WO2016002090A1 - 導電性基材及び、導電性基材の製造方法 - Google Patents

導電性基材及び、導電性基材の製造方法 Download PDF

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WO2016002090A1
WO2016002090A1 PCT/JP2014/067995 JP2014067995W WO2016002090A1 WO 2016002090 A1 WO2016002090 A1 WO 2016002090A1 JP 2014067995 W JP2014067995 W JP 2014067995W WO 2016002090 A1 WO2016002090 A1 WO 2016002090A1
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layer
conductive
film
transparent conductive
conductive film
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PCT/JP2014/067995
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English (en)
French (fr)
Japanese (ja)
Inventor
淳一 桐山
栄治 柴田
渡部　健
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光村印刷株式会社
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Priority to PCT/JP2014/067995 priority Critical patent/WO2016002090A1/ja
Priority to CN201480079897.XA priority patent/CN106463369B/zh
Priority to JP2014553567A priority patent/JP5835633B1/ja
Priority to TW104120350A priority patent/TWI597175B/zh
Publication of WO2016002090A1 publication Critical patent/WO2016002090A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition

Definitions

  • the present invention is applicable to, for example, an electrode material constituting an apparatus such as a flat panel display, a touch screen, and a solar cell, and is made of a conductive substrate made of a material replacing indium tin oxide (hereinafter referred to as “ITO”).
  • ITO indium tin oxide
  • the present invention relates to a method for producing a conductive substrate and a method for patterning a conductive layer.
  • Transparent conductive films are widely used as electrode materials applied to flat panel displays and touch screens mounted on personal computers, mobile phones, smartphones, etc., or as electrode materials constituting cells such as solar cells.
  • ITO which shows a high transmittance with respect to visible light has been adopted as a material for the transparent conductive film.
  • indium constituting ITO is one of rare metals, its stability is feared from the viewpoint of long-term supply.
  • the ITO film is formed by a sputtering method.
  • the properties of the formed ITO film tend to vary due to the difference in the sputtering method, the atmosphere for growing the film, and the like.
  • an ITO film formed on a flexible base material is susceptible to stress such as bending, and tends to cause functional degradation such as an increase in resistance.
  • a material for a transparent conductive film replacing ITO a carbon material having high electrical conductivity and a high aspect ratio, for example, a nanometer-sized structure such as a carbon nanotube (hereinafter referred to as “CNT”), a carbon nanohorn or the like.
  • CNT carbon nanotube
  • various technical problems remain in order to easily and efficiently pattern a transparent conductive film including a conductive film composed of these carbon materials. For example, when a laser is used for patterning a conductive film containing CNTs, an expensive laser device is required, and it takes time to produce the pattern.
  • Patent Document 1 it has been proposed to use a conductive film remover (etching paste) for patterning of a conductive film containing CNTs.
  • etching paste a conductive film remover
  • Patent Document 2 a conductive film containing CNT on a substrate is arbitrarily coated and infiltrated into a special stripping solution and mechanically or scientifically stirred to select a conductive film containing uncoated CNT.
  • a technique for patterning a conductive film has been proposed.
  • this method cannot be achieved by simply using a solvent such as water and alcohol when stripping CNTs, and it requires a special stripping solution and lacks versatility.
  • Patent Document 3 a method for producing a transparent conductive film formed by combining a conductive layer of conductive fibers containing CNT and a photosensitive resin layer is proposed.
  • the photosensitive resin layer is left on the substrate as a permanent film, special characteristics such as transparency are required for the photosensitive resin layer to be used.
  • the present invention has been proposed in view of the above circumstances, and a nanometer-sized structure portion that can be partially substituted even with an ITO film processing apparatus, can be produced in a short time, and can be obtained by a technique that is not difficult to handle. It aims at providing the manufacturing method of the electroconductive base material containing the electrically conductive film comprised from the conductive fiber which has, and an electroconductive base material.
  • the conductive base material according to the present invention is a hydrophilic layer comprising a support layer to be a substrate, and a film formed on the support layer by coating, the main component of which is a solidified colloidal particle. It is characterized by comprising an intervening layer and a conductive layer made of a film containing conductive fibers formed on the intervening layer by coating and having a nanometer-sized structure. Further, the conductive layer is selectively disposed on the intervening layer.
  • the conductive substrate according to the present invention is formed by coating a hydrophilic intervening layer composed of a film mainly composed of a solidified colloidal particle on a support layer serving as a substrate, and nanometers on the intervening layer.
