JP2014178465A - Method for forming wiring line, conductive pattern substrate, touch panel sensor and photosensitive conductive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a conductive pattern, by which a wiring line as thin as about 15 μm or less can be formed through a small number of steps.SOLUTION: A method for forming a wiring pattern is provided, which includes steps in the following order: a step of laminating a substrate 20 with a photosensitive conductive film 10 having a support film 1, a conductive film 2 disposed on the support film 1, and photosensitive resin layer 3 disposed on the conductive film 2, while arranging the photosensitive resin layer 3 to be located in the substrate 20 side; a step of partially irradiating the photosensitive resin layer 3 with active rays; a step of peeling the support film 1 and developing the photosensitive resin layer 3 so as to partially remove the photosensitive resin layer 3 together with the conductive film 2 and to form a cured resin pattern and a conductive pattern 2a disposed on the cured resin pattern; and a step of forming a metal layer that partially covers the conductive pattern 2a by electroless plating.

Description

  The present invention relates to a wiring formation method, a conductive pattern substrate, a touch panel sensor, and a photosensitive conductive film.

  The touch sensor part of the touch panel is a sensor part that senses information touched by a human finger, etc. without blocking the information on the screen in the viewable area (view area), and a wiring (drawer wiring part) for transmitting the information It consists of.

  A transparent conductive pattern that absorbs less visible light and has conductivity is provided as an electrode in the sensor portion of the view area. Further, a metal having a small resistance value is used for the lead-out wiring. These sensor parts and lead-out wiring parts are manufactured as follows, for example.

<First method>
First, the photosensitive resin layer is laminated | stacked on the transparent electrode layer provided on support base materials, such as a polyethylene terephthalate board | substrate or a glass substrate (lamination process). Next, the exposed portion is cured (or dissolved) by irradiating a predetermined portion of the photosensitive resin layer with an actinic ray (exposure step). Thereafter, an uncured portion (or dissolved portion) is removed (developed) from the substrate, whereby a resist pattern made of a cured product of the photosensitive resin composition is formed on the supporting substrate (developing step). The obtained resist pattern is etched to form a view area sensor pattern on the substrate, and then the resist is peeled and removed (peeling step). Subsequently, the sensor part and the lead-out wiring part of the touch panel are manufactured by forming the lead-out wiring from the formed transparent electrode sensor by screen printing using silver paste or the like.

  FIG. 3 is a schematic cross-sectional view showing the first method. In this manufacturing method, as a laminating process, a photosensitive resin layer is laminated on the transparent electrode layer 14 (FIG. 3A) of the laminated substrate composed of the transparent electrode layer 14 and the support substrate 12, and the photosensitive resin layer is formed. The exposed portion is irradiated with actinic rays to cure the exposed portion, the uncured portion is removed from the substrate, and a resist pattern comprising the cured portion of the photosensitive resin layer is formed. Next, the laminated base material on which the resist pattern is formed is subjected to an etching process so that a part of the transparent electrode layer 14 is removed from the support base material 12, and then the resist pattern is peeled and removed. A sensor pattern of a view area is formed on 12 (FIG. 3B). By forming the lead wiring 18 from the formed sensor pattern by screen printing using silver paste or the like, the sensor part and lead wiring part of the touch panel are manufactured (FIG. 3C).

<Second method>
In the second method, after forming the sensor pattern in the above <first method> using the photosensitive conductive film described in Patent Document 1 or 2, the lead-out wiring from the sensor of the formed transparent electrode is silver paste or the like This is a method in which the sensor part and the lead-out wiring part of the touch panel are manufactured by forming the screen by using screen printing.

<Third method>
Using a laminated base material composed of a three-layer structure of a metal layer (for lead wiring formation), a transparent electrode layer (for view area sensor formation), and a supporting base material (film), a photosensitive resin is formed on the laminated base material. Layers are laminated (lamination process). Next, a predetermined portion of the photosensitive resin layer is irradiated with actinic rays to cure (or dissolve) the exposed portion (exposure process). Then, the resist pattern which consists of hardened | cured material of the photosensitive resin composition is formed on a base material by removing (developing) an uncured site | part (or melt | dissolution part) from a base material (development process). The metal layer and the transparent electrode layer are removed from the obtained resist pattern by an etching process (first etching step) to form a lead-out wiring and a transparent electrode pattern in the view area. Subsequently, a photosensitive resin layer is newly laminated, exposed, and developed to remove only unnecessary metal layers in the view area (second etching). By this method, a touch sensor part having a narrow lead wiring pitch is manufactured (for example, see Patent Document 3).

  FIG. 4 is a schematic cross-sectional view showing the third method. On the metal layer 26 of the laminated substrate comprising the support substrate 22, the transparent conductive layer 24 provided on one surface of the support substrate 22, and the metal layer 26 provided on the transparent conductive layer 24, A resist pattern 29 made of a cured product of the conductive resin composition is formed (FIG. 4B). The metal layer 26 and the transparent conductive layer 24 in a region not masked by the resist pattern 29 are removed from the support base material 22 by the etching process (FIG. 4C), from which the resist pattern 29 is removed. (FIG. 4D) First, the photosensitive resin layer 30 is formed on the laminated base material that has undergone the second step (FIG. 4E), and then the photosensitive resin layer 30 is exposed and developed. Then, a resist 31 made of a cured product of the photosensitive resin layer 30 is formed (Fig. 4 (f)), Fig. 4 (g) is a diagram showing an etching process, and in Fig. 4 (g), a supporting substrate A transparent electrode made up of the remainder of the transparent conductive layer 24 is formed on 22 and a laminated body made up of the metal layer 26 and the resist 31 is formed on a part of the transparent electrode. 4 (h). As shown in, on a supporting substrate 22, a transparent electrode and a metal wiring made of the remainder of the metal layer 26 is formed consisting of the remainder of the transparent conductive layer 24.

International Publication No. 2010/021224 International Publication No. 2011/142360 Japanese Patent No. 4855536

  By the way, it is required to narrow the pitch of the lead-out wiring by narrowing the frame (bezel) of the touch panel. Recently, miniaturization of L / S (line width / space width) of 15/15 (unit: μm) or less is required.

  However, in the first method, only a wiring having an L / S (line width / space width) of about 70/70 (unit: μm) can be formed. In the second method, the sensor part can be miniaturized, but there is a problem that the lead wiring part cannot be finely formed.

  Furthermore, in the third method, it is possible to cope with the miniaturization of L / S of about 30/30, but it is still difficult to form a finer wiring of about 15 μm. There was room for.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a wiring forming method that makes it possible to form a wiring miniaturized to about 15 μm or less with fewer steps.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have reduced the number of lead-out wirings having a line width and space width of 15 μm or less by a novel process combining a photosensitive conductive film and electroless plating. And found that it can be formed.

That is, in the first aspect of the present invention, a photosensitive conductive film having a support film, a conductive film provided on the support film, and a photosensitive resin layer provided on the conductive film is formed on the substrate. Laminating the photosensitive resin layer in the direction located on the substrate side;
Irradiating a part of the photosensitive resin layer with actinic rays;
Peeling the support film and developing the photosensitive resin layer to form a cured resin pattern and a conductive pattern provided on the cured resin pattern;
And a step of forming a metal layer covering a partial region of the conductive pattern by electroless plating in this order.

  Said 1st aspect can include the process of providing the overcoat layer which covers the one part area | region of the said conductive pattern after a image development process. Thereby, plating deposition to an unnecessary part can be prevented.

  The conductive film may contain at least one type of conductor selected from the group consisting of an inorganic conductor and an organic conductor.

  The conductive film may include conductive fibers. When the conductive film contains conductive fibers, both conductivity and transparency can be achieved, developability can be further improved, and a conductive pattern with excellent resolution can be formed as wiring.

  The conductive fiber is preferably silver fiber. By using silver fibers, the conductivity of the formed conductive pattern can be easily adjusted.

