JP5507898B2 - Production method of transparent conductive pattern and substrate with transparent conductive pattern - Google Patents

Description

  The present invention relates to a method for producing a transparent conductive pattern and a substrate with a transparent conductive pattern.

  Transparent conductive films are widely used in fields that have recently been remarkably developed such as liquid crystal displays, PDPs, and touch panels, and can be widely applied to next-generation devices such as organic EL and solar cells. In applying a transparent conductive film to these devices, it is usually required to form a conductive pattern with a fine pattern in the transparent conductive film.

  In forming a conductive pattern on a transparent conductive film, a wet etching method is usually used for a transparent conductive film made of a metal oxide material such as ITO, which has been conventionally used (see Patent Documents 1 to 3). ). In recent years, a transparent conductive film using nanowires has been proposed. In this case as well, a conductive pattern is similarly formed by a wet etching method (see Patent Document 4).

JP 2000-67662 A JP 2003-57673 A Japanese Patent No. 3393470 Special table 2009-505358

  The method of forming a conductive pattern by the above-described wet etching method is a method that has been industrially established conventionally, and is performed in a process as shown in FIG. That is, using a transparent conductive film 2 formed on the surface of the transparent substrate 1 as shown in FIG. 2A, first, a resist 11 is applied to the surface of the transparent conductive film 2 as shown in FIG. Next, as shown in FIG. 2C, the mask 13 provided with the translucent part 12 is overlaid on the surface of the resist 11, and exposure is performed to cure the part of the resist 11 corresponding to the translucent part 12 by irradiating ultraviolet rays UV. Then, as shown in FIG. 2D, development for dissolving and removing the uncured portion of the resist 11 is performed. Next, by processing with an etching solution, as shown in FIG. 2E, the transparent conductive film 2 covered with the resist 11 is left, and the transparent conductive film 2 in other portions is removed by etching. By dissolving and removing the resist 11, a conductive pattern in which the transparent conductive film 2 as shown in FIG. 2 (f) is laminated on the surface of the transparent substrate 1 in a pattern shape can be formed.

  As described above, the wet etching method starts from the application of a resist material, and includes various processes such as masking, exposure, development, etching, and removal of the resist material, and is a costly and time consuming method. In addition, since residues are generated during etching, it is necessary to prepare peripheral facilities such as a recovery facility from the viewpoint of environmental load, and there is also a problem that productivity is low due to a slow etching rate.

  Furthermore, in the wet etching method, a conductive pattern is formed by leaving the transparent conductive film in a pattern shape on the surface of the transparent base material, so that the transparent conductive film remains as a portion from which the transparent conductive film has been removed and the conductive pattern. The transmittance difference and the refractive index difference become large between the portions. For this reason, there has been a commercial problem that a conductive pattern requiring transparency can be visually recognized by a difference in transmittance and a difference in refractive index.

  The present invention has been made in view of the above points, and provides a method for producing a transparent conductive pattern capable of forming a conductive pattern with low pattern recognition by a simple method without using a wet etching method. It is intended.

In the method for producing a transparent conductive pattern according to the present invention, the metal nanofiller is contained in a transparent conductive film in which a metal nanofiller is contained by applying a resin solution containing a metal nanofiller to the surface of a transparent substrate. A step of forming with holes through which oxygen radicals can enter, a step of placing a mask having a patterned opening on the surface of the transparent conductive film, and a plasma treatment from the opposite side of the mask to the transparent conductive film Alternatively, a corona treatment is performed to generate oxygen radicals, and the generated oxygen radicals penetrate into the holes to oxidize the metal nanofiller in the transparent conductive film corresponding to the openings of the mask to oxidize. Forming a non-conductive portion in the transparent conductive film with the formed metal nanofiller and forming a conductive portion with the non-oxidized metal nanofiller. The one in which the features.

