JP2010257690A - Method for manufacturing pattern electrode, and pattern electrode - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a pattern electrode excellent in conductivity, transparency and etching property, and a pattern electrode manufactured by the method. <P>SOLUTION: The method for manufacturing a pattern electrode including a conductive layer containing metal fine particles, which is formed on a support includes steps of adhering a conductive layer 2 containing metal fine particles, which is formed on a first support 1, onto a second support through a resin layer and peeling the first support; and pattern-printing a metal fine particle removing liquid on the conductive layer transferred onto the second support followed by washing with water. The conductive layer contains a water-soluble binder 3 on the outermost surface side of the transferred conductive layer. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a pattern electrode manufacturing method and a pattern electrode excellent in conductivity, transparency, and etching properties.

Conventionally, as transparent electrodes, various metal thin films such as Au, Ag, Pt, Cu, indium oxide doped with tin or zinc (ITO, IZO), zinc oxide doped with aluminum or gallium (AZO, GZO), fluorine, Metal oxide thin films such as tin oxide (FTO, ATO) doped with antimony, conductive nitride thin films such as TiN, ZrN, and HfN, and conductive boride thin films such as LaB ₆ are known and combinations thereof. and _{Bi 2 O 3 / Au / Bi} 2 O 3, also known various electrodes, such as TiO ₂ / Ag / TiO 2. In addition to the transparent electrode described above, a transparent electrode using CNT (carbon nanotube) or a conductive polymer has also been proposed (for example, see Non-Patent Document 1).

  However, since the metal thin film, nitride thin film, boron thin film and conductive polymer thin film described above cannot achieve both high light transmission and conductive characteristics, It is used only in the touch panel field where even a high resistance value is allowed.

  On the other hand, metal oxide thin films are becoming mainstream of transparent electrodes because they can achieve both high light transmittance and conductivity and are excellent in durability. In particular, ITO has a good balance between light transmittance and conductivity, and it is easy to form fine electrode patterns not only by vacuum processes such as sputtering, but also by wet processes using solutions. It is frequently used as a transparent electrode. However, expensive equipment is required to form a transparent conductive film by a vacuum process such as sputtering. On the other hand, in the wet process, an annealing process at a high temperature of 500 ° C. or higher is necessary to obtain high conductivity.

  As other transparent electrodes, a conductive substrate having a random network structure made of self-organized silver fine particles (for example, see Patent Document 1) and a transparent electrode having a fine mesh using metal nanowires are disclosed. (For example, refer to Patent Document 2). In particular, metal nanowires using silver can achieve both good conductivity and transparency due to the inherent high conductivity of silver.

  On the other hand, a transparent electrode with a smooth surface is required for electrodes for LCDs and organic electroluminescence elements. As a method for producing a smooth transparent electrode, an electrode layer is formed on a temporary support plate having a smooth surface, and this electrode layer is temporarily formed using a resin film provided with a thermosetting or ultraviolet curable resin layer. A method for producing a highly smooth flexible resin film with an electrode layer by peeling off from a support plate is disclosed (for example, see Patent Document 3).

  Moreover, as a transparent electrode pattern formation method using metal nanowires, a method using printing ink containing electrically conductive microwires (for example, refer to Patent Document 4), a nanowire patterning method using photolithography (for example, patents) References 5 and 6).

  However, in either method, the conductivity decreases due to an increase in contact resistance between the metal nanowires caused by the binder, or the resist resin that has entered between the fine meshes of the metal nanowires is insufficiently removed, resulting in a decrease in transmittance. Further, when removing the resist, the metal nanowires are also detached together, and the conventional pattern forming method is not satisfactory.

International Patent Application Publication No. 2007/114076 US Patent Application Publication No. 2007/0074316 JP 2006-236626 A Special Table 2003-515622 US Patent Application Publication No. 2005/0196707 US Patent Application Publication No. 2008/0143906

"Technology of transparent conductive film", page 80 (Ohm Publishing Co.)

  The objective of this invention is made | formed in view of the said situation, and is providing the pattern electrode manufactured by the manufacturing method of the pattern electrode excellent in electroconductivity, transparency, and etching property, and the said manufacturing method.

  The above object of the present invention can be achieved by the following configuration.

  1. In the method for producing a patterned electrode comprising a conductive layer containing metal fine particles formed on a support, the pattern electrode comprises a conductive layer containing metal fine particles formed on a first support via a resin layer. And a step of peeling off the first support, pattern printing of the metal fine particle removing liquid on the conductive layer transferred onto the second support, and then washing with water. A process for producing a patterned electrode, comprising the steps of: and a conductive layer containing a water-soluble binder on the outermost surface side of the conductive layer after transfer.

  2. 2. The method for producing a patterned electrode according to 1, wherein the resin layer is a thermosetting resin or a photocurable resin.

  3. 3. The method for producing a patterned electrode according to 1 or 2, wherein the metal fine particles are metal nanowires.

