JP2019101984A - Conductive material laminate - Google Patents

Abstract

To provide a conductive material laminate excellent in temporal stability.SOLUTION: The conductive material laminate has, at least in the stated order on a face having an optically transparent conductive layer and a conductive peripheral metal part, an adhesive layer and a functional material. The line width of an exposed part of the conductive peripheral metal part exposed from the adhesive layer is 15 μm or more. The laminate has a compound represented by general formula (1) on the exposed part.SELECTED DRAWING: None

Description

  The present invention relates to a conductive material laminate excellent in temporal stability.

  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. Usually, the light transmitting conductive layer is located on the display, and in the prior art, the light transmitting conductive layer is generally formed of an ITO (indium tin oxide) conductive film.

  In a projected capacitive touch panel sensor, by arranging a sensor unit having a plurality of sensors formed by patterning a light transmitting conductive layer on a support, it is possible to simultaneously detect multiple points or move points. It enables detection. In order to take out a change in capacitance detected by the sensor unit as an electric signal to the outside, a terminal unit having a plurality of terminals provided for taking an electric signal to the outside for all the sensors included in the conductive material, A conductive peripheral metal portion such as a peripheral wiring portion having a plurality of peripheral wiring lines electrically connecting the sensor portion and the terminal portion is provided. Usually, the conductive peripheral metal portion is located outside the display, that is, in the so-called frame portion, and in the prior art, the conductive peripheral metal portion is formed of a metal having a low electrical resistivity such as gold, silver, copper, nickel, aluminum or the like. It is common to

  For example, in JP 2012-138018 A (patent document 1), a conductive oxide such as ITO or IZO (indium zinc oxide) is used as a material of the light transmitting conductive layer, and a lead wire (peripheral wiring portion) or A touch panel using a metal material such as metal or alloy as a material of a conductive peripheral metal portion such as a connection terminal (terminal portion) is disclosed.

  In recent years, a conductive material has also been disclosed in which the light transmitting conductive layer is formed of a mesh-like metal fine wire pattern, and the conductive peripheral metal part is formed of the same metal as the mesh-like metal fine wire pattern. For example, in JP-A-2017-33369 (Patent Document 2), a method of using a silver halide photosensitive material, a method of printing a conductive ink, a method of using a silver halide photosensitive material, a mesh metal fine wire pattern and a conductive peripheral metal portion It is described that it can be formed by various methods such as a method of providing a layer, forming a resist pattern, and then etching away a metal layer.

  On the other hand, when using the above-mentioned conductive material, for example in the use which manufactures a touch panel sensor, the conductive material layered product which provided the adhesive layer and the functional material in the field of the side which has a transparent conductive layer and a conductive peripheral metal part. And to be known. For example, JP-A-2014-198811 (Patent Document 3) discloses a touch panel laminate having a pressure-sensitive adhesive layer formed of a pressure-sensitive adhesive sheet on a touch panel sensor and a protective substrate (functional material) on the pressure-sensitive adhesive layer. There is.

  However, because it is necessary to connect a wiring member such as a flexible printed wiring board or the like responsible for electrical connection with the outside to the conductive peripheral metal portion, a part of the conductive peripheral metal portion is exposed from the adhesive layer It is necessary to provide an exposed part. In such a case, the exposed portion of the conductive peripheral metal portion is not completely covered even after the wiring member is connected, and a part of the exposed portion continues to be exposed. Therefore, the protection of the exposed part of the conductive peripheral metal part becomes insufficient, the resistance value of the exposed part of the conductive peripheral metal part changes with the passage of a long time, and the change of the capacitance detected by the sensor part There was a case that it could not be taken out outside normally as a signal. As a result, there is a case where the reliability of the touch panel sensor is significantly reduced due to a decrease in detection sensitivity of the touch panel sensor and erroneous recognition. That is, a conductive material laminate more excellent in temporal stability has been required.

  JP-A-2009-188360 (Patent Document 4) discloses that benzotriazole and benzotriazole in a metal wiring portion are used as an electronic circuit which prevents migration of the electronic circuit and the insulation resistance does not decrease even when driven for a long time. Disclosed is an electronic circuit in which a metal ion trapping agent such as a derivative or a mercapto compound is adsorbed. However, further improvement in stability over time has been sought.

