WO2017051826A1

WO2017051826A1 - Laminate, production method therefor, film set, and photosensitive conductive film

Info

Publication number: WO2017051826A1
Application number: PCT/JP2016/077863
Authority: WO
Inventors: 豪鈴木; 征志南; 絵美子太田; 山崎　宏; 泰洋瀬里
Original assignee: 日立化成株式会社
Priority date: 2015-09-24
Filing date: 2016-09-21
Publication date: 2017-03-30
Also published as: JP2018183878A

Abstract

Laminates 40a, 40b, 40c comprising a transparent base material 20, a conductive pattern 2a, and light-transmitting layers 3e, 3f, 3g. The conductive pattern 2a is provided upon the transparent base material 20 and contains a conductive material. The light-transmitting layers 3e, 3f, 3g are provided upon the transparent base material 20 and contain at least one type of colorant 9 selected from the group consisting of a blue dye, a blue pigment, a purple dye, and a purple pigment.

Description

LAMINATE, ITS MANUFACTURING METHOD, FILM SET, AND PHOTOSENSITIVE CONDUCTIVE FILM

The present invention relates to a laminate and a method for producing the same, a film set, and a photosensitive conductive film, and more particularly, a laminate used for a flat panel display such as a liquid crystal display element, a touch panel (touch screen), a solar cell, and the production thereof. The present invention relates to a method, a film set, and a photosensitive conductive film.

Liquid crystal display elements or touch panels are used in large electronic devices (such as personal computers and televisions), small electronic devices (such as car navigation systems, mobile phones, and electronic dictionaries), and display devices (such as OA / FA devices).

Various types of touch panels have already been put into practical use, but in recent years, the use of capacitive touch panels has progressed. In a capacitive touch panel, when a fingertip (conductor) contacts the touch input surface, the fingertip and the conductive film are capacitively coupled to form a capacitor. For this reason, the capacitive touch panel detects the coordinates by capturing the change in the charge at the contact position of the fingertip.

In particular, the projected capacitive touch panel can detect multiple points on the fingertip, and thus has a good operability of giving a complicated instruction. Utilization is progressing as an input device on a display surface in a device (such as a mobile phone or a portable music player).

In general, in a projected capacitive touch panel, a plurality of X electrodes and a plurality of Y electrodes orthogonal to the X electrodes have a two-layer structure in order to express two-dimensional coordinates based on the X and Y axes. Forming. A transparent conductive film material is used for the electrode.

Conventionally, indium tin oxide (Indium-Tin-Oxide: ITO), indium oxide, tin oxide, and the like have been used as transparent conductive film materials because of their high transmittance to visible light. Attempts have been made to form transparent conductive patterns using alternative materials. For example,

Patent Documents

1 and 2 below propose a method for forming a conductive pattern using a photosensitive conductive film having a conductive layer containing conductive fibers. If this technique is used, a conductive pattern can be easily formed directly on various substrates by a photolithography process.

International Publication No. 2010/021224 International Publication No. 2014/196154

By the way, in a conductive layer (conductive pattern or the like) containing a conductive material such as conductive fiber, the conductive material tends to have a yellowish color, and a problem in appearance tends to occur.

Therefore, an object of the present invention is to provide a laminate that can suppress an increase in yellowishness while using a conductive layer containing a conductive material, and a method for manufacturing the same. Moreover, an object of this invention is to provide the film set and photosensitive conductive film for obtaining such a laminated body.

As a result of examining the above problems in detail, the present inventors have used conductive materials (conductive fibers, etc.) by using at least one colorant selected from the group consisting of blue dyes, blue pigments, purple dyes and purple pigments. It was found that it is possible to suppress an increase in yellowness in a laminate having a conductive layer containing). In addition, when the present invention uses a black dye or a gray dye without using a blue dye, a blue pigment, a violet dye or a violet pigment, a silver paste (for example, silver The knowledge that yellowishness rose after the drying process (drying conditions: 145 degreeC / 70min) of the paste containing a fiber was acquired.

The present invention comprises a transparent substrate, a conductive layer, and a light transmissive layer, and the conductive layer is provided on the transparent substrate and contains a conductive material, and the light transmissive layer comprises: Provided is a laminate that is provided on the transparent substrate and contains at least one colorant selected from the group consisting of a blue dye, a blue pigment, a purple dye, and a purple pigment.

According to the laminated body according to the present invention, it is possible to suppress the yellowness from increasing (b * increases) while using a conductive layer containing a conductive material (conductive fiber or the like). It is possible to prevent yellowishness from increasing (for example, b * increases) in a process (for example, after a process such as a silver paste drying process). Moreover, according to the laminated body which concerns on this invention, a high transmittance | permeability can be achieved, suppressing the raise of yellowishness.

By the way, when a light resistance test used for a reliability test is performed on a laminate having a conductive layer containing a conductive material (conductive fiber, etc.), the conventional color material fades and b * increases. May be a problem. On the other hand, according to the laminated body which concerns on this invention, even if it is a case where the light resistance test is given with respect to the said laminated body, it can suppress that b * raises.

In the laminate according to the present invention, the conductive layer may be provided on the light transmission layer, and the light transmission layer is provided on the side of the conductive layer opposite to the transparent substrate. It may be an embodiment. The conductive layer may be a conductive pattern.

The content of the coloring material is preferably more than 0% by mass and 0.2% by mass or less based on the total amount of the light transmission layer.

The conductive material preferably contains at least one type of conductor selected from the group consisting of inorganic conductors and organic conductors.

The conductive material preferably contains conductive fibers.

The conductive fiber is preferably silver fiber.

Further, the present invention comprises a light transmissive layer forming step of providing a light transmissive layer and a conductive layer on a transparent substrate, the conductive layer is provided on the light transmissive layer and contains a conductive material, Provided is a method for producing a laminate, wherein the light transmission layer contains at least one color material selected from the group consisting of a blue dye, a blue pigment, a violet dye, and a violet pigment. According to the manufacturing method of the laminated body which concerns on this invention, the said effect similar to the laminated body which concerns on this invention can be acquired.

In the method for producing a laminate according to the present invention, the light transmitting layer forming step includes a light transmitting layer forming composition layer and a conductive layer provided on the light transmitting layer forming composition layer. Including a step of forming a layer on the transparent substrate, and an exposure step of irradiating the photosensitive layer with actinic rays, wherein the composition layer for forming a light transmission layer comprises a binder polymer, a photopolymerizable compound, The aspect which contains a photoinitiator and at least 1 type of color material selected from the group which consists of a blue dye, a blue pigment, a purple dye, and a purple pigment may be sufficient.

In the method for producing a laminate according to the present invention, a photosensitive conductive film having a structure in which a support film, a conductive layer, and a photosensitive resin composition layer are laminated in this order is used as the photosensitive resin composition. The photosensitive layer is formed on the transparent substrate by laminating so that the layer is in contact with the transparent substrate, and the photosensitive resin composition layer includes a binder polymer, a photopolymerizable compound, and a photopolymerization initiator. And at least one colorant selected from the group consisting of blue dyes, blue pigments, purple dyes and purple pigments.

In the method for producing a laminate according to the present invention, the conductive layer is a conductive pattern, the exposure step is a step of irradiating the photosensitive layer with an actinic ray in a pattern, and the light transmission layer forming step is performed as described above. The aspect which further includes the image development process which develops the said photosensitive layer after an exposure process may be sufficient.

The light transmission layer forming step may further include a step of irradiating at least a part or all of an unexposed portion of the photosensitive layer in the exposure step with an actinic ray in the presence of oxygen before the development step. Good.

In the method for manufacturing a laminate according to the present invention, the content of the coloring material is preferably more than 0% by mass and 0.2% by mass or less based on the total amount of the light transmission layer.

Furthermore, the present invention provides a photosensitive film having a first support film and a first photosensitive resin composition layer provided on the first support film, and a second support film, Including a photosensitive conductive film having a structure in which a conductive layer containing a conductive material and a second photosensitive resin composition layer are laminated in this order, the first photosensitive resin composition layer, Containing a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and at least one colorant selected from the group consisting of a blue dye, a blue pigment, a violet dye and a violet pigment; A film set is provided in which the photosensitive resin composition layer contains a binder polymer, a photopolymerizable compound, and a photopolymerization initiator. According to the film set concerning the present invention, the same effect as the layered product concerning the present invention can be acquired.

The film set according to the present invention may be used in the method for manufacturing the laminate.

The present invention is selected from the group consisting of a support film, a conductive layer containing a conductive material, a binder polymer, a photopolymerizable compound, a photopolymerization initiator, a blue dye, a blue pigment, a purple dye, and a purple pigment. A photosensitive conductive film having a structure in which a photosensitive resin composition layer containing at least one colorant is laminated in this order is provided. According to the photosensitive conductive film which concerns on this invention, the said effect similar to the laminated body which concerns on this invention can be acquired.

According to the present invention, while using a conductive layer containing a conductive material (conductive fiber or the like), it is possible to suppress yellowness (b * increases), particularly after heating (for example, silver It is possible to suppress the yellowness from increasing (b * increases) after the paste drying step or the like. Moreover, according to this invention, a high transmittance | permeability can be achieved, suppressing the raise of yellowishness. According to the present invention as described above, good visibility can be obtained.

It is a schematic cross section which shows embodiment of the laminated body which concerns on this invention. It is a schematic cross section which shows other embodiment of the laminated body which concerns on this invention. It is a schematic cross section which shows other embodiment of the laminated body which concerns on this invention. It is a schematic cross section for demonstrating one Embodiment of the photosensitive conductive film which concerns on this invention. It is a schematic cross section for explaining one embodiment of a manufacturing method of a layered product concerning the present invention. It is a schematic cross section for demonstrating a part of manufacturing method of the laminated body of FIG.3 (c). 8 is a schematic plan view (FIG. 7A) showing an embodiment of an electronic component according to the present invention, and a partially cutaway perspective view of FIG. 7A (FIG. 7B).

Hereinafter, embodiments of the present invention will be described in detail.

In the present specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid corresponding to it, and “(meth) acrylate” means acrylate or methacrylate corresponding thereto. Further, “A or B” only needs to include either A or B, and may include both. Furthermore, the materials exemplified below may be used alone or in combination of two or more unless otherwise specified. In the present specification, the content of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. Means.

In the present specification, the “conductive pattern” has a predetermined shape and includes a conductor. For example, a substrate having a conductive pattern has a portion including a conductor and a portion not including a conductor, and the conductive pattern is configured by the portion including the conductor.