  According to the present invention, the oxidized metal nanofiller is oxidized by oxidizing the metal nanofiller in the transparent conductive film corresponding to the opening of the mask by plasma treatment or corona treatment to increase the electrical resistance value. A non-conductive portion can be formed in the transparent conductive film, and a conductive portion can be formed with an unoxidized metal nanofiller, and a conductive pattern can be formed in the transparent conductive film with this conductive portion. In addition, a conductive pattern can be formed on the transparent conductive film by simple methods such as masking and plasma or corona treatment without using a wet etching method. And since the conductive part that becomes the conductive pattern and the non-conductive part other than the conductive pattern are formed on the same film surface of the transparent conductive film, the difference in transmittance and refractive index can be reduced, and the pattern recognition of the conductive pattern The property can be lowered.

  In the present invention, the metal nanofiller is a metal nanowire.

  Since the metal nanowire has a large aspect ratio, a highly conductive conductive pattern can be formed.

  Moreover, the base material with a transparent conductive pattern which concerns on this invention comprises the transparent conductive film by which the conduction | electrical_connection part and the non-conduction part were patterned by the same film surface manufactured by said method on the surface of a transparent base material. It is characterized by.

  According to this invention, since the conductive portion that becomes the conductive pattern and the non-conductive portion other than the conductive pattern are formed on the same film surface of the transparent conductive film, the transmittance difference and the refractive index difference can be reduced, The pattern recognizability of the conductive pattern can be lowered.

Moreover, the base material with a transparent conductive pattern which concerns on this invention provides the transparent conductive film containing a metal nanofiller on the surface of a transparent base material, and oxidizes the metal nanofiller contained in the one part part of a transparent conductive film. to form the non-conductive portion, Ri formed by forming a conductive portion in the metal nanofiller unoxidized other parts of the transparent conductive film, the holes can oxygen radicals penetrate the portion where the metal nano filler is contained And the oxidation of the metal nanofiller is caused by oxygen radicals generated by plasma treatment or corona treatment entering the pores .

  According to this invention, since the conductive portion that becomes the conductive pattern and the non-conductive portion other than the conductive pattern are formed on the same film surface of the transparent conductive film, the transmittance difference and the refractive index difference can be reduced, The pattern recognizability of the conductive pattern can be lowered.

  According to the present invention, the oxidized metal nanofiller is oxidized by oxidizing the metal nanofiller in the transparent conductive film in the portion corresponding to the opening of the mask by plasma treatment or corona treatment to increase the electrical resistance value. A non-conductive portion can be formed in the transparent conductive film, and a conductive portion can be formed with an unoxidized metal nanofiller, and a conductive pattern can be formed in the transparent conductive film with this conductive portion. In addition, a conductive pattern can be formed on the transparent conductive film by simple methods such as masking and plasma or corona treatment without using a wet etching method. And since the conductive part that becomes the conductive pattern and the non-conductive part other than the conductive pattern are formed on the same film surface of the transparent conductive film, the difference in transmittance and refractive index can be reduced, and the pattern recognition of the conductive pattern The property can be lowered.

An example of embodiment of this invention is shown and (a) thru | or (c) is the schematic which shows each process. The construction method of a prior art example is shown, (a) thru | or (f) is the schematic which shows each process.

  Embodiments of the present invention will be described below.

  In the present invention, metal nanofillers having various shapes can be used as long as they are nano-sized metals such as metal nanoparticles, metal nanowires, metal nanodisks, and metal nanogauges. Among these, in order to achieve high conductivity with a small amount of filler, it is more advantageous to reduce the number of contacts between each metal, so it is preferable to use metal nanowires.

  There is no restriction | limiting in particular in the manufacturing method of the metal nanowire used by this invention, For example, well-known means, such as a liquid phase method and a gaseous-phase method, can be used. Moreover, there is no restriction | limiting in particular 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, etc. as a method for producing Au nanowires, Japanese Patent Laid-Open No. 2006-233252, etc., as a method for producing Cu nanowires, Japanese Patent Laid-Open No. 2002-266007, etc. as a method for producing Co nanowires JP, 2004-149871, A, etc. can be mentioned. In particular, the above Adv. Mater. And Chem. Mater. The method for producing Ag nanowires reported in 1) can produce Ag nanowires easily and in large quantities in an aqueous system, and since the conductivity of silver is the largest among metals, production of metal nanowires used in the present invention It can be preferably applied as a method.

