JP2019121580A - Conductive material - Google Patents

Abstract

To provide a conductive material that suppresses a fluctuation in resistance values caused by sunlight irradiation.SOLUTION: A conductive material has a mesh-like metal silver fine line pattern 11 on a support, and further has, on the support, at least one metal element selected from copper, iron, tin, nickel, and cobalt of 1 mg/mor more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a conductive material having an improved resistance variation.

  In electronic devices such as smartphones, personal digital assistants (PDAs), notebook PCs, tablet PCs, OA devices, medical devices, and car navigation systems, touch panel sensors are widely used as input means for these displays.

  Touch panel sensors include an optical method, an ultrasonic method, a resistive film method, a surface capacitance method, a projected capacitance method, etc. depending on the position detection method, and in the display application described above, the resistive film method and the projection type The capacitance method is preferably used. The resistive film type touch panel sensor has a structure in which two conductive materials having a light transmitting conductive layer on a support are used, and these conductive materials are disposed opposite to each other via a dot spacer. The light transmitting conductive layers are brought into contact with each other by applying a force to a point, and the voltage applied to the light transmitting conductive layer is measured through the other light transmitting conductive layer to detect the position to which the force is applied. To do. On the other hand, a projected capacitive touch panel uses one conductive material having two light transmission conductive layers or two conductive materials having one light transmission conductive layer, a finger or the like Changes in capacitance between the light-transmissive conductive layers when the light source is brought close to each other, and detection of the position where the finger approaches is detected. The latter is particularly widely used in smartphones, tablet PCs, and the like, because it is excellent in durability because it has no movable part and can simultaneously detect multiple points.

  In the prior art, the light transmitting conductive layer is generally formed of a conductive film containing a transparent conductive oxide such as ITO (indium-tin oxide). For example, in JP-A-2015-32183 (Patent Document 1), a touch panel sensor using a transparent conductor such as ITO, IZO (indium-zinc oxide), ZnO (zinc oxide) or the like as a material of the light transmitting conductive layer A component is disclosed.

  Moreover, in recent years, a conductive material having a mesh-like metallic silver fine line pattern as a light transmitting conductive layer is also disclosed. For example, in JP-A-2015-133239 (Patent Document 2), a method of forming a mesh-like metallic silver fine line pattern by printing an ink containing silver fine particles, or printing a resin paint containing an electroless plating catalyst It can be formed by various methods such as a method of applying electroless plating later, a subtractive method in which a photoresist layer is provided on a metal layer, a resist pattern is formed, and then the metal layer is etched away, a method using a silver salt photosensitive material Is described.

  Also known is a conductive material laminate having a pressure-sensitive adhesive layer on a light-transmitting conductive layer having a mesh-like metallic silver fine line pattern and a functional material on the pressure-sensitive adhesive layer, for example, JP-A-2014-198811. In the gazette (patent document 3), the malfunction in a wide temperature environment by the laminate for a touch panel having a pressure sensitive adhesive layer having a low temperature dependence of relative dielectric constant on a touch panel sensor and a protective substrate on the pressure sensitive adhesive layer. It is disclosed that it is possible to suppress The pressure-sensitive adhesive layer is generally used to closely contact members such as a display device and a touch panel sensor.

  The conductive material laminate as described above is used in various places, for example, in places where sunlight is irradiated. However, when a pressure-sensitive adhesive layer is provided on a light-transmitting conductive layer having a mesh-like metallic silver fine line pattern to form a conductive material laminate, the resistance value of the light-transmitting conductive layer fluctuates when it is irradiated with sunlight. There was a problem and there was a need for improvement.

