JP2019152898A - Conductive sheet for touch panel, manufacturing method of conductive sheet for touch panel and touch panel - Google Patents

Abstract

A method for producing a conductive sheet for a touch panel and a touch panel are provided, in which a touch panel in which the metal part has excellent conductivity and the screen looks blacker when the screen is displayed in black or when the backlight is off is obtained. do. A touch panel conductive sheet (10) has a support (12) and a conductive part (14) disposed on the support and containing a binder and a metal part. The binder contains a first polymer and a second polymer having a lower glass transition temperature than the first polymer, and the content of the second polymer with respect to the total content of the first polymer and the second polymer At least one selected from the group consisting of the formula RM < RU and the formula RM < RL, where RU is the value in the upper region, RM is the value in the middle region, and RL is the value in the lower region. The formula holds. [Selection drawing] Fig. 1

Description

  The present invention relates to a conductive sheet for a touch panel, a method for manufacturing a conductive sheet for a touch panel, and a touch panel.

  In recent years, smartphones, tablet terminals, portable game devices, and the like are equipped with a touch panel having an image display device and a capacitive touch sensor that is arranged on the image display device and can detect multiple points. Is increasing. A conductive sheet for a touch panel used for manufacturing such a touch panel is known in which a conductive portion is disposed on a transparent support. As a manufacturing method thereof, Patent Document 1 discloses a “support. And a conductive thin wire containing a binder and a metal part disposed on the support, and in the vertical cross section of the conductive thin wire, from the surface X opposite to the support side of the conductive thin wire, the support side When the contour line along the surface shape of the surface X of the conductive thin wire is moved toward the support side, the position where the contour line reaches the metal part included in the conductive thin wire is defined as the upper end position from the upper end position to the support side. When the average area ratio VA of the metal part in the region up to 100 nm toward the substrate is 1% or more and less than 50%, and the contour line is moved to the support side from the upper end position, the metal part is not included in the conductive thin wire. Bottom position The conductive film in which the average area ratio VM1 of the metal part in the region of 50 nm from the intermediate position between the upper end position and the lower end position toward the support side and 50 nm toward the surface X side is 50% or more. Are listed.

International Publication No. 2006-157585

The conductive film described in Patent Document 1 has excellent conductivity, and when applied to a touch panel, the conductive film has an excellent feature that it is difficult for a touch panel user to visually recognize a conductive thin wire. . However, the present inventors have examined the conductive film of Patent Document 1 by applying it to a touch panel. As a result, when the screen display is black or when the backlight is turned off, the screen may be white in some cases. I found out that it might be visible.
Accordingly, the present invention provides a touch panel that is excellent in conductivity of the metal part, and that makes the screen less white when the screen display is black or when the backlight is turned off, in other words, a touch panel that looks blacker. It is an object to provide a conductive sheet for use. Moreover, this invention also makes it the subject to provide the manufacturing method of the electroconductive sheet for touch panels, and a touch panel.

  As a result of intensive studies to achieve the above-described problems, the present inventors have found that the above-described problems can be achieved by the following configuration.

[1] A conductive sheet for a touch panel that includes a support and a conductive part that is disposed on the support and includes a binder and a metal part. The binder includes a first polymer and a first polymer. And a second polymer having a low glass transition temperature, and in the vertical cross section of the conductive part, the surface shape of the surface X of the conductive part is changed from the surface X opposite to the support side of the conductive part toward the support side. The first polymer and the second height in the region from the upper end position to 100 nm from the upper end position to the support side, with the position where the outline has reached the metal part included in the conductive part as the upper end position when the contour line is moved along the second polymer-containing mass ratio of the content of to the total content of the molecule as R _U, when moving the contour on the support side than the upper end position, as the lower end position a position free of the metal part with a conductive portion , Top and bottom position The second polymer-containing mass ratio of the content of relative from the intermediate position the total content of the first polymer and second polymer in the 50nm region toward 50nm and surface X side to the support side and R _M of When the content ratio of the content of the second polymer to the total content of the first polymer and the second polymer in the region of 100 nm from the lower end position toward the surface X side is R _L , 1 and Formula 2; The conductive sheet for touch panels in which at least one selected from the group consisting of Formula 1 _RM <R _U and Formula 2 _RM <R _L is satisfied.
[2] The conductive sheet for a touch panel according to [1], wherein the glass transition temperature of the second polymer is 25 ° C. or lower.
[3] The conductive sheet for a touch panel according to [1] or [2], wherein the metal part contains at least one metal selected from the group consisting of gold, silver, copper, nickel, and palladium.
[4] An easy-adhesion layer is provided between the support and the conductive part, and a non-conductive part arranged adjacent to the conductive part is further provided on the easy-adhesive layer, and the refractive index of the non-conductive part is set to RI. _{1 When} the refractive index of the easy-adhesion layer is RI ₂ and the refractive index of the support is RI ₃ , the following formula 3; formula 3 RI ₁ <RI ₂ <RI ₃ is satisfied, [1] to [3 ] The electroconductive sheet for touchscreens in any one of.
[5] The method for producing a conductive sheet for a touch panel according to any one of [1] to [4], wherein the metal part contains metallic silver, wherein at least silver halide and the first polymer are formed on the support. A silver halide-containing coating solution containing at least a second polymer and a composition-adjusting coating solution containing at least a second polymer to form a silver halide photosensitive layer by simultaneous multilayer coating; A conductive sheet for a touch panel, comprising: exposing a conductive layer, and then developing the conductive part containing metal silver by developing.
[6] The method for producing a conductive sheet for a touch panel according to [5], wherein the composition-adjusting coating solution further contains silver halide.
[7] The conductive material for a touch panel according to [5] or [6], wherein at least one selected from the group consisting of a silver halide-containing coating solution and a composition-adjusting coating solution further contains non-metallic fine particles. Sheet manufacturing method.
[8] The method for producing a conductive sheet for a touch panel according to any one of [5] to [7], further including a step F of performing a process of fusing the metallic silver of the conductive portion to each other after the step B.
[9] After step A, before step B, the step of contacting the silver halide photosensitive layer with a compound having a metal-adsorbing substituent or a metal-adsorbing structure is included, or The method for producing a conductive sheet for a touch panel according to [8], which includes a step C2 of bringing the conductive portion into contact with the compound after the step B and before the step F.
[10] The metal-adsorptive substituent is at least one selected from the group consisting of a carboxyl group or a salt thereof, an acid amide group, an amino group, an imidazole group, a pyrazole group, a thiol group, a thioether group, and a disulfide group. The manufacturing method of the electroconductive sheet for touchscreens as described in [9].
[11] Manufacturing of the conductive sheet for a touch panel according to any one of [8] to [10], further including a step D for consolidating the conductive portion after the step B and before the step F. Method.
[12] At least one selected from the group consisting of a silver halide-containing coating solution and a composition-adjusting coating solution further contains gelatin and is further conductive after step B and before step D. The process for producing a conductive sheet for a touch panel according to [11], comprising a step E of removing part of the gelatin.
[13] The process for producing a conductive sheet for a touch panel according to [11] or [12], wherein the process D is a calendering process in which a support having a conductive portion is passed through at least a pair of rolls under pressure. .
[14] A touch panel having the conductive sheet for touch panel according to any one of [1] to [4].

  According to the present invention, it has excellent conductivity, and when the screen display is black or when the backlight is turned off, the screen does not appear white, in other words, appears black (hereinafter referred to as “black tightening is good”). It is also referred to as “.” A conductive sheet for a touch panel from which a touch panel can be obtained can be provided. Moreover, according to this invention, the manufacturing method of the electroconductive sheet for touchscreens, and a touchscreen can also be provided.

It is sectional drawing of the electroconductive sheet for touchscreens concerning the 1st Embodiment of this invention. It is a partial expanded sectional view of the electroconductive part of the electroconductive sheet for touchscreens concerning the 1st Embodiment of this invention. It is a partial expanded sectional view of the electroconductive part of the electroconductive sheet for touchscreens concerning the 1st Embodiment of this invention. It is a top view of the electroconductive part of the electroconductive sheet for touchscreens concerning the 1st Embodiment of this invention. It is sectional drawing of the electroconductive sheet for touchscreens which concerns on the modification of the 1st Embodiment of this invention. It is sectional drawing of the electroconductive sheet for touchscreens which concerns on the 2nd modification of the 1st Embodiment of this invention. It is sectional drawing for demonstrating the condition of simultaneous multilayer coating.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

  The conductive sheet for a touch panel according to the embodiment of the present invention has a conductive part on a support, and the conductive part includes a metal part and a binder. One of the features of the present invention is that the binder composition in the conductive portion and the distribution in the thickness direction are controlled.

The present inventors manufactured a touch panel using a conductive sheet for a touch panel manufactured by a conventional technique, and the cause that the screen appears white when the screen display is black or the backlight is turned off. I have been studying earnestly. As a result, in the case of black display, the present inventors often have relatively strong external light compared to the light emitted from the inside of the touch panel, and in such a case, the metal part emits external light. I found out that the screen looks white because of the reflection.
This tendency is relatively high in the metal content per unit volume of the conductive part in the side (viewing side) arranged on the user side when applied to the touch panel among the front and back of the conductive sheet for touch panel. (Hereinafter, also referred to as “the metal part has a high density”).

The conductive sheet for a touch panel according to the embodiment of the present invention controls the distribution of two types of polymers having different glass transition temperatures in the conductive part. Specifically, the second polymer (polymer having a lower glass transition temperature, hereinafter referred to as “low Tg high”) in the interface region including the support X and / or the opposite surface X of the conductive part. In the intermediate region in the thickness direction of the conductive portion, the first polymer (polymer having a higher glass transition temperature, hereinafter also referred to as “high Tg polymer”) is contained. ) Content is increased. Thereby, reflection of the external light resulting from the form of the metal part or the like is suppressed.
The mechanism by which the reflection of external light is suppressed is not necessarily clear, but in the interface region where the content of the low Tg polymer (second polymer) is higher, the metal part is less likely to be dense (intermediate) It is estimated that the density is lower than that of the region. In other words, it is presumed that the binder content in the conductive portion is likely to increase in the interface region as compared with the intermediate region described later. Thereby, it is estimated that the reflection of the external light originating in the metal part is more easily suppressed.
On the other hand, it is presumed that in the intermediate region where the content of the high Tg polymer (first polymer) is higher, the metal part tends to have a high density. In other words, it is presumed that the content of the binder in the conductive portion tends to decrease in the intermediate region as compared with the interface region. As a result, it is presumed that excellent conductivity as a conductive sheet for a touch panel is also maintained.

The above-mentioned tendency is more remarkable in the conductive sheet for a touch panel obtained through a process in which the metal part contains a metal and the metal is fused to each other by heating or the like. That is, in the interface region where the content of the low Tg polymer (second polymer) is higher, the above treatment has a lower glass transition temperature when the metal is fused and densified. It is presumed that the second polymer is deformed at the same time as or prior to the deformation of the metal portion and enters the fine voids between the metals, so that the metals are hardly fused together, and as a result, the density is not easily increased.
On the other hand, in the intermediate region where the content of the first polymer is higher, it is difficult for the polymer to enter the fine voids of the metal part, so that the metals are likely to be fused together. It tends to be high density, and as a result, it is presumed that excellent conductivity as a conductive sheet for a touch panel is also maintained.