  When using a metal nanowire as the metal nanofiller, the average diameter of the metal nanowire is preferably 200 nm or less from the viewpoint of transparency, and preferably 10 nm or more from the viewpoint of conductivity. If the average diameter is 200 nm or less, the influence of light scattering can be reduced, and a smaller average diameter is preferable because light transmittance reduction and haze deterioration 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, it is more preferably 20 to 150 nm, and further preferably 40 to 150 nm. The average length of the metal nanowires 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 the average length of the metal nanowires can be obtained from an arithmetic average of measured values of individual metal nanowire images by taking an electron micrograph of a sufficient number of nanowires using SEM or TEM. The length of the metal nanowire should be obtained in a state where it has been stretched in a straight line, but in reality it is often bent, so the projection diameter and projection of the metal nanowire using an image analyzer from an electron micrograph The area is calculated and calculated assuming a cylindrical body (length = projected area / projected diameter). The number of metal nanowires to be measured is preferably at least 100 or more, and more preferably 300 or more metal nanowires.

  The above-mentioned metal nanofiller is used by being dispersed in a resin solution, and as a resin component for forming a film of the resin solution, a resin component that forms a matrix by polymerization of monomers or oligomers is used. .

  When using a resin that undergoes a photopolymerization reaction or a thermal polymerization reaction as the above resin component, a monomer that undergoes a polymerization reaction directly or under the action of an initiator by irradiation with visible light, ionizing radiation such as ultraviolet rays or electron beams Or an oligomer can be used and the monomer or oligomer which has an acryl group or a methacryl group is suitable. 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 KK Thioxanthone or a derivative thereof, etc., and one or a mixture of two or more of these may 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.

  The blending amount of the photopolymerization initiator and the thermal polymerization initiator is usually preferably about 0.1 to 10 parts by mass with respect to 100 parts by mass of the composition (resin component + metal nanofiller).

  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 a resin component that forms the matrix of the resin solution. Examples of the conductive polymer include polyaniline, polypyrrole, polythiophene, polytriphenylamine and the like.

  Moreover, as a resin component which forms the matrix of a resin solution, you may use together two or more types selected from the above-mentioned photopolymerizable resin, thermopolymerizable resin, and conductive polymer.

  The compounding amount of the metal nanofiller in the resin solution is for matrix formation so that when the transparent conductive film is formed as described later, the metal nanofiller is contained in the transparent conductive film in an amount of 0.1 to 90% by mass. It is preferable to adjust and set the compounding quantity with respect to the resin component. When the content of the metal nanofiller in the transparent conductive film is less than 0.1% by mass, the metal nanofiller becomes difficult to be exposed from the matrix resin forming the transparent conductive film, and plasma treatment and corona treatment are performed as described later. Even if it carries out, it becomes difficult to carry out forced oxidation. Conversely, when it exceeds 90 mass%, there exists a possibility that a metal nanofiller cannot fully be hold | maintained with the matrix resin which forms a transparent conductive film. As will be described later, since it is easier to forcibly oxidize the resin matrix with a larger volume, it is particularly desirable that the metal nanofiller be contained in the transparent conductive film in an amount of 50 to 90% by mass.

  In the transparent substrate used in the present invention, the shape, structure, size and the like are not particularly limited and can be appropriately selected according to the purpose. Examples of the shape of the transparent substrate 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 appropriately selected. Can do. There is no restriction | limiting in particular also about the material of a transparent base material, Any of an inorganic material and an organic material can be used suitably. Examples of the inorganic material forming the transparent substrate 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.

  A transparent conductive film 2 can be formed as shown in FIG. 1A by applying a resin solution containing the above-mentioned metal nanofiller to the surface of the transparent substrate 1 and drying and curing the resin solution. It is. 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 layer 2 is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably in the range of about 0.01 to 100 μm.