  JP-A-2015-58662 (Patent Document 4) discloses that the undercoat layer of the light-transmitting conductive layer has an amino group as a method for improving the resistance value fluctuation of the light-transmitting conductive layer due to the irradiation of sunlight. JP-A-2015-106500 (Patent Document 5) discloses a conductive material laminate in which the compound is contained and the pressure-sensitive adhesive layer contains a cationically polymerizable photocurable resin. A conductive material laminate is disclosed, which comprises a compound having an amino group, and a pressure-sensitive adhesive layer containing a resin polymerized using an acylphosphine compound or a trihaloalkyl compound. JP-A-2016-210916 (Patent Document 6) is an interlayer filling material for a touch panel containing an acrylic pressure-sensitive adhesive obtained by polymerizing an acrylic monomer or the like having a molecular skeleton having ultraviolet absorbing ability or light stabilizing ability. A method of bonding on a light transmitting layer conductive layer is disclosed, and JP-A-2016-1608 (Patent Document 7) discloses a resin layer containing metal fibers and metal additives such as metal particles and metal oxide particles. JP-A-2016-21170 (Patent Document 8) discloses a light-transmitting conductive layer containing metal nanowires and light transmitting visible light of a specific wavelength or longer. Disclosed is a display device (conductive material laminate) provided with a capacitive coupling type touch panel input device including a transmissive layer. However, further improvement is desired with respect to the resistance value variation of the light transmitting conductive layer accompanying the irradiation of sunlight.

On the other hand, electroless plating can be mentioned as a method of precipitating a metal element on a support, but when copper strike plating which is thin copper plating is mentioned as an example, JP-A-2015-187303 (Patent Document 9) As shown in the above, the lower limit of the plating amount is 0.01 μm or more, and generally about 90 mg / m ² or more in weight conversion.

Moreover, when the transparent conductive film which coated the metal microparticles as an example as a conductive material which has a metal element on a support body is mentioned as an example, it will be shown by Unexamined-Japanese-Patent No. 2001-256834 (patent document 10). The lower limit of the coating amount is generally 50 mg / m ² or more.

JP, 2015-32183, A JP, 2015-133239, A JP, 2014-198811, A JP, 2015-58662, A JP, 2015-106500, A JP, 2016-210916, A JP, 2016-1608, A Unexamined-Japanese-Patent No. 2016-21170 JP, 2015-187303, A JP 2001-256834 A

  An object of the present invention is to provide a conductive material in which the resistance value variation associated with the irradiation of sunlight is improved.

The above-mentioned object of the present invention is achieved by the following invention.
(1) A conductive material having a reticulated metallic silver fine line pattern on a support, and further comprising 1 mg / hour of one or more metal elements selected from copper, iron, tin, nickel and cobalt on the support A conductive material having m ² or more.

  According to the present invention, it is possible to provide a conductive material in which the resistance value variation associated with the irradiation of sunlight is improved.

Schematic of positive-type transparent original used in the example

Hereinafter, the present invention will be described. The conductive material of the present invention is a conductive material having a reticulated metallic silver fine line pattern on a support, and on the support, at least one metal selected from copper, iron, tin, nickel and cobalt. The element is characterized by having 1 mg / m ² or more.

  The metal element in the present invention is selected from copper, iron, tin, nickel, and cobalt, and among these metal elements, copper and iron cause the resistance value fluctuation of the light transmitting conductive layer of the conductive material caused by the irradiation of sunlight. It is preferable because copper can be effectively suppressed, and copper is particularly preferable.

In the present invention, the metal element is present in the form of metal ion, metal salt or metal colloid on the support and the surface of the reticulated metallic silver fine wire pattern, and the amount of the metal element is 1 mg / m ² or more. In order to suppress the resistance value fluctuation of the light transmitting conductive layer accompanying irradiation, it is necessary. In addition, the amount of the metal element is preferably 15 mg / m ² or less because the effect obtained is not economical and is uneconomical, and the optical properties (haze, total light transmittance, etc.) are also reduced due to the coloring of the support. 10 mg / m ² or less is more preferable.

  The conductive material of the present invention can be produced by treating a conductive material having a reticulated metallic silver fine wire pattern on a support using a treatment liquid containing the following metal salt.