[First Embodiment]
Hereinafter, 1st Embodiment of the electroconductive sheet for touchscreens concerning 1st Embodiment of this invention is described with reference to drawings.
In FIG. 1, sectional drawing of 1st Embodiment of the electroconductive sheet for touchscreens concerning 1st Embodiment of this invention was shown.
The conductive sheet 10 for a touch panel includes a support 12 and a conductive portion 14 disposed on the support 12. In FIG. 1, two conductive portions 14 are illustrated, but the number is not particularly limited.
FIG. 2 shows a partially enlarged cross-sectional view of the conductive portion 14. The conductive portion 14 includes a binder 16 containing a first polymer described later and a second polymer described later, and a plurality of metal portions 18 dispersed in the binder 16.

First, the upper end position UP and the lower end position LP used to define the distribution state of the first polymer and the second polymer will be described with reference to FIG.
As shown in FIG. 2, in the vertical cross section of the conductive portion 14 (cross section taken along a plane perpendicular to the surface of the conductive portion 14), the surface 114 </ b> A of the conductive portion 14 (the surface opposite to the support 12 side), Hereinafter, the contour line along the surface shape of the surface 114A of the conductive portion 14 is moved from the surface X toward the support 12 side. That is, the contour line along the surface shape of the surface 114A of the conductive portion 14 is moved in the direction of the white arrow.
At that time, as shown in FIG. 2, the position where the moved contour line reaches the metal part 18 in the conductive part 14 is defined as an upper end position UP. Here, the fact that the contour line reaches the metal portion 18 means a position where the contour line contacts the metal portion 18 for the first time when the contour line is moved as described above.
Thereafter, the contour line is further moved to the support 12 side from the upper end position UP, and the position where the metal part 18 is not included in the conductive part 14 is defined as the lower end position LP. Here, the position where the metal part 18 is not included is a position where the metal part 18 is not included between the position and the surface of the support 12, and the position closest to the surface X is intended. In other words, the lower end position LP corresponds to the position at which the metal portion closest to the support 12 side and the contour line are closest to the support 12 in the vertical cross section of the conductive portion 14.

  3 is a partially enlarged cross-sectional view of the conductive portion 14 as in FIG. 2 and corresponds to a drawing in which the display of the metal portion 18 is omitted from FIG. 2, and the upper end position UP and the lower end position LP in FIG. The upper end position UP and the lower end position LP in FIG. 3 are at the same position.

Here, the content mass ratio of the content of the second polymer to the total content of the content of the first polymer and the content of the second polymer in the region from the upper end position UP toward the support 12 side to 100 nm Is R _U.
The position of 100 nm from the upper end position UP toward the support body 12 means that the contour line (contour line along the surface shape of the surface 114A of the conductive portion 14) moves 100 nm from the upper end position UP to the support body 12 side. Corresponds to the position P1. That is, the distance between the upper end position UP and the position P1 corresponds to 100 nm. A region sandwiched between the upper end position UP and the position P1 (hereinafter also referred to as the upper region 20) corresponds to a region of 100 nm from the upper end position UP toward the support 12 side.
The contents of the first polymer and the second polymer in the above region are determined by a method that combines surface etching using ion sputtering and measurement by time-of-flight secondary ion mass spectrometry (TOF-SIMS). It is done. The detailed measurement method is as described in the examples.

  The contents of the first polymer and the second polymer in the above region are measured by surface etching using ion sputtering, time-of-flight secondary ion mass spectrometry (TOF-SIMS), or Fourier transform red. It is calculated | required by the method which combined the measurement by the outer spectrophotometer ATR (Attenuated Total Reflection) method. The detailed measurement method is as described in the examples. For time-of-flight secondary ion mass spectrometry (TOF-SIMS) and Fourier transform infrared spectrophotometer ATR, select a method that is easy to separate depending on the composition of the polymer to be measured and the composition of the other mixture. It's okay.

  In the present embodiment, as described above, the distribution of the polymer in the region from the upper end position UP toward the support 12 side to 100 nm is adjusted. As will be described in detail later, the polymer distribution in the 100 nm region is also defined in the intermediate region and the lower region. In other words, the degree of external light reflection caused by the conductive portion is mainly influenced by visible light, and the size of the region affected by the visible light is about 100 nm as the minimum unit. The present inventors have found that this is the case. In fact, as shown in this specification, the visible light reflection characteristics, diffusion characteristics, and interference characteristics can be controlled by adjusting the composition in the range of about 100 nm.

Further, the content of the first polymer and the content of the second polymer in the region of 50 nm from the intermediate position MP between the upper end position UP and the lower end position LP toward the support 12 and 50 nm toward the surface 114A. the content mass ratio of the content of the second polymer to the total content to R _M.
First, as shown in FIG. 3, the intermediate position MP is an intermediate position between the upper end position UP and the lower end position LP. Further, the position of 50 nm from the intermediate position MP toward the support body 12 corresponds to the position P2 obtained by moving the contour line by 50 nm from the intermediate position MP to the support body 12 side. That is, the distance between the intermediate position MP and the position P2 corresponds to 50 nm. Further, the position of 50 nm from the intermediate position MP toward the surface 114A corresponds to a position P3 obtained by moving the contour line by 50 nm from the intermediate position MP to the surface 114A. That is, the distance between the intermediate position MP and the position P3 corresponds to 50 nm. Therefore, a region sandwiched between the positions P2 and P3 (hereinafter also referred to as the intermediate region 22) corresponds to a region of 50 nm from the intermediate position MP toward the support 12 and 50 nm toward the surface 114A. To do.

In addition, the content mass ratio of the content of the second polymer to the total content of the content of the first polymer and the content of the second polymer in the region from the lower end position LP toward the support 12 side to 100 nm is as follows. Let R be _L.
The position of 100 nm from the lower end position LP toward the support 12 side means that the contour line (contour line along the surface shape of the surface 114A of the conductive portion 12) is moved 100 nm from the lower end position LP to the surface 114A side. This corresponds to the position P4. That is, the distance between the lower end position LP and the position P4 corresponds to 100 nm. A region sandwiched between the lower end position LP and the position P4 (hereinafter also referred to as a lower region 24) corresponds to a region up to 100 nm from the lower end position LP toward the support 12 side.

In the conductive sheet for a touch panel according to the embodiment of the present invention, the above R _U , R _M , and R _L are the following formulas 1 and 2;
Formula 1 _RM < _RU
Formula 2 R _M <R _L
At least one selected from the group consisting of:

The state in which Equation 1 is satisfied means that the mass ratio of the second polymer (low Tg polymer) in the upper region of the conductive part is larger than the mass ratio of the second polymer in the intermediate region of the conductive part. ing. In the conductive sheet for a touch panel in which Formula 1 is satisfied, the metal portion in the upper region is not denser (the density is lower, the sparser, and the metal content per unit volume of the conductive portion is relatively small. Therefore, it is preferable to apply such a conductive sheet for a touch panel to a touch panel in which the surface X opposite to the support is the viewing side (user side).
Moreover, the state in which Formula 2 is satisfied represents that the mass ratio of the second polymer in the lower region of the conductive portion is larger than the mass ratio of the second polymer in the intermediate region of the conductive portion. In the conductive sheet for a touch panel in which Equation 2 is satisfied, the metal part in the lower region is not denser (the density is lower, the sparser, and the metal content per unit volume of the conductive part is relatively low. Therefore, it is preferable to apply such a conductive sheet for a touch panel particularly to a touch panel having a support as a viewing side (user side).

  In the conductive sheet for a touch panel, both Formula 1 and Formula 2 may be established. In such a touch panel, the mass ratio of the second polymer in each of the upper region and the lower region is larger than the mass ratio of the second polymer (low Tg polymer) in the middle region. Since the metal part of the region and the lower region is not denser (is less dense), such a conductive sheet for a touch panel is excellent even if either side of the front or back side is the viewing side when applied to a touch panel. A touch panel with black tightening can be obtained.

  In the conductive sheet for touch panels, it is preferable that either one of Formula 1 and Formula 2 is established. In such a case, when Formula 1 is satisfied, the surface X side is applied to the touch panel as the viewing side (user side) when Formula 2 is satisfied, so that the touch panel is more excellent in blackening. Is obtained. In this case, the conductive sheet for touch panel is more preferable in that it has more excellent conductivity.

  Hereinafter, each member which comprises the electroconductive sheet for touchscreens which concerns on embodiment of this invention is demonstrated.

[Support]
The type of the support is not limited as long as it can support the conductive part, and is preferably a transparent support, and particularly preferably a plastic sheet.
Specific examples of the material constituting the support include polyethylene terephthalate (PET) (258 ° C.), polycycloolefin (134 ° C.), polycarbonate (250 ° C.), acrylic film (128 ° C.), polyethylene naphthalate (PEN) ( 269 ° C), polyethylene (PE) (135 ° C), polypropylene (PP) (163 ° C), polystyrene (230 ° C), polyvinyl chloride (180 ° C), polyvinylidene chloride (212 ° C), TAC (290 ° C), etc. A plastic film having a melting point of about 290 ° C. or less is preferable, and PET, polycycloolefin, and polycarbonate are particularly preferable. Figures in parentheses are melting points. The total light transmittance of the support is preferably 85% to 100%.
Although the thickness of a support body is not restrict | limited in particular, Generally 25-500 micrometers is preferable. In addition, when the conductive sheet for touch panels serves as the function of the touch surface in addition to the function of the support, it can be designed with a thickness exceeding 500 μm.

  One preferred embodiment of the support includes a treated support that has been subjected to at least one treatment selected from the group consisting of atmospheric pressure plasma treatment, corona discharge treatment, and ultraviolet irradiation treatment. By performing the above treatment, hydrophilic groups such as OH groups are introduced on the treated support surface, and the adhesion of the conductive portion is further improved.

[Conductive part]
The conductive part contains a binder and a metal part dispersed in the binder.
The binder contains a first polymer and a second polymer having a glass transition temperature lower than that of the first polymer. In addition, in this specification, the glass transition temperature of a polymer means the glass transition temperature measured by the differential scanning calorimetry (DSC) method.

The first polymer and the second polymer are preferably polymers different from gelatin, and are preferably polymers that are not decomposed by an oxidizing agent that decomposes gelatin.
Examples of the first polymer and the second polymer include hydrophobic polymers (hydrophobic resins), and more specifically, acrylic resins, styrene resins, vinyl resins, polyolefin resins, polyesters. Resin, polyurethane resin, polyamide resin, polycarbonate resin, polydiene resin, epoxy resin, silicone resin, cellulose polymer and chitosan polymer, or at least one resin selected from the group consisting of And copolymers composed of monomers constituting these resins.
Further, the polymer preferably contains a reactive group that reacts with a cross-linking agent described later.

The polymer preferably has at least one unit selected from the group consisting of the following formulas A, B, C, and D.
Among them, the first polymer is preferably a polymer composed of one unit selected from the group consisting of formulas A, B, C, and D from the viewpoint of easy control of the glass transition temperature.
A polymer comprising at least one unit selected from the group consisting of B, C and D is more preferred, and a polymer comprising units represented by the formula D is more preferred.