  On the other hand, there is known a method of coating and curing a polyorganosiloxane composition on the exposed portion of the conductive peripheral metal portion to protect the exposed portion, for example, in JP-A-2006-206817 (Patent Document 5). As a room temperature curable organopolysiloxane composition capable of preventing corrosion or migration of an electrode or wiring due to hydrogen sulfide gas, sulfuric acid gas or the like, a room temperature curable organo-composition comprising 1,2,4-triazole or a derivative thereof Disclosed are polysiloxane compositions. Further, JP-A-2004-149611 (Patent Document 6) discloses a room temperature curing method which contains benzotriazole or a derivative thereof on a metal conductive portion exposed to a corrosive substance such as sulfur or a sulfur-containing compound or moisture. Disclosed is a method of protecting a metallic conductive part that is cured after applying a silicone rubber composition.

JP, 2012-138018, A JP 2017-33369 JP, 2014-198811, A JP, 2009-188360, A JP, 2006-206817, A JP 2004-149611 A

  An object of the present invention is to provide a conductive material laminate excellent in temporal stability.

The above-mentioned object of the present invention is achieved by the following invention.
(1) A pressure-sensitive adhesive layer and a functional material on the side of the conductive material having the light-transmitting conductive layer and the conductive peripheral metal portion on the support, on the side having the light-transmitting conductive layer and the conductive peripheral metal portion And the conductive peripheral metal portion has an exposed portion at least a portion of which is exposed from the pressure-sensitive adhesive layer, and the line width of the exposed portion is 15 μm or more. And a conductive material laminate having a compound represented by the following general formula (1) on the exposed portion.

In the general formula (1), R ₁ represents an aliphatic group, an aromatic group or a heterocyclic group. R ₂ and R ₃ each represent an aliphatic group.

  According to the present invention, a conductive material laminate excellent in temporal stability can be provided.

Schematic of positive-type transparent original used in the example

  Hereinafter, the present invention will be described in detail. The conductive material laminate of the present invention adheres to the side of the conductive material having the light-transmitting conductive layer and the conductive peripheral metal portion on the support on the side having the light-transmitting conductive layer and the conductive peripheral metal portion. Agent layer and a functional material in this order, the conductive peripheral metal portion has an exposed portion at least a portion of which is exposed from the adhesive layer, and the line width of the exposed portion is 15 μm or more And the compound represented by the general formula (1) is on the exposed portion.

In the general formula (1), R ₁ is an aliphatic group (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, undecyl group, dodecyl group, Alkyl groups such as tetradecyl group and pentadecyl group, alkenyl groups such as allyl group and butenyl group, alkynyl groups such as propargyl group, benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, 1-naphthylmethyl group, 2-naphthyl The above aliphatic groups may be branched, such as aralkyl group such as methyl group, aromatic group (eg, phenyl group, tolyl group, naphthyl group etc.), heterocyclic group (eg, indolyl group) , Pyridyl group, furyl group, thienyl group and the like). R ₂ and R _{3 each} represent an aliphatic group (as defined for the aliphatic group of R ₁ ). Further, R ₁ , R ₂ and R ₃ mentioned above are substituted or unsubstituted amino group, alkoxy group, aryloxy group, alkylthio group, arylthio group, hydroxy group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, It may have various known substituents such as a halogen atom.

The combination of the preferable substituents of _{R 1,} R 2, _{R 3} described _above, R _1, R 2, _{R 3} carbon atoms _{(R 1,} R 2, the total number of carbon atoms including a _{substituent R 3} has) Is a combination of 5 or more, and R ₁ is an aliphatic group or an aromatic group having 4 or more carbon atoms (the total number of carbon atoms including substituents) is 4 and R ₂ and R ₃ are all methyl groups. The combination is more preferred.

  Among the compounds mentioned above, those having a bis structure represented by the following general formula (2) can be mentioned as further preferable compounds.

In the general formula (2), L represents a divalent linking group composed of a combination of the substituent groups described for R ₁ in the general formula (1). Among them, preferable divalent linking groups include aliphatic groups having 4 or more carbon atoms in total, alkoxy groups, and alkylthio groups.