  4). 4. The method for producing a patterned electrode according to any one of 1 to 3, wherein the metal fine particle removing liquid contains a photographic bleach-fixing liquid.

  5. A pattern electrode manufactured by the method for manufacturing a pattern electrode according to any one of 1 to 4 above.

  ADVANTAGE OF THE INVENTION According to this invention, the pattern electrode manufactured by the manufacturing method of the pattern electrode excellent in electroconductivity and transparency and the said manufacturing method can be provided simply.

It is a manufacturing method of the pattern electrode of the present invention, and is a sectional view before transferring a conductive layer to the 2nd support (non-display) via a resin layer. It is a manufacturing method of the pattern electrode of the present invention, and is a sectional view of a transparent electrode after transferring a conductive part to the 2nd support via a resin layer. It is the manufacturing method of the pattern electrode of this invention, Comprising: It is the conceptual diagram which showed the manufacturing method of the pattern electrode.

  The present invention relates to a method for producing a patterned electrode comprising a conductive layer containing metal fine particles formed on a support, wherein the conductive layer containing metal fine particles formed on the first support is passed through a resin layer. After the adhesion on the second support, the step of peeling the first support, pattern printing of the metal fine particle removing liquid on the conductive layer transferred onto the second support, The present invention relates to a method for producing a patterned electrode having excellent conductivity and transparency, comprising a step of washing with water.

  Hereafter, the manufacturing method of the pattern electrode of this invention is demonstrated with figures.

  In FIG. 1, a conductive layer 2 made of metal nanowires and a conductive polymer, and a water-soluble binder layer 3 are placed on a first support 1 through a resin layer (not shown). It is sectional drawing before transcribe | transferring to display.

  FIG. 2 shows a transparent electrode 11 produced by transferring the conductive layer 2 on the first support 1 to the second support 10 via the resin layer 4 and then peeling the first support 1. FIG.

  FIG. 3 shows a manufacturing process in which a patterned electrode 30 can be produced by treating a transparent electrode 11 having a non-patterned portion formed of a patterned conductive layer 2 and a non-conductive resin layer 4 with a metal fine particle removing solution 20. It is the conceptual diagram which showed the law.

  Hereinafter, the present invention and its components will be described in detail.

[Support]
There is no restriction | limiting in particular as a support body used for this invention, About the material, a shape, a structure, thickness, hardness, etc., it can select suitably from well-known things, but it has high light transmittance. It is preferable. For example, polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate, modified polyester, polyethylene (PE) resin films, polypropylene (PP) resin films, polystyrene resin films, polyolefin resin films such as cyclic olefin resins, Vinyl resin films such as polyvinyl chloride and polyvinylidene chloride, polyvinyl acetal resin films such as polyvinyl butyral (PVB), polyether ether ketone (PEEK) resin films, polysulfone (PSF) resin films, polyether sulfone (PES) Resin film, polycarbonate (PC) resin film, polyamide resin film, polyimide resin film, acrylic resin film, triacetyl cellulose (TA ) Can be exemplified a resin film or the like, as long as it is a resin film transmittance of 80% or more at a wavelength in the visible range (380 to 780 nm), it can be preferably applied to the present invention. Among these, from the viewpoint of transparency, heat resistance, ease of handling, strength and cost, it is preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, or a polycarbonate film, and biaxially stretched. A polyethylene terephthalate film and a biaxially stretched polyethylene naphthalate film are more preferable.

  The first support used in the present invention is preferably one having excellent surface smoothness in order to smooth the peeled surface of the transferred conductive layer. The smoothness (unevenness) of the surface of the first support is preferably such that the arithmetic average roughness Ra is 5 nm or less, the maximum height Rz is 50 nm or less, Ra is 2 nm or less, and Rz is 30 nm or less. More preferably, Ra is 1 nm or less, and Rz is 20 nm or less.

  The surface of the first support may be smoothed by applying an undercoat layer such as a thermosetting resin, an ultraviolet curable resin, an electron beam curable resin, or a radiation curable resin, or by machining such as polishing. It can be smooth. Further, a release layer may be formed to facilitate peeling, and as a release layer forming material, a polymer or wax that forms a known release layer can be appropriately selected and used. For example, paraffin wax, acrylic , Urethane, silicon, melamine, urea, urea-melamine, cellulose, benzoguanamine, and other resins and surfactants, either alone or in a mixture of these solvents in organic solvents or water The applied paint is applied onto the support by a normal printing method such as gravure printing, screen printing, offset printing, etc., and dried (thermosetting resin, ultraviolet curable resin, electron beam curable resin, radiation A curable coating such as a curable resin may be formed by curing). There is no restriction | limiting in particular as thickness of a mold release layer, It employ | adoptes suitably from the range of about 0.1-3 micrometers.

  Here, the smoothness (unevenness) of the surface can be determined according to the surface roughness standard (JIS B 0601-2001) from measurement using an atomic force microscope (AFM) or the like.

