JP6155996B2 - Transparent conductive laminate, touch panel, and method for producing transparent conductive laminate - Google Patents

Description

  The technology of the present disclosure relates to a transparent conductive laminate including a resin layer, a touch panel including the transparent conductive laminate, and a method for manufacturing the transparent conductive laminate.

  In general, a projected capacitive touch panel includes two electrodes for detecting a change in capacitance. For example, as described in Patent Document 1, the two electrodes face each other with a single transparent substrate interposed therebetween. These two electrodes are formed by patterning a transparent conductive film formed on a substrate, and photolithography is used for patterning the conductive film.

  In an exposure process in photolithography, an exposure source that emits exposure light exposes two resists formed on each of two conductive films. At this time, in the technique described in Patent Document 1, the resin layer formed between the substrate and the conductive film has a function of absorbing ultraviolet light that is exposure light. And the resin layer formed between the board | substrate and the electrically conductive film absorbs the light which permeate | transmitted one resist among the light which exposes one resist. Therefore, even if the exposure source that emits the exposure light exposes each of the two resists simultaneously, the exposure of the other resist to the exposure of the other resist can be suppressed.

Japanese Patent No. 4683164

  Incidentally, the resin layer positioned between the substrate and the conductive film is required to have good adhesion to other layers stacked on the resin layer in addition to the function of absorbing ultraviolet rays. However, the resin layer, which is a coating film to which an organic ultraviolet absorber is added, has a chemical surface state that is significantly different from the vapor-grown inorganic film. And the adhesiveness of the resin layer which is a coating film to which the organic ultraviolet absorber is added and the vapor-grown inorganic film is lower than that of the resin layer to which no organic ultraviolet absorber is added. In particular, in a configuration in which a conductive film made of ITO (indium tin oxide) or the like is directly laminated on a resin layer by sputtering, one resin layer has a function of absorbing ultraviolet light and a function of maintaining adhesion with other layers. It is extremely difficult to achieve both.

  The technology of the present disclosure improves the adhesion between a vapor-grown inorganic film and a resin layer, and also has a transparent conductive laminate, a touch panel, and a transparent conductive laminate having a function of absorbing ultraviolet light that is exposure light. An object is to provide a manufacturing method.

  The transparent conductive laminate for solving the above problems is a substrate, a first resin layer that is a coating film positioned on the substrate, and a second coating film that is positioned below the substrate. A layer including a first transparent electrode layer, a first constituent layer located on the first resin layer, and a layer including a second transparent electrode layer, A second constituent layer located below the two resin layers. The first resin layer transmits ultraviolet rays, the second resin layer includes an organic ultraviolet absorber, and a layer in contact with the first resin layer among the layers included in the first constituent layer. Is a vapor-grown inorganic film. Of the layers included in the second constituent layer, the layer in contact with the second resin layer is a coated organic-inorganic hybrid film.

  In the above configuration, the functions of the two resin layers provided in the transparent conductive laminate are different from each other. The first resin layer is a coating film that transmits ultraviolet rays, and the second resin layer is a coating film containing an organic ultraviolet absorber. Then, the vapor-grown inorganic film is laminated on the first resin layer, and the coated organic-inorganic hybrid film is laminated on the second resin layer. Therefore, the adhesion between the first resin layer and the layer laminated on the first resin layer is compared with the conventional configuration in which the vapor-grown inorganic film is laminated on the coating film containing the organic ultraviolet absorber. And adhesion between the second resin layer and the layer laminated on the second resin layer is improved.

  When the transparent conductive laminate having such a structure is exposed to ultraviolet light, for example, in the resist on the first constituent layer and the resist on the second constituent layer, the ultraviolet light transmitted through one resist is It is absorbed by the second resin layer before reaching the resist. Therefore, since it is suppressed that the ultraviolet-ray with respect to one resist reaches the other resist, two resists can be exposed collectively before development of these resists. As a result, it is possible to improve both the adhesion between the resin layer and the other layer laminated on the resin layer and to suppress the ultraviolet rays for one resist from reaching the other resist.

  In the transparent conductive laminate, the first constituent layer includes an optical adjustment layer for adjusting visible light transmission characteristics in the transparent conductive laminate, and the optical adjustment layer is in contact with the first resin layer. It is preferable that the second transparent electrode layer is a layer in contact with the second resin layer.

  According to the said structure, it is an organic-inorganic hybrid film | membrane which has improved the visibility in a transparent conductive laminated body with an optical adjustment layer, and the adhesiveness of an optical adjustment layer and a 1st resin layer, and electroconductivity. Adhesiveness between the second transparent electrode layer and the second resin layer is enhanced.

In the transparent conductive laminate, it is preferable that the first transparent electrode layer is a vapor-grown inorganic film, and the second transparent electrode layer is a coated organic-inorganic hybrid film.
According to the said structure, two transparent electrode layers have a mutually different characteristic. Therefore, the transparent conductive laminate can enjoy the advantages of each film.

In the transparent conductive laminate, it is preferable that the first resin layer is an organic-inorganic hybrid film, and the second resin layer includes an acrylic resin.
According to the above configuration, since the organic-inorganic hybrid resin is included in the first resin layer, the adhesion between the vapor-grown inorganic film and the first resin layer is good. Moreover, the addition of the organic ultraviolet absorber to the second resin layer is easy due to the acrylic resin contained in the second resin layer.

In the transparent conductive laminate, it is preferable that the second resin layer has blocking resistance.
According to the said structure, since the 2nd resin layer has blocking resistance, even if it is a case where a resin layer is accumulated in the middle of manufacture of a transparent conductive laminated body, it is suppressed that generation | occurrence | production of blocking occurs. . As a result, the adhesion between the resin layer and the other layer laminated on the resin layer is enhanced, and the occurrence of blocking is suppressed.

