaporation can be used. From the viewpoint of crystallinity, single-walled carbon nanotubes obtained by an arc discharge method are preferred. This is easily available.
  • the single-walled carbon nanotube is preferably a single-walled carbon nanotube subjected to acid treatment.
  • the acid treatment is performed by immersing single-walled carbon nanotubes in an acidic liquid. A technique called spraying may be employed instead of immersion.
  • acidic liquids There are various types of acidic liquids. For example, an inorganic acid or an organic acid is used. However, inorganic acids are preferred.
  • nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, or a mixture thereof can be used.
  • acid treatment using nitric acid or a mixed acid of nitric acid and sulfuric acid is preferable.
  • the single-walled carbon nanotube and the carbon fine particles are physically bonded via the amorphous carbon, the amorphous carbon is decomposed. Both separated.
  • the fine particles of the metal catalyst used in the production of the single-walled carbon nanotube were decomposed.
  • a functional group is attached by the acid treatment.
  • the conductivity was improved by the acid treatment.
  • the single-walled carbon nanotube is preferably a single-walled carbon nanotube in which impurities are removed by filtration and purity is improved.
  • the conductive layer (carbon nanotube layer) 1 preferably contains fullerene in addition to the CNT.
  • the conductive layer 1 preferably contains the above-mentioned CNT and fullerene.
  • fullerene includes “fullerene analog”. This is because heat resistance is improved by including fullerene. It is because it was excellent also in electroconductivity.
  • the fullerene may be any fullerene. For example, C60, C70, C76, C78, C82, C84, C90, C96 etc. are mentioned. Of course, a mixture of plural kinds of fullerenes may be used. C60 is particularly preferable from the viewpoint of dispersion performance. Furthermore, C60 is easy to obtain.
  • fullerene may contain metal atoms.
  • the fullerene analog include those having a functional group (for example, a functional group such as OH group, epoxy group, ester group, amide group, sulfonyl group, ether group).
  • Examples also include phenyl-C61-propyl acid alkyl ester and phenyl-C61-butyric acid alkyl ester.
  • Examples thereof include hydrogenated fullerene.
  • fullerene having an OH group (hydroxyl group) (fullerene hydroxide) is preferable.
  • the number of OH groups is preferably 5 to 30 per molecule of fullerene. In particular, 8 to 15 are preferable.
  • the amount of fullerene is preferably 10 to 1000 parts by mass (particularly 20 parts by mass or more and 100 parts by mass or less) with respect to 100 parts by mass of CNT.
  • the transparent conductive carbon layer (carbon nanotube layer) 1 may contain a binder resin. However, from the viewpoint of conductivity, it is preferable not to include a binder resin. For example, when entangled CNTs are used, there is no need for a binder resin. The CNTs that are intertwined are in direct contact with each other. Since there is no intervening insulator, the conductivity is good. If the surface of the conductive film is observed with a scanning electron microscope, it can be confirmed / determined whether the structure is intertwined with CNTs.
  • the transparent conductive carbon layer 1 is configured by applying a CNT dispersion liquid (a dispersion liquid in which the CNT having the above characteristics and fullerene added as needed are dispersed) on the substrate 2.
  • a CNT dispersion liquid a dispersion liquid in which the CNT having the above characteristics and fullerene added as needed are dispersed
  • the coating method include die coating, knife coating, spray coating, spin coating, slit coating, micro gravure, flexo and the like. Of course, it is not limited to this.
  • the carbon nanotube dispersion liquid is applied to the entire surface of the substrate 2.
  • the transparent conductive carbon layer (carbon nanotube layer) 1 is preferably formed uniformly in order to uniformly promote insulation during ultraviolet irradiation.
  • Various materials are appropriately used as the constituent material of the substrate 2.
  • PS polystyrene
  • PMMA polymethyl methacrylate
  • MS polycarbonate
  • PC polycarbonate
  • COP cycloolefin polymer
  • COC cycloolefin copolymer
  • PET polyethylene terephthalate
  • a resin such as polyethylene naphthalate (PEN) is used.
  • PEN polyethylene naphthalate
  • an inorganic glass material or a ceramic material can be used.
  • the overcoat layer (protective layer) 3 is provided on the transparent conductive carbon layer 1.