<Processing solution containing metal salt>
The metal salt (water-soluble metal salt) contained in the treatment solution containing the metal salt includes water-soluble inorganic metals such as sulfates, nitrates and chlorides of metals selected from copper, iron, tin, nickel and cobalt Examples thereof include water-soluble organic salts such as salts, formates of the same metal, acetates and the like. Moreover, these metal salts can be used individually by 1 type or in mixture of 2 or more types.

  The content of the metal salt contained in the treatment liquid containing the metal salt is 0.0001 mol / L or more, and effectively suppress the resistance value fluctuation of the light transmitting conductive layer of the conductive material accompanying the irradiation of sunlight. Since it can be carried out, it is preferable, more preferably 0.0003 mol / L or more. In addition, the upper limit is preferably 0.4 mol / L or less, more preferably 0.1 mol / L or less, from the viewpoint that the effect obtained is uneconomical without increasing and the dissolution of the metal salt takes time.

  The pH of the treatment liquid containing the metal salt is not particularly limited, but is preferably 2 to 9 from the viewpoint of effectively suppressing the resistance value fluctuation of the conductive material accompanying the irradiation of sunlight. For pH adjustment, the treatment solution containing a metal salt may contain a pH adjuster such as hydrochloric acid, sulfuric acid, acetic acid, sodium hydroxide, potassium hydroxide, phosphate, carbonate, ammonium salt and the like. Furthermore, the processing solution containing the metal salt in the present invention contains known additives such as surfactant, antifoaming agent, foam inhibitor, thickener, preservative and the like, as necessary, in addition to the pH adjuster. May be

  On the other hand, if the processing solution containing the metal salt contains a complexing agent or a brightener, it is not preferable because the resistance value fluctuation of the light transmitting conductive layer of the conductive material caused by the irradiation of sunlight can not be effectively suppressed. .

  The above complexing agent is a component effective for preventing the precipitation of metal salts in a general electroless plating solution and further suppressing the decomposition of the plating bath by setting the deposition reaction of the plating metal at an appropriate speed. These are various complexing agents used in known electroless plating solutions. As specific examples of such complexing agents, oxycarboxylic acids such as tartaric acid and malic acid, soluble salts thereof; amino compounds such as ethylenediamine and triethanolamine; ethylenediaminetetraacetic acid (EDTA), versanol (N-hydroxyethyl ethylenediamine) Ethylenediamine derivatives such as -N, N ', N'-triacetic acid), quadrole (N, N, N', N'-tetrahydroxyethyl ethylenediamine), soluble salts thereof; 1-hydroxyethane-1,1-diphosphone Examples thereof include acids, phosphonic acids such as ethylenediaminetetra (methylene phosphonic acid), and soluble salts thereof.

  The above-mentioned brighteners are effective components for obtaining the gloss of the plating surface in a general electrolytic plating solution, and are various brighteners used in known electrolytic plating solutions. As specific examples of such brighteners, organic thio compounds, oxygen-containing high molecular weight organic compounds and the like are known, and as organic thio compounds, 3-mercaptopropanesulfonic acid and its sodium salt, bis (3-sulfo) Examples include propyl) disulfide and its disodium salt, N, N-dimethyldithiocarbamic acid (3-sulfopropyl) ester, and its sodium salt. Further, as the oxygen-containing high molecular weight organic compound, an oxyalkylene polymer, polyethylene glycol, polypropylene glycol, a copolymer of ethylene oxide and propylene oxide, and the like are exemplified.

