JP2022057907A - Etching solution, conductive pattern and manufacturing method of the same, and touch panel - Google Patents

Abstract

To provide an etchant which enables formation of a conductive pattern with small LWR when etching a silver-containing conductive layer and which has high etching speed, a conductive pattern, a manufacturing method of the same, and a touch panel.SOLUTION: There is provided the etchant for etching a silver-containing conductive layer. The etchant has a nitrate ion content of 16.0 mass% to 35.0 mass% relative to the total etchant content. There are also provided the conductive pattern, and the manufacturing method of the same, and the touch panel.SELECTED DRAWING: None

Description

The present disclosure relates to an etching solution, a conductive pattern and a method for manufacturing the same, and a touch panel.

For example, touch panels are widely used in displays, smartphones, tablets and the like. Such a touch panel is provided with a conductive pattern, and the conductive pattern is generally formed by etching a metal conductive layer with an etching solution. Further, as the metal conductive layer, a silver-containing conductive layer is widely used.

For example, Patent Document 1 describes that an etching solution containing nitrate ions is used for etching a silver-containing conductive layer.

Japanese Unexamined Patent Publication No. 2014-203626

Techniques for etching a silver-containing conductive layer, including techniques such as Patent Document 1, have been conventionally studied. However, at present, there is insufficient technology for improving the LWR (Line Width Roughness) and the etching rate of the conductive pattern obtained by etching the silver-containing conductive layer.

The present disclosure has been made in view of such a situation, and the problem to be solved by one embodiment of the present invention is that it is possible to form a conductive pattern having a small LWR when the silver-containing conductive layer is etched. It is to provide an etching solution which is present and has a high etching rate.
An object to be solved by another embodiment of the present invention is to provide a method for producing a conductive pattern.
An object to be solved by another embodiment of the present invention is to provide a conductive pattern obtained from the above-mentioned method for manufacturing a conductive pattern.
An object to be solved by another embodiment of the present invention is to provide a touch panel provided with the above-mentioned conductive pattern.

The disclosure includes the following aspects:
<1> An etching solution for etching a silver-containing conductive layer.
An etching solution having a nitrate ion content of 16.0% by mass to 35.0% by mass with respect to the total amount of the etching solution.
<2> The etching solution according to <1>, wherein the ion source of nitrate ion contains iron (III) nitrate.
<3> The etching solution according to <2>, wherein the ion source of nitrate ions is iron (III) nitrate.
<4> The etching solution according to any one of <1> to <3>, wherein the nitrate ion content is 23.0% by mass to 33.0% by mass with respect to the total amount of the etching solution.
<5> The etching solution according to any one of <1> to <4>, wherein the silver-containing conductive layer contains sintered silver particles.
<6> The etching solution according to <5>, wherein the silver-containing conductive layer contains an organic substance.
<7> The etching solution according to <6>, wherein the silver-containing conductive layer contains at least one of a dispersant and a dispersion aid as an organic substance.
<8> The etching solution according to <7>, which comprises at least one of a dispersant and a dispersant aid.
<9> The etching solution according to <7> or <8>, wherein the dispersant is a polymer compound containing an acid group.
<10> The etching solution according to any one of <7> to <9>, wherein the dispersion aid is a compound containing a hydroxy group.
<11> The etching solution according to <10>, wherein the compound containing a hydroxy group is a polyglycerin compound.
<12> A step of preparing a conductive material having a base material and a silver-containing conductive layer,
A step of forming a photosensitive resin layer on the surface of the silver-containing conductive layer opposite to the side having the base material.
The process of pattern exposure of the photosensitive resin layer,
A step of developing the photosensitive resin layer exposed to the pattern and a step of etching the silver-containing conductive layer with the etching solution according to any one of <1> to <11> in which the nitrate ion content is contained. A method for manufacturing a conductive pattern.
<13> The method for producing a conductive pattern according to <12>, which comprises a step of removing the photosensitive resin layer after the etching step.
<14> The method for producing a conductive pattern according to <12> or <13>, wherein the temperature of the etching solution is 40 ° C. or lower.
<15> A conductive pattern obtained by the method for manufacturing a conductive pattern according to any one of <12> to <14>.
<16> A touch panel provided with the conductive pattern according to <15>.

According to one embodiment of the present invention, there is provided an etching solution capable of forming a conductive pattern having a small LWR and having a high etching rate.
According to another embodiment of the present invention, a method for producing a conductive pattern is provided.
According to another embodiment of the present invention, the conductive pattern obtained from the above-mentioned method for producing a conductive pattern is provided.
According to another embodiment of the present invention, a touch panel having the above conductive pattern is provided.

Hereinafter, the etching solution, the conductive pattern and its manufacturing method, and the details of the touch panel according to the present disclosure will be described.

The numerical range indicated by using "-" in the present disclosure means a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in another stepwise description. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
In the present disclosure, the amount of each component means the total amount of a plurality of kinds of substances when there are a plurality of kinds of substances corresponding to each component, unless otherwise specified.
In the present disclosure, "light" is a concept including active energy rays such as γ-rays, β-rays, electron rays, ultraviolet rays, and visible rays.
In the present disclosure, the term "process" is included in this term as long as the intended purpose of the process is achieved, not only in an independent process but also in cases where it cannot be clearly distinguished from other processes. ..
In the present disclosure, "(meth) acrylic" is a term used in a concept that includes both acrylic and methacrylic, and "(meth) acrylate" is a term that is used in a concept that includes both acrylate and methacrylate. be.
In the present disclosure, unless otherwise specified, the weight average molecular weight (Mw) is gel permeation chromatography (GPC) using TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names, manufactured by Tosoh Corporation) as columns. It is a molecular weight converted by using THF (tetrahydrofuran) as an eluent by an analyzer, detecting by a differential refractometer (RI) detector, and using polystyrene as a standard substance.
In the present disclosure, the acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample, and the unit is described as mgKOH / g in the present specification. The acid value is determined by a measuring method based on Japanese Industrial Standards (JIS; Japanese Industrial Standards) K0070: 1992.
In the present disclosure, the amine value represents the total amount of primary amines, secondary amines and tertiary amines, and is the mass [mg] of potassium hydroxide and equivalent potassium hydroxide required to neutralize 1 g of sample. In the present specification, the unit is described as mgKOH / g. The amine value can be calculated, for example, from the average content of amine groups in the compound. The amine value is determined by using a 0.1 N hydrochloric acid aqueous solution, determining an equivalence point by a potentiometric titration method, and converting it into an equivalent of potassium hydroxide.
In the present disclosure, the "total solid content" means the total mass of the components excluding the solvent from the total composition. Further, the "solid content" is a component obtained by removing the solvent from the entire composition, and may be, for example, a solid or a liquid at 25 ° C.
In the present disclosure, the nitrate ion content may be referred to as "nitrate ion concentration".

<Etching liquid>
The etching solution according to the present disclosure is an etching solution for etching a silver-containing conductive layer, and the content of nitrate ions is 16.0% by mass to 35.0% by mass with respect to the total amount of the etching solution. ..

As described above, the conductive pattern provided on the touch panel or the like is generally formed by etching the metal conductive layer with an etching solution, and the silver-containing conductive layer is widely used as the metal conductive layer. There is. However, since silver has a high redox potential, the etching progresses slowly. For example, the etching solution described in Patent Document 1 has a low nitrate ion concentration and is not suitable for etching a silver-containing conductive layer. Moreover, it is difficult to obtain a good LWR only by increasing the nitrate ion concentration.

On the other hand, in the etching solution according to the present disclosure, the nitrate ion content is controlled in the range of 16.0% by mass to 35.0% by mass. Therefore, even silver having a high nitrate ion concentration and being difficult to be oxidized can be easily etched at a low oxidation potential, and the etching rate can be increased. Further, since the nitrate ion concentration is not excessively high, it is possible to prevent the obtained conductive pattern from being excessively invaded by nitrate ions while increasing the etching rate. Therefore, when the silver-containing conductive layer is etched, a conductive pattern having a small LWR can be formed and the etching rate can be increased.

[Nitrate ion content]
The etching solution according to the present disclosure is an aqueous solution containing nitrate ions, and the content of nitrate ions is 16.0% by mass to 35.0% by mass with respect to the total amount of the etching solution. By setting the nitrate ion content to 16.0% by mass or more, the silver-containing conductive layer can be etched.
On the other hand, by setting the nitrate ion content to 35.0% by mass or less, the LWR can be reduced and a good conductive pattern shape can be obtained. Further, since it becomes easy to dissolve the ion source of nitrate ion (for example, the ion source described later) in the etching solution, it is possible to prevent the erosion of the conductive pattern by the ion source remaining without being dissolved, and the LWR is deteriorated. Can be easily suppressed.

The content of nitrate ion is preferably 23.0% by mass to 33.0% by mass with respect to the total amount of the etching solution from the viewpoint of improving the etching rate and reliability, and improving LWR and reliability. From the viewpoint, it is more preferably 26.0% by mass to 31.5% by mass.

The nitrate ion content is measured by ion chromatography by a gradient elution method.

[Ion source of nitrate ion]
The ion source of nitrate ion is not particularly limited as long as it can be dissolved in water to generate nitrate ion. Examples of nitric acid ion sources include nitric acid (concentrated nitric acid, dilute nitric acid); and potassium nitrate, sodium nitrate, ammonium nitrate, uranyl nitrate, calcium nitrate, silver nitrate, iron (II) nitrate, iron (III) nitrate, and lead nitrate ( II), barium nitrate, cobalt nitrate (II), bismuth nitrate, strontium nitrate, magnesium nitrate, calcium nitrate, diammonium cerium nitrate (IV), manganese nitrate (II), sodium nitrate, palladium (II) nitrate, copper nitrate (II) II), cadmium nitrate, tallium nitrate (I), cerium nitrate (III), zinc nitrate, nickel nitrate (II), zirconyl nitrate, formium nitrate, aluminum nitrate, lithium nitrate, mercury (II) nitrate, cesium nitrate, gadolinium nitrate. , Placeodim nitrate (III), Elbium nitrate, Europium nitrate (III), Lutethium nitrate, Lantern (III) nitrate, Indium nitrate (III), Ittrium nitrate, Gallium nitrate (II), Samalium nitrate, Neodim nitrate, Itterbium nitrate, Nitrate Examples thereof include nitrates such as dysprosium, chromium (III) nitrate, scandium nitrate, and rubidium nitrate.
From the viewpoint of increasing the etching rate more easily, the ion source of nitrate ion preferably contains one or more selected from the group consisting of nitric acid, iron (II) nitrate and iron (III) nitrate. Iron (III) acts as an effective catalyst for nitric acid to oxidize silver in terms of redox potential. Therefore, from the viewpoint of increasing the etching rate more easily, the ion source of nitrate ion is more preferably containing iron (III) nitrate, and further preferably iron (III) nitrate.

From the viewpoint of more easily enhancing the etchability, the molar ratio of hydrogen ions to nitrate ions is preferably 0.2 or less, more preferably 0.1 or less, and further preferably 0.05 or less. preferable.
The hydrogen ion content (mоl / l) can be determined by the following formula (1) by measuring the pH of the etching solution at 25 ° C. using a pH meter.
Hydrogen ion content = 10- ^pH formula (1)

[Other ingredients]
The etching solution may contain nitrate ions and other components other than counterions derived from the ion source thereof. Examples of other components include dispersants and dispersion aids described later, binder resins, surfactants, component stabilizers, defoamers and the like. As for each of the other components, one kind may be used alone, or two or more kinds may be used in combination.
Examples of the binder resin include polyester resin, polyurethane resin, polyacrylate resin, polyacrylamide resin, polyether resin, melamine resin, terpene resin and the like.

[impurities]
The etching solution preferably has a low content of impurities.
Specific examples of impurities include those containing metal elements such as sodium, potassium, magnesium, calcium, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, strontium, ions and fluoride thereof. Examples include silicon acid. The content of such impurities can be 10% by mass or less with respect to the total amount of the etching solution, more preferably 5% by mass or less, still more preferably 1% by mass or less. The lower limit of the content of impurities in the etching solution can be 1 ppb or more or 0.1 ppm or more on a mass basis with respect to the total amount of the etching solution.
Specific examples of impurities include organic substances such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane. Be done. The content of such impurities can be 1.0% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less, based on the total amount of the etching solution. The lower limit of the content of impurities in the etching solution can be 1 ppb or more or 0.1 ppm or more on a mass basis.

[Manufacturing method of etching solution]
The method for producing the etching solution is not particularly limited, and the etching solution may be produced by dissolving the above-mentioned components in water. The water preferably has few impurities such as ion-exchanged water and distilled water.

[Silver-containing conductive layer]
The silver-containing conductive layer contains silver, and examples of silver include metallic silver and an alloy of silver and another metal (hereinafter, may be referred to as "silver alloy"). In the silver alloy, the ratio of the silver element in the silver alloy is preferably more than 50% by mass.

The silver-containing conductive layer is not particularly limited as long as it contains silver, and for example, a conductive layer made of silver, a conductive layer made of a silver alloy, and a conductive layer containing sintered silver particles (hereinafter, "silver particle conductive layer"). "), Etc. can be mentioned. The silver particles may be particles made of silver, particles made of a silver alloy, or a mixture thereof.
Hereinafter, sintered silver particles and unsintered silver particles may be referred to as "silver particles" without distinction. Further, the sintered silver particles have a porous structure in which gaps are present between the silver particles.

The conductive layer made of silver and the conductive layer made of silver alloy may be, for example, a sputtering film formed by a sputtering method.
The silver particle conductive layer may be formed by, for example, heat-treating a dried product of a silver ink composition containing silver particles.

The thickness of the silver-containing conductive layer is not particularly limited and may be appropriately adjusted depending on the intended purpose, and may be, for example, 0.1 μm to 3.0 μm. The thickness of the silver-containing conductive layer can be measured by, for example, a stylus type step meter, a three-dimensional surface structure analysis microscope, or the like. As a commercially available stylus type step meter, for example, "SURFACE PROFILER P-10" manufactured by KLA-TENCOR can be mentioned, and as a commercially available three-dimensional surface structure analysis microscope, for example, "New View 5022" manufactured by ZYGO Corporation. ".

From the viewpoint of easier etching, the silver-containing conductive layer is preferably a silver particle conductive layer. In the silver particle conductive layer, the etching solution can penetrate into the gaps between the sintered silver particles, so that etching can be performed faster. Further, since the sintered silver particles are more flexible than the sputtering film, they can be suitably used for forming electrodes (that is, conductive patterns) of a flexible substrate used for a touch panel, for example.