  • the overcoat layer 3 is composed of an organic polymer material, an inorganic polymer material, or an organic-inorganic hybrid resin.
  • organic polymer materials include thermoplastic resins, thermosetting resins, cellulose resins, and photocurable resins. It is appropriately selected from the viewpoints of visible light transmittance, substrate heat resistance, glass transition point, film curing degree, and the like.
  • the thermoplastic resin include polymethyl methacrylate, polystyrene, polyethylene terephthalate, polycarbonate, polylactic acid, and ABS resin.
  • thermosetting resin examples include phenol resin, melamine resin, alkyd resin, polyimide, epoxy resin, fluorine resin, and urethane resin.
  • cellulose resin examples include acetyl cellulose and triacetyl cellulose.
  • photocurable resin examples include various oligomers, monomers, resins containing a photopolymerization initiator, and the like.
  • the inorganic material examples include silica sol, alumina sol, zirconia sol, titania sol and the like. Examples thereof include a polymer obtained by hydrolyzing and dehydrating and condensing water or an acid catalyst to the inorganic material.
  • the organic-inorganic hybrid resin examples include, for example, a resin in which a part of the inorganic material is modified (for example, substituted or added) with an organic functional group, or a resin mainly composed of various coupling agents such as a silane coupling agent. Etc. If the overcoat layer 3 is too thick, the contact resistance of the conductive film increases. On the contrary, if the overcoat layer 3 is too thin, it is difficult to obtain an effect as a protective film. Accordingly, the thickness of the overcoat layer 3 is preferably 1 nm to 1 ⁇ m. In particular, 10 nm or more is preferable. 200 nm or less is preferable. Furthermore, 150 nm or less is preferable.
  • the overcoat layer 3 provided on the transparent conductive carbon layer (carbon nanotube layer) 1 is particularly preferably composed of a composition containing, for example, a hydrolyzate of hydrolyzable organosilane.
  • a composition containing for example, a hydrolyzate of hydrolyzable organosilane.
  • it consists of a composition containing a tetrafunctional hydrolyzable organosilane.
  • it comprises a composition containing a hydrolyzate of a tetrafunctional hydrolyzable organosilane and a hydrolyzable organosilane having an epoxy group and an alkoxy group.
  • the content of the hydrolyzable organosilane hydrolyzate having an epoxy group and an alkoxy group is preferably 1 to 10% by weight based on the total solid content of the resin.
  • the epoxy group of the cohydrolyzate is a hydroxyl group contained in the substrate when the composition is applied and cured. And oxygen sites such as carbonyl groups. For this reason, the adhesion between the overcoat layer (protective film) and the transparent conductive carbon layer (carbon nanotube layer) 1 is improved. It consists of a composition containing silica-based metal oxide fine particles. In some cases, the composition further comprises a hydrolyzate of hydrolyzable organosilane having a fluorine-substituted alkyl group.
  • the hydrolyzate of the hydrolyzable organosilane is preferably a product obtained by reacting at a water ratio of 1.0 to 3.0 with respect to the alkoxy group contained in the hydrolyzable organosilane.
  • the hydrolyzate of the hydrolyzable organosilane is preferably a compound having a polystyrene equivalent weight average molecular weight of 1000 to 2000.
  • the tetrafunctional hydrolyzable organosilane is a compound represented by, for example, SiX 4 .
  • X is a hydrolyzable group.
  • R 1 is preferably a monovalent hydrocarbon group.
  • it is a monovalent hydrocarbon group having 1 to 8 carbon atoms.
  • the tetrafunctional hydrolyzable organosilane used in the present embodiment include tetramethoxysilane and tetraethoxysilane.
  • the hydrolyzable organosilane having an epoxy group and an alkoxy group is, for example, a compound represented by R 2 Si (OR 3 ) 3 or R 2 R 4 Si (OR 3 ) 2 .
  • R 2 is a group selected from an epoxy group, a glycidoxy group, and substituted products thereof.
  • R 3 is a monovalent hydrocarbon group as in R 1 .
  • R 4 is a group selected from hydrogen, an alkyl group, a fluoroalkyl group, an aryl group, an alkenyl group, a methacryloxy group, an epoxy group, a glycidoxy group, an amino group, and substituents thereof.
  • Examples of the hydrolyzable organosilane having an epoxy group and an alkoxy group used in this embodiment include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, and ⁇ -glycidoxypropyltrisilane. Examples thereof include ethoxysilane and ⁇ -glycidoxypropyldimethoxymethylsilane.