In this specification, the boundary between the conductive layer (conductive pattern and the like) and the photosensitive resin composition layer is not necessarily clear. The aspect with which the conductive layer and the photosensitive resin composition layer were mixed may be sufficient. For example, the composition constituting the photosensitive resin composition layer may be impregnated in the conductive layer, or the composition constituting the photosensitive resin composition layer may be present on the surface of the conductive layer.

In this specification, a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value of a numerical range in a certain step may be replaced with the upper limit value or the lower limit value of a numerical range in another step. In the numerical range described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.

<Laminate>
The laminate according to the present embodiment (for example, the laminate according to the first embodiment and the second embodiment) includes a transparent substrate, a conductive layer, and a light transmission layer, and the conductive layer is transparent. The conductive layer is provided on the base material, and the light transmission layer is provided on the transparent base material, and is selected from the group consisting of a blue dye, a blue pigment, a purple dye, and a purple pigment. Containing at least one kind of coloring material. The conductive layer may be patterned (conductive pattern) or may not be patterned.

In the laminate according to the first embodiment, the conductive layer is provided on the light transmission layer, and the light transmission layer is provided between the transparent substrate and the conductive layer.

In the laminate according to the second embodiment, the light transmission layer is provided on the side opposite to the transparent base material of the conductive layer. The laminate according to the second embodiment includes a transparent substrate and a substrate with a conductive layer (such as a substrate with a conductive pattern) having a conductive layer (such as a conductive pattern) provided on the transparent substrate. A light-transmitting layer provided on the side of the conductive layer opposite to the transparent substrate, the conductive layer containing a conductive material, and the light-transmitting layer is a blue dye, a blue pigment, a purple dye, and a purple pigment. The aspect containing at least 1 type of color material selected from the group which consists of may be sufficient.

In the laminate according to this embodiment, the light transmission layer contains at least one color material selected from the group consisting of a blue dye, a blue pigment, a violet dye, and a violet pigment, so that a conductive material (conductive fiber or the like) is contained. It can suppress that yellowishness rises (b * rises), using the conductive layer containing this. For example, in the laminated body according to the present embodiment, the total light transmittance is 86.0% or more even after a severe condition such as after a heating step such as a drying step (145 ° C./70 min) of the silver paste, and the transmission. b * is 0.4 or less. Furthermore, since the light transmission layer contains at least one color material selected from the group consisting of blue dyes, blue pigments, purple dyes and purple pigments, the total light transmittance and transmission b * can be maintained even after the light resistance test. Change can be suppressed. According to the laminated body which concerns on 2nd Embodiment, since the light transmissive layer is provided on the conductive layer, it is easy to obtain excellent total light transmittance and transmission b *.

FIG. 1 is a schematic cross-sectional view showing the laminate according to the first embodiment. As shown in FIG. 1, the

laminated bodies

40a, 40b, and 40c according to the first embodiment include a transparent substrate 20, a transparent conductive pattern (conductive layer) 2a provided on the transparent substrate 20, and a light transmission layer. 3e, 3f, 3g. The transparent base material 20, the conductive pattern 2a, and the

light transmission layers

3e, 3f, 3g constitute a transparent base material with a conductive pattern (a base material with a conductive pattern).

The conductive pattern 2a is provided on the

light transmission layers

3e, 3f, and 3g. The conductive pattern 2a contains a conductive material. The

light transmission layers

3e, 3f, and 3g are made of a cured resin material containing the color material 9, and the color material 9 is dispersed in the cured resin material. The color material 9 is at least one color material selected from the group consisting of a blue dye, a blue pigment, a purple dye, and a purple pigment. The laminated body 40a shown in FIG. 1A may further include a cured resin (not shown) that covers the conductive pattern 2a and the light transmission layer 3e. In the

laminates

40b and 40c shown in FIGS. 1B and 1C, the light transmission layers 3f and 3g are resin cured patterns. In the laminated body 40c shown in FIG. 1C, the transparent substrate 20, the conductive pattern 2a, and the light transmission layer 3g are covered with a cured resin 8a. As shown in FIGS. 1B and 1C, the light transmission layer may locally cover the transparent substrate without covering the entire transparent substrate.

FIG. 2 is a schematic cross-sectional view showing a laminate according to the second embodiment. As shown in FIG. 2, the laminated body 50 which concerns on 2nd Embodiment is provided with the transparent base material with a conductive pattern (base material with a conductive pattern) 30, and the light transmissive layer 7a. The transparent substrate 30 with a conductive pattern has a transparent substrate 20, a transparent conductive pattern 2a provided on the transparent substrate 20, and a resin layer (resin cured layer) 3a. The conductive pattern 2a is provided on the resin layer 3a. The conductive pattern 2a contains a conductive material. The light transmission layer 7a has a cured resin 8a and a color material 9 dispersed in the cured resin 8a. The color material 9 is at least one color material selected from the group consisting of a blue dye, a blue pigment, a purple dye, and a purple pigment.

FIG. 3 is a schematic cross-sectional view showing another aspect of the laminate according to the second embodiment. The laminated body shown in FIG. 3A is a light transmissive material containing a transparent substrate with a conductive pattern (substrate with conductive pattern) 31 in which a conductive pattern 2a is directly provided on a transparent substrate 20, and a color material 9. A layer 7a. The laminated body shown by FIG.3 (b) is a transparent base material with a conductive pattern (resin layer (resin hardening pattern) 3b and the conductive pattern 2a are arrange | positioned in this order from the transparent base material 20 side on the transparent base material 20). (Substrate with conductive pattern) 32 and a light transmission layer 7 a containing the color material 9. The laminate shown in FIG. 3C is a transparent substrate with a conductive pattern in which a conductive pattern 2a and a resin layer (resin cured pattern) 3c are arranged in this order from the transparent substrate 20 side on a transparent substrate 20. (Substrate with conductive pattern) 33 and a light transmission layer 7 a containing the color material 9. The laminate shown in FIG. 3D has a conductive pattern in which a conductive pattern 2a and a resin layer (light transmissive layer, resin cured pattern) 3d are arranged in this order from the transparent substrate 20 side on a transparent substrate 20. A transparent substrate (substrate with a conductive pattern) 34 and a resin layer 7b made of a cured resin 8a are provided. As shown in FIG. 3D, the light transmission layer may cover only the conductive pattern 2a locally without covering the entire transparent substrate with the conductive pattern.

It should be noted that in the light transmissive layers (

light transmissive layers

3e, 3f, 3g, 7a, resin layer 3d, etc.) shown in FIGS. 1 to 3, for convenience, it can be seen that the color material is contained in the cured resin. In particular, a color material is shown. For example, when the color material is a dye, a blue dye or a violet dye may be dissolved in a medium constituting the light transmission layer. When the color material is a pigment, the light transmission layer may be A state in which a blue pigment or a violet pigment is dispersed in the medium to be formed may be used.

The laminate according to this embodiment includes a light transmission layer (

light transmission layers

3e, 3f, 3g, 7a, a resin layer 3d, and the like), so that a conductive layer is formed, and other portions (for example, In FIG. 2, the haze difference from the resin layer 3a) where the conductive pattern 2a is not formed can be reduced. The haze difference is preferably 1.0 or less, more preferably 0.7 or less, and further preferably 0.5 or less. In order to obtain such a haze difference, it is preferable to adjust the type and content of the color material in the light transmission layer, the thickness of the layer, and the like.

The laminate according to the present embodiment has a haze of 1.5 or less in the portion where the conductive layer is formed from the viewpoint of further improving the visibility of an electronic component including the laminate (for example, the sensing region portion of the touch sensor). Preferably there is. Moreover, it is preferable that the haze of the part in which the electroconductive layer is not formed is 2.0 or less from a viewpoint which is further excellent in the visibility of the electronic component (for example, sensing region part of a touch sensor) provided with a laminated body.

The details of the method for manufacturing the laminate according to this embodiment will be described later, but the transparent substrate with a conductive pattern 30 shown in FIG. 2 can be produced, for example, by the method described in International Publication No. 2013/051516. it can.
A transparent substrate 31 with a conductive pattern shown in FIG. 3A is obtained by forming an ITO film or a tin oxide film on a transparent substrate by the method described in JP-A-2007-257963, for example, or by sputtering. It can be produced by a method of patterning by etching or the like.
The transparent substrate 32 with a conductive pattern shown in FIG. 3B can be produced by, for example, the method described in Patent Document 1 (International Publication No. 2010/021224).
The

transparent substrates

33 and 34 with conductive patterns shown in FIG. 3C and FIG. 3D can be produced by, for example, the method described in US Patent Application Publication No. 2007/0074316.

Examples of the transparent substrate 20 include glass substrates; plastic substrates such as polyethylene terephthalate, polycarbonate, cycloolefin polymer, and triacetyl cellulose. The transparent substrate preferably has a minimum light transmittance of 80% or more in a wavelength region of 450 to 650 nm. From the viewpoint of reducing the weight of the electronic component to be manufactured, a plastic substrate is preferable, and a plastic substrate of polyethylene terephthalate, polycarbonate, cycloolefin polymer, or triacetyl cellulose is more preferable.

The conductive material contained in the conductive layer (conductive pattern 2a and the like) may be any material that can ensure the conductivity of the conductive layer. From the viewpoint of ensuring high conductivity, from the inorganic conductor and the organic conductor. At least one electric conductor selected from the group consisting of

Examples of inorganic conductors include metal oxide particles such as indium tin oxide (ITO), indium oxide, and tin oxide; metal fibers such as gold, silver, copper, and platinum, metal particles, or metal mesh. Can be mentioned. Examples of the organic conductor include carbon fibers such as vapor grown carbon fiber (VGCF) and carbon nanotube; carbon powder such as carbon black, and the like.

The form of the conductive material is not particularly limited, but is preferably fibrous, and more preferably conductive fiber. When the conductive layer (conductive pattern 2a and the like) contains conductive fibers, both conductivity and transparency can be achieved at a high level. In addition, when the conductive pattern shown in FIG. 1, FIG. 2 or FIG. 3B is formed using a transfer type photosensitive conductive film, which will be described later, by using conductive fibers as a conductive material, developability is achieved. Can be further improved, and a conductive pattern with excellent resolution can be formed.