(Silver particles)
The silver particles are not particularly limited, and known ones can be used. The silver particles may be surface-treated with an organic substance such as alkoxyamine from the viewpoint of improving dispersibility.

The shape of the silver particles is not particularly limited, and may be spherical, elliptical spherical, needle-shaped, flat plate-shaped, or the like. When the silver particles are spherical or elliptical spherical, the bending resistance of the silver particle conductive layer obtained by sintering the silver particles can be easily improved. Such a silver particle conductive layer can be suitably used, for example, to form an electrode (that is, a conductive pattern) of a flexible substrate used for a touch panel.

The average particle size of the silver particles is not particularly limited, but is preferably 1 nm to 400 nm from the viewpoint of dispersibility. It is more preferably 2 nm to 200 nm, and particularly preferably 5 nm to 100 nm. For example, in an embodiment in which the silver particle conductive layer is formed from a silver ink composition, the average particle size of the silver particles can be measured by a dynamic light scattering method as described later.

The content of the silver particles is preferably 80% by mass to 99.9% by mass, more preferably 85% by mass to 99% by mass, based on the total amount of the silver particle conductive layer.

The silver particle conductive layer may contain an organic substance. Examples of the organic substance include a surface treatment agent for silver particles, a dispersant, a dispersion aid, and the like. Such an organic substance improves the dispersibility of silver particles in the silver-containing conductive layer. Therefore, a more uniform silver-containing conductive layer can be obtained, and more uniform etching can be performed.

From the viewpoint of improving LWR more easily, the silver particle conductive layer preferably contains at least one of a dispersant and a dispersion aid as an organic substance. The mechanism by which LWR is improved is not clear, but during etching, the dispersion component (meaning "at least one of the dispersant and the dispersion aid") contained in the conductive layer of silver particles elutes into the etching solution while etching. It is presumed that this is because local erosion of the edge portion of the etching pattern is likely to be suppressed by the progress of. Further, the etching solution also preferably contains at least one of a dispersant and a dispersant aid. As a result, it is presumed that the effect of suppressing erosion is further enhanced, and it becomes easier to improve the LWR. The scope of this disclosure is not limited by the above speculation.

In an embodiment in which the etching solution contains at least one of a dispersant and a dispersion aid, the dispersant and the dispersion aid that can be contained in the etching solution are the same compound group as the dispersant and the dispersion aid that can be contained in the silver-containing conductive layer. It means that it has nothing to do with the presence or absence of dispersibility.
Further, an etching solution containing at least one compound selected from the same compound group as the dispersant and the dispersion aid that can be contained in the silver-containing conductive layer is added to the etching solution with the intention that the compound exerts a dispersing ability. Regardless of whether it is contained or not, it is within the range of the etching solution according to the present disclosure.

(Dispersant)
The dispersant is not particularly limited and may be, for example, a compound containing at least one acid group or an amine group, and may be, for example, a polymer compound (for example, a graft polymer). From the viewpoint of improving LWR more easily, the dispersant is preferably a polymer compound having an acid group. The type of the acid group is not particularly limited, and may be, for example, a carboxyl group or a functional group derived from phosphoric acid.

When the dispersant has an acid group, the acid value of the dispersant is not particularly limited, but is preferably, for example, 5 mgKOH / g to 200 mgKOH / g, more preferably 10 mgKOH / g to 180 mgKOH / g, and 20 mgKOH. It is more preferably / g to 160 mgKOH / g.

When the dispersant has an amine group, the amine value of the dispersant is not particularly limited, but is preferably, for example, 5 mgKOH / g to 200 mgKOH / g, more preferably 10 mgKOH / g to 180 mgKOH / g, and 20 mgKOH. It is more preferably / g to 160 mgKOH / g.

When the dispersant has an acid group and an amine group, the acid value of the dispersant is preferably larger than the amine value.
The absolute value of the difference between the acid value and the amine value of the dispersant is not particularly limited, but is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and further preferably 20 mgKOH / g or more. preferable. The absolute value is not particularly limited, and may be, for example, 100 mgKOH / g or less.

When the dispersant is a polymer compound, the weight average molecular weight of the dispersant is not particularly limited, and may be, for example, 2,000 to 100,000, preferably 3,000 to 80,000. It is more preferably 000 to 60,000, and even more preferably 6,000 to 40,000.

A commercially available product can be used as the dispersant. Commercially available products of dispersants, which are polymer compounds having an acid group, include, for example, DisperBYK-101 (acid value: 30 mgKOH / g, amine value: 0 mgKOH / g), DisperBYK-102 (acid value: 101 mgKOH / g, amine value). : 0 mgKOH / g), DisperBYK-103 (acid value: 101 mgKOH / g, amine value: 0 mgKOH / g), DisperBYK-110 (acid value: 53 mgKOH / g, amine value: 0 mgKOH / g), DisperBYK-111 (acid value) 129 mgKOH / g, amine value: 0 mgKOH / g), DisperBYK-170 (acid value: 11 mgKOH / g, amine value: 0 mgKOH / g), DisperBYK-190 (acid value: 10 mgKOH / g, amine value: 0 mgKOH / g) , DisperBYK-194N (acid value: 75 mgKOH / g, amine value: 0 mgKOH / g), DisperBYK-2015 (acid value: 10 mgKOH / g, amine value: 0 mgKOH / g), DisperBYK-2090 (acid value: 60 mgKOH / g, Amin value: 0 mgKOH / g), DisperBYK-2096 (acid value: 40 mgKOH / g, amine value: 0 mgKOH / g) (above, BYK Chemie); : 0 mgKOH / g), Solsperse 41000 (acid value: 50 mgKOH / g, amine value: 0 mgKOH / g), Solsperse 21000 (acid value: 72 mgKOH / g, amine value: 0 mgKOH / g), Solsperse 26000 (acid value: 50 mgKOH / g) g, amine value: 0 mgKOH / g), sol sparse 36600 (acid value: 23 mgKOH / g, amine value: 0 mgKOH / g), sol sparse 39000 (acid value: 33 mgKOH / g, amine value: 0 mgKOH / g), sol sparse 4100, sol sparse 41090 (acid value: 23 mgKOH / g, amine value: 0 mgKOH / g), Solsperth 43000 (acid value: 8 mgKOH / g, amine value: 0 mgKOH / g), Solsperth 44000 (acid value: 12 mgKOH / g, amine value: 0 mgKOH / g) g), Solsperse 46000, Solsperse 53095 (acid value: 47 mgKOH / g, amine value: 0 mgKOH / g), Solsperse 54000 (acid value: 47 mgKOH / g, amine value: 0 mgKOH / g)
(Solspers dispersant; above, manufactured by Zeneca); TEGO Dispers 610 (acid value: about 140 mgKOH / g, amine value: 0 mgKOH / g), TEGO Dispers 610S (acid value: about 120 mgKOH / g, amine value: 0 mgKOH / g). ), TEGO Dispers 630 (acid value: about 50 mgKOH / g, amine value: 0 mgKOH / g), TEGO Dispers 651 (acid value: about 1 mgKOH / g, amine value: 0 mgKOH / g), TEGO Dispers 655 (acid value: about). 100 mgKOH / g, amine value: 0 mgKOH / g), TEGO Dispers 750W (acid value: about 15 mgKOH / g, amine value: 0 mgKOH / g), TEGO Dispers 755W (acid value: about 15 mgKOH / g, amine value: 0 mgKOH / g) (Above, manufactured by Ebonic); Disparon DA-375 (acid value: 14 mgKOH / g, amine value: 0 mgKOH / g), Disparon DA-1200 (above, manufactured by Kusumoto Kasei Co., Ltd.); Floren WK-13E, Floren G- 700 (acid value: 60 mgKOH / g, amine value: 0 mgKOH / g), Floren G-900, Floren GW-1500 (acid value: 55 mgKOH / g, amine value: 0 mgKOH / g), Floren GW-1640 (acid value: 20 mgKOH / g, amine value: 0 mgKOH / g) (above, manufactured by Kyoei Chemical Industry Co., Ltd.); John Krill 611 (acid value: 53 mgKOH / g, amine value: 0 mgKOH / g, weight average molecular weight: 8100) (manufactured by BASF) Can be mentioned.
In addition, examples of the graft polymer include the above-mentioned DisperBYK-190 and Solsperth 44000.

Commercially available products of the dispersant, which is a polymer compound having an amine group, include, for example, DisperBYK-161 (acid value: 0 mgKOH / g, amine value: 11 mgKOH / g), DisperBYK-162 (acid value: 0 mgKOH / g, amine value). : 13 mgKOH / g), DisperBYK-163 (acid value: 0 mgKOH / g, amine value: 10 mgKOH / g), DisperBYK-164 (acid value: 0 mgKOH / g, amine value: 18 mgKOH / g), DisperBYK-166 (acid value) : 0 mgKOH / g, amine value: 20 mgKOH / g), DisperBYK-167 (acid value: 0 mgKOH / g, amine value: 13 mgKOH / g), DisperBYK-168 (acid value: 0 mgKOH / g, amine value: 10 mgKOH / g) , DisperBYK-182 (acid value: 0 mgKOH / g, amine value: 13 mgKOH / g) (all manufactured by BYK Chemie); EFKA 4046 (acid value: 0 mgKOH / g, amine value: 17 mgKOH / g-21 mgKOH / g), EFKA 4060 (acid value: 0 mgKOH / g, amine value: 6 mgKOH / g to 10 mgKOH / g), EFKA 4080 (acid value: 0 mgKOH / g, amine value: 3.6 mgKOH / g to 4.1 mgKOH / g), EFKA 4800 (Acid value: 0 mgKOH / g, amine value: 37 mgKOH / g to 43 mgKOH / g), EFKA 7462 (acid value: 0 mgKOH / g, amine value: 8 mgKOH / g) (all manufactured by Fuka Additive); (Solsperse dispersant), Solsperse 13940 (basic dispersant), Solsperse 28000 (basic dispersant), Solsperse 71000 (acid value: 0 mgKOH / g, amine value: 77.4 mgKOH / g), (Solsperse dispersant; above , Zeneca); Alkylamines such as butylamine, hexylamine, heptylamine, octylamine, decylamine, dodecylamine, octadecylamine, oleylamine; and having 5 or less carbon atoms such as 3-methoxypropylamine and 2-methoxyethylamine. Alkoxyamines can be mentioned.

As a commercially available product of a dispersant which is a polymer compound having an acid group and an amine group, for example, DisperBYK-106 (acid value: 132 mgKOH / g, amine value: 74 mgKOH / g).
(Manufactured by BYK Chemie); EFKA 4010 (acid value: 10 mgKOH / g to 15 mgKOH / g, amine value: 4 mgKOH / g to 8 mgKOH / g) (above, manufactured by Fuka Additive); Solsperse 24000 (acid value: 24 mgKOH /) g, amine value: 47 mgKOH / g), Solsperce 32000 (acid value: 15 mgKOH / g, amine value: 180 mgKOH / g) (Solspers dispersant; above, manufactured by Zeneca); Disparon DA-234 (acid value: 16 mgKOH / g) , Amin value: 20 mgKOH / g), Disparon DA-325 (acid value: 14 mgKOH / g, amine value: 20 mgKOH / g) (all manufactured by Kusumoto Kasei Co., Ltd.).
Examples of commercially available dispersants having an acid group and an amine group and having an acid value larger than the amine value include DisperBYK-106 and EFKA 4010 described above.

As the dispersant, one type may be used alone, or two or more types may be used in combination.

When the silver particle conductive layer contains a dispersant, the content of the dispersant is preferably 0.1% by mass to 7.0% by mass, preferably 0.2% by mass, based on the total amount of the silver particle conductive layer. It is more preferably% to 5.0% by mass.
When the etching solution contains a dispersant, the content of the dispersant is preferably 0.01% by mass to 1.0% by mass, and 0.05% by mass to 1.% by mass with respect to the total amount of the etching solution. It is more preferably 0% by mass, and even more preferably 0.1% by mass to 0.5% by mass.

(Dispersion aid)
The dispersion aid is not particularly limited, but is preferably a compound containing a hydroxy group from the viewpoint of more easily improving the LWR. Further, from the viewpoint of the reliability of the obtained conductive pattern (stability of the electric resistance value with time) and further improvement of the LWR, the dispersion aid is more preferably a polyglycerin compound. The mechanism by which the LWR is improved is not clear, but it is presumed that the surface-active effect of the polyglycerin compound also contributes to the improvement of the LWR. The scope of this disclosure is not limited by the above speculation.

The polyglycerin compound is not particularly limited as long as it has a polyglycerin skeleton (a structure in which a plurality of glycerin molecules are condensed). Examples of the polyglycerin compound include polyglycerin, polyglycerin ester, polyglycerin ether and the like.

Examples of the polyglycerin ester include compounds represented by the following formula (2).
R ¹ COO- (C ₃ H ₆ O ₂ ) _n -H (2)
[In the formula (2), R ¹ may have a linear or branched alkyl group having 8 to 22 carbon atoms which may have a hydroxy group, or may have a hydroxy group and has 8 carbon atoms. Represents ~ 22 linear or branched alkenyl groups. n is an integer from 1 to 20]

C ₃ H ₆ O ₂ in parentheses of the formula (2) has any of the structures represented by the following formulas (3) and (4).
-CH ₂ -CHOH-CH ₂ O- (3)
-CH (CH ₂ OH) CH ₂ O- (4)

In the formula (2), n indicates an average degree of polymerization and is 1 to 20. From the viewpoint of etching time and LWR, n is preferably 2 to 18, and more preferably 3 to 12. The average degree of polymerization can be calculated by obtaining the distribution of m by gas chromatography-mass spectrometry (GC-MS; Gas Chromatography Mass Spectrometry). For example, the average degree of polymerization may be measured by combining a heat desorption device "Model JTD-505III" manufactured by Nippon Analytical Industry Co., Ltd. and a gas chromatograph mass spectrometer "QP2010 Ultra" manufactured by Shimadzu Corporation.

As the linear alkyl group having 8 to 22 carbon atoms which may have a hydroxy group, for example, one or more hydrogen atoms of the following "linear alkyl group having 8 to 22 carbon atoms" is a hydroxy group. Can be mentioned as a group substituted with. Examples of the linear alkyl group having 8 to 22 carbon atoms include n-octyl group, n-nonyl group, n-decyl group, n-undecylic group, n-lauryl group, n-tridecylic group and n-tetradecyl group. , N-pentadecylic group, n-palmityl group, n-heptadecyl group, n-stearyl group, n-nonadecyl group, n-eicosyl group, n-heneicosyl group, n-docosyl group and the like. These can be used alone or in combination of two or more.