The touch panel for solving the said subject is equipped with the said transparent conductive laminated body.
According to the said structure, in the transparent conductive laminated body with which a touch panel is provided, it has adhesiveness with the layer laminated | stacked on a resin layer and a resin layer.

  The method for producing a transparent conductive laminate for solving the above-described problems includes a step of forming a first resin layer that transmits ultraviolet light on a first surface of a substrate by coating, and a second surface of the substrate. A step of forming a second resin layer containing an organic ultraviolet absorber by coating, a step of laminating a first laminated layer containing a first transparent conductive layer on the first resin layer, Laminating a second laminated layer including a second transparent conductive layer on the second resin layer. The step of laminating the first laminated layer includes the step of forming an inorganic film by vapor deposition on the surface of the first resin layer, and the step of laminating the second laminated layer includes the step of laminating the second laminated layer. Forming an organic-inorganic hybrid film on the surface of the resin layer by coating.

  According to the above method, the vapor-grown inorganic film is laminated on the first resin layer that is a coating film that transmits ultraviolet light, and the coating is applied to the second resin layer that is a coating film that absorbs ultraviolet light. The organic / inorganic hybrid films thus formed are laminated. Therefore, the adhesion between the first resin layer and the layer laminated on the first resin layer is good. In addition, adhesion between the second resin layer and the layer laminated on the second resin layer is also ensured.

  When the transparent conductive laminate having such a structure is exposed to ultraviolet rays, for example, in the resist on the first laminated layer and the resist on the second laminated layer, the ultraviolet rays transmitted through one resist are It is absorbed by the second resin layer before reaching the resist. Therefore, since it is suppressed that the ultraviolet-ray with respect to one resist reaches the other resist, two resists can be exposed collectively before development of these resists. As a result, it is possible to improve both the adhesion between the resin layer and the other layer laminated on the resin layer and to suppress the ultraviolet rays for one resist from reaching the other resist.

  According to the technique of the present disclosure, it is possible to obtain a transparent conductive laminate having improved adhesion between the vapor-grown inorganic film and the resin layer and having an ultraviolet absorbing function.

It is sectional drawing which shows the cross-section of the transparent conductive laminated body in one Embodiment in the technique of this indication. It is sectional drawing which shows the cross-section of the touchscreen in one Embodiment in the technique of this indication. It is a figure which shows the manufacturing process of the transparent conductive laminated body in one Embodiment, Comprising: It is a figure which shows the formation process of a 1st resin layer. It is a figure which shows the manufacturing process of the transparent conductive laminated body in one Embodiment, Comprising: It is a figure which shows the formation process of a 2nd resin layer. It is a figure which shows the manufacturing process of the transparent conductive laminated body in one Embodiment, Comprising: It is a figure which shows the formation process of a 1st transparent conductive layer. It is a figure which shows the manufacturing process of the transparent conductive laminated body in one Embodiment, Comprising: It is a figure which shows the formation process of a metal layer. It is a figure which shows the manufacturing process of the transparent conductive laminated body in one Embodiment, Comprising: It is a figure which shows the formation process of a 2nd transparent conductive layer. It is a figure which shows the manufacturing process of the transparent conductive laminated body in one Embodiment, Comprising: It is a figure which shows the formation process of a resist. It is a figure which shows the manufacturing process of the transparent conductive laminated body in one Embodiment, Comprising: It is a figure which shows an exposure process. It is a figure which shows the manufacturing process of the transparent conductive laminated body in one Embodiment, Comprising: It is a figure which shows a image development process. It is a figure which shows the manufacturing process of the transparent conductive laminated body in one Embodiment, Comprising: It is a figure which shows an etching process. It is sectional drawing which shows the cross-section of the transparent conductive laminated body in a modification. It is sectional drawing which shows the cross-section of the transparent conductive laminated body in a modification.

With reference to FIGS. 1-11, one Embodiment of the manufacturing method of a transparent conductive laminated body, a touch panel, and a transparent conductive laminated body is described.
[Configuration of transparent conductive laminate]
With reference to FIG. 1, the structure of a transparent conductive laminated body is demonstrated. A transparent conductive laminated body is used as one of the structural members of a touch panel, for example.

  As shown in FIG. 1, the transparent conductive laminate 10 includes a transparent substrate 11, a first resin layer 12 a that is two coating films facing each other across the substrate 11, and a second resin layer 12 b. It has. The transparent conductive laminate 10 includes a first transparent electrode layer 13a that is two conductive films facing each other across a laminate composed of the substrate 11, the first resin layer 12a, and the second resin layer 12b. And a second transparent electrode layer 13b.

  A first resin layer 12a and a first transparent electrode layer 13a are laminated in this order on the first surface, which is the surface of the substrate 11. A second resin layer 12b and a second transparent electrode layer 13b are laminated in this order on the second surface, which is the back surface of the substrate 11. The first transparent electrode layer 13a is an example of a first constituent layer, and the second transparent electrode layer 13b is an example of a second constituent layer.

  As the substrate 11, for example, glass or a resin film is used. The resin used for the resin film is not limited as long as the film has the strength required for the substrate in the film forming step and the subsequent step, and the surface smoothness is good. Examples of the resin used for the resin film include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyethersulfone, polysulfone, polyarylate, cyclic polyolefin, polyimide, and the like. The substrate 11 is preferably 10 μm or more and 300 μm or less in order to reduce the thickness of the transparent conductive laminate 10 and maintain the flexibility of the substrate 11.

