JP2011070820A - Base material with transparent conductive film, and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a base material with a transparent conductive film capable of lowering haze, while securing conductivity of the transparent conductive film containing metallic nanowires, and to provide a manufacturing method for the base material. <P>SOLUTION: The base material with a transparent conductive film has on the surface of a transparent base material 1 a transparent conductive film 4 formed containing metal nanowires 3 in a matrix resin 2, and the metal nanowires 3 are surface-blackening treated, as well as, the surface resistance value of the transparent conductive film 4 is 1,000 Ω/sq. or less. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a substrate with a transparent conductive film containing metal nanowires and a method for producing the same.

  Transparent conductive films are widely used as transparent electrodes. And in forming such a transparent conductive film that expresses conductivity, in addition to the method of using a transparent and conductive material, the transparent resin contains a conductive substance, and the shape of the conductive substance There is a method in which the transparency is ensured by the orientation and the conductivity is exhibited.

  In general, since a conductive substance has many free electrons that exhibit conductive characteristics, it is often colored by absorption of plasma resonance vibration generated from a visible light wavelength region. For this reason, for example, when a particulate conductive material is contained, transparency is ensured by visible light by reducing the particle size to the nano order. However, when the particle size is reduced, the surface area increases, so that aggregation between particles tends to occur. In order to prevent this, it is necessary to modify the surface with a dispersant, but this dispersant hinders conductivity. In this case, it is possible to increase the conductivity by increasing the addition amount of the conductive substance, but on the contrary, the transparency is lowered, and it becomes difficult to achieve both transparency and conductivity.

  One way to solve this trade-off between transparency and conductivity is to change the shape of the conductive material from particulate to fiber, increase the contact probability of the conductive material, and increase the amount of conductive material blended. There are ways to reduce it. In particular, in recent years, a method of forming a transparent conductive film using a material such as carbon nanofiber or carbon nanotube has been reported. For example, Patent Document 1 has an example using vapor grown carbon fiber. However, since the carbon-based material has a specific resistance of about 50 S / cm, it is difficult to apply it to a transparent electrode that requires a low surface resistance value of 1000 Ω / □ or less.

  As a conventional example that solves this problem, there is a transparent conductive film forming material made of a metal nanowire material as described in Patent Document 2. According to this, high conductivity can be obtained while ensuring transparency.

  However, when the metal nanowire material is used, there is a problem that the haze value of the transparent conductive film is increased by the scattered light of the metal nanowire.

JP 2002-266170 A Special table 2009-505358

  This invention is made | formed in view of said point, and provides the base material with a transparent conductive film which can reduce a haze, ensuring the electroconductivity of the transparent conductive film containing metal nanowire, and its manufacturing method. It is intended.

  The substrate with a transparent conductive film according to the present invention is a substrate with a transparent conductive film provided on the surface of the transparent substrate 1 with a transparent conductive film 4 formed by containing metal nanowires 3 in the matrix resin 2. The metal nanowire 3 has a surface blackened, and the transparent conductive film 4 has a surface resistance value of 1000Ω / □ or less. Thereby, the surface gloss of the metal nanowire 3 can be lowered, and the haze can be lowered while ensuring the conductivity of the transparent conductive film 4.

  Moreover, the manufacturing method of the base material with a transparent conductive film which concerns on this invention apply | coats the resin solution containing the metal nanowire 3 on the surface of the transparent base material 1, and forms the transparent conductive film 4, and the said transparent conductive film 4 and a step of blackening the metal nanowires 3. Accordingly, the metal nanowire 3 can be blackened while securing the contact between the metal nanowires 3 by blackening the metal nanowires 3 after the formation of the transparent conductive film 4 including the metal nanowires 3. The transparent conductive film 4 having a low haze can be formed while ensuring the properties.

  Moreover, in this invention, while using at least one of silver or copper as the metal nanowire 3, it is preferable to perform a sulfidation process as a blackening process. In this case, the conductivity of the transparent conductive film 4 can be increased, and the blackening treatment of the metal nanowire 3 can be easily performed.

  According to the substrate with a transparent conductive film according to the present invention, the surface gloss of the metal nanowire can be reduced by blackening the surface of the metal nanowire, and thereby the conductivity of the transparent conductive film containing the metal nanowire. The haze can be lowered while ensuring.