As the linear alkenyl group having 8 to 22 carbon atoms which may have a hydroxy group, for example, one or more hydrogen atoms of the following "linear alkenyl group having 8 to 22 carbon atoms" is a hydroxy group. Can be mentioned as a group substituted with. Examples of the linear alkenyl group having 8 to 22 carbon atoms include n-octenyl group, n-nonenyl group, n-decenyl group, n-undecenyl group, n-dodecenyl group, n-tridecenyl group and n-tetradecenyl group. , N-pentadecenyl group, n-hexadecenyl group, n-heptadecenyl group, n-oleyl group, n-nonadesenyl group, n-eicosenyl group, n-heneicosenyl group, n-docosenyl group and the like. These can be used alone or in combination of two or more.

As the branched chain alkyl group having 8 to 22 carbon atoms which may have a hydroxy group, for example, one or more hydrogen atoms of the following "branched chain alkyl group having 8 to 22 carbon atoms" are hydroxy groups. Can be mentioned as a group substituted with. Examples of the branched alkyl group having 8 to 22 carbon atoms include an isooctyl group, an s-octyl group, a t-octyl group, an isononyl group, an s-nonyl group, a t-nonyl group, an isodecyl group and an s-decyl group. t-decyl group, isoundecyl group, s-undecyl group, t-undecyl group, isolauryl group, s-lauryl group, t-lauryl group, isotridecylic group, s-tridecylic group, t-tridecylic group, isotetradecyl group, s -Tetradecyl group, t-tetradecyl group, isopentadecylic group, s-pentadecylic group, t-pentadecylic group, isopalmicyl group, 2-hexyldecyl group, s-palmityl group, t-palmicyl group, isoheptadecyl group, s-heptadecyl group. , T-heptadecyl group, isostearyl group, s-stearyl group, t-stearyl group, isononadecyl group, s-nonadecil group, t-nonadecyl group, 2-octyllauryl group, isoeicocil group, s-eicosyl group, t-eicosyl Examples thereof include a group, an isohen eikosyl group, an s-hen eikosyl group, a t-hen eikosyl group, an isodocosyl group, an s-docosyl group, a t-docosyl group and the like. These can be used alone or in combination of two or more.

As the branched chain alkenyl group having 8 to 22 carbon atoms which may have a hydroxy group, for example, one or more hydrogen atoms of the following "branched chain alkenyl group having 8 to 22 carbon atoms" is a hydroxy group. Can be mentioned as a group substituted with. Examples of the branched chain alkenyl group having 8 to 22 carbon atoms include an isooctenyl group, an s-octenyl group, a t-octenyl group, an isononenyl group, an s-nonenyl group, a t-nonenyl group, an isodecenyl group and an s-decenyl group. t-decenyl group, isoundecenyl group, s-undecenyl group, t-undodecenyl group, isododecenyl group, s-dodecenyl group, t-dodecenyl group, isotridecenyl group, s-tridecenyl group, t-tridecenyl group, isotetradecenyl group , S-tetradecenyl group, t-tetradecenyl group, isopentadecenyl group, s-pentadecenyl group, t-pentadecenyl group, isohexadecenyl group, s-hexadecenyl group, t-hexadecenyl group, isoheptadecenyl Group, s-heptadecenyl group, t-heptadecenyl group, isooleyl group, s-oleyl group, t-oleyl group, isononadecenyl group, s-nonadesenyl group, t-nonadesenyl group, isoeicosenyl group, s-eicosenyl group, t-eicosenyl group , Isoheneicosenyl group, s-heneicosenyl group, t-heneicosenyl group, isodocosenyl group, s-docosenyl group, t-docosenyl group and the like. These can be used alone or in combination of two or more.

Examples of the polyglycerin ester include polyglyceryl monostearate (eg, tetraglyceryl stearate, decaglyceryl stearate), polyglyceryl tristearate, polyglyceryl tetrastearate, polyglyceryl monooleate (eg, decaglyceryl oleate), and pentaoleic acid. Polyglyceryl, polyglyceryl monolaurate (eg, polyglyceryl laurate-10), polyglyceryl monocaprate, polyglyceryl polyricinoleate, polyglyceryl sesquistearate, polyglyceryl decaooleate, polyglyceryl sesquioleate, tetraglyceryl monooleate, hexaglyceryl monooleate , Decaglyceryl trioleate, tetraglyceryl monoisostearate, hexaglyceryl monoisostearate, decaglyceryl diisostearate and the like.

Examples of the polyglycerin ether include a compound represented by the following formula (5).
R ² O- (C ₃ H ₆ O ₂ ) _m -H (5)
[In the formula (5), R ² may have a linear or branched alkyl group having 8 to 22 carbon atoms which may have a hydroxy group, or may have a hydroxy group and has 8 carbon atoms. Represents ~ 22 linear or branched alkenyl groups. m is an integer from 1 to 20]

Examples of the polyglycerin ether represented by the formula (5) include (poly) glycerin monoalkyl ether and (poly) glycerin monoalkenyl ether.

C ₃ H ₆ O ₂ in parentheses of the formula (5) has any of the structures represented by the following formulas (3) and (4).
-CH ₂ -CHOH-CH ₂ O- (3)
-CH (CH ₂ OH) CH ₂ O- (4)

In the formula (5), m indicates an average degree of polymerization and is 1 to 20. From the viewpoint of etching time and LWR, m is preferably 2 to 18, and more preferably 3 to 12. The average degree of polymerization can be determined by the same method as described above for polyglycerin esters.

As the linear alkyl group having 8 to 22 carbon atoms which may have a hydroxy group, for example, one or more hydrogens of the above-mentioned "linear alkyl group having 8 to 22 carbon atoms" for polyglycerin ester. A group in which the atom is substituted with a hydroxy group can be mentioned.

As the linear alkenyl group having 8 to 22 carbon atoms which may have a hydroxy group, for example, one or more hydrogens of the above-mentioned "linear alkenyl group having 8 to 22 carbon atoms" for polyglycerin ester. A group in which an atom is substituted with a hydroxy group can be mentioned.

Examples of the branched alkyl group having 8 to 22 carbon atoms which may have a hydroxy group include one or more hydrogens of the above-mentioned “branched chain alkyl group having 8 to 22 carbon atoms” for polyglycerin ester. A group in which an atom is substituted with a hydroxy group can be mentioned.

As the branched chain alkenyl group having 8 to 22 carbon atoms which may have a hydroxy group, for example, one or more hydrogens of the above-mentioned “branched chain alkenyl group having 8 to 22 carbon atoms” for polyglycerin ester. A group in which an atom is substituted with a hydroxy group can be mentioned.

The weight average molecular weight of the dispersion aid is not particularly limited, and is, for example, preferably 300 to 3000, more preferably 300 to 2000, further preferably 300 to 1500, and 300 or more and less than 1000. Is most preferable.

Commercially available products can be used as the dispersion aid, and examples of the commercially available products include PGLE ML10 (polyglycerin ester: polyglyceryl laurate-10) and PGLAL (polyglycerin ether: polyglyceryl-4 lauryl ether) (hereinafter, Dicel). Poem J-4081V (Tetraglyceryl stearate), Poem J-0021 (Decaglyceryl laurate), Poem J-0081HV (Decaglyceryl stearate), Poem J-0381V (Decaglyceryl oleate), Poem PR -100 (polyglyceryl polylysinoleate), Poem PR-300 (polyglyceryl polylysinoleate) (all manufactured by RIKEN Vitamin Co., Ltd.) and the like can be mentioned.

As the dispersion aid, one type may be used alone, or two or more types may be used in combination.

When the silver particle conductive layer contains a dispersion aid, the content of the dispersion aid is preferably 0.1% by mass to 7.0% by mass, based on the total amount of the silver particle conductive layer. It is more preferably 2% by mass to 5.0% by mass.
When the etching solution contains a dispersion aid, the content of the dispersion aid is preferably 0.01% by mass to 1.0% by mass, preferably 0.05% by mass or more, based on the total amount of the etching solution. It is more preferably 1.0% by mass, and even more preferably 0.1% by mass to 0.5% by mass.

(Method of forming a silver-containing conductive layer)
The method for forming the silver-containing conductive layer will be described in detail later in the method for producing a conductive pattern according to the present disclosure.

<Manufacturing method of conductive pattern>
The etching solution according to the present disclosure can be suitably used for producing a conductive pattern obtained by etching a silver-containing conductive layer. The method for producing such a conductive pattern is not particularly limited, but the conductive pattern can be preferably produced by the method for producing a conductive pattern according to the present disclosure described below.

The method for manufacturing a conductive pattern according to the present disclosure is as follows.
A step of preparing a conductive material having a base material and a silver-containing conductive layer (hereinafter, may be referred to as a "conductive material preparation step").
A step of forming a photosensitive resin layer on the surface of the silver-containing conductive layer opposite to the side having the base material (hereinafter, may be referred to as a "photosensitive resin layer forming step").
A process of pattern-exposing a photosensitive resin layer (hereinafter, may be referred to as an "exposure process"),
The step of developing the pattern-exposed photosensitive resin layer (hereinafter, may be referred to as “development step”) and the content of nitrate ions are 16.0% by mass to 35. A step of etching a silver-containing conductive layer with an etching solution of 0% by mass (hereinafter, may be referred to as an "etching step").
including.

[Conductive material preparation process]
The conductive material preparation step is a step of preparing a conductive material having a base material and a silver-containing conductive layer.

(Base material)
The base material is not particularly limited, and the shape and material of the base material may be appropriately selected. For example, the base material may be a glass base material or a resin base material. When the base material is flexible, the base material is preferably a resin base material from the viewpoint of flexibility.

The base material may be referred to as an electrode pattern other than the silver-containing conductive layer (for example, an electrode pattern provided in the touch sensor) or another conductive layer (hereinafter, referred to as "another electrode pattern" or "another conductive layer"). Yes) may be preformed. Further, in the method for producing a conductive pattern according to the present disclosure, in addition to the silver-containing conductive layer, such other electrode patterns or other conductive layers may be etched. Examples of the material of other electrode patterns and other conductive layers include ITO (Indium Tin Oxide), silver nanowires, silver whose surface has been blackened, AZO (Aluminum dropped Zinc Oxide, ZnO: Al), and GZO (Gallium doubled Zinc). Oxide, ZnO: Ga) and the like can be mentioned.

Examples of the material of the resin base material include polycarbonate, ABS (Acrylonitril-Polyimide) resin, AS (Acrylonitril-Stylerene) resin, polypropylene, polyethylene, polyamide, polyacetal, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, and polyether. Examples thereof include ether ketone, polystyrene, polymethylmethacrylate, polyphenylene ether, polysulfone, polyether sulfone, polyamideimide, polyetherimide, polyimide, polyvinyl chloride, polycycloolefin and the like.

(Silver-containing conductive layer)
As the silver-containing conductive layer, those described above can be used.

The method for forming the silver-containing conductive layer is not particularly limited.
When forming a conductive layer made of silver or a conductive layer made of a silver alloy, for example, a film may be formed by a sputtering method.
The silver particle conductive layer may be formed, for example, by heating a dried product of a silver ink composition containing silver particles. Hereinafter, an embodiment of forming a silver particle conductive layer using a silver ink composition will be described.

(Silver ink composition)
The silver ink composition contains silver particles. The average particle size of the silver particles is not particularly limited, but is preferably 1 nm to 400 nm from the viewpoint of dispersibility. The average particle size is a volume-based median diameter (D50) measured by a dynamic light scattering method, and is a commercially available dynamic light scattering type particle size distribution measuring device (for example, "LB-550" manufactured by HORIBA, Ltd. " ) Can be used for measurement.
Further, the silver ink composition preferably contains at least one of a dispersant and a dispersant aid.
Other details of the silver particles, the dispersant and the dispersion aid are the same as those described above for the silver particle conductive layer, but for their content, "for the total amount of the silver particle conductive layer" is referred to as "silver". It shall be read as "relative to the total solid content of the ink composition".

The silver ink composition may contain other resin components, surfactants, thickeners, surface tension adjusters, rust preventives, solvents and the like as components other than silver particles, dispersants and dispersant aids. ..

Examples of the rust preventive agent include heterocyclic compounds (eg, imidazole compounds, benzoimidazole compounds, oxazole compounds, benzoxazole compounds, thiazole compounds) described in paragraphs [0061] to [0079] of JP-A-2020-91322. , And benzothiazole compounds).

The solvent is not particularly limited and may be appropriately selected in consideration of the types of silver particle treatment materials, dispersants, dispersion aids and the like, and may be water, an organic solvent, or a mixture thereof.

The organic solvent is not particularly limited, and for example, hexane, triethylamine, ethyl ether, n-octane, cyclohexane, n-amyl acetate, isobutyl acetate, methyl isopropyl ketone, amylbenzene, butyl acetate, carbon tetrachloride, ethylbenzene, p-xylene. , Toluene, methylpropylketone, ethyl acetate, tetrahydrofuran, methylethylketone, chloroform, acetone, dioxane, pyridine, isobutanol, n-butanol, nitroethane, isopropyl alcohol, m-cresol, acetonitrile, n-propanol, furfuryl alcohol, nitromethane, Ethanol, cresol, ethylene glycol, methanol, phenol, p-cresol, propyl acetate, isopropyl acetate, t-butanol, 1-pentanol, 2-pentanol, 4-methyl-2-pentanol, 3-methyl-1- Pentanol, 3-methyl-2-pentanol, 2-butanol, 1-hexanol, 2-hexanol 2-pentanone, 2-heptanone, 2- (2-ethoxyethoxy) ethyl acetate, -2-butoxyethyl acetate, acetate Examples thereof include 2- (2-butoxyethoxy) ethyl, -2-methoxyethyl acetate, 2-hexyloxyethanol, 2-methylpentane-2,4-diol, tetrahydronaphthalene, dihydroterpineol, 1,3-propanediol and the like. ..

As the solvent, one type may be used alone, or two or more types may be used in combination.

When the silver ink composition contains a solvent, the content of the solvent may be, for example, 30% by mass to 80% by mass with respect to the total amount of the silver ink composition.