  • a conductive layer made of a film containing conductive fibers having a metric size structure is formed by coating. Further, after forming the conductive layer, a protective layer for protecting the conductive layer is selectively disposed on the conductive layer by a predetermined treatment on the surface of the conductive layer opposite to the intervening layer, and then in water The conductive layer is separated from the intervening layer except for the conductive layer covered with the protective layer that is selectively disposed by the ultrasonic treatment.
  • the conductive substrate preferably has an overcoat layer. Moreover, it is preferable that the value of the total light transmittance measured after removing the support layer is 80% or more.
  • a hydrophilic intervening layer composed of a film mainly composed of a solidified colloidal particle is formed by coating on a support layer serving as a substrate, and the intervening layer is formed on the intervening layer.
  • a conductive base material is manufactured by forming a conductive layer made of a film containing conductive fibers having a nanometer-sized structure by coating.
  • a protective layer for protecting the conductive layer is selectively disposed on the conductive layer by a predetermined treatment on the surface of the conductive layer opposite to the intervening layer, and then in water
  • the conductive layer is separated from the intervening layer except for the conductive layer covered by the protective layer that is selectively disposed by the ultrasonic treatment.
  • membrane which comprises the said intervening layer is a particle
  • colloidal silica solution with silicon oxide as colloidal particles titanium oxide colloidal solution with metal titanium oxide as colloidal particles, and other metal colloidal solutions with various colloidal particles with hydrophilicity as coagulated products are supported and supported.
  • the intervening layer can be constituted.
  • the dispersion medium in which the colloidal particles are dispersed may be water, alcohol (methanol, ethanol, propanol, etc.), or other solvents (dimethylacetamide, ethylene glycol, ethylene glycol mono n-propyl ether, Propylene glycol monomethyl ether, tetrabutyl alcohol, diethylene glycol monoethyl ether acetate, ethyl acetate, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, etc.).
  • a small amount of a dispersant, a resin, or the like may be included in the colloidal particle dispersion to promote dispersibility and strengthen adhesion to the substrate.
  • the conductive base material according to the present invention includes a support layer to be a substrate, a hydrophilic intervening layer formed on the support layer by coating, and a film composed mainly of a solidified colloidal particle, and the intervening layer. And a conductive layer made of a film containing conductive fibers formed on the top and having a nanometer-sized structure. Therefore, by ultrasonic treatment in water, it is based on the difference between the physical properties of the hydrophilic intervening layer mainly composed of the solidified colloidal particles and the physical properties of the hydrophobic conductive layer made of a film containing conductive fibers. Thus, the conductive layer can be detached from the intervening layer.
  • the conductive layer is selectively disposed from the intervening layer by ultrasonic treatment in water.
  • the conductive layer covered with can be removed except for the conductive layer. Therefore, the conductive layer can be selectively separated from the intervening layer, that is, the conductive layer can be patterned.
  • the protective layer is not necessarily left as a permanent film on the substrate, it is not necessary that the protective layer is transparent, and an inexpensive material can be used, and provided as a versatile conductive base material. be able to.
  • a special apparatus such as a laser is not required for patterning the conductive layer in the present invention. Moreover, this patterning is achieved in a short time.
  • the conductive substrate according to the present invention has an overcoat layer, in addition to strengthening the adhesion between the intervening layer and the conductive layer, the conductive substrate as a whole is protected and durable. Effects such as imparting light, improving light transmittance, and reducing pattern bone appearance. Further, in the conductive substrate according to the present invention, if the total light transmittance value measured after removing the support layer is 80% or more, a flat panel display or touch screen can be used as a transparent electrode material. It can be applied to devices such as solar cells. Then, an electrode can be comprised with the material (this invention) which replaces an ITO film
  • FIG. 1A is a schematic view showing an example of the configuration of a conductive substrate according to the present invention.
  • (B) is the schematic which shows another example of a structure of the electroconductive base material which concerns on this invention.
  • FIG. 2 is a schematic view of carbon nanotubes exemplified as the material of the film constituting the conductive layer in the conductive substrate according to the present invention.
  • FIG. 3 is an explanatory diagram for explaining the conductive substrate manufacturing method (from the intervening layer forming step to the ultrasonic treatment step) according to the first embodiment with a schematic diagram of the conductive substrate.
  • FIG. 4 is an explanatory diagram for explaining the manufacturing method (after the resist stripping step) of the conductive substrate in the first embodiment with a schematic diagram of the conductive substrate.