  In addition, according to the method for manufacturing a substrate with a transparent conductive film according to the present invention, the metal nanowires can be blackened while securing the contact points between the metal nanowires, and thus the low haze transparency while ensuring conductivity. A conductive film can be formed.

(A) (b) is a schematic sectional drawing which shows an example of the blackening process of the metal nanowire which concerns on this invention. It is a schematic sectional drawing which shows the base material with a transparent conductive film containing metal nanowire.

  Embodiments of the present invention will be described below.

  In the present invention, any metal nanowire 3 can be used as long as it can be blackened, and there are no particular limitations on the means for producing the metal nanowire 3, and examples thereof include a liquid phase method and a gas phase. Known means such as a method can be used. There is no restriction | limiting in particular also in a specific manufacturing method, A well-known manufacturing method can be used. For example, as a method for producing Ag nanowires, Adv. Mater. 2002, 14, P833-837, Chem. Mater. 2002, 14, P4736-4745, Patent Document 2 described above, etc., as a method for producing Au nanowires, JP 2006-233252A, etc., as a method for producing Cu nanowires, JP 2002-266007 A, etc. As a method for producing Co nanowires, JP-A No. 2004-148771 can be cited. In particular, the above Adv. Mater. And Chem. Mater. The method for producing Ag nanowires reported in 1 can easily produce Ag nanowires in water and in large quantities, and since the conductivity of silver is the highest among metals, the method of producing metal nanowires 3 used in the present invention It can apply preferably as a manufacturing method.

  In the present invention, the average diameter of the metal nanowire 3 is preferably 200 nm or less from the viewpoint of transparency, and preferably 10 nm or more from the viewpoint of conductivity. It is preferable that the average diameter is 200 nm or less because a decrease in light transmittance can be suppressed. On the other hand, if the average diameter is 10 nm or more, the function as a conductor can be expressed significantly, and a larger average diameter is preferable because conductivity is improved. Therefore, the average diameter is more preferably 20 to 150 nm, and further preferably 40 to 150 nm. The average length of the metal nanowires 3 is preferably 1 μm or more from the viewpoint of conductivity, and preferably 100 μm or less from the viewpoint of the effect on the transparency due to aggregation. More preferably, it is 1-50 micrometers, and it is still more preferable that it is 3-50 micrometers. The average diameter and average length of the metal nanowires 3 can be obtained from the arithmetic average of the measured values of the individual metal nanowires 3 by taking an electron micrograph of a sufficient number of metal nanowires 3 using SEM or TEM. . The length of the metal nanowire 3 should be obtained in a state where the metal nanowire 3 is linearly extended. However, in reality, the length of the metal nanowire 3 is often bent. And the projected area is calculated, assuming a cylindrical body (length = projected area / projected diameter). The number of metal nanowires 3 to be measured is preferably at least 100 or more, and more preferably 300 or more metal nanowires 3 are measured.

  The metal nanowire 3 is used by being dispersed in a resin solution. As a resin component for forming the matrix resin 2 in the resin solution, a matrix is formed by polymerizing by polymerization reaction of monomers and oligomers. Things are used.

  When a resin that undergoes a photopolymerization reaction or a thermal polymerization reaction is used as the matrix resin component, a polymerization reaction is caused by irradiation with ionizing radiation such as visible light, ultraviolet light, or an electron beam, or by the action of an initiator. Monomers or oligomers can be used, and monomers or oligomers having an acrylic group or a methacryl group are preferred. Among them, a polyfunctional binder component is preferable in order to increase the scratch resistance and hardness by crosslinking.

  As one having one functional group in one molecule, specifically, for example, isoamyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxy-diethylene glycol (meta ) Acrylate, methoxy-triethylene glycol (meth) acrylate, methoxy-polyethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate phenoxyethyl (meth) acrylate, phenoxy-polyethylene glycol (meth) ) Acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, -Hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, (meth) acrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxyethyl phthalate Acid, isooctyl (meth) acrylate, isomyristyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, Examples include cyclohexyl methacrylate, benzyl (meth) acrylate, (meth) acryloylmorpholine, and the like.