R ₂₁ has the same meaning as R ₂ in the general formula (1), and R ₃₁ has the same meaning as R ₃ in the general formula (1).

  Although the specific example of a compound represented by General formula (1) and General formula (2) is described below, this invention is not limited to these.

  The above compounds can be easily synthesized by methods described in known synthesis methods (for example, JP 2009-138258 A, etc.).

  In the present invention, the conductive material laminate may have only one type of the compound represented by the general formula (1), or may have two or more types.

  The method for causing the compound of the present invention (hereinafter also described as the compound of the present invention) represented by the general formula (1) to be present on the conductive peripheral metal portion exposed from the pressure-sensitive adhesive layer is not particularly limited. A solution obtained by dissolving the compound of the formula (I) in a known solvent such as water or an organic solvent (hereinafter also described as a compound solution of the present invention) and contacting the conductive peripheral metal portion with the compound solution And a compound of the present invention are dissolved in a known solvent together with the compound of the present invention, the coating liquid is applied onto the conductive peripheral metal portion and then dried to form a film, the compound of the present invention is contained For example, a method of forming a film by applying a room temperature curable organopolysiloxane composition onto a conductive peripheral metal portion and curing the composition can be exemplified. Among the above, the method of contacting the conductive peripheral metal portion with the compound solution of the present invention is simple and preferred.

  The conductive peripheral metal portion exposed from the pressure-sensitive adhesive layer may be brought into contact with the compound solution of the present invention by immersing the conductive peripheral metal portion in the compound solution, bar coating method, spin coating method, die coating method, Method of applying the compound solution on the conductive peripheral metal portion by known coating methods such as blade coating method, gravure coating method, curtain coating method, spray coating method, kiss coating method, gravure printing, flexo printing, inkjet printing, A method of printing the compound solution on the conductive peripheral metal part by a known printing method such as screen printing, offset printing, gravure offset printing, dispenser printing, pad printing and the like can be exemplified.

  The content of the compound of the present invention in the compound solution of the present invention is not particularly limited, but is preferably 0.50 g / L or more because the stability with time of the conductive material laminate is excellent, and more preferably 0.75 g / L or more, and particularly preferably 1.0 g / L or more. The upper limit is preferably 5.0 g / L or less.

  The solvent of the compound solution of the present invention is preferably a solvent containing 75% by mass or more of water, more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Examples of the substance which the solvent may contain in addition to water include alcohols (methanol, ethanol, propanol, benzyl alcohol etc.) and polyhydric alcohols (ethylene glycol, propylene glycol, polyethylene glycol, glycerin etc.) .

  The compound solution of the present invention has a pH adjuster (hydrochloric acid, sulfuric acid, acetic acid, sodium hydroxide, potassium hydroxide, phosphate, carbonate, etc., pH, etc.) in addition to the compound and solvent represented by the general formula (1). Substances having a regulating action), surfactants, antifoaming agents, foam inhibitors, thickeners, preservatives and the like known additives can be included.

  The time for bringing the compound solution of the present invention into contact with the conductive peripheral metal portion exposed from the pressure-sensitive adhesive layer is not particularly limited, but it is preferably 1 second or longer because the conductive material laminate has excellent temporal stability. More preferably, it is 3 seconds or more, and particularly preferably 5 seconds or more. The upper limit is preferably 10 minutes or less. The temperature of the compound solution at the time of bringing the compound solution of the present invention into contact with the conductive peripheral metal part is not particularly limited, but it is preferably 5 ° C. or higher because the stability with time of the conductive material laminate is excellent, and more preferable 10 ° C. or higher. The upper limit is preferably 90 ° C. or less.

  After the conductive peripheral metal portion exposed from the pressure-sensitive adhesive layer is brought into contact with the compound solution of the present invention by the method described above, the conductive peripheral metal portion is preferably washed with water for the purpose of removing excess compound solution. . The water washing may be carried out with water alone, with water containing a pH adjuster such as phosphate, carbonate or the like, or with water containing a preservative for the purpose of preventing putrefaction.

  The method of washing with water is not particularly limited, and a method of removing while spraying a warm water shower using a scrubbing roller or the like, or a method of removing warm water by jet of a nozzle with a momentum of water can be exemplified. A plurality of showers or nozzles can be provided to increase the removal efficiency. After washing with water, it is preferable to dry the remaining moisture on the conductive peripheral metal portion by heating or natural drying.