  • FIG. 5 is an explanatory diagram for explaining the manufacturing method of the conductive substrate according to the second embodiment in a flow with a schematic view of the conductive substrate.
  • the conductive substrate according to the present invention is configured by laminating at least an intervening layer and a conductive layer on a support layer as a substrate.
  • the present invention can be used, for example, as a transparent conductive film, as an electrode material for devices such as flat panel displays, touch screens, and solar cells.
  • the conductive substrate is defined as “transparent”.
  • the total light transmittance may be measured in accordance with JIS K 7136, JIS K 7361, etc.
  • a transparent conductive film 1a according to the present invention is formed on a support layer 2 by coating, and as a colloidal particle, for example, from a film containing, as a main component, a colloidal silica coagulum.
  • the hydrophilic intervening layer 3 is provided.
  • the transparent conductive film 1a includes an overcoat layer 5 that encloses and protects the intervening layer 3 and the conductive layer 4 on the support layer 2.
  • another transparent conductive film 1b which concerns on this invention is formed by the application
  • the intervening layer 3 and a hydrophobic conductive layer 4 made of a film including single-walled CNTs are provided, and a photocurable resist layer 6 is provided on the conductive layer 4.
  • the photocurable resist layer 6 serves as an overcoat that covers and protects the intervening layer 3 and the conductive layer 4 on the support layer 2.
  • Examples of the material of the photocurable resist layer 6 include various known materials such as a photocurable resist that is cured by ultraviolet rays or heat.
  • the support layer 2 functions as a substrate for the transparent conductive films 1a and 1b.
  • Examples of the material of the support layer 2 include a polyethylene terephthalate (hereinafter referred to as “PET”) film excellent in heat resistance, solvent resistance, and transparency.
  • PET polyethylene terephthalate
  • polyesters such as a polyethylene film and a polypropylene film
  • polycarbonates such as a polycarbonate film, polyethylene naphthalate, a triacetyl cellulose, and cyclic olefin resin
  • thermoplastic resins such as polymethyl methacrylate and polyvinyl chloride, polyparaphenylene sulfide, polyamide resin, polyimide resin, polyacrylic resin, urethane resin, alkyd resin, phenol resin, epoxy resin, silicone resin, ABS resin, etc. You can also.
  • various kinds of glass such as raw glass and quartz may be used.
  • an easy adhesion treatment is performed on the surface of the support layer 2, particularly on the surface on which the colloidal silica that is the main component of the intervening layer 3 is applied. This is because it is advantageous for bringing the intervening layer 3 into close contact with the support layer 2.
  • the easy adhesion treatment to the surface of the support layer 2 can be achieved by various known treatment methods such as physical treatment and chemical treatment.
  • the intervening layer 3 is composed of a film whose surface is mainly composed of a colloidal silica coagulum.
  • a hydrophilic intermediate layer 3 can be obtained as a film in which colloidal silica is agglomerated or solidified by applying a silicon oxide-based hydrophilic treatment agent on the support layer 2, for example, bar-coating and heating and drying this. it can.
  • the intervening layer 3 is made of, for example, a film composed mainly of a coagulated product of titanium oxide colloid as colloidal particles, instead of a film composed mainly of a coagulated product of colloidal silica.
  • a titanium oxide colloidal solution in which metal titanium oxide is dispersed is applied onto the support layer 2, and this is heated and dried to form an intervening layer composed of a film mainly composed of a solidified titanium colloid. can do.
  • colloidal particles constituting the intervening layer various metal colloids can be used in addition to colloidal silica and metal titanium oxide.
  • a material for the intervening layer any material can be employed as long as it is a component that exhibits hydrophilicity in water subjected to ultrasonic treatment.
  • the dispersion medium in which the colloidal particles are dispersed may be water, alcohol (methanol, ethanol, propanol, etc.), and other solvents (dimethylacetamide, ethylene glycol, ethylene glycol mono n-propyl ether).
  • the conductive layer 4 is made of a film that includes conductive fibers having a nanometer-sized structure. In the transparent conductive films 1a and 1b, the conductive layer 4 is composed of a film containing single-walled CNTs.
  • the conductive layer 4 can be obtained by applying an aqueous dispersion of single-walled carbon nanotubes on the intervening layer 3, for example, bar-coating and heating and drying it.
  • the carbon nanotube 41 is a carbon material in which a structure portion 41 a having a nanometer-sized six-membered ring structure is repeated to form a tube-like or cylindrical structure as a whole.
