JP2024052221A - LAMINATE AND METHOD FOR MANUFACTURING LAMINATE - Google Patents

Abstract

[Problem] To provide a laminate having excellent lamination suitability and suppressing the occurrence of migration, and a method for manufacturing the laminate. [Solution] A laminate having a substrate and a wiring portion in which a transparent wiring layer and a metal wiring layer are laminated in this order on the substrate, in which a width R1 of the metal wiring layer and a width R2 of the transparent wiring layer satisfy the following formula (1), and a method for manufacturing the laminate. 0.1 μm≦R2-R1≦6.0 μm (1) [Selected Figure] FIG. 1

Description

This disclosure relates to a laminate and a method for manufacturing the laminate.

In display devices equipped with a touch panel such as a capacitance-type input device (e.g., organic electroluminescence (EL) display devices and liquid crystal display devices), conductive patterns such as an electrode pattern corresponding to a sensor in the visible area, wiring in the peripheral wiring portion, wiring in the extraction wiring portion, etc. are provided inside the touch panel.
Generally, for the formation of a patterned layer, a method is widely used in which a layer of a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material is exposed through a mask having a desired pattern, and then developed, because the number of steps required to obtain a required pattern shape is small. In addition, a conductive pattern has also been formed by printing in the past, and the printed conductive pattern is widely used in various fields such as various sensors such as pressure sensors and biosensors, printed circuit boards, solar cells, capacitors, electromagnetic wave shields, touch panels, antennas, etc.

As an example of a conductive pattern of wiring formed using a photosensitive transfer material, Patent Document 1 discloses a conductive pattern in which a transparent electrode, a transparent insulating film, and a wiring electrode are laminated in this order on a glass substrate.

International Publication No. 2011/129210

An object of one embodiment of the present disclosure is to provide a laminate that has excellent lamination suitability and suppresses the occurrence of migration.
Another problem to be solved by another embodiment of the present disclosure is to provide a method for producing a laminate that has excellent lamination suitability and suppresses the occurrence of migration.

Specific means for solving the above problems include the following embodiments.
[1] A laminate having a substrate and a wiring portion in which a transparent wiring layer and a metal wiring layer are laminated in this order on the substrate,
A laminate in which the width R1 of the metal wiring layer and the width R2 of the transparent wiring layer satisfy the following formula (1).
0.1 μm≦R2−R1≦6.0 μm (1)
[2] The metal wiring layer contains at least one of a metal element and a metal alloy,
The metal element is at least one selected from the group consisting of gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese;
The laminate according to [1], wherein the metal alloy is an alloy of two or more metal elements selected from the group consisting of gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese.
[3] The laminate according to [2], wherein the metal wiring layer further contains a resin.
[4] The laminate according to any one of [1] to [3], wherein the transparent wiring layer contains at least one metal oxide selected from indium tin oxide and indium zinc oxide.
[5] The laminate according to any one of [1] to [4], wherein the transparent wiring layer contains at least one metal nanowire selected from gold nanowires, silver nanowires, copper nanowires, and platinum wires, and a resin.
[6] The laminate according to any one of [1] to [5], wherein the width R1 of the metal wiring layer is 8 μm to 14 μm.
[7] The laminate according to any one of [1] to [6], wherein the width R2 of the transparent wiring layer is 8.1 μm to 14.5 μm.
[8] The laminate according to any one of [1] to [7], wherein the thickness R3 of the metal wiring layer is 0.2 μm to 5 μm.
[9] The width R1 of the metal wiring layer, the width R2 of the transparent wiring layer, and the thickness R3 of the metal wiring layer satisfy the following formula (2). [1] to [8] Any one of the laminates described above.
0.3≦(R2−R1)/R3≦4.0 (2)
[10] The laminate according to any one of [1] to [9], wherein the transparent wiring layer has a thickness of 0.01 μm to 1 μm.
[11] The laminate according to any one of [1] to [10], wherein the distance between adjacent patterns of the transparent wiring layer is 1 μm to 20 μm.
[12] A method for producing the laminate according to any one of [1] to [11],
preparing a conductive substrate having the substrate, a transparent conductive layer, and a metal layer in this order;
forming an etching resist on the metal layer;
A step of patterning the etching resist to obtain an etching resist pattern;
etching the transparent conductive layer and the metal layer using the etching resist pattern as a mask;
in that order,
A method for producing a laminate, in which a width R1 of the metal wiring layer, a width R2 of the transparent wiring layer, and a width R4 of the etching resist pattern satisfy the following formula (3):
R1<R2≦R4 (3)

According to one embodiment of the present disclosure, a laminate having excellent lamination suitability and suppressed occurrence of migration is provided.
According to another embodiment of the present disclosure, there is provided a method for producing a laminate having excellent lamination suitability and suppressed occurrence of migration.

1 is a schematic cross-sectional view showing an example of a laminate according to the present disclosure. FIG. 2 is a schematic plan view showing pattern A. FIG. 13 is a schematic plan view showing pattern B.

The present disclosure will be described in detail below. The following explanation of the requirements may be based on representative embodiments of the present disclosure, but the present disclosure is not limited to such embodiments, and can be implemented with appropriate modifications within the scope of the purpose of the present disclosure.

In the present disclosure, a numerical range indicated using "to" means a range that includes the numerical values before and after "to" as the lower and upper limits, respectively.
In the numerical ranges described in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in the present disclosure. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.

In this disclosure, when referring to the amount of each component in a composition, if there are multiple substances corresponding to each component in the composition, it means the total amount of the multiple components present in the composition, unless otherwise specified.

In this disclosure, a combination of two or more preferred aspects is a more preferred aspect.

In this disclosure, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

In the present disclosure, "transparent" means that the average transmittance of visible light having a wavelength of 400 nm to 700 nm is 70% or more, preferably 80% or more, and more preferably 90% or more.
In the present disclosure, the "average transmittance of visible light" is a value measured using a spectrophotometer. As the spectrophotometer, for example, a spectrophotometer (model number: U-3310) manufactured by Hitachi, Ltd. can be used. However, the spectrophotometer is not limited to this.

In this disclosure, the molecular weight of a compound with a molecular weight distribution is the weight average molecular weight (Mw; the same applies below) unless otherwise specified.

In the present disclosure, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) unless otherwise specified.
The GPC measurement was performed using a GPC analyzer equipped with a TSKgel (registered trademark) GMHxL, TSKgel (registered trademark) G4000HxL, or TSKgel (registered trademark) G2000HxL (all of which are product names manufactured by Tosoh Corporation) column, tetrahydrofuran (THF) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance, and the polystyrene-equivalent values were measured using the GPC analyzer.

In this disclosure, "water-soluble" means that the solubility in 100 g of water at pH 7.0 and a liquid temperature of 22° C. is 0.1 g or more. For example, "water-soluble resin" means a resin that satisfies the above solubility conditions.

In this disclosure, the "solid content" of a composition means the components that form a composition layer formed using the composition, and in the case where the composition contains a solvent, means all components excluding the solvent. In addition, liquid components other than the solvent are also considered to be solid content, so long as they form a composition layer. In this disclosure, "solvent" means water and organic solvent.

In this disclosure, unless otherwise specified, "exposure" includes not only exposure using light, but also drawing using particle beams such as electron beams and ion beams. In addition, light used for exposure generally includes the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, active light rays (active energy rays) such as electron beams, etc.

In this disclosure, "(meth)acrylic" is a term that encompasses both "acrylic" and "methacrylic", "(meth)acrylate" is a term that encompasses both "acrylate" and "methacrylate", and "(meth)acryloyl" is a term that encompasses both "acryloyl" and "methacryloyl".

In the description of groups (atomic groups) in the present disclosure, descriptions that do not indicate whether they are substituted or unsubstituted include those that have no substituents as well as those that have a substituent. For example, an "alkyl group" includes not only an alkyl group that has no substituents (also called an "unsubstituted alkyl group"), but also an alkyl group that has a substituent (also called a "substituted alkyl group").
Chemical structural formulae in the present disclosure may be described as simplified structural formulae in which hydrogen atoms are omitted.

In this disclosure, "mass %" and "weight %" are synonymous, and "parts by mass" and "parts by weight" are synonymous.

In this disclosure, the "width" of the transparent wiring layer and metal wiring layer refers to the length in the direction perpendicular to the longitudinal direction, and means the so-called line width.

[Laminate]
The laminate according to the present disclosure is a laminate having a base material and a wiring portion in which a transparent wiring layer and a metal wiring layer are laminated in this order on the base material, and a width R1 of the metal wiring layer and a width R2 of the transparent wiring layer satisfy the following formula (1):
0.1 μm≦R2−R1≦6.0 μm (1)

Conventionally, a technique for forming circuit wiring by etching a metal layer such as copper using a wiring pattern formed by an etching resist as a mask has been widely known. The wiring pattern obtained by such a process has a wiring portion made of the remaining metal layer, and the non-wiring portion has a concave shape where the metal layer has been removed by etching, and the circuit surface has unevenness corresponding to the thickness of the wiring portion.
In general, when protecting a wiring pattern on a wiring board, a protective film is laminated by laminating an optical film having adhesiveness (e.g., an OCA (Optical Clear Adhesive) film) on the circuit surface. However, if the circuit surface has the above-mentioned unevenness, air may be entrapped during lamination, resulting in air bubbles between the optical film and the wiring board. The air bubbles not only affect visibility, but may also cause malfunction.
In contrast, the laminate according to the present disclosure has a substrate and a wiring portion in which a transparent wiring layer and a metal wiring layer are laminated on the substrate in this order, the width of the transparent wiring layer is wider than the width of the metal wiring layer, and the difference between the width of the transparent wiring layer and the width of the metal wiring layer is equal to or greater than a specific value. In the laminate according to the present disclosure, since an appropriate step is formed in the recess, it is considered that air is less likely to be entrained during lamination and air bubbles are less likely to occur. Therefore, the laminate according to the present disclosure has excellent lamination suitability. In addition, the laminate according to the present disclosure has a substrate and a wiring portion in which a transparent wiring layer and a metal wiring layer are laminated on the substrate in this order, the width of the transparent wiring layer is wider than the width of the metal wiring layer, and the difference between the width of the transparent wiring layer and the width of the metal wiring layer is equal to or less than a specific value, which can suppress the occurrence of migration that may cause a short circuit.

Note that the above speculation is not intended to limit the interpretation of the laminate according to this disclosure, but is merely an example.

The laminate according to this disclosure is described in detail below.

An example of a laminate according to the present disclosure will be described below with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing an example of a laminate according to the present disclosure.
However, the laminate according to the present disclosure is not limited to having the configuration shown in Fig. 1. Furthermore, the size of each component in Fig. 1 is conceptual, and the relative relationship of the size between the components is not limited to that shown in Fig. 1.
1 has a substrate 30 and a wiring section 60 provided on the substrate 30. The wiring section 60 has a transparent wiring layer 40 and a metal wiring layer 50. The transparent wiring layer 40 and the metal wiring layer 50 are laminated in this order from the substrate 30 side. The width R2 of the transparent wiring layer 40 is wider than the width R1 of the metal wiring layer 50, and the metal wiring layer 50 is laminated on the surface of the transparent wiring layer 40 without its ends protruding.

<<Relationship between Width R1 of Metal Wiring Layer and Width R2 of Transparent Wiring Layer>>
In the laminate according to the present disclosure, the width R1 of the metal wiring layer and the width R2 of the transparent wiring layer satisfy the following formula (1).
When R2-R1 is 0.1 μm or more, the lamination suitability tends to be excellent.
When R2-R1 is 6.0 μm or less, the occurrence of migration can be suppressed.
From the viewpoints of lamination suitability and suppression of migration, the laminate according to the present disclosure preferably satisfies the following formula (1-1), more preferably satisfies the following formula (1-2), and even more preferably satisfies the following formula (1-3).
0.1 μm≦R2−R1≦6.0 μm (1)
0.2 μm≦R2−R1≦5.5 μm (1-1)
0.3 μm≦R2−R1≦5.0 μm (1-2)
0.5 μm≦R2−R1≦4.5 μm (1-3)

<<Width R1 of Metal Wiring Layer>>
The width R1 of the metal wiring layer is not particularly limited, but is, for example, preferably 4 μm to 18 μm, more preferably 6 μm to 16 μm, further preferably 8 μm to 14 μm, and particularly preferably 8 μm to 12 μm.
When the width R1 of the metal wiring layer is 4 μm or more, the etching resist is less likely to peel off during the process, and the yield tends to be good.
When the width R1 of the metal wiring layer is 18 μm or less, the metal wiring can be arranged densely, which tends to make it possible to narrow the frame.

In the present disclosure, the width R1 of the metal wiring layer is measured by the following method.
The laminate is cut using an ultramicrotome to prepare a cross section of the line-and-space wiring pattern. In preparation, the laminate is cut so that the cross section is approximately perpendicular to the longitudinal direction of the pattern. The cross section is then observed using a scanning electron microscope (SEM) at an acceleration voltage of 5 kV, and the width of the metal wiring layer pattern in the thickness direction is measured in the cross section. The above preparation and measurement are repeated five times (in other words, five cross sections are prepared, and the width of the metal wiring layer pattern in the thickness direction in each cross section is measured in the thickness direction), and the five measured values are arithmetically averaged. The value obtained in this manner is taken as the width R1 of the metal wiring layer.
As the scanning electron microscope, a scanning electron microscope (model number: JSM-7200F) manufactured by JEOL Ltd. can be suitably used. However, the scanning electron microscope is not limited to this.

<<Width R2 of Transparent Wiring Layer>>
The width R2 of the transparent wiring layer is not particularly limited, but is, for example, preferably 4.5 μm to 18.5 μm, more preferably 6.5 μm to 16.5 μm, even more preferably 8.1 μm to 14.5 μm, and particularly preferably 8.5 μm to 12.5 μm.
When the width R2 of the transparent wiring layer is 4.5 μm or more, the etching resist is less likely to peel off during the process, and the yield tends to be good.
When the width R2 of the transparent wiring layer is 18.5 μm or less, the metal wiring can be arranged densely, which tends to make it possible to narrow the frame.

In the present disclosure, the width R2 of the transparent wiring layer is measured by the following method.
The laminate is cut using an ultramicrotome to prepare a cross section of the line and space wiring pattern. In preparation, the laminate is cut so that the cross section is approximately perpendicular to the longitudinal direction of the pattern. The cross section is then observed using a scanning electron microscope (SEM) at an acceleration voltage of 5 kV, and the width of the transparent wiring layer pattern in the thickness direction is measured in the cross section. The above preparation and measurement are repeated five times (in other words, five cross sections are prepared, and the width of the transparent wiring layer pattern in the thickness direction in each cross section is measured in the thickness direction), and the five measured values are arithmetically averaged. The value obtained by the above is the width R2 of the transparent wiring layer.
As the scanning electron microscope, a scanning electron microscope (model number: JSM-7200F) manufactured by JEOL Ltd. can be suitably used. However, the scanning electron microscope is not limited to this.

<<Thickness R3 of Metal Wiring Layer>>
The thickness R3 of the metal wiring layer is not particularly limited, but is preferably, for example, 6 μm or less, more preferably 0.1 μm to 6 μm, even more preferably 0.2 μm to 5 μm, and particularly preferably 0.3 μm to 4 μm.
When the thickness R3 of the metal wiring layer is 6 μm or less, air is less likely to be entrained during lamination, and lamination suitability tends to be superior.

In the present disclosure, the thickness R3 of the metal wiring layer is measured by the following method.
The laminate is cut using an ultramicrotome to prepare a cross section of the line-and-space wiring pattern. In preparation, the laminate is cut so that the cross section is approximately perpendicular to the longitudinal direction of the pattern. The cross section is then observed using a scanning electron microscope (SEM) at an acceleration voltage of 5 kV, and the thickness of the metal wiring layer pattern in the width direction is measured in the cross section. The above preparation and measurement are repeated five times (in other words, five cross sections are prepared, and the thickness of the metal wiring layer pattern in the width direction in each cross section is measured in the width direction), and the five measured values are arithmetically averaged. The value obtained in this manner is taken as the thickness R3 of the metal wiring layer.
As the scanning electron microscope, a scanning electron microscope (model number: JSM-7200F) manufactured by JEOL Ltd. can be suitably used. However, the scanning electron microscope is not limited to this.

<<Relationship between Width R1 of Metal Wiring Layer, Width R2 of Transparent Wiring Layer, and Thickness R3 of Metal Wiring Layer>>
In the laminate according to the present disclosure, it is preferable that the width R1 of the metal wiring layer, the width R2 of the transparent wiring layer, and the thickness R3 of the metal wiring layer satisfy the following formula (2a), it is more preferable that they satisfy the following formula (2b), and it is even more preferable that they satisfy the following formula (2).
When (R2-R1)/R3 is 0.15 or more, air is less likely to be entrained during lamination, and lamination suitability tends to be superior.
When (R2-R1)/R3 is 5.0 or less, the occurrence of migration tends to be further suppressed.
0.15≦(R2−R1)/R3≦5.0 (2a)
0.2≦(R2−R1)/R3≦4.5 (2b)
0.3≦(R2−R1)/R3≦4.0 (2)

<<Thickness of transparent wiring layer>>
The thickness of the transparent wiring layer is not particularly limited, but is preferably, for example, 1 μm or less, more preferably 0.01 μm to 1 μm, even more preferably 0.03 μm to 0.8 μm, and particularly preferably 0.05 μm to 0.5 μm.
When the thickness of the transparent wiring layer is 1 μm or less, the transparency tends to be more excellent. Also, when the thickness of the transparent wiring layer is 1 μm or less, air is less likely to be entrapped during lamination, and the lamination suitability tends to be more excellent.

In the present disclosure, the thickness of the transparent wiring layer is measured by the following method.
The laminate is cut using an ultramicrotome to prepare a 100 nm thick slice of the line and space wiring pattern. In the preparation, the laminate is cut so that the cross section is approximately perpendicular to the longitudinal direction of the pattern. If necessary, the cross section may be prepared after Pt coating, embedding and polymerization treatment with Araldite resin. The cross section is then observed using a transmission electron microscope (TEM) at an acceleration voltage of 100 kV, and the thickness of the transparent wiring layer pattern in the width direction at the center of the cross section is measured. The above preparation and measurement are repeated five times (in other words, five cross sections are prepared, and the thickness of the transparent wiring layer pattern in the width direction at the center of each cross section is measured), and the five measured values obtained are arithmetically averaged. The value obtained above is the thickness of the transparent wiring layer.
As the transmission electron microscope, a transmission electron microscope (model number: FHT7700) manufactured by Hitachi High-Technologies Corporation can be suitably used. However, the transmission electron microscope is not limited to this.

<<Distance between patterns of transparent wiring layer>>
The distance between adjacent transparent wiring layer patterns is not particularly limited, but is preferably, for example, 1 μm to 20 μm, more preferably 3 μm to 15 μm, and even more preferably 5 μm to 10 μm.
When the distance between the patterns of the transparent wiring layer is 1 μm or more, the ionized metal becomes less likely to move, and the occurrence of migration tends to be more suppressed. Also, when the distance between the patterns of the transparent wiring layer is 1 μm or more, air is less likely to be entrained during lamination, and lamination suitability tends to be better.
If the distance between the patterns of the transparent wiring layer is 20 μm or less, for example, when the wiring portion in the laminate according to the present disclosure is used as peripheral wiring, extraction wiring, or the like of a touch panel, the wiring tends to be denser.

In the present disclosure, the distance between patterns of the transparent wiring layer is measured by the following method.
The laminate is cut using an ultramicrotome to prepare a cross section of the line-and-space wiring pattern. In preparation, the laminate is cut so that the cross section is approximately perpendicular to the longitudinal direction of the pattern. The cross section is then observed using a scanning electron microscope (SEM) at an acceleration voltage of 5 kV, and the distance between adjacent transparent wiring layers is measured. The above preparation and measurement are repeated five times (in other words, five cross sections are prepared, and the shortest distance between the ends of adjacent transparent wiring layers is measured in each cross section), and the five measured values obtained are arithmetically averaged. The value obtained by the above is the distance between the patterns of the transparent wiring layers.
As the scanning electron microscope, a scanning electron microscope (model number: JSM-7200F) manufactured by JEOL Ltd. can be suitably used. However, the scanning electron microscope is not limited to this.

〔Base material〕
The laminate according to the present disclosure has a substrate.
As the substrate used in the present disclosure, a known substrate may be used.
The substrate may have an arbitrary layer that is not conductive, as necessary.
Examples of the substrate include a resin substrate, a glass substrate, and a semiconductor substrate.
Preferred embodiments of the substrate include, for example, those described in paragraph [0140] of International Publication No. 2018/155193, the contents of which are incorporated herein by reference.

Examples of materials that can be used to form the substrate include glass, silicon, and resin.
The substrate is preferably transparent.
Examples of the transparent glass substrate include tempered glass, such as Gorilla Glass from Corning Inc. In addition, the materials used in JP-A-2010-86684, JP-A-2010-152809, and JP-A-2010-257492 can be used as the transparent glass substrate.

When a film substrate is used as the substrate, it is preferable to use a film substrate that has small optical distortion and/or high transparency. Examples of such film substrates include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, polyimide, and cycloolefin polymer.

When produced by a roll-to-roll method, the substrate is preferably a film substrate.
When circuit wiring for a touch panel is produced by a roll-to-roll method, the substrate is preferably a sheet-shaped resin composition.

The substrate may have the wiring portion described below on only one side or on both sides.

The thickness of the substrate is not particularly limited, but is preferably 50 μm to 300 μm, more preferably 50 μm to 200 μm, and even more preferably 50 μm to 150 μm.

The thickness of the substrate means the average thickness measured by the following method.
In a cross-sectional observation image of the substrate in the thickness direction, the arithmetic average value of the thicknesses of the substrate measured at 10 arbitrarily selected points is calculated, and the obtained value is regarded as the average thickness of the substrate. The cross-sectional observation image of the substrate in the thickness direction is obtained by using a scanning electron microscope (SEM).

[Wiring section]
The laminate according to the present disclosure has a wiring portion on a substrate, The wiring portion is formed by laminating a transparent wiring layer and a metal wiring layer in this order.

<Transparent wiring layer>
The transparent wiring layer may be any layer that is transparent and conductive.
In the present disclosure, "electrically conductive" refers to a property in which the volume resistivity is less than 1 x ¹⁰⁶ Ωcm. The volume resistivity of the transparent wiring layer is preferably less than 1 x ¹⁰⁴ Ωcm.
The volume resistivity is measured by a commercially available resistivity measuring device (for example, Loresta GX MCP-T700 (product name) manufactured by Nitto Seiko Analytech Co., Ltd.).

The transparent wiring layer preferably contains at least one selected from the group consisting of metal oxides and metal nanowires. The transparent wiring layer also preferably contains a resin.
The transparent wiring layer may be, for example, a layer containing a metal oxide, a layer containing metal nanowires, or a layer containing metal nanowires and a resin.
Examples of metal oxides include indium tin oxide (ITO) and indium zinc oxide (IZO).
Among these, the metal oxide is preferably indium tin oxide.
Metal nanowires include, for example, gold nanowires, silver nanowires, copper nanowires, and platinum wires.
Among these, silver nanowires are preferable as the metal nanowires.

The transparent wiring layer preferably contains at least one metal oxide selected from indium tin oxide and indium zinc oxide.
The transparent wiring layer also preferably contains at least one type of metal nanowire selected from gold nanowires, silver nanowires, copper nanowires, and platinum wires, and a resin.

Examples of the shape of the metal nanowire include a cylindrical shape, a rectangular parallelepiped shape, and a columnar shape with a polygonal cross section.
For example, in applications requiring high transparency, the metal nanowires preferably have at least one of a cylindrical shape and a columnar shape having a polygonal cross section.

The cross-sectional shape of the metal nanowires can be observed, for example, using a transmission electron microscope (TEM).

The diameter (so-called short axis length) of the metal nanowire is not particularly limited, but from the viewpoint of transparency, it is preferably 50 nm or less, more preferably 35 nm or less, and even more preferably 20 nm or less.
The lower limit of the diameter of the metal nanowires is preferably 5 nm or more, for example, from the viewpoint of oxidation resistance and durability.

The length of the metal nanowires (so-called major axis length) is not particularly limited, but from the viewpoint of electrical conductivity, it is preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 30 μm or more.
The upper limit of the length of the metal nanowires is preferably 1 mm or less, for example, from the viewpoint of suppressing the formation of aggregates during the manufacturing process.

The diameter and length of the metal nanowires can be measured, for example, by using a transmission electron microscope (TEM) or an optical microscope.
Specifically, the diameter and length of 300 randomly selected metal nanowires are measured from the metal nanowires magnified and observed using a transmission electron microscope (TEM) or an optical microscope. The measured values are arithmetically averaged, and the obtained values are regarded as the diameter and length of the metal nanowire.

When the transparent wiring layer contains metal nanowires, it may contain only one type of metal nanowires, or it may contain two or more types of metal nanowires.

When the transparent wiring layer contains metal nanowires, the content of the metal nanowires in the transparent wiring layer is preferably 1% by mass to 30% by mass, more preferably 1% by mass to 20% by mass, and even more preferably 1% by mass to 15% by mass, relative to the total mass of the transparent wiring layer, from the viewpoints of, for example, transparency, conductivity, and dispersion stability.