  The substrate 11 may contain various additives and stabilizers. Examples of the additives and stabilizers include antistatic agents, plasticizers, lubricants, and easy adhesives. The substrate 11 is subjected to corona treatment, low-temperature plasma treatment, ion bombardment treatment, chemical treatment, or the like as pretreatment in order to improve adhesion between the layer laminated on the substrate 11 and the substrate 11. Also good.

  Each of the first resin layer 12 a and the second resin layer 12 b has a function of improving the mechanical strength of the transparent conductive laminate 10. Each of the resin constituting the first resin layer 12a and the resin constituting the second resin layer 12b preferably has appropriate hardness and mechanical strength in addition to transparency.

  In addition to the function of improving the mechanical strength of the transparent conductive laminate 10, the first resin layer 12a has a function of transmitting ultraviolet light that is light having a wavelength in the ultraviolet region. The wavelength in the ultraviolet region is about 200 nm to about 380 nm, and the wavelength in the visible region is about 380 nm to about 780 nm. In addition, the first resin layer 12a has a property that the adhesiveness with the inorganic film grown by vapor deposition by sputtering or the like is higher than that of the second resin layer 12b.

  The material for forming the first resin layer 12a includes a resin that does not include an organic ultraviolet absorber and does not have a skeleton that absorbs ultraviolet rays in a main chain or a side chain constituting the resin. The material for forming the first resin layer 12a is, for example, an organic resin such as an acrylic resin, an epoxy resin, or a urethane resin, or an organic inorganic material in which inorganic particles such as silica particles or metal oxide particles are added to the organic resin. Any one selected from the group consisting of hybrid resins. From the viewpoint of high adhesion to an inorganic film formed by vapor phase growth, the material for forming the first resin layer 12a is preferably an organic-inorganic hybrid resin containing inorganic particles.

Although the thickness of the 1st resin layer 12a is not specifically limited, In order to achieve thickness reduction of the transparent conductive laminated body 10, it is preferable that they are 1 micrometer or more and 10 micrometers or less.
In addition, the liquid phase grown inorganic film such as coating is a sintered film of inorganic particles having a predetermined primary particle size, and has not a few grain boundaries between the inorganic particles used for liquid phase growth. . On the other hand, the inorganic film formed by vapor phase growth is a film in which inorganic particles in the gas phase are stacked, and is usually a film in which inorganic particles are sufficiently smaller than the inorganic particles used for liquid phase growth. . Therefore, the vapor-grown inorganic film does not have a grain boundary according to the particle size of such inorganic particles.

  The second resin layer 12 b has a function of absorbing ultraviolet rays in addition to a function of improving the mechanical strength of the transparent conductive laminate 10. The second resin layer 12b has lower adhesion to the inorganic film formed by vapor phase growth than the first resin layer 12a. The second resin layer 12b has higher blocking resistance than the first resin layer 12a. Blocking resistance is a state in which a layer having blocking resistance and another layer overlap each other, and a load is applied from the other layer to the layer having blocking resistance. It is a property that can be easily separated from other layers that overlap.

  Although the thickness of the 2nd resin layer 12b is not specifically limited, In order to achieve thickness reduction of the transparent conductive laminated body 10, it is preferable that they are 1 micrometer or more and 10 micrometers or less. The laminated body of the substrate 11 and the second resin layer 12b preferably has a transmittance of light having a wavelength of 365 nm of 0% to 1%. The transmittance of light having a wavelength of 365 nm is a value obtained with a spectrophotometer of U4100 manufactured by Hitachi High-Tech.

  The arithmetic average roughness (Ra) according to JIS B0601-1994 of the second resin layer 12b is preferably 1 nm or more and 10 nm or less. When the arithmetic average roughness is in the above range, appropriate blocking resistance is imparted to the second resin layer 12b by the irregularities on the surface of the second resin layer 12b. The arithmetic average roughness is a value obtained by Vertscan manufactured by Ryoka System. The measuring method is based on JISB0601-1994 edition.

  The forming material of the second resin layer 12b includes a resin having blocking resistance and includes an organic ultraviolet absorber. The resin having blocking resistance is, for example, at least one selected from the group consisting of organic resins such as acrylic resins, epoxy resins, and urethane resins. When the resin having blocking resistance is an acrylic resin, the haze value and transparency are improved, and the blocking resistance is easily exhibited, which is preferable.

  The organic ultraviolet absorber is, for example, at least one selected from the group consisting of benzophenone, benzotriazole, benzoate, salicylate, triazine, and cyanoacrylate. The organic ultraviolet absorber may be a low compound having a function of absorbing ultraviolet rays, a resin having a function of absorbing ultraviolet rays, or a co-polymerization with a resin having blocking resistance. It may be a coalescence. When the organic ultraviolet absorber is a copolymer with a resin having blocking resistance, the organic ultraviolet absorber preferably has a polymerizable vinyl group in a monomer state. Such organic ultraviolet absorbers include, for example, 2- (2′-hydroxy-5′-methacryloxyethylphenyl) 2H-benzotriazole, 2-hydroxy-4- (methacryloxy) benzophenone, phenyl-5-methacryloxymethyl. It is at least one selected from the group consisting of salicylates. The organic ultraviolet absorber is preferably ester-bonded to a side chain of an acrylic resin which is an example of a resin having blocking resistance. The molecular weight of the resin containing the ultraviolet absorber is not particularly limited, but is preferably 10,000 or more in order to suppress the occurrence of bleeding out.

The first transparent electrode layer 13a is an inorganic film grown in a vapor phase by sputtering or the like.
The material for forming the first transparent electrode layer 13a includes, for example, at least one selected from the group consisting of indium oxide, zinc oxide, and tin oxide. Further, the material for forming the first transparent electrode layer 13a may further contain an additive in addition to the metal oxide. From the viewpoint of high reliability of electrical characteristics and high reliability of shape processing, the forming material of the first transparent electrode layer 13a preferably contains indium tin oxide.