  As those having two or more functional groups, specifically, for example, polyethylene glycol diacrylate, glycerin triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, diester Examples thereof include pentaerythritol hexaacrylate, alkyl-modified dipentaerythritol hexaacrylate, and the compounds having a benzene ring include ethylene oxide-modified bisphenol A diacrylate, modified bisphenol A diacrylate, ethylene glycol diacrylate, and ethylene oxide propylene oxide-modified bisphenol. A diacrylate, propylene oxide tetramethylene oxide Modified bisphenol A diacrylate, bisphenol A- diepoxy - acrylic acid adduct, ethylene oxide-modified bisphenol F diacrylate, and polyfunctional acrylates or methacrylates such as polyester acrylates.

  1,2-bis (meth) acryloylthioethane, 1,3-bis (meth) acryloylthiopropane, 1,4-bis (meth) acryloylthiobutane, 1,2-bis (meth) acryloylmethylthiobenzene, The use of sulfur-containing (meth) acrylates such as 1,3-bis (meth) acryloylmethylthiobenzene is also effective for increasing the refractive index.

  Further, a light or thermal polymerization initiator may be blended in order to promote curing by ultraviolet rays or heat.

  Although what is generally marketed may be used as a photoinitiator, when it illustrates especially, benzophenone, 2, 2- dimethoxy- 1, 2- diphenyl ethane- 1-one (Ciba Specialty Chemicals Co., Ltd. product " Irgacure 651 "), 1-hydroxy-cyclohexyl-phenyl-ketone (" Irgacure 184 "manufactured by Ciba Specialty Chemicals), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Ciba Specialty Chemicals' “Darocur 1173”, Lamberti's “Esacure KL200”), Oligo (2-hydroxy-2-methyl-1-phenyl-propan-1-one) (Lamberti's “Esacure KIP150” "), 2-hydroxyethyl-phenyl-2-hydride Xyl-2-methyl-1-propan-1-one (“Irgacure 2959” manufactured by Ciba Specialty Chemicals Co., Ltd.), 2-methyl-1 (4- (methylthio) phenyl) -2-morpholinopropane-1 -ON ("Irgacure 907" manufactured by Ciba Specialty Chemicals Co., Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Ciba Specialty Chemicals Co., Ltd. " Irgacure 369 "), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (" Irgacure 819 "manufactured by Ciba Specialty Chemicals Co., Ltd.), bis (2,6-dimethoxybenzoyl) -2,4 , 4-Trimethyl-pentylphosphine oxide (Ciba Specialty Chemical) ("CGI403" manufactured by Co., Ltd.), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (= TMDPO) ("Lucirin TPO" manufactured by BASF AG, "Darocur TPO" manufactured by Ciba Specialty Chemicals Co., Ltd.) Thioxanthone or a derivative thereof, and the like can be used, and one or a mixture of two or more of these can be used.

  Further, a tertiary amine such as triethanolamine, ethyl-4-dimethylaminobenzoate, isopentylmethylaminobenzoate or the like may be added for the purpose of photosensitization.

  As a polymerization initiator by heat, a peroxide such as benzoyl peroxide (= BPO) or an azo compound such as azobisisobutylnitrile (= AIBN) is mainly used.

  In general, the amount of the photopolymerization initiator or the thermal polymerization initiator is preferably about 0.1 to 10 parts by mass with respect to 100 parts by mass of the composition (resin component + metal nanowire 3).

  Moreover, you may use the monomer or oligomer which has cationic polymerizable functional groups, such as an epoxy group, a thioepoxy group, and an oxetanyl group. Further, if necessary, a photocationic initiator or the like can be used in combination. These are likewise preferably polyfunctional.

  Moreover, about resin to thermally polymerize, a sol-gel type material is mentioned generally, Sol-gel type materials, such as alkoxy silane and alkoxy titanium, are preferable. Of these, alkoxysilane is preferred. The sol-gel material forms a polysiloxane structure. Specific examples of the alkoxysilane include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, and methyl. Tributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylto Trialkoxysilanes such as ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Examples include diethyldimethoxysilane and diethyldiethoxysilane. These alkoxysilanes can be used as a partial condensate thereof. Among these, tetraalkoxysilanes or partial condensates thereof are preferable. In particular, tetramethoxysilane, tetraethoxysilane or a partial condensate thereof is preferable.

  Furthermore, a conductive polymer can also be used as the matrix resin component of the resin solution. Examples of the conductive polymer include polyaniline, polypyrrole, polythiophene, polytriphenylamine and the like.

  In addition, as the matrix resin component of the resin solution, two or more kinds selected from the above-described photopolymerizable resin, thermopolymerizable resin, and conductive polymer may be used in combination.