Examples of the conductive fibers contained in the conductive layer include metal fibers such as gold, silver, copper, and platinum; carbon fibers such as vapor grown carbon fibers (VGCF) and carbon nanotubes. From the viewpoint of excellent conductivity, it is preferable to use gold fiber or silver fiber. From the viewpoint of easily adjusting the conductivity of the formed conductive layer, silver fiber is more preferable. From the viewpoint of easily suppressing the phenomenon in which light is reflected on the surface of the conductive fiber in the conductive layer containing the conductive fiber and the conductive layer (conductive pattern portion or the like) appears white, the conductive layer is made of conductive fiber (silver fiber). Etc.), the component (D) described later is preferably used in the light transmission layer.

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

The fiber diameter of the conductive fiber is preferably 1 nm or more, more preferably 2 nm or more, further preferably 3 nm or more, and particularly preferably 10 nm or more from the viewpoint of obtaining excellent electrostatic resistance. Preferably, it is very preferably 20 nm or more. The fiber diameter of the conductive fiber is preferably 50 nm or less, more preferably 45 nm or less, and still more preferably 40 nm or less, from the viewpoint of easily obtaining excellent visibility. From these viewpoints, the fiber diameter of the conductive fiber is preferably 1 to 50 nm, more preferably 2 to 45 nm, still more preferably 3 to 40 nm, and particularly preferably 10 to 40 nm. A thickness of 20 to 40 nm is particularly preferable.

The fiber length of the conductive fiber is preferably 1 μm or more, more preferably 2 μm or more, and more preferably 3 μm or more from the viewpoint of easily reducing the amount of the conductive fiber used for obtaining sufficient visibility. More preferably. The fiber length of the conductive fiber is preferably 100 μm or less, more preferably 50 μm or less, further preferably 10 μm or less, and more preferably 5 μm or less, from the viewpoint of easily suppressing aggregation of the conductive fibers. It is particularly preferred. From these viewpoints, the fiber length of the conductive fiber is preferably 1 to 100 μm, more preferably 2 to 50 μm, still more preferably 3 to 10 μm, and particularly preferably 3 to 5 μm. preferable.

The fiber diameter and fiber length can be measured with a scanning electron microscope.

The thickness of the conductive layer (conductive pattern 2a and the like) varies depending on the conductivity and transparency required for the conductive layer, but is preferably in the following range. The thickness of the conductive layer is preferably 1 μm or less, more preferably 0.5 μm or less, from the viewpoint of high light transmittance in a wavelength region of 450 to 650 nm, particularly suitable for a transparent electrode. More preferably, it is 0.1 μm or less. The thickness of the conductive layer is preferably 1 nm or more, more preferably 5 nm or more, further preferably 10 nm or more, and particularly preferably 50 nm or more, from the viewpoint of ensuring uniform conductivity. preferable. From these viewpoints, the thickness of the conductive layer is preferably 1 μm or less, more preferably 1 nm to 0.5 μm, further preferably 5 nm to 0.1 μm, and more preferably 10 nm to 0.1 μm. Particularly preferred is 50 nm to 0.1 μm. In addition, the thickness of a conductive layer points out the value measured with a scanning electron microscope.

The conductive layer preferably has a network structure in which conductive fibers are in contact with each other. If the conductive fiber having such a network structure has conductivity in the surface direction on the surface exposed when the conductive layer is formed, the surface layer portion in the layer in contact with the conductive layer (for example, the conductive pattern 2a And the

resin layers

3a, 3b, 3c, 3d and the

light transmission layers

3e, 3f, 3g on the conductive pattern 2a side) may be present.

The resin layers 3a, 3b and the

light transmission layers

3e, 3f, 3g may be any material that can hold the conductive pattern 2a on the transparent substrate 20 by bonding the transparent substrate 20 and the conductive pattern 2a. The resin layers 3c and 3d only need to be able to be held on the conductive pattern 2a. The resin layers 3a, 3b, 3c, 3d and the

light transmission layers

3e, 3f, 3g are, for example, resins that are cured products of a layer made of a photosensitive resin composition (hereinafter also referred to as a photosensitive resin composition layer). In this case, the resin layer and the conductive pattern can be collectively formed using a transfer type photosensitive conductive film described later.

Examples of the photosensitive resin composition include (A) a binder polymer (hereinafter sometimes referred to as “component (A)”), (B) a photopolymerizable compound (hereinafter sometimes referred to as “component (B)”), And the composition containing (C) photoinitiator (henceforth "(C) component" depending on the case) is mentioned. By using such a composition, both the resolution of the conductive pattern 2a and the adhesiveness with the transparent substrate 20 can be achieved.

(A) As the binder polymer, conventionally known ones can be used without particular limitation, but acrylic resins are preferred. The acrylic resin can be produced, for example, by radical polymerization of at least one selected from the group consisting of (meth) acrylic acid and (meth) acrylic acid ester. That is, the acrylic resin can have at least one selected from the group consisting of structural units derived from (meth) acrylic acid and structural units derived from (meth) acrylic acid esters.

As (meth) acrylic acid ester, (meth) acrylic acid alkyl ester, (meth) acrylic acid aryl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid Examples include diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and the like.

Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like. Examples of the (meth) acrylic acid aryl ester include benzyl (meth) acrylate. The acrylic resin may include a structural unit based on styrene (a structural unit derived from styrene).

(A) The binder polymer preferably has a carboxyl group from the viewpoint of improving alkali developability. Examples of the polymerizable monomer having a carboxyl group for obtaining such a binder polymer include (meth) acrylic acid as described above.

(A) Regarding the ratio of the carboxyl group that the binder polymer has, the ratio of the polymerizable monomer having a carboxyl group is based on the total amount of the polymerizable monomer used to obtain the (A) binder polymer, as described below. A range is preferable. The ratio of the polymerizable monomer having a carboxyl group is preferably 10% by mass or more, more preferably 12% by mass or more, and more preferably 15% by mass or more from the viewpoint of excellent alkali developability. Further preferred. The proportion of the polymerizable monomer having a carboxyl group is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less from the viewpoint of excellent alkali resistance. It is preferably 25% by mass or less. From these viewpoints, the proportion of the polymerizable monomer having a carboxyl group is preferably 10 to 50% by mass, more preferably 12 to 40% by mass, and 15 to 30% by mass. Further preferred is 15 to 25% by mass. Similarly, the content of the structural unit derived from the polymerizable monomer having a carboxyl group is preferably within these ranges based on the total amount of the (A) binder polymer.

(A) The weight average molecular weight of the binder polymer is preferably 10,000 or more, more preferably 15000 or more, from the viewpoint that adhesion is likely to be suppressed due to low alkali resistance of the cured film during development. Preferably, it is more preferably 30000 or more, and particularly preferably 50000 or more. (A) The weight average molecular weight of the binder polymer is preferably 200000 or less, and preferably 150,000 or less, from the viewpoint that it is easy to suppress the difficulty of obtaining a good pattern due to low developability of the unexposed area during development. It is more preferable that it is 100000 or less. From these viewpoints, the weight average molecular weight of the (A) binder polymer is preferably 10,000 to 200,000, more preferably 15,000 to 150,000, still more preferably 30,000 to 150,000, and more preferably 30,000 to 100,000. Particularly preferred is 50,000 to 100,000. (A) The weight average molecular weight of the binder polymer is preferably 15000 to 150,000, more preferably 30000 to 150,000, still more preferably 30,000 to 100,000, and more preferably 50,000 to 100,000 from the viewpoint of excellent resolution. It is particularly preferred. In addition, a weight average molecular weight can be measured with reference to the measuring method of the Example mentioned later.

As the photopolymerizable compound as component (B), a photopolymerizable compound having an ethylenically unsaturated group can be used. Thereby, the resolution of the conductive pattern 2a and the adhesiveness with the transparent base material 20 can be made more highly compatible.

Examples of the photopolymerizable compound having an ethylenically unsaturated group include a monofunctional vinyl monomer, a bifunctional vinyl monomer, and a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups.

Examples of the monofunctional vinyl monomer include (meth) acrylic acid, (meth) acrylic acid alkyl ester and monomers copolymerizable therewith.

Bifunctional vinyl monomers include polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, polypropylene glycol di (meth) acrylate, and 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane ), Bisphenol A diglycidyl ether di (meth) acrylate, and the like.

Examples of the polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups include trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, and dipentaerythritol. Compounds obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, such as tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; Examples thereof include compounds obtained by adding an α, β-unsaturated carboxylic acid to a glycidyl group-containing compound such as glycidyl ether triacrylate.

The content of the component (A) is preferably in the following range with respect to 100 parts by mass of the total amount of the component (A) and the component (B). The component (A) content is excellent in coating properties and prevents edge fusion (resin oozes out from the film end) when the transfer type photosensitive conductive film described later is formed and rolled up. From an easy viewpoint, it is preferable that it is 40 mass parts or more, It is more preferable that it is 50 mass parts or more, It is further more preferable that it is 60 mass parts or more. The content of the component (A) is high sensitivity, and is preferably 80 parts by mass or less, and more preferably 70 parts by mass or less from the viewpoint of improving the mechanical strength of the cured film. From these viewpoints, the content of the component (A) is preferably 40 to 80 parts by mass, more preferably 50 to 70 parts by mass, and further preferably 60 to 70 parts by mass.

The content of the component (B) is preferably in the following range with respect to 100 parts by mass of the total amount of the component (A) and the component (B). The content of the component (B) is high sensitivity, and is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, from the viewpoint that the mechanical strength of the cured film can be increased. More preferably, it is at least part. The content of the component (B) is excellent in coating properties, forms a transfer-type photosensitive conductive film described later, and is easy to prevent edge fusion from occurring when wound into a roll, and is 60 parts by mass or less. It is preferable that it is 50 mass parts or less. From these viewpoints, the content of component (B) is preferably 20 to 60 parts by mass, more preferably 30 to 50 parts by mass, and even more preferably 40 to 50 parts by mass.

As the photopolymerization initiator which is the component (C), conventionally known photopolymerization initiators can be used without particular limitation. Specific examples of the component (C) include aromatic ketones, oxime ester compounds, phosphine oxide compounds, benzyl derivatives, 2,4,5-triarylimidazole dimers, acridine derivatives, N-phenylglycine, N- Examples thereof include phenylglycine derivatives, coumarin compounds, and oxazole compounds.

Among these, from the group which consists of an oxime ester compound and a phosphine oxide compound at the point which is excellent in the pattern formation ability when it is set as a thin film (for example, film | membrane of thickness of 10 micrometers or less), and is easy to form the conductive pattern excellent in transparency. At least one selected is preferred.