  The first transparent electrode layer 13a is patterned into a predetermined shape. For example, the first transparent electrode layer 13a has a pattern in which a plurality of conductive regions 14a extending in the X direction are arranged in parallel with a gap in the Y direction orthogonal to the X direction. The conductive region 14a is formed in, for example, a linear shape or a shape in which a plurality of rhombuses are connected in one direction. A gap formed between two conductive regions 14a adjacent to each other is a non-conductive region 15a where the conductive region 14a is not formed.

The second transparent electrode layer 13b is a coated organic-inorganic hybrid film grown in a liquid phase.
The 2nd transparent electrode layer 13b contains fibrous metals, such as metal nanowire which bears conductivity, and organic resin. As a metal which bears conductivity, it is at least one selected from the group consisting of gold, silver, copper, and cobalt, for example. The resin contained in the second transparent electrode layer 13b is preferably a thermosetting resin or a photocurable resin such as a monomer or an oligomer mainly composed of an acrylic resin. Additives such as a polymerization initiator may be mixed in the resin portion. The second transparent electrode layer 13b may include a resin layer that does not contain a metal as the outermost layer. With such a configuration, the fibrous metal is protected by the resin layer.

  The second transparent electrode layer 13b is formed, for example, in a pattern in which a plurality of conductive regions 14b extending in the Y direction are arranged side by side in the X direction. The fibrous metals contained in the conductive region 14b of the second transparent electrode layer 13b are in contact with each other in the conductive region 14b, and thereby the conductive region 14b has conductivity. Each of the conductive regions 14b is formed in the same shape as the conductive region 14a of the first transparent electrode layer 13a. The non-conductive region 15b is a region between the plurality of conductive regions 14b and is insulated from each of the conductive regions 14b.

  Each of the conductive regions 14a and 14b is connected to a circuit that detects a change in capacitance formed between the conductive regions 14a and 14b by a change in current. When a human finger or the like approaches the conductive regions 14a and 14b, the capacitance changes. Based on the detection of the change in capacitance, the contact position of a human finger or the like is determined.

  As shown in FIG. 2, the first transparent electrode layer 13 a is laminated with a cover layer 30 made of glass or the like via an adhesive layer, thereby forming a touch panel 31. The surface of the cover layer 30 becomes a contact surface such as a human finger. Further, a display panel 32 such as a liquid crystal panel is laminated on the second transparent electrode layer 13 b, and the display device 33 is configured by the touch panel 31 and the display panel 32. The cover layer 30 may be laminated on the second transparent electrode layer 13b, and the display panel 32 may be laminated on the first transparent electrode layer 13a.

[Method for producing transparent conductive laminate]
With reference to FIGS. 3-11, the manufacturing method of a transparent conductive laminated body is demonstrated.
As shown in FIG. 3, first, the first resin layer 12 a is formed on the surface of the substrate 11.

  In the method of forming the first resin layer 12a, first, a solution in which an ultraviolet transmissive resin or the like as a main component is dissolved in a solvent is applied to the surface of the substrate 11. Next, the coating film is cured on the surface of the substrate 11, whereby the first resin layer 12 a is formed.

  The solvent is not limited as long as it dissolves the main component resin and the like. Specific examples of the solvent include ethanol, isopropyl alcohol, isobutyl alcohol, benzene, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate, methyl cellosolve, ethyl cellosolve, butyl cellosolve. , Methyl cellosolve acetate, propylene glycol, or monomethyl ether acetate. These solvents may be used alone or in combination of two or more solvents.

  As a coating method, a known coating method such as a die coater, curtain flow coater, roll coater, reverse roll coater, gravure coater, knife coater, bar coater, spin coater, or micro gravure coater is used. As the ultraviolet irradiator used for curing the first resin layer 12a, for example, a metal halide lamp, a high-pressure mercury lamp, or the like is used.

  As shown in FIG. 4, the second resin layer 12 b is formed on the back surface of the substrate 11. In the method of forming the second resin layer 12b, first, a solution containing a resin having blocking resistance and an organic ultraviolet absorber, or a solution containing a resin having blocking resistance containing an organic ultraviolet absorber is used as a substrate. 11 is coated on the back surface. Next, the coating film is cured on the back surface of the substrate 11 to form the second resin layer 12b.

  At this time, when the second resin layer 12b is applied, for example, the resin having blocking resistance and the organic ultraviolet absorber are dissolved in a solvent and used. The solvent is not particularly limited as long as it dissolves these constituent materials. Specific examples of the solvent include the solvents exemplified in the method for forming the first resin layer 12a.

  The blending ratio of the organic ultraviolet absorber (A), the resin (B) having blocking resistance, and the solvent (C) is suitable for properly imparting blocking resistance and an ultraviolet absorbing function to the second resin layer 12b. Is preferably A: B: C = 10 wt% or more and 30 wt% or less: 35 wt% or more and 55 wt% or less: 20 wt% or more and 50 wt% or less.

  In the second resin layer 12b, the phase separation resin is 5 wt% or more and 10 wt% or less, the acrylic resin is 50 wt% or more and 75 wt% or less, and the organic ultraviolet absorber is 15 wt% or more and 45 wt% or less. It is preferable that each is contained in a proportion. In order to achieve such a content ratio, for example, in a solution in which each constituent material is dissolved in a solvent, the phase separation resin is 1.8% by weight to 2.5% by weight, and the acrylic resin is 16% by weight to 23% by weight. % Or less, and an organic ultraviolet absorber may be contained in a ratio of 5 wt% to 13 wt%. The phase separation resin is dispersed together with other constituent materials in the layer immediately after the solution is applied, while being separated from the other constituent materials and precipitated as the solvent evaporates. With such a forming method, the surface roughness described above is easily formed on the surface of the second resin layer 12b.