As the silver ink composition, a commercially available product can be used, and a commercially available product containing at least one of a dispersant and a dispersion aid may be used. Examples of commercially available silver ink compositions include "Flow Metal SR7500", "Flow Metal SR7000", and "Flow Metal SR6000" manufactured by Bando Chemical Industries, Ltd. Further, as the silver ink composition, one prepared by containing at least one of a dispersant and a dispersion aid in a commercially available product may be used.

The method for producing the silver ink composition is not particularly limited, and the silver ink composition may be produced by mixing the above-mentioned components.

(Giving silver ink composition)
The method of applying the silver ink composition to the substrate is not particularly limited, and examples thereof include a bar coater method, a doctor blade method, a spray coating method, a screen printing method, and an inkjet method. The number of grants may be once or may be multiple. The imparting portion may be the entire surface of the base material, or may be a part of the surface of the base material on which the conductive pattern is formed.

The suitable thickness of the silver ink film formed by applying the silver ink composition depends on the application method and the total solid content of the silver ink composition, but is preferably 0.1 μm to 20 μm, for example, 0. More preferably, it is 2 μm to 10 μm. As a result, it is possible to more easily form a conductive pattern that is difficult to peel off when the base material is curved, and while suppressing erosion in the width direction of the electrode pattern, etching proceeds in the thickness direction thereof. Will be easier. Further, it becomes easier to impart a desired resistance value to the conductive pattern. The thickness of the silver ink film can be measured by, for example, a stylus type step meter, a three-dimensional surface structure analysis microscope, or the like. As a commercially available stylus type step meter, for example, "SURFACE PROFILER P-10" manufactured by KLA-TENCOR can be mentioned, and as a commercially available three-dimensional surface structure analysis microscope, for example, "New View 5022" manufactured by ZYGO Corporation. ".

The silver ink film formed by applying the silver ink composition may be dried, if necessary. The drying conditions are not particularly limited, and may be appropriately adjusted in consideration of the type of the base material and the like. The drying temperature may be, for example, 50 ° C to 150 ° C. The dry atmosphere may be, for example, air, generally air.

(Heat treatment)
By applying the silver ink film heat treatment, the silver particles are sintered to obtain a silver particle conductive layer. When the silver ink composition contains a dispersion component (meaning "at least one of a dispersant and a dispersion aid"), at least a part of the dispersion component remains in the porous structural portion of the obtained silver particle conductive layer.

The heating conditions are not particularly limited. As the heating furnace, various types can be used, and examples thereof include a batch type heating furnace, a roller type heating furnace, a belt type heating furnace, and the like. Above all, a belt-type heating furnace capable of continuously heating is preferable in terms of productivity. The heating temperature is preferably 100 ° C to 130 ° C, more preferably 110 ° C to 120 ° C. The heating time is not particularly limited as long as it is a time from short-time heating to long-time heating, as long as the silver ink film becomes a conductive silver particle conductive layer, but from the viewpoint of heat resistance of the base material, short-time heating is possible. preferable. The heating atmosphere is not particularly limited, and may be in air, in a non-oxidizing atmosphere, in a reducing atmosphere, in a vacuum, or the like. The non-oxidizing atmosphere is an atmosphere containing no oxygen, for example, any gas such as argon, helium, nitrogen, etc., or a mixed gas atmosphere containing a plurality of these gases. Further, a reducing gas, for example, hydrogen gas or the like may be mixed with the gas having a non-oxidizing atmosphere to obtain a reducing atmosphere.

[Photosensitive resin layer forming process]
The photosensitive resin layer forming step is a step of forming the photosensitive resin layer on the surface of the silver-containing conductive layer opposite to the side having the base material. The method for forming the photosensitive resin layer is not particularly limited, and for example, a method of applying the photosensitive resin composition onto the silver-containing conductive layer, or a method of bonding a photosensitive transfer member containing the photosensitive resin layer to the silver-containing conductive layer. The method and the like can be mentioned. The former may be applied, for example, by coating or the like, and the same application method as described above for the silver ink composition may be used. Hereinafter, the step of forming the photosensitive resin layer will be specifically described by taking as an example a method using a photosensitive transfer member.

(Photosensitive transfer member)
Examples of the photosensitive transfer member include a temporary support, an intermediate layer, and a photosensitive resin layer in this order. The intermediate layer means all layers between the temporary support and the photosensitive resin layer, and may have at least a thermoplastic resin layer. The thickness of each layer is not particularly limited, and the thickness of the photosensitive resin layer may be, for example, less than 5 μm, and the total thickness of the temporary support and the intermediate layer may be, for example, 35 μm or less. ..

-Temporary support-
The temporary support is a removable support, and when the photosensitive resin layer is exposed to a pattern, it is preferable to have light transmission from the viewpoint that the photosensitive resin layer can be exposed via the temporary support.
Having light transmittance means that the transmittance of the main wavelength of the light used for the pattern exposure is 50% or more, and the transmittance of the main wavelength of the light used for the pattern exposure is from the viewpoint of improving the exposure sensitivity. Therefore, 60% or more is preferable, and 70% or more is more preferable. Examples of the method for measuring the transmittance include a method of measuring using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
Examples of the temporary support include a glass substrate, a resin film, paper, and the like, and a resin film is particularly preferable from the viewpoint of strength, flexibility, and the like. Examples of the resin film include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, polycarbonate film, polyimide film and the like. Of these, a biaxially stretched polyethylene terephthalate film is particularly preferable.

The thickness of the temporary support is preferably 25 μm or less, and more preferably 20 μm or less, for the reason that the resolution of the photosensitive transfer member is further improved. As the lower limit, from the viewpoint of transportability and supportability, 5 μm or more is preferable, and 10 μm or more is more preferable.
The thickness of the temporary support can be measured by the following method.
In the cross-sectional observation image in the thickness direction of the temporary support, the arithmetic mean value of the thickness of the temporary support measured at 10 randomly selected points is obtained, and the obtained value is taken as the thickness of the temporary support. A cross-sectional observation image of the temporary support in the thickness direction can be obtained by using a scanning electron microscope (SEM).

The haze of the temporary support is preferably 0.5 or less, more preferably 0.4 or less, and more preferably 0.3 or less, for the reason that the resolution of the photosensitive transfer member is further improved. Is even more preferable. The lower limit is not particularly limited, but may be more than 0.0.
The haze of the temporary support can be measured as a total light haze using a haze meter (device name: NDH2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.).

The temporary support preferably has a particle-containing layer on the surface opposite to the intermediate layer. The average particle size of the particles contained in the particle-containing layer is preferably 30 nm to 600 nm, more preferably 30 nm to 200 nm, and even more preferably 40 nm to 100 nm. When the average particle size of the particles contained in the particle-containing layer is 30 nm or more, the laminating property of the photosensitive transfer member at high speed is further improved, and the average particle size of the particles contained in the particle-containing layer is 600 nm or less. , The resolution of the photosensitive transfer member is more excellent.

The average particle size of the particles contained in the particle-containing layer can be measured by the following method.
In the cross-sectional observation image in the thickness direction of the temporary support, the layer containing particles is specified as the particle-containing layer.
Next, using a transmission electron microscope (TEM; Transmission Electron Microscope), arbitrary 5 points of the cross section of the particle-containing layer are photographed under the conditions of a magnification of 20000 times and an acceleration voltage of 100 kV, and cross-sectional photographs are obtained. The diameters of all the particles in the obtained cross-sectional photograph are measured, the average value (arithmetic mean particle size) is obtained, and the average particle size of the particles is used. Obviously large aggregates (foreign matter, dust, etc.) are not counted.

Examples of the particles contained in the particle-containing layer include inorganic particles and organic particles.
Examples of the inorganic particles include silicon oxide (silica) particles, titanium oxide (titania) particles, zirconium oxide (zirconia) particles, magnesium oxide (magnesia) particles, aluminum oxide (alumina) particles, and the like, among which silica particles are used. Is particularly preferable.
Examples of the organic particles include acrylic resin particles, polyester particles, polyurethane particles, polycarbonate particles, polyolefin particles, polystyrene particles and the like.

The particle-containing layer may contain one kind of particles alone or two or more kinds of particles.
The content of the particles in the particle-containing layer is preferably 0.01% by mass to 20% by mass, preferably 0.1% by mass, from the viewpoint of easy control of surface roughness and suppression of wrinkle generation during transportation. It is more preferably to 10% by mass, and particularly preferably 0.5% by mass to 5% by mass.
Further, the particles in the particle-containing layer may be present inside the particle-containing layer or may be partially exposed on the surface of the particle-containing layer. For example, when the particle-containing layer is provided on the surface of the temporary support opposite to the intermediate layer, the particles may be exposed on the surface of the temporary support on the opposite side.

The material other than the particles contained in the particle-containing layer is not particularly limited, and may include, for example, the same material as the material of the temporary support described above. The particle-containing layer preferably contains a resin, and particularly preferably an acrylic resin. The particle-containing layer may contain one kind of resin alone or two or more kinds of resin.

The thickness of the particle-containing layer is preferably 5 nm to 300 nm, more preferably 10 nm to 100 nm, and particularly preferably 30 nm to 70 nm, because the resolution of the photosensitive transfer member and the laminating property at high speed are further improved. The particle-containing layer may be one layer or two layers. When the number of particle-containing layers is two or more, the preferable thickness of the particle-containing layer is a preferable thickness for each particle-containing layer.
The thickness of the particle-containing layer can be measured by the same method as the thickness of the temporary support described above.

Examples of commercially available products of the temporary support having a particle-containing layer include Lumirer (registered trademark, the same applies hereinafter) 12QS62, Lumirer 16KS40, 16FB40 (all manufactured by Toray Industries, Inc.) and the like.

Further, it is preferable that the film used as the temporary support does not have any deformation such as wrinkles or scratches.
From the viewpoint of pattern formation during pattern exposure via the temporary support and transparency of the temporary support, it is preferable that the number of fine particles, foreign substances and defects contained in the temporary support is small. The number of fine particles, foreign matter and defects having a diameter of 1 μm or more is preferably 50 pieces / 10 mm ² or less, more preferably 10 pieces / 10 mm ² or less, and further preferably 3 pieces / 10 mm ² or less. , 0 pieces / 10 mm ² is particularly preferable.

Preferred embodiments of the provisional support include, for example, paragraphs [0017] to paragraph [0018] of JP-A-2014-85643, paragraphs [0019] to paragraph [0026] of JP-A-2016-27363, and International Publication No. 1. It is described in paragraphs [0041] to [0057] of 2012/081680 and paragraphs [0029] to [0040] of International Publication No. 2018/179370, and the contents of these publications are incorporated in the present specification.

-Middle layer-
The photosensitive transfer member may have an intermediate layer between the temporary support and the photosensitive resin layer.
The thickness of the intermediate layer is preferably set so that the total thickness of the temporary support and the intermediate layer is 35 μm or less, and the photosensitive transfer member has excellent developing speed and resolution. For the reason of further improvement, 20 μm or less is preferable, 15 μm or less is more preferable, and 10 μm or less is further preferable. As the lower limit, 2 μm or more is preferable, and 4 μm or more is more preferable, because the photosensitive transfer member has better laminating property at high speed.

The total thickness of the temporary support and the intermediate layer may be 35 μm or less, preferably 34 μm or less, and more preferably 32 μm or less. The lower limit is preferably 10 μm or more because the laminating property of the photosensitive transfer member at high speed is further improved.

The ratio (thickness) of the total thickness of the temporary support and the intermediate layer (hereinafter, abbreviated as "thickness B") to the thickness of the photosensitive resin layer (hereinafter, abbreviated as "thickness A") described later. The B / thickness A) is preferably 6.0 to 12.0, and more preferably 7.0 to 11.5, for the reason that the resolution of the photosensitive transfer member is further improved. It is preferably 8.0 to 10.5, and more preferably 8.0 to 10.5.
The thickness of the intermediate layer and the photosensitive resin layer can be measured by the same method as the thickness of the temporary support described above.

－－Thermoplastic resin layer －－
The intermediate layer preferably has at least a thermoplastic resin layer.
The thermoplastic resin layer preferably does not have photosensitivity, and preferably does not have a photopolymerization initiator.

The thermoplastic resin layer preferably has a thermoplastic resin.
The thermoplastic resin is not particularly limited as long as it is a resin that is plasticized by heat, but for example, acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinylformal, polyamide resin, polyester resin, polyamide. Examples thereof include resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols. Above all, from the viewpoint of developability and transferability, the thermoplastic resin is preferably an acrylic resin.
Here, the acrylic resin is selected from the group consisting of a structural unit formed of (meth) acrylic acid, a structural unit formed of (meth) acrylic acid ester, and a structural unit formed of (meth) acrylic acid amide. It refers to a resin having at least one structural unit, and the content of the structural unit is preferably 50% by mass or more with respect to the total amount of the resin.

The thermoplastic resin preferably contains a polymer having an acid group because the development speed is good.
Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group and the like, and among them, the carboxy group is preferably used.
The polymer having an acid group as a thermoplastic resin is preferably an acrylic resin having an acid value of 60 mgKOH / g or more, and a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more, for the reason that the development speed is good. More preferred.
The carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited, and can be appropriately selected from known resins and used. For example, among the polymers described in paragraph [0025] of JP-A-2011-95716, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more, paragraphs [0033] to paragraphs [0052] of JP-A-2010-237589. ], Acrylic resin containing a carboxy group having an acid value of 60 mgKOH / g or more among the polymers described in Japanese Patent Application Laid-Open No. 2016-224162, and an acid value of 60 mgKOH / among the binder polymers described in paragraphs [0053] to [0068]. Acrylic resins containing g or more of carboxy groups are preferably used.
The copolymerization ratio of the monomer having a carboxy group in the carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, and preferably 10% by mass to 40% by mass, based on the total amount of the acrylic resin. It is more preferably 12% by mass to 30% by mass.

The acid value of the thermoplastic resin is preferably 60 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 180 mgKOH / g, from the viewpoint of alkali developability.

The weight average molecular weight of the thermoplastic resin is preferably 2,000 or more, more preferably 10,000 to 100,000, and even more preferably 20,000 to 70,000.

The thermoplastic resin layer may contain one type of thermoplastic resin alone or may contain two or more types of thermoplastic resin.
The content of the thermoplastic resin is preferably 10% by mass to 99% by mass, preferably 20% by mass, based on the total amount of the thermoplastic resin layer, from the viewpoint of further improving the resolution and the laminating property at high speed. It is more preferably to 90% by mass, and even more preferably 30% by mass to 80% by mass.