When the transparent wiring layer contains a resin, the resin is preferably a binder polymer from the viewpoint of durability.
Examples of the resin include acrylic resins (e.g., benzyl methacrylate/methacrylic acid/acrylic acid copolymers), polyester resins (e.g., polyethylene terephthalate (PET)), polycarbonate resins, polyimide resins, polyamide resins, polyurethane resins, polyolefins (e.g., polypropylene), polynorbornene, cellulose resins (e.g., cellulose resins such as hydroxypropylmethylcellulose (HPMC), hydroxyethylcellulose (HEC), methylcellulose (MC), hydroxypropylcellulose (HPC), carboxymethylcellulose (CMC), and cellulose), polyvinyl alcohol (PVA), and polyvinylpyrrolidone.
The resin preferably contains at least one selected from the group consisting of acrylic resins and polyurethane resins, and more preferably contains at least one selected from the group consisting of acrylic resins and polyurethane resins, from the viewpoints of transparency and durability, for example.

The glass transition temperature (Tg) of the resin is not particularly limited, but is preferably 180°C or lower, more preferably 40°C to 160°C, and even more preferably 60°C to 150°C.

In the present disclosure, the glass transition temperature of a resin is measured using differential scanning calorimetry (DSC). Specifically, the glass transition temperature of a resin is measured in accordance with the method described in JIS K 7121:1987 or JIS K 6240:2011. The glass transition temperature in the present disclosure is the extrapolated glass transition onset temperature (also referred to as "Tig").
The method for measuring the glass transition temperature will now be described more specifically.
When determining the glass transition temperature, the apparatus is maintained at a temperature about 50° C. lower than the expected Tg of the resin until the apparatus becomes stable, and then the apparatus is heated at a heating rate of 20° C./min to a temperature about 30° C. higher than the temperature at which the glass transition ends, and a differential thermal analysis (DTA) curve or a DSC curve is prepared.
The extrapolated glass transition onset temperature (Tig), i.e., the glass transition temperature Tg in the present disclosure, is determined as the temperature at the intersection of a straight line extending the low-temperature side baseline of a DTA curve or DSC curve to the high-temperature side and a tangent drawn at the point where the gradient of the curve of the step-like change in the glass transition is maximum.

The weight average molecular weight of the resin is not particularly limited, but is preferably, for example, 1,000 to 2,000,000, and more preferably 10,000 to 1,200,000.

When the transparent wiring layer contains a resin, it may contain only one type of resin, or two or more types.

When the transparent wiring layer contains a resin, the content of the resin in the transparent wiring layer is preferably 20% by mass to 90% by mass, more preferably 30% by mass to 80% by mass, and even more preferably 40% by mass to 70% by mass, relative to the total mass of the transparent wiring layer, from the viewpoints of formability, conductivity, and transparency of the transparent wiring layer, for example.

When both the transparent wiring layer and the metal wiring layer contain a resin, the resin contained in the transparent wiring layer may be the same as or different from the resin contained in the metal wiring layer.
When both the transparent wiring layer and the metal wiring layer contain a resin, the transparent wiring layer preferably contains the same resin as that contained in the metal wiring layer, from the viewpoint of adhesion to the metal wiring layer.

The transparent wiring layer may contain various additives.
Examples of the additives include known additives such as antioxidants, e.g., hindered phenols, and rust inhibitors, e.g., benzotriazole.

The transparent wiring layer may be a single layer or a multi-layer structure of two or more layers.
When the transparent wiring layer is a multi-layer structure, the multiple transparent wiring layers may be made of the same material or different materials.

<Metal Wiring Layer>
The metal wiring layer may be any layer that contains a metal and has electrical conductivity.
The volume resistivity of the metal wiring layer is preferably less than 1×10 ⁴ Ωcm.
The metal wiring layer preferably contains at least one selected from the group consisting of a simple metal and a metal alloy. It is also preferable that the metal wiring layer further contains a resin in addition to the at least one selected from the group consisting of a simple metal and a metal alloy.
The metal wiring layer may be, for example, made of a simple metal, may be made of a metal alloy, or may contain at least one selected from the group consisting of simple metals and metal alloys, and a resin.

Examples of elemental metals include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, nickel, platinum, palladium, and manganese.
The metal element is preferably at least one selected from the group consisting of gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and more preferably at least one selected from silver and copper.
Examples of the metal alloy include alloys made of two or more metal elements selected from the group consisting of gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, nickel, platinum, palladium, and manganese.
The metal alloy is preferably an alloy of two or more metal elements selected from the group consisting of gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and is more preferably an alloy of silver and copper.

The metal wiring layer preferably includes at least one of a metal element and a metal alloy, the metal element being at least one selected from the group consisting of gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and the metal alloy being an alloy consisting of two or more metal elements selected from the group consisting of gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese. It is also preferable that the metal wiring layer includes at least one of a metal element and a metal alloy, and a resin, the metal element being at least one selected from the group consisting of gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and the metal alloy being an alloy consisting of two or more metal elements selected from the group consisting of gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese.

When the metal wiring layer contains at least one of an elemental metal and a metal alloy and a resin, the elemental metal and the metal alloy are preferably metal nanostructures.
The shape of the metal nanobody is not particularly limited, and may be any known shape.
The metal nanostructures are preferably metal nanoparticles.

The metal nanoparticles may be spherical particles, tabular particles, or particles of irregular shape.
From the viewpoints of stability and fusion temperature, the average primary particle size of the metal nanoparticles is preferably 0.1 nm to 500 nm, more preferably 1 nm to 200 nm, and even more preferably 1 nm to 100 nm.

The average primary particle size of metal nanoparticles in this disclosure is obtained by taking scanning electron micrographs (SEM images) of 100 particles using a scanning electron microscope (e.g., S-3700N (model number) manufactured by Hitachi High-Technologies Corporation), measuring the particle size of the particles using an image processing measuring device (e.g., Luzex AP manufactured by Nireco Corporation), and calculating the arithmetic average value. That is, the particle size in this disclosure is expressed as the diameter when the projected shape of the particle is circular, and is expressed as the diameter of a circle with the same area as the projected area when the particle has an irregular shape other than spherical.

From the viewpoint of electrical conductivity, the metal nanoparticles preferably contain a metal more noble than silver, and in this case, it is more preferable for the metal nanoparticles to contain flat particles at least a portion of which is coated with gold.
The term "metal more noble than silver" means "a metal having a standard electrode potential higher than the standard electrode potential of silver."

In the metal nanoparticles, the ratio of the metal nobler than silver to silver is preferably 0.01 atomic % to 5 atomic %, more preferably 0.1 atomic % to 2 atomic %, and even more preferably 0.2 atomic % to 0.5 atomic %.
The content of metals nobler than silver can be measured, for example, by dissolving a sample in an acid or the like and then subjecting the sample to high-frequency inductively coupled plasma (ICP) emission spectrometry.

As metal nanoparticles, from the viewpoint of dispersibility and conductivity, for example, metal nanoparticles with an aspect ratio of 1:1 to 1:10 and a sphere-equivalent diameter of 1 nm to 200 nm are preferred.

When the metal wiring layer contains metal nano-bodies, it may contain only one type of metal nano-bodies, or it may contain two or more types of metal nano-bodies.

When the metal wiring layer contains metal nano-bodies, the content of the metal nano-bodies in the metal wiring layer is preferably 30% by mass to 99% by mass, more preferably 50% by mass to 95% by mass, and even more preferably 70% by mass to 90% by mass, relative to the total mass of the metal wiring layer, from the viewpoints of, for example, electrical conductivity and dispersion stability.

When the metal wiring layer contains a resin, the resin is preferably a binder polymer, for example, from the viewpoint of durability.
Examples of the resin include acrylic resins (e.g., benzyl methacrylate/methacrylic acid/acrylic acid copolymers), polyester resins (e.g., polyethylene terephthalate (PET)), polycarbonate resins, polyimide resins, polyamide resins, polyurethane resins, polyolefins (e.g., polypropylene), polynorbornene, cellulose resins (e.g., cellulose resins such as hydroxypropylmethylcellulose (HPMC), hydroxyethylcellulose (HEC), methylcellulose (MC), hydroxypropylcellulose (HPC), carboxymethylcellulose (CMC), and cellulose), polyvinyl alcohol (PVA), and polyvinylpyrrolidone.
The resin preferably contains an acrylic resin, and is more preferably an acrylic resin, from the viewpoint of durability, for example.

The resin may be a conductive polymeric material.
Examples of the conductive polymer material include polyaniline and polythiophene.

The glass transition temperature (Tg) of the resin is not particularly limited, but is preferably 180°C or lower, more preferably 40°C to 160°C, and even more preferably 60°C to 150°C.

In the present disclosure, the glass transition temperature of a resin is measured using differential scanning calorimetry (DSC). Specifically, the glass transition temperature of a resin is measured in accordance with the method described in JIS K 7121:1987 or JIS K 6240:2011. The glass transition temperature in the present disclosure is the extrapolated glass transition onset temperature (also referred to as "Tig").
The method for measuring the glass transition temperature will now be described more specifically.
When determining the glass transition temperature, the apparatus is maintained at a temperature about 50° C. lower than the expected Tg of the resin until the apparatus becomes stable, and then the apparatus is heated at a heating rate of 20° C./min to a temperature about 30° C. higher than the temperature at which the glass transition ends, and a differential thermal analysis (DTA) curve or a DSC curve is prepared.
The extrapolated glass transition onset temperature (Tig), i.e., the glass transition temperature Tg in the present disclosure, is determined as the temperature at the intersection of a straight line extending the low-temperature baseline of a DTA curve or DSC curve to a high-temperature side and a tangent drawn at the point where the gradient of the curve of the step-like change in the glass transition is maximum.

The weight average molecular weight of the resin is not particularly limited, but is preferably, for example, 1,000 to 2,000,000, and more preferably 10,000 to 1,200,000.

When the metal wiring layer contains a resin, it may contain only one type of resin, or two or more types.

When the metal wiring layer contains a resin, the content of the resin in the metal wiring layer is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 50% by mass, and even more preferably 10% by mass to 30% by mass, based on the total mass of the metal wiring layer, from the viewpoint of formability and conductivity of the metal wiring layer, for example.

The metal wiring layer may contain various additives.
The additives include known additives such as rust inhibitors such as benzotriazole.

The metal wiring layer may also contain inorganic particles.
Examples of inorganic particles include silica particles, mullite particles, and alumina particles.

The metal wiring layer may be a single layer or a multi-layer structure of two or more layers.
When the metal wiring layer is a multi-layer structure, the multiple metal wiring layers may be made of the same material or different materials.

The metal wiring layer preferably has an average transmittance of less than 70% for visible light with wavelengths of 400 nm to 700 nm, and more preferably 60% or less.

<Applications>
The laminate according to the present disclosure can be suitably used for circuit wiring of a touch panel, circuit wiring of various electronic devices, etc. The conductive portion in the laminate according to the present disclosure can be suitably used as, for example, peripheral wiring or extraction wiring of a touch panel.
The laminate according to the present disclosure can be applied to various devices.
Applicable devices include, for example, input devices, preferably touch panels, and more preferably capacitive touch panels.
An input device including a laminate according to the present disclosure can be applied to display devices such as organic electroluminescence display devices and liquid crystal display devices.
Furthermore, the laminate according to the present disclosure can be suitably used in flexible display devices (for example, flexible touch panels).

[Method of manufacturing laminate]
The method for producing the laminate according to the present disclosure (hereinafter also simply referred to as the "production method") is not particularly limited as long as it can produce the laminate according to the present disclosure described above.
The production method according to the present disclosure is preferably a roll-to-roll production method.
As the production method according to the present disclosure, for example, from the viewpoint of ease of producing the laminate according to the present disclosure, the production method according to the first embodiment described below is preferred.

[Manufacturing method according to the first embodiment]
The manufacturing method according to the first embodiment includes, in this order, a step of preparing a conductive base material having a base material, a transparent conductive layer, and a metal layer (also referred to as "step 1-1"); a step of forming an etching resist on the metal layer (also referred to as "step 1-2"); a step of patterning the etching resist to obtain an etching resist pattern (also referred to as "step 1-3"); and a step of etching the transparent conductive layer and the metal layer using the etching resist pattern as a mask (also referred to as "step 1-4").
In the manufacturing method according to the first embodiment, the width R1 of the metal wiring layer, the width R2 of the transparent wiring layer, and the width R4 of the etching resist pattern have a relationship that satisfies the following formula (3).
R1<R2≦R4 (3)

The steps for the above process are explained in detail below.

<Step 1-1>
Step 1-1 is a step of preparing a conductive substrate having a substrate, a transparent conductive layer, and a metal layer in this order.
As the substrate, the substrates already described can be suitably used.

There are no limitations on the material of the transparent conductive layer as long as it is transparent and conductive.
The transparent conductive layer preferably contains at least one selected from the group consisting of metal oxides and metal nanowires, and further preferably contains a resin.
The transparent conductive layer may be, for example, a layer containing a metal oxide, a layer containing metal nanowires, or a layer containing metal nanowires and a resin.
The metal oxide in the transparent conductive layer is the same as the metal oxide in the transparent wiring layer described above, and the preferred embodiments are also the same, so the description will be omitted here.
The metal nanowires in the transparent conductive layer are synonymous with the metal nanowires in the transparent wiring layer described above, and preferred embodiments are also the same, so a description thereof will be omitted here.
The resin in the transparent conductive layer is the same as the resin in the transparent wiring layer described above, and the preferred embodiments are also the same, so a description thereof will be omitted here.

When the transparent conductive layer contains metal nanowires, it may contain only one type of metal nanowires, or may contain two or more types of metal nanowires.
When the transparent conductive layer contains metal nanowires, the content of the metal nanowires in the transparent conductive layer is, for example, preferably 1 mass % to 30 mass %, more preferably 1 mass % to 20 mass %, and even more preferably 1 mass % to 15 mass %, relative to the total mass of the transparent conductive layer.

When the transparent conductive layer contains a resin, it may contain only one type of resin, or may contain two or more types of resin.
When the transparent conductive layer contains a resin, the content of the resin in the transparent conductive layer is, for example, preferably 20% by mass to 90% by mass, more preferably 30% by mass to 80% by mass, and even more preferably 40% by mass to 70% by mass, relative to the total mass of the transparent conductive layer.

The transparent conductive layer may contain various additives.
Examples of the additives include known additives such as antioxidants, e.g., hindered phenols, and rust inhibitors, e.g., benzotriazole.

The transparent conductive layer may be a single layer or a multi-layer structure of two or more layers.
When the transparent conductive layer is a multi-layer structure, the multiple transparent conductive layers may be made of the same material or different materials.

The thickness of the transparent conductive layer is not particularly limited, but is preferably, for example, 1 μm or less, more preferably 0.01 μm to 1 μm, even more preferably 0.03 μm to 0.8 μm, and particularly preferably 0.05 μm to 0.5 μm.
The thickness of the transparent conductive layer is the average value of thicknesses at 10 points (i.e., average thickness) measured by observing a cross section perpendicular to the in-plane direction using a scanning electron microscope (SEM).

The method for forming the transparent conductive layer is not particularly limited.
For example, when the transparent conductive layer is a layer containing a metal oxide, preferred methods for forming the transparent conductive layer include sputtering and vapor deposition.
In the case of sputtering, an inert gas (mainly argon) is introduced into a vacuum and a negative voltage is applied to a target (e.g., a plate-shaped film-forming material). This application generates a glow discharge and ionizes the inert gas atoms. The gas ions collide violently at high speed with the surface of the target, ejecting particles (e.g., atoms and/or molecules) of the film-forming material that constitutes the target, which then adhere or deposit vigorously on the surface of the base material or substrate to form a thin film.
Examples of the deposition method include induction heating deposition, resistance heating deposition, laser beam deposition, and electron beam deposition. Any deposition method may be used, but electron beam deposition is preferably used from the viewpoint of high film formation speed. During deposition, deposition may be performed while cooling the substrate so that the temperature of the substrate does not increase.

For example, in the case of a layer containing metal nanowires, a method for forming a transparent conductive layer includes a method of forming the layer by applying a material in which a conductive material containing metal nanowires is dispersed in a liquid (also referred to as "conductive ink X"). After application, drying, baking, etc. may be performed as necessary.
The method for applying the conductive ink X is not particularly limited, and examples thereof include an inkjet method, a spray method, a roll coating method, a bar coating method, a curtain coating method, and a die coating method (that is, a slit coating method).
The conductive ink X may be a curable ink, for example, a heat curable ink, a light curable ink, or a heat and light curable ink.
The conductive ink X preferably contains metal nanowires and a resin.
As the metal nanowires in the conductive ink X, the metal nanowires in the transparent wiring layer described above are preferably used.
The conductive ink X may contain only one type of metal nanowire, or may contain two or more types of metal nanowires.
The content of the metal nanowires in the conductive ink X is preferably 0.001% by mass to 30% by mass, more preferably 0.001% by mass to 20% by mass, and even more preferably 0.001% by mass to 15% by mass, relative to the total mass of the conductive ink X.
As the resin in the conductive ink X, the resin in the transparent wiring layer described above is preferably used.
When the conductive ink X contains a resin, it may contain only one type of resin, or may contain two or more types of resin.
When the conductive ink X contains a resin, the content of the resin in the conductive ink X is preferably 0.02% by mass to 90% by mass, more preferably 0.03% by mass to 80% by mass, and even more preferably 0.04% by mass to 70% by mass, relative to the total mass of the conductive ink X.

The conductive ink X may contain a polymerizable compound.
When the conductive ink X contains a polymerizable compound, the conductive ink X preferably contains a polymerization initiator in addition to the polymerizable compound.

From the viewpoint of strength of the transparent conductive layer, the polymerizable compound is preferably an ethylenically unsaturated compound, more preferably a (meth)acrylate compound. As the (meth)acrylate compound, a urethane (meth)acrylate compound is also preferable.
Moreover, from the viewpoint of strength of the transparent conductive layer, the polymerizable compound preferably contains a bifunctional or more polymerizable compound, more preferably contains a trifunctional to decafunctional polymerizable compound, and further preferably contains a tetrafunctional to octafunctional polymerizable compound.
Furthermore, from the viewpoint of strength of the transparent conductive layer, the polymerizable compound preferably contains a di- or higher functional ethylenically unsaturated compound, and more preferably contains a di- or higher functional (meth)acrylate compound.

As the polymerizable compound, commercially available products can be used.
Examples of commercially available polymerizable compounds include ARONIX (registered trademark) M-350 and ARONIX (registered trademark) M-1960 manufactured by Toagosei Co., Ltd.

As the polymerizable compound, the polymerizable compounds used in the photosensitive resin layer described below can also be suitably used.

When the conductive ink X contains a polymerizable compound, it may contain only one type of polymerizable compound, or it may contain two or more types of polymerizable compounds.

When the conductive ink X contains a polymerizable compound, the content of the polymerizable compound in the conductive ink X is preferably 0.02% by mass to 90% by mass, more preferably 0.03% by mass to 80% by mass, and even more preferably 0.04% by mass to 70% by mass, based on the total solid content in the conductive ink X, from the viewpoint of the strength of the transparent conductive layer.

The polymerization initiator is not particularly limited, but a photopolymerization initiator is preferred.
The photopolymerization initiator is preferably a photoradical polymerization initiator.
The photopolymerization initiator is not particularly limited, and any known photopolymerization initiator can be used.

Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter also referred to as an "oxime-based photopolymerization initiator"), a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter also referred to as an "α-aminoalkylphenone-based photopolymerization initiator"), a photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter also referred to as an "α-hydroxyalkylphenone-based polymerization initiator"), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter also referred to as an "acylphosphine oxide-based photopolymerization initiator"), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter also referred to as an "N-phenylglycine-based photopolymerization initiator").
Among these, the photopolymerization initiator is preferably an α-hydroxyalkylphenone-based polymerization initiator (for example, Omnirad (registered trademark) 184 manufactured by IGM Resins BV).
As the polymerization initiator, a polymerization initiator used in the photosensitive resin layer described below can also be suitably used.

When the conductive ink X contains a polymerization initiator, it may contain only one type of polymerization initiator, or may contain two or more types of polymerization initiators.
When the conductive ink X contains a polymerization initiator, the content of the polymerization initiator in the conductive ink X is, from the viewpoint of the strength of the transparent conductive layer, preferably 0.001% by mass to 20% by mass, more preferably 0.002% by mass to 15% by mass, and even more preferably 0.003% by mass to 10% by mass, relative to the total solid content in the conductive ink X.

The conductive ink X may contain various additives.
The additives include known additives such as dispersants.
An example of the dispersant is DisperBYK-111 (manufactured by BYK-Chemie).

The conductive ink X may contain a solvent.
The solvent contained in the conductive ink X may be water, an organic solvent, or a mixture thereof.
As the organic solvent, preferred are hydrocarbons such as toluene, dodecane, tetradecane, cyclododecene, n-heptane, and n-undecane; alcohols such as ethanol and isopropyl alcohol; and propylene glycol ethers such as propylene glycol monomethyl ether acetate.

The metal layer is a layer containing a metal, and preferably contains at least one selected from the group consisting of a simple metal and a metal alloy. It is also preferable that the metal layer further contains a resin in addition to the at least one selected from the group consisting of a simple metal and a metal alloy.
The metal layer may be, for example, made of a simple metal, may be made of a metal alloy, or may contain at least one selected from the group consisting of simple metals and metal alloys, and a resin.
The metal element in the metal layer has the same meaning as the metal element in the metal wiring layer described above, and the preferred embodiments are also the same, so the explanation will be omitted here.
The metal alloy in the metal layer has the same meaning as the metal alloy in the metal wiring layer described above, and the preferred embodiments are also the same, so the description will be omitted here.
The resin in the metal layer has the same meaning as the resin in the metal wiring layer described above, and the preferred embodiments are also the same, so the explanation will be omitted here.

The metal layer preferably includes at least one of a metal element and a metal alloy, the metal element being at least one selected from the group consisting of gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and the metal alloy being an alloy consisting of two or more metal elements selected from the group consisting of gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese. The metal layer preferably includes at least one of a metal element and a metal alloy, and a resin, the metal element being at least one selected from the group consisting of gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and the metal alloy being an alloy consisting of two or more metal elements selected from the group consisting of gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese.

When the metal layer contains at least one of an elemental metal and a metal alloy and a resin, the elemental metal and the metal alloy are preferably metal nanostructures.
The metal nanostructures in the metal layer are the same as the metal nanostructures in the metal wiring layer described above, and the preferred embodiments are also the same, so a description thereof will be omitted here.

When the metal layer contains metal nanostructures, it may contain only one type of metal nanostructure, or may contain two or more types of metal nanostructures.
When the metal layer contains metal nanostructures, the content of metal nanostructures in the metal layer is, for example, preferably 30% by mass to 99% by mass, more preferably 50% by mass to 95% by mass, and even more preferably 70% by mass to 90% by mass, relative to the total mass of the metal layer.

When the metal layer contains a resin, it may contain only one type of resin, or may contain two or more types of resin.
When the metal layer contains a resin, the content of the resin in the metal layer is, for example, preferably 1 mass % to 70 mass %, more preferably 5 mass % to 50 mass %, and even more preferably 10 mass % to 30 mass %, relative to the total mass of the metal layer.

The metal layer may contain various additives.
The additives include known additives such as rust inhibitors such as benzotriazole.

The metal layer may contain inorganic particles.
Examples of inorganic particles include silica particles, mullite particles, and alumina particles.

The metal layer may be a single layer or a multi-layer structure of two or more layers.
When the metal layer is a multi-layer structure, the multiple metal layers may be made of the same material or different materials.

The metal layer preferably has an average transmittance of less than 70% for visible light with wavelengths of 400 nm to 700 nm, and more preferably 60% or less.

The thickness of the metal layer is not particularly limited, but is, for example, preferably 6 μm or less, more preferably 0.1 μm to 6 μm, even more preferably 0.2 μm to 5 μm, and particularly preferably 0.3 μm to 4 μm.
The thickness of the metal layer is the average value (ie, average thickness) of thicknesses at 10 points measured by observing a cross section perpendicular to the in-plane direction using a scanning electron microscope (SEM).

The method for forming the metal layer is not particularly limited.
For example, when the metal layer contains metal nano-bodies, the metal layer can be formed by applying a material in which a conductive material containing metal nano-bodies is dispersed in a liquid (also referred to as "conductive ink Y"). After application, drying, baking, etc. may be performed as necessary.
The method for applying the conductive ink Y is not particularly limited, and examples thereof include an inkjet method, a spray method, a roll coating method, a bar coating method, a curtain coating method, and a die coating method (that is, a slit coating method).
The conductive ink Y may be a curable ink, for example, a heat curable ink, a light curable ink, or a heat and light curable ink.
The conductive ink Y preferably contains metal nanostructures and a resin.
Preferred examples of the metal nano-structures in the conductive ink Y include the metal nano-structures in the metal wiring layer described above.
The conductive ink Y may contain only one type of metal nanobody, or may contain two or more types.
The content of metal nanoparticles in the conductive ink Y is preferably 1% by mass to 99% by mass, more preferably 1% by mass to 95% by mass, and even more preferably 1% by mass to 90% by mass, relative to the total mass of the conductive ink Y.
As the resin in the conductive ink Y, the resin in the metal wiring layer described above is preferably used.
When the conductive ink Y contains a resin, it may contain only one type of resin, or may contain two or more types of resin.
When the conductive ink Y contains a resin, the content of the resin in the conductive ink Y is preferably 0.1 mass % to 70 mass %, more preferably 0.3 mass % to 50 mass %, and even more preferably 0.5 mass % to 30 mass %, relative to the total mass of the conductive ink Y.