  • silica-based metal oxide fine particles hollow silica fine particles are preferably used.
  • the hollow silica fine particles are those in which cavities are formed inside the outer shell of the silica-based metal oxide.
  • the outer shell is preferably a porous one having pores. It may be one in which the pores are closed and the cavity is sealed. As long as it contributes to lowering the refractive index of the formed film, it is not necessarily limited to the hollow silica described above.
  • the overcoat layer having such a composition In the case of the overcoat layer having such a composition, the light reflectance was lowered and the light transmittance was high. High physical protection against friction. Protection was high against environmental changes such as heat and humidity.
  • the transparent conductive carbon layer (carbon nanotube layer) 1 was modified from conductive to insulating by ultraviolet irradiation in a short time.
  • such an overcoat layer is provided on the transparent conductive carbon layer (carbon nanotube layer) 1 prior to the ultraviolet irradiation step.
  • the overcoat layer 3 is provided by applying a paint containing the above composition.
  • a paint containing the above composition As the application method, the method described in the application of the CNT dispersion liquid is employed. The coating is performed on the conductive layer (carbon nanotube layer). Moreover, it is applied to the entire surface. It is preferable that the overcoat layer 3 is also formed uniformly in order to make the insulation at the time of ultraviolet irradiation progress uniformly.
  • a resin layer 4 having a predetermined pattern was provided on the overcoat layer 3.
  • the transparent conductive carbon layer (carbon nanotube layer) 1 below the location where the resin layer 4 exists is not irradiated with ultraviolet rays.
  • the transparent conductive carbon layer (carbon nanotube layer) 1 below the location where the resin layer 4 does not exist is irradiated with ultraviolet rays.
  • the resin layer 4 functions as a mask.
  • the resin constituting the resin layer 4 is a resin that does not transmit ultraviolet light having a wavelength used for insulation.
  • a resist material eg, novolak resin, melamine resin, etc.
  • a photocurable resin eg, acryloyl group-modified resin, etc.
  • a thermosetting resin eg, epoxy resin, etc.
  • a thermoplastic resin eg, acrylic resin, Aromatic resin
  • the resin layer 4 does not only have a function of shielding ultraviolet rays.
  • the resin layer 4 has high adhesion to the overcoat layer 3 to prevent leakage of ultraviolet rays (around) to a portion where conductivity is desired to be maintained, or leakage of active oxygen such as ozone generated from oxygen (entrance). To prevent. Thereby, highly accurate patterning was obtained.
  • the formation method of the resin layer 4 is not specifically limited. For example, printing means such as screen printing, offset printing, ink jet printing, and gravure printing can be used. If the printing means is employed, a resin can be provided on the overcoat layer 3 at a predetermined pattern corresponding portion.
  • UV rays were applied to the transparent conductive carbon layer (carbon nanotube layer) 1.
  • This ultraviolet ray preferably has a wavelength of 10 to 400 nm. More preferably, the wavelength is 150 to 260 nm. Particularly preferably, the wavelength is 150 to 180 nm. More preferably, the wavelength is 160 to 175 nm.
  • ultraviolet rays having a long wavelength exceeding 400 nm are irradiated, denaturation from conductive carbon nanotubes to insulating carbon nanotubes hardly occurs. By the way, it was difficult for the denaturation to occur when the high pressure mercury lamp used in a normal photolithography process was irradiated with ultraviolet rays (wavelength: 365 nm).
  • the irradiated ultraviolet light had a wavelength of 260 nm or less. More preferably, the ultraviolet ray was 180 nm or less.
  • the irradiated ultraviolet light (wavelength: 185 nm, 254 nm) from a low-pressure mercury lamp, the carbon nanotubes were easily denatured from conductive to insulating at the irradiated site.
  • the substrate 2 is made of resin, the substrate 2 sometimes has a phenomenon called discoloration. For this reason, it was particularly preferable that the irradiated ultraviolet light has a wavelength of 180 nm or less, and further 175 nm or less.
  • ultraviolet rays (wavelength: 172 nm) from a xenon excimer lamp were particularly preferable.