  The conductive film may contain at least one conductor selected from the group consisting of polythiophene, polythiophene derivatives, polyaniline, and polyaniline derivatives. In this case, sufficient conductivity can be obtained even with a thin film that can be easily removed in the development step.

  The photosensitive resin layer may contain a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator. When the photosensitive resin layer contains the above components, the adhesion between the substrate and the conductive pattern and the patterning property can be further improved.

  The photosensitive resin layer may further contain a compound containing one or more electron-donating atoms selected from N, P, O, and S. Thereby, it is possible to further increase the definition of the lead-out wiring and shorten the process.

  A 2nd aspect of this invention is related with a conductive pattern board | substrate provided with a board | substrate and the wiring formed on this board | substrate by the said wiring formation method. According to the conductive pattern substrate of the present invention, since the wiring is formed by the wiring forming method of the present invention, the wiring is hardly visible. Further, according to the conductive pattern substrate according to the present invention, since the step of the wiring is small, for example, a photosensitive conductive film, an optical improvement film (OCA), an index matching film (IMF), etc. on the wiring. When the films are bonded together, it is possible to reduce entrainment of bubbles due to the steps.

  A 3rd aspect of this invention is related with a touchscreen sensor provided with the said conductive pattern board | substrate. The touch panel sensor according to the present invention can have good visibility and aesthetics by including the conductive pattern substrate according to the present invention.

  4th aspect of this invention is a photosensitive conductive film which has a support film, the electrically conductive film provided on this support film, and the photosensitive resin layer provided on this electrically conductive film, Comprising: The said photosensitive resin layer Includes a) a binder polymer, b) a photopolymerizable compound having an ethylenically unsaturated bond, c) a photopolymerization initiator, and d) one or more electron-donating substances selected from N, P, O, and S. The present invention relates to a photosensitive conductive film containing a compound containing an atom. The component d) is other than the components a) to c).

  According to the present invention, it is possible to form a wiring miniaturized to about 15 μm or less with a small number of steps. The method of the present invention is particularly suitable for forming a conductive pattern used as an electrode wiring of a device such as a flat panel display such as a liquid crystal display element, a touch panel (touch screen), a solar cell, or illumination.

It is a schematic cross section showing one embodiment of a photosensitive conductive film. It is a partially cutaway perspective view showing one embodiment of a photosensitive conductive film. It is a schematic cross section which shows the formation method (1st method) of the conventional wiring. It is a schematic cross section which shows the formation method (3rd method) of the conventional wiring. It is a schematic cross section for demonstrating one Embodiment of the formation method of the wiring using a photosensitive conductive film. It is process drawing which shows the electroless-plating process using a photosensitive conductive film. It is a top view which shows one Embodiment of a touch panel.

  Hereinafter, preferred embodiments of the present invention will be described in detail. In the present specification, “(meth) acrylate” means “acrylate” and “methacrylate” corresponding thereto. Similarly, “(meth) acrylic” means “acrylic” and “methacrylic” corresponding thereto, “(meth) acrylic acid” means “acrylic acid” or “methacrylic acid”, and “(meth) acrylic”. ) "Acryloyl" means "acryloyl" and the corresponding "methacryloyl". In addition, “(meth) acrylic acid alkyl ester” means “acrylic acid alkyl ester” and “methacrylic acid alkyl ester” corresponding thereto. Further, “EO” represents ethylene oxide, and “EO-modified” means a compound having an ethylene oxide group. Similarly, “PO” represents propylene oxide, and “PO-modified” means a compound having a propylene oxide group.

  In the wiring forming method according to the present embodiment, a photosensitive conductive film having a support film, a conductive film provided on the support film, and a photosensitive resin layer provided on the conductive film is formed on a substrate. Photosensitive layer by laminating in the direction in which the photosensitive resin layer is positioned on the substrate side, irradiating a part of the photosensitive resin layer with actinic rays, peeling the support film, and developing the photosensitive resin layer A part of the resin layer is removed together with the conductive film to form a cured resin pattern and a conductive pattern provided on the cured resin pattern, and a metal layer covering a part of the conductive pattern is formed by electroless plating. And forming a conductive pattern and a wiring composed of a metal layer in this order.

  The boundary between the conductive film and the photosensitive resin layer is not necessarily clear. The conductive film only needs to have conductivity in the surface direction of the photosensitive layer, and the conductive film and the photosensitive resin layer may be mixed. For example, the composition constituting the photosensitive resin layer may be impregnated in the conductive film, or the composition constituting the photosensitive resin layer may be present on the surface of the conductive film.

  According to the method according to this embodiment, the lead-out wiring of the touch panel can be miniaturized by a novel process in which a photosensitive conductive film and selective electroless plating are combined. Hereinafter, this embodiment will be described.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of a photosensitive conductive film used in the present embodiment. A photosensitive conductive film 10 shown in FIG. 1 has a support film 1 and a photosensitive layer 4 provided on the support film 1. The photosensitive layer 4 includes a conductive film 2 provided on the support film 1 and a photosensitive resin layer 3 provided on the conductive film 2.

  As the support film 1, a polymer film can be used, and a polymer film having heat resistance and solvent resistance is preferable. Examples of such a polymer film include a polyethylene terephthalate film, a polyethylene film, a polypropylene film, and a polycarbonate film. Among these, a polyethylene terephthalate film is preferable from the viewpoint of transparency and heat resistance.

  The above polymer film may be subjected to a release treatment so that it can be easily peeled off from the photosensitive layer 4 later.

  When peeling a support film at the below-mentioned 2nd exposure process, the support film 1 may further have layers, such as a gas barrier layer.

  From the viewpoint of mechanical strength, the thickness of the support film 1 is preferably 5 μm or more, more preferably 10 μm or more, and further preferably 15 μm or more. By setting the thickness of the support film 1 to the above numerical value or more, for example, a step of applying a conductor dispersion liquid or a conductor solution to form the conductive film 2, or a photosensitive property to form the photosensitive resin layer 3. It is possible to prevent the support film 1 from being broken in the step of applying the resin composition or the step of peeling the support film 1 from the photosensitive layer 4 during the second exposure step. Further, from the viewpoint of sufficiently ensuring the resolution of the conductive pattern when the photosensitive resin layer 3 is irradiated with actinic rays through the support film 1, the thickness of the support film 1 is preferably 300 μm or less, and 200 μm or less. More preferably, it is more preferably 100 μm or less.

  From the above viewpoint, the thickness of the support film 1 is preferably 5 to 300 μm, more preferably 10 to 200 μm, and particularly preferably 15 to 100 μm.

  The haze value of the support film 1 is preferably 0.01 to 5.0%, more preferably 0.01 to 3.0%, from the viewpoint of improving sensitivity and resolution. -2.0% is particularly preferred, and 0.01-1.5% is very particularly preferred. The haze value can be measured according to JIS K 7105. For example, it can be measured with a commercially available turbidimeter such as NDH-1001DP (trade name, manufactured by Nippon Denshoku Industries Co., Ltd.). .

  The conductive film 2 can contain at least one type of conductor selected from the group consisting of inorganic conductors and organic conductors. If the electroconductivity of the electrically conductive film 2 is acquired, an inorganic conductor and an organic conductor can be especially used without a restriction | limiting, These conductors can be used individually or in combination of 2 or more types.

  Examples of the inorganic conductor include metal fibers described later. Examples of the organic conductor include a conductive polymer. As the conductive polymer, at least one type of conductor selected from the group consisting of polythiophene, polythiophene derivatives, polyaniline, and polyaniline derivatives can be used. For example, one or more of polyethylenedioxythiophene, polyhexylthiophene and polyaniline can be used in combination. When the conductive film 2 includes an organic conductor, it is preferable that the conductive film 2 includes an organic conductor and a photosensitive resin.

  The conductive film 2 preferably contains conductive fibers. When the conductive film contains conductive fibers, both conductivity and transparency can be achieved, developability is further improved, and a conductive pattern with excellent resolution can be formed.