Examples of oxime ester compounds include 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzoyloxime)], 1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl] ethanone 1- (O-acetyloxime) and the like. Examples of the phosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

The content of the component (C) is preferably in the following range with respect to 100 parts by mass of the total amount of the component (A) and the component (B). The content of the component (C) is preferably 0.1 parts by mass or more, more preferably 2 parts by mass or more, and 6 parts by mass or more from the viewpoint of sufficiently increasing sensitivity. Is more preferable. The content of the component (C) is preferably 15 parts by mass or less from the viewpoint of easily preventing absorption at the surface of the composition from increasing during photoexposure and insufficient photocuring inside. The amount is more preferably 12 parts by mass or less, and further preferably 10 parts by mass or less. From these viewpoints, the content of the component (C) is preferably 0.1 to 15 parts by mass, more preferably 2 to 12 parts by mass, and further preferably 6 to 10 parts by mass. .

The photosensitive resin composition is, if necessary, (D) at least one colorant selected from the group consisting of a blue dye, a blue pigment, a purple dye and a purple pigment (hereinafter referred to as “component (D)” in some cases). ) May be further contained. For example, as shown in FIG. 3D, when the resin layer 3d is disposed on the surface of the conductive pattern 2a opposite to the transparent substrate 20, and the resin layer 3d contains the component (D). May mix | blend (D) component with the photosensitive resin composition. Thereby, it is possible to easily suppress a significant decrease in transparency and a significant change in hue.

The blue dye refers to a dye having similar absorption in the entire range of 400 to 500 nm in the visible light region. The blue dye is preferably a dye having an absorption intensity in the entire range of 400 to 500 nm within a range of 0.7 to 1.3 when the absorption intensity at 450 nm is 1, and the absorption intensity is 0.8 to More preferred are dyes within the range of 1.2. As a blue dye, VALIFAST BLUE 2606 (manufactured by Orient Chemical Industry Co., Ltd.) can be used as a commercially available product.

Purple dye means a dye having the same level of absorption in the entire visible light range of 380 to 430 nm. The purple dye is preferably a dye having an absorption intensity in the range of 380 to 430 nm within a range of 0.7 to 1.3, assuming that the absorption intensity at 400 nm is 1, and the absorption intensity is 0.8 to More preferred are dyes within the range of 1.2. As a purple dye, OPLAS VIOLET 730 (manufactured by Orient Chemical Co., Ltd.) can be used as a commercially available product.

The absorption intensity (absorbance) can be measured using a UV spectrophotometer (trade name “U-3310” manufactured by Hitachi, Ltd.).

As the dye, it is preferable not to select a thiol group-containing compound whose surface resistivity tends to increase under high temperature and high humidity, or a colored compound which easily causes discoloration and precipitation under high temperature and high humidity. Furthermore, when the light transmission layer is a photosensitive resin layer, it is preferable that the dye does not have strong absorption in the ultraviolet region in order to suppress a decrease in photosensitive characteristics.

Blue pigment refers to a pigment having the same degree of absorption in the entire visible light range of 400 to 500 nm. The blue pigment is preferably a pigment having an absorption intensity in the entire range of 400 to 500 nm within a range of 0.7 to 1.3 when the absorption intensity at 450 nm is 1, and the absorption intensity is 0.8 to More preferred are pigments in the range of 1.2. As the blue pigment, commercially available products such as NX-051 and NX-053 (manufactured by Dainichi Seika Kogyo Co., Ltd.) can be used.

Purple pigment means a pigment having the same level of absorption in the entire visible light range of 380 to 430 nm. The purple pigment is preferably a pigment having an absorption intensity in the range of 380 to 430 nm within the range of 0.7 to 1.3 when the absorption intensity at 400 nm is 1, and the absorption intensity is 0.8 to More preferred are pigments in the range of 1.2. As the purple pigment, NX-043 (manufactured by Dainichi Seika Kogyo Co., Ltd.) can be used as a commercial product.

As the pigment, it is preferable not to select a thiol group-containing compound whose surface resistivity tends to increase under high temperature and high humidity, or a colored compound which easily causes discoloration and precipitation under high temperature and high humidity. Furthermore, when the light transmission layer is a photosensitive resin layer, it is preferable that the pigment does not have strong absorption in the ultraviolet region in order to suppress a decrease in photosensitive characteristics.

Among the components (D), at least one selected from the group consisting of blue pigments and purple pigments is preferable. Thereby, yellowness peculiar to conductive material (for example, conductive fibers, such as silver fiber), can further be controlled.

When the photosensitive resin composition contains the component (D), the content of the component (D) is 0 on the basis of the total amount of the component (A) and the component (B) from the viewpoint of easily obtaining high transparency. It is preferably 2% by mass or less, more preferably 0.18% by mass or less, further preferably 0.15% by mass or less, and particularly preferably 0.1% by mass or less. On the other hand, the content of the component (D) exceeds 0% by mass on the basis of the total amount of the components (A) and (B) from the viewpoint of easily suppressing the increase in yellowness, and the conductive material (conductive 0.05 mass% or more is preferable from the viewpoint of further suppressing the phenomenon of appearing white due to reflection of the conductive layer (conductive pattern or the like) by the fiber or the like, and further suppressing the appearance of the pattern.

The conductive pattern 2a and the light transmission layer 3e shown in FIG. 1A are, for example, a photosensitive resin composition layer (layer for obtaining the light transmission layer 3e) provided on the transparent substrate 20, and a photosensitive property. A first exposure step of irradiating a photosensitive layer including a conductive layer provided on the surface of the resin composition layer opposite to the transparent substrate 20 with actinic rays in a pattern; and in the presence of oxygen, the photosensitive layer A conductive pattern 2a is formed by developing a photosensitive layer after a second exposure step of irradiating at least a part or all of the unexposed portion in the first exposure step with actinic rays, and after the second exposure step. It can be obtained through a development step. According to such a method for forming a conductive pattern, a region having a conductive pattern and a region where a part of the conductive layer is removed and the cured resin layer is exposed can be formed in a lump.

Moreover, the conductive pattern 2a and the light transmission layers 3f and 3g shown in FIGS. 1B and 1C are, for example, a photosensitive resin composition layer (light transmission layer 3f) provided on the transparent substrate 20. , 3 g) and a photosensitive layer including a conductive layer provided on the surface of the photosensitive resin composition layer on the side opposite to the transparent substrate 20 is irradiated with actinic rays in a pattern. And a developing process for forming the conductive pattern 2a by developing the exposed photosensitive layer.

The conductive pattern 2a and the resin layer 3a shown in FIG. 2 are, for example, a photosensitive resin composition layer (layer for obtaining the resin layer 3a) provided on the transparent substrate 20, as will be described later with reference to FIG. And a photosensitive layer including a conductive layer provided on the surface of the photosensitive resin composition layer on the side opposite to the transparent substrate 20, and actinic rays are irradiated in a pattern, and in the presence of oxygen. In the second exposure step of irradiating at least a part or all of the unexposed portion in the first exposure step of the photosensitive layer with active light, and developing the photosensitive layer after the second exposure step, the conductive pattern It can be obtained through a development step for forming 2a. According to such a method for forming a conductive pattern, a region having a conductive pattern and a region where a part of the conductive layer is removed and the cured resin layer is exposed can be formed in a lump.

Moreover, the conductive pattern 2a and the resin layer 3b shown in FIG. 3B are, for example, a photosensitive resin composition layer (layer for obtaining the resin layer 3b) provided on the transparent substrate 20, and a photosensitive property. A photosensitive layer including a conductive layer provided on the surface opposite to the transparent substrate 20 of the resin composition layer is exposed to an actinic ray in a pattern, and the exposed photosensitive layer is developed to develop the conductive layer. It can be obtained through a development step for forming the pattern 2a.

Moreover, the conductive pattern 2a and the resin layers 3c and 3d shown in FIG. 3C and FIG. 3D include, for example, a conductive layer provided on the transparent substrate 20, and a transparent substrate 20 of the conductive layer. Is a photosensitive layer including a photosensitive resin composition layer (layer for obtaining the resin layers 3c and 3d) provided on the opposite surface, an exposure step of irradiating actinic rays in a pattern, and an exposed photosensitive layer Can be obtained through a developing process for forming the conductive pattern 2a (see FIG. 6 described later).

The photosensitive layer (photosensitive resin composition layer and conductive layer) may be directly provided on the transparent substrate 20 by a method such as coating, or separately, a support and a photosensitive layer provided on the support. The photosensitive resin composition layer or the conductive layer may be laminated so as to be in contact with the transparent substrate 20. By using such a transfer type photosensitive conductive film, a conductive pattern can be easily formed on a substrate with sufficient resolution. In addition, it is possible to easily connect a connection terminal or the like provided on the substrate surface and the conductive pattern.

FIG. 4 is a schematic cross-sectional view for explaining the photosensitive conductive film according to the present embodiment. As shown in FIG. 4, the photosensitive conductive film 10 includes a support film 1 and a photosensitive layer 4 provided on the support film 1. The photosensitive layer 4 includes a conductive layer 2 containing a conductive material and a photosensitive resin composition layer 3 provided on the surface of the conductive layer 2 opposite to the support film 1. That is, the photosensitive conductive film 10 has a structure in which the support film 1, the conductive layer 2, and the photosensitive resin composition layer 3 are laminated in this order.

As the support film 1, a polymer film having heat resistance and solvent resistance can be used. Examples of the polymer film include a polyethylene terephthalate film, a polyethylene film, a polypropylene film, and a polycarbonate film. Among these, from the viewpoint of excellent transparency and heat resistance, at least one selected from the group consisting of a polyethylene terephthalate film and a polypropylene film is preferable.

As the support film 1, a polymer film having gas (especially oxygen) permeability may be used. In this case, for example, in the conductive pattern forming method having the first exposure step and the second exposure step, the support film 1 is not peeled off by adjusting the oxygen concentration of the atmosphere in the second exposure step. Even in the presence of oxygen, the second exposure step can be performed.

For the components contained in the conductive layer 2, the components described for the conductive pattern 2a can be used. The conductive layer 2 is prepared, for example, by preparing a conductive material dispersion liquid containing the above-described conductive material and water, an organic solvent, a dispersion stabilizer (surfactant, etc.), and the conductive material dispersion liquid on the support film 1. After coating, it can be formed by drying. After drying, the conductive layer 2 formed on the support film 1 may be laminated as necessary.