  • the ultraviolet irradiation time having the above characteristics was, for example, about 10 seconds to 1 hour. Preferably it was 1 minute or more. Preferably it was 40 minutes or less.
  • the cumulative amount of UV irradiation was, for example, about 50 to 500,000 mJ / cm 2 . Preferably, it was 100 to 100,000 mJ / cm 2 . More preferably, it was 500 to 30,000 mJ / cm 2 .
  • the preferable integrated light amount varies somewhat depending on the thickness of the carbon nanotube layer 1. It varied greatly depending on the presence or absence of the overcoat layer.
  • the carbon nanotubes were modified from conductive to insulating in a short time. It also varied depending on the type and thickness of the overcoat layer.
  • the overcoat layer was a composition containing a hydrolyzate of hydrolyzable organosilane, the irradiation time was significantly shortened.
  • the thickness of the overcoat layer 3 was preferably 10 to 200 nm. More preferably, it was 50 to 150 nm.
  • 1a is an ultraviolet irradiation location.
  • the ultraviolet irradiation part 1a is denatured to be insulating.
  • Reference numeral 1b denotes a portion not irradiated with ultraviolet rays. The portion 1b not irradiated with ultraviolet rays remains conductive.
  • oxygen or active oxygen
  • the atmosphere containing oxygen preferably had an oxygen pressure of 101 to 21273 Pa. More preferably, the oxygen pressure was 507-20260 Pa. Particularly preferably, the oxygen pressure was 1013 to 10130 Pa.
  • the transparent conductive carbon layer (carbon nanotube layer) 1 becomes a conductive (or insulating) film having a predetermined pattern by ultraviolet irradiation.
  • the present invention and the conventional pattern forming method are greatly different. That is, the overcoat layer (coating layer) 3 remains as it is.
  • the conductive layer (insulating layer) remains covered with the overcoat layer 3. Not exposed.
  • the protective effect of the conductive layer (insulating layer) is high. That is, the durability is high. For example, the conductive layer (insulating layer) is hardly chipped (dropped off). It is difficult for moisture (humidity) to enter the conductive layer (insulating layer).
  • the resin layer 4 was removed as necessary.
  • the removal method is not particularly limited. For example, a method of peeling using an adhesive sheet or roll, a method of rubbing using a brush or the like, and a method of dissolving (or peeling) using a chemical solution that dissolves or swells are appropriately used.
  • Example 1 The single wall carbon nanotubes (commercially available) synthesized by arc discharge were subjected to acid treatment, water washing, centrifugation and filtration. A surfactant (sodium dodecylbenzenesulfonate: SDBS) 0.2 wt% aqueous solution was added to the purified carbon nanotubes. The carbon nanotube-containing aqueous solution was subjected to a dispersion treatment using an ultrasonic device. Centrifugation was then performed. Thus, a carbon nanotube dispersion liquid (CNT: 3200 ppm) was obtained.
  • SDBS sodium dodecylbenzenesulfonate
  • the carbon nanotube dispersion was applied onto the substrate 2.
  • the substrate 2 is a PET film (MKZ-T4A: manufactured by Higashiyama Film).
  • the application method is die coating.
  • the coating thickness is 0.05 ⁇ m (thickness after drying).
  • ion exchange water cleaning was performed. Thereby, the surfactant contained in the coating film (carbon nanotube layer) was removed. This was followed by drying (1.5 minutes; 120 ° C.).
  • the carbon nanotube layer (transparent conductive carbon layer) 1 was provided on the PET film 2.
  • An overcoat layer 3 was provided on the carbon nanotube layer 1.
  • 1.8 wt% Aerocera hydrolyzable organosilane-containing composition: manufactured by Panasonic Corporation
  • the application method is die coating.
  • the coating thickness was 0.1 ⁇ m (thickness after drying).
  • a resin layer (mask) 4 was provided on the overcoat layer 3.
  • the mask (resin layer) 4 having a predetermined pattern was formed by screen printing. That is, a UV curable resin (JELCON GEC-10H: manufactured by Jujo Chemical Co., Ltd.) was printed at a predetermined location. The coating thickness was 50 ⁇ m. Thereafter, ultraviolet rays (wavelength 365 nm) were irradiated. The integrated light amount was 1,330 mJ / cm 2 . The resin was cured by UV irradiation. A portion where the resin layer 4 is not provided is an opening 5. Ultraviolet rays are irradiated to the carbon nanotube layer (transparent conductive carbon layer) 1 from the opening 5.
  • the opening 5 has a square shape with a line width of 100 ⁇ m and a side length of 5 mm.