  The compounding amount of the metal nanowires 3 in the resin solution is such that when the transparent conductive film 4 is formed as described later, the metal nanowires 3 are contained in the transparent conductive film 4 in an amount of 0.01 to 90% by mass. It is preferable to adjust and set the compounding quantity with respect to the resin component. As for content of the metal nanowire 3, 0.1-30 mass% is more preferable, More preferably, it is 0.5-10 mass%.

  Here, it is essential that the resin solution contains a solvent for dissolving or dispersing solid components such as resin solids and metal nanowires 3, but the type of the solvent is not particularly limited. For example, alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons; aromatic hydrocarbons such as toluene and xylene Or mixtures thereof can be used. Among these, it is preferable to use a ketone-based organic solvent. When a resin solution is prepared using a ketone-based solvent, it can be easily and uniformly applied to the surface of the transparent substrate 1, and after coating. Since the evaporation rate of the solvent is moderate and it is difficult to cause uneven drying, a transparent conductive film 4 having a uniform area and a large area can be easily obtained. In addition to the above organic solvent, water may be used as the solvent, or an organic solvent and water may be used in combination. The amount of the solvent can uniformly dissolve and disperse each of the above solid components so that the concentration does not cause aggregation during storage after preparing the resin solution and is not too dilute during coating. Adjust as appropriate. Prepare a high-concentration resin solution by reducing the amount of solvent used within the range that satisfies this condition, store it in a state that does not take up the volume, take out the necessary amount at the time of use, and adjust the solvent to a concentration suitable for coating work. It is preferable to dilute with. When the total amount of the solid content and the solvent is 100 parts by mass, the amount of the solvent is preferably set to 50 to 99.9 parts by mass with respect to 0.1 to 50 parts by mass of the total solids, and more preferably By using 70 to 99.5 parts by mass of the solvent with respect to 0.5 to 30 parts by weight of the total solid content, a resin solution that is particularly excellent in dispersion stability and suitable for long-term storage can be obtained. . The combination of the resin and the solvent to be used is not particularly defined, but it is preferable to use a solvent in which the compounded resin is easily dissolved. Further, depending on the transparent substrate 1 to be coated, dissolution may occur depending on the solvent used. Therefore, it is desirable to design an appropriate solvent composition after confirming the solubility in the transparent substrate 1 in advance.

  On the other hand, in the transparent base material 1 used by this invention, there is no restriction | limiting in particular about the shape, a structure, a magnitude | size, etc., It can select suitably according to the objective. Examples of the shape of the transparent substrate 1 include a flat plate shape, a sheet shape, and a film shape, and the structure may be, for example, a single layer structure or a laminated structure, and may be selected as appropriate. be able to. There is no restriction | limiting in particular also about the material of the transparent base material 1, Any of an inorganic material and an organic material can be used suitably. Examples of the inorganic material forming the transparent substrate 1 include glass, quartz, and silicon. Examples of organic materials include acetate resins such as triacetyl cellulose (TAC); polyester resins such as polyethylene terephthalate (PET); polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, and polyimides. Resin, polyolefin resin, acrylic resin, polynorbornene resin, cellulose resin, polyarylate resin, polystyrene resin, polyvinyl alcohol resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyacrylic resin Etc. These may be used individually by 1 type and may use 2 or more types together.

  In the present invention, the transparent substrate 1 may be a single substrate as described above, or may be one in which one or more hard coat layers are formed on the surface of the substrate. . Thus, when the transparent base material 1 is provided with a hard-coat layer, the transparent conductive film 4 is formed on a hard-coat layer.

  The hard coat layer may be formed of a resin obtained by polymerizing a monomer, and particles or the like may be included in the resin. The resin is not particularly limited, but the same resin as the matrix resin 2 forming the transparent conductive film 4 can be used, and the particles have a lower refractive index or higher refractive index than the resin. Those having various functions such as those having a higher hardness than resins, those having higher heat resistance, and the like can be used.

  And the transparent conductive film 4 can be formed like FIG. 2 by apply | coating the resin solution which mix | blended said metal nanowire 3 to the surface of the transparent base material 1, and drying and hardening. In the transparent conductive film 4 formed in this way, the metal nanowires 3 are contained in the matrix resin 2 in an almost uniformly dispersed state as shown in FIG. Is secured. Examples of the resin solution coating method include spin coating, casting, roll coating, flow coating, printing, dip coating, casting film formation, bar coating, and gravure printing. The thickness of the transparent conductive film 4 is not particularly limited and can be appropriately selected depending on the purpose, but is preferably in the range of about 0.01 to 100 μm, more preferably in the range of 0.05 to 10 μm, and further preferably. Is in the range of 0.1 to 3 μm.