  Examples of the conductive fiber include metal fibers such as gold, silver, and platinum, and carbon fibers such as carbon nanotubes. These can be used alone or in combination of two or more. From the viewpoint of conductivity, it is preferable to use gold fiber and / or silver fiber, and from the viewpoint of easily adjusting the conductivity of the conductive film, it is more preferable to use silver fiber.

The metal fiber can be prepared by, for example, a method of reducing metal ions with a reducing agent such as NaBH ₄ or a polyol method. Commercially available products such as Unipym's Hipco single-walled carbon nanotubes can be used as the carbon nanotubes.

  The fiber diameter of the conductive fiber is preferably 1 nm to 50 nm, more preferably 2 nm to 20 nm, and particularly preferably 3 nm to 10 nm. The fiber length of the conductive fiber is preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm, and particularly preferably 3 μm to 10 μm. The fiber diameter and fiber length can be measured with a scanning electron microscope.

  FIG. 2 is a partially cutaway perspective view showing an embodiment of a photosensitive conductive film. As shown in FIG. 2, the conductive film 2 preferably has a network structure composed of a plurality of conductive fibers in contact with each other. The conductive film 2 having such a network structure may be formed on the surface of the photosensitive resin layer 3 on the support film 1 side, but on the surface of the photosensitive layer 4 exposed when the support film 1 is peeled off. As long as conductivity is obtained in the surface direction, the conductive film 2 may be formed so that a part of the photosensitive resin layer 3 enters the conductive film 2, and the conductive film is formed on the surface layer of the photosensitive resin layer 3 on the support film 1 side. 2 may be included.

  The conductive film 2 is, for example, a conductor dispersion liquid containing one or more of the above-described inorganic conductors and organic conductors, water and / or organic solvents, and, if necessary, a dispersion stabilizer such as a surfactant. Alternatively, the conductive solution can be formed by coating the support film 1 and then drying. The coating can be performed by a known method such as a roll coating method, a comma coating method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, or a spray coating method. The drying can be performed at 30 to 150 ° C. for about 1 to 30 minutes using a hot air convection dryer or the like. In the conductive film 2, the inorganic conductor or the organic conductor may coexist with the surfactant or the dispersion stabilizer. The conductive film 2 may be composed of a plurality of films obtained by sequentially coating and drying a plurality of conductor dispersion liquids or conductor solutions on the support film 1.

  The thickness of the conductive film 2 varies depending on the use of the conductive pattern (wiring) to be formed and required conductivity, but is preferably 1 μm or less, more preferably 1 nm to 0.5 μm, and more preferably 5 nm to 0. More preferably, it is 1 μm. When the thickness of the conductive film 2 is 1 μm or less, the light transmittance in the wavelength region of 450 to 650 nm is sufficiently high, the pattern forming property is excellent, and particularly suitable for the production of a transparent electrode. In addition, the thickness of the electrically conductive film 2 points out the value measured by a scanning electron micrograph.

  In the present embodiment, after the conductive film 2 is formed on the support film 1, the photosensitive resin layer 3 is further provided. If necessary, the conductive film 2 formed on the support film 1 may be formed on the substrate. It may be laminated on the photosensitive resin layer provided on the substrate.

  The photosensitive resin layer 3 can be formed from a photosensitive resin composition containing (a) a binder polymer, (b) a photopolymerizable compound having an ethylenically unsaturated bond, and (c) a photopolymerization initiator. When the photosensitive resin layer 3 contains the above components, the adhesion between the substrate and the conductive pattern and the patterning property can be further improved.

  (A) As a binder polymer, for example, obtained by reaction of acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, ester resin, urethane resin, epoxy resin and (meth) acrylic acid Examples thereof include epoxy acrylate resins and acid-modified epoxy acrylate resins obtained by reaction of epoxy acrylate resins and acid anhydrides. These resins can be used alone or in combination of two or more.

  Among these, it is preferable to use an acrylic resin from the viewpoint of excellent alkali developability and film formability. Also. It is more preferable that the acrylic resin has a monomer unit derived from (meth) acrylic acid and (meth) acrylic acid alkyl ester as a constituent unit. Here, “acrylic resin” means a polymer mainly having monomer units derived from a polymerizable monomer having a (meth) acrylic group.

  The acrylic resin is produced, for example, by radical polymerization of a polymerizable monomer having a (meth) acryl group. These acrylic resins can be used alone or in combination of two or more.

  Examples of the polymerizable monomer having a (meth) acryl group include acrylamide such as diacetone acrylamide, (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, and (meth) acrylic acid dimethylamino. Ethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (Meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid.

  The acrylic resin is substituted at the α-position or aromatic ring such as styrene, vinyltoluene, α-methylstyrene, etc., in addition to the polymerizable monomer having the (meth) acrylic group as described above. Polymerizable styrene derivatives, esters of vinyl alcohol such as acrylonitrile and vinyl-n-butyl ether, maleic acid monoester such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid One or two or more polymerizable monomers such as cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid and the like may be copolymerized.

  Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, and (meth) acrylic acid. Pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (meth) acrylic acid Examples include decyl ester, (meth) acrylic acid undecyl ester, and (meth) acrylic acid dodecyl ester. These can be used alone or in combination of two or more.

  (A) It is preferable that a binder polymer has a carboxyl group from a viewpoint of making alkali developability more favorable. Examples of the polymerizable monomer having a carboxyl group for obtaining such a binder polymer include (meth) acrylic acid as described above.

  (A) The ratio of the carboxyl group of the binder polymer is 10 to 50% by mass as the ratio of the polymerizable monomer having a carboxyl group to the total polymerizable monomer used to obtain the binder polymer. Preferably, it is 12-40 mass%, More preferably, it is 15-30 mass%, It is especially preferable that it is 15-25 mass%. In terms of excellent alkali developability, the content is preferably 10% by mass or more, and in terms of excellent alkali resistance, it is preferably 50% by mass or less.

  (A) The acid value of the binder polymer is preferably 50 mgKOH / g or more and 150 mgKOH / g or less from the viewpoint of improving developability for various known developing solutions in the development step.

  (A) The acid value of the binder polymer can be measured as follows. Weigh precisely 1 g of the binder polymer whose acid value is to be measured.

Add 30 g of acetone to the binder polymer and dissolve it uniformly. Subsequently, phenolphthalein as an indicator can be measured by adding an appropriate amount to the above solution and titrating with a 0.1N aqueous KOH solution. The acid value can be calculated by the following formula.
Acid value = 10 × Vf × 56.1 / (Wp × I)
In the formula, Vf represents the titration amount (mL) of the KOH aqueous solution, Wp represents the weight (g) of the measured resin solution, and I represents the ratio (mass%) of the non-volatile content in the measured resin solution.

  In addition, when a synthetic solvent and a dilution solvent are contained in a binder polymer, it heats for about 1 to 4 hours at about 10 degreeC higher than the boiling point of the said solvent beforehand before precise weighing, and removes a volatile matter. At this time, volatile components such as a low molecular weight photopolymerizable compound may be removed.

  (A) The weight average molecular weight of the binder polymer is preferably 5,000 to 300,000, more preferably 20,000 to 150,000, from the viewpoint of balancing mechanical strength and alkali developability. 30,000 to 100,000 is particularly preferable. In terms of excellent developer resistance, the weight average molecular weight is preferably 5,000 or more. Further, from the viewpoint of development time, it is preferably 300,000 or less. In addition, the measurement conditions of a weight average molecular weight shall be the same measurement conditions as the Example of this-application specification.

  (A) A binder polymer can use the resin mentioned above individually or in combination of 2 or more types. When two or more kinds of resins are used in combination, for example, a binder polymer made of a mixture containing two or more kinds of resins composed of different copolymerization components, or a mixture containing two or more kinds of resins having different weight average molecular weights. Examples thereof include a binder polymer and a binder polymer composed of a mixture containing two or more kinds of resins having different dispersities.