  • ultraviolet rays (wavelength: 172 nm) from a xenon excimer lamp were irradiated from above the resin layer (mask) 4 having a predetermined pattern.
  • the atmosphere during ultraviolet irradiation was 94% nitrogen and 6% oxygen.
  • the pressure by the mixed gas is 1.013 ⁇ 10 5 Pa.
  • the integrated light quantity of irradiated ultraviolet rays was 10,560 mJ / cm 2 .
  • the resin layer 4 was peeled off and removed using an adhesive sheet.
  • the pattern shape ( ⁇ shape) of the opening 5 of the mask 4 was compared with the pattern shape ( ⁇ shape) of the carbon nanotube conductive layer. The agreement between the two was extremely high. That is, the transparent conductive film was formed with high accuracy.
  • the conductivity evaluation pattern shown in FIG. 4 was formed in the same manner as the ⁇ shape pattern.
  • the portion corresponding to the resin layer is the conductive portion 41
  • the portion corresponding to the opening is the insulating portion 51.
  • the inter-terminal resistance values at both ends of the conductive portion 41 in the conductive evaluation pattern were measured with a tester. As a result, the resistance value between terminals was about 20 k ⁇ .
  • the width of the thin line portion 6 in the conductive film was 729 ⁇ m, while the width of the thin line portion 6 in the resin film was 721 ⁇ m.
  • Example 2 In Example 1, a thermosetting resin (X-100 CL1: manufactured by Taiyo Ink Mfg. Co., Ltd.) was used for the resin layer 4, and a curing treatment method at 100 ° C. for 30 minutes was used in an oven. The same was done.
  • X-100 CL1 manufactured by Taiyo Ink Mfg. Co., Ltd.
  • the pattern shape ( ⁇ shape) of the opening of the mask was compared with the pattern shape ( ⁇ shape) of the carbon nanotube conductive layer.
  • the agreement between the two was extremely high. That is, the transparent conductive film was formed with high accuracy.
  • the conductivity evaluation pattern shown in FIG. 4 was formed in the same manner as the ⁇ shape pattern.
  • the resistance value between terminals at both ends of the conductive portion 41 of the conductive evaluation pattern was measured with a tester. As a result, the resistance value between terminals was about 20 k ⁇ .
  • the width of the fine line portion in the resin film was 699 ⁇ m, whereas the width of the thin line portion 6 in the conductive film was 729 ⁇ m.
  • Example 1 In Example 1, it carried out similarly except having set it as nitrogen atmosphere (oxygen partial pressure 0Pa: no oxygen).
  • the ultraviolet irradiation site was not modified from conductive to insulating in Comparative Example 1.
  • Example 2 In Example 1, it carried out similarly except that the overcoat layer 3 was not provided.
  • the ultraviolet irradiation site was not modified from conductive to insulating even in Comparative Example 2.
  • Example 3 In Example 1, a metal (Ni) mask was used instead of the resin mask. The metal mask was only placed on the overcoat and was not in close contact.
  • the continuity between the inside and outside of the shaped opening was examined with a tester. As a result, it was found that there was no conduction (insulation) between the two.
  • the pattern shape ( ⁇ shape) of the mask opening was compared with the pattern shape ( ⁇ shape) of the carbon nanotube conductive layer. As a result, the insulated part was wider than the mask opening. That is, the formation accuracy of the transparent conductive pattern was low.
  • a conductive evaluation pattern was formed on the conductive film in the same manner as the ⁇ -shaped pattern except that the metal mask pattern was changed to the conductive evaluation pattern shown in FIG.
  • the resistance value between terminals at both ends of the conductive portion 41 of the pattern was measured with a tester. As a result, the resistance value between the terminals was 356 k ⁇ , and the resistance value was larger than that of the example.
  • Example 2 In Example 2, a thermosetting resin (JELCON MS-03B: manufactured by Jujo Chemical Co., Ltd.) was used, and the procedure was the same except that a curing treatment method at 100 ° C. for 1 minute was used in an oven.
  • JELCON MS-03B manufactured by Jujo Chemical Co., Ltd.
  • thermosetting resin was repelled from the coated surface. For this reason, a result like Example 2 was not obtained.
  • Transparent conductive carbon layer (carbon nanotube layer) 1a UV irradiation location (insulation modified location) 1b UV-irradiated area (transparent conductive area) 2 Substrate 3 Overcoat layer (hydrolyzable organosilane-containing composition layer) 4 Resin layer (mask) 5 opening (ultraviolet ray transmission part) 41 Conducting part 51 Insulating part 6 Fine wire part