R ¹ represents a methyl group or a halogen atom, preferably a methyl group, a chlorine atom, or a bromine atom. p represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

R ² represents a methyl group or an ethyl group, and a methyl group is preferable.
R ³ represents a hydrogen atom or a methyl group, and preferably a hydrogen atom. L represents a divalent linking group and is preferably a group represented by the following general formula (2).
Formula ^{(2) :-( CO-X 1} ) r-X 2 -
In the formula, X ¹ represents an oxygen atom or —NR ³⁰ —. Here, R ³⁰ represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group, and each may have a substituent (for example, a halogen atom, a nitro group, a hydroxyl group, etc.). R ³⁰ is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, n-butyl group, n-octyl group, etc.), acyl group (for example, acetyl group, benzoyl group, etc.) It is. Particularly preferred as X ¹ is an oxygen atom or —NH—.
X ² represents an alkylene group, an arylene group, an alkylene arylene group, an arylene alkylene group, or an alkylene arylene alkylene group, and these groups include —O—, —S—, —OCO—, —CO—, and —COO. -, - NH -, - SO 2 -, - N (R 31) -, - N (R 31) SO 2 - and the like may be inserted in the middle. Here, R ³¹ represents a linear or branched alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, and an isopropyl group. Preferred examples of X ² include dimethylene group, trimethylene group, tetramethylene group, o-phenylene group, m-phenylene group, p-phenylene group, —CH ₂ CH ₂ OCOCH ₂ CH ₂ —, and —CH ₂ CH _2. And OCO (C ₆ H ₄ )-
r represents 0 or 1;
q represents 0 or 1, and 0 is preferable.

R ⁴ represents an alkyl group having 1 to 80 carbon atoms, an alkenyl group, or an alkynyl group. The first polymer is preferably an alkyl group having 1 to 5 carbon atoms, and the second polymer has a carbon number. An alkyl group having 5 to 50 carbon atoms is preferable, an alkyl group having 5 to 30 carbon atoms is more preferable, and an alkyl group having 5 to 20 carbon atoms is still more preferable.
R ⁵ is a hydrogen atom, a methyl group, an ethyl group, a halogen atom, or represents -CH ₂ COOR ^6, a hydrogen atom, a methyl group, a halogen atom, or a -CH ₂ COOR ⁶ is preferably a hydrogen atom, a methyl group Or —CH ₂ COOR ⁶ is more preferred, and a hydrogen atom is particularly preferred.
R ⁶ represents a hydrogen atom or an alkyl group having 1 to 80 carbon atoms, and may be the same as or different from R ^4, and R ⁶ preferably has 1 to 70 carbon atoms, and more preferably 1 to 60 carbon atoms.

Another preferred form of the first polymer and 2 is a polymer (copolymer) represented by the following general formula (1) from the viewpoint that water can be further prevented from entering.
General formula (1):-(A) x- (B) y- (C) z- (D) w-
In general formula (1), A, B, C, and D each represent the above-described repeating unit.

In general formula (1), x, y, z, and w represent the molar ratio of each repeating unit.
As x, it is 3-60 mol%, Preferably it is 3-50 mol%, More preferably, it is 3-40 mol%.
y is 30 to 96 mol%, preferably 35 to 95 mol%, more preferably 40 to 90 mol%.
z is 0.5 to 25 mol%, preferably 0.5 to 20 mol%, more preferably 1 to 20 mol%.
As w, it is 0.5-40 mol%, Preferably it is 0.5-30 mol%.
In the general formula (1), it is particularly preferable that x is 3 to 40 mol%, y is 40 to 90 mol%, z is 0.5 to 20 mol%, and w is 0.5 to 10 mol%.

  The polymer represented by the general formula (1) is preferably a polymer represented by the following general formula (2) or general formula (3).

  In general formula (2), x, y, z, and w are as defined above.

In the above formula, a1, b1, c1, d1, and e1 represent the molar ratio of each monomer unit, a1 is 3 to 60 (mol%), b1 is 30 to 95 (mol%), and c1 is 0.5 to 25 (mol%), d1 represents 0.5 to 40 (mol%), and e1 represents 1 to 10 (mol%).
The preferred range of a1 is the same as the preferred range of x, the preferred range of b1 is the same as the preferred range of y, the preferred range of c1 is the same as the preferred range of z, and the preferred range of d1 is The same as the preferable range of w.
e1 is 1 to 10 mol%, preferably 2 to 9 mol%, more preferably 2 to 8 mol%.

1000-1 million are preferable, as for the weight average molecular weight of the polymer represented by General formula (1), 2000-750,000 are more preferable, and 3000-500,000 are still more preferable.
The polymer represented by the general formula (1) can be synthesized with reference to, for example, Japanese Patent No. 3305459 and Japanese Patent No. 3754745.

The glass transition temperatures of the first polymer and the second polymer are not particularly limited, but the glass transition temperature of the first polymer is obtained in that a more excellent conductive sheet for a touch panel having the effect of the present invention can be obtained. Is preferably 0 ° C. or higher, more preferably 25 ° C. or higher, and even more preferably 40 ° C. or higher. Although it does not restrict | limit especially as an upper limit, Generally 120 degrees C or less is preferable.
The glass transition temperature of the second polymer is not particularly limited, but is preferably 40 ° C. or less, more preferably 25 ° C. or less, further preferably less than 25 ° C., particularly preferably 0 ° C. or less, and most preferably less than 0 ° C. . Although it does not restrict | limit especially as a minimum, Generally -50 degreeC or more is preferable.

  The difference (absolute value) between the glass transition temperature of the first polymer and the glass transition temperature of the second polymer is not particularly limited, but is generally preferably 20 to 100 ° C. When the difference (absolute value) between the glass transition temperature of the first polymer and the glass transition temperature of the second polymer is within the above range, the conductive sheet for touch panel has more excellent effects of the present invention.

The metal part in a conductive part is a part which ensures the conductive characteristic of a conductive part, and a metal part is comprised with a metal. The metal constituting the metal part is composed of gold (metal gold), silver (metal silver), copper (metal copper), nickel (metal nickel), and palladium (metal palladium) in that the conductive properties are more excellent. At least one metal selected from the group is preferred.
In addition, in FIG. 2, although the metal part described the form which became a particle form and disperse | distributed to the electroconductive part, it does not restrict | limit to the above as a form of a metal part, A metal part becomes layered and becomes an electroconductive part. It may be in a dispersed form.

The conductive part may contain materials other than those described above. Examples of the material other than the above include non-metallic fine particles. Examples of the non-metallic fine particles include resin particles and metal oxide particles, and metal oxide particles are preferable.
Examples of the metal oxide particles include silicon oxide particles and titanium oxide particles.

The average particle diameter of the non-metallic fine particles is not particularly limited, but is preferably 1 to 1000 nm, more preferably 10 to 500 nm, and still more preferably 20 to 200 nm in terms of a sphere equivalent diameter. If it is in the said range, the electroconductive sheet for touchscreens tends to have more excellent transparency, and it is easy to have more excellent electroconductivity.
The equivalent sphere diameter of the non-metallic fine particles is an arithmetic average of 50 equivalent sphere diameters calculated using a transmission electron microscope.

The shape of the conductive portion is not particularly limited, but is preferably linear (straight line, curved line, and a combination thereof) so that a better touch position detection performance can be obtained when applied to a touch panel. At this time, the line width of the conductive part is not particularly limited, but is preferably 30 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less, and further preferably 5 μm or less from the viewpoint of the balance between the conductive characteristics of the conductive part and difficulty in visual recognition. Particularly preferred is 4 μm or less, most preferred is 0.5 μm or more, and more preferred is 1.0 μm or more.
The thickness of the conductive part is not particularly limited, but is preferably 200 μm or less, more preferably 30 μm or less, still more preferably 10 μm or less, and particularly preferably 0.3 to 5 μm in terms of the balance between thinning and conductive properties. Most preferably, it is 0.5-5 micrometers.

  The conductive part may form a pattern. Examples of patterns include triangles such as regular triangles, isosceles triangles, right triangles, squares, rectangles, rhombuses, parallelograms, trapezoids, and other (positive) hexagons, (positive) octagons, etc. A geometric figure combining an n-gon, a circle, an ellipse, a star, and the like is preferable, and a mesh shape (mesh pattern) is more preferable. As shown in FIG. 4, the mesh shape means a shape including a plurality of square-shaped openings (lattices) 26 formed by intersecting conductive portions 14.

The length Pa of one side of the opening 26 is not particularly limited, but is preferably 1500 μm or less, more preferably 1300 μm or less, further preferably 1000 μm or less, more preferably 5 μm or more, more preferably 30 μm or more, and even more preferably 80 μm or more. preferable. When the length of the side of the opening is in the above range, it is possible to keep transparency even better, and when the conductive film is attached to the front surface of the display device, the display can be visually recognized without a sense of incongruity. Can do.
From the viewpoint of visible light transmittance, the aperture ratio of the mesh pattern formed by the conductive portion is preferably 85% or more, more preferably 90% or more, and still more preferably 95% or more. The aperture ratio corresponds to the ratio of the area on the support excluding the area where the conductive portion is present to the whole.

<Modification of First Embodiment>
In FIG. 5, the modification of the conductive sheet for touchscreens which concerns on this embodiment was shown. The conductive sheet for a touch panel in FIG. 5 has the conductive portion 14 already described on the support 12 and further has a non-conductive portion 51 disposed on the support 12 so as to be adjacent to the conductive portion 14. The conductive sheet for a touch panel in FIG. 5 has three non-conductive portions 51, but the conductive sheet for a touch panel according to the present embodiment is not limited to the above.
Although it does not restrict | limit especially as thickness of a nonelectroconductive part, Generally, below the thickness of an electroconductive part is preferable.
Although it does not restrict | limit especially as a material of a nonelectroconductive part, It is preferable that it is the same as that of the material of an electroconductive part except not containing a metal part. By doing so, the conductive sheet for touch panels which has the effect of this invention more excellent is obtained.

<Modification 2 of the first embodiment>
In FIG. 6, the 2nd modification of the conductive sheet for touchscreens which concerns on this embodiment was shown. The conductive sheet for a touch panel in FIG. 6 further includes an easy-adhesion layer 61 between the support 12 and the conductive part 14, and is disposed on the easy-adhesion layer 61 so as to be adjacent to the conductive part 14. 51.
When the conductive sheet for touch panel has an easily bonding layer, the adhesiveness of the support body 12 and the electroconductive part 14 improves more, and the conductive sheet for touch panels which has the more excellent durability is easy to be obtained.

At this time, the relationship between the refractive indexes of the respective members is not particularly limited, but the refractive index RI ₁ of the non-conductive portion and the refractive index RI of the easy-adhesion layer are more difficult to reflect external light even when applied to a touch panel. ₂ and the refractive index RI ₃ of the support:
Formula 3 RI ₁ <RI ₂ <RI ₃
Is preferably satisfied.