  The second support used in the present invention can be subjected to a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesion of the coating solution. A conventionally well-known technique can be used about a surface treatment or an easily bonding layer. For example, the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment. Examples of the easy adhesion layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, and epoxy copolymer. When the film substrate is a biaxially stretched polyethylene terephthalate film, the interface reflection between the film substrate and the easy-adhesion layer is achieved by setting the refractive index of the easy-adhesion layer adjacent to the film to 1.57 to 1.63. Since it can reduce and can improve the transmittance | permeability, it is more preferable. The method for adjusting the refractive index can be carried out by appropriately adjusting the ratio of the oxide sol having a relatively high refractive index such as tin oxide sol or cerium oxide sol and the binder resin. The easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion. Moreover, a barrier coat layer may be formed in advance on the film base as necessary, or a hard coat layer may be formed in advance.

[Conductive layer]
The conductive layer in the present invention contains metal fine particles. The method for forming a conductive layer in the present invention is not particularly limited as long as it is a liquid phase film forming method in which a dispersion containing metal fine particles is applied and dried to form a film, a roll coating method, a bar coating method, a dip coating method, It is preferable to use a coating method such as a spin coating method, a casting method, a die coating method, a blade coating method, a bar coating method, a gravure coating method, a curtain coating method, a spray coating method, or a doctor coating method. Moreover, you may install the conductive layer or binder resin containing a conductive polymer or a metal oxide as needed.

  The patterned electrode of the present invention is characterized by containing a water-soluble binder on the outermost surface of the conductive layer after transfer. The metal fine particles in the conductive layer are held by the resin layer, and the presence of the water-soluble binder on the outermost surface makes it possible to achieve both the adhesion between the conductive layer and the substrate and the etching property of the metal fine particles. The film thickness of the water-soluble binder is preferably 1/20 or more and 2/3 or less, more preferably 1/10 or more and 1/2 or less of the film thickness of the entire conductive layer.

[Metal fine particles]
The metal fine particles of the present invention refer to fine metal particles having a particle diameter of from atomic scale to nm size. The average particle size of the metal fine particles is preferably 10 to 300 nm, and more preferably 30 to 200 nm. In the metal fine particles of the present invention, as long as the minor axis of the particle diameter is nm size, the shape may be a particle shape, a rod shape or a wire shape, but from the viewpoint of conductivity and transparency, It is preferable that the metal nanowire has a shape.

[Metal nanowires]
In general, a metal nanowire refers to a fibrous structure having a metal element as a main component. In particular, the metal nanowire in the present invention means a large number of fibrous structures having a minor axis from the atomic scale to the nm size.

  As the metal nanowire used in the present invention, in order to form a long conductive path with one metal nanowire, the average length is preferably 3 μm or more, more preferably 3 to 500 μm, and particularly preferably 3 to 300 μm. It is preferable. In addition, the relative standard deviation of the length is preferably 40% or less. Moreover, although there is no restriction | limiting in particular in an average breadth, it is preferable that it is small from a transparency viewpoint, and the larger one is preferable from a conductive viewpoint. In the present invention, the average minor axis of the metal nanowire is preferably 10 to 300 nm, and more preferably 30 to 200 nm. In addition, the relative standard deviation of the minor axis is preferably 20% or less.

  Copper, iron, cobalt, gold, silver, or the like can be used as the metal used in the metal nanowire according to the present invention, but silver is preferable from the viewpoint of conductivity. Moreover, although the metal used for the metal nanowire according to the present invention may be used alone, it becomes a main component in order to achieve both conductivity and stability (sulfurization and oxidation resistance and migration resistance of the metal nanowire). Metals and one or more other metals may be included in any proportion.

  In the present invention, the means for producing the metal nanowire is not particularly limited, and for example, known means such as a liquid phase method and a gas 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 silver nanowires, Adv. Mater. , 2002, 14, 833-837; Chem. Mater. 2002, 14, 4736-4745, a method for producing gold nanowires is disclosed in Japanese Patent Application Laid-Open No. 2006-233252, a method for producing copper nanowires is disclosed in Japanese Patent Application Laid-Open No. 2002-266007, and the like. Reference can be made to 2004-149871. In particular, the method for producing silver nanowires described above can easily produce silver nanowires in an aqueous solution, and since the conductivity of silver is the highest in metals, the method for producing metal nanowires according to the present invention is as follows. It can be preferably applied.

[Resin layer]
The resin constituting the resin layer used in the present invention is not particularly limited as long as it is transparent in the visible region (that is, has sufficient transmittance). The resin may be a curable resin or a thermoplastic resin, but is preferably a curable resin. Examples of the curable resins include thermosetting resins, ultraviolet curable resins, and electron beam curable resins. Among these curable resins, the equipment for resin curing is simple and excellent in workability. Therefore, an ultraviolet curable resin is preferable. The resin layer is preferably an acrylic polymer or an epoxy polymer from the viewpoint of transparency. The resin layer of the present invention may be provided on a conductive layer containing metal nanowires formed on a first support, or may be provided on a second support, and a conductive layer containing metal nanowires. Is cured on the resin layer side and then cured.