The conductive ink Y may contain a polymerizable compound.
When the conductive ink Y contains a polymerizable compound, the conductive ink Y preferably contains a polymerization initiator in addition to the polymerizable compound.
The polymerizable compound in the conductive ink Y is the same as the polymerizable compound in the conductive ink X, and the preferred embodiments are also the same, so a description thereof will be omitted here.
The polymerization initiator in the conductive ink Y is the same as the polymerization initiator in the conductive ink X, and the preferred embodiments are also the same, so a description thereof will be omitted here.

When the conductive ink Y contains a polymerizable compound, it may contain only one type of polymerizable compound, or may contain two or more types of polymerizable compounds.
When the conductive ink Y contains a polymerizable compound, the content of the polymerizable compound in the conductive ink Y is, from the viewpoint of the strength of the metal layer, preferably 0.1 mass % to 60 mass %, more preferably 0.3 mass % to 50 mass %, and even more preferably 0.5 mass % to 30 mass %, relative to the total solid content in the conductive ink Y.

When the conductive ink Y contains a polymerization initiator, it may contain only one type of polymerization initiator, or may contain two or more types of polymerization initiators.
When the conductive ink Y contains a polymerization initiator, the content of the polymerization initiator in the conductive ink Y is, from the viewpoint of the strength of the metal layer, preferably 0.01 mass % to 20 mass %, more preferably 0.03 mass % to 15 mass %, and even more preferably 0.05 mass % to 10 mass %, relative to the total solid content in the conductive ink Y.

The conductive ink Y may contain various additives.
The additives include known additives such as dispersants.
An example of the dispersant is DisperBYK-111 (manufactured by BYK-Chemie).

The conductive ink Y may contain a solvent.
The solvent in the conductive ink Y is the same as the solvent in the conductive ink X, and the preferred embodiments are also the same, so a description thereof will be omitted here.

<Step 1-2>
Step 1-2 is a step of forming an etching resist on the metal layer of the conductive base material prepared in step 1-1.
The method for forming an etching resist on the metal layer is not particularly limited, and any known resist forming method can be used.
Step 1-2 is preferably a step of forming an etching resist by contacting a photosensitive transfer material onto a metal layer and transferring it, and more preferably a step of forming an etching resist by contacting a photosensitive transfer material that has been formed in advance on a temporary support onto a metal layer and transferring it.
A preferred method for transferring the etching resist onto the metal layer using a photosensitive transfer material is to bring the metal layer into contact with the photosensitive resin layer (corresponding to the etching resist) in the photosensitive transfer material and press the photosensitive transfer material and the metal layer together.
According to this method, the adhesion between the photosensitive resin layer and the metal layer in the photosensitive transfer material is improved, so that the photosensitive resin layer can be more suitably used as an etching resist when etching the transparent conductive layer and the metal layer.
A preferred embodiment of the photosensitive transfer material used in the method for producing a laminate according to the present disclosure will be described later.

The etching resist may be either positive or negative.
The etching resist may contain a polymerizable compound, a photopolymerization initiator, and an alkali-soluble resin, or may contain a resin whose polarity changes under the action of acid (preferably an acid-decomposable resin (i.e., a polymer having a structural unit having an acid group protected by an acid-decomposable group)) and a photoacid generator, or may contain a resin having a structural unit having a phenolic hydroxyl group, and a quinone diazide compound.
Among these, the etching resist preferably contains a polymerizable compound, a photopolymerization initiator, and an alkali-soluble resin.

The method for bonding the metal layer and the photosensitive transfer material by pressure is not particularly limited, and known transfer and lamination methods can be used.
The photosensitive transfer material is preferably bonded to the metal layer by overlapping the outermost layer having the photosensitive resin layer and the metal layer on the temporary support of the photosensitive transfer material, and applying pressure and heat using a means such as a roll.
For lamination, a known laminator such as a laminator or a vacuum laminator can be used. For lamination, an autocut laminator that can further improve productivity can also be used.
The lamination temperature is not particularly limited, but is preferably from 70°C to 130°C, for example.

When the photosensitive transfer material has a protective film, it is preferable to include a step of peeling off the protective film before step 1-2.
The method for peeling off the protective film is not particularly limited, and any known method can be applied.

When a photosensitive transfer material is used, it is preferable to include a peeling step of peeling off the temporary support between step 1-2 and step 1-3, or between exposure and development treatment in step 1-3.
The method for peeling off the temporary support is not particularly limited, and the same method as the method for peeling off the cover film described in paragraphs [0161] to [0162] of JP-A No. 2010-072589 can be applied.

<Step 1-3>
Step 1-3 is a step of patterning the etching resist formed in step 1-2 to obtain an etching resist pattern.
Step 1-3 is preferably a step of obtaining a patterned etching resist (ie, an etching resist pattern) by pattern-exposing and developing the etching resist.
The pattern exposure is a pattern-like exposure process, that is, an exposure process in which exposed areas and non-exposed areas exist.
The positional relationship between the exposed and unexposed regions in the pattern exposure is not particularly limited and may be appropriately adjusted.

The detailed arrangement and specific size of the pattern in the pattern exposure are not particularly limited.
For example, from the viewpoint of improving the display quality of a display device (e.g., a touch panel) equipped with an input device having circuit wiring manufactured by an etching method and reducing the area occupied by the lead-out wiring, at least a portion of the pattern (preferably, the electrode pattern and/or the lead-out wiring portion of the touch panel) preferably includes thin lines having a width of 20 μm or less, and more preferably includes thin lines having a width of 10 μm or less.

The width R4 of the etching resist pattern obtained in step 1-3 has a relationship with the width R1 of the metal wiring layer and the width R2 of the transparent wiring layer in the finally obtained laminate according to the present disclosure that satisfies the following formula (3), and preferably satisfies the following formula (3-1).
R1<R2≦R4 (3)
R1 < R2 < R4 (3-1)

The width R4 of the etching resist pattern obtained in step 1-3 is preferably 4.5 μm to 19.5 μm, more preferably 6.5 μm to 17.5 μm, even more preferably 8.1 μm to 15.5 μm, and particularly preferably 8.5 μm to 13.5 μm.

In order to better exert the effects of the present disclosure, the etching resist pattern obtained in step 1-3 preferably has a distance between patterns of 1 μm to 20 μm, more preferably has a distance between patterns of 3 μm to 15 μm, and even more preferably has a distance between patterns of 5 μm to 10 μm.

The light source used for exposure can be appropriately selected as long as it is a light source that irradiates light with a wavelength (for example, 365 nm, 405 nm, or 436 nm) that can expose the etching resist formed in step 1-2.
Specific examples of light sources used for exposure include discharge lamps such as extra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps; and semiconductor light sources such as LEDs (Light Emitting Diodes).
The exposure dose is preferably from 5 mJ/cm ² to 200 mJ/cm ² , and more preferably from 10 mJ/cm ² to 100 mJ/cm ² .
In the method for producing a laminate according to the present disclosure, preferred embodiments of the light source, exposure dose, and exposure method used for exposure are, for example, those described in paragraphs [0146] to [0147] of International Publication No. WO 2018/155193, the contents of which are incorporated herein by reference.

When a photosensitive transfer material is used, in step 1-3, pattern exposure may be performed after peeling off the temporary support from the transfer layer (e.g., a photosensitive resin layer), or pattern exposure may be performed through the temporary support before peeling off the temporary support, and then the temporary support may be peeled off.
When the temporary support is peeled off before exposure, the mask may be exposed in contact with the transfer layer, or may be exposed in close proximity to the transfer layer without contacting it. When the temporary support is not peeled off and the mask is exposed, the mask may be exposed in contact with the temporary support, or may be exposed in close proximity to the temporary support without contacting it. From the viewpoint of preventing the mask contamination caused by the contact between the transfer layer and the mask and avoiding the influence of foreign matter attached to the mask on the exposure, it is preferable to perform pattern exposure without peeling off the temporary support.
For example, in the case of contact exposure, the contact exposure method is selected, and in the case of non-contact exposure, the proximity exposure method, the lens system or mirror system projection exposure (so-called projection exposure) method, and the direct exposure (so-called direct writing exposure) method using an exposure laser or the like can be appropriately selected. In the case of lens system or mirror system projection exposure, an exposure machine having an appropriate lens numerical aperture (NA) can be used according to the required resolution, focal depth, etc. In the case of the direct exposure method, writing may be performed directly on the etching resist, or reduced projection exposure may be performed on the etching resist through a lens. Exposure may be performed not only under atmospheric conditions, but also under reduced pressure or vacuum, and exposure may be performed by interposing a liquid such as water between the light source and the transfer layer.
From the viewpoint of reducing light diffraction and light scattering to improve resolution, the exposure in step 1-3 is preferably performed by contact exposure in which the transfer layer is brought into contact with a mask after peeling the temporary support from the transfer layer. Also, from the viewpoint of reducing the influence on the mask and the etching resist, the exposure in step 1-3 is preferably performed by direct writing exposure or projection exposure.

The development treatment in step 1-3 is preferably carried out using a developer.
The developer is not particularly limited as long as it can remove non-image areas (so-called unnecessary areas) of the etching resist (photosensitive resin layer). For example, known developers such as the developer described in JP-A-5-72724 can be used.
The developer is preferably an aqueous alkaline developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol/L to 5 mol/L (liter).
The developer may contain a water-soluble organic solvent and/or a surfactant.
Examples of alkaline compounds that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).
Preferred examples of the developer include the developer described in paragraph [0194] of International Publication No. 2015/093271. The contents of this description are incorporated herein by reference.
A preferred example of the development method is described in paragraph [0195] of WO 2015/093271, the contents of which are incorporated herein by reference.

The development method is not particularly limited, and may be, for example, any of paddle development, shower development, shower and spin development, and dip development.
Shower development is a development process in which a developer is sprayed onto the etching resist (photosensitive resin layer) after exposure by showering, thereby removing non-image areas.
After the development step, it is preferable to spray a cleaning agent by showering to remove development residues.
The temperature of the developer is not particularly limited, but is preferably, for example, from 20°C to 40°C.

<Step 1-4>
Step 1-4 is a step of etching the transparent conductive layer and the metal layer using the etching resist pattern obtained in step 1-3 as a mask.
The etching treatment may be performed on the metal layer and the transparent conductive layer all at once or successively, but is preferably performed on the metal layer and then the transparent conductive layer in that order.

As the etching method, a known method can be applied.
The etching method is preferably a wet etching method using an etching solution.
The etching solution used in the wet etching method may be an acidic or alkaline etching solution appropriately selected depending on the target to be etched.

Examples of the acidic etching solution include an aqueous solution of an acidic component selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and an aqueous solution of a mixture of an acidic component and a salt selected from the group consisting of iron (II) chloride, iron (III) chloride, iron (II) nitrate, iron (III) nitrate, iron (II) sulfate, iron (III) sulfate, ammonium fluoride, and potassium permanganate.
The acidic component may be a combination of multiple acidic components.

Examples of the alkaline etching solution include an aqueous solution of an alkaline component selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, an organic amine, and a salt of an organic amine (e.g., tetramethylammonium hydroxide), and an aqueous solution of a mixture of an alkaline component and a salt (e.g., potassium permanganate).
The alkaline component may be a combination of multiple alkaline components.

The etching solution may be used in combination with organic solvents, surfactants, amines, inorganic salts, etc., in order to control the etching rate, the shape of the material to be etched, etc.

The etching treatment can be carried out by contacting the metal layer and the transparent conductive layer with an etching solution using a known method such as a spray method, a shower method, or a dipping method.
The method for bringing the metal layer and the transparent conductive layer into contact with the etching solution is preferably a shower method.

The temperature of the etching solution is not particularly limited, but is preferably, for example, 20°C to 60°C.

In step 1-4, the metal layer and the transparent conductive layer are etched using the etching resist pattern as a mask, thereby removing the metal layer and the transparent conductive layer in the areas not masked by the etching resist pattern.
Removal of the metal layer and the transparent conductive layer in the unmasked portions can be controlled, for example, by the composition of the etching solution (e.g., the type of acidic or alkaline component contained in the etching solution, the concentration of the acid or alkali, the type of additive, etc.), the liquid temperature of the etching solution, the etching time, etc.

In steps 1-4, it is preferable to use an etching solution that can remove only the metal layer in the unmasked areas, and then use an etching solution that can remove only the transparent conductive layer in the unmasked areas.

The degree of removal of the metal layer and the transparent conductive layer in the unmasked portions can be controlled, for example, by the etching time.
For example, the longer the etching time, the more the unmasked portions of the metal layer and transparent conductive layer tend to be removed, and the width R1 of the metal wiring layer and the width R2 of the transparent wiring layer in the final laminate according to the present disclosure become narrower.
The etching time is not particularly limited, and may be appropriately set depending on the desired width R1 of the metal wiring layer and the width R2 of the transparent wiring layer.
The etching time is, for example, 10 seconds to 500 seconds.

Note that since the etching solution has the effect of dissolving metal, if the metal layer and/or the transparent conductive layer contains a resin, the resin contained in the metal layer and/or the transparent conductive layer may remain in the parts not masked by the etching resist pattern. Although it is not necessary for the resin contained in the metal layer and/or the transparent conductive layer to be partially removed, it is preferable that it is completely removed. The resin contained in the metal layer and/or the transparent conductive layer can be completely removed, for example, by controlling the shower pressure, the etching process time, etc.

<Step 1-5>
The manufacturing method according to the first embodiment preferably includes, after step 1-4, a step of removing the etching resist pattern and forming a wiring portion (also referred to as "step 1-5").

The method for removing the remaining etching resist pattern is not particularly limited, and examples thereof include a method of removing the pattern by chemical treatment, and a method of removing the pattern by using a removing liquid is preferred.
As a method for removing the etching resist pattern, there is a method in which the remaining etching resist pattern is immersed in a removing liquid while being stirred.
The temperature of the removal solution is preferably 30° C. to 80° C., and more preferably 40° C. to 80° C. The immersion time is not particularly limited, and may be, for example, 1 minute to 30 minutes.

The removal liquid may be, for example, a removal liquid obtained by dissolving an inorganic alkaline component or an organic alkaline component in water, dimethylsulfoxide, N-methylpyrrolidone, or a mixed solution of these.
Examples of inorganic alkaline components include sodium hydroxide and potassium hydroxide. Examples of organic alkaline components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.
The remaining etching resist pattern may be removed by a known method such as a spray method, a shower method, or a paddle method using a remover.

<Other processes>
The method for producing a laminate according to the present disclosure may include any steps (other steps) other than the steps described above. Examples of the other steps include the following steps. However, the other steps are not limited to these steps.

--Step of reducing visible light reflectance--
The method for producing a laminate according to the present disclosure may include a step of performing a treatment to reduce the visible light reflectance of a part or all of the conductive portion.
An example of a treatment for reducing the visible light reflectance is an oxidation treatment.
For example, when the conductive portion contains copper, the visible light reflectance of the conductive portion can be reduced by subjecting the copper to an oxidation treatment to turn it into copper oxide and blackening the conductive portion.
Treatment for reducing visible light reflectance is described in paragraphs [0017] to [0025] of JP 2014-150118 A, and paragraphs [0041], [0042], [0048] and [0058] of JP 2013-206315 A, the contents of which are incorporated herein by reference.

--Step of forming an insulating film, and step of forming a new conductive layer on the surface of the insulating film--
The method for producing a laminate according to the present disclosure also preferably includes a step of forming an insulating film on the surface of the conductive portion, and a step of forming a new conductive portion on the surface of the insulating film.
Through the above steps, a first electrode pattern and a second electrode pattern insulated from each other can be formed.
The step of forming the insulating film is not particularly limited, and may be a known method for forming a permanent film. Alternatively, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties.
The process of forming new conductive portions on the surface of the insulating film is not particularly limited, and for example, new conductive portions of a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

In addition, examples of the exposure process, development process, and other processes that can be applied to the manufacturing method of the laminate according to the present disclosure include the processes described in paragraphs [0035] to [0051] of JP 2006-23696 A. The contents of these descriptions are incorporated herein by reference.

[Photosensitive Transfer Material]
The photosensitive transfer material used in the manufacturing method of the laminate according to the present disclosure preferably has a temporary support and a transfer layer including a photosensitive resin layer, and more preferably has a temporary support, a transfer layer including a photosensitive resin layer, and a protective film in that order.
The photosensitive transfer material used in the present disclosure may have other layers between the temporary support and the photosensitive resin layer, between the photosensitive resin layer and the protective film, or the like.
Examples of the other layers include a thermoplastic resin layer and a water-soluble resin layer.
Each of the photosensitive resin layer, the protective film, and the other layers may be a single layer or a multilayer having two or more layers.
The photosensitive transfer material used in the present disclosure preferably has a structure of temporary support/photosensitive resin layer/protective film.
The photosensitive transfer material used in the present disclosure may be a roll-shaped photosensitive transfer material.

Below, we explain each element that makes up the photosensitive transfer material.

<Temporary Support>
The photosensitive transfer material used in the present disclosure preferably has a temporary support.
The temporary support is a support which supports the photosensitive resin layer or the transfer layer containing the photosensitive resin layer and is peelable.

The temporary support may be a single layer or a multi-layer structure of two or more layers.

The temporary support preferably has light transparency from the viewpoint that the photosensitive resin layer can be exposed through the temporary support when the photosensitive resin layer is subjected to pattern exposure.
In the present disclosure, "having optical transparency" means that the transmittance of light of the wavelength used for pattern exposure is 50% or more.
From the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, the temporary support preferably has a transmittance of light having a wavelength used for pattern exposure (more preferably a wavelength of 365 nm) of 60% or more, and more preferably 70% or more.
The transmittance of a layer of a photosensitive transfer material is the ratio of the intensity of the emitted light that has passed through the layer to the intensity of the incident light when light is incident in a direction perpendicular to the main surface of the layer (thickness direction), and is measured using a multichannel spectrometer (e.g., the MCPD Series manufactured by Otsuka Electronics Co., Ltd.).

Examples of materials constituting the temporary support include a glass substrate, a resin film, and paper. From the viewpoints of strength, flexibility, and light transmittance, a resin film is preferred.
Examples of the resin film include a polyethylene terephthalate (PET) film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film.
Among these, the resin film is preferably a PET film, and more preferably a biaxially stretched PET film.

The thickness of the temporary support is not particularly limited, and may be selected according to the material from the viewpoints of, for example, the strength as a support, the flexibility required for lamination, and the light transmittance.
The thickness of the temporary support is preferably from 5 μm to 100 μm.
The thickness of the temporary support is, for example, more preferably from 10 μm to 50 μm, further preferably from 10 μm to 20 μm, and particularly preferably from 10 μm to 16 μm, from the viewpoints of ease of handling and versatility.
Furthermore, the thickness of the temporary support is preferably 50 μm or less, more preferably 25 μm or less, even more preferably 20 μm or less, and particularly preferably 16 μm or less, from the viewpoints of, for example, defect suppression, resolution, and linearity of the resin pattern.
The thickness of the temporary support is calculated as an average value of the thicknesses at any five points measured by cross-sectional observation using a scanning electron microscope (SEM).

It is also preferable that the film used as the temporary support is free of deformations such as wrinkles and scratches.

From the viewpoints of pattern formability during pattern exposure through the temporary support and the transparency of the temporary support, it is preferred that the temporary support contains fewer fine particles, foreign matter and defects.
The total number of fine particles, foreign matter, and defects having a diameter of 1 μm or more contained in the temporary support is preferably 50 pieces/ ¹⁰ mm2 or less, more preferably 10 pieces/ ¹⁰ mm2 or less, even more preferably 3 pieces/ ¹⁰ mm2 or less, and particularly preferably 0 pieces/ ¹⁰ mm2.

From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 1.0% or less, even more preferably 0.5% or less, and particularly preferably 0.1% or less.
The haze value in the present disclosure is measured using a haze meter (for example, NDH-2000 (model number) manufactured by Nippon Denshoku Industries Co., Ltd.) according to a method in accordance with JIS K 7105:1981.

A layer containing fine particles (also called a "lubricant layer") may be provided on the surface of the temporary support in order to provide ease of handling.
The lubricant layer may be provided on one surface or both surfaces of the temporary support.
The diameter of the particles contained in the lubricant layer can be, for example, 0.05 μm to 0.8 μm, and the thickness of the lubricant layer can be, for example, 0.05 μm to 1.0 μm.

From the viewpoints of transportability, suppression of defects in the resin pattern, and resolution, it is preferable that the arithmetic mean roughness Ra of the surface of the temporary support opposite the photosensitive resin layer side is equal to or greater than the arithmetic mean roughness Ra of the surface of the temporary support facing the photosensitive resin layer.
The arithmetic mean roughness Ra of the surface of the temporary support opposite the photosensitive resin layer side is preferably 100 nm or less, more preferably 50 nm or less, even more preferably 20 nm or less, and particularly preferably 10 nm or less, from the viewpoints of transportability, suppression of defects in the resin pattern, and resolution.
The arithmetic mean roughness Ra of the surface of the temporary support facing the photosensitive resin layer is preferably 100 nm or less, more preferably 50 nm or less, even more preferably 20 nm or less, and particularly preferably 10 nm or less, from the viewpoints of releasability of the temporary support, defect suppression of the resin pattern, and resolution.
The value of "arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive resin layer side" minus "arithmetic mean roughness Ra of the surface of the temporary support facing the photosensitive resin layer" is preferably 0 nm to 10 nm, and more preferably 0 nm to 5 nm, from the viewpoints of transportability, suppression of defects in the resin pattern, and resolution.

The arithmetic mean roughness Ra of the surface of the temporary support or protective film in the present disclosure is measured by the following method.
Using a three-dimensional optical profiler (New View 7300, manufactured by Zygo Corporation), the surface of the temporary support or protective film is measured under the following conditions to obtain a surface profile.
As the measurement and analysis software, Microscope Application of MetroPro ver. 8.3.2 is used. Next, the Surface Map screen is displayed in the measurement and analysis software, and histogram data is obtained in the Surface Map screen. From the obtained histogram data, the arithmetic average roughness is calculated, and the Ra value of the surface of the temporary support or protective film is obtained.
When a temporary support or a protective film is attached to a photosensitive resin layer or the like, the temporary support or protective film is peeled off from the photosensitive resin layer, and the Ra value of the surface on the peeled side is measured.

The peeling force of the temporary support, specifically, the peeling force between the temporary support and the photosensitive resin layer is preferably 0.5 mN/mm or more, and more preferably 0.5 mN/mm to 2.0 mN/mm, from the viewpoint of suppressing peeling of the temporary support caused by adhesion between stacked laminates when the wound laminate is transported again by the roll-to-roll method.

The peel strength of the temporary support in the present disclosure is measured as follows.
A copper layer having a thickness of 200 nm is formed on a polyethylene terephthalate (PET) film having a thickness of 100 μm by a sputtering method to prepare a PET substrate having a copper layer.
The protective film is peeled off from the prepared photosensitive transfer material, and the material is laminated on the above-mentioned copper-layered PET substrate under lamination conditions of a lamination roll temperature of 100° C., a linear pressure of 0.6 MPa, and a linear speed (i.e., lamination speed) of 1.0 m/min. Next, a tape (PRINTACK manufactured by Nitto Denko Corporation) is attached to the surface of the temporary support, and then the laminate having at least the temporary support and the photosensitive resin layer on the copper-layered PET substrate is cut to 70 mm×10 mm to prepare a sample. The PET substrate side of the above sample is fixed on a sample stand.
Using a tensile compression tester (model number: SV-55, manufactured by Imada Manufacturing Co., Ltd.), the tape is pulled in a 180 degree direction at 5.5 mm/sec to peel the photosensitive resin layer from the temporary support, and the force required for peeling (peeling force) is measured.

Preferred embodiments of the temporary support are described, for example, in paragraphs [0017] and [0018] of JP 2014-85643 A, paragraphs [0019] to [0026] of JP 2016-27363 A, paragraphs [0041] to [0057] of WO 2012/081680 A, paragraphs [0029] to [0040] of WO 2018/179370 A, and paragraphs [0012] to [0032] of JP 2019-101405 A, the contents of which are incorporated herein by reference.

<Photosensitive resin layer>
The photosensitive transfer material used in the present disclosure preferably has a photosensitive resin layer.
In the photosensitive transfer material used in the manufacturing method according to the first embodiment, the photosensitive resin layer may be a positive-type photosensitive resin layer or a negative-type photosensitive resin layer, but is preferably a negative-type photosensitive resin layer.
The negative type photosensitive resin layer preferably contains a polymerizable compound, a photopolymerization initiator, and an alkali-soluble resin, and more preferably contains, based on the total mass of the photosensitive resin layer, 5% by mass to 70% by mass of an ethylenically unsaturated compound, 0.01% by mass to 20% by mass of a photopolymerization initiator, and 10% by mass to 90% by mass of an alkali-soluble resin.
The positive photosensitive resin layer is not limited, and a known positive photosensitive resin layer can be used. The positive photosensitive resin layer preferably contains an acid decomposable resin, i.e., a polymer having a structural unit having an acid group protected by an acid decomposable group, and a photoacid generator. The positive photosensitive resin layer preferably contains a resin having a structural unit having a phenolic hydroxyl group, and a quinone diazide compound. The positive photosensitive resin layer is more preferably a chemically amplified positive photosensitive resin layer containing a polymer having a structural unit having an acid group protected by an acid decomposable group, and a photoacid generator.
Each component will be described below in order. In the following description, the term "photosensitive resin layer" refers to both a positive-type photosensitive resin layer and a negative-type photosensitive resin layer.