The refractive index of each layer is not particularly limited, but the refractive index RI ₁ of the non-conductive portion is preferably 1.40 to 1.75, more preferably 1.40 to 1.55. The refractive index RI ₂ of the easy adhesion layer is preferably 1.40 to 1.75, and more preferably 1.40 to 1.55. The refractive index RI ₃ of the support is preferably 1.40 to 1.75, more preferably 1.40 to 1.55.
The refractive index of the support is an Abbe refractometer (Abago refractometer manufactured by Atago Co., Ltd.), the light source is a sodium lamp (Na-D line, 589 nm), the mounting liquid is methylene iodide, 23 ° C. Under a relative humidity of 65%, two orthogonal directions of the sample, or the longitudinal direction and the width direction are measured, and the average value of these values is obtained. The refractive index of each layer is measured by an Abbe refractometer in the same manner as the base material by preparing a dry film of each layer independently for measurement.

  The material for the easy adhesion layer is not particularly limited, and a known material for the easy adhesion layer can be used. The easy adhesion layer is not particularly limited, and for example, a suitable application example of the first adhesive layer described in JP-A-2008-208310 can be suitably used.

  Although the thickness of an easily bonding layer is not specifically limited, 0.02-0.3 micrometer is preferable at the point which the adhesiveness of a support body and an electroconductive part improves more.

  The method for adjusting the refractive index of the support, the easy-adhesion layer, and the non-conductive portion is not particularly limited, and examples thereof include a method in which each member contains the non-metallic fine particles already described.

The conductive film for a touch panel according to this embodiment is preferably used for a capacitive touch panel.
The conductive sheet for a touch panel according to this embodiment can also be used as an electromagnetic wave shield that blocks electromagnetic waves such as radio waves or microwaves (extremely short waves) generated from personal computers, workstations, and the like and prevents static electricity. . In addition to the electromagnetic wave shield used for the personal computer body, it can also be used as an electromagnetic wave shield used in video imaging equipment, electronic medical equipment, and the like.
In addition, the conductive sheet for a touch panel according to the present embodiment can be used as a transparent heating element.

[Method for Producing Conductive Sheet for Touch Panel According to First Embodiment]
There are no particular limitations on the method for producing a conductive sheet for a touch panel according to the present embodiment, already R _U, R M _described, and, only to be obtained touch panel conductive sheet that satisfies the relationship of R _L. Especially, when a metal part contains silver (metal silver), the method which has the following processes at the point from which more excellent productivity is obtained is preferable.

-Process A:
A silver halide-containing coating solution containing at least silver halide and a first polymer and a composition-adjusting coating solution containing at least a second polymer are simultaneously coated on the support, and silver halide is coated. Forming a photosensitive layer;
-Process B:
A step of exposing the silver halide photosensitive layer and developing it to form a conductive portion containing silver metal.
Below, each process is explained in full detail.

<Process A>
In step A, a silver halide-containing coating solution containing at least a silver halide and a first polymer and a composition-adjusting coating solution containing at least a second polymer are applied simultaneously on the support. And a step of forming a silver halide photosensitive layer.
In addition, there is no restriction | limiting in particular as a lamination order of each coating liquid in the case of simultaneous multilayer coating. However, when the silver halide-containing coating solution and the composition-adjusting coating solution are laminated in this order from the support side, a conductive sheet for a touch panel that satisfies Formula 1 is easily obtained. Conversely, when the composition-adjusting coating solution and the silver halide-containing coating solution are laminated in this order from the support side, it is easy to obtain a conductive sheet for a touch panel that satisfies Formula 2. Furthermore, when the composition-adjusting coating solution, the silver halide-containing coating solution, and the composition-adjusting coating solution are laminated in this order, a conductive sheet for a touch panel that satisfies Equations 1 and 2 is easily obtained.

In the present specification, “applying on a support” includes the case of direct application on the surface of the support and the case where a separate layer is disposed on the support and applied on that layer.
In this step, since a silver halide-containing coating solution containing silver halide and a composition-adjusting coating solution not containing silver halide are applied simultaneously, a two-layer coating film formed from both coating solutions The diffusion of components proceeds at the interface. More specifically, as shown in FIG. 7, a composition-adjusting coating solution from a coating film 28 (hereinafter also referred to as coating film A) formed from a silver halide-containing coating solution disposed on the support 12. The diffusion of a part of the silver halide 32 and the first polymer proceeds in the coating film 30 (hereinafter also referred to as coating film B). As a result, the area on the coating film A side in the coating film B contains the silver halide and the first polymer, and the content thereof is the silver halide and the first polymer in the coating film A. Less than the content of.
The region on the coating film A side in the coating film B (hereinafter also referred to as “region W”) contains silver halide that has moved from the coating film A. Will form an upper region in the conductive portion. In this case, among the conductive portions, containing the mass ratio of the content of the second polymer to the content and the total amount of content of the second polymer of the first polymer in the region W is, than R _M of the intermediate region Also tends to be large.

  The silver halide-containing coating solution may contain at least silver halide and the first polymer, and may further contain the second polymer. In this case, the content ratio of the second polymer to the content of the first polymer and the content of the second polymer in the silver halide-containing coating solution is the content of the first polymer in the composition-adjusted coating solution. And it is preferable that it is smaller than the content mass ratio of the 2nd polymer with respect to content of the 2nd polymer.

The composition-adjusting coating solution may contain at least the second polymer, and may further contain silver halide and / or the first polymer. When the composition-adjusting coating solution further contains silver halide, the content thereof is not particularly limited, but the content of silver halide in the composition-adjusting coating solution is determined based on the silver halide content in the silver halide-containing coating solution. It is preferable that the content is smaller. By doing so, it is easy to obtain a conductive sheet for a touch panel with less external light reflection.
When the composition adjustment coating solution further contains the first polymer, the content ratio of the first polymer to the content of the first polymer and the content of the second polymer in the composition adjustment coating solution is silver halide. It is preferable that the content ratio of the first polymer to the content of the first polymer and the content of the second polymer in the containing coating liquid is smaller than the content ratio.

The silver halide contained in the silver halide-containing coating solution is not particularly limited, and known silver halides can be used. The halogen element contained in the silver halide may be any of chlorine, bromine, iodine and fluorine, or a combination thereof. For example, silver halide mainly composed of silver chloride, silver bromide, or silver iodide is preferably used, and silver halide mainly composed of silver bromide or silver chloride is preferably used. Silver chlorobromide, silver iodochlorobromide, or silver iodobromide is also preferably used. More preferably, it is silver chlorobromide, silver bromide, silver iodochlorobromide, or silver iodobromide, and most preferably silver chlorobromide or iodine salt containing 50 mol% or more of silver chloride. Silver bromide is used.
Here, “silver halide mainly composed of silver bromide” refers to silver halide in which the molar fraction of bromide ions in the silver halide composition is 50% or more. The silver halide grains mainly composed of silver bromide may contain iodide ions and chloride ions in addition to bromide ions.

The silver halide is in the form of a solid grain, and the average grain size of the silver halide is preferably 0.1 to 1000 nm (1 μm) in terms of sphere equivalent diameter, more preferably 0.1 to 300 nm. More preferably, it is -200 nm.
The sphere equivalent diameter of silver halide grains is the diameter of grains having the same volume and having a spherical shape.

The shape of the silver halide grains is not particularly limited. For example, various shapes such as a spherical shape, a cubic shape, a flat plate shape (hexagonal flat plate shape, triangular flat plate shape, tetragonal flat plate shape, etc.), octahedral shape, and tetrahedral shape are available. It can be in shape.
Regarding the use of metal compounds belonging to Group VIII and VIIB, such as rhodium compounds and iridium compounds, and palladium compounds, which are used for stabilizing or enhancing the sensitivity of silver halide, paragraphs 0039- of JP2009-188360A Reference can be made to the description in paragraph 0042. Further, regarding chemical sensitization, reference can be made to the technical description in paragraph 0043 of JP-A-2009-188360.

The first polymer that is contained in the silver halide-containing coating solution and may be contained in the composition-adjusting coating solution, and the first polymer that is contained in the composition-adjusting coating solution and may be contained in the silver halide-containing coating solution. Since the two polymer forms are as already described, the description thereof is omitted.
The silver halide-containing coating solution and the composition-adjusting coating solution may contain components other than silver halide, the first polymer, and the second polymer, and these components are silver halide-containing coatings. This is common in the liquid and the composition-adjusting coating liquid, as described below.

The silver halide-containing coating solution and the composition-adjusting coating solution may further contain gelatin.
The type of gelatin is not particularly limited. For example, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate, gelatin enzyme-degraded product, and gelatin modified with amino group or carboxyl group (phthalate) Gelatinized gelatin, acetylated gelatin) can also be used.

  The silver halide-containing coating solution and the composition-adjusting coating solution may further contain a solvent. Examples of the solvent used include water, organic solvents (for example, alcohols such as methanol, ketones such as acetone, amides such as formamide, sulfoxides such as dimethyl sulfoxide, esters such as ethyl acetate, ethers, and the like. Etc.), ionic liquids, and mixed solvents thereof.

  The silver halide-containing coating solution and the composition-adjusting coating solution may contain other materials than the above-described materials as necessary. For example, it is preferable that a crosslinking agent used for crosslinking the first polymer and the second polymer is included. By including the cross-linking agent, cross-linking between the polymers proceeds, and even when gelatin is decomposed and removed in a process described later, the connection between the metal silvers is maintained, and as a result, the conductive properties are more excellent.

  The method for simultaneous multilayer coating of the silver halide-containing coating solution and the composition-adjusting coating solution is not particularly limited, and a known method can be adopted. For example, it is preferable to use a die coating method. The die coating method includes a slide coating method, an extrusion coating method, and a curtain coating method, but a slide coating method or an extrusion coating method is preferable, and an extrusion coating method having high suitability for thin layer coating is most preferable.

  In addition, when applying the simultaneous multi-layer coating, the film (surface film) formed when applied on a predetermined substrate from the point that the form of the first embodiment of the conductive film for touch panel described above is easily obtained. It is preferable to use a composition-adjusting coating solution containing a second polymer having a composition such that the dry thickness is 300 nm or more.

  Moreover, after implementing simultaneous multilayer coating, you may perform a drying process with respect to the obtained coating film as needed. By carrying out the drying treatment, the solvent contained in the coating film obtained from the silver halide-containing coating liquid and the coating film obtained from the composition-adjusting coating liquid can be easily removed.

  By the above treatment, a photosensitive layer containing silver halide can be formed on the support. In the present specification, the above “photosensitive layer containing silver halide” may be referred to as “silver halide photosensitive layer” or simply “photosensitive layer”.

<Process B>
Step B is a step of forming a conductive portion containing metallic silver by exposing the silver halide photosensitive layer and developing it.
By this step, the silver halide is reduced and a conductive part containing metallic silver is formed. In general, the exposure process is performed in a pattern, and a conductive part containing metallic silver is formed in the exposed part. On the other hand, in the non-exposed portion, silver halide is eluted by a development process described later. A non-conductive portion containing the gelatin and the polymer is formed. The non-conductive portion is substantially free of metallic silver, and the non-conductive portion is intended to indicate a region that does not exhibit conductivity.
Below, the exposure process and development process implemented at this process are explained in full detail.