<Treatment with treatment solution containing metal salt>
There is no particular limitation on the method of treating a conductive material having a reticulated metallic silver fine wire pattern on a support using a processing solution containing a metal salt, and a metal is used as a conductive material having a reticulated metallic silver fine wire pattern on a support A salt-containing treatment solution may be brought into contact. Specifically, a method of immersing the conductive material in a treatment liquid containing a metal salt, a bar coating method, a spin coating method, a die coating method, a blade coating method, a gravure coating method, a curtain coating method, a spray coating method, a kiss coating method A method of applying a treatment solution containing a metal salt to a conductive material having a reticulated metallic silver fine line pattern on a support by a known application method such as, gravure printing, flexographic printing, inkjet printing, screen printing, offset printing, gravure A method of printing a treatment liquid containing a metal salt on a conductive material having a reticulated metallic silver fine line pattern on a support by a known printing method such as offset printing, dispenser printing and pad printing can be exemplified. Among the methods described above, the method of immersing the conductive material in the treatment liquid containing the metal salt is to easily bring the treatment liquid containing the metal salt into contact with the conductive material having the reticulated metallic silver fine line pattern on the support. Because it can be

  The time for which the treatment liquid containing the metal salt is brought into contact with the conductive material having a reticulated metallic silver fine line pattern on the support is not particularly limited, but preferably 1 second or longer because the resistance value fluctuation can be effectively suppressed. More preferably, it is 3 seconds or more, Especially preferably, it is 5 seconds or more. The upper limit is preferably 10 minutes or less. The temperature of the treatment liquid containing the metal salt when bringing the treatment liquid containing the metal salt into contact with the conductive material having the reticulated metal silver fine line pattern on the support is not particularly limited, but the resistance of 10 ° C. or higher Preferably, the temperature is 30 ° C. or higher because the value fluctuation can be effectively suppressed. The upper limit is preferably 70 ° C. or less.

<Flushing>
After the conductive material having the reticulated metallic silver fine line pattern on the support is treated with the treatment solution containing the metal salt by the method described above, the conductive material is used for the purpose of removing the treatment solution containing the excess metal salt. Is preferably washed with water. Thereby, the fall of the optical characteristic (a haze, the total light transmittance, etc.) accompanying adhesion of a process liquid can be avoided. The washing may be carried out with washing water consisting only of water, washing water containing pH adjuster such as phosphate, carbonate etc., washing water containing preservative for the purpose of preventing decay. You may go.

  Although the washing method is not particularly limited, a method of jetting a washing water shower using a scrubbing roller or the like, and a method of jetting washing water by a nozzle or the like can be exemplified. A plurality of showers or nozzles can be provided to increase the removal efficiency. Alternatively, the conductive material may be immersed in the flush water. After washing with water, it is preferable to dry the remaining water on the conductive material by heating or natural drying.

<Conductive material>
The support of the conductive material of the present invention is not particularly limited, but when the conductive material is used for applications requiring light transmission such as a touch panel sensor, since the conductive material is required to have transparency, the support is transparent to light It is particularly preferred to have the property. The light transmitting support includes polyolefin resins such as polyethylene and polypropylene, vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymer, epoxy resin, polyarylate, polysulfone, polyether sulfone, polyimide, Various resin films such as fluorine resin, phenoxy resin, triacetyl cellulose, polyethylene terephthalate, polyimide, polyphenylene sulfide, polyethylene naphthalate, polycarbonate, acrylic resin, cellophane, nylon, polystyrene resin, ABS resin, quartz glass, alkali-free glass Glass etc. can be illustrated. The total light transmittance of the support is preferably 60% or more, particularly preferably 70% or more, and the haze of the support is preferably 0 to 3% because the transparency of the conductive material is excellent, in particular Preferably it is 0 to 2%. The support has an easily adhesive layer, a hard coat layer, an antireflective layer, an antiglare layer, and an ITO on the surface having the light transmitting conductive layer and the surface opposite to the surface having the light transmitting conductive layer. It may have a known layer such as a layer containing a nonmetallic conductive material such as polythiophene or the like.

  In the present invention, the metal composition of the metallic silver fine wire constituting the reticulated metallic silver fine wire pattern is such that the mass ratio of silver to the total metal amount is preferably 50% by mass or more, more preferably 80% by mass or more, 90 Mass% or more is particularly preferable. Moreover, it is preferable that the mass ratio of the binder component which comprises a metal silver fine wire is less than 20 mass%, More preferably, it is less than 10 mass%. The metal silver fine wire as described above can obtain high conductivity, but on the other hand, the present invention works particularly effectively in such a case, since the resistance value variation accompanying the irradiation of sunlight is particularly large.