Thus, the transparent conductive layer 2 formed on the surface of the transparent substrate 1 has high electrical conductivity due to the contained metal nanofiller, and the surface resistance of the transparent conductive film 2 is 1.0 × 10. ⁵ Ω / □ or less is preferable, and a range of 1.0 to 10 ⁴ Ω / □ is more preferable. This surface resistance value can be measured, for example, by the four probe method. The transparent conductive layer 2 preferably has a transmittance in the visible light region (400 nm to 800 nm) of 50% or more, and more preferably 70% or more. This transmittance can be measured by, for example, an ultraviolet-visible spectrometer (“V-560” manufactured by JASCO Corporation). Since the transparent conductive film 2 formed as described above has high transparency in the visible light region, and has a low surface resistance and excellent conductivity, a conductive paste, a wiring material, an electrode material, a conductive paint Suitable for conductive coatings, conductive films, etc., such as optical filters, wiring materials, electrode materials, catalysts, colorants, inks for inkjet, color materials for color filters, filters, cosmetics, near infrared absorbing materials, It can be applied to anti-counterfeiting inks, electromagnetic wave shielding films, surface-enhanced fluorescence sensors, surface-enhanced Raman scattering sensors, biomarkers, recording materials, drug delivery drug carriers, biosensors, DNA chips, test drugs, and the like.

  After forming the transparent conductive film 2 on the surface of the transparent substrate 1 as shown in FIG. 1A, the mask 4 having the openings 3 is disposed on the surface of the transparent conductive film 2 and overlapped. The opening 3 is formed in a pattern opposite to the conductive pattern formed in the transparent conductive film 2. As the mask 4, a metal mask, a film mask, or the like can be used, but it is preferable that a physical contact can be obtained between the surface of the transparent conductive film 2 and the surface of the mask 4. In addition, since there is a step of peeling the mask 4 as a later step as will be described later, not the complete adhesion, but the adhesion sufficient to prevent oxygen radicals or the like from entering the surface of the mask 4 during the forced oxidation treatment is obtained. It is desirable that the contact be in such a degree that does not affect the peeling. Further, since the surface of the mask 4 is also exposed to oxygen radicals or the like, it is preferable that the material be resistant to oxidative degradation. In particular, if the mask 4 is formed in the form of a roll film, the mask 4 can be placed on the transparent conductive film 2 by using a protection film installation method used for surface protection. Therefore, if the mask 4 is formed by providing the protective film with the openings 3 in a pattern shape, the mask can be installed simply and with excellent productivity. Of course, this construction method is an example, and the construction method of the mask 4 is not limited to this.

  After superposing the mask 4 having the opening 3 on the surface of the transparent conductive film 2 as described above, the mask 4 is introduced into a plasma generator or a corona treatment machine, and plasma treatment or corona treatment is performed as shown in FIG. Any plasma treatment or corona treatment may be used as long as it can oxidize the surface of the metal nanofiller by generating oxygen radicals such as oxygen plasma treatment and atmospheric pressure plasma treatment. The conditions for plasma treatment and corona treatment are not particularly limited. For example, in the case of plasma treatment, a frequency of 10 Hz to 4 GHz, an oxygen concentration of 0.01 to 25%, and a plasma irradiation distance of 0.1 to 30 mm are preferable. Preferably, the frequency is 5 kHz to 100 kHz, the oxygen concentration is 0.03 to 1.0%, and the plasma irradiation distance is 0.5 to 10 mm. In the case of corona treatment, an output of 0.1 kW or more and an interelectrode distance of 1 mm or more are preferable, and an output of 0.2 kW or more and an interelectrode distance of 5 mm or more are more preferable.

When plasma treatment or corona treatment is performed, oxygen radicals act on the metal nanofiller of the transparent conductive film 2 through the opening 3 of the mask 4, and the metal nanofiller contained in the transparent conductive film 2 corresponding to the opening 3. The surface of is oxidized. Here, the metal nanofiller in the transparent conductive film 2, particularly the metal nanowire, has a large volume with respect to the resin matrix, and a portion containing the metal nanofiller has a large number of fine pores and is transparent. The surface of the metal nanofiller can be forcibly oxidized even in a portion where oxygen radicals enter the conductive film 2 from the surface and are buried in the transparent conductive film 2. Thus, when the surface of the metal nanofiller is oxidized, the surface resistance value becomes high and becomes electrically insulating. The surface resistance value of the metal nanofiller is at least 10 ⁶ Ω / □ or more, preferably 10 ⁸ Ω. It is preferable to oxidize the metal nanofiller so that it becomes more than / □. In addition, paragraph [0128] of the above-mentioned Patent Document 4 describes that plasma treatment is performed on a network layer made of metal nanowires, but metal nanowires are used to improve transparency and conductivity. The plasma treatment is considered to be performed to remove the oxide film formed on the surface of the film, which is different from the plasma treatment for forced oxidation in the present invention.