The exposure process is a process for exposing the photosensitive layer. By subjecting the photosensitive layer to pattern exposure, the silver halide in the photosensitive layer in the exposed region forms a latent image. In the region where the latent image is formed, a conductive portion is formed by development processing described later. On the other hand, in an unexposed area that has not been exposed, the silver halide dissolves and flows out of the photosensitive layer during the development processing described later, and a transparent film (non-conductive part) is obtained.
The light source used in the exposure is not particularly limited, and examples thereof include light such as visible light and ultraviolet light, and radiation such as X-rays.
The method for performing pattern exposure is not particularly limited. For example, surface exposure using a photomask may be performed, or scanning exposure using a laser beam may be performed. The shape of the pattern is not particularly limited, and is appropriately adjusted according to the pattern of the conductive part to be formed.

The development processing method is not particularly limited, and for example, a normal development processing technique used for silver salt photographic film, photographic paper, printing plate making film, photomask emulsion mask and the like can be used.
The type of developer used in the development process is not particularly limited, and for example, PQ (phenidone hydroquinone) developer, MQ (Metal hydroquinone) developer, and MAA (methol ascorbic acid) developer are used. You can also
The development process can include a fixing process performed for the purpose of removing and stabilizing the silver salt in the unexposed part. For the fixing process, a technique of a fixing process used for a silver salt photographic film, a photographic paper, a printing plate-making film, a photomask emulsion mask, or the like can be used.
The fixing temperature in the fixing step is preferably about 20 ° C. to about 50 ° C., and more preferably 25 to 45 ° C. The fixing time is preferably 5 seconds to 1 minute, and more preferably 7 seconds to 50 seconds.
The photosensitive layer that has been subjected to development and fixing treatment is preferably subjected to water washing treatment and stabilization treatment.

The manufacturing method of the conductive sheet for touch panels which concerns on this embodiment may have processes other than the said process A and the process B.
As other processes, for example,
After Step B, Step F in which metallic silver of the conductive part is fused to each other;
After Step A and before Step B, the silver halide photosensitive layer is contacted with a compound having a metal-adsorbing substituent or a metal-adsorbing structure (hereinafter also referred to as “specific compound”). Step C1 of causing;
Step C2 after contacting the conductive part and the specific compound after Step B and before Step F;
Step D after step B and before step F, further consolidating the conductive part;
When at least one selected from the group consisting of a silver halide-containing coating solution and a composition-adjusting coating solution contains gelatin, after step B and before step D, in the conductive part Removing gelatin E;
Etc. In addition, examples of other processes include an easy-adhesion layer forming process described later. Hereinafter, other steps will be described.

(Process F)
Step F is a step of fusing metallic silver (contained in the conductive portion) of the conductive portion to each other after Step B. As a result of the fusion of the metallic silver, this step provides a conductive sheet for a touch panel provided with a conductive part having better conductivity.

Although it does not restrict | limit especially as a method of a heating, The process which makes the support body which has an electroconductive part contact superheated steam is mentioned at the point from which the electroconductive sheet for touchscreens which has the more excellent effect of this invention is obtained.
It does not restrict | limit especially as superheated steam, Superheated steam may be sufficient, and what mixed other gas with superheated steam may be used.
The superheated steam is preferably brought into contact with the conductive portion within a supply time of 10 to 300 seconds. When the supply time is 10 seconds or more, the conductivity is greatly improved. Moreover, since it will fully improve electroconductivity as it is 300 seconds or less, it is more preferable from the point of economical efficiency.
Moreover, it is preferable that superheated steam is made to contact an electroconductive part in the range whose supply amount is 500-600 g / m < ³ >, and it is preferable that the temperature of superheated steam is controlled to 100-160 degreeC at 1 atmosphere.

As another method of heat treatment, heat treatment at 80 to 150 ° C. may be mentioned.
The heating time is not particularly limited, but is preferably from 0.1 to 5.0 hours, and more preferably from 0.5 to 1.0 hours, from the viewpoint that the above effect is more excellent.

(Process C1)
Step C1 is a step that is performed after Step A and before Step B, and brings the silver halide photosensitive layer into contact with the specific compound. By this step, the metallic silver produced in the subsequent step B becomes more difficult to fuse. In this step, since the specific compound is brought into contact with the silver halide photosensitive layer, the silver halide photosensitive layer has an effect that metal silver is hardly fused in a region closer to the surface (interface region). . Therefore, particularly in the conductive portion obtained by the subsequent process, the fusion between the metal silvers is more likely to be inhibited in the interface region, and as a result, a conductive sheet for a touch panel having better black tightening can be easily obtained. Even in this case, it is considered that metal silver is sufficiently fused in the intermediate region of the conductive portion, and a conductive sheet for a touch panel having excellent conductivity can be obtained.

  The method for manufacturing a conductive sheet for a touch panel according to an embodiment of the present invention preferably includes a step C1 or a step C2 described later, and may include a step C1 and a step C2.

The method for bringing the specific compound into contact with the silver halide photosensitive layer is not particularly limited, but typically a method in which the solution in which the specific compound is dissolved and / or dispersed is brought into contact with the silver halide photosensitive layer. Is mentioned. Moreover, the method of making the gas containing a specific compound and a silver halide photosensitive layer contact may be sufficient.

  The method of bringing the solution containing the specific compound into contact with the silver halide photosensitive layer is not particularly limited, but the method of immersing the silver halide photosensitive layer in the solution and applying the solution to the silver halide photosensitive layer The method of immersing a silver halide photosensitive layer in a solution is more preferable. The method of immersing the silver halide photosensitive layer in the solution is preferable because it can be carried out more stably with a simpler apparatus, and if it is washed after immersion, the excess solution can be removed more easily.

  In addition, the method of bringing the silver halide photosensitive layer into contact with a gas containing a compound having a metal adsorbing site and / or a solution is as follows. It also has the feature of being easily adsorbed. Thereby, it is easy to inhibit that metal silver fuse | melts mutually on the surface of an electroconductive part.

  The specific compound is a compound having a metal-adsorptive substituent or a metal-adsorptive structure (hereinafter also referred to as “metal-adsorptive site”).

  The metal-adsorbing substituent is not particularly limited, but the metal-adsorbing substituent includes a carboxyl group or a salt thereof, an acid amide group in that a conductive sheet for a touch panel having more excellent effects of the present invention can be obtained. , At least one selected from the group consisting of an amino group, an imidazole group, a pyrazole group, a thiol group, a thioether group, and a disulfide group.

Although it does not restrict | limit especially as a metal adsorptive structure, A nitrogen-containing heterocyclic ring is preferable, 5- or 6-membered ring azoles are preferable and 5-membered ring azoles are more preferable.
Examples of the nitrogen-containing heterocycle include tetrazole ring, triazole ring, imidazole ring, thiadiazole ring, oxadiazole ring, selenodiazole ring, oxazole ring, thiazole ring, benzoxazole ring, benzthiazole ring, benzimidazole ring, pyrimidine Ring, triazaindene ring, tetraazaindene ring, benzoindazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, pyridine ring, quinoline ring, piperidine ring, piperazine ring, quinoxaline ring, morpholine ring, and pentaaza And indene ring.
These rings may have a substituent. Examples of the substituent include a nitro group, a halogen atom (for example, chlorine atom and bromine atom), a cyano group, a substituted or unsubstituted alkyl group (for example, methyl group). Group, ethyl group, propyl group, t-butyl group, and cyanoethyl group), aryl group (for example, phenyl group, 4-methanesulfonamidophenyl group, 4-methylphenyl group, 3,4-dichloro) Phenyl group and naphthyl group), alkenyl group (for example, allyl group), aralkyl group (for example, benzyl group, 4-methylbenzyl group, and phenethyl group), sulfonyl group (for example, methane) Sulfonyl group, ethanesulfonyl group and p-toluenesulfonyl group), carbamoyl group (for example, unsubstituted carbamoyl group, methylcarbamoyl) And phenylcarbamoyl groups), sulfamoyl groups (for example, unsubstituted sulfamoyl groups, methylsulfamoyl groups, and phenylsulfamoyl groups), carbonamide groups (for example, acetamide groups, and Benzamide group), sulfonamide group (for example, methanesulfonamide group, benzenesulfonamide group, and p-toluenesulfonamide group), acyloxy group (for example, acetyloxy group, and benzoyloxy group) Each group), sulfonyloxy group (for example, methanesulfonyloxy group), ureido group (for example, unsubstituted ureido group, methylureido group, ethylureido group, and phenylureido group), acyl group (for example, Acetyl group and benzoyl group), oxycarbonyl group ( In example, a methoxycarbonyl group, and each group) phenoxycarbonyl group, and include a hydroxyl group. Multiple substituents may be substituted on one ring.

As the above compound, a compound having a nitrogen-containing 6-membered ring (nitrogen-containing 6-membered ring compound) is preferable. Examples of the nitrogen-containing 6-membered ring compound include triazine ring, pyrimidine ring, pyridine ring, pyrroline ring, piperidine ring, pyridazine ring, Alternatively, a compound having a pyrazine ring is preferable, and a compound having a triazine ring or a pyrimidine ring is more preferable. These nitrogen-containing 6-membered ring compounds may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3), and 1 to 6 carbon atoms (preferably 1 to 1 carbon atoms). 3) an alkoxy group, a hydroxyl group, a carboxyl group, a mercapto group, an alkoxyalkyl group having 1 to 6 carbon atoms (preferably 1 to 3), and a hydroxyalkyl group having 1 to 6 carbon atoms (preferably 1 to 3). Can be mentioned.
Specific examples of the nitrogen-containing 6-membered ring compound include triazine, methyltriazine, dimethyltriazine, hydroxyethyltriazine, pyrimidine, 4-methylpyrimidine, pyridine, and pyrroline.

  The above compound may have one kind of metal adsorbing site alone or may have two or more kinds, but in that a conductive sheet for a touch panel having further excellent effects of the present invention can be obtained. The compound preferably has two or more metal adsorbing sites.

(Process C2)
Step C2 is a step that is performed after Step B and before Step F, and brings the conductive portion into contact with the specific compound. This step makes it more difficult for metal silver (contained in the conductive portion) of the conductive portion to be fused together. In this step, since the specific compound is brought into contact with the conductive portion, there is an effect that the metal silver is hardly fused in a region closer to the surface (interface region) of the conductive portion. Therefore, fusion between metallic silvers is more likely to be inhibited in the interface region of the conductive part, and as a result, a conductive sheet for a touch panel having better black tightening can be easily obtained. Even in this case, it is considered that metal silver is sufficiently fused in the intermediate region of the conductive portion, and a conductive sheet for a touch panel having excellent conductivity can be obtained.

  In this step, the method for bringing the conductive portion into contact with the specific compound, the form of the specific compound, and the like are the same as those in the step C1 already described, and thus the description thereof is omitted.

(Process D)
Step D is a step of consolidating the conductive portion after Step B and before Step F. By this step, the conductivity of the conductive portion is further improved, and the adhesion of the conductive portion to the support is more likely to be improved.

  The method for consolidating the conductive part is not particularly limited, but for example, a calendering process in which a support having a conductive part is passed between at least a pair of rolls under pressure is preferable. Hereinafter, consolidation processing using a calendar roll is referred to as calendar processing.