  The bonding method is not particularly limited and can be performed by a sheet press, a roll press or the like, but is preferably performed using a roll press machine. The roll press is a method in which a film to be bonded is sandwiched between the rolls, and the rolls are rotated. The roll press is uniformly pressed and has better productivity than the sheet press.

(Water-soluble binder)
Examples of the water-soluble binder used in the present invention include a synthetic water-soluble binder and a natural water-soluble binder, and any of them can be preferably used.

  Among these, examples of the synthetic water-soluble binder include those having a nonionic group in the molecular structure, those having an anionic group, and those having a nonionic group and an anionic group. Examples of the nonionic group include an ether group, an ethylene oxide group, and a hydroxy group. Examples of the anionic group include a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and the like. Is mentioned.

  These synthetic water-soluble binders may be not only homopolymers but also copolymers with one or more monomers. Furthermore, this copolymer may be a copolymer with a partially hydrophobic monomer as long as it remains water-soluble. However, it is necessary to make the composition range that does not cause side effects upon addition.

  Examples of the natural water-soluble binder include those having a nonionic group, those having an anionic group, and those having a nonionic group and an anionic group in the molecular structure. The natural water-soluble binder in the present invention is described in detail in the comprehensive technical data collection of water-soluble polymer water-dispersed resins (Management Development Center Publishing Department), but lignin, starch, pullulan, cellulose, alginic acid, dextran, Dextrin, guar gum, gum arabic, pectin, casein, agar, xanthan gum, cyclodextrin, locust bean gum, tragacanth gum, carrageenan, glycogen, laminaran, lichenin, nigeran and the like are preferred.

  Derivatives of natural water-soluble binders include sulfonated, carboxylated, phosphorylated, sulfoalkylenated, carboxyalkylenated, alkyl phosphorylated, and salts thereof, polyoxyalkylene (eg, ethylene, glycerin, propylene, etc.) And alkylation (methyl, ethyl, benzylation, etc.) are preferred.

  Among natural water-soluble binders, glucose polymers and derivatives thereof are preferable, and among glucose polymers and derivatives thereof, starch, glycogen, cellulose, lichenin, dextran, dextrin, cyclodextrin, nigeran and the like are particularly preferable. Cellulose, dextrin, cyclodextrin and derivatives thereof are preferred.

  Examples of cellulose derivatives include carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose and the like.

  The water-soluble binder in the present invention may be contained in the metal fine particle dispersion, or after being transferred to the resin layer, if it is present on the outermost surface side in the form finally contained in the conductive layer, it is applied separately. Or both. For example, after forming a conductive layer containing metal fine particles on the first support, a water-soluble binder may be overcoated on the conductive layer and then transferred to the resin layer. The water-soluble binder in the conductive layer penetrates into the gaps between the metal fine particles forming the conductive layer after coating, and can be present on the release surface side of the first support after being transferred to the resin layer.

  The water-soluble binder in the present invention may be crosslinked to such an extent that does not impair the penetration of the metal fine particle removing solution. As the crosslinking agent, an aldehyde-based, epoxy-based, melamine-based, or isocyanate-based crosslinking agent can be used. The method of applying the crosslinking agent is to apply the coating solution of the crosslinking agent on a transparent substrate in advance and dry it, and then apply a metal fine particle layer thereto, or apply and dry the metal fine particle layer, A cross-linking agent may be applied there, or a metal fine particle dispersion and a cross-linking agent may be applied simultaneously in two layers, or a mixture thereof may be applied and dried.

  Moreover, the crosslinking agent solution may contain an acid, an alkali, and a salt as a pH adjuster, and ammonia and an ammonium salt are preferable because they can be easily removed by heating. Furthermore, in order to promote a crosslinking reaction, it is preferable to heat at 100-150 degreeC.

[Pattern printing]
As the method for pattern printing of the metal fine particle removing liquid in the present invention, letterpress (letter) printing, stencil (screen) printing, planographic (offset) printing, intaglio (gravure) printing, spray printing, ink jet printing Or the like can be used. The metal fine particle removing liquid in the present invention is subjected to pattern printing on a portion that is not necessary for forming a patterned electrode on the conductive layer containing the metal fine particles in the present invention. Next, by performing a water washing treatment, it is possible to remove a portion of the metal fine particles that is not necessary for forming the pattern electrode, thereby forming the pattern electrode.
[Metal fine particle removal solution]
As the composition of the metal fine particle removing solution used in the present invention, a bleach-fixing solution used for developing a silver halide color photographic light-sensitive material can be preferably used. The solution is preferably an aqueous solution, but may be an organic solvent such as ethanol as long as it can dissolve the bleaching agent and fixing agent described below.