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Non-Insulated Conductors (AREA)
  • Manufacturing Of Electric Cables (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Conductive Materials (AREA)

Abstract

L'invention concerne un film structuré ayant une haute résolution. Le procédé de formage de film comprend : une étape dans laquelle est réalisée une couche de carbone conducteur ; une étape dans laquelle une couche de recouvrement est réalisée sur la couche de carbone conducteur ; une étape dans laquelle une couche de résine d'un motif prédéterminé est réalisée sur la couche de recouvrement ; et une étape dans laquelle des portions de la couche de carbone conducteur sur lesquelles n'est pas réalisée la couche de résine sont irradiées avec de la lumière ultraviolette dans une atmosphère contenant de l'oxygène.
PCT/JP2013/083982 2012-12-19 2013-12-18 Procédé de formage de film, film conducteur et film isolant WO2014098157A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2014553187A JPWO2014098157A1 (ja) 2012-12-19 2013-12-18 膜形成方法、導電膜、及び絶縁膜

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-277489 2012-12-19
JP2012277489 2012-12-19

Publications (1)

Publication Number Publication Date
WO2014098157A1 true WO2014098157A1 (fr) 2014-06-26

Family

ID=50978477

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/083982 WO2014098157A1 (fr) 2012-12-19 2013-12-18 Procédé de formage de film, film conducteur et film isolant

Country Status (3)