Examples of the roll used for the calendar process include a plastic roll and a metal roll. From the viewpoint of preventing wrinkles, a plastic roll is preferable. The pressure between the rolls is not particularly limited. The pressure between the rolls can be measured using a prescale (for high pressure) manufactured by FUJIFILM Corporation.
The surface roughness Ra of the roll used for the calendering process is preferably 0 to 2.0 μm, more preferably 0.3 to 1.0 μm, in that the obtained conductive part is less visible.

  The temperature of the consolidation treatment is not particularly limited, but is preferably 10 ° C (no temperature control) to 100 ° C, and varies depending on the line density, shape, and binder type of the conductive part pattern, but 10 ° C (no temperature control). ~ 50 ° C is more preferred.

(Process E)
When at least one selected from the group consisting of a silver halide-containing coating solution and a composition-adjusting coating solution contains gelatin, step E is after step B and before step D. This is a step of removing gelatin in the conductive part (contained in the conductive part). By removing the gelatin, as a result, the content of the metallic silver in the conductive part is relatively increased, so that a conductive part having better conductivity can be obtained.
Step E may be a step of removing all of gelatin or a step of removing a part of gelatin. Further, in step E, gelatin may be removed from a portion (for example, non-conductive portion) other than the conductive portion on the support in addition to the conductive portion.

The method for removing gelatin is not particularly limited, and examples thereof include a method for decomposing and removing using a proteolytic enzyme and a method for decomposing and removing using a predetermined oxidizing agent.
As a method for degrading and removing gelatin using a proteolytic enzyme, for example, the method described in paragraphs 0084 to 0077 of JP-A-2014-209332 can be employed.
Moreover, as a method for decomposing and removing gelatin using an oxidizing agent, for example, the method described in paragraphs 0064 to 0066 of JP-A-2014-112512 can be employed.

(Easily adhesive layer forming process)
The easy-adhesion layer forming step is a step of forming an easy-adhesion layer (hereinafter also referred to as “undercoat layer”) on the support before Step A to obtain a support with an easy-adhesion layer (undercoat layer). . The method for forming the undercoat layer on the support is not particularly limited, and examples thereof include a method of applying the undercoat layer forming composition on the support. In the undercoat layer forming step, the formed undercoat layer is adjusted so that the absolute value of the difference in refractive index between other adjacent layers (such as the support and the non-conductive portion) becomes smaller. It is preferable. The method for adjusting the difference in refractive index between the undercoat layer and another adjacent layer is not particularly limited, but examples include a method for adjusting the type of each component contained in the composition used for forming each layer. It is done.

Although it does not restrict | limit especially as a method of forming an easily bonding layer, The method of apply | coating the composition for easily bonding layer on a support body and heat-processing as needed is mentioned. The composition for easily bonding layer formation may contain a solvent. The type of the solvent is not particularly limited, and is as already described as the solvent that may be contained in the silver halide-containing coating solution.
The thickness of the easy-adhesion layer is not particularly limited, but is preferably 0.02 to 0.3 μm from the viewpoint that the adhesion between the support, the silver halide photosensitive layer and the conductive part is further improved.
The easy adhesion layer is not particularly limited, and for example, a suitable application example of the first adhesive layer described in JP-A-2008-208310 can be suitably used.

  Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[Example 1]
(Preparation of silver halide emulsion)
To the following 1 liquid maintained at 30 ° C. and pH 4.5, an amount corresponding to 90% by volume of each of the following 2 and 3 liquids was simultaneously added over 20 minutes while stirring to form 0.12 μm core particles. . Subsequently, the following 4 and 5 solutions were added over 8 minutes, and the remaining 10% of the following 2 and 3 solutions were added over 2 minutes to grow to 0.15 μm. Further, 0.15 g of potassium iodide was added and ripened for 5 minutes to complete the grain formation.

1 liquid:
750 ml of water
9g gelatin
Sodium chloride 3g
1,3-Dimethylimidazolidine-2-thione 20mg
Sodium benzenethiosulfonate 10mg
Citric acid 0.7g
Two liquids:
300 ml of water
150 g silver nitrate
3 liquids:
300 ml of water
Sodium chloride 38g
Potassium bromide 32g
Potassium hexachloroiridium (III) (0.005% KCl 20% aqueous solution) 8 ml
Ammonium hexachlororhodate
(0.001% NaCl 20% aqueous solution) 10 ml
4 liquids:
100ml water
Silver nitrate 50g
5 liquids:
100ml water
Sodium chloride 13g
Potassium bromide 11g
Yellow blood salt 5mg

  Then, it washed with water by the flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., and the pH was lowered using sulfuric acid until the silver halide precipitated (the pH was in the range of 3.6 ± 0.2). Next, about 3 liters of the supernatant was removed (first washing). Further, 3 liters of distilled water was added, and sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second water wash). The same operation as the second water washing was further repeated once (third water washing) to complete the water washing / desalting step. The emulsion after washing with water and desalting was adjusted to pH 6.4 and pAg 7.5, and gelatin 3.9 g, sodium benzenethiosulfonate 10 mg, sodium benzenethiosulfinate 3 mg, sodium thiosulfate 15 mg and chloroauric acid 10 mg were added. Chemical sensitization is performed to obtain an optimum sensitivity at 0 ° C., and 100 mg of 1,3,3a, 7-tetraazaindene is added as a stabilizer and 100 mg of proxel (trade name, manufactured by ICI Co., Ltd.) is used as a preservative. It was. The finally obtained emulsion contains 0.08 mol% of silver iodide, and the ratio of silver chlorobromide is 70 mol% of silver chloride and 30 mol% of silver bromide. It was a silver iodochlorobromide cubic grain emulsion having a coefficient of 10%.

(Preparation of silver halide-containing coating solution 1)
1,3,3a, 7-tetraazaindene 1.2 × 10 ⁻⁴ mol / mol Ag, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻⁴ mol / Mol Ag, 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 0.90 g / mol Ag, a trace amount of hardener was added, and the coating solution pH was adjusted to 5.6 using citric acid. Adjusted.
For the gelatin contained in the coating solution, a polymer (corresponding to “first polymer”) represented by the following (P-1) and having a glass transition temperature of + 45 ° C. measured by differential scanning calorimetry (DSC) Hereinafter, the polymer latex 1 containing a dispersant composed of a dialkylphenyl PEO sulfate ester and water (also referred to as “P-1”) (dispersant / polymer mass ratio is 2.0 / 100 = 0.0.00). 02, solid content concentration: 22% by mass) was added so that P-1 / gelatin (mass ratio) = 0.2 / 1. Here, in the silver halide-containing coating solution 1, the ratio R1 (P-1 / silver halide) of the mass of P-1 to the mass of silver halide was 0.024.

Furthermore, EPOXY RESIN DY 022 (trade name: manufactured by Nagase ChemteX Corporation) was added as a crosslinking agent. In addition, the addition amount of the crosslinking agent was adjusted so that the amount of the crosslinking agent in the photosensitive layer described later would be 0.09 g / m ² .
A silver halide-containing coating solution 1 was prepared as described above.
In addition, P-1 represented by the above (P-1) was synthesized with reference to Japanese Patent No. 3305459 and Japanese Patent No. 3754745.

(Preparation of support with undercoat layer)
On one side of a 40 μm biaxially oriented PET support, an undercoat layer-forming composition 1 to be described later was applied so that the film thickness after drying was 60 nm, dried at 90 ° C. for 1 minute, and supported with an undercoat layer The body was made. The film thickness of the undercoat layer was measured with an electronic micro film thickness meter manufactured by Anritsu Corporation.
(Undercoat layer forming composition 1 (curable composition 1))
The following components were mixed to prepare composition 1 for forming the undercoat layer.
-Acrylic polymer 66.4 parts by mass (AS-563A, manufactured by Daicel Finechem Co., Ltd., solid content: 27.5% by mass)
Carbodiimide-based crosslinking agent 16.6 parts by mass (Carbodilite V-02-L2, manufactured by Nisshinbo Co., Ltd., solid content: 10% by mass)
・ Colloidal silica 4.4 parts by mass
(Snowtex XL, manufactured by Nissan Chemical Co., Ltd., solid content: 10% by weight water dilution)
・ Slip agent: 27.7 parts by mass of carnauba wax (Cerosol 524, manufactured by Chukyo Yushi Co., Ltd., solid content: 3% by weight diluted with water)
Surfactant: 23.3 parts by weight of anionic surfactant (Lapisol A-90, manufactured by NOF Corporation, solid content: 1% by weight aqueous solution)
-Surfactant: 14.6 parts by mass of nonionic surfactant (Naroacty CL95, manufactured by Sanyo Chemical Industries, Ltd., solid content: 1% by mass aqueous solution)
・ 847.0 parts by mass of distilled water

(Silver halide photosensitive layer forming step (1))
Next, on the undercoat layer of the support with the undercoat layer, the composition adjustment coating solution 1 described later, the silver halide-containing coating solution 1 and the composition adjustment coating solution 2 described below are applied in this order from the undercoat layer side. The silver halide photosensitive layer was formed on the support by simultaneous multilayer coating at a liquid flow ratio (composition adjustment coating solution 1 / silver halide-containing coating solution 1 / composition adjustment coating solution 2) 25/25/5. This was designated as sheet A.
The composition-adjusting coating solution 1 was prepared by mixing the polymer latex 1 and gelatin at a mixing mass ratio (mass of P-1 / mass of gelatin) 2/1, and having an optical density of about 1.0. It is a composition which consists of a mixture containing the dye decolored by the alkali. The composition-adjusted coating solution 1 was adjusted in concentration so that the P-1 amount (coating amount) in the layer formed from the composition-adjusted coating solution 1 was 0.65 g / m ² . In addition, since the layer formed from the composition adjustment coating liquid 1 contains a dye, it has an antihalation function.
The composition-adjusting coating liquid 2 is composed of a repeating unit represented by the following (P-2), and has a glass transition temperature measured by differential scanning calorimetry (DSC) of −20 ° C. (“second polymer” The polymer latex 2 containing a dispersant composed of a dialkylphenyl PEO sulfate ester and water (dispersant / polymer mass ratio is 7.5 / 100 = 0). 0.075, solid content concentration: 20% by mass) is a composition in which polymer latex 2 and gelatin are mixed at a mixing mass ratio (P-2 / gelatin) 2/1. The concentration of the composition-adjusted coating solution 2 was adjusted so that the amount of gelatin in the layer formed from the composition-adjusted coating solution 2 was 0.10 g / m ² .

(P-2)

Moreover, in the layer formed from the silver halide containing coating liquid 1, it apply | coated so that the silver amount might be 6.2 g / m < ² >.

(Exposure development process)
On one side of the sheet A (the silver halide photosensitive layer side), exposure is performed using parallel light using a high-pressure mercury lamp as a light source through a photomask having a square mesh pattern with an opening line width of 2 μm and a pitch of 300 μm. It was. After the exposure, development was performed with the following developer, and further development processing was performed using a fixing solution (trade name: N3X-R for CN16X, manufactured by Fuji Film Co., Ltd.). Furthermore, by rinsing with pure water and drying, a conductive mesh made of a conductive part containing Ag (line width 2 μm) and a layer containing gelatin and a polymer adjacent thereto (non-conductive part) were formed. A support was obtained. Note that the layer containing gelatin and polymer was formed between the conductive parts containing Ag. The obtained sheet is referred to as a sheet B.