As a coating method, the coating method illustrated by the formation method of the 1st resin layer 12a above can be used.
Here, the second resin layer 12b has blocking resistance. Therefore, for example, when the first resin layer 12a and the second resin layer 12b are formed by a roll-to-roll method, for example, when another layer is stacked on the second resin layer 12b in the manufacturing process. The occurrence of blocking is suppressed.

  As shown in FIG. 5, the first transparent conductive layer 16 a is formed on the surface of the first resin layer 12 a on the surface side of the substrate 11. The first transparent conductive layer 16a is formed by a vapor deposition method such as sputtering. The first transparent conductive layer 16a is an example of a first stacked layer.

  As shown in FIG. 6, the metal layer 17 is formed on the surface of the first resin layer 12 a on the surface side of the substrate 11. The metal layer 17 is formed by applying a solution in which a fibrous metal is dispersed to the first resin layer 12a. As the solvent for dispersing the fibrous metal, a highly hydrophilic solvent such as water or alcohol, specifically methanol, ethanol or isopropanol is preferable. These solvents may be used alone or in combination of two or more solvents. As the coating method, a known coating method or printing method is used.

  As shown in FIG. 7, a solution containing a resin is applied onto the metal layer 17 to form the second transparent conductive layer 16b. The solution applied to the metal layer 17 penetrates into the gap between the fibrous metals included in the metal layer 17. The solvent of the solution is not particularly limited as long as it can dissolve the constituent material of the resin portion of the second transparent electrode layer 13b. Specific examples of the solvent include the solvents exemplified in the method for forming the first resin layer 12a. As the coating method, a known coating method or printing method is used. The second transparent conductive layer 16b is an example of a second stacked layer.

  Note that the first resin layer 12a and the first transparent conductive layer 16a may be continuously formed on the surface of the substrate 11 before the second resin layer 12b is formed. Further, the second resin layer 12b and the second transparent conductive layer 16b may be continuously formed on the back surface of the substrate 11 before the first resin layer 12a is formed. In short, before the resist is formed, the first resin layer 12a and the first transparent conductive layer 16a are provided on the surface of the substrate 11, and the second resin layer 12b and the second transparent conductive layer are provided on the back surface of the substrate 11. The laminated body provided with 16b should just be formed.

  As shown in FIG. 8, next, on the surface side of the substrate 11, a first resist 18a is formed on the surface of the first transparent conductive layer 16a, and on the back side of the substrate 11, the second transparent conductive layer 16b A second resist 18b is formed on the surface.

  As the resists 18a and 18b, negative resists or positive resists may be used. A known material is used for the resists 18a and 18b, and the resists 18a and 18b are formed by a known method.

  As shown in FIG. 9, next, a laminate in which the resists 18a and 18b are formed is disposed between the two light sources 21a and 21b that irradiate the resists 18a and 18b with light. The light sources 21a and 21b emit light composed of light having a wavelength in the ultraviolet region and light having a wavelength in the visible region.

  On the surface side of the substrate 11, a hole having a shape matching the shape of the conductive region 14 a of the first transparent electrode layer 13 a is formed between the first resist 18 a and the first light source 21 a from the side closer to the first resist 18 a. One mask 19a and a first optical filter 20a that blocks light having a wavelength in the visible region are arranged in this order. On the back side of the substrate 11, there is a second hole between the second resist 18 b and the second light source 21 b that has a shape matching the shape of the conductive region 14 b of the second transparent electrode layer 13 b from the side closer to the second resist 18 b. The two masks 19b and the second optical filter 20b that blocks light having a wavelength in the visible region are arranged in this order.

  And the 1st resist 18a is exposed by irradiating light with respect to the 1st resist 18a from the 1st light source 21a. Further, the second resist 18b is exposed by irradiating light from the second light source 21b to the second resist 18b. At this time, since light having a wavelength in the visible region is blocked by the optical filters 20a and 20b, the resists 18a and 18b are exposed to light having a wavelength in the ultraviolet region among the light emitted from the light sources 21a and 21b. The exposure of the first resist 18a and the exposure of the second resist 18b may be performed almost simultaneously or separately, and the development of the first resist 18a and the development of the second resist 18b. It is only necessary to be carried out collectively before.

  Here, the first resin layer 12a does not absorb ultraviolet rays, while the second resin layer 12b has a function of absorbing ultraviolet rays. Therefore, of the light irradiated from the first light source 21a to the first resist 18a through the first optical filter 20a, the light that is not absorbed by the first resist 18a is absorbed by the second resin layer 12b. Of the light emitted from the second light source 21b to the second resist 18b via the second optical filter 20b, the light that has not been absorbed by the second resist 18b is absorbed by the second resin layer 12b. As a result, it is possible to suppress the light irradiated to one resist from being transmitted through the laminate and exposing the other resist.

  Further, the wavelength of the light blocked by the optical filters 20a and 20b and the wavelength of the light absorbed by the second resin layer 12b are adjusted, whereby the wavelength of the exposure light and the light absorbed by the second resin layer 12b. The wavelength is matched. Therefore, exposure of the resists 18a and 18b and absorption of unnecessary exposure light are performed accurately.

  As shown in FIG. 10, when the resists 18a and 18b are of the negative type, the portions not exposed to light by the exposure of the resists 18a and 18b are removed by the developer. Alternatively, when the resists 18a and 18b are positive type, the portions exposed by the exposure of the resists 18a and 18b are removed by the developer. As a result, patterns corresponding to the shapes of the masks 19a and 19b are formed on the resists 18a and 18b. That is, the resists 18a and 18b are processed into resist masks that match the patterns of the conductive regions 14a and 14b.