  (B) As the photopolymerizable compound having an ethylenically unsaturated bond, for example, a compound obtained by reacting a polyhydric alcohol with α, β-unsaturated carboxylic acid, a glycidyl group-containing compound with α, β-unsaturated Compound obtained by reacting carboxylic acid, urethane monomer such as (meth) acrylate compound having urethane bond, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxy Examples include phthalic acid compounds such as ethyl-β '-(meth) acryloyloxyethyl-o-phthalate and β-hydroxypropyl-β'-(meth) acryloyloxyethyl-o-phthalate, and (meth) acrylic acid alkyl esters. It is done. These may be used alone or in combination of two or more.

  Examples of the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2- Bisphenol A-based (meth) acrylate compounds such as bis (4-((meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, Polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, 2 to 14 ethylene groups, Polyethylene polypropylene glycol di (meth) acrylate and trimethylol having 2 to 14 numbers Propane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropane Tetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, polypropylene glycol dipropylene having 2 to 14 propylene groups (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate

  Examples of the urethane monomer include (meth) acrylic monomers having a hydroxyl group at the β-position and diisocyanate compounds such as isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-hexamethylene diisocyanate. Addition reaction product, tris [(meth) acryloxytetraethylene glycol isocyanate] hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate.

  Examples of the EO-modified urethane di (meth) acrylate include “UA-11” (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). Examples of EO and PO-modified urethane di (meth) acrylate include “UA-13” (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.).

  (B) The content of the photopolymerizable compound having an ethylenically unsaturated bond is 30 to the total amount of 100 parts by mass of the (a) binder polymer and (b) the photopolymerizable compound having an ethylenically unsaturated bond. The amount is preferably 80 parts by mass, and more preferably 40 to 70 parts by mass. It is preferably 30 parts by mass or more in terms of excellent photocurability and coating properties on the formed conductive film 2, and 80 parts by mass or less in terms of excellent storage stability when wound as a film. It is preferable that

  The photosensitive resin layer may contain, in addition to the binder polymer, photopolymerizable compound, and photopolymerization initiator, a compound containing one or more kinds of atoms having electron donating properties selected from P, O, N, and S. Good. These compounds include amino group-containing silane coupling agents that do not have CO next to the amino group, or isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl (dioctyl phosphite) titanate. Tetraoctyl bis (didodecyl phosphite) titanate, tetra (2,2′-diallyloxydimethyl-1-butyl) bis (ditridodecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyro) Phosphate) Titanium coupling agent containing phosphorus such as ethylene titanate, isopropyl trioctanoyl titanate, isopropyl tri (dioctyl phosphate) titanate; 4-aminoquinoxaline, -Aminoquinoline, 4-amino-5-aminomethylpyridine dihydrochloride, 8-azaquanin, 2-aminopyridine, 2-aminopyrimidine, 5-amino-1H-tetrazole, hydroxy-2,4,5-triaminopyrimidine Amino compounds such as sulfate, 2,4-diamino-6-hydroxypyrimidine; glycine, alanine, valine, leucine, isoleucine, serine, threoline, lysine, arginine, aspartic acid, glutamic acid, asparagine, glutamine, cysteine, cystine, methionine, Amino acids such as phenylalanine, tyrosine, proline, hydroxyproline, tryptophan, histidine, β-alanine, ε-aminocaproic acid, sarcosine, DL-pyroglutamic acid; R-(−)-2-amino-1-bu Nord, 3-amino-2, 2-dimethyl-1-propanol, 2- (2-aminoethylamyl) ethanol, 6-amino-1-hexanol, 5-amino-1-pentanol, 3-amino-1- Amino alcohol such as propanol, ethyl diethylphosphonoacetate, isopropyl azido phosphate, ethyl azido phosphate, phosphorous compound such as tris (2-butoxydiethyl) phosphate, dimethyl phosphate, O-phosphorylethanolamine, mercapto group or sulfide group Silane coupling agents; triazine thiol compounds and the like.

  (C) The photopolymerization initiator is not particularly limited as long as it can cure the photosensitive resin layer 3 by irradiation with actinic rays. From the viewpoint of excellent photocurability, a radical polymerization initiator is used. It is preferable to use it. For example, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2 Aromatic ketones such as -benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1; benzoin Benzoin ether compounds such as methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin; 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O -Benzoyloxime), 1- [9- Oxime ester compounds such as til-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime); benzyl derivatives such as benzyldimethyl ketal; 2- (o-chlorophenyl)- 4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer 2,4,5-triarylimidazole dimers such as 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer Ameridine derivatives such as 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane; N— Enirugurishin, N- phenylglycine derivatives, coumarin-based compounds, oxazole-based compounds. Moreover, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may be the same to give the target compound, or differently give an asymmetric compound. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid.

  Among these, from the viewpoint of transparency, it is preferable to contain an aromatic ketone compound or an oxime ester compound, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 or 1, It preferably contains 2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime). These are used alone or in combination of two or more.

  (C) The content rate of a photoinitiator is 0.1-20 mass parts with respect to 100 mass parts of total amounts of the photopolymerizable compound which has (a) binder polymer and (b) ethylenically unsaturated bond. It is preferably 1 to 10 parts by mass, more preferably 1 to 5 parts by mass. In terms of excellent photosensitivity, it is preferably 0.1 parts by mass or more, and in terms of excellent photocurability inside the photosensitive resin layer 3, it is preferably 20 parts by mass or less.

  Various additives can be contained in the photosensitive resin layer 3 as needed. Additives include plasticizers such as p-toluenesulfonamide, fillers, antifoaming agents, flame retardants, stabilizers, adhesion promoters, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, heat Additives such as a crosslinking agent can be contained alone or in combination of two or more. The addition amount of these additives is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of (a) binder polymer and photopolymerizable compound.

  The photosensitive resin layer 3 is formed on the conductive film 2 formed on the support film, as required, with methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol. It can form by apply | coating the solution of the photosensitive resin composition about 10-60 mass% of solid content melt | dissolved in solvents, such as monomethyl ether, or these mixed solvents, and drying. However, in this case, the amount of the remaining organic solvent in the photosensitive resin layer after drying is preferably 2% by mass or less in order to prevent the organic solvent from diffusing in the subsequent step.

  Coating can be performed by a known method. Examples thereof include a roll coating method, a comma coating method, a gravure coating method, an air knife coating method, a die coating method, a bar coating method, and a spray coating method. After coating, drying for removing the organic solvent and the like can be performed at 70 to 150 ° C. for about 5 to 30 minutes with a hot air convection dryer or the like.

  Although the thickness of the photosensitive resin layer 3 changes with uses, it is preferable that it is 1-200 micrometers in thickness after drying, it is more preferable that it is 1-15 micrometers, and it is especially preferable that it is 1-10 micrometers. When this thickness is 1 μm or more, layer formation by coating tends to be easy, and when it is 200 μm or less, light transmittance is good and sufficient sensitivity can be obtained, and the photosensitive resin layer 3 From the viewpoint of photo-curing property. The thickness of the photosensitive resin layer 3 can be measured with a scanning electron microscope.

  In the photosensitive conductive film 10, the photosensitive layer 4 (laminated body of the conductive film 2 and the photosensitive resin layer 3) preferably has a minimum light transmittance of 80% or more in a wavelength region of 450 to 650 nm, 85 % Or more is more preferable. When the photosensitive layer 4 satisfies such a condition, it is easy to increase the brightness in a display panel or the like. Further, when the film thickness of the photosensitive layer 4 is 1 to 10 μm, the minimum light transmittance in the wavelength region of 450 to 650 nm is preferably 80% or more, and more preferably 85% or more. When the photosensitive layer 4 (laminated body of the conductive film 2 and the photosensitive resin layer 3) satisfies such a condition, it is easy to increase the luminance in a display panel or the like.

  The photosensitive conductive film 10 used in the present embodiment may further be provided with a protective film so as to be in contact with the surface of the photosensitive resin layer 3 opposite to the support film 1 side.

  As the protective film, a polymer film having heat resistance and solvent resistance can be used. For example, a polyethylene terephthalate film, a polypropylene film, and a polyethylene film are mentioned. Moreover, you may use the polymer film similar to the above-mentioned support body film as a protective film.