(Developer composition)
The following compounds are contained in 1 liter (L) of the developer.
Hydroquinone 0.037mol / L
N-methylaminophenol 0.016 mol / L
Sodium metaborate 0.140 mol / L
Sodium hydroxide 0.360 mol / L
Sodium bromide 0.031 mol / L
Potassium metabisulfite 0.187 mol / L

(Gelatin decomposition treatment)
The sheet B was immersed for 120 seconds in an aqueous solution of proteolytic enzyme (Biolase AL-15FG manufactured by Nagase ChemteX Corporation) (proteolytic enzyme concentration: 0.5 mass%, liquid temperature: 40 ° C.). The sheet B is taken out from the aqueous solution, immersed in warm water (liquid temperature: 50 ° C.) for 120 seconds, washed, and contains a conductive mesh composed of a conductive portion (line width 3 μm) containing Ag, gelatin and P-1. The sheet C having a non-conductive portion from which gelatin was removed was obtained from the layer to be coated and the layer containing gelatin and P-2.

(Calendar processing)
The sheet C was calendered at a pressure of 30 kN by using a calender device comprising a combination of a metal roller and a resin roller. The obtained sheet was designated as Sheet D.

(Fusion processing)
The sheet D was heated by passing it through a superheated steam bath at 150 ° C. over 120 seconds. The obtained sheet was designated as sheet E (corresponding to a conductive sheet for touch panel).

(Measurement of component distribution)
The component distribution was measured using TOF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry, Argon GCIB: Gas Cluster Ion Beam) along the thickness direction of the conductive portion. P-1 and P-2 were measured in advance as standard substances, and ionic species for judging the component distribution were selected. First, measurement was repeated while excavating with an ion beam from the surface opposite to the support side to obtain a profile of component distribution in the thickness direction. Specifically, a region near the depth (thickness) where metal silver detection starts (upper region), a lower region near the depth (thickness) where metal silver detection ends, and an intermediate region are detected, Table 1 shows the mass ratio of the content of P-2 to the total content of P-1 and P-2 in the region.

[Example 2]
In Example 1, the following composition adjustment coating liquid 1-2 was used instead of the composition adjustment coating liquid 1, and the following composition adjustment coating liquid 2-2 was used instead of the composition adjustment coating liquid 2. In the same manner as in Example 1, a conductive sheet for a touch panel was obtained.

(Method for preparing composition-adjusting coating liquid 1-2)
The composition-adjusting coating solution 1-2 is prepared by mixing polymer latex 2 and gelatin at a mixing mass ratio (second polymer / gelatin) 2/1, and decolorizing with an alkali of the developer at an optical density of about 1.0. It is a composition which consists of a mixture containing the dye to do. Further, the concentration of the composition-adjusting coating solution 1-2 was adjusted so that the amount of P-2 (coating amount) in the layer formed from the composition-adjusting coating solution 1-2 was 0.65 g / m ² . In addition, since the layer formed from the composition adjustment coating liquid 1-2 includes a dye, it has an antihalation function.

(Method for preparing composition-adjusting coating liquid 2-2)
The composition-adjusting coating solution 2-2 is a composition in which the polymer latex 1 and gelatin are mixed at a mixing mass ratio (P-1 / gelatin) 2/1. The concentration of the composition-adjusting coating solution 2-2 was adjusted so that the amount of gelatin in the layer formed from the composition-adjusting coating solution 2-2 was 0.10 g / m ² .

[Example 3]
(Fusion inhibition treatment)
In Example 1, a conductive sheet for a touch panel was obtained in the same manner as in Example 1 except that the fusion inhibition treatment process was performed as a process between the calendar treatment process and the fusion treatment process. The fusion inhibition treatment in the fusion inhibition treatment step is a step in which the sheet D is immersed in a 0.3 wt% aqueous solution of the following compound A for 30 seconds, washed with running water for 90 seconds, and dried at 65 ° C. for 15 minutes. is there.

(Compound A)

[Example 4]
In the silver halide light-sensitive layer forming step of Example 3, instead of “undercoat layer forming composition 1 (curable composition 1)” used in preparing the support with the undercoat layer, an undercoat described later is used. The layer forming composition 2 (curable composition 2) was applied onto a support so that the film thickness after drying was 100 nm, and dried at 90 ° C. for 1 minute to prepare a support with an undercoat layer. Except that, a conductive sheet for a touch panel was obtained in the same manner as in Example 3.

  The conductive sheet for a touch panel has a refractive index of 1.64, 1.58, 1.49, 1.49 (wavelength: 589 nm) in the order of the support, the undercoat layer (easy adhesion layer), the antihalation layer, and the non-conductive portion. ).

In addition, the electroconductive sheet for touchscreens of Examples 1-3 is 1.64, 1.49, 1.49, 1.49 in order of the support, the undercoat layer (easy adhesion layer), the antihalation layer, and the non-conductive portion. It had a refractive index of 49 (wavelength: 589 nm).
In addition, the conductive sheets for touch panels of Examples 5 to 7 are 1.64, 1.58, 1.49, 1.49 in the order of the support, the undercoat layer (easy adhesion layer), the antihalation layer, and the non-conductive portion. It had a refractive index of 49 (wavelength: 589 nm).

(Composition of composition 2 for forming undercoat layer (curable composition 2))
The composition of the undercoat layer forming composition 2 is as follows.
Acrylic polymer: 25.6 parts by mass (“AS-563A”, manufactured by Daicel FineChem, Inc., solid content: 27.5% by mass)
Polyester polymer: 21.2 parts by mass (“Plus Coat Z-690”, manufactured by Kyoyo Chemical Industry Co., Ltd., solid content: 25.0% by mass)
Carbodiimide-based crosslinking agent: 22.0 parts by mass (“Carbodilite V-02-L2”, manufactured by Nisshinbo Co., Ltd., solid content: 10% by mass)
Colloidal silica: 3.2 parts by mass (“Snowtex ZL”, manufactured by Nissan Chemical Industries, Ltd., solid content: 10% by mass, water dilution)
・ Slip agent: 18.5 parts by mass (Carnauba wax, “Cerosol 524”, manufactured by Chukyo Yushi Co., Ltd., solid content: 3% by mass, water dilution)
Anionic surfactant: 58.2 parts by mass (“Lapisol A-90”, manufactured by NOF Corporation, solid content: 1% by mass, aqueous solution)
Nonionic surfactant: 73.2 parts by mass (“Naroacty CL95”, manufactured by Sanyo Chemical Industries, Ltd., solid content: 1% by mass, aqueous solution)
-Distilled water: 778.2 parts by mass

[Example 5]
In Example 4, composition-adjusting coating solution 1, silver halide-containing coating solution 1, silver halide-containing coating solution 2, and composition-adjusting coating on the undercoat layer of the support with the undercoat layer in order from the undercoat layer side. Liquid 2 was applied simultaneously at a coating liquid flow ratio (composition adjustment coating liquid 1 / silver halide-containing coating liquid 1 / silver halide-containing coating liquid 2 / composition adjustment coating liquid 2) at 25/25/10/5. A conductive sheet for a touch panel was obtained in the same manner as in Example 4 except that a silver halide photosensitive layer was formed on the support.

(Preparation of silver halide-containing coating solution 2)
Pure water was added to the emulsion described in Example 1 to dilute it 10 times, and further 4 times equivalent of gelatin was added to the contained gelatin. Further, polymer latex 2 was mixed with P-2 / gelatin (mass). Ratio) = 0.4 / 1. The coating solution pH was adjusted to 5.6 using citric acid. Here, in the silver halide-containing coating solution 2, the ratio R2 (P-2 / silver halide) of the mass of P-2 to the mass of silver halide was 0.24.

[Example 6]
In Example 4, composition-adjusting coating solution 1-2, silver halide-containing coating solution 2, silver halide-containing coating solution 1, and composition on the undercoat layer of the support with the undercoat layer in order from the undercoat layer side. The adjusted coating solution 2-2 is mixed with the coating solution flow rate ratio (composition adjusting coating solution 1-2 / silver halide-containing coating solution 2 / silver halide-containing coating solution 1 / composition adjusting coating solution 2-2). A conductive sheet for a touch panel was obtained in the same manner as in Example 4 except that a simultaneous multilayer coating was applied at 25/5 to form a silver halide photosensitive layer on the support.

[Example 7]
In Example 4, the composition-adjusting coating solution 1-2, the silver halide-containing coating solution 2, the silver halide-containing coating solution 1, and the halogen on the undercoat layer of the support with the undercoat layer in order from the undercoat layer side. The silver halide-containing coating solution 2 and the composition-adjusting coating solution 2 are mixed into a coating solution flow rate ratio (composition-adjusting coating solution 1-2 / silver halide-containing coating solution 2 / silver halide-containing coating solution 1 / silver halide-containing coating. Solution 2 / Composition Adjustment Coating Solution 2) Touch panel in the same manner as in Example 4 except that 25/10/25/10/5 was applied simultaneously and a silver halide photosensitive layer was formed on the support. A conductive sheet was obtained.

[Comparative Example 1]
In Example 1, the conductive sheet for touch panels was obtained like Example 1 except having used the said composition adjustment coating liquid 2-2 instead of the composition adjustment coating liquid 2. FIG.

[Comparative Example 2]
In Comparative Example 1, a conductive sheet for a touch panel was obtained in the same manner as Comparative Example 1 except that polymer latex 2 was used instead of polymer latex 1.

(Evaluation 1)
The surface resistance value of the conductive sheet for touch panel was measured. The measurement was performed using CONDUCTANCE MONITOR MODEL 717B manufactured by DELCOM INSTRUMENTS. The results were evaluated according to the following criteria. The smaller the surface resistance value is, the higher the conductivity is, indicating that the conductive sheet for touch panel has excellent performance.

A: The surface resistance value is 20Ω / sq. Is less than.
B: The surface resistance value is 20Ω / sq. 50 Ω / sq. Is less than.
C: Surface resistance value is 50Ω / sq. 70 Ω / sq. Is less than.
D: The surface resistance value is 70Ω / sq. That's it.
In addition, Ω / sq. Represents ohms per square (Ω per square).

(Evaluation 2)
YOGA Table2-830L manufactured by Lenovo Corporation was immersed in liquid nitrogen to deactivate the adhesive, and then decomposed to take out a display and a cover glass. Further, the display and the cover glass were rubbed with a waste cloth containing ethyl acetate to remove the adhesive material. Using the 3M transparent adhesive film 8146-4 between the taken out display and the cover glass, the conductive sheet for the touch panel was laminated and laminated, and a visibility evaluation module was produced (in addition, the configuration of the bonding) Is display / adhesive film / transparent conductive film / adhesive film / cover glass.) A module in which the upper region side of the conductive sheet for touch panel is arranged on the viewing surface side (in other words, a module in which the surface opposite to the support is arranged on the viewing surface side) and the lower region side is arranged on the viewing surface side. Modules (in other words, modules in which the support is arranged on the viewing surface side) were produced and evaluated. The module in which the upper region side is arranged on the viewing surface side is bonded with the upper region side of the conductive film for touch panel facing the cover glass side. On the other hand, the module in which the lower region side is arranged on the viewing surface side is bonded with the lower region side of the touch panel conductive sheet facing the cover glass side.