  As a method of confirming that the compound of the present invention is present on the conductive peripheral metal part after washing with water, X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), energy dispersive X-ray A method of evaluating the amount of elemental sulfur using an analysis method such as spectroscopy (EDS) can be exemplified. If the amount of sulfur element on the conductive peripheral metal part is increased before and after the contact of the compound solution of the present invention and the water washing step applied thereafter, the compound of the present invention exists on the conductive peripheral metal part It can be determined that

  As long as the conductive material laminate of the present invention has the compound of the present invention on the conductive peripheral metal portion exposed from the pressure-sensitive adhesive layer, the conductive material laminate can be formed on the conductive peripheral metal portion coated with the pressure-sensitive adhesive layer. It may have the compound of the invention.

  Next, the conductive material which comprises the conductive material laminated body of this invention is demonstrated. When the conductive material laminate of the present invention is used for applications requiring light transmittance such as a touch panel sensor, the support preferably has light transmittance from the viewpoint of the transparency of the conductive material. 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. From the viewpoint of the transparency of the conductive material to be obtained, the total light transmittance of the support is preferably 60% or more, particularly preferably 70% or more. The support may have known layers such as an easily adhesive layer, a hard coat layer, an antireflective layer and an antiglare layer.

  The conductive peripheral metal portion that the conductive material has on the support includes a terminal portion having a plurality of terminals provided for taking out an electrical signal to the outside of the change in capacitance detected by the sensor portion, the sensor portion and the terminal The peripheral wiring part which has a plurality of peripheral wiring which electrically connects with a part can be illustrated. The type of metal contained in the conductive peripheral metal portion is not limited, and examples thereof include known metals such as gold, silver, copper, aluminum, and nickel, and alloys made of known metals. It is preferable from the viewpoint of having excellent properties, and it is particularly preferable to contain silver. The metal content of the conductive peripheral metal portion is preferably 50% by mass or more from the viewpoint of excellent conductivity, more preferably 70% by mass or more, and particularly preferably 80% by mass or more.

The amount of metal in the conductive peripheral metal portion is not particularly limited, but if the amount of metal is too large, the conductive peripheral metal portion may be thick and the effects of the present invention may be insufficient. When the amount of metal is too small, the conductivity of the conductive peripheral metal portion may be insufficient. Thus the metal content of the conductive peripheral metal portion is preferably 0.2~10.0g / ^{m 2,} more preferably 0.3~8.0g / ^{m 2,} particularly preferably 0.4 to It is 6.0 g / m ² . The metal content of the conductive peripheral metal part is obtained by partially cutting the conductive material to obtain a measurement sample, measuring the amount (g) of the metal in the measurement sample by fluorescent X-ray, and having the conductive peripheral metal part of the measurement sample It can be calculated by dividing the area by the area (m ² ) of only the portion where the conductive peripheral metal portion exists.

  In the conductive material laminate of the present invention, the conductive peripheral metal portion has an exposed portion at least a portion of which is exposed from the pressure-sensitive adhesive layer described later. When the conductive material laminate of the present invention is used for a touch panel sensor, the exposed portion is preferably provided to connect a wiring member such as a flexible printed wiring board or the like responsible for electrical connection with the outside to the conductive peripheral metal portion. Therefore, the exposed portion is preferably a terminal portion. The line width of the exposed portion exposed from the pressure-sensitive adhesive layer is required to be 15 μm or more from the viewpoint of the temporal stability of the conductive material laminate, preferably 30 μm or more, and particularly preferably 60 μm or more. When the line width of the exposed portion exposed from the pressure-sensitive adhesive layer is less than 15 μm, the temporal stability of the conductive material laminate becomes insufficient. The upper limit is not particularly limited, but in order to miniaturize the member by suppressing the mounting area, the line width of the exposed portion is preferably 2000 μm or less. The distance between the exposed portions is not particularly limited, but is preferably 1 μm or more from the viewpoint of insulation between the exposed portions. The upper limit of the distance between the exposed portions is preferably 2000 μm or less because the mounting area can be suppressed.