  The method of forming the reticulated metal silver fine wire pattern on the support is not particularly limited. For example, according to the method disclosed in JP-A-2015-69877, a conductive metal ink and a conductive paste containing a metal and a binder are used. A silver halide emulsion layer was provided on the support according to the method of forming a reticulated metallic silver fine line pattern by applying a method such as printing on the support or the method disclosed in JP-A-2007-59270. A method of forming a reticulated metallic silver fine line pattern using a silver halide photosensitive material as a conductive material precursor and curing development method, methods disclosed in JP-A 2004-221564, JP-A 2007-12314, etc. According to the above, a silver halide photosensitive material provided with a silver halide emulsion layer on a support is used as a conductive material precursor, and a network metal silver fine line pattern is formed using a direct development method. Physical development nuclei on a support according to the methods disclosed in JP-A-2003-77350, JP-A-2005-250169, JP-A-2007-188655, JP-A-2004-207001, etc. Layer and a silver halide photosensitive material having at least a silver halide emulsion layer in this order as a conductive material precursor, and using a so-called silver salt diffusion transfer method in which a soluble silver salt forming agent and a reducing agent According to a method of forming a reticulated metal silver fine wire pattern, a method disclosed in JP-A-2014-197531, a photosensitive resist material in which an underlayer and a photosensitive resist layer are laminated on a support is used as a conductive material precursor After exposing the photosensitive resist layer to an arbitrary pattern, it is developed to form a resist image, and then electroless plating is performed to form a resist image. On the support according to the method disclosed in JP-A-2015-82178, a method of localizing a metal on an uninverted underlayer and thereafter removing a resist image to form a reticulated metallic silver fine wire pattern Forming a metal film and a resist film on the substrate, exposing and developing the resist film to form an opening, and etching and removing the metal film at the opening to form a reticulated metal silver fine wire pattern; According to the method disclosed in Japanese Patent Application Publication No. 2012-28183, a layer containing metal nanowires may be formed on a support, and the layer may be patterned to form a network metal silver fine wire pattern.

  Among the methods described above, the method of using a silver salt photosensitive material as a conductive material precursor and the method of using a photosensitive resist material as a conductive material precursor are reticulated metal silver fine wire patterns containing silver excellent in conductivity. It is preferable because it can be easily formed, and a method using a silver salt diffusion transfer method using a silver salt photosensitive material as a conductive material precursor is particularly preferable, because it is easy to miniaturize metal silver fine lines.

  In the present invention, the light transmitting conductive layer may be subjected to known metal surface treatment before and after treatment with a treatment solution containing a metal salt. For example, a reducing substance as described in JP-A-2008-34366, a water-soluble phosphorus oxo acid compound, or a water-soluble halogen compound may be allowed to act, as described in JP-A-2013-196779. A triazine having two or more mercapto groups in the molecule or a derivative thereof may be allowed to act, and a blackening treatment by a sulfurization reaction may be performed as described in JP-A-2011-209626. Also, in the case of forming a light transmitting conductive layer having a mesh-like metallic silver fine line pattern by using a silver salt photosensitive material as a conductive material precursor, from the viewpoint of improving the adhesion between the light transmitting conductive layer and the pressure sensitive adhesive layer. As described in Japanese Patent Application Laid-Open No. 2007-12404, the light transmitting conductive layer may be treated with a treatment solution containing an enzyme such as a proteolytic enzyme to reduce the remaining gelatin and the like.