  As a bleaching agent used in the bleach-fixing solution, a known bleaching agent can also be used. In particular, an organic complex salt of iron (III) (for example, a complex salt of an aminopolycarboxylic acid) or an organic compound such as citric acid, tartaric acid, malic acid or the like. Acid, persulfate, hydrogen peroxide and the like are preferable.

  Of these, an organic complex salt of iron (III) is particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids useful for forming iron (III) organic complex salts, or salts thereof, are listed. Biodegradable ethylenediamine disuccinic acid (SS form), N- (2-carboxylate ethyl) -L-aspartic acid, beta-alanine diacetic acid, methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid In addition to glycol ether diamine tetraacetic acid, compounds represented by general formula (I) or (II) of European Patent 0789275 can be mentioned.

  These compounds may be sodium, potassium, thylium or ammonium salts. Among these compounds, ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, beta-alanine diacetic acid, ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, methylimino The diacetic acid is preferably its iron (III) complex salt. These ferric ion complex salts may be used in the form of complex salts or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a ferric ion complex salt may be formed in a solution using a chelating agent such as aminopolycarboxylic acid. Moreover, you may use a chelating agent in excess rather than forming a ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount is 0.01 to 1.0 mol / liter, preferably 0.05 to 0.50 mol / liter, and more preferably 0.10 to 0.00. 50 mol / liter, more preferably 0.15 to 0.40 mol / liter.

  Fixing agents used in the bleach-fixing solution are known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, ethylenebisthioglycolic acid, 3, These are water-soluble silver halide solubilizers such as thioether compounds such as 6-dithia-1,8-octanediol and thioureas, and these can be used alone or in combination. A special bleach-fixing agent comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of halide such as potassium iodide can also be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The amount of the fixing agent per liter is preferably 0.3 to 2 mol, and more preferably 0.5 to 1.0 mol.

  The pH range of the bleach-fixing solution used in the present invention is preferably from 3 to 8, more preferably from 4 to 7. In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary.

  It is preferable to add a thickener to the bleach-fixing solution of the present invention in order to impart a viscosity suitable for each printing method. Examples of the thickener include a water-soluble binder and fine particle silica. The molecular weight of the water-soluble binder can be arbitrarily selected according to the required viscosity.

  In addition to the water-soluble binder, the bleach-fixing solution may contain various antifoaming agents or surfactants, and organic solvents such as polyvinylpyrrolidone and methanol. Bleach fixers use sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfites (eg, bisulfite) as preservatives. For example, it contains sulfite ion releasing compounds such as potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc., and arylsulfinic acid such as p-toluenesulfinic acid and m-carboxybenzenesulfinic acid. preferable. These compounds are preferably contained in an amount of about 0.02 to 1.0 mol / liter in terms of sulfite ion or sulfinate ion.

  As a preservative, ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, or the like may be added in addition to the above. Furthermore, you may add a buffering agent, a chelating agent, an antifoamer, an antifungal agent, etc. as needed.

[Pattern electrode]
The total light transmittance of the pattern portion in the pattern electrode of the present invention is preferably 60% or more, preferably 70% or more, and particularly preferably 80% or more. The total light transmittance can be measured according to a known method using a spectrophotometer or the like.

The electric resistance value of the pattern portion in the pattern electrode of the present invention is preferably 10 ² Ω / □ or less, more preferably 10 Ω / □ or less as the surface specific resistance. The surface specific resistance can be measured based on, for example, JIS K6911, ASTM D257, etc., and can be easily measured using a commercially available surface resistivity meter.

  An anchor coat, a hard coat, etc. can also be provided to the pattern electrode of the present invention. Moreover, you may install the conductive layer containing a conductive polymer or a metal oxide as needed.

  The pattern electrode of the present invention can be preferably used for transparent electrodes such as LCDs, electroluminescent elements, plasma displays, electrochromic displays, solar cells and touch panels, electronic paper, electromagnetic wave shielding materials and the like.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

<< Production of pattern electrode >>
[Preparation of Pattern Electrode TCF-1; Comparative Example]
As metal fine particles, Adv. Mater. , 2002, 14, 833 to 837, by using PVP K30 (molecular weight 50,000; manufactured by ISP), silver nanowires having an average minor axis of 75 nm and an average length of 35 μm were produced. Silver nanowires were separated by filtration using a filtration membrane, washed with water, redispersed in ethanol, and 25% by mass of hydroxypropylmethylcellulose as a water-soluble binder was added to silver to prepare a silver nanowire dispersion.