Country Link
JP (1) JPWO2014098157A1 (fr)
TW (1) TW201436001A (fr)
WO (1) WO2014098157A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016018724A (ja) * 2014-07-09 2016-02-01 株式会社クラレ 膜、及び膜形成方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105573542B (zh) * 2014-11-07 2018-07-24 宸鸿光电科技股份有限公司 制作纳米级导电薄膜的方法及其触控显示装置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009035059A1 (fr) * 2007-09-12 2009-03-19 Kuraray Co., Ltd. Film électroconducteur, élément électroconducteur et processus de production de film électroconducteur
JP2011082092A (ja) * 2009-10-09 2011-04-21 Fujifilm Corp パターン状透明導電材料、表示素子及び太陽電池
JP2011175972A (ja) * 2008-08-22 2011-09-08 Hitachi Chem Co Ltd 感光性導電フィルム、導電膜の形成方法、導電パターンの形成方法及び導電膜基板
JP2012164519A (ja) * 2011-02-07 2012-08-30 Shin Etsu Polymer Co Ltd 導電パターン形成基板の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009035059A1 (fr) * 2007-09-12 2009-03-19 Kuraray Co., Ltd. Film électroconducteur, élément électroconducteur et processus de production de film électroconducteur
JP2011175972A (ja) * 2008-08-22 2011-09-08 Hitachi Chem Co Ltd 感光性導電フィルム、導電膜の形成方法、導電パターンの形成方法及び導電膜基板
JP2011082092A (ja) * 2009-10-09 2011-04-21 Fujifilm Corp パターン状透明導電材料、表示素子及び太陽電池
JP2012164519A (ja) * 2011-02-07 2012-08-30 Shin Etsu Polymer Co Ltd 導電パターン形成基板の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016018724A (ja) * 2014-07-09 2016-02-01 株式会社クラレ 膜、及び膜形成方法

Also Published As

Publication number Publication date
TW201436001A (zh) 2014-09-16
JPWO2014098157A1 (ja) 2017-01-12

Similar Documents

Publication Publication Date Title
JPWO2012176905A1 (ja) 導電膜形成方法、導電膜、絶縁化方法、及び絶縁膜
JP4412315B2 (ja) 同一表面上に異なる親水性及び親油性を呈する領域を有する基板の製造方法
WO2013176155A1 (fr) Procédé de production d'une base conductrice à motifs, base conductrice à motifs produite par ledit procédé et écran tactile
US20050266162A1 (en) Carbon nanotube stripping solutions and methods
TWI519616B (zh) 以碳奈米管為主之透明導電膜及其製備與圖案化之方法
Aleksandrova Specifics and Challenges to Flexible Organic Light‐Emitting Devices
Li et al. High resolution patterning of Ag nanowire flexible transparent electrode via electrohydrodynamic jet printing of acrylic polymer-silicate nanoparticle composite overcoating layer
WO2014098158A1 (fr) Procédé de formation de film, film conducteur et film isolant
Kim et al. Transparent and Multi‐Foldable Nanocellulose Paper Microsupercapacitors
WO2014098157A1 (fr) Procédé de formage de film, film conducteur et film isolant
JP2011082165A (ja) 電極基板の製造方法
WO2014098230A1 (fr) Procédé de formation de film, film conducteur, et film d'isolation
KR101197336B1 (ko) 탄소나노튜브를 이용하여 투명 전도성 필름을 제작하는 방법 및 그 방법을 이용하여 생성된 투명 전도성 필름
JP2016018713A (ja) 導電膜
Sun et al. Carbon nanotube transparent electrode
JP2013008877A (ja) カーボンナノチューブ層とオーバーコート層とを具備する複合層のパターン形成方法、及び前記方法で形成されたパターン
JP5688395B2 (ja) 導電性パターンの形成方法、および透明導電性フィルム
TWI441577B (zh) 元件散熱方法
JP2019194010A (ja) 透明導電膜を有する光学積層体、及びコーティング組成物
JP2015173010A (ja) 透明導電パターンの製造方法及び透明導電性シート
JP5835633B1 (ja) 導電性基材の製造方法
Mun et al. Linewidth Control and the Improved Adhesion of Inkjet‐Printed Ag on Polyimide Substrate, Textured Using Near‐Atmospheric Pressure Plasmas
JP6352085B2 (ja) 膜、及び膜形成方法
KR20160114935A (ko) 투명 전극 패턴의 제조 방법
JP2016018714A (ja) 導電膜

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13865049

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014553187

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13865049

Country of ref document: EP

Kind code of ref document: A1

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载