For the components contained in the photosensitive resin composition layer 3, the components described for the photosensitive resin composition can be used. The photosensitive resin composition layer 3 contains, for example, a binder polymer, a photopolymerizable compound (for example, a photopolymerizable compound having an ethylenically unsaturated bond) and a photopolymerization initiator, and, if necessary, a blue dye, It further contains at least one colorant selected from the group consisting of blue pigments, purple dyes and purple pigments. These components include (A) a binder polymer, (B) a photopolymerizable compound (for example, a photopolymerizable compound having an ethylenically unsaturated bond), and (C) a photopolymerization initiator in the photosensitive resin composition. And the above-described components can be used as the component (D) in the light-transmitting

layers

3e, 3f, 3g, and 7a.

The photosensitive resin composition layer 3 is prepared by preparing a solution of the photosensitive resin composition (which may contain a solid content such as a pigment. The same applies hereinafter) on the conductive layer 2 formed on the support film 1. After coating the solution, it can be formed by drying. The photosensitive resin composition solution is obtained by dissolving the components of the photosensitive resin composition in a solvent such as methanol, acetone, methyl ethyl ketone, methyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof. Alternatively, it may be dispersed. The solid content concentration of the photosensitive resin composition solution can be about 10 to 60% by mass.

The thickness of the photosensitive resin composition layer 3 varies depending on the application, but is preferably the following range in terms of the thickness after drying. The thickness of the photosensitive resin composition layer 3 is preferably 0.05 μm or more, more preferably 0.1 μm or more, and more preferably 0.5 μm or more from the viewpoint of easy application. Is more preferable and 1 μm or more is particularly preferable. The thickness of the photosensitive resin composition layer 3 is preferably 20 μm or less, more preferably 15 μm or less, further preferably 10 μm or less, and more preferably 8 μm or less, from the viewpoint of easily preventing a decrease in sensitivity. Particularly preferred is 5 μm or less. From these viewpoints, the thickness of the photosensitive resin composition layer 3 is preferably 0.05 to 20 μm, more preferably 0.05 to 15 μm, and further preferably 0.1 to 10 μm. 0.1 to 8 μm is particularly preferable, 0.1 to 5 μm is very preferable, 0.5 to 5 μm is very preferable, and 1 to 5 μm is even more preferable. In addition, it is preferable that the thickness of the layer (

resin layers

3a, 3b, 3c, 3d,

light transmission layers

3e, 3f, 3g, etc.) obtained by curing the photosensitive resin composition layer 3 is also in these ranges.

The coating can be performed by a known method such as a roll coating method. The drying can be performed at 30 to 150 ° C. for about 1 to 30 minutes with a hot air convection dryer or the like. In the conductive layer 2, the conductive material may coexist with a surfactant or a dispersion stabilizer.

The photosensitive conductive film 10 may have a protective film 5 as necessary (see FIG. 6 described later). As the protective film, the film exemplified by the support film 1 can be used. In this case, it is preferable to adjust the thickness or surface treatment of the support film 1 and the protective film so that the peel strength of the protective film is smaller than the peel strength of the support film 1.

The thickness of the protective film is preferably 10 to 200 μm, more preferably 15 to 150 μm, and still more preferably 15 to 100 μm.

In the photosensitive layer 4 (the conductive layer 2 and the photosensitive resin composition layer 3), the minimum light transmittance in the wavelength region of 450 to 650 nm is 80% or more when the total thickness of both layers is 1 to 10 μm. Is preferable, and it is more preferable that it is 85% or more. When the conductive layer 2 and the photosensitive resin composition layer 3 satisfy such conditions, visibility is further improved when the laminate is applied to an electronic component such as a touch panel.

The

light transmissive layers

3e, 3f, 3g, 7a and the resin layer (light transmissive layer) 3d are at least selected from the group consisting of component (D) (blue dye, blue pigment, violet dye, and violet pigment) as the color material 9. A kind of coloring material). The

light transmissive layers

3e, 3f, 3g, and 7a and the resin layer (light transmissive layer) 3d are layers for suppressing an increase in yellow tint, and conductive materials (conductive layers) of the conductive layer (conductive pattern 2a and the like). This is a layer capable of absorbing the reflected light from the conductive fiber and the like and suppressing the phenomenon that the conductive layer looks white due to the reflection of the light on the surface of the conductive material. The

light transmissive layers

3e, 3f, 3g, 7a and the resin layer (light transmissive layer) 3d are preferably a photosensitive resin composition layer or a cured product thereof from the viewpoint of ease of formation.

As the component (D) contained in the light transmission layer, the same component as the component (D) in the photosensitive resin composition can be used.

The medium containing the component (D) may be a resin cured product, a resin composition layer before curing, an organic glass, or the like.

Examples of the cured resin include a cured product of a photosensitive resin composition. Examples of the photosensitive resin composition include a binder polymer, a photopolymerizable compound (for example, a photopolymerizable compound having an ethylenically unsaturated bond), a photopolymerization initiator and a component (D), and other components as necessary. A composition containing can be used. Examples of the binder polymer, photopolymerizable compound (for example, photopolymerizable compound having an ethylenically unsaturated bond), photopolymerization initiator, and other components include the

resin layers

3a, 3b, 3c, 3d and the light transmitting layer 3e described above. , 3f, and 3g are the same materials.

The light-transmitting

layers

3e, 3f, and 3g may be formed by applying the photosensitive resin composition on the transparent substrate 20 and then drying it, and layering the photosensitive resin composition on the support film. It is also possible to prepare a photosensitive film on which is formed and transfer the layer of the photosensitive resin composition. The light transmissive layer 7a may be formed by applying the photosensitive resin composition on the transparent substrate with

conductive pattern

30, 31, 32, 33 and then drying, and may be formed on the support film. You may provide the photosensitive film in which the layer of the resin composition was formed, and may provide by transferring the layer of the photosensitive resin composition. The resin layer 3d may be formed by applying the photosensitive resin composition on the conductive pattern 2a and then drying, or a photosensitive film having a layer of the photosensitive resin composition formed on a support film. May be prepared and exposed and developed after transferring the layer of the photosensitive resin composition.

The content of the component (D) in the light-transmitting

layers

3e, 3f, 3g, 7a and the resin layer (light-transmitting layer) 3d is 0. 0% based on the total amount of the light-transmitting layer from the viewpoint that high transparency is easily obtained. It is preferably 2% by mass or less, more preferably 0.18% by mass or less, and further preferably 0.15% by mass or less. On the other hand, the content of the component (D) exceeds 0% by mass on the basis of the total amount of the light transmission layer from the viewpoint of easily suppressing an increase in yellowness, and on the surface of the conductive material (conductive fiber, etc.). 0.05 mass% or more is preferable from the viewpoint of further suppressing the phenomenon in which light is reflected and the conductive layer (conductive pattern or the like) appears white and the pattern appearance is suppressed. The content of the component (D) is, for example, more than 0% by mass and 0.2% by mass or less based on the total amount of the light transmission layer.

The thicknesses of the

light transmissive layers

3e, 3f, 3g, 7a and the resin layer (light transmissive layer) 3d are preferably in the following ranges from the viewpoint of obtaining further excellent light transmittance and haze value. The thicknesses of the

light transmission layers

3e, 3f, 3g, 7a and the resin layer 3d are preferably 0.5 μm or more, more preferably 1 μm or more, further preferably 2 μm or more, and 2.5 μm or more. It is particularly preferred that The thicknesses of the

light transmission layers

3e, 3f, 3g, 7a and the resin layer 3d are preferably 25 μm or less, more preferably 15 μm or less, further preferably 8 μm or less, and preferably 5 μm or less. Particularly preferred. From these viewpoints, the thicknesses of the

light transmission layers

3e, 3f, 3g, 7a and the resin layer 3d are preferably 0.5 to 25 μm, more preferably 1 to 15 μm, and 2 to 8 μm. Is more preferably 2.5 to 8 μm, and most preferably 2.5 to 5 μm.

In a transparent substrate with a conductive layer (such as a transparent substrate with a conductive pattern), the minimum light transmittance in the wavelength region of 450 to 650 nm is preferably 80% or more, and more preferably 85% or more.

The transparent substrate with a conductive layer (transparent substrate with a conductive pattern, etc.) is obtained by the method for forming a conductive layer (conductive pattern, etc.) described above. The surface resistivity of the conductive layer (conductive pattern 2a, etc.) is preferably 400Ω / □ or less, more preferably 300Ω / □ or less, from the viewpoint that it can be effectively used as wiring, electrodes (transparent electrodes, etc.). Preferably, it is 150Ω / □ or less. In addition, by setting the surface resistivity of the conductive layer in such a range, it is possible to easily ensure good electrical connection with a connection terminal or the like provided on the surface of the base material. The surface resistivity can be adjusted by, for example, the concentration of the conductive material dispersion (conductive fiber dispersion or the like), the coating amount, or the like. In addition, the surface resistivity of the conductive pattern obtained by patterning the conductive layer can be measured as the surface resistivity of the conductive layer.

The total light transmittance of the transparent substrate with a conductive layer (such as a transparent substrate with a conductive pattern) is preferably 86.0% or more, and more preferably 88.0% or more. When the transparent substrate with a conductive layer satisfies such conditions, the visibility on a display panel or the like is further improved.

The total light transmittance of the laminate according to this embodiment is preferably 86.0% or more, more preferably 87.0% or more, further preferably 88.0% or more, 90 It is especially preferable that it is 0.0% or more. When the said laminated body satisfy | fills such conditions, it is easy to ensure sufficient transparency and the visibility in a display panel etc. further improves.

<Method for producing laminate>
The manufacturing method of the laminated body which concerns on this embodiment (For example, the manufacturing method of the laminated body which concerns on 1st Embodiment and 2nd Embodiment) is demonstrated. The manufacturing method of the laminated body which concerns on this embodiment is equipped with the light transmissive layer formation process which provides a light transmissive layer and a conductive layer on a transparent base material, a conductive layer contains a conductive material, a light transmissive layer is a blue dye, It contains at least one colorant selected from the group consisting of blue pigments, purple dyes and purple pigments.

In the method for manufacturing a laminate according to the first embodiment, the conductive layer is provided on the light transmission layer. The conductive layer and the light transmission layer may be simultaneously formed on the transparent substrate, or may be separately formed on the transparent substrate.

In the method for manufacturing a laminated body according to the second embodiment, the light transmission layer is provided on the side opposite to the transparent base material of the conductive layer. For example, the manufacturing method of the laminated body which concerns on 2nd Embodiment is a transparent base material (for example, with a conductive pattern) which has a transparent base material and a conductive layer (conductive pattern etc.) provided on the transparent base material. A light-transmitting layer forming step of forming a light-transmitting layer on the opposite side of the conductive layer of the conductive layer of a conductive pattern such as a transparent substrate). In other words, in the light transmissive layer forming step, the light transmissive layer is provided on the side where the conductive layer of the transparent base material and the transparent base material with a conductive layer having the conductive layer provided on the transparent base material is provided. Form.