  Next, with the display turned off, the obtained module was visually observed while varying the light irradiation angle, distance, and observation angle of the three-wavelength fluorescent lamp, and the blackness of the display view area was sensorially evaluated. did. In the sensory evaluation, as a reference sample with good black tightening, a module (lamination structure; display / adhesive film / cover glass) to which the transparent conductive film was not bonded was produced, and this black tightening was set to 10 points (good). Moreover, the black tightening of the module in which the lower region side of the conductive sheet for a touch panel of Comparative Example 1 having the worst black tightening was arranged on the viewing surface side was defined as one point (defect). An arbitrary six persons scored the sensory evaluation value of black tightening based on the above-mentioned 10 points and 1 point of the reference sample, respectively. Based on the average value of scoring by 6 people, the following ranking was performed and used as an evaluation value.

AAA: 9 to 10 points AA: 8 to less than 9 A: 7 to less than 8 B: 6 to less than 7 C: 5 to less than 6 D: Less than 5

  In Table 1, the content ratio of the content of P-2 to the total content of P-1 and P-2 in each region of the conductive sheet for each touch panel, the results of Evaluation 1 and Evaluation 2 are shown. It was.

In Table 1, the column “second polymer / (first polymer + second polymer)” includes the second polymer with respect to the total content of the first polymer and the second polymer in a predetermined region. The content mass ratio of the contents is shown. In the “Fusion inhibition treatment” column, the presence or absence of a step of bringing the silver halide photosensitive layer or conductive portion into contact with the specific compound is shown. In the “undercoat refractive index adjustment” column, when the refractive index of the non-conductive portion is RI ₁ , the refractive index of the easy adhesion layer (undercoat layer) is RI ₂ , and the refractive index of the support is RI ₃ , Formula 3; the composition of the undercoat layer forming composition adjusted to satisfy RI ₁ <RI ₂ <RI ₃ was defined as “Yes”, and the others were defined as “None”. Also, in the “surface resistance” column, the result of evaluation 1 and in the “black tightening” column, the result of evaluation 2 are the results when the upper region side of each touch panel conductive sheet is the viewing side, and The results when the lower region side is the viewing side are shown.

From the results described in Table 1, the conductive sheets for touch panels according to Examples 1 to 7 satisfying Formula 1 or Formula 2 in which R _U , R _M , and R _L have already been described have excellent conductivity. And when applied to a touch panel, the screen appears blacker (has excellent black tightening).
On the other hand, the conductive sheet for a touch panel of Comparative Example 1 and Comparative Example 2 did not satisfy both of the above formulas 1 and 2, and a desired effect was not obtained.
Also, R M _<touch panel conductive sheet of Example 1 satisfying R _U in the case where the upper area side to the viewing side, was found to have a better black interference.
On the other hand, it was found that the conductive sheet for a touch panel of Example 2 satisfying R _M <R _L has better black tightening when the lower region side is the viewing side.
Further, after the calendar processing step (step D for consolidating the conductive portion) and before the fusion processing step (step F for performing processing for fusing the metallic silver of the conductive portion to each other), fusion inhibition The conductive sheet for the touch panel of Example 3 manufactured by the method having the processing step (the step C2 for bringing the conductive part and the specific compound into contact) is manufactured by the manufacturing method that does not have the step C2 (and step C1). Compared with the conductive sheet for a touch panel of Example 1, it had better black tightening.
Also it has an easy-adhesion layer between the support and the conductive portion, further comprising a non-conductive portion that is disposed adjacent to the conductive portion on the adhesion layer, RI ₁ a refractive index of the non-conductive portion The conductive sheet for a touch panel of Example 4 that satisfies Formula 3 RI ₁ <RI ₂ <RI ₃ when the refractive index of the easy-adhesion layer is RI ₂ and the refractive index of the support is RI ₃ is Compared with the conductive sheet for touch panel of Example 1, it had a further excellent black tightening.
Moreover, the conductive sheet for a touch panel of Example 7 that satisfies both the formulas 1 and 2 is particularly excellent in both cases where the upper region is the viewing side and the lower region is the viewing side. Had black tightening.
On the other hand, the conductive sheet for the touch panel of Example 1 and Example 2 that satisfies either one of Formula 1 and Formula 2 has excellent conductivity with a lower surface resistance value, and one of the upper or lower region. It had excellent black tightening when the side was the viewing side.

[Example 8]
A conductive sheet for a touch panel was obtained in the same manner as in Example 1 except that the composition-adjusting coating solution 2-3 was used instead of the composition-adjusting coating solution 2.
The composition-adjusting coating solution 2-3 is a composition in which Movinyl LDM7523 manufactured by Nippon Synthetic Chemical Co., Ltd. and gelatin are mixed at a mixing mass ratio (mobile LDM7523 solid content / gelatin) 2/1. In addition, the concentration of the composition-adjusted coating solution 2-3 was adjusted so that the amount of gelatin in the layer formed from the composition-adjusted coating solution 2-3 was 0.10 g / m ² . The glass transition temperature measured by differential scanning calorimetry (DSC) of the solid content of mobile LDM7523 was + 17 ° C.

[Example 9]
A conductive sheet for a touch panel was obtained in the same manner as in Example 1 except that the composition adjustment coating liquid 2-4 was used instead of the composition adjustment coating liquid 2.
The composition-adjusting coating solution 2-4 is a composition in which Nipol LX415M manufactured by Nippon Zeon Co., Ltd. and gelatin are mixed at a mixing mass ratio (Nipol LX415M solid content / gelatin) 2/1. In addition, the concentration of the composition-adjusted coating solution 2-4 was adjusted so that the amount of gelatin in the layer formed from the composition-adjusted coating solution 2-4 was 0.10 g / m ² . The glass transition temperature measured by differential scanning calorimetry (DSC) of the solid content of Nipol LX415M was + 27 ° C.

  About the conductive sheet for touch panels obtained by Example 8 and Example 9, the black tightening was evaluated by the method of (Evaluation 2) described above, and the results are shown in Table 2. In addition, the evaluation results of the conductive sheets for touch panels of Example 1 and Comparative Example 1 are also shown in Table 2. In Table 2, the sensory average represents the average value of the sensory evaluation, and after the determination, the evaluation result of the black tightening was expressed, and the evaluation was performed with the upper region side as the viewer side. .

  From the results shown in Table 2, the conductive sheets for the touch panel of Example 1 and Example 8, in which the glass transition temperature of the second polymer is 25 ° C., the glass transition temperature of the second polymer is 27 ° C. or higher. Compared with the conductive sheet for a touch panel of Example 9, it had a better black tightening.

DESCRIPTION OF SYMBOLS 10 Electroconductive sheet 12 for touchscreens Support body 14 Conductive part 16 Binder 18 Metal part 114A Surface 26 Opening part 51 Nonconductive part 61 Easy adhesion layer

Claims (14)

A conductive sheet for a touch panel having a support and a conductive part disposed on the support and containing a binder and a metal part,
The binder contains a first polymer and a second polymer having a glass transition temperature lower than that of the first polymer,
When the contour line along the surface shape of the surface X of the conductive part is moved from the surface X opposite to the support side of the conductive part toward the support side in the vertical cross section of the conductive part. The first polymer and the second polymer in a region from the upper end position to 100 nm toward the support side with the position where the contour line reaches the metal part included in the conductive part as the upper end position. the content mass ratio of the content of the second polymer and R _U to the total content,
When the contour line is moved to the support side relative to the upper end position, the position where the conductive portion does not include the metal part is defined as a lower end position, and an intermediate position between the upper end position and the lower end position is moved to the support side. toward 50nm and containing mass ratio of the content of the second polymer to the total content of the first polymer and the second polymer in the 50nm region toward the surface X side is R _M, the
When the content mass ratio of the content of the second polymer to the total content of the first polymer and the second polymer in a region of 100 nm from the lower end position toward the surface X side is _RL. ,
Formula 1 and Formula 2 below;
Formula 1 _RM < _RU
Formula 2 R _M <R _L
A conductive sheet for a touch panel, wherein at least one selected from the group consisting of:   The conductive sheet for a touch panel according to claim 1, wherein the glass transition temperature of the second polymer is 25 ° C. or lower.   The conductive sheet for a touch panel according to claim 1 or 2, wherein the metal part contains at least one metal selected from the group consisting of gold, silver, copper, nickel, and palladium. Having an easy-adhesion layer between the support and the conductive portion;
On the easy-adhesion layer, it further has a non-conductive part arranged adjacent to the conductive part,
When the refractive index of the non-conductive portion is RI ₁ , the refractive index of the easy adhesion layer is RI ₂ , and the refractive index of the support is RI ₃ , the following formula 3;
Formula 3 RI ₁ <RI ₂ <RI ₃
The conductive sheet for touch panels as described in any one of Claims 1-3 which satisfy | fills. The said metal part is a manufacturing method of the electroconductive sheet for touchscreens as described in any one of Claims 1-4 containing metal silver,
A silver halide-containing coating solution containing at least silver halide and a first polymer and a composition-adjusting coating solution containing at least a second polymer are simultaneously coated on the support, and silver halide is coated. Forming a photosensitive layer A;
A process for producing a conductive sheet for a touch panel, comprising: exposing the silver halide photosensitive layer and then developing the conductive part to form a conductive part containing metallic silver.   The manufacturing method of the conductive sheet for touchscreens of Claim 5 in which the said composition adjustment coating liquid contains a silver halide further.   The conductive sheet for a touch panel according to claim 5 or 6, wherein at least one selected from the group consisting of the silver halide-containing coating solution and the composition-adjusting coating solution further contains non-metallic fine particles. Method.   The manufacturing method of the conductive sheet for touchscreens as described in any one of Claims 5-7 which further has the process F which performs the process which fuse | melts the said metal silver of the said electroconductive part mutually after the said process B. After Step A and before Step B, the step of contacting the silver halide photosensitive layer with a compound having a metal-adsorptive substituent or a metal-adsorptive structure, or
The manufacturing method of the conductive sheet for touchscreens of Claim 8 which has the process C2 which makes the said electroconductive part and the said compound contact after the said process B and before the said process F. FIG.   The metal adsorbing substituent is at least one selected from the group consisting of a carboxyl group or a salt thereof, an acid amide group, an amino group, an imidazole group, a pyrazole group, a thiol group, a thioether group, and a disulfide group. The manufacturing method of the electroconductive sheet for touchscreens of Claim 9.   The process for producing a conductive sheet for a touch panel according to any one of claims 8 to 10, further comprising a step D for consolidating the conductive portion after the step B and before the step F. Method. At least one selected from the group consisting of the silver halide-containing coating solution and the composition-adjusting coating solution further contains gelatin,
The manufacturing method of the conductive sheet for touchscreens of Claim 11 which has the process E which removes the gelatin of the said electroconductive part further after the said process B and before the said process D.   The manufacturing method of the conductive sheet for touchscreens of Claim 11 or 12 whose said process D is a calendar process process which passes the said support body which has the said electroconductive part between at least a pair of rolls under pressure.   The touch panel which has the electroconductive sheet for touch panels as described in any one of Claims 1-4.