  At the time when the transparent conductive film 2 is formed on the surface of the transparent substrate 1 as described above, the entire surface of the transparent conductive film 2 has electrical conductivity, but the mask 4 having the openings 3 is overlapped as described above to generate plasma. When the treatment or corona treatment is performed, the metal nanofiller in the portion of the transparent conductive film 2 corresponding to the opening 3 is oxidized to increase the electrical resistance value, so that the portion of the transparent conductive film 2 corresponding to the opening 3 Becomes the non-conductive portion 5 where electricity is not conducted. On the other hand, since the transparent conductive film 2 other than the portion corresponding to the opening 3 is covered with the mask 4, the plasma conductive or corona treatment is not applied to this portion of the transparent conductive film 2, so that the electrical conductivity is maintained as it is. The portion of the transparent conductive film 2 other than the portion corresponding to the opening 3 becomes the conduction portion 6. Thus, the conducting part 6 and the non-conducting part 5 are formed in the same film of the transparent conductive film 2, and a transparent conductive pattern is formed by the conducting part 6.

  After performing plasma treatment or corona treatment as described above to form a conductive pattern on the transparent conductive film 2, the mask 4 is peeled off as shown in FIG. The method for peeling the mask is not particularly limited, but it is preferable to perform the method in consideration of charging, heat and the like after the plasma treatment or the corona treatment. In particular, the film mask has a great influence on the transparent conductive film 2 at the time of peeling, and thus needs to be sufficiently considered.

  As described above, a substrate with a transparent conductive pattern provided by laminating a transparent conductive pattern 2 with a transparent conductive film 2 on the transparent substrate 1 as shown in FIG. A transparent conductive pattern can be easily formed by a simple dry method such as a step of overlaying the mask 4 on the transparent conductive film 2, a step of plasma treatment or corona treatment, and a step of peeling the mask 4 without depending on the method. is there.

  And in the transparent conductive pattern formed in the transparent conductive film 2 in this way, the conduction | electrical_connection part 6 which forms a conductive pattern, and the non-conduction part 5 between the conduction | electrical_connection parts 6 are formed in the same surface of the transparent conductive film 2. Therefore, a difference in transmittance and a difference in refractive index can be reduced between the conducting part 6 and the non-conducting part 5. Therefore, the pattern shape of the conductive part 6 does not become conspicuous due to the difference in transmittance and refractive index between the conductive part 6 and the surrounding non-conductive part 5, and the pattern recognition of the conductive pattern formed by the conductive part 6 is eliminated. The property can be lowered.

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

Example 1
16.0 parts by mass of photocurable acrylic resin (“A-DPH” manufactured by Shin-Nakamura Chemical Co., Ltd.), 124.8 parts by mass of methyl ethyl ketone and 160.0 parts by mass of methyl isobutyl ketone, and a mixture in which the acrylic resin is dissolved A was prepared. Moreover, the silver B (made by DOWA electronics company: average particle diameter 17.6nm) was used as a metal nanofiller, and the mixture B which disperse | distributed 63.96 mass parts of this metal nanofiller in 34.44 mass parts of methyl ethyl ketone was prepared. Then, after thoroughly mixing the mixture A and the mixture B, 0.8 parts by mass of a photopolymerization initiator (“Irgacure 184” manufactured by Ciba Geigy Co.) is added and mixed well, and further stirred for 1 hour in a constant temperature atmosphere at 25 ° C. By mixing, the coating material composition which consists of a resin solution containing a metal nano filler was obtained.