The light transmitting layer forming step in the method for manufacturing the laminate according to the first embodiment includes, for example, a light transmitting layer forming composition layer and a conductive layer (conductive material) provided on the light transmitting layer forming composition layer. And a light-sensitive layer-forming composition layer comprising a binder polymer, a step of forming a photosensitive layer comprising a transparent substrate on the transparent substrate, and an exposure step of irradiating the photosensitive layer with actinic rays. Photopolymerizable compound (for example, photopolymerizable compound having an ethylenically unsaturated bond), photopolymerization initiator, and at least one colorant selected from the group consisting of blue dyes, blue pigments, purple dyes and purple pigments Containing. The photosensitive layer comprises a photosensitive conductive film having a structure in which a support film, a conductive layer (a layer containing a conductive material), and a photosensitive resin composition layer are laminated in this order. It may be formed on the transparent substrate by laminating so that the layer contacts the transparent substrate.

The light-transmitting layer forming step in the method for producing a laminate according to the second embodiment includes, for example, a binder polymer, a photopolymerizable compound (for example, a photopolymerizable compound having an ethylenically unsaturated bond), a photopolymerization initiator, and The transparent base material of the conductive layer (conductive pattern etc.) is a composition layer for forming a light transmission layer containing at least one colorant selected from the group consisting of blue dyes, blue pigments, purple dyes and purple pigments Forming the light transmitting layer by irradiating the composition layer for forming the light transmitting layer with actinic rays. The composition layer for forming a light transmission layer is a photosensitive film having a support film and a photosensitive resin composition layer provided on the support film, and the photosensitive resin composition layer is a transparent substrate with a conductive layer. It may be formed by laminating so as to be in contact with (a transparent substrate with a conductive pattern or the like).

The composition layer for forming a light transmission layer is a composition layer for forming a light transmission layer. For example, a binder polymer, a photopolymerizable compound (for example, a photopolymerizable compound having an ethylenically unsaturated bond), light It contains a polymerization initiator and at least one colorant selected from the group consisting of blue dyes, blue pigments, purple dyes and purple pigments. The said photosensitive resin composition layer of a photosensitive conductive film or a photosensitive film is a layer used as the light transmission layer forming composition layer. The photosensitive resin composition layer contains the same constituents as the light transmission layer forming composition layer, for example, a binder polymer, a photopolymerizable compound (for example, a photopolymerizable compound having an ethylenically unsaturated bond). ), A photopolymerization initiator, and at least one colorant selected from the group consisting of blue dyes, blue pigments, purple dyes and purple pigments.

In the laminate manufacturing method according to the first embodiment, the conductive layer is a conductive pattern, the exposure step is a step of irradiating the photosensitive layer with actinic rays in a pattern, and the light transmission layer forming step is a step of the exposure step. The aspect which further includes the image development process which develops a photosensitive layer later may be sufficient. The light transmitting layer forming step is a step of irradiating at least a part or all of the unexposed portion in the exposure step (first exposure step) of the photosensitive layer with oxygen in the presence of oxygen before the development step. (Second exposure step) may further be included.

FIG. 5 is a schematic cross-sectional view for explaining the manufacturing method of the laminated body according to the second embodiment. In the method shown in FIG. 5, first, a conductive pattern 2a is formed on a transparent substrate 20 to produce a transparent substrate with a conductive pattern (substrate with a conductive pattern) 30 (FIGS. 5A to 5D). reference). In addition, when the photosensitive resin composition layer 3 and the resin layer 3a of FIG. 5 contain the coloring material 9, it replaces with the transparent base material 30 with a conductive pattern, and is a laminated body which is a laminated body which concerns on 1st Embodiment. 40a (FIG. 1 (a)) can be obtained.

The transparent substrate with a conductive pattern 30 is a photosensitive layer forming step (FIG. 5A) in which the photosensitive layer 4 is provided on the transparent substrate 20, and a first exposure that irradiates the photosensitive layer 4 with an actinic ray L in a pattern. Step (FIG. 5B) and a second exposure step (FIG. 5B) in which a part or all of the unexposed portion of at least the first exposure step of the photosensitive layer 4 is irradiated with actinic rays L in the presence of oxygen c)) and a developing step (FIG. 5D) for forming the conductive pattern 2a by developing the photosensitive layer 4 after the second exposure step. The photosensitive layer 4 includes the photosensitive resin composition layer 3 on the transparent substrate 20 and the conductive layer 2 provided on the surface of the photosensitive resin composition layer 3 opposite to the transparent substrate 20.

The photosensitive layer forming step may include a laminating step of providing the photosensitive layer 4 by laminating the photosensitive conductive film 10. In the laminating step, the photosensitive layer 4 may be provided by laminating the photosensitive conductive film 10 described above so that the photosensitive resin composition layer 3 is in contact with the transparent substrate 20. In this case, in the first exposure step, the support film 1 may be disposed on the photosensitive layer 4, and the support film 1 may be peeled off before the second exposure step. The first exposure step is preferably performed in a vacuum or in an inert gas atmosphere.

The laminating step is performed by, for example, a method of laminating the photosensitive resin composition layer 3 on the transparent substrate 20 while heating the photosensitive conductive film 10. In addition, it is preferable to perform this operation under reduced pressure from the viewpoint of adhesion and followability. In the lamination of the photosensitive conductive film 10, the conductive layer 2 and the photosensitive resin composition layer 3 or the transparent substrate 20 are preferably heated to 70 to 130 ° C., and the pressure bonding pressure is 0.1 to 1.0 MPa. Although it is preferable to set it to a level (about 1 to 10 kgf / cm ² ), these conditions are not particularly limited. Further, if the conductive layer 2 or the photosensitive resin composition layer 3 is heated to 70 to 130 ° C. as described above, it is not necessary to pre-heat the transparent substrate 20 in advance, but in order to further improve the laminating property. In addition, the transparent substrate 20 can be preheated.

In the first and second exposure steps, the photosensitive resin composition layer 3 is cured by irradiation with actinic rays. In the method for forming a conductive pattern, the conductive layer 2 is fixed by the cured product, whereby the conductive pattern 2a and the resin layer (resin cured layer) 3a are formed on the transparent substrate 20.

As an exposure method in the exposure step, for example, there is a method (mask exposure method) of irradiating an actinic ray L in an image form through a mask pattern 6 called an artwork (FIG. 5B). As the active light source, a known light source, for example, a light source that effectively emits ultraviolet light, visible light, or the like, such as a high-pressure mercury lamp or a xenon lamp, is used. A light source that effectively emits ultraviolet light, visible light, or the like, such as an Ar ion laser or a semiconductor laser, is also used. Furthermore, a light source that effectively emits visible light, such as a photographic flood bulb or a solar lamp, is also used. Alternatively, a method of irradiating actinic rays in an image shape by a direct drawing method using a laser exposure method or the like may be employed.

Although the support film 1 may be peeled off before the second exposure step, a gas permeable film is used as the support film, and the first exposure step is performed under vacuum, under an inert gas atmosphere, or under reduced oxygen pressure. The target conductive pattern can be obtained without peeling off the support film 1 by adjusting the atmosphere during exposure, such as by performing the second exposure step in the presence of oxygen in the air (preferably under high-pressure oxygen). Can be formed.

In the developing process, portions other than the exposed portion of the photosensitive layer 4 are removed. Specifically, when the transparent support film 1 is present on the photosensitive layer 4, the support film 1 is first removed, and then the portions other than the exposed portions of the photosensitive layer 4 are removed by wet development. . Thereby, the part containing a conductive material remains on the resin layer (resin cured layer) 3a having a predetermined pattern, and the conductive pattern 2a is formed.

The wet development is performed by a known method such as spraying, rocking dipping, brushing, scraping, or the like using a developer corresponding to the photosensitive resin such as an alkaline aqueous solution, an aqueous developer, or an organic solvent developer.

As the developer, it is preferable to use an alkaline aqueous solution or the like that is safe and stable and has good operability. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium or potassium hydroxide; alkali carbonates such as lithium, sodium, potassium or ammonium carbonate or bicarbonate.

Examples of the alkaline aqueous solution used for development include 0.1 to 5% by weight sodium carbonate aqueous solution, 0.1 to 5% by weight potassium carbonate aqueous solution, 0.1 to 5% by weight sodium hydroxide aqueous solution, and 0.1 to 5% by weight four. A sodium borate aqueous solution or the like is preferable. The pH of the alkaline aqueous solution used for development is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition 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 may be used.

In this embodiment, the resin layer may be further cured by heating at about 60 to 250 ° C. or exposure at about 0.2 to 10 J / cm ² as necessary after development.

Next, the transparent substrate 30 with a conductive pattern having a transparent substrate 20, a resin layer (resin cured layer) 3a provided on the transparent substrate 20, and a conductive pattern 2a provided on the resin layer 3a. On the side where the conductive pattern 2a is provided, a light transmitting layer forming composition layer 7 having a photosensitive resin composition layer 8 and a color material 9 dispersed in the photosensitive resin composition layer 8 is formed. Then, a light transmissive layer forming step is carried out to obtain a light transmissive layer 7a by exposure (FIGS. 5E and 5F).

The light transmitting layer forming step includes, for example, a binder polymer, a photopolymerizable compound (for example, a photopolymerizable compound having an ethylenically unsaturated bond) on the side where the conductive pattern 2a of the transparent substrate with a conductive pattern 30 is provided, For forming a light transmission layer forming composition layer 7 for forming a light transmission layer containing a photopolymerization initiator and at least one colorant selected from the group consisting of a blue dye, a blue pigment, a purple dye and a purple pigment A composition layer forming step (FIG. 5 (e)) and an exposure step of irradiating the composition layer 7 for forming a light transmitting layer with an actinic ray to obtain the light transmitting layer 7a may be included.

For example, the light transmission layer forming composition layer forming step includes at least one selected from the group consisting of a support film and a color material (blue dye, blue pigment, purple dye, and purple pigment provided on the support film) The photosensitive film having the light-transmitting layer-forming composition layer 7 containing 9 is prepared in advance, and the conductive pattern 2a of the transparent substrate 30 with the conductive pattern and the conductive pattern 2a are not formed. It can also be set as the process of laminating | stacking a photosensitive film so that the said composition layer 7 for light transmissive layer formation may contact | connect the resin layer (resin cured layer) 3a.