  When the conductive material of the present invention is used for a touch panel sensor, it is preferable to form a light transmitting conductive layer with a reticulated metal silver fine wire pattern, and in the reticulated metal silver fine wire pattern, a plurality of unit lattices are arranged in a reticulated shape It is preferable from the viewpoint of the sensitivity of the sensor, visibility (low visibility), etc. to have the above-mentioned geometrical shape. The shape of the unit cell may, for example, be a triangle such as an equilateral triangle, an isosceles triangle or a right triangle, a square, a rectangle, a rhombus, a parallelogram, a quadrangle such as a trapezoid, a hexagon, an octagon, a dodecagon, a dodecagon etc. The shape which combined the n-gon, the star shape, etc. of S is mentioned, Moreover, the single repetition of these shapes, or the combination of two or more types of several shapes is mentioned. Above all, the shape of the unit cell is preferably square or rhombus. In addition, irregular geometric shapes represented by Voronoi figures, Delaunay figures, Penrose tile figures and the like are also preferred shapes of the reticulated metallic silver fine line pattern.

  When the conductive material of the present invention is used for a touch panel sensor, it is preferable that the light transmitting conductive layer have a sensor section having a plurality of sensors formed by a mesh-like metallic silver fine line pattern. Further, from the viewpoint of the visibility (low visibility) of the sensor unit, the light transmitting conductive layer may have a dummy unit electrically insulated from the sensor. In addition to the sensor unit and the dummy unit, a terminal unit provided for extracting an electric signal to the outside, and a peripheral wiring unit for electrically connecting the sensor unit and the terminal unit may be provided. The terminal portion and the peripheral wiring portion may be made of a mesh-like metal silver fine line pattern, or may be a fill pattern.

  In the present invention, the line width of the metal silver fine wire constituting the mesh-like metal silver fine wire pattern is preferably 1.0 to 20 μm, more preferably 1.5 to 20 from the viewpoint of achieving both light transmittance and conductivity. It is 15 μm. When the reticulated metallic silver fine line pattern has a geometric shape in which unit lattices are arranged in a reticulated manner, the repetition period of the unit cell is preferably 100 to 1000 μm, more preferably 100 to 400 μm.

  A functional material can be provided on the side having the reticulated metallic silver fine line pattern of the conductive material of the present invention or the other side via an adhesive layer to form a conductive material laminate. The pressure-sensitive adhesive layer means a layer containing a known pressure-sensitive adhesive such as a rubber-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, or a urethane-based pressure-sensitive adhesive. The thickness of the pressure-sensitive adhesive layer is preferably 5 to 500 μm because the transparency of the conductive material laminate is excellent, and more preferably 10 to 250 μm. From the same viewpoint, the total light transmittance of the pressure-sensitive adhesive layer is preferably 90% or more, particularly preferably 95% or more, and the haze of the pressure-sensitive adhesive layer is preferably 0 to 3%, particularly preferably 0 2%.

  A pressure-sensitive adhesive tape for optics using a highly transparent acrylic pressure-sensitive adhesive as exemplified in JP-A-9-251159, JP-A-2011-74308, etc. as a PSA layer, JP-A 2009-48214 Alternatively, a cured product of a highly transparent curable resin exemplified in JP-A-2010-257208 may be used. Adhesive tapes for optical use and curable resins having high transparency are both commercially available, and as the former, high transparency adhesive transfer tape (8171CL / 8172CL / 8146-1 / 8146-2 / 8146- from Sumitomo 3M Co., Ltd.) 3 / 8146-4, etc., transparent adhesive sheet for optics (LUCIACS (registered trademark) CS9622T / CS9862UA etc.) from Nitto Denko Corp., etc., and as the latter, photoelastic resin SVR (registered trademark) from Dexerials Inc. Series (SVR1150, SVR1320, etc.), WORLD ROCK (registered trademark) series (HRJ (registered trademark)-46, HRJ-203, etc.) from Kyoritsu Chemical Industry Co., Ltd., UV curable optical transparent from Henkel Japan Ltd. Adhesive Loctite (registered trademark) LOCA series (Loctite 3) 92, Loctite3193 etc.) and the like can be exemplified, it is possible to obtain them use.