  The thickness of the protective film is preferably 1 to 100 μm, more preferably 5 to 50 μm, still more preferably 5 to 40 μm, and particularly preferably 15 to 30 μm. The thickness of the protective film is preferably 1 μm or more from the viewpoint of excellent mechanical strength, and preferably 100 μm or less from the viewpoint of being relatively inexpensive.

  The adhesive force between the protective film and the photosensitive resin layer 3 is such that the protective film 1 and the photosensitive layer 4 (the conductive film 2 and the photosensitive resin layer 3) are formed so that the protective film can be easily peeled off from the photosensitive resin layer 3. It is preferable that it is smaller than the adhesive force between.

Moreover, it is preferable that the number of fish eyes with a diameter of 80 micrometers or more contained in a protective film is 5 pieces / m < ² > or less. "Fish eye" means that when a material is melted by heat, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidized degradation products, etc. It is taken in.

  The photosensitive conductive film 10 may further have layers such as an adhesive layer and a gas barrier layer on the protective film.

  The photosensitive conductive film 10 can be stored, for example, in the form of a flat plate as it is or in the form of a roll wound around a cylindrical core. At this time, it is preferable that the support film 1 is wound up so as to be the outermost side.

  Moreover, when the photosensitive conductive film 10 does not have a protective film, this photosensitive conductive film 10 can be stored in a flat plate form as it is.

The core is not particularly limited as long as it is conventionally used. For example, plastic such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene copolymer), etc. Is mentioned. Moreover, it is preferable to install an end face separator on the end face of the photosensitive conductive film wound up in a roll shape from the viewpoint of end face protection, and in addition, it is preferable to install a moisture-proof end face separator from the viewpoint of edge fusion resistance. Moreover, when packing a photosensitive conductive film, it is preferable to wrap and wrap in a black sheet with small moisture permeability.
(Overcoat layer)

  The method according to the present embodiment includes a step of providing an overcoat layer that covers a partial region of the conductive pattern after the development step of forming the conductive pattern, and plating on a region that is not protected by the overcoat layer of the conductive pattern. And providing a metal layer.

  The overcoat layer can be formed using a resin composition similar to that of the photosensitive resin layer (herein, referred to as a photocurable resin composition). However, it is desirable that the photocurable resin composition does not contain a compound having one or more electron-donating atoms selected from P, O, N, and S in order to suppress deposition of plating in the overcoat forming portion. . Moreover, in order to prevent pattern appearance, it is preferable that the absolute value of the refractive index difference between this photocurable resin composition and the photosensitive resin layer of the photosensitive conductive film is 0.03 or less.

  Since the photocurable resin composition and the photosensitive resin layer are composed mainly of a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator, the absolute value of the refractive index difference is 0. In order to achieve 0.03 or less, it is preferable that the photocurable resin composition and the photosensitive resin layer are made of the same material, or a material having a close refractive index is used.

  In order to improve properties such as resolution, developability, heat resistance, etc., if the composition of the photocurable resin composition and the photosensitive resin layer are different, mix a material with a high refractive index with a composition with a low refractive index to change the refractive index. The refractive index difference between the two is reduced to 0.03 or less by increasing or mixing a high refractive index composition with a low refractive index material to lower the refractive index. For example, when a monomer copolymer is used as the binder polymer, the refractive index of polyethyl acrylate is 1.469 (20 ° C.), the refractive index of polymethyl methacrylate is 1.491 (20 ° C.), polystyrene. The refractive index of 1.59 is 1.59, so if you want to lower the refractive index of the binder polymer, increase the copolymerization ratio of ethyl acrylate monomer, and if you want to increase the refractive index of the binder polymer, copolymerization ratio of styrene monomer You just need to increase it.

  In order to make the difference in refractive index 0.03 or less, the average particle size is 0.04 μm or more and 0.13 μm or less, preferably 0.05 μm or more and 0.1 μm or less, more preferably 0.055 μm or more, 0 An inorganic filler and an organic filler that are 0.08 μm or less, more preferably 0.06 μm or more and 0.075 μm or less can also be blended. The above range is preferable in order to prevent reflection of visible light and ultraviolet light by the filler. Examples of inorganic fillers include glass beads (refractive index 1.51), silicon carbide (2.63), Canadian balsam (1.52), and organic fillers include melamine beads (refractive index 1.57). , Polymethyl methacrylate beads (refractive index 1.49), methyl methacrylate / styrene copolymer resin beads (refractive index 1.50 to 1.59), polycarbonate beads (refractive index 1.55), polyethylene beads (refractive 1.53), polystyrene beads (refractive index 1.6), silicone resin beads (refractive index 1.43), and the like.

  Further, the binder polymer may be blended with polyvinyl chloride (1.53 to 1.549), vinyl acetate (1.46), polystyrene-butadiene (1.56) or the like.

  FIG. 5 is a schematic cross-sectional view for explaining an embodiment of a wiring forming method using a photosensitive conductive film. In the method of this embodiment, the above-described photosensitive conductive film 10 is laminated so that the photosensitive resin layer 3 is in contact with the substrate 20 (FIG. 5A), and the photosensitive layer 4 having the support film 1. A first exposure step (FIG. 5 (b)) for irradiating a predetermined portion of actinic rays, and then, after the support film 1 is peeled off, in the presence of oxygen, the exposed portion and the unexposed portion in the first exposure step A second exposure step (FIG. 5C) for irradiating a part or all of the exposed portion with actinic rays, and a development step (FIG. 5D) for developing the photosensitive layer 4 after the second exposure step; It is preferable to provide.

  Examples of the substrate 20 include a glass substrate and a plastic substrate such as polycarbonate. The thickness of the substrate 20 can be appropriately selected according to the purpose of use, and a film-like substrate may be used. Examples of the film-like substrate include a polyethylene terephthalate film, a polycarbonate film, and a cycloolefin polymer film. The substrate 20 preferably has a minimum light transmittance of 80% or more in a wavelength region of 450 to 650 nm. When the substrate 20 satisfies such a condition, it is easy to increase the brightness in a display panel or the like.

In the laminating step, for example, the photosensitive conductive film 10 can be laminated by pressure-bonding the photosensitive resin layer 3 side to the substrate 20 while heating after removing the protective film, if any. In this step, the photosensitive conductive film is preferably laminated under reduced pressure from the viewpoint of adhesion and followability. The lamination of the photosensitive conductive film 10 is preferably performed while heating the photosensitive resin layer 3 and / or the substrate 20 to 70 to 130 ° C., and the pressure bonding pressure is about 0.1 to 1.0 MPa (1 to 10 kgf / it is preferable that the cm order of ^2), but not particularly limited to these conditions. Further, if the photosensitive resin layer 3 is heated to 70 to 130 ° C. as described above, it is not necessary to preheat the substrate 20 in advance, but the substrate 20 is preheated in order to further improve the stackability. You can also

  According to the method of this embodiment, it is possible to more easily form the photosensitive layer 4 on the substrate 20 by providing the photosensitive layer 4 by laminating the separately prepared photosensitive conductive film 10 to the substrate 20. , Productivity can be improved.

  As an exposure method in the first exposure step, there is a method (mask exposure method) in which an actinic ray L is irradiated in an image form through a negative or positive mask pattern 5 called an artwork as shown in FIG. Can be mentioned.

  A known light source may be used as the active light source in the first exposure step. For example, a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp that can effectively radiate ultraviolet rays, visible light, or the like is used. Ar ion lasers and semiconductor lasers are also used. Further, those that effectively radiate visible light, such as photographic flood bulbs and solar lamps, are also used. Alternatively, a method of irradiating actinic rays in an image form by a direct drawing method using a laser exposure method or the like may be employed.