The exposure process and the lamination process can be performed under the same conditions as described above. The photosensitive film can also be laminated to the transparent substrate with a conductive pattern under the same conditions.

The laminated body 50 can be manufactured by the above (FIG.5 (f)). The laminated body 50 can further be provided with a layer such as a visibility improving film or a hard coat layer. After providing these layers in the laminate of FIG. 5 (e), the light transmission layer may be cured.

The above-mentioned photosensitive film (film having no conductive layer) can be provided as a film set together with the photosensitive conductive film (film having a conductive layer). That is, a photosensitive film having a first support film and a first photosensitive resin composition layer provided on the first support film, a second support film, and a conductive material Including a photosensitive conductive film having a structure in which a conductive layer and a second photosensitive resin composition layer are laminated in this order, and the first photosensitive resin composition layer includes a binder polymer, a light A polymerizable compound (for example, a photopolymerizable compound having an ethylenically unsaturated bond), a photopolymerization initiator, and at least one colorant selected from the group consisting of a blue dye, a blue pigment, a violet dye, and a violet pigment; And the second photosensitive resin composition layer contains a binder polymer, a photopolymerizable compound (for example, a photopolymerizable compound having an ethylenically unsaturated bond), and a photopolymerization initiator. It may provide a door. A film set can be used for the manufacturing method of the laminated body mentioned above.

By using the above film set to produce a laminate having a transparent substrate and a conductive layer (such as a conductive pattern), a conductive material while suppressing an increase in surface resistivity and a decrease in light transmittance of the conductive layer It is possible to provide a laminate in which light is reflected on the surface of (conductive fibers or the like) and the phenomenon that the conductive layer looks white is sufficiently suppressed. As a manufacturing method of the laminated body using a film set, the method mentioned above is mentioned, for example. For example, the laminate 40c in FIG. 1C can be obtained by producing the conductive pattern 2a and the light transmission layer 3g using a photosensitive conductive film and producing the cured resin 8a using the photosensitive film. it can. The laminated body 50 of FIG. 2 can be obtained by producing the transparent substrate 30 with a conductive pattern using a photosensitive conductive film and producing the light transmission layer 7a using the photosensitive film.

The photosensitive conductive film includes a support film, a conductive layer containing a conductive material, a binder polymer, a photopolymerizable compound (for example, a photopolymerizable compound having an ethylenically unsaturated bond), a photopolymerization initiator, and blue. A photosensitive conductive film having a structure in which a photosensitive resin composition layer containing at least one colorant selected from the group consisting of a dye, a blue pigment, a purple dye, and a purple pigment is laminated in this order. There may be. When such a photosensitive conductive film is used, the

light transmission layers

3e, 3f, 3g and the conductive pattern 2a provided on the

light transmission layers

3e, 3f, 3g are collectively shown in FIG. Can be formed. Further, when a photosensitive conductive film is used, as shown in FIG. 3D, the conductive pattern 2a and the resin layer (light transmission layer) 3d provided on the conductive pattern 2a can be formed in a lump. In this case, it is not necessary to further form a light transmission layer containing at least one color material selected from the group consisting of a blue dye, a blue pigment, a purple dye and a purple pigment on the conductive pattern 2a and / or the resin layer 3d. However, since the conductive pattern 2a is easy to see a step on the surface, the form is not limited, but it is preferable to further form a light transmission layer to eliminate surface irregularities.

The photosensitive resin composition layer of the photosensitive conductive film may be an embodiment that does not contain a color material. For example, the transparent substrate with a conductive pattern of the laminate shown in FIG. 3C is obtained by the procedure shown in FIG. 6 using a photosensitive conductive film having a photosensitive resin composition layer not containing a colorant. be able to. First, a photosensitive conductive film having a structure in which the support film 1, the photosensitive layer 4 (the conductive layer 2 and the photosensitive resin composition layer 3), and the protective film 5 are laminated in this order is prepared. While peeling off the support film 1, the photosensitive layer 4 and the protective film 5 are laminated on the transparent substrate 20 (FIGS. 6A and 6B). Next, a transparent substrate with a conductive pattern of the laminate shown in FIG. 3C can be obtained by irradiating actinic rays L in an image form through the mask pattern 6 (FIG. 6C) and developing. (FIG. 6 (d)). The support film 1, the photosensitive resin composition layer 3, and the conductive layer 2 are formed by laminating the photosensitive layer 4 and the support film 1 on the transparent substrate 20 while peeling the protective film 5 using the laminate roll 60. Can be obtained in this order.

<Electronic parts>
The electronic component according to the present embodiment includes the laminate according to the present embodiment. The laminated body which concerns on this embodiment can be used for electronic components, such as a touch panel, a liquid crystal display, a solar cell, and illumination.

FIG. 7A is a schematic plan view showing a touch panel as an electronic component according to the present embodiment. FIG. 7B is a partially cutaway perspective view of FIG.

The touch panel (capacitance type touch panel) shown in FIG. 7 has a transparent electrode 103 and a transparent electrode 104 for detecting a change in capacitance on a transparent base material (transparent base material, touch panel base material) 100. The

transparent electrodes

103 and 104 have a light transmission layer 102 containing a color material on the surface opposite to the transparent substrate 100. The transparent electrode 103 detects an X position coordinate signal. The transparent electrode 104 detects a signal of the Y position coordinate. The transparent electrode 103 and the transparent electrode 104 exist on the resin layer 101. These electrodes and the resin layer can be provided by the conductive pattern forming method described above. The

transparent electrodes

103 and 104 are connected to a lead-out wiring 105a and a lead-out wiring 105b for connection to a control circuit of a driver element circuit (not shown) that controls an electrical signal as a touch panel. An insulating film 124 is disposed between the transparent electrode 103 and the transparent electrode 104 at a portion where the transparent electrode 103 and the transparent electrode 104 intersect (see FIG. 7B). A light transmission layer 102 is laminated on the transparent electrode and the resin layer.

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

<Preparation of conductive fiber dispersion (silver fiber dispersion)>
[Preparation of silver fiber by polyol method]
In a 2000 mL three-necked flask, 500 mL of ethylene glycol was added and heated to 160 ° C. with an oil bath while stirring with a magnetic stirrer under a nitrogen atmosphere. A separately prepared solution prepared by dissolving ₂ mg of PtCl 2 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 80,000 (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 150 mL of ethylene glycol were respectively obtained. From the dropping funnel in 1 minute, and then stirred at 160 ° C. for 60 minutes.

The reaction solution was allowed to stand at 30 ° C. or lower and then diluted 10 times with acetone. Next, centrifugation was performed at 2000 rpm for 20 minutes using a centrifuge, and the supernatant was decanted. Acetone was added to the precipitate, and after stirring, the mixture was centrifuged 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 an optical microscope, the fiber diameter (diameter) was about 40 nm, and the fiber length was about 4 μm.

[Preparation of silver fiber dispersion]
The silver fiber obtained above was dispersed in pure water so that the content was 0.2% by mass and dodecyl-pentaethylene glycol was 0.1% by mass to obtain a conductive fiber dispersion 1. .

<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. On the other hand, a solution in which 100 g of methacrylic acid, 250 g of methyl methacrylate, 100 g of ethyl acrylate and 50 g of styrene are mixed with 0.8 g of azobisisobutyronitrile as an initiator (hereinafter referred to as “solution a”). Prepared. Next, the solution a was added dropwise to the solution s heated to 80 ° C. over 4 hours, and then kept at 80 ° C. with stirring 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 for 3 hours, stirring, Then, it heated at 90 degreeC over 30 minutes. The mixture was kept at 90 ° C. for 2 hours and then cooled to obtain a binder polymer solution. Acetone was added to the binder polymer solution to adjust the non-volatile component (solid content) to 50% by mass to obtain a binder polymer solution as the component (A). The weight average molecular weight of the obtained binder polymer was 80000 in terms of standard polystyrene conversion by GPC. This was designated as acrylic polymer (A1). In addition, the measurement conditions of GPC which measured the weight average molecular weight are as follows.

[GPC measurement conditions]
Model: Hitachi L6000 (manufactured by Hitachi, Ltd.)
Detection: L3300RI (manufactured by Hitachi, Ltd.)
Column: Gelpack GL-R440 + GL-R450 + GL-R400M (manufactured by Hitachi Chemical Co., Ltd.)
Column specifications: Diameter 10.7mm x 300mm
Solvent: THF (tetrahydrofuran)
Sample concentration: 120 mg of NV (non-volatile content) 50% by mass resin solution was collected and dissolved in 5 mL of THF Injection amount: 200 μL
Pressure: 4.9 MPa
Flow rate: 2.05 mL / min

<Preparation of solution of photosensitive resin composition>
The materials shown in Table 1 and Table 2 were blended in the blending amounts (unit: parts by mass) shown in the same table to prepare photosensitive resin composition solutions X1 to X11.

Details of the materials shown in Tables 1 and 2 are as follows.

(A) Component (A1): The above acrylic polymer (A1)

Component (B) TMPTA: trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD TMPTA)
T-1420: Dipentaerythritol tetraacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD T-1420)

Component (C) TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF, LUCIRIN TPO)

Component (D) VALIFAST BLUE 2606: alpha-Bis [4- (diethylamino) phenyl] -4- (ethylamino) naphthalene-1-methylol (blue dye, product name, manufactured by Orient Chemical Co., Ltd.)
OPLAS VIOLET 730: 1-hydroxy-4- (p-tolyamino) anthracene-9,10-dione (purple dye, trade name, manufactured by Orient Chemical Co., Ltd.)
NX-051: Phthalocyanine Blue (blue pigment, manufactured by Dainichi Seika Kogyo Co., Ltd., NX-051 Blue)
NX-053: Chromofne Blue (blue pigment, manufactured by Dainichi Seika Kogyo Co., Ltd., NX-053 Blue)
NX-043: Dioxazine violet (purple pigment, manufactured by Dainichi Seika Kogyo Co., Ltd., NX-043 Violet)

(Other)
OIL BLACK 860: Solvent Black 3 (black dye, manufactured by Orient Chemical Industry Co., Ltd., OIL BLACK 860)
SZ-6030: γ-methacryloyloxypropyltrimethoxy silane (SZ-6030, manufactured by Toray Dow Corning Co., Ltd., SZ-6030)

<Preparation of photosensitive conductive film>
The conductive fiber dispersion 1 was uniformly applied at 26 g / m ² onto a 50 μm-thick polyethylene terephthalate film (PET film, manufactured by Teijin Ltd., trade name: G2-50) as a support film, and then 100 ° C. A hot air convection dryer was used for 10 minutes, and pressurization was performed at a linear pressure of 1 MPa at room temperature (25 ° C.) to form a conductive layer containing conductive fibers on the support film. In addition, when measured by a scanning electron micrograph, the film thickness after drying of the conductive layer was about 0.1 μm.