The prepared silver nanowire dispersion is applied to the hard coat surface of a polyethylene terephthalate film support subjected to hard coating so that the weight of silver nanowires is 0.05 g / m ^2. After applying and drying using, the silver nanowire coating layer was calendered to produce a silver nanowire-coated film. Next, an ultraviolet curable resin (Optomer NN, manufactured by JSR) is applied as a resin layer on the easy adhesion surface of the polyethylene terephthalate film support that has been subjected to easy adhesion processing to a thickness of 3 μm using a spin coater. , Press-bond so that the coated surface side of the silver nanowire coated film prepared in front faces, and irradiate ultraviolet rays from the easy-adhesive film support side to cure the ultraviolet curable resin, and then peel off the hard coat film support A silver nanowire transfer film was obtained. In addition, the average film thickness of the conductive layer containing silver nanowires on the transfer surface at this time was 250 nm, and the film thickness of the water-soluble binder on the outermost surface side in the conductive layer was 80 nm. The film thickness of each layer was measured by taking tomographic photographs with a transmission electron microscope (H9000NAR, manufactured by Hitachi, Ltd.).

  The obtained silver nanowire transfer film was patterned using a known photolithography method to produce a stripe pattern electrode TCF-1 having an electrode pattern width of 10 mm.

[Preparation of Pattern Electrode TCF-2; Comparative Example]
A gravure coating machine K printing proofer (manufactured by Matsuo Sangyo Co., Ltd.) was attached with a plate with a 10 mm stripe pattern, and the viscosity of the silver nanowire dispersion used in the preparation of TCF-1 was adjusted to sodium carboxymethylcellulose (SIGMA-ALDRICH). The weight of silver nanowires in the pattern portion is 0.00 on the hard coat surface of a polyethylene terephthalate film support that is adjusted to 1 Pa · s (1000 cP) by C5013 (hereinafter abbreviated as CMC). Gravure printing was performed by adjusting the number of times of printing so as to be 05 g / m ² to prepare a silver nanowire gravure printing film. Next, as in TCF-1, an ultraviolet curable resin (Optomer NN, manufactured by JSR) is used as a resin layer on the easy adhesion surface of the polyethylene terephthalate film support that has been subjected to easy adhesion processing, and a thickness of 3 μm using a spin coater. And then applying pressure so that the resin layer and the coated surface side of the silver nanowire gravure printing film prepared earlier face each other, irradiate ultraviolet rays from the easy-adhesive film support side to cure the ultraviolet curable resin, and then The hard coat film support was peeled off to produce a stripe pattern electrode TCF-2 having an electrode pattern width of 10 mm. At this time, the average film thickness of the conductive layer containing silver nanowires on the transfer surface was 430 nm, and the film thickness of the water-soluble binder on the outermost surface side in the conductive layer was 300 nm.

[Preparation of Pattern Electrode TCF-3; Present Invention]
<Preparation of metal fine particle removing liquid E-1>
Ethylenediaminetetraacetic acid ferric ammonium 60g
Ethylenediaminetetraacetic acid 2g
Sodium metabisulfite 15g
70g ammonium thiosulfate
Maleic acid 5g
Finished to 1 L with pure water, and adjusted to pH 5.5 with sulfuric acid or ammonia water, metal fine particle removal solution E-1 was prepared.

  With a TCF-3, a polyester mesh for screen printing (Mitani Micronics Co., Ltd .; 255T) having a 10 mm stripe pattern formed on the silver nanowire transfer film obtained in the same manner as the production of TCF-1 The viscosity of the produced metal fine particle removal liquid BF-1 was adjusted to 10 Pa · s (10000 cP) with CMC, and screen printing was performed on the conductive layer containing the transferred silver nanowires so as to have a coating thickness of 30 μm. After printing, it was left for 1 minute, and then washed with running water to produce a stripe pattern electrode TCF-3.

[Preparation of Pattern Electrode TCF-4; Present Invention]
In the production of TCF-3, a striped pattern electrode TCF is used in the same manner as TCF-3 except that a thermosetting resin (Optomer SS, manufactured by JSR) is used instead of an ultraviolet curable resin to perform heating and curing. -4 was produced.

[Preparation of Pattern Electrode TCF-5; Present Invention]
In the production of TCF-3, a striped pattern electrode TCF-5 is produced in the same manner as TCF-3 except that a thermoplastic resin (EP varnish, manufactured by The Inktec) is used instead of the ultraviolet curable resin. did.

[Preparation of Pattern Electrode TCF-6; Present Invention]
In preparation of TCF-3, after applying the silver nanowire dispersion liquid, a 0.1% hydroxypropylmethylcellulose aqueous solution was applied on the silver nanowire coating layer using a spin coater so that the dry film thickness was 50 nm, and dried. After that, a striped pattern electrode TCF-6 was prepared in the same manner as TCF-3 except that the silver nanowire coating layer and the hydroxypropylmethylcellulose coating layer were calendered to produce a silver nanowire coating film. did. At this time, the average film thickness of the conductive layer containing silver nanowires on the transfer surface was 250 nm, and the film thickness of the water-soluble binder on the outermost surface side in the conductive layer was 130 nm.