The glass transition temperature (Tg) of the thermoplastic resin contained in the thermoplastic resin layer is preferably 100 ° C. or lower because the photosensitive transfer member is more excellent in laminating property at high speed.
The method for measuring the glass transition temperature is as follows.
The specific measurement method was carried out according to the method described in JIS K 7121 (1987). As the glass transition temperature, the extrapolated glass transition start temperature (hereinafter, may be referred to as Tig) is used.
The method for measuring the glass transition temperature will be described more specifically.
When determining the glass transition temperature, after holding the device at a temperature about 50 ° C. lower than the expected Tg of the polymer until the apparatus stabilizes, the heating rate is 20 ° C./min, which is about 30 ° C. than the temperature at which the glass transition is completed. The temperature is heated to a high temperature, and a DTA (Differential Thermal Analysis) curve or a DSC (Differential Scanning Calimorimetry) curve is drawn.
The extra glass transition start temperature (Tig), that is, the glass transition temperature Tg in the present specification is a straight line extending the baseline on the low temperature side of the DTA curve or the DSC curve to the high temperature side, and the stepwise change portion of the glass transition. It is calculated as the temperature at the intersection with the tangent line drawn at the point where the slope of the curve becomes maximum. A differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Inc.) was used as the analyzer.
The lower limit of the glass transition temperature of the thermoplastic resin is preferably 40 ° C. or higher because it suppresses a phenomenon in which the resin composition exudes from the end face of the roll when it is wound into a roll and stored, that is, so-called edge fusion.

The thermoplastic resin layer preferably has a plasticizer because the photosensitive transfer member is more excellent in laminating property at high speed.
The plasticizer preferably has a smaller molecular weight or weight average molecular weight than the thermoplastic resin.
The molecular weight of the plasticizer is preferably 200 to 2,000.
The plasticizer is not particularly limited as long as it is a compound that is compatible with the thermoplastic resin and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and is a polyalkylene glycol. More preferably, it is a compound. The alkylene oxy group contained in the plasticizer is more preferably a polyethylene oxy structure or a polypropylene oxy structure.

The plasticizer preferably contains a (meth) acrylate compound, and the thermoplastic resin is an acrylic resin and the plasticizer is plastic from the viewpoint of compatibility, resolution and adhesion to a substrate. It is more preferable that the agent contains a (meth) acrylate compound.
As the (meth) acrylate compound used as the plasticizing agent, a (meth) acrylate compound contained in the polymerizable compound in the photosensitive resin layer described later is preferably mentioned, and has a polyfunctional (meth) acrylate compound and an acid group ( A meta) acrylate compound, a urethane (meth) acrylate compound and the like can also be preferably used.
In particular, from the viewpoint of storage stability, it is preferable that both the thermoplastic resin layer and the photosensitive resin layer contain the same (meth) acrylate compound. By containing the same (meth) acrylate compound in both the thermoplastic resin layer and the photosensitive resin layer, diffusion of components between layers is suppressed and storage stability is improved.
When the (meth) acrylate compound is contained as the plasticizer, it is preferable that the (meth) acrylate compound does not polymerize in the thermoplastic resin layer even in the exposed portion after exposure from the viewpoint of resolution.

The thermoplastic resin layer may contain one type of plasticizer alone, or may contain two or more types of plasticizer.
When the thermoplastic resin layer contains a plasticizer, the content of the plasticizer is 1% by mass to 70% by mass with respect to the total amount of the thermoplastic resin layer because the photosensitive transfer member is more excellent in laminating property at high speed. %, More preferably 5% by mass to 50% by mass.

In addition to the thermoplastic resin and the plasticizer, the thermoplastic resin layer includes an acid-reactive dye or a base-reactive dye (hereinafter abbreviated as “dye B”), a photoacid generator or a photobase generator, a surfactant, and the like. It may have other components such as a sensitizer, a polymerization inhibitor, and a rust preventive.

(Dye B)
The thermoplastic resin layer preferably has an acid-reactive dye or a base-reactive dye (dye B). The dye B represents a dye whose maximum absorption wavelength changes depending on an acid or a base. The dye B preferably has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development.
Here, the phrase "the maximum absorption wavelength changes depending on the acid or base" means that the dye in the color-developing state is decolorized from the acid or base, and the dye in the decolorized state is colored by the acid or base. It may refer to any aspect of a mode in which a dye in a color-developing state is changed to a color-developing state of another hue by an acid or a base.
From the viewpoint of visibility and resolution of the exposed and non-exposed areas, the dye B is preferably a dye whose maximum absorption wavelength is changed by an acid, and the dye B is a dye whose maximum absorption wavelength is changed by an acid. Moreover, it is particularly preferable to use a photoacid generator described later in combination.

As an example of the color-developing mechanism of the dye B, an acid-reactive dye is obtained by adding a photoacid generator or a photobase generator to the thermoplastic resin layer, and using an acid or a base generated from the photoacid generator or the like after exposure. Alternatively, an embodiment in which a base-reactive dye (for example, a leuco dye) develops a color can be mentioned.

The method for measuring the maximum absorption wavelength is to measure the transmission spectrum in the range of 400 nm to 780 nm using a spectrophotometer (device name: UV3100, manufactured by Shimadzu Corporation) at 25 ° C in an atmospheric atmosphere. The wavelength at which the intensity becomes the minimum (maximum absorption wavelength) shall be measured.

Examples of the dye B include leuco compounds, diarylmethane dyes, oxadin dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, anthraquinone dyes and the like, and the visibility of the exposed part and the non-exposed part is improved. From the viewpoint, leuco compounds are preferable.
Preferred embodiments of the dye B include the same as those of the specific latent dye described in paragraphs [0023] to [0039] of International Publication No. 2019/022089.
Specific examples of Dye B include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuxin, Methyl Violet 2B, Kinaldine Red, Rose Bengal, Metanyl Yellow, Timor Sulfophthalein, Xylenol Blue, Methyl Orange, and Para. Methyl Red, Congofred, Benzopurpurin 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malakite Green, Parafuxin, Victoria Pure Blue-Naphthalene Sulfate, Victoria Pure Blue BOH (Hodoya Chemical Industry) Oil Blue # 603 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Pink # 312 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industry Co., Ltd.), Oil Scarlet # 308 (manufactured by Orient Chemical Industry Co., Ltd.) , Oil Red OG (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green # 502 (manufactured by Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (manufactured by Hodoya Chemical Industry Co., Ltd.), m-cresol Purple, Cresol Red, Rhodamine B, Rhodamine 6G, Sulfonrodamine B, Auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p -N, N-bis (hydroxyethyl) amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, 1-β-naphthyl-4-p-diethylaminophenylimino- Examples thereof include dyes such as 5-pyrazolone and leuco compounds such as p, p', p "-hexamethyltriaminotriphenylmethane (leucocrystal violet) and Pergascript Blue SRB (manufactured by Ciba Geigy).

The dye B may be used alone or in combination of two or more.
When the thermoplastic resin layer contains the dye B, the content of the dye B shall be 0.01% by mass or more with respect to the total amount of the thermoplastic resin layer from the viewpoint of visibility of the exposed portion and the non-exposed portion. Is preferable, and 0.02% by mass to 6% by mass is more preferable.

(Photoacid generator or photobase generator)
The thermoplastic resin layer preferably contains a photoacid generator or a photobase generator in combination with the dye B for the reason of improving the visibility of the exposed portion and the non-exposed portion. A more preferred embodiment is an embodiment comprising an acid-reactive dye and a photoacid generator.

The photoacid generator or photobase generator is a compound capable of generating an acid or a base by irradiating with active rays such as ultraviolet rays, far ultraviolet rays, X-rays, and electron beams.
The photoacid generator or photobase generator is preferably a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 nm to 450 nm and generates an acid or a base, but its chemical structure is not limited. Further, a photoacid generator or a photobase generator that is not directly sensitive to active rays having a wavelength of 300 nm or more is also a compound that is sensitive to active rays having a wavelength of 300 nm or more and generates an acid or a base when used in combination with a sensitizer. If there is, it can be preferably used in combination with a sensitizer.

Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.
Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. Of these, onium salt compounds are preferable, and triarylsulfonium salts and diaryliodonium salts are particularly preferable.
As the ionic photoacid generator, the ionic photoacid generator described in paragraphs [0114] to [0133] of JP-A-2014-85643 can also be preferably used.
Examples of the nonionic photoacid generator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, oxime sulfonate compounds and the like. Specific examples of the trichloromethyl-s-triazines, the diazomethane compound and the imide sulfonate compound include the compounds described in paragraphs [0083] to [0088] of JP-A-2011-22149.
Among these, from the viewpoint of sensitivity, resolution, and adhesion, the photoacid generator is preferably an oxime sulfonate compound.

As the oxime sulfonate compound, those described in paragraphs [0084] to [0088] of International Publication No. 2018/179640 can be preferably used.

As the thermoplastic resin layer, one type of photoacid generator or photobase generator may be used alone, or two or more types may be used.

(Surfactant)
The thermoplastic resin layer preferably contains a surfactant from the viewpoint of thickness uniformity. The details of the surfactant are the same as those described later for the photosensitive resin layer, but the content thereof is "relative to the total amount of the photosensitive resin layer" and "relative to the total amount of the thermoplastic resin layer". It shall be read as.

Further, the thermoplastic resin layer may contain other additives other than those described above. The other additives are not particularly limited, and known additives can be used.
Further, for a preferred embodiment of the thermoplastic resin layer, paragraphs [0189] to [0193] of JP-A-2014-85643 can also be referred to.

The thickness of the thermoplastic resin layer is preferably 18 μm or less, more preferably 15 μm or less, and more preferably 10 μm or less, because the developing speed of the photosensitive transfer member is excellent and the resolution is further improved. It is more preferably present, and particularly preferably 6 μm or less. If the thermoplastic resin layer is too thick, it takes a long time to develop, so that a residue remains between the formed patterns and the resolution may be deteriorated. The lower limit is preferably 0.5 μm or more because the photosensitive transfer member is more excellent in laminating property at high speed.
The thickness of the thermoplastic resin layer can be measured by the same method as the thickness of the temporary support described above.

At 70 ° C., the viscosity of the thermoplastic resin layer is preferably lower than the viscosity of the photosensitive resin layer described above. When the viscosity of the thermoplastic resin layer is lower than the viscosity of the photosensitive resin layer at 70 ° C., the thermoplastic resin layer is deformed without being deformed and can follow the substrate, so that the resolution is high. And the laminating property at high speed is more excellent.
For the viscosity of the thermoplastic resin layer at 70 ° C. and the viscosity of the photosensitive resin layer described later, values measured by the following method using a rheometer are adopted.
First, the thermoplastic resin layer or the photosensitive resin layer is taken out as a sample from the photosensitive transfer member.
Next, the sample is placed on the Pelche plate, and the Gap of the 20 mmf parallel plate and the Pelche plate is set to 0.25 to 0.40 mm. After the sample is melted or softened at 90 ° C ± 5 ° C, it is cooled to 50 ° C at a temperature lowering rate of 5 ° C / min, and in Gap constant mode, the temperature is 50 to 100 ° C, the temperature rise rate is 5 ° C / min, the frequency is 1 Hz, and the strain is distorted. The temperature of the sample is raised under the condition of 0.5%, and the viscosity is measured.
The ratio (viscosity A / viscosity C) of the viscosity of the thermoplastic resin layer (hereinafter abbreviated as "viscosity C") to the viscosity of the photosensitive resin layer (hereinafter abbreviated as "viscosity A") is preferably 1 or more. 1 to 10 is more preferable, and 1 to 5 is even more preferable.

－－Water-soluble resin layer －－
The intermediate layer preferably has a water-soluble resin layer, and is between the thermoplastic resin layer and the photosensitive resin layer for the reason of suppressing mixing between the thermoplastic resin layer and the photosensitive resin layer. It is more preferable to have a water-soluble resin layer.

The water-soluble resin layer preferably contains a water-soluble resin.
Here, the term "water-soluble" means that the solubility in 100 g of water having a pH of 7.0 at 22 ° C. is 0.1 g or more.
Examples of the water-soluble resin include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and resins such as copolymers thereof. Can be configured using.
From the viewpoint of suppressing the mixing of the components of the thermoplastic resin layer and the water-soluble resin layer described later when producing the photosensitive transfer member, the water-soluble resin is a thermoplastic resin contained in the thermoplastic resin layer. It is preferably a different resin.
Among them, the water-soluble resin preferably contains polyvinyl alcohol, and particularly preferably polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoint of oxygen blocking property and suppressing component mixing with the adjacent layer.
The water-soluble resin layer may contain the above-mentioned resin alone or in combination of two or more.

The content of the water-soluble resin in the water-soluble resin layer is not particularly limited, but is 60% by mass or more with respect to the total amount of the water-soluble resin layer from the viewpoint of oxygen blocking property and suppressing component mixing with the adjacent layer. It is preferably 100% by mass, more preferably 80% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass.
Additives such as a surfactant may be added to the water-soluble resin layer, if necessary.

The thickness of the water-soluble resin layer is preferably set so that the total thickness of the temporary support and the intermediate layer is 35 μm or less, and the laminating property at high speed is further improved. It is preferably 5 μm or less, more preferably 3 μm or less. The lower limit is not particularly limited, but is preferably 0.1 μm or more.
The thickness of the water-soluble resin layer can be measured by the same method as the thickness of the temporary support described above.

-Photosensitive resin layer-
The photosensitive transfer member has a photosensitive resin layer.
The thickness of the photosensitive resin layer is preferably less than 5 μm, preferably 4 μm or less, and more preferably 3 μm or less, because the developing speed of the photosensitive transfer member is excellent and the resolution is further improved. The lower limit is not particularly limited, but may be 0.1 μm or more.

The photosensitive resin layer is not particularly limited, and a known photosensitive resin layer can be used, but a negative photosensitive resin layer is preferable because the laminating property at high speed is more excellent.
Here, the negative type photosensitive resin layer refers to a photosensitive resin layer whose solubility in a developing solution is reduced by exposure.

From the viewpoint of pattern formability, the photosensitive resin layer preferably has a polymerizable compound, a polymer having an acid group, and a photopolymerization initiator.
Examples of the photosensitive resin layer include a photosensitive resin layer made of the photosensitive resin composition (1) described in JP-A-2016-224162 and / or a photosensitive resin layer made of the photosensitive resin composition (2). You may use it.