<<Polymerizable compounds>>
The negative photosensitive resin layer preferably contains a polymerizable compound.
In the present disclosure, the term "polymerizable compound" refers to a compound that polymerizes under the action of a photopolymerization initiator described below, and is different from the alkali-soluble resin described below.

The polymerizable group of the polymerizable compound is not particularly limited as long as it is a group that participates in a polymerization reaction, and examples thereof include groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, or a maleimide group, and groups having a cationic polymerizable group such as an epoxy group or an oxetane group.
The polymerizable group is preferably a group having an ethylenically unsaturated group, and more preferably an acryloyl group or a methacryloyl group.
The polymerizable compound preferably contains an ethylenically unsaturated compound, and more preferably contains a (meth)acrylate compound.

From the viewpoints of resolution and pattern formability, the negative photosensitive resin layer preferably contains a bifunctional or higher polymerizable compound (so-called polyfunctional polymerizable compound), and more preferably contains a trifunctional or higher polymerizable compound. Here, a bifunctional or higher polymerizable compound means a compound having two or more polymerizable groups in one molecule.
From the viewpoint of excellent resolution and peelability, the number of polymerizable groups that the polymerizable compound has in one molecule is preferably 6 or less.

The negative photosensitive resin layer preferably contains a difunctional or trifunctional ethylenically unsaturated compound, and more preferably contains a difunctional ethylenically unsaturated compound, in that a better balance between photosensitivity, resolution, and peelability is achieved.
The content ratio of the bifunctional or trifunctional ethylenically unsaturated compound to the total content of the ethylenically unsaturated compound in the negative photosensitive resin layer is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, from the viewpoint of excellent peelability. The upper limit is not particularly limited, and may be 100% by mass. That is, all of the ethylenically unsaturated compounds contained in the negative photosensitive resin layer may be bifunctional ethylenically unsaturated compounds.

From the viewpoints of resolution and pattern formability, the negative photosensitive resin layer preferably contains a polymerizable compound having a polyalkylene oxide structure, and more preferably contains a polymerizable compound having a polyethylene oxide structure.
Preferred examples of the polymerizable compound having a polyalkylene oxide structure include polyalkylene glycol di(meth)acrylate, which will be described later.

--Ethylenically unsaturated compound B1--
The negative photosensitive resin layer preferably contains an ethylenically unsaturated compound B1 having an aromatic ring and two ethylenically unsaturated groups. The ethylenically unsaturated compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule, among the above-mentioned ethylenically unsaturated compounds.

In the negative photosensitive resin layer, the ratio of the mass content of the ethylenically unsaturated compound B1 to the mass content of the ethylenically unsaturated compound is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more, from the viewpoint of superior resolution. There is no particular upper limit, but from the viewpoint of peelability, it is preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

Examples of the aromatic ring contained in the ethylenically unsaturated compound B1 include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an anthracene ring; aromatic heterocycles such as a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a triazole ring, and a pyridine ring; and condensed rings thereof.
Among these, the aromatic ring contained in the ethylenically unsaturated compound B1 is preferably an aromatic hydrocarbon ring, more preferably a benzene ring.
The aromatic ring contained in the ethylenically unsaturated compound B1 may have a substituent.
The ethylenically unsaturated compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

The ethylenically unsaturated compound B1 preferably has a bisphenol structure, since this improves the resolution by suppressing swelling of the negative photosensitive resin layer caused by a developer.
Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane).
Among these, the bisphenol structure is preferably a bisphenol A structure.

Examples of the ethylenically unsaturated compound B1 having a bisphenol structure include a compound having a bisphenol structure and two ethylenically unsaturated groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure.
Both ends of the bisphenol structure and the two ethylenically unsaturated groups may be bonded directly or via one or more alkyleneoxy groups.
The alkyleneoxy groups added to both ends of the bisphenol structure are preferably ethyleneoxy or propyleneoxy, and more preferably ethyleneoxy.
The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16 per molecule, and more preferably 6 to 14 per molecule.
The ethylenically unsaturated compound B1 having a bisphenol structure is described in paragraphs [0072] to [0080] of JP2016-224162A, the contents of which are incorporated herein by reference.

As the ethylenically unsaturated compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferable, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferable.
Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane ("FA-324M" manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane ("BPE-500" manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxy Examples of such bisphenol A diacrylate include 2,2-bis(4-(dodecaethoxytetrapropoxy)phenyl)propane (manufactured by Hitachi Chemical Co., Ltd. under the title "FA-3200MY"); 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (manufactured by Shin-Nakamura Chemical Co., Ltd. under the title "BPE-1300"); 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (manufactured by Shin-Nakamura Chemical Co., Ltd. under the title "BPE-200"); and ethoxylated (10) bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. under the title "NK Ester A-BPE-10").

As the ethylenically unsaturated compound B1, a compound represented by the following formula (Bis) can be used.

In formula (Bis), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n ₁ and n ₃ each independently represent an integer from 1 to 39, and n ₁ +n ₃ is an integer from 2 to 40, n ₂ and n ₄ each independently represent an integer from 0 to 29, and n ₂ +n ₄ is an integer from 0 to 30, and the arrangement of the repeating units -(A-O)- and -(B-O)- may be random or in a block. In the case of a block, either -(A-O)- or -(B-O)- may be on the bisphenol structure side.
In one embodiment, n ₁ +n ₂ +n ₃ +n ₄ is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 12. Furthermore, n ₂ +n ₄ is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 2, and particularly preferably 0.

The ethylenically unsaturated compound B1 may be used alone or in combination of two or more kinds.
The content of the ethylenically unsaturated compound B1 in the negative photosensitive resin layer is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the negative photosensitive resin layer, from the viewpoint of better resolution. The upper limit is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge fusion (i.e., the phenomenon in which components in the negative photosensitive resin layer bleed out from the edge of the photosensitive transfer material).

The negative photosensitive resin layer may contain an ethylenically unsaturated compound other than the above-mentioned ethylenically unsaturated compound B1.
The ethylenically unsaturated compound other than the ethylenically unsaturated compound B1 is not particularly limited and can be appropriately selected from known compounds. For example, a compound having one ethylenically unsaturated group in one molecule (so-called monofunctional ethylenically unsaturated compound), a bifunctional ethylenically unsaturated compound having no aromatic ring, and a trifunctional or higher ethylenically unsaturated compound can be mentioned.

Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

Examples of difunctional ethylenically unsaturated compounds having no aromatic ring include alkylene glycol di(meth)acrylates, polyalkylene glycol di(meth)acrylates, urethane di(meth)acrylates, and trimethylolpropane diacrylate.
Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate ("A-DCP" manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate ("DCP" manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate ("A-NOD-N" manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate ("A-HD-N" manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.
Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.
Examples of urethane di(meth)acrylates include propylene oxide modified urethane di(meth)acrylates, and ethylene oxide and propylene oxide modified urethane di(meth)acrylates. Commercially available urethane di(meth)acrylates include "8UX-015A" manufactured by Taisei Fine Chemical Co., Ltd., "UA-32P" manufactured by Shin-Nakamura Chemical Co., Ltd., and "UA-1100H" manufactured by Shin-Nakamura Chemical Co., Ltd.

Examples of tri- or higher functional ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa)(meth)acrylate, pentaerythritol (tri/tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified versions of these.
Here, "(tri/tetra/penta/hexa)(meth)acrylate" is a concept that encompasses tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate, and "(tri/tetra)(meth)acrylate" is a concept that encompasses tri(meth)acrylate and tetra(meth)acrylate.
In one embodiment, the negative photosensitive resin layer preferably contains the above-mentioned ethylenically unsaturated compound B1 and a trifunctional or higher ethylenically unsaturated compound, and more preferably contains the above-mentioned ethylenically unsaturated compound B1 and two or more trifunctional or higher ethylenically unsaturated compounds. In this case, the ratio of the total mass content of the ethylenically unsaturated compound B1 to the total mass content of the trifunctional or higher ethylenically unsaturated compounds is preferably (total mass content of the ethylenically unsaturated compound B1):(total mass content of the trifunctional or higher ethylenically unsaturated compounds)=1:1 to 5:1, more preferably 1.2:1 to 4:1, and even more preferably 1.5:1 to 3:1.

Examples of alkylene oxide modified ethylenically unsaturated compounds having three or more functionalities include caprolactone modified (meth)acrylate compounds (such as "KAYARAD (registered trademark) DPCA-20" manufactured by Nippon Kayaku Co., Ltd. and "A-9300-1CL" manufactured by Shin-Nakamura Chemical Co., Ltd.), alkylene oxide modified (meth)acrylate compounds (such as "KAYARAD (registered trademark) RP-1040" manufactured by Nippon Kayaku Co., Ltd., "ATM-35E" and "A-9300" manufactured by Shin-Nakamura Chemical Co., Ltd., and "EBECRYL (registered trademark)" manufactured by Daicel-Allnex Corporation). 135" etc.), ethoxylated glycerin triacrylate [A-GLY-9E" manufactured by Shin-Nakamura Chemical Co., Ltd., etc.], Aronix (registered trademark) TO-2349 [manufactured by Toagosei Co., Ltd.], Aronix M-520 [manufactured by Toagosei Co., Ltd.], and Aronix M-510 [manufactured by Toagosei Co., Ltd.] are included.

In addition, as an ethylenically unsaturated compound other than the ethylenically unsaturated compound B1, an ethylenically unsaturated compound having an acid group described in paragraphs [0025] to [0030] of JP-A-2004-239942 may be used.

The ratio Mm/Mb of the content Mm of the ethylenically unsaturated compound to the content Mb of the alkali-soluble resin in the negative photosensitive resin layer is preferably 1.0 or less, more preferably 0.9 or less, and further preferably 0.5 to 0.9, from the viewpoints of resolution and linearity.
From the viewpoints of curability and resolution, the ethylenically unsaturated compound in the negative photosensitive resin layer preferably contains a (meth)acrylic compound.
Further, from the viewpoints of curability, resolution and linearity, it is more preferable that the ethylenically unsaturated compound in the negative photosensitive resin layer contains a (meth)acrylic compound, and the content of the acrylic compound relative to the content of the (meth)acrylic compound in the negative photosensitive resin layer is 60 mass% or less.

The molecular weight of the ethylenically unsaturated compound including the ethylenically unsaturated compound B1 [if it has a molecular weight distribution, the weight average molecular weight (Mw)] is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

When the negative photosensitive resin layer contains a polymerizable compound, it may contain only one type of polymerizable compound or may contain two or more types of polymerizable compounds.

When the negative photosensitive resin layer contains a polymerizable compound, the content of the polymerizable compound in the negative photosensitive resin layer is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and even more preferably 20% by mass to 50% by mass, relative to the total mass of the negative photosensitive resin layer.

<<Photopolymerization initiator>>
The negative photosensitive resin layer preferably contains a photopolymerization initiator.
A photopolymerization initiator is a compound that initiates polymerization of an ethylenically unsaturated compound when exposed to actinic rays such as ultraviolet light, visible light, X-rays, etc. The photopolymerization initiator is not particularly limited, and any known photopolymerization initiator can be used.
Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator.
Among these, the photopolymerization initiator is preferably a photoradical polymerization initiator from the viewpoints of resolution and pattern formability.

Examples of photoradical polymerization initiators include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenone structure, photopolymerization initiators having an α-hydroxyalkylphenone structure, photopolymerization initiators having an acylphosphine oxide structure, photopolymerization initiators having an N-phenylglycine structure, and biimidazole compounds.

As the photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs [0031] to [0042] of JP 2011-95716 A and paragraphs [0064] to [0081] of JP 2015-14783 A may be used.

Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name, manufactured by Midori Chemical Co., Ltd.), benzophenone, TAZ-111 (trade name, manufactured by Midori Chemical Co., Ltd.), Irgacure (registered trademark) OXE01, OXE02, OXE03, and OXE04 (all trade names, manufactured by BASF), Omnirad (registered trademark) 651 and 369 (all trade names, manufactured by IGM Resins B.V.), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

Commercially available photoradical polymerization initiators include, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) [trade name: IRGACURE (registered trademark) OXE01, manufactured by BASF Corporation], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) [trade name: IRGACURE (registered trademark) OXE02, manufactured by BASF Corporation], IRGACURE (registered trademark) OXE03 [manufactured by BASF Corporation], 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: Omnirad 379EG, manufactured by IGM Resins B.V. manufactured by IGM Resins B.V.], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: Omnirad 907, manufactured by IGM Resins B.V.], 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one [trade name: Omnirad 127, manufactured by IGM Resins B.V.], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 [trade name: Omnirad 369, manufactured by IGM Resins B.V.], 2-hydroxy-2-methyl-1-phenylpropan-1-one [trade name: Omnirad 1173, manufactured by IGM Resins B.V.] manufactured by IGM Resins B.V.], 1-hydroxycyclohexyl phenyl ketone [trade name: Omnirad 184, manufactured by IGM Resins B.V.], 2,2-dimethoxy-1,2-diphenylethan-1-one [trade name: Omnirad 651, manufactured by IGM Resins B.V.], 2,4,6-trimethylbenzoyl-diphenylphosphine oxide [trade name: Omnirad TPO H, manufactured by IGM Resins B.V.], bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide [trade name: Omnirad 819, manufactured by IGM Resins B.V.] manufactured by DKSH Japan Co., Ltd.), oxime ester photopolymerization initiator [trade name: Lunar 6, manufactured by DKSH Japan Co., Ltd.], 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) [trade name: B-CIM, manufactured by Hampford Co., Ltd.], and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer [trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.].

A photocationic polymerization initiator (so-called photoacid generator) is a compound that generates an acid when exposed to actinic rays. As the photocationic polymerization initiator, a compound that responds to actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid is preferred, but the chemical structure is not limited. In addition, even if a photocationic polymerization initiator is not directly sensitive to actinic rays having a wavelength of 300 nm or more, it can be preferably used in combination with a sensitizer as long as it responds to actinic rays having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer.
As the photocationic polymerization initiator, a photocationic polymerization initiator that generates an acid having a pKa of 4 or less is preferable, a photocationic polymerization initiator that generates an acid having a pKa of 3 or less is more preferable, and a photocationic polymerization initiator that generates an acid having a pKa of 2 or less is particularly preferable. The lower limit of the pKa is not particularly limited, but is preferably, for example, −10.0 or more.

Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.
Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.
As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiators described in paragraphs [0114] to [0133] of JP-A-2014-85643 may be used.

Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As the trichloromethyl-s-triazines, diazomethane compounds, and imide sulfonate compounds, the compounds described in paragraphs [0083] to [0088] of JP 2011-221494 A may be used. As the oxime sulfonate compounds, the compounds described in paragraphs [0084] to [0088] of WO 2018/179640 A may be used.

When the negative photosensitive resin layer contains a photopolymerization initiator, it may contain only one type of photopolymerization initiator or may contain two or more types of photopolymerization initiator.

When the negative photosensitive resin layer contains a photopolymerization initiator, the content of the photopolymerization initiator in the negative photosensitive resin layer is not particularly limited, but is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1.0 mass% or more, relative to the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but is preferably 10 mass% or less, and more preferably 5 mass% or less, relative to the total mass of the negative photosensitive resin layer.

<<Alkali-soluble resin (negative type)>>
The negative photosensitive resin layer preferably contains an alkali-soluble resin.
In the present disclosure, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous sodium carbonate solution at a liquid temperature of 22°C is 0.1 g or more.
The alkali-soluble resin is not particularly limited, and suitable examples thereof include known alkali-soluble resins used in etching resists.
The alkali-soluble resin is preferably a binder polymer.
The alkali-soluble resin is preferably an alkali-soluble resin having an acid group.
As the alkali-soluble resin, polymer A described below is preferred.

--Polymer A--
The alkali-soluble resin preferably contains polymer A.
The acid value of the polymer A is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g, and even more preferably less than 190 mgKOH/g, from the viewpoint of suppressing swelling of the negative photosensitive resin layer by the developer and further improving the resolution. The lower limit is not particularly limited, but is preferably 60 mgKOH/g or more, more preferably 120 mgKOH/g or more, even more preferably 150 mgKOH/g or more, and particularly preferably 170 mgKOH/g or more, from the viewpoint of further improving the developability.

The acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of a sample, and in the present disclosure, the unit is expressed as mgKOH/g. The acid value can be calculated, for example, from the average content of acid groups in a compound.
The acid value of polymer A can be adjusted by the type of structural unit constituting polymer A and the content of the structural unit containing an acid group.

The weight average molecular weight of polymer A is preferably from 5,000 to 500,000.
When the weight average molecular weight of the polymer A is 500,000 or less, the resolution and developability can be further improved.
The weight average molecular weight of polymer A is more preferably 100,000 or less, further preferably 60,000 or less, and particularly preferably 50,000 or less.
When the weight average molecular weight of polymer A is 5,000 or more, the properties of the development aggregates and the properties of the unexposed film, such as edge fuse property and cut chip property, can be more easily controlled.
The weight average molecular weight of polymer A is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more.
The edge fusing property refers to the degree of easiness of the photosensitive resin layer to protrude from the edge of a roll when the photosensitive transfer material is wound into a roll.
The cut chip property refers to the degree of ease with which chips fly off when an unexposed film is cut with a cutter. If the chips adhere to the upper surface of the photosensitive resin layer, they will be transferred to the mask in the subsequent exposure process, causing defective products.
The dispersity of polymer A is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, even more preferably from 1.0 to 4.0, and even more preferably from 1.0 to 3.0.
In the present disclosure, the weight average molecular weight and the like are values measured using gel permeation chromatography, and the dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).

From the viewpoint of suppressing line width thickening and deterioration of resolution caused by deviation of the focal position during exposure, the negative photosensitive resin layer preferably contains a monomer component having an aromatic hydrocarbon group as the polymer A. Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups.
The content of the monomer component having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more, based on the total mass of all the monomer components. The upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 85% by mass or less. In addition, when multiple types of polymer A are included, the content of the monomer component having an aromatic hydrocarbon group is determined as a weight average value.

Examples of monomers having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.).
Among these, as the monomer having an aromatic hydrocarbon group, a monomer having an aralkyl group or styrene is preferable.
In one embodiment, when the monomer component having an aromatic hydrocarbon group in polymer A is styrene, the content of the styrene monomer component is preferably 20% by mass to 50% by mass, more preferably 25% by mass to 45% by mass, even more preferably 30% by mass to 40% by mass, and particularly preferably 30% by mass to 35% by mass, based on the total mass of all the monomer components.

Aralkyl groups include, for example, substituted or unsubstituted phenylalkyl groups (excluding benzyl groups), and substituted or unsubstituted benzyl groups.
Among these, the aralkyl group is preferably a substituted or unsubstituted benzyl group.

An example of a monomer having a phenylalkyl group is phenylethyl (meth)acrylate.

Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group (e.g., benzyl (meth)acrylate, chlorobenzyl (meth)acrylate, etc.) and vinyl monomers having a benzyl group (e.g., vinylbenzyl chloride, vinylbenzyl alcohol, etc.).
Among these, benzyl (meth)acrylate is preferred as the monomer having a benzyl group.
In one embodiment, when the monomer component having an aromatic hydrocarbon group in polymer A is benzyl (meth)acrylate, the content of the benzyl (meth)acrylate monomer component is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, even more preferably 70% by mass to 90% by mass, and particularly preferably 75% by mass to 90% by mass, based on the total mass of all monomer components.

It is preferable that polymer A containing a monomer component having an aromatic hydrocarbon group is obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one type of a first monomer described below and/or at least one type of a second monomer described below.

Polymer A, which does not contain a monomer component having an aromatic hydrocarbon group, is preferably obtained by polymerizing at least one type of first monomer described below, and more preferably by copolymerizing at least one type of first monomer with at least one type of second monomer described below.

The first monomer is a monomer having a carboxy group in the molecule.
The first monomer includes, for example, (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester.
Among these, (meth)acrylic acid is preferred as the first monomer.
The content of the first monomer in polymer A is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and even more preferably 15% by mass to 30% by mass, based on the total mass of all monomer components.

The copolymerization ratio of the first monomer is preferably 10% by mass to 50% by mass based on the total mass of all the monomer components.
It is preferable to set the copolymerization ratio of the first monomer to 10% by mass or more from the viewpoint of exhibiting good developability and controlling edge fusing property, and it is more preferable to set it to 15% by mass or more, and further more preferable to set it to 20% by mass or more.
Setting the copolymerization ratio of the first monomer to 50 mass % or less is preferable from the viewpoints of high resolution and foot shape of the resist pattern, and also from the viewpoint of the chemical resistance of the resist pattern, and from these viewpoints, it is more preferable to set it to 35 mass % or less, even more preferably to set it to 30 mass % or less, and particularly preferably to set it to 27 mass % or less.

The second monomer is a monomer which is non-acidic and has at least one polymerizable unsaturated group in the molecule.
Examples of the second monomer include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile.
Among these, the second monomer is preferably at least one selected from the group consisting of methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate, and more preferably methyl (meth)acrylate.
The content of the second monomer in polymer A is preferably 5% by mass to 60% by mass, more preferably 15% by mass to 50% by mass, and even more preferably 20% by mass to 45% by mass, based on the total mass of all monomer components.

From the viewpoint of suppressing line width thickening and deterioration of resolution when the focal position is shifted during exposure, polymer A preferably contains, as a monomer, a monomer having an aralkyl group and/or styrene.
Polymer A is preferably, for example, a copolymer containing methacrylic acid, benzyl methacrylate, and styrene, or a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene.
In one embodiment, the polymer A is preferably a polymer containing 25% by mass to 40% by mass of a monomer component having an aromatic hydrocarbon group, 20% by mass to 35% by mass of a first monomer component, and 30% by mass to 45% by mass of a second monomer component, and in another embodiment, the polymer A is preferably a polymer containing 70% by mass to 90% by mass of a monomer component having an aromatic hydrocarbon group, and 10% by mass to 25% by mass of the first monomer component.

The polymer A may have a linear structure, a branched structure, or an alicyclic structure in the side chain. By using a monomer containing a group having a branched structure in the side chain, or a monomer containing a group having an alicyclic structure in the side chain, a branched structure or an alicyclic structure can be introduced into the side chain of the polymer A. The group having an alicyclic structure may be monocyclic or polycyclic.
Specific examples of monomers containing a group having a branched structure in the side chain include i-propyl (meth)acrylate, i-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, i-amyl (meth)acrylate, t-amyl (meth)acrylate, iso-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, and t-octyl (meth)acrylate.
Among these, the monomer containing a group having a branched structure in its side chain is preferably at least one selected from the group consisting of i-propyl (meth)acrylate, i-butyl (meth)acrylate, and t-butyl methacrylate, and more preferably at least one selected from the group consisting of i-propyl methacrylate and t-butyl methacrylate.
Examples of monomers containing a group having an alicyclic structure in a side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group. Examples of monomers containing a group having an alicyclic structure in a side chain include (meth)acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms.
More specific examples of the monomer containing a group having an alicyclic structure in the side chain include (bicyclo[2.2.1]heptyl-2(meth)acrylate), (meth)acrylate-1-adamantyl, (meth)acrylate-2-adamantyl, (meth)acrylate-3-methyl-1-adamantyl, (meth)acrylate-3,5-dimethyl-1-adamantyl, (meth)acrylate-3-ethyladamantyl, (meth)acrylate-3-methyl-5-ethyl-1-adamantyl, (meth)acrylate-3,5,8-triethyl-1-adamantyl, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylate-2-methyl-2-adamantyl, (meth)acrylate-2-ethyl-2-adamantyl, (meth)acrylate, Examples of such acrylates include 3-hydroxy-1-adamantyl acrylate, octahydro-4,7-menthanoinden-5-yl (meth)acrylate, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl (meth)acrylate, 3,7,7-trimethyl-4-hydroxybicyclo[4.1.0]heptyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, and cyclohexyl (meth)acrylate.
Among these, the monomer containing a group having an alicyclic structure in its side chain is preferably at least one selected from the group consisting of cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fenchyl (meth)acrylate, 1-menthyl (meth)acrylate, and tricyclodecane (meth)acrylate, and more preferably at least one selected from the group consisting of cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, and tricyclodecane (meth)acrylate.

The polymer A may be used alone or in combination of two or more.
When two or more kinds of polymer A are used, it is preferable to use two kinds of polymer A containing a monomer component having an aromatic hydrocarbon group, or to use a polymer A containing a monomer component having an aromatic hydrocarbon group and a polymer A not containing a monomer component having an aromatic hydrocarbon group. In the latter case, the proportion of the polymer A containing a monomer component having an aromatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total amount of the polymer A.

Polymer A is preferably synthesized by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting the above-described single or multiple monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and then heating and stirring the solution. In some cases, the synthesis is performed while dropping a portion of the mixture into the reaction solution. After the reaction is completed, further solvent may be added to adjust the concentration to the desired level. As a synthesis method, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

The glass transition temperature (Tg) of the polymer A is preferably from 30°C to 135°C.
In the negative photosensitive resin layer, when the polymer A having a Tg of 135° C. or less is used, the line width thickening and the deterioration of the resolution when the focal position is shifted during exposure can be suppressed. From this viewpoint, the Tg of the polymer A is more preferably 130° C. or less, further preferably 120° C. or less, and particularly preferably 110° C. or less. In addition, when the polymer A having a Tg of 30° C. or more is used in the negative photosensitive resin layer, the edge fuse resistance can be improved. From this viewpoint, the Tg of the polymer A is more preferably 40° C. or more, further preferably 50° C. or more, particularly preferably 60° C. or more, and most preferably 70° C. or more.