[Preparation of Pattern Electrode TCF-7; Comparative Example]
In the production of TCF-3, a striped pattern electrode TCF-7 was produced in the same manner as TCF-3 except that hydroxypropylmethylcellulose was not added to the silver nanowire dispersion. At this time, the average film thickness of the conductive layer containing silver nanowires on the transfer surface was 240 nm, and the silver nanowires in the conductive layer were almost completely buried in the ultraviolet curable resin.

[Preparation of Pattern Electrode TCF-8; Present Invention]
In the preparation of TCF-3, after applying the silver nanowire dispersion liquid, an epoxy-based binder cross-linking agent EX512 (manufactured by Nagase ChemteX Corporation) is coated on the silver nanowire coating layer with a binder in the silver nanowire dispersion liquid. It was applied and dried using a spin coater so as to be 10% of the mass. Next, a striped pattern electrode TCF-7 was produced in the same manner as TCF-3 except that binder crosslinking was performed by heat treatment at 120 ° C. for 30 minutes to produce a silver nanowire-coated film.

[Preparation of Pattern Electrode TCF-9; Present Invention]
In the production of TCF-3, instead of performing screen printing, a plate with a 10 mm stripe pattern was attached to the gravure coating machine K printing proofer (manufactured by Matsuo Sangyo Co., Ltd.), and the produced metal fine particle removal solution E- The viscosity of No. 1 was adjusted to 0.5 Pa · s (500 cP) with CMC, and gravure printing was performed by adjusting the number of printings so that the coating film thickness was 30 μm on the transferred conductive layer containing silver nanowires. After printing, it was left for 1 minute, and then washed with running water to produce a stripe pattern electrode TCF-9.

[Preparation of Pattern Electrode TCF-10; Present Invention]
In the production of TCF-3, instead of screen printing, using an inkjet printer, a 10 mm stripe pattern was formed, and the viscosity of the metal fine particle removal solution E-1 produced with TCF-3 was 30 mPa · s (30 cP) with CMC. Ink jet printing was performed by adjusting the number of times of printing so that the coating film thickness was 30 μm on the transferred conductive layer containing silver nanowires. After printing, it was left for 1 minute, and then washed with running water to produce a stripe pattern electrode TCF-10.
[Preparation of Pattern Electrode TCF-11; Comparative Example]
In preparation of TCF-3, the prepared silver nanowire dispersion liquid was prepared so that the basis weight of the silver nanowire was 0.05 g / m ^{2 on} the easy adhesion surface of the polyethylene terephthalate film support subjected to easy adhesion processing. The nanowire dispersion liquid was applied and dried using a spin coater, and then the silver nanowire coating layer was calendered to produce a silver nanowire-coated film. Next, an ultraviolet curable resin (Optomer NN, manufactured by JSR) is applied as a resin layer using a spin coater so that the silver nanowires in the conductive layer are almost completely buried, and ultraviolet rays are irradiated from the resin layer application side. A stripe pattern electrode TCF-11 was produced in the same manner as TCF-3 except that the ultraviolet curable resin was cured to produce a silver nanowire resin laminated film. In addition, the average film thickness of the conductive layer containing silver nanowires at this time was 250 nm, and the water-soluble binder in the conductive layer was coated with an ultraviolet curable resin and was not present on the outermost surface side of the conductive layer.
[Preparation of Pattern Electrode TCF-12; Present Invention]
In the production of TCF-3, the same as TCF-3 except that the metal fine particle removing liquid E-2 prepared by the following formulation was adjusted to 10 Pa · s (10000 cP) with CMC. Pattern electrode TCF-12 was produced.