  • the carbon nanotube 41 serving as a film material for forming the conductive layer 4 may be a single layer or a multilayer.
  • various conductive nanowires, especially metal nanowires, such as silver nanowires can be used as the conductive fiber material with a structural unit of nanometer size. It can also be used.
  • the overcoat layer 5 functions as a layer that protects the conductive layer 4 constituting the transparent conductive film 1a from external stress or the like. Moreover, the overcoat layer 5 can give effects, such as improvement of adhesiveness, provision of durability, improvement of light transmittance, and reduction of bone appearance of the pattern, to the transparent conductive film 1a.
  • the material for the overcoat layer 5 examples include polyvinyl alcohol having excellent heat resistance, solubility resistance, and transparency. Further, other transparent thermoplastic resins, polyamide resins, polyimide resins, polyacrylic resins, urethane resins, alkyd resins, phenol resins, epoxy resins, silicone resins, and ABS resins can be employed. As described above, in the transparent conductive film 1b shown in FIG. 1 (b), the photocurable resist layer 6 wraps the intervening layer 3 and the conductive layer 4 on the support layer 2 and protects them. As a role. Hereafter, the outline is demonstrated regarding the manufacturing method of the electroconductive base material which concerns on this invention. (First embodiment) ⁇ Intervening layer forming step S11> As shown in FIG.
  • a silicon oxide-based hydrophilic treatment agent is applied to the surface of the support layer 2 that has been subjected to the easy adhesion treatment. This is dried at about room temperature to about 100 ° C. for about 5 seconds to about 10 minutes, and a hydrophilic intervening layer 3 made of a film containing, for example, a colloidal silica coagulum as a main component is formed on the support layer 2.
  • a hydrophilic intervening layer 3 made of a film containing, for example, a colloidal silica coagulum as a main component is formed on the support layer 2.
  • ⁇ Conductive layer forming step S12> A monolayer CNT aqueous dispersion is applied onto the intervening layer 3. This is dried at room temperature to 100 ° C.
  • a conductive layer 4 made of a film containing single-walled CNTs as conductive fibers having nanometer-sized structures on the intervening layer 3. . Then, it is immersed for about 5 seconds to 10 minutes in an acidic aqueous solution at room temperature to 60 ° C. for about 5 seconds to 10 minutes to remove impurities of the single-layer CNT film of the conductive layer 4 and perform doping to obtain a low-resistance transparent conductive film 1a.
  • the acid for doping nitric acid is suitable, and a mixed acid containing nitric acid is preferred.
  • ⁇ Light decay type resist layer forming step S13> Next, on the surface of the conductive layer 4 of the transparent conductive film 1a subjected to the acid treatment on the side opposite to the intervening layer 3, a photo-disintegrating resist layer 8 is formed in a thin film by a spin coater or a slit coater. . ⁇ Light decay type resist layer exposure step S14> The photoconductive resist layer 8 is exposed to ultraviolet light by using the mask 9 on which the pattern is formed on the transparent conductive film 1a on which the photoconductive resist layer 8 is formed.
  • ⁇ Photodisintegration type resist layer selective arrangement step S15> The transparent conductive film 1a on which the light-disintegrating resist layer 8 has been exposed is developed with a developer, and a pattern is drawn on the light-disintegrating resist layer 8 on the conductive layer 4. That is, the photodegradable resist layer 8 exposed without being shielded by the mask 9 is removed by development, whereby the photodegradable resist layer 8 as a protective layer is selectively disposed on the conductive layer 4.
  • the intervening layer is formed from a film containing a colloidal silica solid as a main component and an alkaline developer is used for development
  • the time is controlled, It is necessary to finish development before colloidal silica is transformed into a gel-like substance by the alkali silica reaction (ASR).
  • ASR alkali silica reaction
  • ⁇ Ultrasonic treatment step S16> By selectively disposing the photo-disintegrating resist layer 8, the transparent conductive film 1a having a pattern drawn on the photo-disintegrating resist layer 8 is submerged in water and 20K in warm water of 25 ° C. or higher (preferably 35 ° C. or higher). Perform ultrasonic treatment at about 1 MHz for 5 seconds to 30 minutes. As a result, a region of the conductive layer 4 that is not covered with the photo-disintegrating resist layer 8 is separated from the intervening layer 3. Specifically, water enters the region of the conductive layer 4 that is not covered by the photo-disintegrating resist layer 8 and part of the water reaches the intervening layer 3.