  In the conductive material laminate of the present invention, the line width of the conductive peripheral metal portion other than the exposed portion is not particularly limited, but 3 μm or more is preferable because the conductivity of the conductive peripheral metal portion is excellent, preferably 5 μm. Or more, and particularly preferably 7 μm or more. The upper limit is preferably 2000 μm or less because the mounting area can be suppressed. The distance between the conductive peripheral metal portions other than the exposed portion is not particularly limited, but is preferably 1 μm or more from the viewpoint of insulation between the conductive peripheral metal portions. The upper limit of the distance between the conductive peripheral metal portions other than the exposed portion is preferably 2000 μm or less because the mounting area can be suppressed.

  The method for forming the conductive peripheral metal portion on the support in the present invention is not particularly limited, and a conductive metal ink containing metal and a binder and conductivity according to the method disclosed in, for example, JP-A-2015-69877. The silver halide emulsion layer is provided on the support in accordance with the method of forming the conductive peripheral metal portion by applying the paste on the support by a method such as printing, or the method disclosed in JP-A-2007-59270. A method of forming a conductive peripheral metal portion using a silver halide photosensitive material as a conductive material precursor and curing development method, according to the methods disclosed in JP-A 2004-221564, JP-A 2007-12314, etc. A method of forming a conductive peripheral metal part using a direct development method, using a silver halide photosensitive material having a silver halide emulsion layer on a support as a conductive material precursor, According to the methods disclosed in 003-77350, JP-A-2005-250169, JP-A-2007-188655, JP-A-2004-207001, etc., a physical development nucleus layer and silver halide on a support The conductive peripheral metal portion is formed using a so-called silver salt diffusion transfer method in which a silver salt photosensitive material having at least an emulsion layer in this order is used as a conductive material precursor, and a soluble silver salt forming agent and a reducing agent According to the method of formation, the method disclosed in JP-A-2014-197531, a base layer and a photosensitive resist layer are laminated on a support, and the photosensitive resist layer is exposed to light in an arbitrary pattern and developed. After forming the image, electroless plating is performed to localize the metal on the underlayer not covered with the resist image, and then the resist image is removed Metal film and a resist film are provided on the support according to the method disclosed in JP-A-2015-82178, and the resist film is exposed and developed to form an opening according to the method disclosed in JP-A-2015-82178. A method of forming the conductive peripheral metal portion by etching and removing the metal film of the opening can be exemplified.

  Among the methods of forming the conductive peripheral metal portion on the above-described support, since the conductive peripheral metal portion containing silver excellent in conductivity can be easily formed, the conductive metal ink and the conductive paste are used to conduct the conductivity. Particularly preferred is a method of forming a conductive peripheral metal portion or a method of forming a conductive peripheral metal portion using a silver salt photosensitive material as a conductive material precursor.

  After forming the conductive peripheral metal portion on the support, the conductive peripheral metal portion may be subjected to known metal surface treatment before applying the compound of the present invention. 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. In addition, when a conductive peripheral metal portion is formed using a silver salt photosensitive material as a conductive material precursor, it is disclosed in Japanese Patent Application Laid-Open No. 2007-12404 for the purpose of further improving the effect of the present invention. Alternatively, the surface of the conductive peripheral metal part may be treated with a treatment solution containing an enzyme such as a proteolytic enzyme to reduce the remaining gelatin and the like.

  The light transmitting conductive layer which the conductive material has on the support will be described. When the conductive material laminate of the present invention is used for a touch panel sensor, the light transmissive conductive layer may be a sensor unit having a plurality of sensors electrically insulated from each other. The configuration of the light transmitting conductive layer is not particularly limited, and may be a mesh-like fine metal wire pattern formed according to the method of forming the conductive peripheral metal portion described above, as disclosed in JP2009-215594A, etc. It may be a layer containing the metal nanowire described, conductive metal oxides such as ITO (indium tin oxide), IZO (indium zinc oxide), ZnO (zinc oxide), etc., polythiophene, polyacetylene, polypyrrole, It may be a nonmetallic conductive film formed of a conductive polymer such as polyaniline, graphene or the like.