  As the functional material, the conductive material of the present invention, a glass such as chemically strengthened glass, soda glass, quartz glass, non-alkali glass, a film containing various resins such as polyethylene terephthalate, and at least one of the above-described glass and films Examples thereof include materials having known functional layers such as a hard coat layer, an antireflective layer, an antiglare layer, a polarizing layer, and an ITO conductive film on the surface.

  Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

<Production of Conductive Material 1>
A polyethylene terephthalate film with a thickness of 100 μm was used as a support. The total light transmittance of the support was 91.8%, and the haze was 0.7%.

  Next, a physical development nucleus layer coating solution having the following composition was uniformly coated by gravure coating on a support and dried to form a physical development nucleus layer.

<Preparation of palladium sulfide sol>
Liquid A: 5 g of palladium chloride
Hydrochloric acid 40mL
Distilled water 1000mL
Liquid B sodium sulfide 8.6g
Distilled water 1000mL
Solution A and solution B were mixed while stirring, and after 30 minutes, passed through a column packed with ion exchange resin to obtain palladium sulfide sol.

<Physical development nuclear layer coating solution / per ² m ² >
0.4 mg of the palladium sulfide sol (as solid content)
2 mass% glyoxal aqueous solution 200 mg
Surfactant (S-1) 4 mg
Denacol (R) EX-830 25 mg
(Nagase Chemtex Co., Ltd. polyethylene glycol diglycidyl ether)
10% by mass Epomin (registered trademark) HM-2000 aqueous solution 500 mg
(Nippon Shokuhin Co., Ltd. polyethyleneimine; average molecular weight 30,000)

  Subsequently, an intermediate layer of the following composition, a silver halide emulsion layer, and a protective layer are applied in the order from the side closer to the support by slide coating uniformly on the physical development nucleus layer and dried to obtain the conductive material precursor. Obtained. The silver halide emulsion contained in the silver halide emulsion layer was produced by a controlled double jet method. The silver halide grains contained in this silver halide emulsion were prepared so as to have an average particle size of 0.15 μm with 95 mol% of silver chloride and 5 mol% of silver bromide. The silver halide grains thus obtained were subjected to gold-sulfur sensitization using sodium thiosulfate and chloroauric acid according to a conventional method. The silver halide emulsion thus obtained contains 0.5 g of gelatin per 1 g of silver as a protective colloid (binder).

<Intermediate layer composition / 1 m ² per>
Gelatin 0.5g
Surfactant (S-1) 5 mg
Dye 1 5 mg

<Silver halide emulsion layer composition / 1m ² per>
Silver halide emulsion 3.0 g equivalent of silver 1-phenyl-5-mercaptotetrazole 3 mg
Surfactant (S-1) 20 mg

<Per protective layer composition / 1m ^2>
1 g of gelatin
Amorphous silica matting agent (average particle size 3.5 μm) 10 mg
Surfactant (S-1) 10 mg

  The conductive material precursor was brought into close contact with the positive-type transparent original shown in FIG. 1 and exposed through a resin filter that cuts light of 400 nm or less with a contact printer using a mercury lamp as a light source. The positive-type transparent original has test patterns 13 (five lines 13a to 13e) composed of a mesh pattern 11 and a fill pattern 12, 12 '. Filled patterns 12 and 12 'constituting test pattern 13 are connected via a mesh pattern 11 having a line width of 5.0 μm, a side length of 300 μm, and a narrow angle of 60 °. There is. In addition, the broken line represents the bonding area | region 20 of the functional material mentioned later in the figure. Thereafter, it was immersed in the following diffusion transfer developing solution at 20 ° C. for 60 seconds, and then the silver halide emulsion layer, the intermediate layer and the protective layer were removed by washing with warm water at 40 ° C. and dried. Thus, the conductive material 1 was obtained. The shape, line width, and the like of the pattern of the obtained conductive material 1 were the same as those of the above-described positive-type transparent original.