  • the conductive layer 4 that is not covered with the photo-disintegrating resist layer 8 is detached from the intervening layer 3 made of a colloidal silica coagulum. As a result, the conductive layer 4 is selectively removed from the intervening layer 3. That is, a pattern is formed in the conductive layer 4 (we call this “ultrasonic etching”).
  • ⁇ Resist stripping step S17> Thereafter, as shown in FIG. 4, the photo-disintegrating resist layer 8 remaining on the conductive layer 4 is removed by an appropriate means such as a resist stripping solution. In addition, it is desirable to perform a process such as additional exposure on the photo-disintegrating resist layer 8 before peeling with the resist stripping solution.
  • ⁇ Post-processing step S18> Furthermore, it is immersed in an acidic solution and washed, and the single layer CNT of the conductive layer 4 is doped to obtain a low resistance transparent conductive film 1a.
  • Nitric acid is suitable for the doping acid, and a mixed acid containing nitric acid is preferred.
  • ⁇ Overcoat layer forming step S19> After obtaining the low-resistance transparent conductive film 1a, finally, the entire surface of the transparent conductive film 1a is covered with the overcoat agent by applying the overcoat agent, and dried to form the overcoat layer 5 To do.
  • the influence of the overcoat agent on the resistance of the transparent conductive film 1a is slight.
  • the intervening layer forming step S21 and the conductive layer forming step S22 are performed to obtain the transparent conductive film 1b.
  • the photo-curable resist layer forming step S23, the photo-curable resist layer exposing step S24, and the photo-curable resist layer selection are selected.
  • Arrangement process S25 is performed.
  • the ultrasonic treatment step S26 of the second embodiment can be performed by the same method as the ultrasonic treatment step S16 of the first embodiment.
  • a pattern is formed on the conductive layer 4 of the transparent conductive film 1b (ultrasonic etching).
  • the second embodiment does not require a step after the ultrasonic treatment step S26.
  • the photocurable resist layer 6 serves as an overcoat layer and functions as a layer that protects the conductive layer 4 from external stresses and the like. Therefore, the photocurable resist layer 6 is not removed with a resist stripping solution or the like.
  • the example using the photo collapse type photoresist 8 and the photocurable photoresist 6 was demonstrated.
  • screen printing resists that are patterned using screen printing, plating resists that are used for partial protection during plating, solder resists that are applied to parts that are not soldered on the substrate, and solder bridges that prevent solder bridges, dry film resists, etc.
  • a frequency in the range of 18 K to 1 MHz may be given, and a preferable frequency range is 20 K to 75 KHz, more preferably. Is 20 K to 40 KHz.
  • a frequency in the range exceeding 75 KHz it is possible to implement even at a frequency in the range exceeding 75 KHz, but there is a possibility that the processing time becomes long for the reliable formation of a fine pattern, resulting in inefficiency. Further, from the viewpoint of such efficiency, it is preferable that the processing time be completed within 30 minutes, particularly within 15 minutes.
  • the water temperature may be in a liquid state of 0 to 100 ° C., and a preferable water temperature range is 20 to 75 ° C., more preferably about 30 to 50 ° C.
  • the water temperature is preferably a temperature at which water bubbles do not occur, for example, a temperature lower than about 75 ° C., so that the conductive layer 4 is removed from the intervening layer 3 even though the water temperature is high.
  • a water temperature lower than 30 ° C. there is a possibility that the processing time becomes long for the reliable formation of a fine pattern, resulting in inefficiency.
  • pure water, city water (tap water), or water mixed with a solvent such as acid, alkali, isopropyl alcohol and the like can be used.
  • Example 1 An organic solvent-dispersed silica sol (“IPA-ST” manufactured by Nissan Chemical Industries, Ltd.) is bar coated on the surface of the PET film (Cosmo Shine (registered trademark) “A4100” manufactured by Toyobo Co., Ltd.) that has been subjected to easy adhesion treatment. By drying at 80 ° C. for 5 minutes, a hydrophilic colloidal silica coagulated layer was formed on the PET film.
  • IPA-ST organic solvent-dispersed silica sol
  • PET film Cosmo Shine (registered trademark) “A4100” manufactured by Toyobo Co., Ltd.
  • a single-walled carbon nanotube aqueous dispersion (“Water Solution Gen2.2” manufactured by KH Chemical Co.) is bar-coated on the colloidal silica coagulated layer, and dried at 80 ° C. for 5 minutes, whereby a single-walled carbon nanotube is obtained.
  • a transparent conductive film containing nanotubes was formed to form the transparent conductive film of Example 1.