  As shown in FIG. 11, the exposed portion of the first transparent conductive layer 16a is etched according to the pattern of the first resist 18a, and the exposed portion of the second transparent conductive layer 16b is etched according to the pattern of the second resist 18b. Of these, the metal layer 17 is etched. A known method is used as the etching method. As a result, the first transparent conductive layer 16a is patterned to form the first transparent electrode layer 13a. The remaining portion of the first transparent conductive layer 16a becomes the conductive region 14a in the first transparent electrode layer 13a, and the removed portion of the first transparent conductive layer 16a is partitioned as the non-conductive region 15a. Further, the second transparent conductive layer 16b is patterned to form the second transparent electrode layer 13b. The remaining portion of the metal layer 17 becomes the conductive region 14b in the second transparent electrode layer 13b, and the removed portion of the metal layer 17 is partitioned as the non-conductive region 15b. Note that the non-conductive region 15b only needs to be insulated from the conductive region 14b, and the fibrous metal may not be completely removed in the non-conductive region 15b.

  Finally, the transparent conductive laminate 10 is obtained by removing the resists 18a and 18b. In addition, it is preferable that each said process is performed by a roll-to-roll system. According to this, since a transparent conductive laminated body can be manufactured efficiently, the time concerning manufacture of the transparent conductive laminated body 10 is shortened.

[Action]
The effect | action which the above-mentioned transparent conductive laminated body, a touch panel, and the manufacturing method of a transparent conductive laminated body bring about is demonstrated.

  The transparent conductive laminate 10 is a coating film in which a first transparent electrode layer 13a made of a vapor-grown inorganic film is laminated on a first resin layer 12a, which is a coating film that transmits ultraviolet rays, and absorbs ultraviolet rays. A second transparent electrode layer 13b, which is a coated organic-inorganic hybrid film, is laminated on a certain second resin layer 12b. Accordingly, the adhesion between the first resin layer 12a and the first transparent electrode layer 13a is higher than the adhesion between the resin coating film that absorbs ultraviolet rays and the first transparent electrode layer 13a. Moreover, the adhesiveness of the 2nd resin layer 12b which is a coating film which absorbs an ultraviolet-ray, and the 2nd transparent electrode layer 13b which is an electroconductive coating film is also hold | maintained.

  Further, in the exposure process by photolithography, the second resin layer 12b absorbs light that has not been absorbed by the resist among light irradiated to expose one resist. As a result, the exposure light for one resist can be prevented from reaching the other resist. Therefore, even when the two transparent electrode layers 13a and 13b have different patterns, it is possible to suppress the pattern formed in one resist from affecting the pattern formed in the other resist. Therefore, the two resists 18a and 18b facing each other with the substrate 11 interposed therebetween can be exposed together. As a result, compared with the manufacturing method which repeats processes, such as formation of resist, exposure, and development for every surface in which transparent conductive layers 16a and 16b are formed, the flow of the manufacturing process of transparent conductive laminate 10 is simplified. can do.

  As described above, each of the two resin layers 12a and 12b and the two transparent conductive layers 16a and 16b has different functions, so that the resin layers 12a and 12b and the resin layers 12a and 12b are stacked. And the transparent conductive laminate 10 having an exposure light absorption function is realized.

  Moreover, since the 2nd resin layer 12b has blocking resistance, even if it is a case where another layer is piled up on the 2nd resin layer 12b in the manufacturing process of the transparent conductive laminated body 10, blocking generate | occur | produces. Is suppressed. Blocking can also be suppressed by attaching a film to the second resin layer 12b during the manufacturing process or changing the arrangement of the laminate in the manufacturing process. In such a case, the second resin layer 12b may not have blocking resistance. That is, the 2nd resin layer 12b does not need to contain resin which has blocking resistance.

(Example)
The characteristic which the transparent conductive laminated body mentioned above has is demonstrated using the specific Example given below and a comparative example.

<Example>
Polyethylene terephthalate film (Toyobo Co., Ltd .: A4300-125) is used as a substrate, and UNIDIC V-6841 (manufactured by DIC) is dissolved in MIBK as a coating solution for forming the first resin layer on the surface of the substrate. After coating the working solution, the coating film was cured to form a first resin layer having a thickness of 3 μm. Furthermore, as a coating liquid for forming the second resin layer on the back surface of the substrate, an organic ultraviolet absorber (manufactured by Ciba Japan: TINUVIN99-2) and a resin having blocking resistance (manufactured by Nippon Paint Co., Ltd .: NAB-001) and solvent (manufactured by Toyo Ink Co., Ltd .: VC104) were applied at a coating weight of 20% by weight: 40% by weight: 40% by weight. A second resin layer having a thickness of 5 μm was formed.

  Subsequently, an ITO film of 25 nm was laminated as a first transparent conductive layer on the first resin layer using a sputtering method. Further, after coating a coating solution in which gold nanowires are dispersed in pure water on the second resin layer, a solution obtained by dissolving UV curable acrylic HC in IPA as a protective film is coated and cured. Then, a 200 nm second transparent conductive layer was formed. Then, the first transparent conductive layer is patterned to form the first transparent electrode layer, and the second transparent conductive layer is patterned to form the second transparent electrode layer, thereby obtaining the transparent conductive laminate of the example. It was.

<Comparative Example 1>
As the second transparent conductive layer, a 25 nm ITO film was laminated on the second resin layer using a sputtering method, and the transparent conductive laminate of Comparative Example 1 was obtained in the same manner as in the examples except for the above. It was.