Exposure at the first exposure step may vary depending on the composition of the device or a photosensitive resin composition to be used, preferably from ^{5mJ / cm 2 ~1000mJ / cm 2} , more preferably 10mJ ^/ cm 2 ~200mJ ^/ cm ² . In terms of excellent photocurability, it is preferably 10 mJ / cm ² or more, and in terms of resolution, it is preferably 200 mJ / cm ² or less.

  In this embodiment, when the photosensitive layer 4 is exposed without peeling off the support film 1, the influence of oxygen is reduced and the photosensitive resin composition is easily cured.

  The first exposure step can be performed in air, vacuum, or the like, and the atmosphere of exposure is not particularly limited.

  As an exposure method in the second exposure step, if necessary, a mask exposure method and a method of irradiating the entire photosensitive resin layer 3 with actinic rays without using a mask as shown in FIG. And can be selected. In the case of performing the mask exposure method, for example, the actinic ray L can be irradiated in an image form through the mask pattern 5.

  In the present embodiment, the exposed portion in the first exposure step is also exposed in the second exposure step, but by performing such exposure twice, the portion exposed in the first exposure step is Compared to the case where no exposure is performed in the second exposure step, it is possible to prevent and form a boundary portion between the portion exposed in the first exposure step and the portion exposed in the second exposure step. It can prevent that the level | step difference of a cured resin pattern becomes large. In addition, when an exposure part is fully hardened | cured at a 1st exposure process, the said part does not need to be exposed at a 2nd exposure process.

  As a light source for actinic rays in the second exposure step, a known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, or the like is effectively radiated. Things are used. In addition, an Ar ion laser, a semiconductor laser that effectively emits ultraviolet light, visible light, or the like may be used. Further, those that effectively radiate visible light, such as photographic flood bulbs and solar lamps, are also used.

Exposure at the second exposure step may vary depending on the composition of the device or a photosensitive resin composition to be used ^is preferably from ^{5mJ / cm 2 ~1000mJ / cm 2} , 10mJ / cm 2 ~200mJ / cm 2 more ^preferably, it is more preferably ^{30mJ / cm 2 ~150mJ / cm 2} . In terms of excellent photocurability, it is preferably 10 mJ / cm ² or more, and in terms of work efficiency, it is preferably 200 mJ / cm ² or less.

  In the second exposure step according to this embodiment, the support film 1 is removed and the photosensitive layer 4 is exposed in the presence of oxygen to expose the photosensitive layer 4 (the conductive film 2 and the photosensitive resin layer 3). In this step, the reactive species generated from the initiator can be deactivated by oxygen, and an insufficiently cured region can be provided on the conductive film 2 side of the photosensitive resin layer 3. Since excessive exposure sufficiently cures the entire photosensitive resin composition, the exposure amount in the second exposure step is preferably within the above range.

  The second exposure step is performed in the presence of oxygen, for example, preferably in the air. Further, the condition of increasing the oxygen concentration may be used.

  In the development process according to this embodiment, the surface layer portion that is not sufficiently cured of the photosensitive resin layer 3 exposed in the second exposure process is removed. Specifically, the surface layer portion of the photosensitive resin layer 3 that is not sufficiently cured is removed together with the conductive film 2 by wet development. Thereby, it consists of the photosensitive resin layer hardened | cured by the 1st and 2nd exposure process, and the cured resin layer 3a by which the convex part as a cured resin pattern and the recessed part between cured resin patterns were formed in the surface Is formed. The conductive film (conductive pattern 2a) having a predetermined pattern remains on the cured resin pattern, and there is no conductive film 2 in the portion where the surface layer portion of the photosensitive resin layer has been removed in the development process, and the cured resin layer 3a is disposed on the bottom surface. A recess is formed. Thus, as shown in FIG. 5D, the step Ha between the conductive pattern 2a formed on the cured resin layer 3a and the bottom surface of the concave portion of the cured resin layer 3a is reduced, and the conductive pattern ( A conductive pattern substrate 40 having wiring) is obtained.

  The wet development is performed by a known method such as spraying, rocking immersion, brushing, or scraping, using, for example, an alkaline aqueous solution, an aqueous developer, or an organic solvent developer.

  As the developer, an alkaline aqueous solution is preferably used because it is safe and stable and has good operability. As alkaline aqueous solution, 0.1-5 mass% sodium carbonate aqueous solution, 0.1-5 mass% potassium carbonate aqueous solution, 0.1-5 mass% sodium hydroxide aqueous solution, 0.1-5 mass% sodium tetraborate An aqueous solution or the like is preferable. Moreover, it is preferable to make pH of the alkaline aqueous solution used for image development into the range of 9-11, and the temperature is adjusted according to the developability of the photosensitive resin layer. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed.

  Further, an aqueous developer composed of water or an aqueous alkali solution and one or more organic solvents can be used. Here, as the base contained in the alkaline aqueous solution, in addition to the above-mentioned bases, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1 , 3-propanediol, 1,3-diaminopropanol-2, morpholine.

  Examples of the organic solvent include methyl ethyl ketone, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether. It is done. These are used alone or in combination of two or more.

  The aqueous developer preferably has an organic solvent concentration of 2 to 90% by mass, and the temperature can be adjusted according to the developability. Furthermore, the pH of the aqueous developer is preferably as low as possible within a range where the resist can be sufficiently developed, preferably pH 8-12, more preferably pH 9-10. In addition, a small amount of a surfactant, an antifoaming agent, or the like can be added to the aqueous developer.

  Examples of the organic solvent developer include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. These organic solvents preferably add water in the range of 1 to 20% by mass in order to prevent ignition.

  Two or more of the above-described developing solutions may be used in combination as necessary.

  Examples of the development method include a dip method, a battle method, a spray method, brushing, and slapping. Among these, it is preferable to use a high-pressure spray system from the viewpoint of improving the resolution.

In the wiring formation method of the present embodiment, the conductive pattern may be further cured by performing heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 J / cm ² as necessary after development. .

  As described above, according to the wiring forming method according to the present embodiment, a transparent wiring can be easily formed on a substrate such as glass or plastic without forming an etching resist like an inorganic film such as ITO. Is possible.

Examples of the method of laminating the overcoat layer include a method of laminating by removing the protective film and then pressing the photosensitive resin layer side to a substrate having a conductive pattern while heating the film. In addition, it is preferable to laminate | stack this operation under pressure reduction from the viewpoint of adhesiveness and followable | trackability. In the lamination of the photosensitive elements, it is preferable to heat the photosensitive resin layer and / or the substrate to 70 to 130 ° C., and the pressure bonding pressure is about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm ² ). However, these conditions are not particularly limited. In addition, if the photosensitive resin layer is heated to 70 to 130 ° C. as described above, it is not necessary to pre-heat the substrate in advance, but it is also possible to perform pre-heat treatment of the substrate in order to further improve the lamination property. .

  As an exposure method in the exposure step in curing the overcoat layer, a method of irradiating actinic rays is performed. At this time, when the support film present on the conductive layer and the photosensitive resin layer is transparent to the active light, the active light can be irradiated through the support film, and the support film is light-shielding. Irradiates the photosensitive resin assembly layer with actinic rays after removing the support film.

  As the active light source, a known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, or the like that effectively emits ultraviolet light, visible light, or the like is used. Also, an Ar ion laser, a semiconductor laser, or the like that effectively emits ultraviolet light, visible light, or the like is used. Further, those that effectively radiate visible light, such as photographic flood bulbs and solar lamps, are also used.

(Electroless plating)
In order to form a metal layer on a conductive pattern by plating, electroless plating or electrolytic plating can be used properly depending on the application. In the case of electroless plating, a metal compound serving as an electroless plating catalyst is brought into contact with the surface of the conductive pattern in advance.

  The metal element for the plating catalyst can be selected from palladium, silver, copper, gold or platinum, and the metal compound is a water-soluble compound of palladium, silver, copper, gold or platinum or a combination thereof. Palladium compounds such as palladium chloride, palladium sulfate, palladium nitrate or palladium acetate, and copper nitrate, silver sulfate, copper sulfate, tetrachlorogold (IV) acid salt, tetrachlorogold ( III) Acid salts and the like can be used, and combinations thereof can also be used.