－－Polymerizable compound －－
The photosensitive resin layer preferably contains a polymerizable compound.
The polymerizable compound is a component that contributes to the photosensitivity (that is, photocurability) of the negative photosensitive resin layer and the strength of the cured film.
As the polymerizable compound, an ethylenically unsaturated compound is preferable, and a bifunctional or higher functional ethylenically unsaturated compound is more preferable.
Here, the ethylenically unsaturated compound is a compound having one or more ethylenically unsaturated groups, and the bifunctional or more functional ethylenically unsaturated compound has two ethylenically unsaturated groups in one molecule. It means the compound having the above.
As the ethylenically unsaturated group, a (meth) acryloyl group is more preferable.
As the ethylenically unsaturated compound, a (meth) acrylate compound is preferable.

The bifunctional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds. Specifically, tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), tricyclodecanedimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,9-nonanediol di. Examples thereof include acrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and the like.
Further, as the bifunctional ethylenically unsaturated compound, a bifunctional ethylenically unsaturated compound having a bisphenol structure is also preferably used.
Examples of the bifunctional ethylenically unsaturated compound having a bisphenol structure include the compounds described in paragraphs [0072] to [0080] of JP-A-2016-224162.
Specific examples thereof include alkylene oxide-modified bisphenol A di (meth) acrylate, such as 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane and 2,2-bis (4- (methacryloxyethoxy) ethoxy). Preferable examples thereof include dimethacrylate (BPE-500, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), which is a polyethylene glycol in which an average of 5 mol of ethylene oxide is added to both ends of propoxy) phenyl) propane and bisphenol A.

The trifunctional or higher functional ethylenically unsaturated compound is not particularly limited and may be appropriately selected from known compounds. For example, dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, dimethylolpropane tetra (meth) acrylate, isocyanul. Examples thereof include acid (meth) acrylate and (meth) acrylate compounds having a glycerintri (meth) acrylate skeleton.

Here, "(tri / tetra / penta / hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. , "(Tri / tetra) (meth) acrylate" is a concept that includes tri (meth) acrylate and tetra (meth) acrylate.

Examples of the ethylenically unsaturated compound include caprolactone-modified (meth) acrylate compound (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), alkylene oxide-modified (meth). Acrylic compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex Co., Ltd.), ethoxylated glycerin triacrylate (New Nakamura Chemical Co., Ltd.) A-GLY-9E manufactured by Kogyo Co., Ltd.), Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix M-520 (manufactured by Toagosei Co., Ltd.), Aronix M-270 (manufactured by Toagosei Co., Ltd.), or Aronix M-510 (manufactured by Toagosei Co., Ltd.) and the like can be mentioned.
As the ethylenically unsaturated compound, a urethane (meth) acrylate compound (preferably a trifunctional or higher functional urethane (meth) acrylate compound) can also be used, and for example, 8UX-015A (manufactured by Taisei Fine Chemical Industry Co., Ltd.), UA-32P ( Examples thereof include Shin-Nakamura Chemical Industry Co., Ltd.) and UA-1100H (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
Further, as the ethylenically unsaturated compound, the polymerizable compound having an acid group described in paragraphs [0025] to [0030] of JP-A-2004-239942 may be used.

The weight average molecular weight (Mw) of the polymerizable compound is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

The polymerizable compound may be used alone or in combination of two or more.
When the photosensitive resin layer contains a polymerizable compound, the content of the polymerizable compound is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, based on the total amount of the photosensitive resin layer. , 20% by mass to 50% by mass is more preferable.

--Polymer having an acid group ---
The photosensitive resin layer preferably contains a polymer having an acid group.
Preferred forms of the polymer having an acid group contained in the photosensitive resin layer include the same polymers having an acid group exemplified as the thermoplastic resin having the above-mentioned thermoplastic resin layer.

The photosensitive resin layer may contain one kind of polymer having an acid group alone, or may contain two or more kinds of polymers.
When the photosensitive resin layer contains a polymer having an acid group, the content of the polymer having an acid group is 10% by mass to 90% by mass with respect to the total amount of the photosensitive resin layer from the viewpoint of photosensitive. It is preferably 20% by mass to 80% by mass, more preferably 30% by mass to 70% by mass.

－－Photopolymerization initiator －－
The photosensitive resin layer preferably contains a photopolymerization initiator.
The photopolymerization initiator receives active rays such as ultraviolet rays and visible rays to initiate the polymerization of the polymerizable compound.
The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferable.
Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, and an acylphosphine oxide. Examples thereof include a photopolymerization initiator having a structure and a photopolymerization initiator having an N-phenylglycine structure.

Further, as the photopolymerization initiator in the photosensitive resin layer, at least one selected from the group consisting of 2,4,5-triarylimidazole dimer and its derivative is selected from the viewpoint of photosensitivity and resolvability. It is preferable to include it.

Further, as the photopolymerization initiator, for example, it is described in paragraphs [0031] to [0042] of JP-A-2011-95716 and paragraphs [0064-paragraphs [0081] of JP-A-2015-014783. A polymerization initiator may be used.

Examples of commercially available photopolymerization initiators include 1- [4- (phenylthio)] -1,2-octanedione-2- (O-benzoyloxime) [trade name: IRGACURE (registered trademark) OXE-01, BASF], 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone-1- (O-acetyloxime) [trade name: IRGACURE (registered trademark) OXE- 02, manufactured by BASF], 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone [trade name: IRGACURE (registered trademark) 379EG, manufactured by BASF], 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [trade name: IRGACURE (registered trademark) 907, manufactured by BASF], 2-hydroxy- 1- {4- [4- (2-Hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one [trade name: IRGACURE (registered trademark) 127, manufactured by BASF], 2-benzyl -2-Dimethylamino-1- (4-morpholinophenyl) butanone-1 [trade name: IRGACURE (registered trademark) 369, manufactured by BASF), 2-hydroxy-2-methyl-1-phenylpropan-1-one [Product name: IRGACURE (registered trademark) 1173, manufactured by BASF], 1-hydroxycyclohexylphenylketone [Product name: IRGACURE (registered trademark) 184, manufactured by BASF], 2,2-dimethoxy-1,2-diphenylethane Oxime ester-based [trade name: Lunar® 6, manufactured by DKSH Japan] such as -1-on [trade name: IRGACURE 651, manufactured by BASF]; and 2,2'-bis (2-chlorophenyl). -4,4', 5,5'-tetraphenylbisimidazole (2- (2-chlorophenyl) -4,5-diphenylimidazole dimer, trade name: B-CIM, manufactured by Hampford), 2- (o) -Chlorophenyl) -4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Kasei Kogyo Co., Ltd.), 1- [4- (Phenylthio) phenyl] -3-cyclopentylpropane-1,2-dione-2- (O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), 1,2-Propanedione, 3-Cyclohexyl-1 -[9-Ethyl-6- (2-furanylcarbonyl) -9H-carbazole-3-yl]-, 2- (O-acetyloxime) (trade name: TR-PBG-326, Changzhou Powerful Electronics New Materials Co., Ltd. ), 3-Cyclohexyl-1- (6- (2- (benzoyloxyimino) hexanoyl) -9-ethyl-9H-carbazole-3-yl) -propane-1,2-dione-2- (O-benzoyl) Oxime) (trade name: TR-PBG-391, manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.) and the like.

The photosensitive resin layer may contain one kind of photopolymerization initiator alone, or may contain two or more kinds of photopolymerization initiators.
When the photosensitive resin layer contains a photopolymerization initiator, the content of the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, preferably 0.5% by mass, based on the total amount of the photosensitive resin layer. It is more preferably mass% or more, and further preferably 1.0 mass% or more.
The content of the photopolymerization initiator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total amount of the photosensitive resin layer.

--Surfactant ---
The photosensitive resin layer may contain a surfactant.
Examples of the surfactant include the surfactants described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of JP-A-2009-237362.

As the surfactant, a nonionic surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferable.

Commercially available products of fluorine-based surfactants include, for example, Megafuck F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144. , F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F -558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-41, R-41-LM , R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, and DS-21 (above, manufactured by DIC); Florard FC430, FC431, and FC171 (all manufactured by Sumitomo 3M); Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S- 393 and KH-40 (above, manufactured by AGC); PolyFox PF636, PF656, PF6320, PF6520, and PF7002 (above, manufactured by OMNOVA); and Surfactant 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F. 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681 (all manufactured by NEOS) and the like can be mentioned.

As the fluorine-based surfactant, an acrylic compound having a molecular structure having a functional group containing a fluorine atom and in which a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes when heat is applied is also suitable. Can be used for. Examples of such a fluorine-based surfactant include the Megafuck DS series manufactured by DIC (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck DS-. 21 is mentioned.

As the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.

As the fluorine-based surfactant, a block polymer can also be used.

The fluorine-based surfactant has a structural unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth). ) A fluorine-containing polymer compound containing a structural unit derived from an acrylate compound can also be preferably used.

As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Examples thereof include Megafuck RS-101, RS-102, RS-718K, RS-72-K (all manufactured by DIC Corporation) and the like.

As the fluorine-based surfactant, from the viewpoint of improving environmental suitability, compounds having a linear perfluoroalkyl group having 7 or more carbon atoms such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) can be used. It is preferable to use a surfactant derived from an alternative material.

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc. Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether; polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; Pluronic L10, L31, L61, L62, 10R5, 17R2, and 25R2 ( (BASF); Tetronic 304, 701, 704, 901, 904, and 150R1 (BASF); Solsparse 20000 (Nippon Lubrizol); NCW-101, NCW-1001, and NCW-1002 (above, manufactured by Fujifilm Wako Junyaku Co., Ltd.); Pionin D-6112, D-6112-W, and D-6315 (above, manufactured by Takemoto Yushi); Orfin E1010, Surfinol 104, 400, and 440. (The above is manufactured by Nissin Chemical Industry Co., Ltd.) and the like.

Examples of the silicone-based surfactant include a linear polymer composed of a siloxane bond and a modified siloxane polymer in which an organic group is introduced into at least one of a side chain and a terminal.

Specific examples of silicone-based surfactants include DOWSIL 8032 ADDITIVE, Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (above, Toray). (Manufactured by Dow Corning); X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643 , X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, and KF-6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.); F-4440, TSF-4300, TSF-4445. , TSF-4460, and TSF-4452 (above, manufactured by Momentive Performance Materials); and BYK307, BYK323, and BYK330 (above, manufactured by Big Chemie).

The surfactant may be used alone or in combination of two or more.

When the photosensitive resin layer contains a surfactant, the content of the surfactant is preferably 0.01% by mass to 3.0% by mass, preferably 0.01, based on the total amount of the photosensitive resin layer. It is more preferably from% by mass to 1.0% by mass, and even more preferably from 0.05% by mass to 0.80% by mass.

--Other additives ---
In addition to the above components, the photosensitive resin layer may contain known additives, if necessary.
As other additives, known ones can be used, and examples thereof include polymerization inhibitors, plasticizers, sensitizers, hydrogen donors, heterocyclic compounds, color formers, decolorizers, solvents and the like.
As the polymerization inhibitor, for example, the thermal polymerization inhibitor described in paragraph [0018] of Japanese Patent No. 4502784 can be used. Among them, phenothiazine, phenoxazine or 4-methoxyphenol can be preferably used.
When the photosensitive resin layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 3% by mass, preferably 0.01% by mass to 1% by mass, based on the total amount of the photosensitive resin layer. The mass% is more preferable, and 0.01% by mass to 0.8% by mass is further preferable.
Examples of the sensitizer include known sensitizers, dyes, pigments and the like.
Examples of the plasticizer and the heterocyclic compound include those described in paragraphs [097] to [0103] and paragraphs [0111] to [0118] of International Publication No. 2018/179640.
As the color-developing agent, for example, the color-developing agent described in paragraph [0417] of JP-A-2007-178459 can be used, and leuco crystal violet, crystal violet lactone, Victoria pure blue-naphthalene sulfonate and the like can be used. It is preferably used.
When the photosensitive resin layer contains a coloring agent, the content of the coloring agent is 0.1% by mass with respect to the total amount of the photosensitive resin layer from the viewpoint of visibility and resolution of the exposed portion and the non-exposed portion. It is preferably ~ 10% by mass, more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass.

Further, the photosensitive resin layer includes metal oxide particles, antioxidants, dispersants, acid growth agents, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, thermal acid generators, and ultraviolet absorbers. , Thickeners, cross-linking agents, and known additives such as organic or inorganic anti-precipitation agents can be further added.
Preferred embodiments of other components are described in paragraphs [0165] to [0184] of JP-A-2014-85643, respectively, and the contents of this publication are incorporated in the present specification.

-Cover film-
The photosensitive transfer member preferably has a cover film on the surface opposite to the intermediate layer of the photosensitive resin layer of the photosensitive transfer member.
Examples of the cover film include a resin film and paper, and a resin film is particularly preferable from the viewpoint of strength, flexibility, and the like. Examples of the resin film include polyethylene film, polypropylene film, polyethylene terephthalate film, cellulose triacetate film, polystyrene film, polycarbonate film and the like. Of these, polyethylene film, polypropylene film, and polyethylene terephthalate film are preferable.

The thickness of the cover film is not particularly limited, and for example, a cover film having a thickness of 1 μm to 2 mm is preferable.

-Other layers-
The photosensitive transfer member may have a layer other than the above-mentioned layer (hereinafter, abbreviated as "other layer"). Examples of other layers include a contrast enhancement layer, an easily peelable layer, and a BARC layer.
Preferred embodiments of the contrast enhancement layer are described in paragraph [0134] of WO 2018/179640, the content of which is incorporated herein.

-Manufacturing method of photosensitive transfer member-
The method for producing the photosensitive transfer member is not particularly limited, and a known production method can be used.
Specifically, a composition such as a thermoplastic resin composition is prepared by mixing the above-mentioned constituent components of each layer and a solvent, and the above composition is applied on a temporary support or a cover film to temporarily prepare the composition. It is possible to obtain a photosensitive transfer member having a support, an intermediate layer having at least a thermoplastic resin layer, and a photosensitive resin layer in this order.
Among them, as a method for manufacturing a photosensitive transfer member, a step of applying a thermoplastic resin composition on a temporary support and drying it to form a thermoplastic resin layer, a step of applying a water-soluble resin composition on the thermoplastic resin layer, and A method including a step of drying to form a water-soluble resin layer and a step of applying a photosensitive resin composition on the water-soluble resin layer and drying to form a photosensitive resin layer is preferable.
Further, it is preferable that the method for manufacturing the photosensitive transfer member further includes a step of providing a cover film on the photosensitive resin layer after the step of forming the photosensitive resin layer.