<Comparative example 2>
As the second resin layer, a coating solution in which UNIDIC V-6841 (manufactured by DIC) was dissolved in MIBK was applied to the back surface of the substrate, and then the coating film was cured to form a resin layer having a thickness of 3 μm. The transparent conductive laminate of Comparative Example 2 was obtained in the same manner as in the examples except for the above conditions.

<Evaluation method>
The following method evaluated the adhesiveness of a resin layer and a transparent electrode layer, and the ultraviolet absorptivity of a transparent conductive laminated body. The results are shown in Table 1. Hereinafter, the first resin layer and the first transparent electrode layer are referred to as a first constituent layer, and the second resin layer and the second transparent electrode layer are referred to as a second constituent layer.

[Adhesion]
Each of the transparent conductive laminates of Examples and Comparative Examples 1 and 2 was put into a weather resistance tester (manufactured by Toyo Seiki Seisakusho Co., Ltd .: Weatherometer Ci4000) to perform a weather resistance test. The first constituent layer of the test piece before and after conducting the weather resistance test, setting the irradiance of 65 kW / m ² , the humidity of 50% RH, the temperature of 40 ° C., the processing time of 500 h as the processing conditions of the weather resistance test Adhesion was evaluated for each of the second constituent layers.

  For the evaluation of adhesion, a cross-cut test was performed according to the following procedure. This is the same as the test described in the old JIS K5400: 1990. First, a test piece of the transparent conductive laminate is cut to produce 100 1 mm square grids, and a cellophane tape is attached to the surface of the cut transparent electrode layer. One minute after the tape is attached, the edge of the tape is held at a right angle to the surface of the transparent electrode layer and peeled off instantaneously, and the number of grids from which the transparent electrode layer has peeled is measured.

[UV absorption]
Each of the transparent conductive laminates of Examples and Comparative Examples 1 and 2 was put into a spectrophotometer (manufactured by Hitachi High-Tech: U4100), and each transparent conductive laminate was transmitted with light having a wavelength of 365 nm. The rate was measured. The transparent conductive laminate having a transmittance of 5% or less was determined to have ultraviolet absorption, and the transparent conductive laminate having a transmittance of more than 5% was determined to have no ultraviolet absorption.

表１に示されるように、実施例の第１構成層、および、第２構成層の各々において、十分な密着性が認められ、その実施例の透明導電性積層体において、紫外線吸収性が認められた。これに対して、比較例１においては、第１構成層に十分な密着性が認められたが、第２構成層の密着性が耐候性試験後に失われることが認められた。また、比較例２においては、第１構成層、および、第２構成層の各々に十分な密着性が認められたが、紫外線吸収性を有していないことも認められた。

As shown in Table 1, sufficient adhesion was observed in each of the first constituent layer and the second constituent layer of the example, and the ultraviolet conductive property was recognized in the transparent conductive laminate of the example. It was. On the other hand, in Comparative Example 1, sufficient adhesion was observed in the first component layer, but it was observed that the adhesion of the second component layer was lost after the weather resistance test. In Comparative Example 2, sufficient adhesion was observed in each of the first component layer and the second component layer, but it was also recognized that the component did not have ultraviolet absorptivity.

  That is, in Comparative Example 1 in which a vapor-grown inorganic film is laminated on a coating film containing an organic ultraviolet absorber, the adhesion is lowered and the comparative example does not have a coating film containing an organic ultraviolet absorber. In case of 2, ultraviolet absorptivity cannot be obtained. In contrast, a transparent electrode layer, which is a vapor-grown inorganic film, is laminated on a resin layer, which is a coating film that transmits ultraviolet light, and a coating is applied to the resin layer, which is a coating film that contains an organic ultraviolet absorber. It was shown that the transparent conductive laminate in which the transparent electrode layer, which is an organic-inorganic hybrid film, was laminated, can provide both good film adhesion and ultraviolet absorbing function.

As described above, according to the present embodiment, the following effects can be obtained.
(1) A layer made of a vapor-grown film is laminated on the first resin layer 12a having improved adhesion to the vapor-grown film, and a liquid is deposited on the second resin layer 12b having a function of absorbing exposure light. Layers of phase-grown films are stacked. Accordingly, the adhesion between the resin layers 12a and 12b and the layer laminated on the resin layers 12a and 12b is improved. Moreover, the absorption function of exposure light is provided to the transparent conductive laminated body 10 by the 2nd resin layer 12b.

  (2) Since the 2nd resin layer 12b has blocking resistance, even if it is a case where a resin layer is piled up in the manufacturing process of the transparent conductive laminated body 10, generation | occurrence | production of blocking is suppressed.

(3) Since the two transparent electrode layers 13a and 13b have different characteristics, the transparent conductive laminate 10 can enjoy the advantages of the respective films.
(4) The first resin layer 12a includes an organic-inorganic hybrid resin, and the second resin layer 12b includes an organic ultraviolet absorber. As a result, the first resin layer 12a has improved adhesion to the vapor-grown inorganic film, and the second resin layer 12b has an appropriate function of absorbing light having a wavelength in the ultraviolet region as exposure light. Can be added.

The embodiment described above can be implemented with the following modifications.
-As FIG. 12 shows, the transparent conductive laminated body 10 may be equipped with the optical adjustment layer 22 between the 1st resin layer 12a and the 1st transparent electrode layer 13a. The optical adjustment layer 22 has a function of adjusting visible light transmission characteristics in the transparent conductive laminate 10. The optical adjustment layer 22 is an inorganic film grown by vapor phase using, for example, an inorganic compound such as oxide, sulfide, fluoride, or nitride. Such a configuration also improves the adhesion between the first resin layer 12a and the layer laminated on the first resin layer 12a. That is, the layer in contact with the first resin layer 12a may be a layer different from the first transparent electrode layer 13a as long as it is a vapor-grown inorganic film.