  In addition, hydrochloric acid, sulfuric acid or the like can be added to increase the solubility of these salts in water. Moreover, you may add the complex salt which forms a complex with the said metal. Moreover, the substitution palladium plating solution marketed as Melplate activator 350 (Meltex Co., Ltd., brand name) and SA-100 (Hitachi Chemical Industry Co., Ltd. brand name) can also be used similarly.

  As a method of bringing these metal compounds into contact with the surface of the conductive pattern, there are a method of immersing in an aqueous solution containing these metal compounds or a method of spraying an aqueous solution of these metal compounds.

  In order to clean the surface of the conductive pattern and increase hydrophilicity, the conductive pattern can be brought into contact with a degreasing liquid before contacting with an aqueous solution of a metal compound serving as a catalyst. -200 (trade name, manufactured by World Metal Co., Ltd.) and S-135 (trade name, manufactured by Okuno Pharmaceutical Co., Ltd.) can be used.

After contacting the conductive pattern with an aqueous solution of a metal compound serving as a catalyst, electroless plating is performed to form a metal layer on the conductive pattern. As electroless plating, electroless copper plating, electroless nickel plating and the like are general-purpose and can be used, but are not limited thereto.
As electroless nickel plating, electroless nickel-phosphorous plating and electroless nickel-boron plating are generally known, but either can be used. If necessary, the electroless plating film may be electroplated to increase the thickness.

  In order to improve the depositability of electroless plating, it is effective to contact the reducing agent solution before electroless plating, and can be performed as necessary. Examples of the reducing agent used at this time include hypophosphites, alkali borohydrides, dimethylamine borane, diethylamine borane, hydrazine, and the like, which are reduced by dipping or spraying the solution.

<Manufacturing method of touch panel>
The manufacturing method of the touchscreen which concerns on this embodiment includes forming the electroconductive pattern in which the electroless-plating process was performed partially on the support base material by the method which concerns on the above-mentioned embodiment. The selective electroless plating treatment is performed on the conductor pattern of the base material using the above-described overcoat layer as a mask. Since the electroless plating is selectively deposited only on the conductive pattern of the pattern portion, the lead-out wiring can be easily formed.

  The touch panel is manufactured by forming the lead wiring and the pattern of the transparent electrode by the etching process.

  FIG. 6 is a schematic cross-sectional view illustrating one embodiment of a touch panel manufacturing method. In the manufacturing method of this aspect, a photosensitive conductive film is laminated on a support substrate, and a part of the photosensitive resin layer of the photosensitive conductive film is cured by irradiation with actinic rays to form a cured resin layer. And removing the region other than the cured resin layer together with the conductive film by development. Thereby, as shown to Fig.6 (a), the transparent conductive pattern 2a is formed on a support base material.

  In the next step, the overcoat film 30 is laminated at a place where the plating is not desired to be deposited (FIG. 6B), and the portion other than the part where the plating is desired to be deposited is cured by irradiation with actinic rays to form a cured product region. Then, areas other than the cured product area are removed by development.

  When selective electroless plating is applied to the laminated structure formed in the above process, a conductive layer is not covered with an overcoat, and a metal layer is formed only at a place where the pattern is present, and a transparent electrode pattern having a lead line 35 Can be formed (FIG. 6C). A conductive pattern substrate having a supporting base and wiring as a substrate can be used to obtain a touch panel sensor, an organic EL element, a PDP element, and the like.

  The metal layer formed by electroless plating includes copper, copper-nickel alloy, nickel-phosphorus alloy, nickel-boron alloy, etc. Copper and copper-nickel alloy have low resistance, Phosphorus and nickel-boron alloys are characterized by a relatively hard coating, and can be selectively used depending on the application.

  FIG. 7 is a top view showing an aspect of a touch panel obtained by using the method according to the present embodiment. In the touch panel 100, X electrodes 52 and Y electrodes 54, which are transparent electrodes, are alternately arranged in parallel, and the X electrodes 52 provided in the same row in the longitudinal direction are connected to each other by a single lead wiring 56, The Y electrodes 54 provided in the same row in the width direction are connected to each other by one lead-out wiring 57.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

<Preparation of conductor dispersion>
(Silver fiber dispersion)
[Preparation of silver fiber by polyol method]
In a 2000 mL three-necked flask, 500 mL of ethylene glycol was placed and heated to 160 ° C. with an oil bath while stirring with a magnetic stirrer under a nitrogen atmosphere. A solution prepared by dissolving ₂ mg of PtCl ₂ separately prepared in 50 mL of ethylene glycol was added dropwise thereto. After 4 to 5 minutes, a solution in which 5 g of AgNO ₃ was dissolved in 300 mL of ethylene glycol and a solution in which 5 g of polyvinylpyrrolidone having a weight average molecular weight of 40,000 (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 150 mL of ethylene glycol were respectively obtained. The reaction solution was prepared by adding dropwise from the dropping funnel in 1 minute. Thereafter, the reaction solution was stirred at 160 ° C. for 60 minutes.

  The reaction solution was allowed to stand at 30 ° C. or lower, diluted 10-fold with acetone, centrifuged at 2000 rpm for 20 minutes with a centrifuge, and the supernatant was decanted. Acetone was added to the precipitate and stirred, followed by centrifugation under the same conditions as described above, and acetone was decanted. Then, it centrifuged twice similarly using distilled water, and obtained the silver fiber. When the obtained silver fiber was observed with a scanning electron micrograph, the fiber diameter (diameter) was about 5 nm, and the fiber length was about 5 μm.

[Preparation of silver fiber dispersion]
The silver fiber obtained above was dispersed in pure water at a concentration of 0.2% by mass and dodecyl-pentaethylene glycol at a concentration of 0.1% by mass to obtain a silver fiber dispersion.
<Synthesis of binder polymer>
(Synthesis of acrylic resin)

  In a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas introduction tube, a mixture of methyl cellosolve and toluene (methyl cellosolve / toluene = 3/2 (mass ratio), hereinafter “solution s 400 g) was added, stirred while blowing nitrogen gas, and heated to 80 ° C. Meanwhile, a solution (hereinafter referred to as “solution a”) prepared by mixing 100 g of methacrylic acid as a monomer, 250 g of methyl methacrylate, 100 g of ethyl acrylate and 50 g of styrene and 0.8 g of azobisisobutyronitrile is prepared. did. Solution a was added dropwise to solution s heated to 80 ° C. over 4 hours. The solution after dropping was kept warm at 80 ° C. for 2 hours. Further, a solution obtained by dissolving 1.2 g of azobisisobutyronitrile in 100 g of the solution s was dropped into the flask over 10 minutes. And the solution after dripping was heat-retained at 80 degreeC, stirring for 3 hours, Then, it heated at 90 degreeC over 30 minutes, The acrylic resin as a binder polymer was produced | generated by superposition | polymerization of the monomer. The mixture was kept at 90 ° C. for 2 hours and then cooled to obtain a binder polymer solution. Acetone was added to this binder polymer solution to prepare a non-volatile component (solid content) of 50% by mass to obtain a binder polymer solution containing an acrylic resin as component (a). The obtained acrylic resin (a) had a weight average molecular weight of 80,000, a carboxyl group ratio of 20% by mass, and an acid value of 130 mgKOH / g.

  The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC), and was derived by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below.

GPC conditions Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd., product name)
Column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (above, manufactured by Hitachi Chemical Co., Ltd., product name)
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., product name)

<Preparation of solution of photosensitive resin composition>
(Photosensitive resin composition for photosensitive conductive film)
The materials shown in Table 1 were blended in the blending amounts (unit: parts by mass) shown in the same table to prepare a photosensitive resin composition solution for forming the photosensitive layer of the photosensitive conductive film.

(Photosensitive resin composition for overcoat layer)
The materials shown in Table 1 were blended in the blending amounts (unit: parts by mass) shown in the same table to prepare a solution of a photosensitive resin composition for forming an overcoat layer.