The negative photosensitive resin layer may contain a resin other than the alkali-soluble resin.
Examples of resins other than alkali-soluble resins include acrylic resins, styrene-acrylic copolymers (with the styrene content being 40 mass% or less), polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamine, and polyalkylene glycols.

When the negative photosensitive resin layer contains an alkali-soluble resin, it may contain only one type of alkali-soluble resin or two or more types of alkali-soluble resin.

When the negative photosensitive resin layer contains an alkali-soluble resin, the content of the alkali-soluble resin in the negative photosensitive resin layer is preferably 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and further preferably 40% by mass to 60% by mass, based on the total mass of the negative photosensitive resin layer.
When the content of the alkali-soluble resin in the negative photosensitive resin layer is 10% by mass or more based on the total mass of the negative photosensitive resin layer, the edge fuse resistance can be further improved.
When the content of the alkali-soluble resin in the negative photosensitive resin layer is 90% by mass or less based on the total mass of the negative photosensitive resin layer, the development time can be more easily controlled.

<<Polymerization inhibitor>>
The negative photosensitive resin layer may contain a polymerization inhibitor.
The polymerization inhibitor is preferably a radical polymerization inhibitor.
Examples of the polymerization inhibitor include the thermal polymerization inhibitors described in paragraph [0018] of Japanese Patent No. 4,502,784.
The thermal polymerization inhibitor is preferably phenothiazine, phenoxazine or 4-methoxyphenol.Other polymerization inhibitors include, for example, naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine.

When the negative photosensitive resin layer contains a polymerization inhibitor, it may contain only one type of polymerization inhibitor, or may contain two or more types.

When the negative photosensitive resin layer contains a polymerization inhibitor, the content of the polymerization inhibitor in the negative photosensitive resin layer is preferably 0.01% by mass to 3% by mass, and more preferably 0.05% by mass to 1% by mass, based on the total mass of the negative photosensitive resin layer.
When the content of the polymerization inhibitor in the negative photosensitive resin layer is 0.01% by mass or more based on the total mass of the negative photosensitive resin layer, storage stability can be imparted to the negative photosensitive resin layer.
When the content of the polymerization inhibitor in the negative photosensitive resin layer is 3% by mass or less based on the total mass of the negative photosensitive resin layer, the sensitivity can be maintained more satisfactorily.

<<Compounds with unshared electron pairs>>
From the viewpoint of adhesion to layer A containing metal nanostructures and a resin, and layer B containing a metal, the photosensitive resin layer preferably contains a compound having an unshared electron pair.
As a compound having an unshared electron pair, from the viewpoint of adhesion to layer A containing a metal nanobody and a resin, and layer B containing a metal, it is preferable that the compound contains at least a nitrogen atom, an oxygen atom, or a sulfur atom, and it is more preferable that the compound is a heterocyclic compound, a thiol compound, or a disulfide compound, and it is even more preferable that the compound is a heterocyclic compound.

The heterocycle contained in the heterocyclic compound may be either a monocyclic or polycyclic heterocycle.
Examples of heteroatoms contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom.
The heterocyclic compound preferably contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably contains a nitrogen atom.
The heterocyclic compound containing a nitrogen atom (i.e., a nitrogen-containing heterocyclic compound) preferably has a heterocycle containing two or more nitrogen atoms, more preferably has a heterocycle containing three or more nitrogen atoms, and further preferably has a heterocycle containing three or four nitrogen atoms.

Examples of the heterocyclic compound include a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, a benzoxazole compound, and a pyrimidine compound.
Among these, the heterocyclic compound is preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds, more preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds, still more preferably at least one compound selected from the group consisting of triazole compounds and tetrazole compounds, and particularly preferably a triazole compound.

Preferable specific examples of the heterocyclic compound are shown below.
Examples of the triazole compound and benzotriazole compound include the following compounds.

Examples of tetrazole compounds include the following compounds:

Examples of thiadiazole compounds include the following compounds:

Examples of triazine compounds include the following compounds:

Examples of rhodanine compounds include the following:

Examples of thiazole compounds include the following:

Examples of benzothiazole compounds include the following compounds:

Examples of benzimidazole compounds include the following compounds:

Examples of benzoxazole compounds include the following compounds:

Examples of the sulfur-containing compound include a thiol compound and a disulfide compound.
The thiol compound may, for example, be an aliphatic thiol compound.
Examples of the aliphatic thiol compound include monofunctional aliphatic thiol compounds and polyfunctional aliphatic thiol compounds (i.e., di- or higher functional aliphatic thiol compounds).
Examples of monofunctional aliphatic thiol compounds include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.
Examples of polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tris(3-mercaptopropionyloxy)ethyl]isocyanurate, ester), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2′-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid, and di(mercaptoethyl)ether.

Examples of disulfide compounds include 2-(4'-morpholinodithio)benzthiazole, 2,2'-benzthiazolyl disulfide, bis(2-benzamidophenyl)disulfide, 1,1-thiobis(2-naphthol), bis(2,4,5-trichlorophenyl)disulfide, 4,4'-dithiomorpholine, tetraethylthiuram disulfide, dibenzyl disulfide, bis(2,4-dinitrophenyl)disulfide, 4,4'-diaminodiphenyl disulfide, diallyl disulfide, di-tert-butyl disulfide, bis(6-hydroxy-2-naphthyl)disulfide, dicyclohexyl disulfide, o-isobutyroylthiamine disulfide, and diphenyl disulfide.

From the viewpoint of adhesion to layer A containing metal nanostructures and a resin, and layer B containing a metal, the molecular weight of the compound having an unshared electron pair is preferably less than 1,000, more preferably 50 to 500, even more preferably 50 to 200, and particularly preferably 50 to 150.

When the photosensitive resin layer contains a compound having an unshared electron pair, it may contain only one type of compound having an unshared electron pair, or may contain two or more types of compounds having an unshared electron pair.
When the photosensitive resin layer contains a compound having an unshared electron pair, the content of the compound having an unshared electron pair in the photosensitive resin layer is, from the viewpoint of adhesion to layer A containing metal nanostructures and a resin, and layer B containing a metal, preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass, even more preferably 0.3% by mass to 8% by mass, and particularly preferably 0.5% by mass to 5% by mass, relative to the total mass of the photosensitive resin layer.

<<Pigments>>
From the viewpoints of visibility of exposed and unexposed parts, pattern visibility after development, and resolution, the photosensitive resin layer preferably contains a dye, and more preferably contains a dye (hereinafter also referred to as "dye N") whose maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development is 450 nm or more and whose maximum absorption wavelength changes with an acid, a base, or a radical. When the photosensitive resin layer contains dye N, although the detailed mechanism is unknown, adhesion with adjacent layers (e.g., temporary support and substrate) is improved, and resolution is more excellent.

In the present disclosure, the dye's "maximum absorption wavelength changes due to an acid, a base, or a radical" may mean any of the following aspects: a dye in a colored state is decolorized by an acid, a base, or a radical; a dye in a decolorized state is colored by an acid, a base, or a radical; and a dye in a colored state is changed to a colored state of another hue.
Specifically, the dye N may be a compound that changes from a decolorized state to a colored state by exposure, or may be a compound that changes from a colored state to a decolored state by exposure. In this case, the dye N may be a dye whose colored or decolored state changes when an acid, base, or radical is generated and acts in the photosensitive resin layer by exposure, or a dye whose colored or decolored state changes when the state (e.g., pH) in the photosensitive resin layer is changed by an acid, base, or radical. The dye N may also be a dye whose colored or decolored state changes when it is directly stimulated by an acid, base, or radical without exposure.

From the viewpoints of the visibility of exposed and unexposed areas and the resolution, dye N is preferably a dye whose maximum absorption wavelength changes in response to an acid or a radical, and more preferably a dye whose maximum absorption wavelength changes in response to a radical.
From the viewpoints of the visibility of exposed and unexposed areas, and of resolution, the photosensitive resin layer preferably contains both a dye whose maximum absorption wavelength changes due to radicals as dye N, and a photoradical polymerization initiator.
From the viewpoint of visibility of exposed and unexposed areas, the dye N is preferably a dye that develops color in response to an acid, a base, or a radical.

An example of the color-developing mechanism of dye N in the present disclosure is a mode in which a photoradical polymerization initiator, a cationic photopolymerization initiator (so-called photoacid generator), or a photobase generator is added to a photosensitive resin layer, and after exposure, a radical-reactive dye, an acid-reactive dye, or a base-reactive dye (e.g., a leuco dye) develops color due to the radicals, acids, or bases generated from the photoradical polymerization initiator, the photocationic photopolymerization initiator, or the photobase generator.

From the viewpoint of visibility of exposed and non-exposed areas, the maximum absorption wavelength of dye N in the wavelength range of 400 nm to 780 nm during color development is preferably 550 nm or more, more preferably 550 nm to 700 nm, and even more preferably 550 nm to 650 nm.

The maximum absorption wavelength of dye N is obtained by measuring the transmission spectrum of a solution containing dye N (liquid temperature: 25°C) in the range of 400 nm to 780 nm using a spectrophotometer (e.g., UV3100 (model number) manufactured by Shimadzu Corporation) in an atmospheric environment, and detecting the wavelength at which the light intensity is minimum in the above wavelength range (maximum absorption wavelength).

Examples of the dye that develops or loses color upon exposure to light include leuco compounds.
Examples of dyes that are decolorized by exposure to light include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.
As the dye N, a leuco compound is preferred from the viewpoint of visibility of exposed and non-exposed areas.

Examples of the leuco compound include leuco compounds having a triarylmethane skeleton (so-called triarylmethane dyes), leuco compounds having a spiropyran skeleton (so-called spiropyran dyes), leuco compounds having a fluoran skeleton (so-called fluoran dyes), leuco compounds having a diarylmethane skeleton (so-called diarylmethane dyes), leuco compounds having a rhodamine lactam skeleton (so-called rhodamine lactam dyes), leuco compounds having an indolylphthalide skeleton (so-called indolylphthalide dyes), and leucoauramine skeleton (so-called leucoauramine dyes).
As the leuco compound, a triarylmethane dye or a fluoran dye is preferable, and a leuco compound having a triphenylmethane skeleton (so-called a triphenylmethane dye) or a fluoran dye is more preferable.

From the viewpoint of visibility of exposed and unexposed areas, the leuco compound preferably has a lactone ring, a sultine ring or a sultone ring.
When the leuco compound has a lactone ring, a sultine ring, or a sultone ring, these rings can be reacted with a radical generated from a photoradical polymerization initiator or an acid generated from a photocationic polymerization initiator to change the leuco compound into a ring-closed state and thereby cause it to lose color, or to change the leuco compound into a ring-open state and cause it to develop color.
The leuco compound is preferably a compound which has a lactone ring, a sultine ring or a sultone ring and develops color by ring-opening the lactone ring, the sultine ring or the sultone ring with the aid of a radical or an acid, and more preferably a compound which has a lactone ring and develops color by ring-opening the lactone ring with the aid of a radical or an acid.

Examples of the dye N include the following dyes and leuco compounds.
Specific examples of dyes among the dyes N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymolsulfophthalein, xylenol blue, methyl orange, paramethyl red, Congo red, benzopurpurin 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria Pure Blue-naphthalenesulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue #603 (manufactured by Orient Chemical Co., Ltd.), Oil Pink #312 (manufactured by Orient Chemical Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Co., Ltd.), and Orient Chemical Industry Co., Ltd.], Oil Red OG [Orient Chemical Industry Co., Ltd.], Oil Red RR [Orient Chemical Industry Co., Ltd.], Oil Green #502 [Orient Chemical Industry Co., Ltd.], Spiron Red BEH Special [Orient Chemical Industry Co., Ltd.], m-Cresol Purple, Cresol Red, Rhodamine B, Rhodamine 6G, Sulforhodamine 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, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

Specific examples of leuco compounds among the dyes N include p,p',p"-hexamethyltriaminotriphenylmethane (so-called leuco crystal violet), Pergascript Blue SRB [manufactured by Ciba-Geigy], crystal violet lactone, malachite green lactone, benzoyl leuco methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)- 6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-diethylamino)-7-benzylaminofluoran, 3-(N,N-diethylamino)-7,8-benzofluoran, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide These include 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthen-3-one, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthen-3-one.

From the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, dye N is preferably a dye whose maximum absorption wavelength changes in response to radicals, and more preferably a dye that develops color in response to radicals.
As the dye N, at least one selected from the group consisting of leuco crystal violet, crystal violet lactone, brilliant green, and Victoria Pure Blue-naphthalenesulfonate is preferable.

When the photosensitive resin layer contains a dye, it may contain only one type of dye, or may contain two or more types of dye.
When the photosensitive resin layer contains a dye, the content of the dye in the photosensitive resin layer is, from the viewpoints of visibility of exposed and unexposed parts, pattern visibility after development, and resolution, preferably 0.1 mass % or more, more preferably 0.1 mass % to 10 mass %, even more preferably 0.1 mass % to 5 mass %, and particularly preferably 0.1 mass % to 1 mass %, relative to the total mass of the photosensitive resin layer.

The content of the dye means the content of the dye when all of the dye N contained in the photosensitive resin layer is in a color-developing state.
Hereinafter, a method for quantifying the content of dye N will be described using a dye that develops color by radicals as an example.
Two types of solutions are prepared by dissolving 0.001 g or 0.01 g of the dye in 100 mL of methyl ethyl ketone. Irgacure (registered trademark) OXE01 (trade name, manufactured by BASF Japan Co., Ltd.), which is a photoradical polymerization initiator, is added to each of the obtained solutions, and radicals are generated by irradiating light of 365 nm, causing all the dyes to develop color. Then, in an air atmosphere, the absorbance of each solution at a liquid temperature of 25° C. is measured using a spectrophotometer (model number: UV3100, manufactured by Shimadzu Corporation) to create a calibration curve.
Next, the absorbance of the solution in which all the dyes have been colored is measured in the same manner as above, except that the photosensitive resin layer 3g is dissolved in methyl ethyl ketone instead of the dye. The content of the dye contained in the photosensitive resin layer is calculated based on the absorbance of the obtained solution containing the photosensitive resin layer and the calibration curve.

<<Thermal crosslinking compounds>>
The photosensitive resin layer preferably contains a thermally crosslinkable compound from the viewpoints of the strength of the obtained cured film and the adhesion of the obtained uncured film. In addition, in the present disclosure, the thermally crosslinkable compound having an ethylenically unsaturated group described later is not treated as a polymerizable compound but as a thermally crosslinkable compound.

Examples of the thermally crosslinkable compound include a methylol compound and a blocked isocyanate compound.
Among these, the thermally crosslinkable compound is preferably a blocked isocyanate compound from the viewpoints of the strength of the resulting cured film and the adhesion of the resulting uncured film.
Since blocked isocyanate compounds react with hydroxyl groups and carboxyl groups, for example, when a resin and/or a polymerizable compound has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film tends to decrease, and the function tends to be enhanced when the film obtained by curing a photosensitive resin layer is used as a protective film. Note that the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent."

The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably from 100°C to 160°C, and more preferably from 130°C to 150°C.
The dissociation temperature of a blocked isocyanate means "the temperature of an endothermic peak accompanying the deprotection reaction of a blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter."
As the differential scanning calorimeter, for example, a differential scanning calorimeter (model number: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used. However, the differential scanning calorimeter is not limited to this.

Examples of blocking agents having a dissociation temperature of 100° C. to 160° C. include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)] and oxime compounds [compounds having a structure represented by -C(═N-OH)- in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, and cyclohexanoneoxime].
Among these, the blocking agent having a dissociation temperature of 100° C. to 160° C. preferably contains an oxime compound, and is more preferably an oxime compound, from the viewpoint of storage stability, for example.

The blocked isocyanate compound preferably has an isocyanurate structure from the viewpoints of, for example, improving the brittleness of the film and improving the adhesive strength to the transfer target.
A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by protecting hexamethylene diisocyanate by converting it into an isocyanurate.
Among blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure in which an oxime compound is used as a blocking agent is preferred from the viewpoints that the dissociation temperature can be set in a preferred range more easily than a compound not having an oxime structure, and that development residues can be reduced.

The blocked isocyanate compound may have a polymerizable group.
The polymerizable group is not particularly limited, and any known polymerizable group can be used, with a radically polymerizable group being preferred.
Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, a (meth)acrylamide group, and a styryl group, and groups having an epoxy group such as a glycidyl group.
Among these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.

As the blocked isocyanate compound, commercially available products can be used.
Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, and Karenz (registered trademark) MOI-BP (all manufactured by Showa Denko K.K.), and the blocked Duranate series (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) SBN-70D, Duranate (registered trademark) WM44-L70G, and Duranate (registered trademark) WT32-B75P, manufactured by Asahi Kasei Chemicals Corporation).
In addition, as the blocked isocyanate compound, a compound having the following structure can also be used.

When the photosensitive resin layer contains a thermally crosslinkable compound, it may contain only one type of thermally crosslinkable compound, or it may contain two or more types of thermally crosslinkable compounds.

When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound in the photosensitive resin layer is preferably 1% by mass to 50% by mass, and more preferably 5% by mass to 30% by mass, relative to the total mass of the photosensitive resin layer.

<<Polymer Having a Structural Unit Having an Acid Group Protected by an Acid-Labeling Group>>
The positive photosensitive resin layer preferably contains a polymer (hereinafter also referred to as “polymer X”) having a structural unit (hereinafter also referred to as “structural unit A”) having an acid group protected by an acid-decomposable group.
When the positive photosensitive resin layer contains a polymer X, it may contain only one type of polymer X, or may contain two or more types of polymer X.

In polymer X, the acid group protected by the acid-decomposable group is converted to an acid group through a deprotection reaction by the action of a catalytic amount of an acidic substance (e.g., acid) generated by exposure to light. The generation of acid groups in polymer X increases the solubility of the positive photosensitive resin layer in the developer.

Polymer X is preferably an addition polymerization type polymer, and more preferably a polymer having structural units derived from (meth)acrylic acid or an ester thereof.

--Structural unit having an acid group protected by an acid-decomposable group--
The polymer X preferably has a structural unit having an acid group protected by an acid-decomposable group (i.e., structural unit A). When the polymer X has the structural unit A, the sensitivity of the positive-type photosensitive resin layer can be improved.

The acid group is not limited, and any known acid group can be used.
The acid group is preferably a carboxy group or a phenolic hydroxyl group.

Examples of the acid-decomposable group include a group that is relatively easily decomposable by acid, and a group that is relatively difficult to decompose by acid.
Examples of groups that are relatively easily decomposed by acid include acetal-type protecting groups (eg, 1-alkoxyalkyl groups, tetrahydropyranyl groups, and tetrahydrofuranyl groups).
Examples of groups that are relatively difficult to decompose with an acid include tertiary alkyl groups (such as a tert-butyl group) and tertiary alkyloxycarbonyl groups (such as a tert-butyloxycarbonyl group).
Among these, the acid-decomposable group is preferably an acetal-type protecting group.

The molecular weight of the acid-decomposable group is preferably 300 or less in order to suppress variation in the line width of the resin pattern.

From the viewpoints of sensitivity and resolution, the structural unit A is preferably a structural unit represented by the following formula A1, a structural unit represented by the following formula A2, or a structural unit represented by the following formula A3, and more preferably a structural unit represented by the following formula A3.
The structural unit represented by formula A3 is a structural unit having a carboxy group protected with an acetal-type acid-decomposable group.

In formula A1, R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ¹¹ and R ¹² is an alkyl group or an aryl group, R ¹³ represents an alkyl group or an aryl group, R ¹¹ or R ¹² and R ¹³ may be linked to form a cyclic ether, R ¹⁴ represents a hydrogen atom or a methyl group, X ¹ represents a single bond or a divalent linking group, R ¹⁵ represents a substituent, and n represents an integer of 0 to 4.

In formula A2, R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ²¹ and R ²² is an alkyl group or an aryl group, R ²³ represents an alkyl group or an aryl group, R ²¹ or R ²² and R ²³ may be linked to form a cyclic ether, R ²⁴ each independently represent a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group, or a cycloalkyl group, and m represents an integer of 0 to 3.

In formula A3, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, R ³³ represents an alkyl group or an aryl group, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an arylene group.

In formula A3, when R ³¹ or R ³² is an alkyl group, the alkyl group represented by R ³¹ or R ³² is preferably an alkyl group having 1 to 10 carbon atoms.
In formula A3, when R ³¹ or R ³² is an aryl group, the aryl group represented by R ³¹ or R ³² is preferably a phenyl group.
In formula A3, R ³¹ and R ³² are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In formula A3, R ³³ is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
In formula A3, the alkyl group and aryl group represented by R ³¹ to R ³³ may have a substituent.
In formula A3, R ³¹ or R ³² and R ³³ are preferably linked to form a cyclic ether. The cyclic ether preferably has 5 or 6 ring members, and more preferably 5 ring members.
In formula A3, X ⁰ is preferably a single bond. The arylene group may have a substituent.
In formula A3, R ³⁴ is preferably a hydrogen atom, from the viewpoint that the glass transition temperature (Tg) of polymer X can be made lower.

The content of structural units in which R ³⁴ in formula A3 is a hydrogen atom is preferably 20 mass % or more relative to the total mass of structural units A contained in polymer X.
The content of the structural unit A in which R ³⁴ in formula A3 is a hydrogen atom can be confirmed by the intensity ratio of peak intensities calculated by a conventional method from ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement.

For preferred embodiments of Formulae A1 to A3, see paragraphs [0044] to [0058] of International Publication No. WO 2018/179640.

In formulae A1 to A3, from the viewpoint of sensitivity, the acid-decomposable group is preferably a group having a cyclic structure, more preferably a group having a tetrahydrofuran ring structure or a tetrahydropyran ring structure, even more preferably a group having a tetrahydrofuran ring structure, and particularly preferably a tetrahydrofuranyl group.

When polymer X has structural unit A, it may have only one type of structural unit A or two or more types of structural unit A.

When polymer X has a structural unit A, the content of the structural unit A in polymer X is preferably 10% by mass to 70% by mass, more preferably 15% by mass to 50% by mass, and even more preferably 20% by mass to 40% by mass, relative to the total mass of polymer X.
When the content of the structural unit A in the polymer X is within the above range, the resolution is further improved.
When the polymer X contains two or more kinds of the structural unit A, the content of the structural unit A represents the total content of the two or more kinds of the structural unit A.
The content of the structural unit A in the polymer X can be confirmed by the intensity ratio of peak intensities calculated by a conventional method from ¹³ C-NMR measurement.

-Structural unit having an acid group-
The polymer X may have a structural unit having an acid group (hereinafter, also referred to as “structural unit B”).

The structural unit B is a structural unit having an acid group that is not protected by an acid-decomposable group, i.e., an acid group that does not have a protecting group. When the polymer X has the structural unit B, the sensitivity during pattern formation is improved. In addition, when the polymer X has the structural unit B, it becomes more soluble in an alkaline developer in the development step after exposure, and therefore the development time can be shortened.

The acid group in the structural unit B means a proton dissociating group having a pKa of 12 or less.
From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, and more preferably 6 or less. Also, the pKa of the acid group is preferably −5 or more.

Examples of the acid group include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfo group, a phenolic hydroxyl group, and a sulfonylimide group.
The acid group is preferably a carboxy group or a phenolic hydroxyl group, and more preferably a carboxy group.

When polymer X has structural unit B, it may have only one type of structural unit B, or may have two or more types of structural unit B.

When polymer X has a structural unit B, the content of structural unit B in polymer X is preferably 0.01% by mass to 20% by mass, more preferably 0.01% by mass to 10% by mass, and even more preferably 0.1% by mass to 5% by mass, relative to the total mass of polymer X.
When the content of the structural unit B in the polymer X is within the above range, the resolution is further improved.
When the polymer X has two or more kinds of the structural unit B, the content of the structural unit B represents the total content of the two or more kinds of the structural unit B.
The content of the structural unit B can be confirmed by the intensity ratio of peak intensities calculated by a conventional method from ¹³ C-NMR measurement.

-Other building blocks-
The polymer X preferably has a structural unit (hereinafter also referred to as "structural unit C") other than the structural unit A and the structural unit B described above. By adjusting at least one of the type and content of the structural unit C, the various properties of the polymer X can be adjusted. By the polymer X having the structural unit C, the glass transition temperature, acid value, and hydrophilicity/hydrophobicity of the polymer X can be easily adjusted.

Examples of monomers that form structural unit C include styrene compounds, (meth)acrylic acid alkyl esters, (meth)acrylic acid cyclic alkyl esters, (meth)acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated dicarboxylic acid anhydrides.

From the viewpoint of adhesion to a substrate, the monomer that forms the structural unit C is preferably an alkyl (meth)acrylate, and more preferably an alkyl (meth)acrylate having an alkyl group having 4 to 12 carbon atoms.
Examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

Examples of the structural unit C include structural units derived from styrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, acrylonitrile, or ethylene glycol monoacetoacetate mono(meth)acrylate.
Examples of the structural unit C include structural units derived from the compounds described in paragraphs [0021] to [0024] of JP-A No. 2004-264623.

From the viewpoint of resolution, it is preferable that the structural unit C contains a structural unit having a basic group.
An example of the basic group is a group having a nitrogen atom.
Examples of the group having a nitrogen atom include an aliphatic amino group, an aromatic amino group, and a nitrogen-containing heteroaromatic ring group. The basic group is preferably an aliphatic amino group.