  • the transparent conductive film was immersed in an aqueous nitric acid solution at 25 ° C. for 5 minutes to remove impurities such as a dispersant, and acid treatment was performed to make the carbon nanotubes of the transparent conductive film low in resistance by doping with acid.
  • L / S line width / line space
  • TMAH tetramethylammonium hydroxide
  • the transparent conductive film of Example 1 on which the fine pattern of the photo-disintegrating photoresist was formed was subjected to ultrasonic treatment for 10 minutes in water at 40 to 50 ° C. at a frequency of 40 KHz.
  • the transparent conductive film layer not protected by the photo-disintegrating photoresist is peeled off from the colloidal silica solidified layer, and the transparent conductive film layer is selectively removed, that is, a fine pattern is formed on the transparent conductive film layer.
  • the photodegradable photoresist on the transparent conductive film layer was irradiated with ultraviolet light and immersed in a TMAH-based stripping solution to remove the photodegradable photoresist.
  • the transparent conductive film by which the fine pattern was formed in the transparent conductive film containing the single-walled carbon nanotube on PET film was able to be comprised. Then, if the transparent conductive film with a fine pattern formed on the transparent conductive film is immersed again in an aqueous nitric acid solution, the contaminants are washed and removed, and at the same time, the single-walled carbon nanotubes are doped with nitric acid. It becomes possible to reliably obtain a low-resistance transparent conductive film. Moreover, since contaminants are washed away, advantageous effects such as being able to be handled as a washing step can be obtained when shifting to the subsequent steps using the transparent conductive film of Example 1.
  • the transparent conductive film of Example 1 having a fine pattern formed on the transparent conductive film is bar-coated with an overcoat agent (“Over Coat Solution” manufactured by KH Chemical) over the entire surface and dried.
  • An overcoat layer was formed.
  • this overcoat layer it is possible to add advantages such as protection of the transparent conductive film, imparting durability, improvement in transmittance, reduction in reflectance, and reduction in pattern bone appearance.
  • the change of the resistance value of the transparent conductive film of Example 1 affected by the overcoat layer is slight.
  • Example 2 In the same manner as in Example 1, a PET film (Cosmo Shine (registered trademark) “A4100” manufactured by Toyobo Co., Ltd.) and an organic solvent-dispersed silica sol (“IPA-ST” manufactured by Nissan Chemical Industries, Ltd.) were bar coated.
  • the transparent conductive film of Example 2 was composed of a single-walled carbon nanotube aqueous dispersion (“Water Solution Gen 2.2” manufactured by KH Chemical Co.). Furthermore, the transparent conductive film of Example 2 was immersed in an aqueous nitric acid solution at 25 ° C. for 5 minutes to remove impurities such as a dispersant, and the carbon nanotubes of the transparent conductive film were doped with acid to make the resistance low.
  • the transparent conductive film of Example 2 on which the fine pattern of the photocurable photoresist was formed was subjected to ultrasonic treatment at a frequency of 40 KHz in water at 40 to 50 ° C. for 10 minutes.
  • the transparent conductive film layer not protected by the photo-curable photoresist is peeled off from the hydrophilic colloidal silica coagulated layer, and the transparent conductive film layer is selectively removed, that is, a single layer in the transparent conductive film.
  • a fine pattern could be formed on the transparent conductive film layer containing carbon nanotubes.
  • An organic solvent-dispersed silica sol (“IPA-ST” manufactured by Nissan Chemical Industries, Ltd.) is bar-coated on the base glass (manufactured by Nippon Sheet Glass Co., Ltd.) and dried at 80 ° C. for 5 minutes to make the glass hydrophilic. A colloidal silica coagulated layer was formed.
  • a single-walled carbon nanotube aqueous dispersion (“Water Solution Gen2.2” manufactured by KH Chemical Co.) is bar-coated on the colloidal silica coagulated layer, and dried at 80 ° C. for 5 minutes, whereby a single-walled carbon nanotube is obtained.
  • a transparent conductive film containing nanotubes was formed to constitute the transparent conductive glass substrate of Example 3. Further, the transparent conductive glass substrate of Example 3 was immersed in an aqueous nitric acid solution at 25 ° C. for 5 minutes to remove impurities such as a dispersant, and acid treatment was performed to make the transparent conductive film layer have a low resistance.
  • the transparent conductive glass substrate of Example 3 on which a fine pattern of a photocurable photoresist was formed was subjected to ultrasonic treatment for 10 minutes in water at 40 to 50 ° C. at a frequency of 40 KHz.