<Diffusion transfer developer composition>
Potassium hydroxide 25 g
Hydroquinone 18g
1-phenyl-3-pyrazolidone 2 g
Potassium sulfite 80g
15 g of N-methylethanolamine
Potassium bromide 1.2 g
The total amount was adjusted to 1000 mL with water and pH = 12.2.

<Preparation of Conductive Materials 2 to 9>
The conductive material 1 obtained as described above is immersed in ion exchange water in treatment solutions 1 to 8 containing metal salts shown in Table 1 at 40 ° C. for 1 minute, and then excess metal salt is obtained by shower water washing. The treatment liquid contained was removed and dried to obtain conductive materials 2-9. The pH of the treatment solution containing each metal salt was adjusted to 5.0 with ammonium chloride. The metal element amounts of the conductive materials 2 to 9 measured by fluorescent X-ray analysis are described in Table 2. The measurement was carried out at two places of the reticulated pattern part and the non-image part where the pattern does not exist, but no significant difference was observed between them.

<Production of Conductive Materials 10 and 11>
Treatment solutions 9 and 10 containing metal salts shown in Table 1 in ion exchange water are applied uniformly on conductive material 1 by slide coating so that the amount of metal element after drying is 8 mg / m ² And conductive materials 10 and 11, respectively.

<Production of Conductive Materials 12 and 13>
Treatment solutions 9 and 10 containing metal salts shown in Table 1 in ion exchange water are applied uniformly on conductive material 1 by slide coating so that the amount of metal element after drying is 13 mg / m ² , Conductive materials 12 and 13 were obtained respectively.

<Production of Conductive Materials 14 and 15>
Treatment solutions 9 and 10 containing metal salts shown in Table 1 in ion exchange water are applied uniformly on conductive material 1 by slide coating so that the amount of metal element after drying is 18 mg / m ² , And conductive materials 14 and 15, respectively.

<Production of laminate>
About each conductive material 1-15, Sumitomo 3M Co., Ltd. high transparency adhesive transfer tape 8146-4 was bonded to the bonding area | region 20 of a functional material, and it was set as the 100-micrometer-thick adhesive layer. Subsequently, EAGLE XG (registered trademark) (non-alkali glass manufactured by Corning Japan Ltd.) as a functional material was laminated on the pressure-sensitive adhesive layer to prepare a laminate.

<Evaluation of resistance value>
The resistance value between the fill patterns 12 and 12 'was measured for each of five test patterns 13a to 13e of the laminate, and initial resistance values Ra to Re (unit: kΩ) of the test patterns 13a to 13e were obtained. . Next, the laminate was irradiated with xenon lamp light (light having a spectral distribution similar to that of sunlight) for 1000 hours using a xenon weather meter NX15 manufactured by Suga Test Instruments Co., Ltd. The conditions were set to irradiance 60 W / m ² (wavelength 300 nm to 400 nm), in-tank temperature 38 ° C., in-tank humidity 50% RH, and black panel temperature 63 ° C. according to JIS K7350-2. After the completion of the irradiation, the resistance values of the five test patterns 13a to 13e were measured again to obtain resistance values R'a to R'e (unit: kΩ). Then, the resistance value change rate (unit:%) before and after irradiation with the xenon lamp light is calculated for each of the individual test patterns (test patterns 13a to 13e) according to the following equation, and further the resistance values of the test patterns 13a to 13e The change rates were averaged to obtain the average resistance value change rate (unit:%) of the conductive materials 1-15. The results are shown in Table 2.
Resistance value change rate of the test pattern 13 x (unit:%) = {(R′x−Rx) / Rx} × 100
In the formula, x represents a to e.

  The results of Table 2 demonstrate the effectiveness of the present invention.

11 Reticulated Pattern 12, 12 'Filled Pattern 13a to 13e Test Pattern 20 Bonding Area of Functional Material

Claims (1)

A conductive material having a reticulated metallic silver fine line pattern on a support, and further comprising at least 1 mg / m ² or more of one or more metal elements selected from copper, iron, tin, nickel and cobalt on the support A conductive material characterized by having.

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