(Lasting process)
The photosensitive resin layer forming step is a step of bringing the surface of the photosensitive transfer member on the side opposite to the intermediate layer of the photosensitive resin layer into contact with the silver-containing conductive layer and bonding them (hereinafter, referred to as “bonding step”). May be included). This makes it possible to form a photosensitive resin layer on the silver-containing conductive layer. When the photosensitive transfer member has a cover film, the surface opposite to the intermediate layer of the photosensitive resin layer means the surface of the photosensitive resin layer exposed when the cover film is peeled off.

In the bonding step, it is preferable that the silver-containing conductive layer and the surface of the photosensitive transfer member on the opposite side of the intermediate layer of the photosensitive resin layer are pressure-bonded so as to be in contact with each other. In such an embodiment, the patterned photosensitive resin layer after exposure and development can be suitably used as an etching resist when etching the silver-containing conductive layer.
The method of crimping the substrate and the photosensitive transfer member is not particularly limited, and a known transfer method or laminating method can be used.

The photosensitive transfer member is bonded to the substrate by superimposing the surface of the photosensitive transfer member on the side opposite to the intermediate layer of the photosensitive resin layer on the substrate, and pressurizing and heating with a roll or the like. It is preferable to be For laminating, a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further increasing productivity can be used. In some embodiments, the conductive pattern is preferably produced by a roll-to-roll method. In that case, the base material is preferably a resin film. By the roll-to-roll method, for example, a conductive pattern such as a touch sensor can be preferably manufactured.
Hereinafter, the roll-to-roll method will be described.
The roll-to-roll method uses a base material that can be wound up and unwound as a base material, and is a base material or a structure containing the base material before any of the steps included in the method for manufacturing a conductive pattern. A step of unwinding (also referred to as “unwinding step”) and a step of winding up the base material or a structure containing the base material (also referred to as “winding-up step”) after any of the steps, at least. A method in which any of the steps (preferably all steps) is performed while transporting a base material or a structure containing the base material.
The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and a known method may be used in the manufacturing method to which the roll-to-roll method is applied.

[Exposure process]
The exposure step is a step of pattern-exposing the photosensitive resin layer.

In the present disclosure, the detailed arrangement and specific size of the pattern are not particularly limited. From the viewpoint of improving the display quality of a display device (for example, a touch panel) provided with an input device having a conductive pattern manufactured by the method for manufacturing a conductive pattern according to the present disclosure, and reducing the area occupied by the take-out wiring as much as possible. At least a part of the conductive pattern (particularly the electrode pattern of the touch panel and the portion of the take-out wiring) is preferably a fine wire of 20 μm or less, and more preferably 10 μm or less. Therefore, it is preferable to perform pattern exposure of the photosensitive resin layer so that such fine lines can be obtained.

Preferred embodiments of the light source, exposure amount, and exposure method used for exposure are described in, for example, paragraphs [0146] to [0147] of International Publication No. 2018/155193, and these contents are incorporated in the present specification. Is done.

[Development process]
The developing step is a step of developing the photosensitive resin layer exposed to the pattern. Development gives a patterned resin layer.

In the embodiment in which the photosensitive transfer member is used, when the photosensitive transfer member has a water-soluble resin layer, in the development step, the thermoplastic resin layer and the water-soluble resin layer in the non-exposed portion are also the photosensitive resin layer in the non-exposed portion. Is removed with. Further, in the developing step, the thermoplastic resin layer and the water-soluble resin layer in the exposed portion may also be removed in the form of being dissolved or dispersed in the developing solution.

Development in the developing step can be performed using a developing solution. The developing solution and developing method are not particularly limited, and known developing solutions and developing methods can be used. Examples of the developer preferably used in the present disclosure include the developer described in paragraph [0194] of International Publication No. 2015/093271, and examples of the developing method preferably used include International Publication No. 2015. The developing method described in paragraph [0195] of No. 093271 can be mentioned.

[Etching process]
The etching step is a step of etching the silver-containing conductive layer with an etching solution in which the content of nitrate ions is 16.0% by mass to 35.0% by mass with respect to the total amount of the etching solution. A conductive pattern can be formed by removing the silver-containing conductive layer with an etching solution from the portion where the photosensitive resin layer has been removed by development.

The specific method of etching is not particularly limited, and for example, a method of immersing the entire substrate in the etching solution, a method of spraying the etching solution onto the substrate, and the like can be adopted.

The etching temperature is not particularly limited, but is preferably 40 ° C. or lower, more preferably 35 ° C. or lower, from the viewpoint of further improving the LWR. The lower limit of the etching temperature is not particularly limited and may be, for example, 15 ° C.

For example, in the embodiment in which another conductive layer is formed in advance on the substrate as described above and the silver-containing conductive layer is provided on the other conductive layer, the photosensitive resin layer is patterned and exposed for development. Later, by etching the other conductive layer together with the silver-containing conductive layer, a conductive pattern in which the silver-containing conductive layer and the other conductive layer are laminated can be obtained.
Further, for example, in the embodiment in which another electrode pattern is formed in advance on the substrate as described above and the silver-containing conductive layer is provided on the other electrode pattern, the same patterning as the other electrode pattern is performed. By patterning and exposing the photosensitive resin layer to develop the photosensitive resin layer and then etching the silver-containing conductive layer, a conductive pattern in which the silver-containing conductive layer and the other conductive layer are laminated can be obtained.

[Removal process]
The method for producing a conductive pattern according to the present disclosure may include a step of removing the patterned resin layer remaining on the silver-containing conductive layer (hereinafter, may be referred to as a "removal step") after the etching step. ..

The method for removing the resin layer is not particularly limited, but a method for removing the resin layer by chemical treatment can be mentioned, and a method using the following removing liquid is particularly preferable.
The removing liquid may be, for example, an inorganic alkali component such as sodium hydroxide or potassium hydroxide, or an organic alkali such as a primary amine compound, a secondary amine compound, a tertiary amine compound or a quaternary ammonium salt compound. Examples thereof include a removal solution in which the components are dissolved in water, dimethylsulfoxide, N-methylpyrrolidone, or a mixed solution thereof.

For example, the resin layer may be removed by a spray method, a shower method, a paddle method, or the like using a removing liquid. Further, for example, the resin layer is removed by immersing the substrate having the resin layer in the removing liquid being stirred at preferably at 30 ° C to 80 ° C, more preferably at 50 ° C to 80 ° C for 1 to 30 minutes. It's okay.

[Other processes]
The method for producing a conductive pattern according to the present disclosure may include any step (other steps) other than those described above. For example, when the photosensitive transfer member has a cover film, the step of peeling off the cover film of the photosensitive transfer member, paragraph [0172] of International Publication No. 2019/22089, reduces the visible light reflectance. Examples thereof include, but are not limited to, a step of forming a new conductive layer on the insulating film described in paragraph [0172] of International Publication No. 2019/22089.

<Touch panel with conductive pattern>
The conductive pattern obtained by the method for producing a conductive pattern according to the present disclosure can be used for various purposes, and can be particularly preferably used for a touch panel. A touch panel provided with such a conductive pattern can be suitably used for, for example, a display, a smartphone, a tablet, or the like. As such a touch panel and a method for manufacturing the same, those described in Japanese Patent Application Laid-Open No. 2015-196369 can be exemplified, and the contents thereof are incorporated in the present specification.

Hereinafter, the present disclosure will be described in more detail with reference to examples. However, the present disclosure is not limited to these examples.

<Preparation of etching solution>
The following raw materials were mixed and dissolved in the compositions (parts by mass) shown in Tables 1 to 3 to prepare etching solutions containing nitrate ions of Examples 1 to 25, Comparative Example 2 and Comparative Example 3. The etching solutions of Examples 19 to 25 are the same as those of Example 5.
In Comparative Example 1, iron (III) nitrate hydrate could not be completely dissolved in ion-exchanged water.
(material)
-Iron (III) nitrate nine hydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent)
-Iron (III) chloride hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent)
Dispersion aid A (manufactured by Daicel, trade name: PGLE ML10, polyglycerin ester: polyglyceryl laurate-10)
-Dispersion aid B (manufactured by Daicel, trade name: PGLAL, polyglycerin ether: polyglyceryl-4 lauryl ether)
・ Dispersion aid C (manufactured by RIKEN Vitamin Co., Ltd., trade name: Poem J-4081V, polyglycerin ester: tetraglyceryl stearate)
・ Dispersion aid D (manufactured by RIKEN Vitamin Co., Ltd., trade name: Poem J-0081HV, polyglycerin ester: decaglyceryl stearate)
・ Dispersion aid E (manufactured by RIKEN Vitamin Co., Ltd., trade name: Poem J-0021, polyglycerin ester: decaglyceryl laurate)
Dispersant F (Solspers 44000 (manufactured by Lubrizol, polymer compound having an acid group, acid value: 12 mgKOH / g, amine value: 0 mgKOH / g) with equal mass of "10% ammonia water" (trade name, Fuji) (Manufactured by Wako Pure Chemical Industries, Ltd.) and adjusted to a solid content of 50% by mass)
Dispersant G (John Krill 611 (manufactured by BASF, polymer compound having an acid group, acid value: 53 mgKOH / g, amine value: 0 mgKOH / g, weight average molecular weight: 8100)) having an equal mass of "10% ammonia water". (Product name, manufactured by Fujifilm Wako Junyaku Co., Ltd.) and adjusted to a solid content of 50% by mass)
・ Dispersant H (3-methoxypropylamine manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
・ Ion-exchanged water

In Tables 1 to 3, the nitrate ion content is measured by the gradient elution method by ion chromatography under the following conditions. Note that Comparative Example 1 is a calculated value assuming that iron (III) nitrate nine hydrate is completely dissolved in ion-exchanged water.
(Measurement condition)
-Use a whole pipette and a volumetric flask to dilute the etching solution at the magnifications shown in Tables 1 to 3 to prepare a diluted solution.-Equipment: "ICS-2100" manufactured by Thermo Fisher Scientific.
-Guard column for dirt removal: "IonPac AG11HC 4.0 mmf x 50 mm" manufactured by Thermo Fisher Scientific.
-Column: "IonPac AS11HC 4.0 mmf x 250 mm" manufactured by Thermo Fisher Scientific.
・ Injection amount of diluted solution: 20 ml
-Column temperature: 35 ° C
-Eluent: KOH
Eluent concentration: 1 mM (0 minutes) → 1 mM (8 minutes) → 15 mM (18 minutes) → 30 mM (28 minutes) → 60 mM (38 minutes)
-Detector: Electrical conductivity detector (using suppressor "AERS500" manufactured by Dionex Thermo Scientific Fisher)
-Determine the nitrate ion concentration by comparing it with the calibration curve prepared for the sample sample whose nitrate ion concentration is known.

<Preparation of conductive material having silver-containing conductive layer>
[Conductive material having a conductive layer of silver particles (bar coater method); Example 1 to Example 23, Comparative Example 1 to Comparative Example 3]
100 g of "Flow Metalal SR7500" manufactured by Bando Chemical Industries, 1.0 g of 2-methylpentane-2,4-diol (manufactured by Wako Pure Chemical Industries, Ltd., first-class reagent), 2-hexyloxyethanol (Wako Pure Chemical Industries, Ltd.) The silver ink composition was prepared by adding 1.0 g of the first-class reagent and 0.25 g of the dispersion aid B and mixing them. The silver ink composition was applied with a Mayer bar on a substrate provided with an electrode pattern (transparent electrode) provided in the touch sensor, dried at 80 ° C. for 3 minutes, and then heated at 120 ° C. for 25 minutes. In this way, a conductive material having a substrate, an electrode pattern, and a silver particle conductive layer in this order was produced. The thickness of the silver particle conductive layer was 0.5 μm in Examples 1 to 21, 0.3 μm in Example 22, and 1.5 μm in Example 23. The thickness was measured by a stylus type step meter "SURFACE PROFILER P-10" manufactured by KLA-TENCOR. The same applies to the measurement of the thickness of the silver-containing conductive layer.

[Conductive material having a conductive layer of silver particles (inkjet method); Example 24]
Prepare the same silver ink composition as that used in the bar coater method and the base material provided with the electrode pattern, and prepare an inkjet printer (“DMP-2831” manufactured by Fujifilm Dimatix) and a cartridge (manufactured by Fujifilm). The silver ink composition was applied onto the substrate using "DMC-11610", ink droplets: 10 pl). The applied silver ink composition was dried at 80 ° C. for 3 minutes and then heated at 120 ° C. for 25 minutes. In this way, a conductive material having a substrate, an electrode pattern, and a silver particle conductive layer in this order was produced. The thickness of the silver particle conductive layer was 0.5 μm.

[Conductive material having a conductive layer made of a silver alloy (sputtering method); Example 25]
A substrate provided with the same electrode pattern as that used in the bar coater method was prepared, the substrate was set in a vacuum chamber, and a silver alloy sputtering target (atomic ratio: Ag: Ga = 98.5:). 1.5), and using Ar gas as a rare gas, silver by DC magnetron sputtering (reaching vacuum degree: 0.27 × mPa or less, sputtering power: 200 W, electrode distance: 55 mm, substrate temperature: room temperature). A conductive layer made of an alloy was formed. In this way, a conductive material having a substrate, an electrode pattern, and a conductive layer made of a silver alloy in this order was produced. The thickness of the conductive layer made of silver alloy was 0.5 μm.

<Preparation of photosensitive transfer member>
In the following synthetic examples, the following abbreviations represent the following compounds, respectively.
St: Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
MAA: Methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
BzMA: Benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
AA: Acrylic acid (manufactured by Tokyo Kasei Co., Ltd.)
PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Showa Denko)
MEK: Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.)
V-601: Dimethyl-2,2'-azobis (2-methylpropionate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

(Polymer A-1)
PGMEA (116.5 parts) was placed in a three-necked flask, and the temperature was raised to 90 ° C. under a nitrogen atmosphere. A solution containing St (52.0 parts), MMA (19.0 parts), MAA (29.0 parts), V-601 (4.0 parts), and PGMEA (116.5 parts) was added to 90 ° C. It was added dropwise over 2 hours into a three-necked flask solution maintained at ± 2 ° C. After completion of the dropping, the mixture was stirred at 90 ° C. ± 2 ° C. for 2 hours to obtain polymer A-1 (solid content concentration 30.0% by mass).