Then, using a PET film as the transparent substrate 1, the above coating composition was applied to the surface of the transparent substrate 1 with a wire bar coater # 10, dried at 120 ° C. for 2 minutes, and then with a UV integrated amount of 400 mJ / cm ² . The transparent conductive film 2 was formed by irradiating UV (see FIG. 1A).

  Next, a mask 4 is formed with a PET film provided with a pattern-shaped opening 3, and the mask 4 is adhered to the surface of the transparent conductive film 2, and corona treatment (output 0.2 kW, electrode distance 5 mm, scan) Oxidation pattern processing was performed by performing 30 cm / min × 1 time (see FIG. 1B). In this manner, a conductive pattern in which the portion covered with the mask 4 is the conductive portion 6 and the portion corresponding to the opening 3 is the nonconductive portion 5 can be formed on the same surface of the transparent conductive film 2 ( (Refer FIG.1 (c)).

(Example 2)
In Example 1, silver nanowires were used as metal nanofillers. 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. Others were the same as in Example 1.

(Example 3)
In Example 1, the oxidation pattern process was performed by an atmospheric pressure plasma process. The atmospheric pressure plasma treatment conditions are an O ₂ concentration of 0.15%, a plasma irradiation distance of 5 mm, and a scan of 10 cm / min × 5 times. Others were the same as in Example 1.

(Comparative Example 1)
Using a glass substrate with an ITO film formed on the surface as a transparent conductive film, and etching the ITO film into a pattern shape, the portion where the ITO film remains is a conductive portion, and the portion where the ITO film is removed becomes a non-conductive portion. A conductive pattern was formed.

  About said Examples 1-3 and the comparative example 1, the surface resistance value and the total light transmittance of the location of a conduction | electrical_connection part and the location of a non-conduction part were measured. Here, the surface resistance value was measured by using a surface resistance meter (“HirestaIP (MCP-HT260)” manufactured by Mitsubishi Chemical Corporation). The total light transmittance was measured using a haze meter (“NDH2000” manufactured by Nippon Denshoku Industries Co., Ltd.).

  The results are shown in Table 1. Table 1 also shows the difference in total light transmittance between the conducting part and the non-conducting part calculated.

表１にみられるように、各実施例のものは導通部と非導通部の全光線透過率の差が小さく、導電パターンのパターン認識性が低いものであった。

As can be seen from Table 1, each example had a small difference in total light transmittance between the conducting part and the non-conducting part, and the pattern recognizability of the conductive pattern was low.

DESCRIPTION OF SYMBOLS 1 Transparent base material 2 Transparent conductive film 3 Opening part 4 Mask 5 Non-conduction part 6 Conduction part

Claims (4)

A step of applying a resin solution containing a metal nanofiller to the surface of a transparent substrate, and forming a transparent conductive film containing the metal nanofiller together with holes through which oxygen radicals can enter the portion containing the metal nanofiller. And a step of disposing a mask having a pattern-shaped opening formed on the surface of the transparent conductive film, and performing plasma treatment or corona treatment from the opposite side of the transparent conductive film to generate oxygen radicals, The generated oxygen radical penetrates into the hole and forcibly oxidizes the metal nanofiller in the transparent conductive film corresponding to the opening of the mask, thereby forming a non-conductive portion with the oxidized metal nanofiller. And a step of forming a conducting portion with a metal nanofiller that is not oxidized, and a method for producing a transparent conductive pattern.   The method for producing a transparent conductive pattern according to claim 1, wherein the metal nanofiller is a metal nanowire.   3. With a transparent conductive pattern, comprising a transparent conductive film produced by the method according to claim 1 and having a conductive portion and a non-conductive portion patterned on the same surface, on the surface of the transparent substrate. Base material. A transparent conductive film containing a metal nanofiller is provided on the surface of the transparent substrate, and the metal nanofiller contained in a part of the transparent conductive film is oxidized to form a non-conductive portion. formed SQLDESC_BASE_TABLE_NAME This of forming a conductive portion in the metal nanofiller unoxidized portion,
Having a hole through which oxygen radicals can enter the part containing the metal nanofiller,
The substrate with a transparent conductive pattern, wherein the oxidation of the metal nanofiller is caused by oxygen radicals generated by plasma treatment or corona treatment entering the holes .

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