  The first transparent electrode layer 13a may be a coating film as long as a vapor-grown inorganic film is sandwiched between the first resin layer 12a and the first transparent electrode layer 13a. In short, if the layer in contact with the first resin layer 12a is a layer made of a vapor-grown inorganic film, the adhesion between the first resin layer 12a that does not have an ultraviolet absorption function and the vapor-grown inorganic film. Is higher than the structure in which the first resin layer 12a has an ultraviolet absorption function. The optical adjustment layer 22 is an example of a first constituent layer and an example of a first stacked layer.

The vapor-grown inorganic film may be a transparent film having no electrical conductivity, such as a silicon oxide film, a silicon oxynitride film, or a silicon nitride film.
The transparent conductive laminate 10 may include a coated organic-inorganic hybrid film as a layer different from the second transparent electrode layer 13b between the second resin layer 12b and the second transparent electrode layer 13b. Good.

  If the coated organic-inorganic hybrid film is sandwiched between the second resin layer 12b and the second transparent electrode layer 13b, the second transparent electrode layer 13b is a vapor-grown inorganic film. Also good. In short, if the layer in contact with the second resin layer 12b is a layer made of a coated organic-inorganic hybrid film, the adhesion between the second resin layer 12b having an ultraviolet absorption function and the organic-inorganic hybrid film is Thus, the ultraviolet ray absorbing function is maintained in the transparent conductive laminate.

-The inorganic compound contained in the coated organic-inorganic hybrid film may be inorganic particles having no electrical conductivity, such as silicon oxide, silicon oxynitride, silicon nitride, titanium oxide and the like.
-As FIG. 13 shows, the board | substrate 11 may be a laminated body which consists of a some layer. In the transparent conductive laminate 23 shown in FIG. 13, the substrate 11 includes two sub-substrates 11a and 11b and an adhesive layer 24 that bonds the sub-substrate 11a and the sub-substrate 11b together. Examples of the resin used for the adhesive layer 24 include acrylic resins, silicone resins, rubber resins, and the like. For the adhesive layer 24, it is preferable to use a resin excellent in cushioning properties and transparency.

  In such a method of manufacturing a transparent conductive laminate, the first resin layer 12a and the first transparent conductive layer 16a are laminated on the surface of the sub-substrate 11a, and the second resin layer 12b and the second resin layer are formed on the surface of the sub-substrate 11b. A transparent conductive layer 16b is laminated. And the back surface of the sub-board | substrate 11a with which each structural member was laminated | stacked and the back surface of the sub-board | substrate 11b are bonded together by the adhesion layer 24. Thereafter, the transparent conductive laminate 23 is manufactured through the same steps as those shown in FIGS.

  DESCRIPTION OF SYMBOLS 10, 23 ... Transparent electroconductive laminated body, 11 ... Board | substrate, 11a, 11b ... Sub-board | substrate, 12a, 12b ... Resin layer, 13a, 13b ... Transparent electrode layer, 14a, 14b ... Conductive area | region, 15a, 15b ... Non-conductive area | region 16a, 16b ... transparent conductive layer, 17 ... metal layer, 18a, 18b ... resist, 19a, 19b ... mask, 20a, 20b ... optical filter, 21a, 21b ... light source, 22 ... optical adjustment layer, 24 ... adhesive layer, 30 ... Cover layer, 31 ... Touch panel, 32 ... Display panel, 33 ... Display device.

Claims (7)

A substrate,
A first resin layer which is a coating film positioned on the substrate;
A second resin layer which is a coating film located under the substrate;
A layer including a first transparent electrode layer, the first constituent layer located on the first resin layer;
A layer including a second transparent electrode layer, and a second constituent layer located below the second resin layer,
The first resin layer transmits ultraviolet rays,
The second resin layer includes an organic ultraviolet absorber,
Of the layers included in the first constituent layer, the layer in contact with the first resin layer is a vapor-grown inorganic film,
Of the layers included in the second constituent layer, the layer in contact with the second resin layer is a coated organic-inorganic hybrid film. The first constituent layer includes an optical adjustment layer that adjusts visible light transmission characteristics in the transparent conductive laminate,
The optical adjustment layer is a layer in contact with the first resin layer;
The transparent conductive laminate according to claim 1, wherein the second transparent electrode layer is a layer in contact with the second resin layer. The first transparent electrode layer is a vapor-grown inorganic film,
The transparent conductive laminate according to claim 1, wherein the second transparent electrode layer is a coated organic-inorganic hybrid film. The first resin layer is an organic-inorganic hybrid film,
The transparent conductive laminate according to claim 1, wherein the second resin layer includes an acrylic resin. The transparent conductive laminate according to any one of claims 1 to 4, wherein the second resin layer has blocking resistance.   A touch panel provided with the transparent conductive laminated body as described in any one of Claims 1-5. Forming a first resin layer that transmits ultraviolet light on the first surface of the substrate by coating;
Forming a second resin layer containing an organic ultraviolet absorber on the second surface of the substrate by coating;
Laminating a first laminated layer including a first transparent conductive layer on the first resin layer;
Laminating a second laminated layer including a second transparent conductive layer on the second resin layer,
The step of laminating the first laminated layer includes a step of forming an inorganic film by vapor deposition on the surface of the first resin layer,
The step of laminating the second laminated layer includes a step of forming an organic-inorganic hybrid film by coating on the surface of the second resin layer. A method for producing a transparent conductive laminate.

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