(Polymer A-2)
Polymer A-2 (solid content concentration 30.0% by mass) was obtained in the same manner as in Polymer A-1, except that the types of monomers were changed as shown in Table 4 below.
The unit of the amount of the monomer in Table 4 is mass%, and Tg is measured by the above-mentioned method.

[Preparation of photosensitive resin composition]
The following components were mixed to prepare a photosensitive resin composition.
-Composition of photosensitive resin composition-
-Polymer A-1: 21.87 parts by mass-LCV (Leuko Crystal Violet, manufactured by Yamada Chemical Industry Co., Ltd., dye that develops color by radical): 0.053 parts by mass-B-CIM (photoradical polymerization initiator, 2- (2-Chlorophenyl) -4,5-diphenylimidazole dimer, manufactured by Hampford): 0.89 parts by mass · EAB-F (photoradical polymerization initiator (sensitizer), 4,4'-bis (diethylamino) ) Benzophenone, manufactured by Tokyo Kasei Co., Ltd.): 0.05 parts ・ NK ester BPE-500 (ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.): 4.85 parts ・ Aronix M-270 (polypropylene radical di) Aacrylate, manufactured by Toa Synthetic Co., Ltd.): 0.51 part ・ Phenothiazine (manufactured by Fujifilm Wako Junyaku Co., Ltd.): 0.025 part ・ 1-phenyl-3-pyrazolidone (manufactured by Fujifilm Wako Junyaku Co., Ltd.): 0.001 part・ Megafuck F-552 (manufactured by DIC): 0.02 parts ・ Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.): 30.87 parts ・ PGMEA (manufactured by Showa Denko Co., Ltd.): 33.92 parts ・ tetrahydrofuran (manufactured by Mitsubishi Chemical Co., Ltd.) ): 6.93 copies

[Preparation of water-soluble resin composition]
The following components were mixed to prepare a water-soluble resin composition.
-Composition of water-soluble resin composition-
-Ion exchanged water: 38.12 parts by mass-Methanol (manufactured by Mitsubishi Gas Chemicals): 57.17 parts by mass-Clarepoval PVA-205 (polyvinyl alcohol, manufactured by Clare): 3.22 parts by mass-Polyvinylpyrrolidone K- 30 (manufactured by Nippon Catalyst): 1.49 parts by mass Megafuck F-444 (fluorosurfactant, manufactured by DIC): 0.0015 parts by mass

[Preparation of thermoplastic resin composition]
The following components were mixed to prepare a thermoplastic resin composition.
-Composition of thermoplastic resin composition-
-Polymer A-2 (thermoplastic resin): 42.85 parts by mass-Compound having the structure shown below (dye developed by acid): 0.08 parts by mass-Compound having the structure shown below (photoacid generation) Agent, compound described in paragraph [0227] of JP2013-47765A, synthesized according to the method described in paragraph [0227] of the same publication): 0.32 part by mass · NK ester A-DCP (thermoplastic agent, Tricyclodecanedimethanol diacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.): 4.63 parts by mass, 8UX-015A (plastic agent, polyfunctional urethane acrylate compound, manufactured by Taisei Fine Chemical Co., Ltd.): 2.31 parts by mass, Aronix TO- 2349 (plastic agent, polyfunctional acrylate compound having a carboxy group, manufactured by Toa Synthetic Co., Ltd.): 0.77 parts by mass, Megafuck F-552 (surfactant, manufactured by DIC): 0.03 parts by mass, methyl ethyl ketone (three) Kyogaku Co., Ltd.): 39.5 parts by mass, PGMEA (manufactured by Showa Denko Co., Ltd.): 9.51 parts by mass

(Dyes that develop color with acid)

(Photoacid generator)

[Manufacturing of photosensitive transfer member]
A slit-shaped nozzle was used on the smooth surface of the outer surface of the temporary support (Toray Industries, Inc. Lumirror 16KS40, polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%), and the coating width was 1.0 m after drying. The thermoplastic composition was applied to a thickness of 4.0 μm and passed through a drying zone at 80 ° C. for 40 seconds to form a thermoplastic resin layer.
Then, the water-soluble resin composition is applied onto the thermoplastic resin layer using a slit-shaped nozzle so that the coating width is 1.0 m and the thickness is 1.1 μm after drying, and a drying zone at 80 ° C. is formed. It was passed over 40 seconds to form a water-soluble resin layer.
Further, a photosensitive resin composition is applied onto the water-soluble resin layer using a slit-shaped nozzle so that the coating width is 1.0 m and the thickness is 3.0 μm after drying, and a drying zone at 80 ° C. is formed. It was passed over 40 seconds to form a negative photosensitive resin layer.
Next, a PET film (manufactured by Toray Industries, Inc., Lumirror 16KS40) was pressure-bonded onto the negative photosensitive resin layer as a cover film. In this way, a photosensitive transfer member having a temporary support, an intermediate layer (thermoplastic resin layer, water-soluble resin layer), and a photosensitive resin layer in this order was produced.

<Evaluation of etching time>
Using the conductive materials having the silver-containing conductive layers of Examples 1 to 25 and Comparative Examples 1 to 3 prepared as described above, the etching time was evaluated in the following manner.
The cover film is peeled off from the photosensitive transfer member, and the surface of the photosensitive transfer member opposite to the intermediate layer of the photosensitive resin layer is brought into contact with the silver-containing conductive layer of the conductive material having the silver-containing conductive layer. It was laminated on the conductive material under the laminating conditions of a roll temperature of 100 ° C., a linear pressure of 1.0 MPa, and a linear velocity of 4.0 m / min. It was autoclaved for 2 hours under the conditions of 50 ° C. and 0.5 MPa, and the temporary support was peeled off and developed without exposure. Development was carried out by shower development for 30 seconds using a 1.0% potassium carbonate aqueous solution at 23 ° C. After development, it was rinsed with pure water and drained with an air knife. Next, the conductive material was immersed in the etching solution set to the temperature shown in Table 5 to determine the time required to completely remove the silver-containing conductive layer, and 1.5 times that time was defined as the etching time. bottom. It is preferable that the etching time is short, and the practical level is within 90 seconds. In Comparative Example 2 and Comparative Example 3, the etching pattern could not be formed even after 90 seconds.

<Formation of conductive pattern-Evaluation of LWR->
Using the conductive materials having the silver-containing conductive layers of Examples 1 to 25 and Comparative Examples 1 to 3 prepared as described above, the LWR was evaluated in the following manner.
The cover film is peeled off from the photosensitive transfer member, and the surface of the photosensitive transfer member opposite to the intermediate layer of the photosensitive resin layer is brought into contact with the silver-containing conductive layer. It was laminated on a conductive material under a laminating condition with a linear velocity of 4.0 m / min. An ultra-high pressure mercury lamp was autoclaved at 50 ° C. and 0.5 MPa for 2 hours through a mask having a line-and-space pattern (duty ratio 1: 1) with a line width of 9 μm without peeling off the temporary support. The photosensitive resin layer was exposed with an exposure amount of 90 mJ / cm ² . After 3 hours from the exposure, the temporary support was peeled off and developed. The development was carried out by shower development for 30 seconds using a 1.0% potassium carbonate aqueous solution at 23 ° C., and after development, rinsed with pure water. Then, the conductive material was immersed in the etching solution for the etching time shown in Table 5, and then rinsed with pure water. Next, it is immersed in a stripping solution at 45 ° C. (a solution in which potassium hydroxide, 1-methoxy-2-propanol, and water are mixed at a mass ratio of 2.5: 25.0: 72.5) for 30 seconds. After removing the photosensitive resin layer, the mixture was rinsed with pure water and dried. In this way, a conductive pattern was produced.

From the obtained conductive pattern, a line is randomly selected, the line width of 50 randomly selected points is measured over a range of 40 μm in the longitudinal direction of the line, and the standard deviation is obtained for the measurement variation. 3σ was calculated. Such calculation of 3σ was performed 5 times, and the average value of 3σ was taken as LWR. The evaluation criteria are as follows. The smaller the LWR, the better the performance. Practical levels are A to F.
-Evaluation criteria-
A: LWR is less than 0.180 μm.
B: LWR is 0.180 μm or more and less than 0.200 μm.
C: LWR is 0.20 μm or more and less than 0.220 μm.
D: LWR is 0.220 μm or more and less than 0.240 μm.
E: LWR is 0.240 μm or more and less than 0.280 μm.
F: LWR is 0.280 μm or more and less than 0.320 μm.
G: LWR is 0.320 μm or more.

<Formation of conductive pattern-evaluation of reliability->
Using the conductive materials having the silver-containing conductive layers of Examples 1 to 25 and Comparative Examples 1 to 3 prepared as described above, the reliability was evaluated in the following manner.
The cover film is peeled off from the photosensitive transfer member, and the surface of the photosensitive transfer member opposite to the intermediate layer of the photosensitive resin layer is brought into contact with the silver-containing conductive layer. It was laminated on a conductive material under a laminating condition with a linear velocity of 4.0 m / min. Autoclaved at 50 ° C. and 0.5 MPa for 2 hours, without peeling off the temporary support, through a mask with a pattern with a line width of 200 μm and a length of 3 cm, using an ultrahigh pressure mercury lamp, 90 mJ / The photosensitive resin layer was exposed with an exposure amount of cm ² . After 3 hours from the exposure, the temporary support was peeled off and developed. The development was carried out by shower development for 30 seconds using a 1.0% potassium carbonate aqueous solution at 23 ° C., and after development, rinsed with pure water. Then, the conductive material was immersed in the etching solution for the etching time shown in Table 5, and then rinsed with pure water. Next, it is immersed in a stripping solution at 45 ° C. (a solution in which potassium hydroxide, 1-methoxy-2-propanol, and water are mixed at a mass ratio of 2.5: 25.0: 72.5) for 30 seconds. After removing the photosensitive resin layer, the mixture was rinsed with pure water and dried. In this way, a conductive pattern was produced.

The resistance value of the obtained conductive pattern was measured using a tester (resistance meter "RM3548" manufactured by Hioki Electric Co., Ltd.). The conductive pattern was stored at 85 ° C. and 85% RH (Relative Humidity) for 500 hours, then taken out and dried, and the resistance value was measured in the same manner, and the evaluation value was obtained by the following formula (6). .. The calculation of such evaluation values was performed 10 times, and the average value of the evaluation values was taken as the reliability.
Evaluation value = (resistance value after storage at 85 ° C. and 85% RH for 500 hours) / (resistance value before storage) Equation (6)
The evaluation criteria are as follows. The closer the reliability is to 1, the more stable the resistance value is and the better the performance is, and the practical level is A to C.
-Evaluation criteria-
A: The reliability is more than 0.95 and less than 1.05.
B: The reliability is more than 0.93 and 0.95 or less, or 1.05 or more and less than 1.07.
C: The reliability is more than 0.90 and 0.93 or less, or 1.07 or more and less than 1.10.
D: The reliability is 0.90 or less, or 1.10 or more.

The above evaluation results are shown in Table 5.

As shown in Table 5, the etching solutions of Examples 1 to 25 were capable of forming a conductive pattern having a small LWR and had a high etching rate.

In Examples 2 to 7, the nitrate ion content is 23.0% by mass to 33.0% by mass, so that the nitrate ion content is 16.9% by mass as compared with Example 1. The etching rate could be further improved, and higher reliability could be obtained as compared with Example 8 in which the nitrate ion content was 34.0% by mass. As described above, in Examples 2 to 7, both the etching rate and the reliability could be achieved at a higher level.

In Examples 5 and 24, since the silver particle conductive layer containing sintered silver particles and further containing a dispersion aid is etched as the silver-containing conductive layer, the conductive layer made of a silver alloy is etched. It was possible to etch faster than in Example 25.

Since the etching solutions of Examples 9 to 18 contained a dispersant or a dispersion aid, the LWR was more excellent. Among them, in Examples 9 to 15, the LWR was particularly excellent because it contained a polyglycerin compound as a dispersion aid.

In Examples 4 to 6, the nitrate ion content was 26.0% by mass to 31.5% by mass, so that the reliability was more excellent.

In Examples 1 to 19 and 22 to 25, the LWR was more excellent because the etching was performed at a temperature of 40 ° C. or lower.

On the other hand, in Comparative Example 1, iron (III) nitrate hydrate was excessive, so that it could not be completely dissolved in ion-exchanged water.

In Comparative Example 2, since the content of nitrate ion was low, the etching rate was slow, and the etching pattern could not be formed even after 90 seconds.

In Comparative Example 3, since nitrate ion was not contained, the etching rate was slow, and the etching pattern could not be formed even if it exceeded 90 seconds.

Claims (16)

An etching solution for etching a silver-containing conductive layer.
An etching solution having a nitrate ion content of 16.0% by mass to 35.0% by mass with respect to the total amount of the etching solution. The etching solution according to claim 1, wherein the ion source of the nitrate ion contains iron (III) nitrate. The etching solution according to claim 2, wherein the ion source of the nitrate ion is iron (III) nitrate. The etching solution according to any one of claims 1 to 3, wherein the nitrate ion content is 23.0% by mass to 33.0% by mass with respect to the total amount of the etching solution. The etching solution according to any one of claims 1 to 4, wherein the silver-containing conductive layer contains sintered silver particles. The etching solution according to claim 5, wherein the silver-containing conductive layer contains an organic substance. The etching solution according to claim 6, wherein the silver-containing conductive layer contains at least one of a dispersant and a dispersion aid as the organic substance. The etching solution according to claim 7, which comprises at least one of the dispersant and the dispersant aid. The etching solution according to claim 7 or 8, wherein the dispersant is a polymer compound containing an acid group. The etching solution according to any one of claims 7 to 9, wherein the dispersion aid is a compound containing a hydroxy group. The etching solution according to claim 10, wherein the compound containing a hydroxy group is a polyglycerin compound. A step of preparing a conductive material having a base material and a silver-containing conductive layer,
A step of forming a photosensitive resin layer on a surface of the silver-containing conductive layer opposite to the side having the base material.
The step of pattern-exposing the photosensitive resin layer,
A conductive pattern comprising a step of developing the photosensitive resin layer exposed to the pattern and a step of etching the silver-containing conductive layer with the etching solution according to any one of claims 1 to 11. Production method. The method for producing a conductive pattern according to claim 12, further comprising a step of removing the photosensitive resin layer after the etching step. The method for producing a conductive pattern according to claim 12 or 13, wherein the temperature of the etching solution is 40 ° C. or lower. A conductive pattern obtained by the method for manufacturing a conductive pattern according to any one of claims 12 to 14. A touch panel having the conductive pattern according to claim 15.