  When the application of the conductive material laminate of the present invention is a touch panel sensor and a mesh-like fine metal wire pattern is used as a light transmitting conductive layer, the mesh-like fine metal wire pattern has a geometry in which a plurality of unit lattices are arranged in a mesh Having a shape is preferable from the viewpoint of the sensitivity of the sensor, visibility (the shape of the sensor is difficult to see), and the like. 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 preferable shapes of the mesh metal fine line pattern.

  The mesh-like metal fine line pattern is a dummy part formed of the mesh-like metal fine line pattern electrically insulated from the sensor on the support from the viewpoint of the visibility (slight visibility) of the sensor part May be included. It is preferable from a viewpoint of visibility that the line width of the thin metal wire which comprises a sensor part and a dummy part is 20 micrometers or less, More preferably, it is 1-10 micrometers. Moreover, it is preferable that the repeating space | interval of a unit cell is 50-600 micrometers from a sensitivity of a sensor, a viewpoint of visibility, More preferably, it is 50-400 micrometers or less. The aperture ratio of the reticulated metal fine wire pattern is preferably 85% or more from the viewpoint of excellent transparency of the conductive material laminate of the present invention, and more preferably 88 to 99%.

  Wiring members, such as a flexible printed wiring board which bears electrical connection with the exterior, are mounted in the conductive peripheral metal part exposed from the adhesive layer which the conductive material laminate of the present invention has. The electrical connection between the exposed portion and the wiring member is carried out by using the conductive metal ink or conductive paste containing the metal and the binder described above, and the anisotropic conductive layer described in JP-A-2016-181442. Can be illustrated.

  The pressure-sensitive adhesive layer constituting the conductive material laminate of the present invention will be described. From the viewpoint of the transparency of the conductive material laminate of the present invention, the pressure-sensitive adhesive layer preferably has a total light transmittance of 90% or more, particularly preferably 95% or more. From the same viewpoint, the haze of the pressure-sensitive adhesive layer is preferably 0 to 3%, particularly preferably 0 to 2%. For forming the pressure-sensitive adhesive layer, known substances having adhesiveness can be used. Specifically, natural rubber-based pressure-sensitive adhesives, synthetic rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives and the like can be exemplified. Among them, acrylic pressure-sensitive adhesives are particularly preferable because they are excellent in weather resistance and transparency.

  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) CS9864UAS / CS9864UA 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 (Loctit 3192, Loctite3193 etc.) and the like can be exemplified, it is possible to obtain them use.

  The functional material which comprises the conductive material laminated body of this invention is demonstrated. As the functional material, the conductive material described above, 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 surface of the above glass or film The material which has well-known functional layers, such as a hard-coat layer, an anti-reflective layer, an anti-glare layer, a polarizing layer, etc. can be illustrated.

  The application of the conductive material laminate of the present invention is not limited, and can be suitably used for a touch panel sensor, an electromagnetic wave shielding material, and the like.

  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 mass% Epomin (registered trademark) SP-200 aqueous solution 500 mg
(Nippon Shokuhin Co., Ltd. polyethyleneimine; average molecular weight 10,000)

  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 is a sensor equivalent portion 21 (four of 21a to 21d), a peripheral wire equivalent portion 22 (four of 22a to 22d), and a peripheral wire equivalent portion 22 '(four of 22a' to 22d '), The terminal equivalent portion 23 (four of 23a to 23d) and the terminal equivalent portion 23 '(four of 23a' to 23d ') are provided. The sensor equivalent portion 21 is formed by a mesh pattern formed of a rhombic unit lattice having a line width of 4.5 μm, a side length of 300 μm, and a narrow angle of 60 °. The ', terminal corresponding parts 23 and 23' are all solid patterns (painted patterns). The line widths of the peripheral wire equivalent parts 22 and 22 'are all 40 μm, and the shortest distance between adjacent peripheral wire equivalent parts is 40 μm. The line width of the terminal equivalent parts 23 and 23 'is 500 μm, and the shortest distance between adjacent terminal equivalent parts is 500 μm. In the drawing, the broken line represents the bonding area 31 of the functional material described later, and the broken line does not exist on the positive-type transparent original.