  Thus, after forming the transparent conductive film 4 on the surface of the transparent base material 1, the blackening process of the metal nanowire 3 surface is performed. As a metal blackening treatment, it is typical to blacken the metal surface by sulfidation treatment or oxidation treatment, but sulfidation treatment makes it easier to blacken only the surface of the metal nanowire than oxidation treatment and does not impair conduction. It is preferable to perform a sulfidation treatment as a blackening treatment on the surface of the metal nanowire 3 because the reaction can be easily performed. Furthermore, it is more preferable to use at least one of silver or copper as the metal nanowire 3 and perform a sulfidation treatment on the surface of the metal nanowire 3. In this case, the conductivity of the transparent conductive film 4 can be increased, and the surface of the metal nanowire 3 can be easily blackened.

Here, a method of sulfiding treatment in which the surface of the metal nanowire 3 is chemically reacted with a sulfur compound to form a metal sulfide will be described. When performing the sulfidation process of the metal nanowire 3, the sulfur compound to be used is not particularly limited, and examples thereof include H ₂ S. The sulfuration treatment of the metal nanowire 3 using H ₂ S can be performed by spraying H ₂ S gas 5 directly on the surface of the transparent conductive film 4 with an injector 7 or the like as shown in FIG. As shown, the solution 6 in which H ₂ S gas is dissolved can be directly applied to the surface of the transparent conductive film 4 with a squeegee 8 or the like. At this time, since the solution 6 in which the H ₂ S gas 5 or the H ₂ S gas is dissolved easily penetrates into the transparent conductive film 4, the metal nanowire 3 is easily sulfidized. It is preferable to use alkoxysilane. Further, even when an acrylic resin is used as the matrix resin 2, the acrylic resin is formed porous so that the H ₂ S gas 5 or the solution 6 in which the H ₂ S gas is dissolved can easily penetrate into the transparent conductive film 4. be able to. Such porous formation of the acrylic resin can be achieved by adjusting the coating amount of the acrylic resin and the content of the metal nanowire 3 when forming the transparent conductive film 4.

Further, when performed by spraying the sulfurization treatment of the metal nanowires 3 H _{2 S} gas 5, the blowing amount and blowing times of H _{2 S} gas 5 to the transparent conductive film 4 surface, the sulfurization treatment of the metal nanowires 3 H _{In the} case of performing application by applying the solution 6 in which ₂ S gas is dissolved, the amount of H ₂ S gas dissolved in the solution 6, the application amount of the solution, the application time, etc. It adjusts suitably according to content etc. of the metal nanowire 3 of.

  When the above sulfiding treatment is performed, only the surface of the metal nanowire 3 is sulfidized and blackened. And since the surface glossiness of the metal nanowire 3 falls, the haze value of a base material with a transparent conductive film can be made small.

  And after forming the transparent conductive film 4 containing the metal nanowire 3, the metal nanowire 3 can be blackened while securing the contact between the metal nanowires 3 by blackening the surface of the metal nanowire 3. Therefore, the low haze transparent conductive film 4 can be formed while ensuring conductivity.

  The use of the substrate with a transparent conductive film according to the present invention obtained as described above is not particularly limited, but is applicable to organic EL elements, transparent wiring, photoelectric conversion elements, electromagnetic wave shields, touch panels, electronic papers, and the like. Is something that can be done.

  Next, the present invention will be specifically described with reference to examples.

Example 1
27.9 parts by mass of photo-curable acrylic resin (“A-DPH” manufactured by Shin-Nakamura Chemical Co., Ltd.), 12.5 parts by mass of methyl ethyl ketone and 33.3 parts by mass of methyl isobutyl ketone are mixed to dissolve the photo-curable acrylic resin. To prepare a mixture A. Silver nanowires were used as the metal nanowires 3. This silver nanowire was prepared according to a known paper “Materials Chemistry and Physics vol. 114 p333-338“ Preparation of Ag nanorods with high yield by polyol process ””, and has an average diameter of 150 nm and an average length of 5 μm. A mixture B was prepared by dispersing 6.0 parts by mass of the silver nanowires in 20.0 parts by mass of methyl ethyl ketone. After mixing the mixture A and the mixture B well, 0.1 parts by mass of a photopolymerization initiator 1-hydroxy-cyclohexyl-phenyl-ketone (“Irgacure 184” manufactured by Ciba Geigy Co.) was added and mixed well. By stirring and mixing for 1 hour in a constant temperature atmosphere at 0 ° C., a coating material composition comprising a resin solution containing the metal nanowires 3 was obtained.