The aliphatic amino group may be a primary amino group, a secondary amino group, or a tertiary amino group, but from the viewpoint of resolution, a secondary amino group or a tertiary amino group is preferable.

Examples of monomers that form structural units having a basic group include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2-(dimethylamino)ethyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 2-(diethylamino)ethyl methacrylate, 2-(dimethylamino)ethyl acrylate, 2-(diethylamino)ethyl acrylate, N-(3-dimethylamino)propyl methacrylate, and acrylic acid. Examples of suitable vinyl acrylates include N-(3-dimethylamino)propyl, N-(3-diethylamino)propyl methacrylate, N-(3-diethylamino)propyl acrylate, 2-(diisopropylamino)ethyl methacrylate, 2-morpholinoethyl methacrylate, 2-morpholinoethyl acrylate, N-[3-(dimethylamino)propyl]acrylamide, 4-aminostyrene, 4-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine, 1-vinylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole, and 1-vinyl-1,2,4-triazole.
Among these, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate is preferred as the monomer that forms a structural unit having a basic group.

From the viewpoint of improving electrical characteristics, the structural unit C is preferably a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton.
Examples of monomers forming these structural units include styrene, α-methylstyrene, dicyclopentanyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and benzyl (meth)acrylate, with cyclohexyl (meth)acrylate being preferred.

When polymer X has structural unit C, it may have only one type of structural unit C, or may have two or more types of structural unit C.

When polymer X has a structural unit C, the content of structural unit C in polymer X is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, based on the total mass of polymer X. In addition, the content of structural unit C in polymer X is preferably 10% by mass or more, and more preferably 20% by mass or more, based on the total mass of polymer X.
When the content of the structural unit C in the polymer X is within the above range, the resolution and the adhesion to the substrate are further improved.
When the polymer X has two or more kinds of the structural unit C, the content of the structural unit C represents the total content of the two or more kinds of the structural unit C.
The content of the structural unit C can be confirmed by the intensity ratio of peak intensities calculated by a conventional method from ¹³ C-NMR measurement.

Preferred examples of polymer X are shown below. However, polymer X is not limited to the following examples. The ratio of each structural unit and the weight average molecular weight in polymer X shown below are appropriately selected to obtain preferred physical properties.

The glass transition temperature (Tg) of the polymer X is preferably 90°C or lower, more preferably 20°C to 60°C, and even more preferably 30°C to 50°C.
In the case where the positive photosensitive resin layer is formed using a photosensitive transfer material described below, if the glass transition temperature of the polymer X is within the above range, the transferability of the positive photosensitive resin layer can be improved.

As a method for adjusting the Tg of polymer X to within the above range, for example, a method using the FOX method can be mentioned. According to the FOX method, for example, the Tg of the target polymer X can be adjusted based on the Tg of the homopolymer of each structural unit in the target polymer X and the mass fraction of each structural unit.

The FOX formula will be explained below using a copolymer having a first structural unit and a second structural unit as an example.
When the glass transition temperature of a homopolymer of the first structural unit is Tg1, the mass fraction of the first structural unit in the copolymer is W1, the glass transition temperature of a homopolymer of the second structural unit is Tg2, and the mass fraction of the second structural unit in the copolymer is W2, the glass transition temperature Tg0 (unit: K) of a copolymer having the first structural unit and the second structural unit can be estimated according to the following formula.
FOX formula: 1/Tg0=(W1/Tg1)+(W2/Tg2)

In addition, the Tg of polymer X can be adjusted by adjusting the weight average molecular weight of polymer X.

From the viewpoint of resolution, the acid value of polymer X is preferably 0 mgKOH/g to 50 mgKOH/g, more preferably 0 mgKOH/g to 20 mgKOH/g, and even more preferably 0 mgKOH/g to 10 mgKOH/g.

The acid value of a polymer represents the mass of potassium hydroxide required to neutralize the acidic components per 1 g of the polymer. A specific measurement method is described below.
First, a measurement sample is dissolved in a mixed solvent containing tetrahydrofuran and water (volume ratio: tetrahydrofuran/water = 9/1). Using a potentiometric titrator (e.g., model number: AT-510, manufactured by Kyoto Electronics Manufacturing Co., Ltd.), the resulting solution is neutralized with a 0.1 mol/L aqueous sodium hydroxide solution at 25°C. The inflection point of the titration pH curve is set as the titration end point, and the acid value is calculated by the following formula.
A = 56.11 x Vs x 0.1 x f/w
A: Acid value (mg KOH / g)
Vs: Amount (mL) of 0.1 mol/L aqueous sodium hydroxide solution required for titration
f: titer of 0.1 mol/L sodium hydroxide aqueous solution w: mass (g) of measurement sample (solid content equivalent)

The weight average molecular weight (Mw) of polymer X is preferably 60,000 or less in terms of polystyrene equivalent. When the positive photosensitive resin layer is formed using a photosensitive transfer material described below, if the weight average molecular weight of polymer X is 60,000 or less, the positive photosensitive resin layer can be transferred at a low temperature (e.g., 130°C or less).

The weight average molecular weight of polymer X is preferably 2,000 to 60,000, and more preferably 3,000 to 50,000.

The ratio of the number average molecular weight to the weight average molecular weight of polymer X (dispersity) is preferably 1.0 to 5.0, and more preferably 1.05 to 3.5.

The weight average molecular weight of polymer X is measured by GPC (gel permeation chromatography). As the measuring device, various commercially available devices can be used. Hereinafter, the method for measuring the weight average molecular weight of polymer X by GPC will be specifically described.
The measurement device used is HLC (registered trademark)-8220GPC (manufactured by Tosoh Corporation).
The column used was a series connection of one each of TSKgel (registered trademark) Super HZM-M (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), Super HZ4000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), Super HZ3000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), and Super HZ2000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation).
THF (tetrahydrofuran) is used as the eluent.
The measurement conditions are as follows: sample concentration 0.2 mass %, flow rate 0.35 mL/min, sample injection amount 10 μL, and measurement temperature 40°C.
A refractive index (RI) detector is used as the detector.
The calibration curve is prepared using any one of the seven samples of "Standard sample TSK standard, polystyrene" manufactured by Tosoh Corporation: "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500", and "A-1000".

When the positive photosensitive resin layer contains polymer X, the content of polymer X in the positive photosensitive resin layer is preferably 50% by mass to 99.9% by mass, and more preferably 70% by mass to 98% by mass, based on the total mass of the positive photosensitive resin layer, from the viewpoint of high resolution.

The method for producing the polymer X is not limited, and any known method can be used.
For example, polymer X can be produced by polymerizing, in an organic solvent, a monomer for forming structural unit A, and, if necessary, a monomer for forming structural unit B and a monomer for forming structural unit C, using a polymerization initiator. Polymer X can also be produced by a so-called polymer reaction.

<<Other polymers>>
When the positive photosensitive resin layer contains a polymer having a structural unit having an acid group protected by an acid-decomposable group, the positive photosensitive resin layer may contain, in addition to the polymer having a structural unit having an acid group protected by an acid-decomposable group, a polymer not having a structural unit having an acid group protected by an acid-decomposable group (hereinafter also referred to as "other polymer").

Other polymers include, for example, polyhydroxystyrene.
Commercially available polyhydroxystyrene products include, for example, SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F manufactured by Sartomer Corporation, ARUFON (registered trademark) UC-3000, ARUFON (registered trademark) UC-3510, ARUFON (registered trademark) UC-3900, ARUFON (registered trademark) UC-3910, ARUFON (registered trademark) UC-3920, and ARUFON (registered trademark) UC-3080 manufactured by Toagosei Co., Ltd., and Joncryl (registered trademark) 690, Joncryl (registered trademark) 678, and Joncryl (registered trademark) manufactured by BASF Corporation. 67, and Joncryl® 586.

When the positive-type photosensitive resin layer contains other polymers, it may contain only one type of other polymer, or may contain two or more types.

When the positive-type photosensitive resin layer contains other polymers, the content of the other polymers in the positive-type photosensitive resin layer is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, based on the total mass of the polymer components.

In this disclosure, the term "polymer component" is a general term for all polymers contained in the positive photosensitive resin layer. For example, when the positive photosensitive resin layer contains polymer X and other polymers, polymer X and the other polymers are collectively referred to as the "polymer component." Note that compounds corresponding to crosslinking agents, dispersants, and surfactants, which will be described later, are not included in the polymer component even if they are polymer compounds.

The content of the polymer component in the positive photosensitive resin layer is preferably 50% by mass to 99.9% by mass, and more preferably 70% by mass to 98% by mass, based on the total mass of the positive photosensitive resin layer.

<<Alkali-soluble resin (positive type)>>
The positive-type photosensitive resin layer preferably contains an alkali-soluble resin, more preferably contains an alkali-soluble resin and a quinone diazide compound, and even more preferably contains a resin having a structural unit with a phenolic hydroxyl group and a quinone diazide compound.

Examples of the alkali-soluble resin include resins having a hydroxyl group, a carboxyl group, or a sulfo group in the main chain or in the side chain.
Examples of the alkali-soluble resin include polyamide resins, polyhydroxystyrene, derivatives of polyhydroxystyrene, styrene-maleic anhydride copolymers, polyvinyl hydroxybenzoate, carboxy group-containing (meth)acrylic resins, and novolak resins.
As the alkali-soluble resin, for example, a condensation polymer of mixed m-/p-cresol and formaldehyde, and a condensation polymer of phenol, cresol and formaldehyde are preferable.

The alkali-soluble resin may have a phenolic hydroxyl group (-Ar-OH), a carboxy group (-CO ₂ H), a sulfo group (-SO ₃ H), a phosphate group (-OPO ₃ H), a sulfonamide group (-SO ₂ NH-R), or a substituted sulfonamide acid group (for example, an active imide group, -SO ₂ NHCOR, -SO ₂ NHSO ₂ R, and -CONHSO ₂ R). Here, Ar represents a divalent aryl group which may have a substituent, and R represents a hydrocarbon group which may have a substituent.

The novolak resin can be obtained, for example, by condensing a phenolic compound with an aldehyde compound in the presence of an acid catalyst.
Examples of phenolic compounds include o-, m-, or p-cresol, 2,5-, 3,5-, or 3,4-xylenol, 2,3,5-trimethylphenol, 2-t-butyl-5-methylphenol, and t-butylhydroquinone.
Examples of aldehyde compounds include aliphatic aldehydes (eg, formaldehyde, acetaldehyde, and glyoxal) and aromatic aldehydes (eg, benzaldehyde and salicylaldehyde).
Examples of the acid catalyst include inorganic acids (eg, hydrochloric acid, sulfuric acid, and phosphoric acid), organic acids (eg, oxalic acid, acetic acid, and p-toluenesulfonic acid), and divalent metal salts (eg, zinc acetate).
The condensation reaction can be carried out according to a conventional method.
The condensation reaction is carried out, for example, at a temperature in the range of 60° C. to 120° C. for 2 to 30 hours.
The condensation reaction may be carried out in a suitable solvent.

As the alkali-soluble resin, a resin having a structural unit with a phenolic hydroxyl group, such as a novolac resin, is preferred.

The weight average molecular weight of the alkali-soluble resin is preferably 5.0×10 ² to 2.0×10 ⁵ from the viewpoint of pattern formability.
The number average molecular weight of the alkali-soluble resin is preferably 2.0×10 ² to 1.0×10 ⁵ from the viewpoint of pattern formability.

For example, a condensation polymer of phenol having an alkyl group having 3 to 8 carbon atoms as a substituent and formaldehyde, such as a condensation polymer of t-butylphenol and formaldehyde and a condensation polymer of octylphenol and formaldehyde described in U.S. Pat. No. 4,123,279, may be used in combination.
Furthermore, condensates of phenol having an alkyl group having 3 to 8 carbon atoms as a substituent with formaldehyde, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin described in U.S. Pat. No. 4,123,279, may be used in combination.

When the positive photosensitive resin layer contains an alkali-soluble resin, it may contain only one type of alkali-soluble resin, or may contain two or more types of alkali-soluble resin.

When the positive photosensitive resin layer contains an alkali-soluble resin, the content of the alkali-soluble resin in the positive photosensitive resin layer is preferably 30% by mass to 99.9% by mass, more preferably 40% by mass to 99.5% by mass, and even more preferably 70% by mass to 99% by mass, based on the total mass of the positive photosensitive resin layer.

<<Photoacid generator>>
The positive photosensitive resin layer preferably contains a photoacid generator as a photosensitive compound.
A photoacid generator is a compound capable of generating an acid upon irradiation with actinic rays (eg, ultraviolet rays, far ultraviolet rays, X-rays, and electron beams).

Preferred photoacid generators are compounds that generate acid in response to actinic rays with wavelengths of 300 nm or more, preferably 300 to 450 nm. In addition, photoacid generators that are not directly sensitive to actinic rays with wavelengths of 300 nm or more can also be preferably used in combination with a sensitizer, as long as they generate acid in response to actinic rays with wavelengths of 300 nm or more when used in combination with a sensitizer.

The photoacid generator is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and even more preferably a photoacid generator that generates an acid having a pKa of 2 or less.
The lower limit of the pKa of the acid derived from the photoacid generator is not limited, but is preferably, for example, −10.0 or more.

Examples of photoacid generators include ionic photoacid generators and nonionic photoacid generators.

Examples of the ionic photoacid generator include onium salt compounds.
Examples of the onium salt compound include diaryliodonium salt compounds, triarylsulfonium salt compounds, and quaternary ammonium salt compounds.
The ionic photoacid generator is preferably an onium salt compound, and more preferably at least one of a triarylsulfonium salt compound and a diaryliodonium salt compound.

As the ionic photoacid generator, the ionic photoacid generators described in paragraphs [0114] to [0133] of JP 2014-85643 A can also be preferably used.

Examples of non-ionic photoacid generators include trichloromethyl-s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.
From the viewpoints of sensitivity, resolution, and adhesion to the substrate, the nonionic photoacid generator is preferably an oxime sulfonate compound.

Specific examples of trichloromethyl-s-triazine compounds, diazomethane compounds, and imide sulfonate compounds include the compounds described in paragraphs [0083] to [0088] of JP 2011-221494 A.

As the oxime sulfonate compound, those described in paragraphs [0084] to [0088] of WO 2018/179640 can be preferably used.

From the viewpoint of sensitivity and resolution, the photoacid generator is preferably at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and more preferably an oxime sulfonate compound.

Preferred examples of photoacid generators include those having the following structures:

An example of a photoacid generator that has absorption at a wavelength of 405 nm is ADEKA ARCLES (registered trademark) SP-601 (manufactured by ADEKA Corporation).

From the viewpoints of heat resistance and dimensional stability, the positive photosensitive resin layer preferably contains a quinone diazide compound as an acid generator (preferably a photoacid generator).
The quinone diazide compound can be synthesized, for example, by subjecting a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid halide to a condensation reaction in the presence of a dehydrohalogenation agent.

Examples of quinone diazide compounds include 1,2-benzoquinone diazide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-5-sulfonic acid ester, 1,2-naphthoquinone diazide-6-sulfonic acid ester, 2,1-naphthoquinone diazide-4-sulfonic acid ester, 2,1-naphthoquinone diazide-5-sulfonic acid ester, 2,1-naphthoquinone diazide-6-sulfonic acid ester, and other quinone diazides. Sulfonic acid ester derivatives include 1,2-benzoquinone diazide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 1,2-naphthoquinone diazide-6-sulfonic acid chloride, 2,1-naphthoquinone diazide-4-sulfonic acid chloride, 2,1-naphthoquinone diazide-5-sulfonic acid chloride, and 2,1-naphthoquinone diazide-6-sulfonic acid chloride.

When the positive-type photosensitive resin layer contains a photoacid generator, it may contain only one type of photoacid generator, or may contain two or more types of photoacid generator.

When the positive photosensitive resin layer contains a photoacid generator, the content of the photoacid generator in the positive photosensitive resin layer is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass to 5% by mass, based on the total mass of the positive photosensitive resin layer, from the viewpoints of sensitivity and resolution.

<<Other ingredients>>
The photosensitive resin layer may contain components other than those mentioned above.

(Surfactant)
From the viewpoint of thickness uniformity, the photosensitive resin layer preferably contains a surfactant.
Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.
Among these, the surfactant is preferably a nonionic surfactant.
Examples of the surfactant include those described in paragraph [0017] of Japanese Patent No. 4,502,784 and paragraphs [0060] to [0071] of JP-A-2009-237362.

The surfactant is preferably a fluorine-based surfactant or a silicone-based surfactant.
Commercially available fluorine-based surfactants include, for example, Megafac (registered trademark) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-444, 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, MFS-578, MFS-579, MFS-586, MFS-587, 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 (all manufactured by DIC Corporation), Fluorad (registered trademark) FC430, FC431, and FC171 (all manufactured by Sumitomo 3M Limited), Surflon (registered trademark) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by AGC Corporation), PolyFox (registered trademark) PF636, PF656, PF6320, PF6520, and PF7002 (all manufactured by OMNOVA), and Futergent (registered trademark) Examples of such products include 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (all manufactured by NEOS Corporation).
Also suitable for use as the fluorosurfactant are acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heat is applied, the functional group containing the fluorine atom is cleaved and the fluorine atom is volatilized. Examples of such fluorosurfactants include Megafac (registered trademark) DS-21 from the Megafac DS series manufactured by DIC Corporation [see Chemical Daily (February 22, 2016) and Nikkei Business Daily (February 23, 2016)].

As the fluorine-based surfactant, 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 can also be suitably used.
Furthermore, as the fluorosurfactant, a block polymer can also be used.
As the fluorine-based surfactant, a fluorine-containing polymer compound containing a constituent unit derived from a (meth)acrylate compound having a fluorine atom and a constituent unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) can also be suitably used.
As the fluorosurfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used, such as Megafac (registered trademark) RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2 (all manufactured by BASF), and Tetronic (registered trademark). 304, 701, 704, 901, 904, and 150R1 (all manufactured by BASF), Solsperse (registered trademark) 20000 (manufactured by Lubrizol Japan Co., Ltd.), NCW-101, NCW-1001, and NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.), Paionin (registered trademark) D-6112, D-6112-W, and D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), Surfynol (registered trademark) 104, 400, and 440, and Olfine (registered trademark) E1010 (all manufactured by Nissin Chemical Industry Co., Ltd.).
In recent years, because there have been concerns about the environmental compatibility of compounds having a linear perfluoroalkyl group having seven or more carbon atoms, it is preferable to use surfactants that use alternative materials to perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS).

Examples of silicone surfactants include linear polymers formed from siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or ends.
Examples of silicone surfactants include DOWSIL (registered trademark) 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), 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, and KF-60 01, and KF-6002 [all manufactured by Shin-Etsu Chemical Co., Ltd.], F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 [all manufactured by Momentive Performance Materials], and BYK307, BYK323, and BYK330 [all manufactured by BYK-Chemie].

When the photosensitive resin layer contains a surfactant, it may contain only one type of surfactant or two or more types of surfactant.

When the photosensitive resin layer contains a surfactant, the content of the surfactant in the photosensitive resin layer is preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 3% by mass, relative to the total mass of the photosensitive resin layer.

(Additive)
The photosensitive resin layer may contain known additives, if necessary, in addition to the above components.
Examples of the additives include a sensitizer, a plasticizer, a heterocyclic compound, an alkoxysilane compound, and a solvent.
Further, examples of additives in the negative photosensitive resin layer and/or the positive photosensitive resin layer include metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, and organic or inorganic suspending agents.
Preferred embodiments of these additives are described in paragraphs [0165] to [0184] of JP 2014-85643 A, the contents of which are incorporated herein by reference.
When the photosensitive resin layer contains an additive, it may contain only one type of additive, or may contain two or more types of additives.

The photosensitive resin layer may contain a sensitizer.
The sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used.
Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (e.g., 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds.

When the photosensitive resin layer contains a sensitizer, the content of the sensitizer in the photosensitive resin layer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and improving the curing speed by balancing the polymerization rate and chain transfer, it is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 1% by mass, based on the total mass of the photosensitive resin layer.

The photosensitive resin layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds.
Examples of the plasticizer and heterocyclic compound include the compounds described in paragraphs [0097] to [0103] and [0111] to [0118] of WO 2018/179640.

The photosensitive resin layer (preferably a positive-type photosensitive resin layer) may contain an alkoxysilane compound.
Examples of alkoxysilane compounds include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriakoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane, and vinyltrialkoxysilane.
Among these, the alkoxysilane compound is preferably a trialkoxysilane compound, more preferably γ-glycidoxypropyltrialkoxysilane or γ-methacryloxypropyltrialkoxysilane, even more preferably γ-glycidoxypropyltrialkoxysilane, and particularly preferably 3-glycidoxypropyltrimethoxysilane.

When the photosensitive resin layer contains an alkoxysilane compound, the content of the alkoxysilane compound in the photosensitive resin layer is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 40% by mass, and even more preferably 1.0% by mass to 30% by mass, based on the total mass of the photosensitive resin layer, from the viewpoints of adhesion to the substrate and etching resistance.

The photosensitive resin layer may contain a solvent. If the photosensitive resin composition for forming the photosensitive resin layer contains a solvent, the solvent may remain in the photosensitive resin layer.

(Impurities, etc.)
The photosensitive resin layer may contain a predetermined amount of impurities.
Impurities include, for example, sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof.
Among these, halide ions, sodium ions, and potassium ions are easily mixed in as impurities, so it is preferable to set the contents thereof to the following amounts.

The content of impurities in the photosensitive resin layer is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 2 ppm by mass or less, based on the total mass of the photosensitive resin layer. The lower limit can be 1 ppb by mass or more, and may be 0.1 ppm by mass or more, based on the total mass of the photosensitive resin layer.

Methods for keeping the impurity content in the photosensitive resin layer within the above range include selecting a raw material for the photosensitive resin composition used to form the photosensitive resin layer that contains a small amount of impurities, preventing impurities from being mixed in when the photosensitive resin layer is produced, and removing impurities by washing. By using such methods, the impurity content in the photosensitive resin layer can be kept within the above range.

Impurities can be quantified by known methods, such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive resin layer is preferably small.
The content of these compounds relative to the total mass of the photosensitive resin layer is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, and even more preferably 4 mass ppm or less. The lower limit can be 10 mass ppb or more, and can be 100 mass ppb or more, relative to the total mass of the photosensitive resin layer.
The content of these compounds can be reduced by the same method as that for the content of the above-mentioned metal impurities, and the content of these compounds can be quantified by a known method.

From the viewpoint of improving reliability and lamination properties, the water content in the photosensitive resin layer is preferably 0.01% by mass to 1.0% by mass, and more preferably 0.05% by mass to 0.5% by mass, relative to the total mass of the photosensitive resin layer.

(Residual Monomer)
The photosensitive resin layer may contain residual monomers corresponding to the respective structural units of the above-mentioned alkali-soluble resin.
From the viewpoint of patterning property and reliability, the content of the residual monomer is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and even more preferably 500 ppm by mass or less, based on the total mass of the alkali-soluble resin. The lower limit is not particularly limited, but is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more.
From the viewpoint of patterning property and reliability, the residual monomer of each constituent unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and even more preferably 100 mass ppm or less, based on the total mass of the photosensitive resin layer. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, and more preferably 1 mass ppm or more.

The amount of residual monomers in the synthesis of an alkali-soluble resin by a polymer reaction is also preferably within the above range. For example, when the alkali-soluble resin is synthesized by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably within the above range.
The amount of the residual monomer can be measured by a known method such as liquid chromatography or gas chromatography.

-Physical properties etc.-
The thickness of the photosensitive resin layer is preferably 0.1 μm to 300 μm, more preferably 0.2 μm to 100 μm, even more preferably 0.5 μm to 50 μm, even more preferably 0.5 μm to 15 μm, particularly preferably 0.5 μm to 10 μm, and most preferably 0.5 μm to 8 μm.
When the thickness of the photosensitive resin layer is within the above range, the developability of the photosensitive resin layer is further improved, and the resolution can be further improved.
In addition, from the viewpoint of better exerting the resolution and the effects of the present disclosure, the thickness of the photosensitive resin layer is preferably 10 μm or less, more preferably 5.0 μm or less, even more preferably 0.5 μm to 4.0 μm, and particularly preferably 0.5 μm to 3.0 μm.

The thickness of each layer of the photosensitive transfer material is the average thickness obtained by observing a cross section of the photosensitive transfer material in a direction perpendicular to the main surface thereof with a scanning electron microscope (SEM), measuring the thickness of each layer at 10 or more points based on the obtained observation image, and calculating the arithmetic average.

The transmittance of the photosensitive resin layer for light having a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. There is no particular upper limit, but it is preferably 99.9% or less.

<Method of forming photosensitive resin layer>
The method for forming the photosensitive resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components.
As a method for forming a photosensitive resin layer, for example, in the case of a negative photosensitive resin layer, a method can be mentioned in which a photosensitive resin composition containing a polymerizable compound, a photopolymerization initiator, an alkali-soluble resin, a solvent, etc. is prepared, the photosensitive resin composition is applied to a surface of a temporary support or the like, and the coating film of the photosensitive resin composition is dried to form the layer.

The photosensitive resin composition used to form the photosensitive resin layer may be, for example, a composition containing a polymerizable compound, a photopolymerization initiator, an alkali-soluble resin, the above-mentioned optional components, and a solvent. The photosensitive resin composition preferably contains a solvent to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive resin layer.