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, a conductive material 1 having a sensor unit having a plurality of sensors, a peripheral wiring unit having a plurality of peripheral wirings, and a terminal unit having a plurality of terminals 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. The sensor portion corresponds to the light transmitting conductive layer formed by the mesh metal fine wire pattern, and the peripheral wiring portion and the terminal portion correspond to the conductive peripheral metal portion. As a result of measurement by fluorescent X-ray analysis, the metal amount of the conductive peripheral metal portion was 1.0 g / m ² .

<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.

<Production of Conductive Material 2>
The conductive material 1 was immersed in the following compound solution 1 at 30 ° C. for 1 minute, then the excess compound solution 1 was removed by showering with water and dried to obtain a conductive material 2.

<Compound solution 1>
Compound M-2 1.5 g
Water 1.0L

<Production of Conductive Material 3>
The conductive material 1 was immersed in the following compound solution 2 at 30 ° C. for 1 minute, then the excess compound solution 2 was removed by showering with water and dried to obtain a conductive material 3.

<Compound solution 2>
Compound M-4 1.5 g
Water 1.0L

<Preparation of Conductive Material 4>
The conductive material 1 was immersed in the following compound solution 3 at 30 ° C. for 1 minute, then the excess compound solution 3 was removed by showering with water and dried to obtain a conductive material 4.

<Compound solution 3>
Compound M-5 1.5 g
Water 1.0L

<Preparation of Conductive Material 5>
After immersing the conductive material 1 in the following compound solution 4 at 30 ° C. for 1 minute, the excess compound solution 4 was removed by showering with water and dried to obtain a conductive material 5.

<Compound solution 4>
Compound M-11 1.5 g
Water 1.0L

<Production of Conductive Material 6>
The conductive material 1 was immersed in the following compound solution 5 at 30 ° C. for 1 minute, then the excess compound solution 5 was removed by showering with water and dried to obtain a conductive material 6.

<Compound solution 5>
Compound M-17 1.5 g
Water 1.0L

<Preparation of Conductive Material 7>
The conductive material 1 was immersed in the following compound solution 6 at 30 ° C. for 1 minute, then the excess compound solution 6 was removed by showering with water and dried to obtain a conductive material 7.

<Compound solution 6>
Compound M-18 1.5 g
Water 1.0L

<Preparation of Conductive Material 8>
The conductive material 1 was immersed in the following compound solution 7 at 30 ° C. for 1 minute, then the excess compound solution 7 was removed by showering with water and dried to obtain a conductive material 8.

<Compound solution 7>
Compound M-19 1.5 g
Water 1.0L

<Preparation of Conductive Material 9>
The conductive material 1 was immersed in the following compound solution 8 at 30 ° C. for 1 minute, then the excess compound solution 8 was removed by showering with water and dried to obtain a conductive material 9.

<Compound solution 8>
Compound M-22 1.5 g
Water 1.0L

<Preparation of Conductive Material 10>
The conductive material 1 was immersed in the following compound solution 9 at 30 ° C. for 1 minute, then the excess compound solution 9 was removed by showering with water and dried to obtain a conductive material 10.

<Compound solution 9>
Compound C-1 1.5 g
Sodium hydroxide 1.5 g
Water 1.0L

<Preparation of Conductive Material 11>
The conductive material 1 was immersed in the following compound solution 10 at 30 ° C. for 1 minute, then the excess compound solution 10 was removed by showering with water and dried to obtain a conductive material 11.

<Compound solution 10>
Compound C-2 1.5 g
Sodium hydroxide 1.5 g
Water 1.0L

<Preparation of Conductive Material 12>
The conductive material 12 is the same as the conductive material 7 except that a positive-type transparent original is used in which the line width of the terminal equivalent parts 23 and 23 'is changed to 200 .mu.m and the shortest distance between adjacent terminal equivalent parts is 800 .mu.m. Obtained. The shape, line width, and the like of the pattern of the obtained conductive material 12 were the same as those of the positive-type transparent original.

<Preparation of Conductive Material 13>
The conductive material 13 is the same as the conductive material 7 except that a positive-type transparent original is used in which the line width of the terminal equivalent parts 23 and 23 'is changed to 80 .mu.m and the shortest distance between adjacent terminal equivalent parts is 920 .mu.m. Obtained. The shape, line width and the like of the pattern of the obtained conductive material 13 were the same as those of the positive-type transparent original.