  • Example 4 a titanium oxide dispersion for forming a titanium oxide colloid used as an intervening layer is first prepared.
  • tetrabutyl alcohol and diethylene glycol monoethyl ether acetate were mixed at a ratio of 1: 2, and stirred to prepare a dispersion medium of a titanium oxide dispersion.
  • 2 grams of powdered titanium oxide (TiO 2 ) 10 grams of the prepared dispersion medium, 0.2 grams of acetylacetone, and 0.1 gram of a 1% aqueous solution of Triton X-100 (registered trademark) were mixed together. The mixture was sealed together with beads and stirred with a disperser to obtain a titanium oxide dispersion.
  • the surface of the PET film (Cosmo Shine (registered trademark) “A4100” manufactured by Toyobo Co., Ltd.) subjected to the easy adhesion treatment is bar-coated with the produced titanium oxide dispersion and dried at 120 ° C. for 60 minutes.
  • a titanium oxide colloid coagulated layer was formed on the PET film.
  • a single-walled carbon nanotube aqueous dispersion (“Water Solution Gen2.2” manufactured by KH Chemical Co., Ltd.) is bar-coated and dried at 80 ° C. for 5 minutes.
  • a transparent conductive film containing carbon nanotubes was formed to form the transparent conductive film of Example 4.
  • the transparent conductive film of Example 4 on which the fine pattern of the photo-disintegrating photoresist was formed was subjected to ultrasonic treatment at a frequency of 40 KHz in water at 40 to 50 ° C. for 10 minutes.
  • the transparent conductive film layer not protected by the photo-disintegrating photoresist is peeled off from the colloidal silica solidified layer, and the transparent conductive film layer is selectively removed, that is, a fine pattern is formed on the transparent conductive film layer.
  • unnecessary light-disintegrating photoresist is removed from the transparent conductive film of Example 4, and it is immersed again in an aqueous nitric acid solution. A membrane was obtained.
  • an overcoat agent (“Over Coat Solution” manufactured by KH Chemical Co.) was bar-coated on the entire surface and dried to form an overcoat layer.
  • An overcoat agent (“Over Coat Solution” manufactured by KH Chemical Co.) was bar-coated on the entire surface and dried to form an overcoat layer.
  • the surface of the PET film (Cosmo Shine (registered trademark) “A4100” manufactured by Toyobo Co., Ltd.) subjected to the easy adhesion treatment was wiped with ethanol and washed.
  • a single-walled carbon nanotube aqueous dispersion (“Water Solution Gen2.2” manufactured by KH Chemical Co.) is bar-coated on this PET film and dried at 80 ° C. for 5 minutes to contain the single-walled carbon nanotube on the PET film.
  • a transparent conductive film was formed to constitute the transparent conductive film of Comparative Example 1.
  • a photo-disintegrating photoresist manufactured by Rohm and Haas Electronic Materials Co., Ltd.
  • the transparent conductive film of Comparative Example 1 on which a fine pattern of a photo-disintegrating photoresist was formed was subjected to ultrasonic treatment at a frequency of 40 KHz for 30 minutes in warm water at 40 to 50 ° C.
  • the transparent conductive film layer that was not protected by the photo-disintegrating photoresist was not peeled off from the PET film surface, and in the transparent conductive film of Comparative Example 1, a fine pattern could not be formed on the transparent conductive film layer.
  • the PET film (Cosmo Shine (registered trademark) “A4100” manufactured by Toyobo Co., Ltd.) was coated with liquid titanium tetraisopropoxide (TTIP), which is not a colloidal solution, and dried. A thin film of a hydrophilic titanium compound whose surface was not particulate was formed. A single-walled carbon nanotube aqueous dispersion (“Water Solution Gen2.2” manufactured by KH Chemical Co.) is bar-coated on the hydrophilic titanium compound thin film to form a transparent conductive film containing single-walled carbon nanotubes. A transparent conductive film was constructed.
  • TTIP liquid titanium tetraisopropoxide
  • a photo-disintegrating photoresist manufactured by Rohm and Haas Electronic Materials Co., Ltd.
  • the transparent conductive film of Comparative Example 2 on which a fine pattern of a photo-disintegrating photoresist was formed was subjected to ultrasonic treatment at a frequency of 40 KHz in water at 40 to 50 ° C. for 30 minutes.
  • unevenness occurred in how the transparent conductive film layer not protected by the photo-disintegrating photoresist was peeled from the hydrophilic titanium compound thin film.
  • Tetramethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.
  • the PET film Cosmo Shine (registered trademark) “A4100” manufactured by Toyobo Co., Ltd.
  • a dry film in which the surface of tetramethoxysilane was not particulate was formed on a PET film.
  • a single-walled carbon nanotube aqueous dispersion (“Water Solution Gen2.2” manufactured by KH Chemical Co., Ltd.) is bar-coated on the dried film of tetramethoxysilane to form a transparent conductive film containing single-walled carbon nanotubes.
  • Comparative Example 3 A transparent conductive film was constructed. The transparent conductive film of Comparative Example 3 was immersed in an aqueous nitric acid solution at 25 ° C. for 5 minutes, and acid treatment was performed to make the transparent conductive film have a low resistance.
  • the transparent conductive film of Comparative Example 3 on which a fine pattern of a photo-disintegrating photoresist was formed was subjected to ultrasonic treatment at a frequency of 40 KHz in water at 40 to 50 ° C. for 30 minutes.
  • the transparent conductive film layer not protected by the photo-disintegrating photoresist does not peel off from the dried film of tetramethoxysilane, and a fine pattern can be formed on the transparent conductive film layer in the transparent conductive film of Comparative Example 3. could not. From the examples and comparative examples described above, the following is suggested. That is, based on Examples 1 to 4 and Comparative Example 1, when a transparent conductive film is provided with a conductive layer made of conductive fibers such as single-walled CNTs, it is between the support layer and the conductive layer. It will be appreciated that it is necessary to provide an intervening layer.
  • the intervening layer is merely a hydrophilic film, and the intervening layer needs to be composed of a film containing colloidal particles as a main component.
  • the hydrophilic surface (hydrophilic group) on the intervening layer is made of hydrophobic conductive fibers (for example, single-walled CNT) applied on the intervening layer, once it becomes non-hydrophilic in the process of drying the applied dispersion.
  • the conductive layer can be brought into close contact with van der Waals force.
  • the hydrophilic surface on the intervening layer is soaked in water that it becomes hydrophilic, and the adhesion to hydrophobic conductive fibers in water is weakened.
  • the electroconductive layer which consists of hydrophobic electroconductive fiber will detach
  • the hydrophilic surface on the intervening layer has a greater surface area, and the effect of adhesion and peeling with the conductive layer made of hydrophobic conductive fibers is more pronounced. That is, it is optimal that the hydrophilic surface on the intervening layer is formed of a solidified body of colloidal particles having a large surface area. Note that water is immersed in the colloidal particles of the intervening layer because the conductive fibers including single-walled CNTs are fibrous and have a large number of openings. It is understood that it is preferable to adopt.
  • the conductive base material according to the present invention can selectively separate the conductive layer from the intervening layer by ultrasonic treatment in water, that is, the conductive layer can be patterned.
  • the transparent conductive film 1a the photodisintegrating resist layer 8 as a protective layer is not left as a permanent film on the substrate, so that it is not necessary for the protective layer to be transparent, and an inexpensive material can be adopted. And can be provided as a versatile conductive substrate. Further, no special device such as a laser is required for patterning the conductive layer. Moreover, this patterning is achieved in a short time. Furthermore, since a harsh environment such as a strong acid or high temperature is not required, the handling is relatively easy.
  • the hydrophilic surface on the intervening layer is formed of a solidified colloidal particle, so that the conductive layer is selectively separated from the intervening layer by ultrasonic treatment in water, and the conductive layer is patterned.
  • a hydrophilic surface be formed on the intervening layer during ultrasonic treatment in water.
  • a colloidal particle constituting the main component of the intervening layer a colloid of titanium oxide that exhibits hydrophilicity by light irradiation. Etc. can also be used suitably.
  • the conductive layer can be a fibrous material exhibiting conductivity, and the support layer can be made of various known materials such as plastic or glass.

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  • Engineering & Computer Science (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Non-Insulated Conductors (AREA)
  • Manufacturing Of Electric Cables (AREA)
  • Laminated Bodies (AREA)
  • Electrodes Of Semiconductors (AREA)
PCT/JP2014/067995 2014-06-30 2014-06-30 導電性基材及び、導電性基材の製造方法 WO2016002090A1 (ja)

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CN201480079897.XA CN106463369B (zh) 2014-06-30 2014-06-30 导电性基体材料以及导电性基体材料的制造方法
JP2014553567A JP5835633B1 (ja) 2014-06-30 2014-06-30 導電性基材の製造方法
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