The solvent contained in the photosensitive resin composition is not particularly limited as long as it can dissolve or disperse the alkali-soluble resin, the polymerizable compound, the photopolymerization initiator, and the above-mentioned optional components, and any known solvent can be used.
Examples of the solvent include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g., methanol and ethanol), ketone solvents (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g., toluene), aprotic polar solvents (e.g., N,N-dimethylformamide), cyclic ether solvents (e.g., tetrahydrofuran), ester solvents, amide solvents, lactone solvents, and mixed solvents containing two or more of these.
The photosensitive resin composition preferably contains at least one solvent selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents.
The photosensitive resin composition is more preferably a mixed solvent containing at least one solvent selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, and at least one solvent selected from the group consisting of ketone solvents and cyclic ether solvents, and even more preferably a mixed solvent containing at least three solvents: at least one solvent selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent.

Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers.
Alkylene glycol ether acetate solvents include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

As the solvent, the solvents described in paragraphs [0092] to [0094] of WO 2018/179640 and the solvents described in paragraph [0014] of JP 2018-177889 A may be used, and the contents of these descriptions are incorporated herein by reference.

When the photosensitive resin composition contains a solvent, it may contain only one type of solvent, or two or more types of solvent.

When the photosensitive resin composition contains a solvent, the content of the solvent in the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, and more preferably 100 parts by mass to 900 parts by mass, per 100 parts by mass of the total solid content in the photosensitive resin composition.

The method for preparing the photosensitive resin composition is not particularly limited, and examples thereof include a method in which each component is dissolved in the above-mentioned solvent to prepare a solution in advance, and the obtained solutions are mixed in a predetermined ratio to prepare the photosensitive resin composition.
From the viewpoint of particle removability, the photosensitive resin composition is preferably filtered using a filter before forming the photosensitive resin layer, more preferably filtered using a filter having a pore size of 0.2 μm to 10 μm, even more preferably filtered using a filter having a pore size of 0.2 μm to 7 μm, and particularly preferably filtered using a filter having a pore size of 0.2 μm to 5 μm.
The material and shape of the filter are not particularly limited, and any known filter can be used.
The above filtration is preferably carried out one or more times, and is also preferably carried out a plurality of times.

The method for applying the photosensitive resin composition is not particularly limited, and any known method may be used for application.
Examples of the method for applying the photosensitive resin composition include slit coating, spin coating, curtain coating, and inkjet coating.

Examples of a method for drying the coating film of the photosensitive resin composition include natural drying, heat drying, and reduced pressure drying. These drying methods may be used alone or in combination.
The drying method is preferably drying under heat and/or drying under reduced pressure.
Here, "drying" means removing at least a part of the solvent contained in the photosensitive resin composition.
The drying temperature is preferably 80° C. or higher, and more preferably 90° C. or higher. There is no particular upper limit, but the upper limit is preferably 130° C. or lower, and more preferably 120° C. or lower. Drying may be performed by continuously changing the temperature.
The drying time is preferably 20 seconds or more, more preferably 40 seconds or more, and even more preferably 60 seconds or more. There is no particular upper limit, but the drying time is preferably 600 seconds or less, and more preferably 300 seconds or less.
The photosensitive resin layer may be formed by applying a photosensitive resin composition onto a protective film described below, and drying the composition.

The photosensitive transfer material in the present disclosure may have another layer between the temporary support and the photosensitive resin layer from the viewpoints of resolution and releasability of the temporary support.

<Protective film>
The photosensitive transfer material preferably has a protective film.
The transfer layer does not include a protective film.
It is preferable that the protective film and the photosensitive resin layer are in direct contact with each other.

Examples of materials constituting the protective film include resin films and paper.
The material constituting the protective film is preferably a resin film from the viewpoints of strength and flexibility.
Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film.
Among these, the resin film is preferably a polyethylene film, a polypropylene film, or a polyethylene terephthalate film.

The thickness of the protective film is not particularly limited, but is preferably 5 μm to 100 μm, and more preferably 10 μm to 50 μm.

From the viewpoints of transportability, suppression of defects in the resin pattern, and resolution, the arithmetic mean roughness Ra of the surface of the protective film opposite the photosensitive resin layer is preferably equal to or less than the arithmetic mean roughness Ra of the surface of the protective film facing the photosensitive resin layer, and is more preferably smaller than the arithmetic mean roughness Ra of the surface of the protective film facing the photosensitive resin layer.
The arithmetic mean roughness Ra of the surface of the protective film opposite to the photosensitive resin layer side is preferably 300 nm or less, more preferably 100 nm or less, even more preferably 70 nm or less, and particularly preferably 50 nm or less, from the viewpoint of transportability and winding property. Also, the arithmetic mean roughness Ra of the surface of the protective film facing the photosensitive resin layer side is preferably 300 nm or less, more preferably 100 nm or less, even more preferably 70 nm or less, and particularly preferably 50 nm or less, from the viewpoint of better resolution.
When the Ra value of the surface of the protective film is within the above range, the uniformity of the thickness of the photosensitive resin layer and the formed resin pattern can be further improved.
The lower limit of the Ra value of the surface of the protective film is not particularly limited, but is preferably 1 nm or more, more preferably 10 nm or more, and even more preferably 20 nm or more, on each of both surfaces.
The peel strength of the protective film is preferably smaller than that of the temporary support.

-Thickness of photosensitive transfer material-
The thickness of the photosensitive transfer material is preferably from 5 μm to 55 μm, more preferably from 10 μm to 50 μm, and even more preferably from 20 μm to 40 μm.
The thickness of the photosensitive transfer material is measured by a method similar to the method for measuring the thickness of each layer described above.
From the viewpoint of better exerting the effects of the present disclosure, the thickness of layers in the photosensitive transfer material excluding the temporary support and protective film is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.
From the viewpoint of better exerting the effects of the present disclosure, the total thickness of the photosensitive resin layer, the water-soluble resin layer, and the thermoplastic resin layer in the photosensitive transfer material is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.

[Method of producing photosensitive transfer material]
The method for producing the photosensitive transfer material used in the present disclosure is not particularly limited, and any known method can be applied.
As a manufacturing method of the photosensitive transfer material used in the present disclosure, for example, from the viewpoint of excellent productivity, there can be mentioned a method including a step of applying a photosensitive resin composition to the surface of a temporary support to form a coating film, and a step of drying the formed coating film to form a photosensitive resin layer.

When the photosensitive transfer material used in the present disclosure has a protective film on the side of the photosensitive resin layer opposite the temporary support side, for example, a photosensitive transfer material having a temporary support/photosensitive resin layer/protective film configuration can be produced by pressing and laminating the protective film onto the photosensitive resin layer formed above.

The method for laminating the protective film and the photosensitive resin layer is not particularly limited, and any known method can be used. For example, a known laminator such as a vacuum laminator or an auto laminator can be used to laminate the protective film and the photosensitive resin layer.
The laminator is preferably equipped with any heatable roller, such as a rubber roller, and is capable of applying pressure and heat.

The photosensitive transfer material produced as described above may be wound up to produce a roll of photosensitive transfer material, which may then be stored. The roll of photosensitive transfer material can be provided in its original form for the lamination step with a substrate in a roll-to-roll system.

(Electronic device and its manufacturing method)
An electronic device according to the present disclosure includes a laminate according to the present disclosure.
The method for producing an electronic device according to the present disclosure is not particularly limited as long as it is a method for producing an electronic device including a laminate according to the present disclosure.

In the method for producing an electronic device, specific aspects of each step, the order in which each step is performed, and the like are as described above in the section "Method for producing a laminate," and the same applies to preferred aspects.
The method for producing an electronic device may refer to known methods for producing an electronic device, except that the wiring for an electronic device is formed by the above-mentioned method.
Furthermore, the method for manufacturing an electronic device may include any steps (other steps) other than those described above.

The electronic device is not particularly limited, but preferred examples thereof include semiconductor packages, printed circuit boards, various wiring formation applications for sensor boards, touch panels, electromagnetic wave shielding materials, conductive films such as film heaters, liquid crystal sealing materials, and structures in the micromachine or microelectronics fields.
Among these, a touch panel is particularly preferred as an electronic device.
Suitable examples of electronic devices include flexible display devices, and in particular flexible touch panels.

An example of a mask pattern used in manufacturing a touch panel is shown in FIG. 2 and FIG.
In the pattern A shown in FIG. 2 and the pattern B shown in FIG. 3, GR is a non-image portion (light-shielding portion), EX is an image portion (exposed portion), and DL is a virtual representation of an alignment frame. In the touch panel manufacturing method, for example, by exposing the photosensitive resin layer through a mask having the pattern A shown in FIG. 2, a touch panel having circuit wiring having a pattern A corresponding to EX can be manufactured. Specifically, it can be manufactured by the method shown in FIG. 1 of International Publication No. 2016/190405. In one example of the manufactured touch panel, the central portion (pattern portion where the electrodes are connected) of the exposed portion EX is a portion where a transparent electrode (electrode for a touch panel) is formed, and the peripheral portion (thin line portion) of the exposed portion EX is a portion where wiring of the peripheral extraction portion is formed.

By the above-described method for manufacturing an electronic device, an electronic device having at least wiring for an electronic device is manufactured, and preferably, for example, a touch panel having at least wiring for a touch panel is manufactured.
The touch panel preferably has a transparent substrate, electrodes, and an insulating layer or a protective layer.
Examples of detection methods for touch panels include known methods such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method.
Among these, the capacitance method is preferable as a detection method for a touch panel.

Examples of touch panel types include the so-called in-cell type (for example, those described in Figures 5, 6, 7, and 8 of JP-T-2012-517051), the so-called on-cell type (for example, those described in Figure 19 of JP-A-2013-168125 and those described in Figures 1 and 5 of JP-A-2012-89102), the OGS (One Glass Solution) type, the TOL (Touch-on-Lens) type (for example, those described in Figure 2 of JP-A-2013-54727), various out-cell types (so-called GG, G1/G2, GFF, GF2, GF1, G1F, etc.), and other configurations (for example, those described in Figure 6 of JP-A-2013-164871).
An example of the touch panel is described in paragraph [0229] of JP2017-120435A.

The present disclosure will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of this disclosure. Therefore, the scope of this disclosure should not be interpreted as being limited by the examples shown below. Note that, unless otherwise specified, "parts" and "%" are based on mass.

[Preparation of Photosensitive Resin Composition P]
The following components were mixed to prepare a photosensitive resin composition P.

--Composition of photosensitive resin composition P--
Propylene glycol monomethyl ether acetate solution of styrene/methacrylic acid/methyl methacrylate copolymer (solid content concentration: 30.0% by mass, ratio of each monomer: 52% by mass/29% by mass/19% by mass, Mw: 70,000): 23.4 parts by mass BPE-500 [ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.]: 4.1 parts by mass NK Ester HD-N [1,6-hexanediol dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.]: 2.2 parts by mass B-CIM [2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, photopolymerization initiator, manufactured by Kurogane Kasei Co., Ltd.]: 0.25 parts by mass SB-PI 701 [4,4'-bis(diethylamino)benzophenone, sensitizer, obtained from Sanyo Trading Co., Ltd.]: 0.04 parts by mass TDP-G [phenothiazine, manufactured by Kawaguchi Chemical Industry Co., Ltd.]: 0.0175 parts by mass 1-phenyl-3-pyrazolidone [manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.]: 0.0011 parts by mass Leuco Crystal Violet [manufactured by Tokyo Chemical Industry Co., Ltd.]: 0.051 parts by mass N-phenylcarbamoylmethyl-N-carboxymethylaniline [manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.]: 0.02 parts by mass 1,2,4-triazole [manufactured by Tokyo Chemical Industry Co., Ltd.]: 0.75 parts by mass Megafac (registered trademark) F-552 [fluorine-based surfactant, manufactured by DIC Corporation]: 0.05 parts by mass Methyl ethyl ketone [manufactured by Sankyo Chemical Co., Ltd.]: 40.4 parts by mass Propylene glycol monomethyl ether acetate (manufactured by Showa Denko K.K.): 26.7 parts by mass Methanol (manufactured by Mitsubishi Gas Chemical Co., Ltd.): 2 parts by mass

[Preparation of Photosensitive Transfer Material P]
The photosensitive resin composition P prepared above was applied onto the surface of a temporary support (polyethylene terephthalate film, thickness: 16 μm, haze: 0.12%) using a slit nozzle so that the application width was 1.0 m and the film thickness after drying was 5.0 μm, and the mixture was dried at 100 ° C. for 2 minutes to form a photosensitive resin layer P. Next, a protective film (polypropylene film, thickness: 12 μm) was attached to the exposed surface of the photosensitive resin layer P formed on the surface of the temporary support to obtain a photosensitive transfer material P (layer structure: temporary support / photosensitive resin layer P / protective film).

[Preparation of silver particles]
200 mL of toluene (Fujifilm Wako Pure Chemical Industries, Ltd., first-grade reagent) and 11 g of butylamine (Fujifilm Wako Pure Chemical Industries, Ltd., first-grade reagent) were mixed and thoroughly stirred using a magnetic stirrer. The molar ratio of the added amine was 2.5 relative to silver. 10 g of silver nitrate (Toyo Kagaku Kogyo Co., Ltd., special-grade reagent) was added to the mixture while stirring. After the silver nitrate was dissolved, 10 g of DISPERBYK-111, a polymer dispersant, and 10 g of hexane (Fujifilm Wako Pure Chemical Industries, Ltd., special-grade reagent) were added. 1 g of sodium borohydride (Fujifilm Wako Pure Chemical Industries, Ltd.) was added to 50 mL of ion-exchanged water to prepare a 0.02 g/mL aqueous solution of sodium borohydride, which was prepared by adding 1 g of sodium borohydride (Fujifilm Wako Pure Chemical Industries, Ltd.), were dropped to obtain a liquid containing silver fine particles. After stirring for 1 hour, 200 mL of methanol (special grade reagent, Fujifilm Wako Pure Chemical Industries, Ltd.) was added to aggregate and settle the silver particles. The silver particles were then completely settled by centrifugation, and the supernatant toluene and methanol were removed, and excess organic matter was removed to obtain approximately 6 g of silver particles.

[Preparation of Silver Ink X]
The following components were preliminarily mixed and then mixed using a three-roll mill to prepare silver ink X.

- Composition of Silver Ink X -
Silver fine particles: 100 parts by mass Benzyl methacrylate/methacrylic acid/acrylic acid copolymer (mass ratio of constituent units: 74.5/10/15.5, acid value: 186 mg KOH/g, weight average molecular weight: 60,000): 1.53 parts by mass ARONIX (registered trademark) M-1960 [polymerizable compound, manufactured by Toagosei Co., Ltd.]: 0.73 parts by mass ARONIX (registered trademark) M-350 [polymerizable compound, manufactured by Toagosei Co., Ltd.]: 0.80 parts by mass Omnirad (registered trademark) 184 [photopolymerization initiator, manufactured by IGM Resins B.V. 0.05 parts by mass Benzophenone (photopolymerization initiator, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.): 0.05 parts by mass Omnirad (registered trademark) 819 (photopolymerization initiator, manufactured by IGM Resins B.V.): 0.16 parts by mass DISPERBYK-111 (polymer dispersant, manufactured by BYK Japan Co., Ltd.): 0.02 parts by mass Propylene glycol monomethyl ether acetate (manufactured by Showa Denko K.K.): 230 parts by mass

Example 1
1. Preparation of conductive substrate On the surface of a substrate [ZeonorFilm (registered trademark) ZF16, thickness: 100 μm, manufactured by Zeon Corporation], a silver nanowire ink manufactured by the method described in paragraphs [0036] to [0042] of Japanese Patent No. 6505777 was applied using a spin coater so as to have a wet film thickness of 10 μm, to form a coating film. Next, the formed coating film was dried at 100° C. for 5 minutes to obtain a substrate having a transparent conductive layer [layer structure: substrate/transparent conductive layer]. Next, the substrate having the transparent conductive layer obtained above was placed in a batch-type vacuum deposition device [model number: EBH-800, manufactured by ULVAC, Inc.]. Next, copper was placed on the deposition boat in an amount to a thickness of 1.0 μm. Next, the substrate was evacuated until the vacuum reached 9.0×10 ⁻³ Pa or less, and then the evaporation boat was heated, and vacuum deposition was performed on the surface of the transparent conductive layer of the substrate to form a metal layer. In this manner, a conductive substrate (layer structure: substrate/transparent conductive layer/metal layer) was prepared.

2. Preparation of Laminate After peeling off the protective film from the photosensitive transfer material P prepared above, the photosensitive transfer material (layer structure: temporary support/photosensitive resin layer) was attached to the exposed surface of the metal layer of the conductive substrate under lamination conditions of a roll temperature of 90° C., a linear pressure of 0.8 MPa, and a linear speed of 3.0 m/min, to obtain a laminate.

A glass mask having a line and space pattern with a line width of 12 μm and a space width of 8 μm and an output terminal pattern connected thereto was attached to the temporary support of the obtained laminate, and then the laminate was exposed to light using an ultra-high pressure mercury lamp [model number: USH-2004MB, manufactured by Ushio Inc.].

The exposure conditions were determined as follows.
The sample was exposed through the above glass mask using an ultra-high pressure mercury lamp (model number: USH-2004MB, manufactured by Ushio Inc.), and then left for 1 hour before being developed. The exposure dose was set so that the remaining pattern width in the 12 μm line/8 μm space pattern area was in the range of 10.9 μm to 11.1 μm.
In the following examples and comparative examples, the exposure conditions were determined from the same viewpoint.

After leaving the laminate for 1 hour after exposure, the temporary support was peeled off, and the uncured portions were removed by shower development for 30 seconds using a 1.0% by weight aqueous potassium carbonate solution (liquid temperature: 30°C) as the developer, forming a resist pattern.

After development, a copper etching solution (product name: Cu-02, manufactured by Kanto Chemical Co., Ltd.) at a liquid temperature of 25°C was sprayed from a shower for 90 seconds onto the side of the laminate on which the resist pattern was formed, etching the metal layer to obtain a metal wiring layer (metal type: Cu).

Next, a 30% by weight aqueous solution of ferric nitrate (liquid temperature: 45°C, pH: 0.6) was sprayed onto the surface of the developed laminate on which the resist pattern was formed for 50 seconds, and the transparent conductive layer in the area where the resist pattern was not present on the surface was etched to obtain a transparent wiring layer.

The laminate after the etching treatment was immersed in a 3% by mass aqueous sodium hydroxide solution (liquid temperature: 50° C.) for 70 seconds to remove the resist pattern remaining on the laminate, thereby obtaining a laminate of Example 1.
When the obtained laminate of Example 1 was observed using an optical microscope, it was confirmed that a transparent wiring layer and a metal wiring layer were formed in that order on the substrate, and that both ends of the transparent wiring layer were located 0.5 μm outward from both ends of the metal wiring layer.

The volume resistivity of the transparent wiring layer and the volume resistivity of the metal wiring layer were measured, and both were found to be less than 1×10 ⁴ Ωcm.

Example 2
1. Preparation of Conductive Substrate A conductive substrate (layer structure: substrate/transparent conductive layer/metal layer) was prepared in the same manner as in Example 1.

2. Preparation of Laminate A laminate was obtained by the same procedure as in Example 1.
A glass mask having a line and space pattern with a line width of 8 μm and a space width of 4 μm and an extraction terminal pattern connected thereto was closely attached to the temporary support of the obtained laminate, and then the laminate was exposed to light using an ultra-high pressure mercury lamp [model number: USH-2004MB, manufactured by Ushio Inc.].
After leaving the laminate for 1 hour after exposure, the temporary support was peeled off, and the uncured portions were removed by shower development for 30 seconds using a 1.0 mass % potassium carbonate aqueous solution (liquid temperature: 30° C.) as a developer, thereby forming a resist pattern.
A copper etching solution (product name: Cu-02, manufactured by Kanto Chemical Co., Ltd.) having a liquid temperature of 25° C. was sprayed for 90 seconds onto the surface of the developed laminate on which the resist pattern was formed, to etch the metal layer, thereby obtaining a metal wiring layer (metal type: Cu).
Next, a 30% by mass aqueous solution of ferric nitrate (liquid temperature: 45°C, pH: 0.6) was sprayed onto the surface of the developed laminate on which the resist pattern was formed for 50 seconds, and the transparent conductive layer in the area where the resist pattern was not present on the surface was etched to obtain a transparent wiring layer.
The laminate after the etching treatment was immersed in a 3% by mass aqueous sodium hydroxide solution (liquid temperature: 50° C.) for 70 seconds to remove the resist pattern remaining on the laminate, thereby obtaining a laminate of Example 2.
When the obtained laminate of Example 2 was observed using an optical microscope, it was confirmed that a transparent wiring layer and a metal wiring layer were formed in this order on the substrate, and that both ends of the transparent wiring layer were located 0.5 μm outward from both ends of the metal wiring layer.

The volume resistivity of the transparent wiring layer and the volume resistivity of the metal wiring layer were measured, and both were found to be less than 1×10 ⁴ Ωcm.

Example 3
1. Preparation of conductive substrate The same operation as in Example 1 was performed to obtain a substrate having a transparent conductive layer [layer structure: substrate/transparent conductive layer]. Next, the substrate having the transparent conductive layer obtained above was placed in a batch-type vacuum deposition apparatus [model number: EBH-800, manufactured by ULVAC, Inc.]. Next, copper was placed on the deposition boat in an amount to give a thickness of 0.5 μm. Next, after evacuation to a vacuum level of 9.0×10 ⁻³ Pa or less, the evaporation boat was heated, and vacuum deposition was performed on the surface of the transparent conductive layer of the substrate to form a metal layer. In this manner, a conductive substrate (layer structure: substrate/transparent conductive layer/metal layer) was prepared.

2. Preparation of Laminate A laminate was obtained by the same procedure as in Example 1.
A glass mask having a line and space pattern with a line width of 12 μm and a space width of 8 μm and an extraction terminal pattern connected thereto was closely attached to the temporary support of the obtained laminate, and then the laminate was exposed to light using an ultra-high pressure mercury lamp [model number: USH-2004MB, manufactured by Ushio Inc.].
After leaving the laminate for 1 hour after exposure, the temporary support was peeled off, and the uncured portions were removed by shower development for 30 seconds using a 1.0 mass % potassium carbonate aqueous solution (liquid temperature: 30° C.) as a developer, thereby forming a resist pattern.
A copper etching solution (product name: Cu-02, manufactured by Kanto Chemical Co., Ltd.) having a liquid temperature of 25° C. was sprayed for 50 seconds onto the surface of the developed laminate on which the resist pattern was formed, to etch the metal layer, thereby obtaining a metal wiring layer (metal type: Cu).
Next, a 30% by mass aqueous solution of ferric nitrate (liquid temperature: 45°C, pH: 0.6) was sprayed onto the surface of the developed laminate on which the resist pattern was formed for 50 seconds, and the transparent conductive layer in the area where the resist pattern was not present on the surface was etched to obtain a transparent wiring layer.
The laminate after the etching treatment was immersed in a 3% by mass aqueous sodium hydroxide solution (liquid temperature: 50° C.) for 70 seconds to remove the resist pattern remaining on the laminate, thereby obtaining a laminate of Example 3.
The obtained laminate of Example 3 was observed using an optical microscope, and it was confirmed that a transparent wiring layer and a metal wiring layer were formed in this order on the substrate, and that both ends of the transparent wiring layer were located 0.5 μm outward from both ends of the metal wiring layer.

The volume resistivity of the transparent wiring layer and the volume resistivity of the metal wiring layer were measured, and both were found to be less than 1×10 ⁴ Ωcm.

Example 4
1. Preparation of Conductive Substrate A conductive substrate (layer structure: substrate/transparent conductive layer/metal layer) was prepared in the same manner as in Example 1.

2. Preparation of Laminate A laminate was obtained by the same procedure as in Example 1.
A glass mask having a line and space pattern with a line width of 15 μm and a space width of 5 μm and an extraction terminal pattern connected thereto was closely attached to the temporary support of the obtained laminate, and then the laminate was exposed to light using an ultra-high pressure mercury lamp [model number: USH-2004MB, manufactured by Ushio Inc.].
After leaving the laminate for 1 hour after exposure, the temporary support was peeled off, and the uncured portions were removed by shower development for 30 seconds using a 1.0 mass % potassium carbonate aqueous solution (liquid temperature: 30° C.) as a developer, thereby forming a resist pattern.
A copper etching solution (product name: Cu-02, manufactured by Kanto Chemical Co., Ltd.) having a liquid temperature of 25° C. was sprayed from a shower for 160 seconds onto the surface of the developed laminate on which the resist pattern was formed, to etch the metal layer, thereby obtaining a metal wiring layer (metal type: Cu).
Next, a 30% by weight aqueous solution of ferric nitrate (liquid temperature: 45°C, pH: 0.6) was sprayed onto the surface of the developed laminate on which the resist pattern was formed for 30 seconds, and the transparent conductive layer in the area where the resist pattern was not present on the surface was etched to obtain a transparent wiring layer.
The laminate after the etching treatment was immersed in a 3% by mass aqueous sodium hydroxide solution (liquid temperature: 50° C.) for 70 seconds to remove the resist pattern remaining on the laminate, thereby obtaining a laminate of Example 4.
When the obtained laminate of Example 4 was observed using an optical microscope, it was confirmed that a transparent wiring layer and a metal wiring layer were formed in that order on the substrate, and that both ends of the transparent wiring layer were located 2.5 μm outward from both ends of the metal wiring layer.

The volume resistivity of the transparent wiring layer and the volume resistivity of the metal wiring layer were measured, and both were found to be less than 1×10 ⁴ Ωcm.