Then, a transparent PET film (thickness 125 μm, refractive index 1.665) is used as the transparent substrate 1, and the above coating material composition is applied to the surface of the transparent substrate 1 with a wire bar coater # 10, and at 120 ° C. for 2 minutes. The transparent conductive film 4 having a film thickness of 0.2 μm was formed by heating and drying, and further irradiating and curing ultraviolet rays at an intensity of 400 mJ / cm ² .

Thereafter, H ₂ S gas 5 was sprayed on the surface of the transparent conductive film 4 for 1 minute to perform a sulfidation treatment, thereby obtaining a substrate with a transparent conductive film in which the metal nanowires 3 were blackened.

(Example 2)
The metal nanowire 3 was prepared according to a well-known paper “Jornal of Physics: Condensed Matter14 (2002) 355-363“ Electrochemical synthesis of copper nanowires ””, except that a copper nanowire having an average diameter of 60 nm and an average length of 30 μm was used. In the same manner as in Example 1, a substrate with a transparent conductive film in which the metal nanowires 3 were blackened was obtained.

(Comparative Example 1)
First, the same silver nanowire as that of Example 1 was used as the metal nanowire 3, and 6.0 parts by mass of the silver nanowire was dispersed in 20.0 parts by mass of methyl ethyl ketone, and H ₂ S gas 5 was bubbled thereto to form the silver nanowire. A mixture C subjected to the blackening treatment was prepared.

  And the coating material composition which consists of a resin solution containing the metal nanowire 3 is prepared like Example 1 except having used the said mixture C instead of the mixture B, and this is made into the surface of the transparent base material 1. It apply | coated and the base material with a transparent conductive film was obtained.

(Comparative Example 2)
The coating material composition which consists of a resin solution containing the metal nanowire 3 was prepared like Example 1, and this was apply | coated to the surface of the transparent base material 1, and the base material with a transparent conductive film was obtained.

  About the base material with a transparent conductive film of said Examples 1 and 2 and Comparative Examples 1 and 2, haze measurement, total light transmittance measurement, and surface resistance value measurement were performed. The haze value and total light transmittance are measured using a haze meter (“NDH2000” manufactured by Nippon Denshoku Industries Co., Ltd.), and the surface resistance value is measured using a surface resistance meter (“HirestaIP (MCP-HT260, manufactured by Mitsubishi Chemical Corporation). ) "). The results are shown in Table 1.

  As can be seen from Table 1, in the case of Comparative Example 1 in which the transparent conductive film 4 is formed after the metal nanowires 3 are blackened, the haze value can be reduced, but conduction can be obtained. In the case of Comparative Example 2 in which the metal nanowire 3 was not blackened, the haze value was increased.

  On the other hand, in Examples 1 and 2 in which the metal nanowire 3 is blackened after the transparent conductive film 4 is formed, the haze value can be reduced, and the surface resistance value can be reduced while maintaining conductivity. Was confirmed.

DESCRIPTION OF SYMBOLS 1 Transparent base material 2 Matrix resin 3 Metal nanowire 4 Transparent electrically conductive film

Claims (3)

  A substrate with a transparent conductive film provided with a transparent conductive film formed on a surface of a transparent substrate containing metal nanowires in a matrix resin, wherein the metal nanowires are blackened on the surface. The surface resistance value of the said transparent conductive film is 1000 ohms / square or less, The base material with a transparent conductive film characterized by the above-mentioned.   A transparent conductive material comprising: a step of applying a resin solution containing metal nanowires on the surface of a transparent substrate to form a transparent conductive film; and a step of blackening the metal nanowires in the transparent conductive film. The manufacturing method of a base material with a film. The method for producing a substrate with a transparent conductive film according to claim 2, wherein at least one of silver and copper is used as the metal nanowire, and a sulfidation treatment is performed as a blackening treatment.

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