<Preparation of Conductive Material 14>
The conductive material 14 is the same as the conductive material 7 except that a positive-type transparent original is used in which the line width of the terminal equivalent parts 23 and 23 'is changed to 40 μm and the shortest distance between adjacent terminal equivalent parts is 960 μm. Obtained. The shape, line width and the like of the pattern of the obtained conductive material 14 were the same as those of the positive-type transparent original.

<Production of Conductive Material 15>
The conductive material 15 is the same as the conductive material 7 except that a positive-type transparent original is used in which the line width of the terminal equivalent parts 23 and 23 'is changed to 20 .mu.m and the shortest distance between adjacent terminal equivalent parts is 980 .mu.m. Obtained. The shape, line width and the like of the pattern of the obtained conductive material 15 were the same as those of the positive-type transparent original.

<Preparation of Conductive Material 16>
The conductive material 16 is the same as the conductive material 7 except that a positive-type transparent original is used in which the line width of the terminal equivalent parts 23 and 23 'is changed to 10 .mu.m and the shortest distance between adjacent terminal equivalent parts is 990 .mu.m. Obtained. The shape, line width, etc. of the pattern of the obtained conductive material 16 were the same as those of the positive-type transparent original.

<Confirmation of the Presence of the Compound of the Present Invention>
The elemental sulfur content of each of the conductive materials 1 to 16 was evaluated using an energy dispersive X-ray spectrometer attached to FE-SEM (S-4800 manufactured by Hitachi High-Technologies Corporation). The amount of sulfur element in the conductive materials 2 to 9 and 12 to 16 was increased as compared to the conductive material 1, and it was confirmed that the compound of the present invention was present.

<Production of Conductive Material Laminates 1 to 16>
For each of conductive materials 1 to 16, a high transparency adhesive transfer tape 8146-4 manufactured by Sumitomo 3M Ltd. is bonded to the bonding area 31 of the functional material, and a 100 μm thick adhesive layer (total light transmittance 99% Above, it was set as the haze 0.4%. 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 obtain conductive material laminates 1 to 16. In each of the conductive material laminates 1 to 16, a part of the terminal portion is exposed from the pressure-sensitive adhesive layer, and this portion corresponds to the exposed portion in the present invention. The same procedure was repeated to prepare 30 samples each of the conductive material laminates 1-16.

<Number of samples that have changed over time>
For all samples of each conductive material laminate, the resistance value between the left and right terminals (4 pairs corresponding to between 23a-23a 'and 23d-23d' in the positive-type transparencies) which are conductive on design is measured initially and the resistance value ^(R 0 ^a~R 0 d). Next, a shielding exposure test (natural ventilation type) according to JIS Z 2381 was carried out for 3 months. After the test, the resistance value between the left and right terminals electrically connected in design was measured for all the samples, and the resistance value after test (Ra to Rd) was used. And the resistance value change rate (unit:%) between terminals was computed according to the following formula. When the resistance value change rate exceeded ± 10% among one set of four terminals, it was determined that the sample changed with time. Of the 30 sheets of each of the conductive material laminates 1 to 16, the number of samples with time-dependent change is shown in Table 1.
Resistance value change rate between terminals (unit:%) = {(Rx- ^R0 x) / ^R0 x} x 100
In the formula, x represents a to d.

  From the results in Table 1, it can be seen that the conductive material laminate having excellent stability over time can be obtained by the present invention. The advantages of the preferred embodiments of the present invention are also apparent.

21 Sensor equivalent portion 22, 22 'Peripheral wire equivalent portion 23, 23' Terminal equivalent portion 31 Bonding area of functional material

Claims (1)

A conductive material having a light transmitting conductive layer and a conductive peripheral metal part on a support, on the side having the light transmitting conductive layer and the conductive peripheral metal part, at least an adhesive layer and a functional material A conductive material laminate having in this order, the conductive peripheral metal portion has an exposed portion at least a part of which is exposed from the adhesive layer, and the line width of the exposed portion is 15 μm or more, A conductive material laminate comprising a compound represented by the following general formula (1) on the exposed portion.
In the general formula (1), R ₁ represents an aliphatic group, an aromatic group or a heterocyclic group. R ₂ and R ₃ each represent an aliphatic group.