<Preparation of photosensitive conductive film>
The silver fiber dispersion was uniformly applied in an amount of 25 g / m ² on a 50 μm thick polyethylene terephthalate film (PET film, manufactured by Teijin Ltd., trade name “G2-50”), and hot air convection at 100 ° C. A conductive film was obtained by drying for 3 minutes with a tumble dryer. The film thickness after drying of the conductive film was about 0.1 μm.

Next, the photosensitive resin composition solution shown in Table 1 was uniformly applied on the conductive film, and dried for 10 minutes with a hot air convection dryer at 100 ° C. to form a photosensitive resin layer. The photosensitive resin layer was covered with a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name “NF-13”) to obtain a photosensitive conductive film. The film thickness after drying of the photosensitive resin layer was 5 μm.
<Preparation of overcoat film>

  The solution of the photosensitive resin composition shown in Table 2 was uniformly applied onto a 16 μm-thick polyethylene terephthalate film (PET film, manufactured by Teijin Ltd., trade name “G2-16”), and hot air convection at 100 ° C. The photosensitive resin layer was formed by drying for 10 minutes with a dryer. The photosensitive resin layer was covered with a polyethylene film (trade name “NF-13” manufactured by Tamapoly Co., Ltd.) to obtain an overcoat film. The film thickness after drying of the photosensitive resin layer was 15 μm.

(Production example)
<Formation of conductive pattern>
A soda glass plate (substrate) having a thickness of 0.7 mm is heated to 80 ° C., and the photosensitive conductive film is peeled off on the surface of the soda glass plate (substrate). Lamination was performed under the condition of 0.4 MPa. After lamination, when the substrate is cooled and the temperature of the substrate reaches 23 ° C., an artwork having a wiring pattern with a line width / space width of 100/100 μm and a length of 100 mm is adhered to the PET film surface as a support film I let you. Then, using an exposure machine (trade name “HMW-201B”, manufactured by Oak Co., Ltd.) having a high-pressure mercury lamp, the conductive film and the photosensitive resin layer were irradiated with light at an exposure amount of 50 mJ / cm ^{2 in} the atmosphere. (First exposure step). Thereafter, the artwork was removed, and the PET film was further peeled to expose the conductive film. At this time, the photosensitive resin layer and the conductive film are laminated in this order on a 0.7 mm thick soda glass plate. Thereafter, using the same exposure equipment, the conductive film and the photosensitive resin layer were irradiated with light at an exposure amount of 50 mJ / cm ^{2 in} the atmosphere (second exposure step).

  After the exposure, the film was allowed to stand at room temperature (25 ° C.) for 15 minutes, and then developed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 30 seconds. By development, a conductive pattern having a line width / space width of about 100/100 μm was formed on the resin pattern of the cured resin layer formed from the photosensitive resin layer. It was confirmed that the formed conductive pattern was difficult to see and the step of the conductive pattern with the cured resin layer was 0.3 μm. The resistance value measured with a tester at both ends of the 100 mm long conductive pattern was 180 kΩ, but it was also confirmed that the cured resin layer other than the conductive pattern was not conductive.

<Formation of overcoat layer>
The overcoat film was laminated under the conditions of 120 ° C. and 0.4 MPa while peeling off the protective film so as to cover the formed conductive pattern. After lamination, when the substrate was cooled and the temperature of the substrate reached 23 ° C., the artwork with the lead electrode portion masked was brought into close contact with the PET film surface of the overcoat film. Then, using an exposure machine (trade name “HMW-201B” manufactured by Oak Co., Ltd.) having a high-pressure mercury lamp lamp, the conductive film and the photosensitive layer were irradiated with light at an exposure dose of 50 mJ / cm ^{2 in} the atmosphere.

  After the exposure, the film was allowed to stand at room temperature (25 ° C.) for 15 minutes, and then developed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 30 seconds. A transparent conductive pattern in which the extraction electrode portion was removed and the central portion was protected with an overcoat was obtained by development.

<Selective plating>
The soda glass plate on which the conductive pattern was formed was immersed in an aqueous palladium chloride hydrochloric acid solution (PdCl2: 1.5 g / l) at a liquid temperature of 25 ° C. and an immersion time of 10 minutes, washed with running water for 30 seconds, and then the liquid temperature of 25 ° C. It was immersed in a dimethylamine borane aqueous solution (dimethylamine borane: 1 g / l) for 5 minutes and washed with running water for 30 seconds.

Then, it was immersed in an electroless plating bath (liquid temperature 70 ° C., pH 4.5) having the following composition for 3 minutes to perform electroless nickel plating.
[Electroless nickel plating composition]
Nickel sulfate hexahydrate 30g / l
Hypophosphorous acid ... 15g / l
Malic acid ... 15g / l
Succinic acid 3g / l
Lead nitrate: 0.8mg / l
As a result, a good electroless nickel-phosphorous plating film was deposited only on the conductive pattern.

  DESCRIPTION OF SYMBOLS 1 ... Support film, 2 ... Conductive film, 2a ... Conductive pattern, 3 ... Photosensitive resin layer, 3a ... Cured resin layer, 4 ... Photosensitive layer, 5 ... Mask pattern, 10 ... Photoconductive conductive film, 12 ... Photosensitive conductive Film, 20 ... substrate, 40 ... conductive pattern substrate, 52 ... transparent electrode (X electrode), 54 ... transparent electrode (Y electrode), 56, 57 ... lead-out wiring, 100 ... touch panel.

Claims (11)

A photosensitive conductive film having a support film, a conductive film provided on the support film, and a photosensitive resin layer provided on the conductive film is disposed on the substrate, and the photosensitive resin layer is positioned on the substrate side. Laminating in the direction;
Irradiating a part of the photosensitive resin layer with actinic rays;
By removing the support film and developing the photosensitive resin layer, a part of the photosensitive resin layer is removed together with the conductive film, and a cured resin pattern and a conductive pattern provided on the cured resin pattern are removed. Forming a step;
Forming a metal layer covering a partial region of the conductive pattern by electroless plating in this order. A photosensitive conductive film having a support film, a conductive film provided on the support film, and a photosensitive resin layer provided on the conductive film is disposed on the substrate, and the photosensitive resin layer is positioned on the substrate side. Laminating in the direction;
Irradiating a part of the photosensitive resin layer with actinic rays;
By removing the support film and developing the photosensitive resin layer, a part of the photosensitive resin layer is removed together with the conductive film, and a cured resin pattern and a conductive pattern provided on the cured resin pattern are removed. Forming a step;
Providing an overcoat layer covering a partial region of the conductive pattern;
Forming a metal layer covering a pattern area other than the area covered with the overcoat layer of the conductive pattern by plating in this order.   The wiring formation method according to claim 1, wherein the conductive film contains at least one kind of conductor selected from the group consisting of an inorganic conductor and an organic conductor.   The formation method of the wiring as described in any one of Claims 1-3 with which the said electrically conductive film contains a conductive fiber.   The wiring forming method according to claim 4, wherein the conductive fibers include silver fibers.   The wiring formation method according to claim 1, wherein the conductive film contains at least one conductor selected from the group consisting of polythiophene, polythiophene derivatives, polyaniline, and polyaniline derivatives.   The wiring formation method according to claim 1, wherein the photosensitive resin layer contains a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator.   The wiring formation method according to claim 7, wherein the photosensitive resin layer further contains a compound containing one or more electron-donating atoms selected from P, O, N, and S.   A conductive pattern substrate comprising: a substrate; and a wiring formed on the substrate by the wiring forming method according to claim 1.   A touch panel sensor comprising the conductive pattern substrate according to claim 9. A photosensitive conductive film having a support film, a conductive film provided on the support film, and a photosensitive resin layer provided on the conductive film,
The photosensitive resin layer is one or more selected from a) a binder polymer, b) a photopolymerizable compound having an ethylenically unsaturated bond, c) a photopolymerization initiator, and d) P, O, N and S. And a compound containing an electron-donating atom.