<Preparation of metal fine particle removing liquid E-2>
Metal fine particle removal liquid E-2 was prepared using pure water as a solvent so that the concentration of sulfuric acid and ferric sulfate was 5 mass% sulfuric acid and 10 mass% ferric sulfate.
[Preparation of Pattern Electrode TCF-13; Present Invention]
TCF-3 was prepared except that the viscosity of the metal fine particle removing liquid E-1 was adjusted to 10 Pa · s (10000 cP) with a thickener Aerosil # 200 (fine particle silica; manufactured by Nippon Aerosil Co., Ltd.) in the production of TCF-3. In the same manner, a stripe pattern electrode TCF-13 was produced.
[Preparation of Pattern Electrode TCF-14; Present Invention]
Self-assembled silver fine particles prepared as follows as metal fine particles on a hydrophilic treatment layer of a biaxially stretched polyethylene terephthalate film (Lumirror (registered trademark) U46 manufactured by Toray Industries, Inc.) subjected to hydrophilic treatment on one side After the layer forming solution C-1 is applied, it is allowed to elapse for 1 minute at 25 ° C., the silver fine particles are self-assembled into a network shape, and the silver fine particle layer is laminated in a random network shape, and then treated at 150 ° C. for 1 minute. did. Next, each film was immersed in 25 ° C. acetone (special grade manufactured by Nacalai Tesque Co., Ltd.) for 30 seconds, the film was taken out, and dried at 25 ° C. for 3 minutes. Subsequently, the whole film was immersed in 1N (1 mol / L) hydrochloric acid (N / 10-hydrochloric acid manufactured by Nacalai Tesque Co., Ltd.) at 25 ° C. for 1 minute, taken out, washed with water, and dried at 150 ° C. for 1 minute. Further, a 0.1% hydroxypropylmethylcellulose aqueous solution was applied on the reticulated silver fine particle layer using a spin coater so as to have a dry film thickness of 100 nm and dried to obtain a reticulated silver fine particle layer forming film. Next, an ultraviolet curable resin (Optomer NN, manufactured by JSR) is applied as a resin layer on the easy adhesion surface of the polyethylene terephthalate film support that has been subjected to easy adhesion processing to a thickness of 5 μm using a spin coater. , Press-bond so that the coated surface of the previously prepared mesh silver fine particle layer-forming film faces, cure the UV-curable resin by irradiating UV from the easy-adhesive film support side, and then support the hydrophilized film The body was peeled off to obtain a reticulated silver fine particle layer transfer film. At this time, the average thickness of the conductive layer containing the reticulated silver fine particles on the transfer surface was 3 μm, and the thickness of the water-soluble binder on the outermost surface side in the conductive layer was 150 nm.

(Self-assembled silver fine particle layer forming solution C-1)
BYK-410 (manufactured by BYK Chemie) 0.11
SPAN-80 (manufactured by Tokyo Chemical Industry) 0.11
Dichloroethane 75.63
Cyclohexanone 0.42
Silver powder (average particle size 70 nm) 3.59
BYK-348 (0.02% aqueous solution; manufactured by BYK Chemie) 19.98
ZonylFSH (DuPont) 0.08
Butver B-76 (Solutia) 0.08
[Preparation of Pattern Electrode TCF-15; Present Invention]
In the production of TCF-3, TCF-3 was used except that instead of silver nanowires, copper nanowires having an average minor axis of 20 nm and an average length of 10 μm were prepared with reference to the method described in JP-A-2002-266007. In the same manner, a stripe pattern electrode TCF-15 was produced.

<< Evaluation of pattern electrode >>
The surface resistivity and transmittance of the pattern electrodes TCF-1 to 15 and the non-pattern part etching property were evaluated by the following methods.

(Surface resistivity)
The surface specific resistance was measured by a four-terminal method using a diamond instrument resistivity meter Loresta GP.

(Transmittance)
The transmittance was determined by measuring the total light transmittance of the striped pattern portion using AUTOMATIC ZEMETER (MODEL TC-HIIIDP) manufactured by Tokyo Denshoku.

(Etching property of non-pattern part)
The etching property of the non-patterned portion was evaluated by visual observation and measuring the surface specific resistance of the non-patterned portion using a resistivity meter Loresta GP and Hiresta UP made by Dia Instruments, based on the following criteria.

A: No silver residue is visually observed, and the surface specific resistance of the non-patterned portion is 10 ¹⁵ Ω / □ or more. ○: No silver residue is visually observed, and the surface specific resistance of the non-patterned portion is 10 ¹³ Ω / □ or more. Δ: Silver residue is visually observed in an uneven shape, and the surface specific resistance of the non-patterned portion is 10 ⁶ Ω / □ or less. X: The silver remaining is almost visually observed, and the surface specific resistance of the non-patterned portion is 10 ² Ω / □ or less. The evaluation results are shown in Table 1.

  From Table 1, it can be seen that the patterned electrode of the present invention is excellent in conductivity (surface specific resistance), transparency (transmittance), and non-patterned portion etching properties.

DESCRIPTION OF SYMBOLS 1 1st support body 2 Conductive layer 3 Water-soluble binder 4 Resin layer 10 2nd support body 11 Transparent electrode 20 Metal fine particle removal liquid 30 Pattern electrode

Claims (5)

  In the method for producing a patterned electrode comprising a conductive layer containing metal fine particles formed on a support, the pattern electrode comprises a conductive layer containing metal fine particles formed on a first support via a resin layer. And a step of peeling off the first support, pattern printing of the metal fine particle removing liquid on the conductive layer transferred onto the second support, and then washing with water. A process for producing a patterned electrode, comprising the steps of: and a conductive layer containing a water-soluble binder on the outermost surface side of the conductive layer after transfer.   The method for producing a patterned electrode according to claim 1, wherein the resin layer is a thermosetting resin or a photocurable resin.   The method for producing a patterned electrode according to claim 1, wherein the metal fine particles are metal nanowires.   The method for producing a patterned electrode according to claim 1, wherein the metal fine particle removing liquid contains a photographic bleach-fixing liquid.   A pattern electrode manufactured by the method for manufacturing a pattern electrode according to claim 1.

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