Next, the photosensitive resin composition solutions X1 to X11 are uniformly applied on the conductive layer formed on the support film, and dried for 10 minutes in a hot air convection dryer at 100 ° C. to form a photosensitive resin layer. Formed. In addition, when measured with the scanning electron micrograph, the film thickness after drying of the photosensitive resin layer was 5 μm. Next, the photosensitive resin layer was covered with a protective film made of polyethylene (cover film, manufactured by Tamapoly Co., Ltd., trade name “NF-13”) to obtain photosensitive conductive films E1 to E11.

<Evaluation of photosensitivity (missing resolution)>
While peeling off the protective films of the photosensitive conductive films E1 to E11 obtained above on the surface of a 125 μm thick PET film (trade name “Cosmo Shine-A300” manufactured by Toyobo Co., Ltd.), the photosensitive resin layer was formed. It was made to oppose a PET film, and it laminated on the conditions of 110 degreeC, 0.6 m / min, and 0.4 MPa.

After lamination, the PET film is cooled, and when the temperature of the substrate reaches 23 ° C., a step tablet for photosensitive property investigation (S / T; L / S = x / 400, x = 6 to 47) is covered, Light was irradiated from the support film side with an exposure amount of 20 mJ / cm ² using an exposure machine having a high-pressure mercury lamp (trade name “EXM-1201” manufactured by Oak Manufacturing Co., Ltd.). After light irradiation, the support film was peeled off and irradiated with light at an exposure amount of 50 mJ / cm ² .

Next, development was performed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 40 seconds. Furthermore, the UV exposure machine irradiated light with the exposure amount of 1 J / cm < ² >.

By the above operation, the conductive pattern shown in FIG. 1A was formed on the PET film.

As an evaluation of missing resolution, the line width L (unit: μm) of a line / space (L / 400 μm) pattern was measured. The narrower the line width, the higher the resolution. The results are shown in Tables 3 and 4.

<Transmission b * and total light transmittance T.I. T. T. et al. Measurement>
Photosensitive conductive films E1 to E11 were laminated by the above method on a SiO ₂ sputtered glass substrate having a thickness of 0.1 mmt cut into an arbitrary size. After the lamination, when the temperature of the glass substrate reaches 23 ° C., 1000 mJ / cm ² is used from the support film side using an exposure machine having a high-pressure mercury lamp (trade name “EXM-1201” manufactured by Oak Manufacturing Co., Ltd.). It was irradiated with light at an exposure amount of. After light irradiation, the support film was peeled off to obtain a substrate for evaluation. Using this evaluation substrate, transmission b * and total light transmittance T.I. T. T. et al. Was measured. The transmission b * of the evaluation substrate was measured by the SCE method from the surface opposite to the substrate using a spectrocolorimeter (manufactured by Konica Minolta, trade name “CM-5”). Total light transmittance of substrate for evaluation T. T. et al. Was measured using a haze meter (trade name “NDH-5000” manufactured by Nippon Denka Kogyo Co., Ltd.). The results are shown in Tables 3 and 4. The unit of total light transmittance is “%”.

Assuming a drying step after the silver paste application (for example, drying conditions: 145 ° C./70 min), after applying the temperature for 70 minutes with a 145 ° C. hot air convection dryer, Transmission b * and total light transmittance T.I. T.A. Was measured.

As a light resistance test, the evaluation substrate (Examples 3 to 7) after the above heat treatment (145 ° C./70 min treatment) was irradiated with a sun test XLS + (manufactured by Toyo Seiki Co., Ltd.) with an irradiation intensity of 60 W / m ² (300 to 400 nm). The test was conducted under the conditions of a black panel temperature of 60 ° C. and a time of 500 hours. After the test, the transmission b * and the total light transmittance T.sub. T. T. et al. Was measured.

<Determination of evaluation results>
The following criteria were used, and “A”, “B” or “C” was evaluated. The determination results are shown in Tables 3 and 4.
1) Initial determination (145 ° C./70 min)
A: Initial value b * ≦ 0.4, T.I. T. T. et al. ≧ 88.0%, and
Fluctuation from initial value b * ≦ ± 0.4, T.P. T. T. et al. ≤ ± 0.4%
B: Initial value b * ≦ 0.4, 88.0%> T. T. T. et al. ≧ 86.0%, and
Fluctuation from initial value b * ≦ ± 0.8, T.P. T. T. et al. ≦ ± 0.8%
C: Other than the above 2) Reliability determination (145 ° C./70 min + light resistance test: 500 h)
A: Initial value b * ≦ 0.4, T.I. T. T. et al. ≧ 88.0%, and
Fluctuation from initial value b * ≦ ± 0.4, T.P. T. T. et al. ≤ ± 0.4%
B: Initial value b * ≦ 0.4, 88.0%> T. T. T. et al. ≧ 86.0%, and
Fluctuation from initial value b * ≦ ± 0.8, T.P. T. T. et al. ≦ ± 0.8%
C: Other than the above

According to the present invention, it is possible to suppress a yellowish increase while using a conductive layer containing a conductive material (conductive fiber or the like). Moreover, according to this invention, the film set and photosensitive conductive film for obtaining such a laminated body can be provided.

DESCRIPTION OF SYMBOLS 1 ... Support film, 2 ... Conductive layer, 2a ... Conductive pattern, 3, 8 ... Photosensitive resin composition layer, 3a, 3b, 3c, 7b, 101 ... Resin layer, 3d ... Resin layer (light transmission layer), 4 DESCRIPTION OF SYMBOLS ... Photosensitive layer, 5 ... Protective film, 6 ... Mask pattern, 7 ... Composition layer for light transmission layer formation, 3e, 3f, 3g, 7a, 102 ... Light transmission layer, 8a ... Resin hardened material, 9 ... Color material, DESCRIPTION OF SYMBOLS 10 ... Photosensitive electrically conductive film 20,100 ... Transparent base material, 30, 31, 32, 33, 34 ... Transparent base material with a conductive pattern (base material with a conductive pattern), 40a, 40b, 40c, 50 ... Laminated body, 60 ... Laminate roll, 103 ... Transparent electrode (X position coordinate), 104 ... Transparent electrode (Y position coordinate), 105a, 105b ... Lead-out wiring, 124 ... Insulating film, L ... Actinic ray.

Claims

A transparent substrate, a conductive layer, and a light transmission layer;
The conductive layer is provided on the transparent substrate and contains a conductive material,
The light-transmitting layer is provided on the transparent substrate, and includes at least one color material selected from the group consisting of a blue dye, a blue pigment, a violet dye, and a violet pigment.
The laminate according to claim 1, wherein the conductive layer is provided on the light transmission layer.
The laminate according to claim 1, wherein the light transmission layer is provided on the side of the conductive layer opposite to the transparent substrate.
The laminate according to any one of claims 1 to 3, wherein the conductive layer is a conductive pattern.
The laminate according to any one of claims 1 to 4, wherein the content of the coloring material is more than 0% by mass and 0.2% by mass or less based on the total amount of the light transmission layer.
The laminate according to any one of claims 1 to 5, wherein the conductive material includes at least one type of conductor selected from the group consisting of inorganic conductors and organic conductors.
The laminate according to any one of claims 1 to 6, wherein the conductive material contains conductive fibers.
The laminate according to claim 7, wherein the conductive fiber is a silver fiber.
A light transmissive layer forming step of providing a light transmissive layer and a conductive layer on a transparent substrate;
The conductive layer is provided on the light transmission layer and contains a conductive material,
The manufacturing method of a laminated body in which the said light transmissive layer contains at least 1 type of color material selected from the group which consists of a blue dye, a blue pigment, a purple dye, and a purple pigment.
The light transmission layer forming step includes
Forming a light-sensitive layer forming composition layer and a conductive layer provided on the light-transmitting layer forming composition layer on the transparent substrate;
Exposure step of irradiating the photosensitive layer with actinic rays,
The light transmitting layer forming composition layer is at least one colorant selected from the group consisting of a binder polymer, a photopolymerizable compound, a photopolymerization initiator, a blue dye, a blue pigment, a purple dye, and a purple pigment. The manufacturing method of the laminated body of Claim 9 containing these.
A photosensitive conductive film having a structure in which a support film, a conductive layer, and a photosensitive resin composition layer are laminated in this order is laminated so that the photosensitive resin composition layer is in contact with the transparent substrate. The photosensitive layer is formed on the transparent substrate by
The photosensitive resin composition layer is a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and at least one colorant selected from the group consisting of a blue dye, a blue pigment, a purple dye, and a purple pigment; The manufacturing method of the laminated body of Claim 10 containing this.
The conductive layer is a conductive pattern;
The exposure step is a step of irradiating the photosensitive layer with actinic rays in a pattern,
The manufacturing method of the laminated body of Claim 10 or 11 with which the said light transmissive layer formation process further includes the image development process which develops the said photosensitive layer after the said exposure process.
The light transmissive layer forming step further includes a step of irradiating at least a part or all of an unexposed portion in the exposure step of the photosensitive layer with an actinic ray in the presence of oxygen before the developing step. The manufacturing method of the laminated body of 12.
The method for producing a laminate according to any one of claims 9 to 13, wherein the content of the coloring material is more than 0% by mass and 0.2% by mass or less based on the total amount of the light transmission layer.
A photosensitive film having a first support film and a first photosensitive resin composition layer provided on the first support film; and
Including a photosensitive conductive film having a structure in which a second support film, a conductive layer containing a conductive material, and a second photosensitive resin composition layer are laminated in this order;
The first photosensitive resin composition layer is at least one color selected from the group consisting of a binder polymer, a photopolymerizable compound, a photopolymerization initiator, a blue dye, a blue pigment, a purple dye, and a purple pigment. Containing, and
The film set in which a said 2nd photosensitive resin composition layer contains a binder polymer, a photopolymerizable compound, and a photoinitiator.
The film set according to claim 15, which is used in the method for producing a laminate according to any one of claims 9 to 14.
Support film,
A conductive layer containing a conductive material, and
Photosensitive resin composition layer containing a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and at least one colorant selected from the group consisting of a blue dye, a blue pigment, a violet dye, and a violet pigment. The photosensitive conductive film which has the structure laminated | stacked in this order.