Example 5
1. Preparation of conductive substrate On the surface of a substrate [ZeonorFilm (registered trademark) ZF16, thickness: 100 μm, manufactured by Zeon Corporation], a silver nanowire ink produced by the method described in paragraphs [0036] to [0042] of Japanese Patent No. 6505777 was applied using a spin coater so as to have a wet film thickness of 20 μm, to form a coating film. Next, the formed coating film was dried at 100 ° C. for 5 minutes to obtain a substrate having a transparent conductive layer [layer structure: substrate / transparent conductive layer]. Next, vacuum deposition was performed by the same operation as in Example 1 to form a metal layer. In this manner, a conductive substrate (layer structure: substrate / transparent conductive layer / metal layer) was prepared.

2. Preparation of Laminate A laminate was obtained by the same procedure as in Example 1.
A glass mask having a line and space pattern with a line width of 11 μm and a space width of 9 μm and an extraction terminal pattern connected thereto was closely attached to the temporary support of the obtained laminate, and then the laminate was exposed to light using an ultra-high pressure mercury lamp [model number: USH-2004MB, manufactured by Ushio Inc.].
After leaving the laminate for 1 hour after exposure, the temporary support was peeled off, and the uncured portions were removed by shower development for 30 seconds using a 1.0 mass % potassium carbonate aqueous solution (liquid temperature: 30° C.) as a developer, thereby forming a resist pattern.
A copper etching solution (product name: Cu-02, manufactured by Kanto Chemical Co., Ltd.) having a liquid temperature of 25° C. was sprayed for 90 seconds onto the surface of the developed laminate on which the resist pattern was formed, to etch the metal layer, thereby obtaining a metal wiring layer (metal type: Cu).
Next, a 30% by mass aqueous solution of ferric nitrate (liquid temperature: 45°C, pH: 0.6) was sprayed onto the surface of the developed laminate on which the resist pattern was formed for 50 seconds, and the transparent conductive layer in the area where the resist pattern was not present on the surface was etched to obtain a transparent wiring layer.
The laminate after the etching treatment was immersed in a 3% by mass aqueous sodium hydroxide solution (liquid temperature: 50° C.) for 70 seconds to remove the resist pattern remaining on the laminate, thereby obtaining a laminate of Example 5.
When the obtained laminate of Example 5 was observed using an optical microscope, it was confirmed that a transparent wiring layer and a metal wiring layer were formed in that order on the substrate, and that both ends of the transparent wiring layer were located 0.25 μm outward from both ends of the metal wiring layer.

The volume resistivity of the transparent wiring layer and the volume resistivity of the metal wiring layer were measured, and both were found to be less than 1×10 ⁴ Ωcm.

Example 6
1. Preparation of conductive substrate A substrate [ZeonorFilm (registered trademark) ZF16, thickness: 100 μm, manufactured by Zeon Corporation] was placed in a batch-type vacuum deposition apparatus [model number: EBH-800, manufactured by ULVAC, Inc.]. Then, an amount of ITO to a thickness of 0.1 μm was placed on the deposition boat. Then, after evacuation until the vacuum reached 9.0×10 ⁻³ Pa or less, the evaporation boat was heated, and vacuum deposition was performed on the surface of the substrate to form a transparent conductive layer. In this manner, a substrate having a transparent conductive layer [layer structure: substrate/transparent conductive layer] was obtained. Next, silver ink X was applied to the surface of the transparent conductive layer of the substrate using a spin coater so as to have a wet film thickness of 42 μm, forming a coating film. The formed coating film was dried at 100° C. for 5 minutes, and then baked at 140° C. for 30 minutes to form a metal layer. In this manner, a conductive substrate (layer structure: substrate/transparent conductive layer/metal layer) was prepared.

2. Preparation of Laminate A laminate was obtained by the same procedure as in Example 1.
A glass mask having a line and space pattern with a line width of 12 μm and a space width of 8 μm and an extraction terminal pattern connected thereto was closely attached to the temporary support of the obtained laminate, and then the laminate was exposed to light using an ultra-high pressure mercury lamp [model number: USH-2004MB, manufactured by Ushio Inc.].
After leaving the laminate for 1 hour after exposure, the temporary support was peeled off, and the uncured portions were removed by shower development for 30 seconds using a 1.0 mass % potassium carbonate aqueous solution (liquid temperature: 30° C.) as a developer, thereby forming a resist pattern.
A silver etching solution (trade name: Pure Etch AS128, manufactured by Hayashi Pure Chemical Industries, Ltd.) having a liquid temperature of 25° C. was sprayed from a shower for 90 seconds onto the surface of the developed laminate on which the resist pattern was formed, thereby etching the metal layer to obtain a metal wiring layer (metal type: Ag).
Next, a 10% by weight aqueous sulfuric acid solution (product name: 10% sulfuric acid, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was sprayed onto the surface of the developed laminate on which the resist pattern was formed for 30 seconds, and the transparent conductive layer in the portion where the resist pattern was not present on the surface was etched to obtain a transparent wiring layer.
The laminate after the etching treatment was immersed in a 3% by mass aqueous sodium hydroxide solution (liquid temperature: 50° C.) for 70 seconds to remove the resist pattern remaining on the laminate, thereby obtaining a laminate of Example 6.
When the obtained laminate of Example 6 was observed using an optical microscope, it was confirmed that a transparent wiring layer and a metal wiring layer were formed in that order on the substrate, and that both ends of the transparent wiring layer were located 1.0 μm outward from both ends of the metal wiring layer.

The volume resistivity of the transparent wiring layer and the volume resistivity of the metal wiring layer were measured, and both were found to be less than 1×10 ⁴ Ωcm.

(Example 7)
1. Preparation of conductive substrate The same operation as in Example 6 was performed to obtain a substrate having a transparent conductive layer [layer structure: substrate/transparent conductive layer]. Next, silver ink X was applied to the surface of the transparent conductive layer of the substrate using a spin coater so that the wet film thickness was 105 μm, forming a coating film. The formed coating film was dried at 100° C. for 10 minutes, and then baked at 140° C. for 30 minutes. In this manner, a conductive substrate (layer structure: substrate/transparent conductive layer/metal layer) was prepared.

2. Preparation of Laminate A laminate was obtained by the same procedure as in Example 1.
A glass mask having a line and space pattern with a line width of 13 μm and a space width of 7 μm and an extraction terminal pattern connected thereto was closely attached to the temporary support of the obtained laminate, and then the laminate was exposed to light using an ultra-high pressure mercury lamp [model number: USH-2004MB, manufactured by Ushio Inc.].
After leaving the laminate for 1 hour after exposure, the temporary support was peeled off, and the uncured portions were removed by shower development for 30 seconds using a 1.0 mass % potassium carbonate aqueous solution (liquid temperature: 30° C.) as a developer, thereby forming a resist pattern.
A silver etching solution (trade name: Pure Etch AS128, manufactured by Hayashi Pure Chemical Industries, Ltd.) having a liquid temperature of 25° C. was sprayed from a shower for 200 seconds onto the surface of the developed laminate on which the resist pattern was formed, thereby etching the metal layer to obtain a metal wiring layer (metal type: Ag).
Next, a 10% by weight aqueous sulfuric acid solution (product name: 10% sulfuric acid, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was sprayed onto the surface of the developed laminate on which the resist pattern was formed for 40 seconds, and the transparent conductive layer in the portion where the resist pattern was not present on the surface was etched to obtain a transparent wiring layer.
The laminate after the etching treatment was immersed in a 3% by mass aqueous sodium hydroxide solution (liquid temperature: 50° C.) for 70 seconds to remove the resist pattern remaining on the laminate, thereby obtaining a laminate of Example 7.
When the obtained laminate of Example 7 was observed using an optical microscope, it was confirmed that a transparent wiring layer and a metal wiring layer were formed in that order on the substrate, and that both ends of the transparent wiring layer were located 0.5 μm outward from both ends of the metal wiring layer.

The volume resistivity of the transparent wiring layer and the volume resistivity of the metal wiring layer were measured, and both were found to be less than 1×10 ⁴ Ωcm.

(Example 8)
1. Preparation of conductive substrate The same operation as in Example 6 was performed to obtain a substrate having a transparent conductive layer [layer structure: substrate/transparent conductive layer]. Next, silver ink X was applied to the surface of the transparent conductive layer of the substrate using a spin coater so that the wet film thickness was 202 μm, forming a coating film. The formed coating film was dried at 100° C. for 15 minutes, and then baked at 140° C. for 30 minutes. In this manner, a conductive substrate (layer structure: substrate/transparent conductive layer/metal layer) was prepared.

2. Preparation of Laminate A laminate was obtained by the same procedure as in Example 1.
A glass mask having a line and space pattern with a line width of 14 μm and a space width of 6 μm and an extraction terminal pattern connected thereto was closely attached to the temporary support of the obtained laminate, and then the laminate was exposed to light using an ultra-high pressure mercury lamp [model number: USH-2004MB, manufactured by Ushio Inc.].
After leaving the laminate for 1 hour after exposure, the temporary support was peeled off, and the uncured portions were removed by shower development for 30 seconds using a 1.0 mass % potassium carbonate aqueous solution (liquid temperature: 30° C.) as a developer, thereby forming a resist pattern.
A silver etching solution (trade name: Pure Etch AS128, manufactured by Hayashi Pure Chemical Industries, Ltd.) having a liquid temperature of 25° C. was sprayed by shower for 400 seconds onto the surface of the developed laminate on which the resist pattern was formed, to etch the metal layer, thereby obtaining a metal wiring layer (metal type: Ag).
Next, a 10% by weight aqueous sulfuric acid solution (product name: 10% sulfuric acid, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was sprayed onto the surface of the developed laminate on which the resist pattern was formed for 50 seconds, and the transparent conductive layer in the portion where the resist pattern was not present on the surface was etched to obtain a transparent wiring layer.
The laminate after the etching treatment was immersed in a 3% by mass aqueous sodium hydroxide solution (liquid temperature: 50° C.) for 70 seconds to remove the resist pattern remaining on the laminate, thereby obtaining a laminate of Example 8.
When the obtained laminate of Example 8 was observed using an optical microscope, it was confirmed that a transparent wiring layer and a metal wiring layer were formed in that order on the substrate, and that both ends of the transparent wiring layer were located 0.5 μm outward from both ends of the metal wiring layer.

The volume resistivity of the transparent wiring layer and the volume resistivity of the metal wiring layer were measured, and both were found to be less than 1×10 ⁴ Ωcm.

Example 9
1. Preparation of conductive substrate The same operation as in Example 6 was performed to obtain a substrate having a transparent conductive layer [layer structure: substrate/transparent conductive layer]. Next, silver ink X was applied to the surface of the transparent conductive layer of the substrate using a spin coater so that the wet film thickness was 223 μm to form a coating film. The formed coating film was dried at 100° C. for 20 minutes, and then baked at 140° C. for 30 minutes. In this manner, a conductive substrate (layer structure: substrate/transparent conductive layer/metal layer) was prepared.

2. Preparation of Laminate A laminate was obtained by the same procedure as in Example 1.
A glass mask having a line and space pattern with a line width of 14.5 μm and a space width of 5.5 μm and an extraction terminal pattern connected thereto was closely attached to the temporary support of the obtained laminate, and then the laminate was exposed to light using an ultra-high pressure mercury lamp [model number: USH-2004MB, manufactured by Ushio Inc.].
After leaving the laminate for 1 hour after exposure, the temporary support was peeled off, and the uncured portions were removed by shower development for 30 seconds using a 1.0 mass % potassium carbonate aqueous solution (liquid temperature: 30° C.) as a developer, thereby forming a resist pattern.
A silver etching solution (trade name: Pure Etch AS128, manufactured by Hayashi Pure Chemical Industries, Ltd.) having a liquid temperature of 25° C. was sprayed by shower for 450 seconds onto the surface of the developed laminate on which the resist pattern was formed, to etch the metal layer, thereby obtaining a metal wiring layer (metal type: Ag).
Next, a 10% by weight aqueous sulfuric acid solution (product name: 10% sulfuric acid, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was sprayed onto the surface of the developed laminate on which the resist pattern was formed for 55 seconds, and the transparent conductive layer in the portion where the resist pattern was not present on the surface was etched to obtain a transparent wiring layer.
The laminate after the etching treatment was immersed in a 3% by mass aqueous sodium hydroxide solution (liquid temperature: 50° C.) for 70 seconds to remove the resist pattern remaining on the laminate, thereby obtaining a laminate of Example 9.
When the obtained laminate of Example 9 was observed using an optical microscope, it was confirmed that a transparent wiring layer and a metal wiring layer were formed in that order on the substrate, and that both ends of the transparent wiring layer were located 0.5 μm outward from both ends of the metal wiring layer.

The volume resistivity of the transparent wiring layer and the volume resistivity of the metal wiring layer were measured, and both were found to be less than 1×10 ⁴ Ωcm.

(Comparative Example 1)
1. Preparation of Conductive Substrate A conductive substrate (layer structure: substrate/transparent conductive layer/metal layer) was prepared in the same manner as in Example 1.

2. Preparation of Laminate A laminate was obtained by the same procedure as in Example 1.
A glass mask having a line and space pattern with a line width of 12 μm and a space width of 8 μm and an extraction terminal pattern connected thereto was closely attached to the temporary support of the obtained laminate, and then the laminate was exposed to light using an ultra-high pressure mercury lamp [model number: USH-2004MB, manufactured by Ushio Inc.].
After leaving the laminate for 1 hour after exposure, the temporary support was peeled off, and the uncured portions were removed by shower development for 30 seconds using a 1.0 mass % potassium carbonate aqueous solution (liquid temperature: 30° C.) as a developer, thereby forming a resist pattern.
A copper etching solution (product name: Cu-02, manufactured by Kanto Chemical Co., Ltd.) having a liquid temperature of 25° C. was sprayed for 90 seconds onto the surface of the developed laminate on which the resist pattern was formed, to etch the metal layer, thereby obtaining a metal wiring layer (metal type: Cu).
Next, a 30% by mass aqueous solution of ferric nitrate (liquid temperature: 45°C, pH: 0.6) was sprayed onto the surface of the developed laminate on which the resist pattern was formed for 90 seconds, and the transparent conductive layer in the area where the resist pattern was not present on the surface was etched to obtain a transparent wiring layer.
The laminate after the etching treatment was immersed in a 3% by mass aqueous sodium hydroxide solution (liquid temperature: 50° C.) for 70 seconds to remove the resist pattern remaining on the laminate, thereby obtaining a laminate of Comparative Example 1.
When the obtained laminate of Comparative Example 1 was observed using an optical microscope, it was confirmed that a transparent wiring layer and a metal wiring layer were formed in that order on the substrate, and that both ends of the transparent wiring layer were aligned with both ends of the metal wiring layer.

(Comparative Example 2)
1. Preparation of Conductive Substrate A conductive substrate (layer structure: substrate/transparent conductive layer/metal layer) was prepared in the same manner as in Example 6.

2. Preparation of Laminate A laminate was obtained by the same procedure as in Example 1.
A glass mask having a line and space pattern with a line width of 12 μm and a space width of 8 μm and an extraction terminal pattern connected thereto was closely attached to the temporary support of the obtained laminate, and then the laminate was exposed to light using an ultra-high pressure mercury lamp [model number: USH-2004MB, manufactured by Ushio Inc.].
After leaving the laminate for 1 hour after exposure, the temporary support was peeled off, and the uncured portions were removed by shower development for 30 seconds using a 1.0 mass % potassium carbonate aqueous solution (liquid temperature: 30° C.) as a developer, thereby forming a resist pattern.
A silver etching solution (trade name: Pure Etch AS128, manufactured by Hayashi Pure Chemical Industries, Ltd.) having a liquid temperature of 25° C. was sprayed from a shower for 90 seconds onto the surface of the developed laminate on which the resist pattern was formed, thereby etching the metal layer to obtain a metal wiring layer (metal type: Ag).
Next, a 10% by weight aqueous sulfuric acid solution (product name: 10% sulfuric acid, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was sprayed onto the surface of the developed laminate on which the resist pattern was formed for 50 seconds, and the transparent conductive layer in the portion where the resist pattern was not present on the surface was etched to obtain a transparent wiring layer.
The laminate after the etching treatment was immersed in a 3% by mass aqueous sodium hydroxide solution (liquid temperature: 50° C.) for 70 seconds to remove the resist pattern remaining on the laminate, thereby obtaining a laminate of Comparative Example 2.
When the obtained laminate of Comparative Example 2 was observed using an optical microscope, it was confirmed that a transparent wiring layer and a metal wiring layer were formed in that order on the substrate, and that both ends of the transparent wiring layer were aligned with both ends of the metal wiring layer.

(Comparative Example 3)
1. Preparation of Conductive Substrate A conductive substrate (layer structure: substrate/transparent conductive layer/metal layer) was prepared in the same manner as in Example 1.

2. Preparation of Laminate A laminate was obtained by the same procedure as in Example 1.
A glass mask having a line and space pattern with a line width of 17 μm and a space width of 3 μm and an extraction terminal pattern connected thereto was closely attached to the temporary support of the obtained laminate, and then the laminate was exposed to light using an ultra-high pressure mercury lamp [model number: USH-2004MB, manufactured by Ushio Inc.].
After leaving the laminate for 1 hour after exposure, the temporary support was peeled off, and the uncured portions were removed by shower development for 30 seconds using a 1.0 mass % potassium carbonate aqueous solution (liquid temperature: 30° C.) as a developer, thereby forming a resist pattern.
A copper etching solution (product name: Cu-02, manufactured by Kanto Chemical Co., Ltd.) having a liquid temperature of 25° C. was sprayed by shower for 200 seconds onto the surface of the developed laminate on which the resist pattern was formed, to etch the metal layer, thereby obtaining a metal wiring layer (metal type: Cu).
Next, a 30% by weight aqueous solution of ferric nitrate (liquid temperature: 45°C, pH: 0.6) was sprayed onto the surface of the developed laminate on which the resist pattern was formed for 30 seconds, and the transparent conductive layer in the area where the resist pattern was not present on the surface was etched to obtain a transparent wiring layer.
The laminate after the etching treatment was immersed in a 3% by mass aqueous sodium hydroxide solution (liquid temperature: 50° C.) for 70 seconds to remove the resist pattern remaining on the laminate, thereby obtaining a laminate of Comparative Example 3.
When the obtained laminate of Comparative Example 3 was observed using an optical microscope, it was confirmed that a transparent wiring layer and a metal wiring layer were formed in that order on the substrate, and that both ends of the transparent wiring layer were 3.5 μm outward from both ends of the metal wiring layer.

[measurement]
[Width R1 of metal wiring layer]
For each of the laminates of Examples 1 to 9 and Comparative Examples 1 to 3, the width R1 of the metal wiring layer was determined.
The laminate was cut using an ultramicrotome to prepare a cross section of the line-and-space wiring pattern. In preparation, the laminate was cut so that the cross section was approximately perpendicular to the longitudinal direction of the pattern. The cross section was then observed using a scanning electron microscope (SEM, model number: JSM-7200F) manufactured by JEOL Ltd. at an acceleration voltage of 5 kV, and the width of the central part of the metal wiring layer pattern in the thickness direction in the cross section was measured. The above preparation and measurement were repeated five times (in other words, five cross sections were prepared, and the width of the central part of the metal wiring layer pattern in the thickness direction in each cross section was measured), and the width R1 of the metal wiring layer was obtained by arithmetically averaging the five measured values obtained. The results are shown in Table 1.

[Transparent wiring layer width R2]
For each of the laminates of Examples 1 to 9 and Comparative Examples 1 to 3, the width R2 of the transparent wiring layer was determined.
The laminate was cut using an ultramicrotome to prepare a cross section of the line-and-space wiring pattern. In preparation, the laminate was cut so that the cross section was approximately perpendicular to the longitudinal direction of the pattern. The cross section was then observed using a scanning electron microscope (SEM, model number: JSM-7200F) manufactured by JEOL Ltd. at an acceleration voltage of 5 kV, and the width of the transparent wiring layer pattern in the thickness direction at the center of the cross section was measured. The above preparation and measurement were repeated five times (in other words, five cross sections were prepared, and the width of the transparent wiring layer pattern in the thickness direction at the center of each cross section was measured), and the width R2 of the transparent wiring layer was calculated by arithmetically averaging the five measured values obtained. The results are shown in Table 1.

[Thickness of metal wiring layer R3]
For each of the laminates of Examples 1 to 9 and Comparative Examples 1 to 3, the thickness R3 of the metal wiring layer was determined.
The laminate was cut using an ultramicrotome to prepare a cross section of the line-and-space wiring pattern. In preparation, the laminate was cut so that the cross section was approximately perpendicular to the longitudinal direction of the pattern. The cross section was then observed using a scanning electron microscope (SEM, model number: JSM-7200F) manufactured by JEOL Ltd. at an acceleration voltage of 5 kV, and the thickness of the metal wiring layer pattern at the center in the width direction in the cross section was measured. The above preparation and measurement were repeated five times (in other words, five cross sections were prepared, and the thickness of the metal wiring layer pattern at the center in the width direction in each cross section was measured), and the thickness R3 of the metal wiring layer was calculated by arithmetically averaging the five measured values obtained. The results are shown in Table 1.

[Thickness of transparent wiring layer]
For each of the laminates of Examples 1 to 9 and Comparative Examples 1 to 3, the thickness of the transparent wiring layer was determined.
The laminate was cut using an ultramicrotome to prepare a 100 nm thick slice of the line and space wiring pattern. In the preparation, the laminate was cut so that the cross section was approximately perpendicular to the longitudinal direction of the pattern. The cross section was then observed using a transmission electron microscope (model number: FHT7700) manufactured by Hitachi High-Tech Corporation at an acceleration voltage of 100 kV, and the thickness of the transparent wiring layer pattern in the width direction was measured in the cross section. The above preparation and measurement were repeated five times (in other words, five cross sections were prepared, and the thickness of the transparent wiring layer pattern in the width direction in each cross section was measured), and the thickness of the transparent wiring layer was obtained by arithmetically averaging the five measured values obtained. The results are shown in Table 1.

[Distance between patterns of transparent wiring layer]
For each of the laminates of Examples 1 to 9 and Comparative Examples 1 to 3, the distance between the patterns of the transparent wiring layer was determined.
The laminate was cut using an ultramicrotome to prepare a cross section of the line-and-space wiring pattern. In preparation, the laminate was cut so that the cross section was approximately perpendicular to the longitudinal direction of the pattern. The cross section was then observed using a scanning electron microscope (SEM, model number: JSM-7200F) manufactured by JEOL Ltd. at an acceleration voltage of 5 kV, and the distance between adjacent transparent wiring layers was measured. The above preparation and measurement were repeated five times (in other words, five cross sections were prepared, and the shortest distance between the ends of adjacent transparent wiring layers was measured in each cross section), and the distance between the patterns of the transparent wiring layers was calculated by arithmetically averaging the five measured values obtained. The results are shown in Table 1.

[evaluation]
The laminates of Examples 1 to 9 and Comparative Examples 1 to 3 were evaluated as follows.

1. Lamination Suitability An OCA (Optical Clear Adhesive) film (model number: 8215, 3M Japan Ltd.) was attached to the laminate under lamination conditions of a roll temperature of 50° C., a linear pressure of 0.2 MPa, and a linear speed of 1.0 m/min to prepare an evaluation sample.
The evaluation samples immediately after lamination, after being left in an environment with an atmospheric temperature of 25° C. and RH of 55% for 30 minutes (hereinafter also referred to as "after lamination aging"), and after being left in a convection oven with a heating temperature set to 50° C. for 30 minutes (hereinafter also referred to as "after heating") were observed using an optical microscope with a magnification of 50 times and evaluated according to the following evaluation criteria. The results are shown in Table 1.
As the wiring board, "3", "4" or "5" is preferable, "4" or "5" is more preferable, and "5" is particularly preferable.

-Evaluation criteria-
5: No bubbles were observed between the OCA film and the wiring pattern of the laminate immediately after lamination.
4: Immediately after lamination, there are minute bubbles between the OCA film and the wiring pattern of the laminate, but these disappear after aging.
3: After lamination and aging, tiny bubbles are present between the OCA film and the wiring pattern of the laminate, but these disappear after heating.
2: After heating, minute bubbles are present between the OCA film and the wiring pattern of the laminate.
1: After heating, large bubbles are present between the OCA film and the wiring pattern of the laminate.

2. Suppression of Migration Whether or not migration was suppressed was evaluated based on the degree of dimensional change of the wiring pattern before and after energization.
The laminate with electrodes connected to the terminals of the wiring pattern was placed in a thermostatic chamber with an internal temperature of 85° C. and an internal humidity of 85% RH, and a direct current (DC) voltage of 5 V was applied for 50 hours. After the voltage application, the width of the transparent wiring layer in the wiring pattern was measured using an optical microscope with a magnification of 500 times, and the change rate of the width of the transparent wiring layer compared to before the voltage application (hereinafter also referred to as the "width change rate") was obtained, and evaluation was performed according to the following evaluation criteria. The results are shown in Table 1.
A smaller width change rate means that the occurrence of migration is more suppressed.
As the wiring board, "3", "4" or "5" is preferable, "4" or "5" is more preferable, and "5" is particularly preferable.

-Evaluation criteria-
5: Width change rate < 10%
4: 10%≦width change rate<15%
3: 15%≦width change rate<20%
2: 20%≦width change rate<25%
1: 25% or less width change rate

As shown in Table 1, it was confirmed that the laminates of the examples were excellent in lamination suitability and suppressed the occurrence of migration.
On the other hand, it was confirmed that the laminates of the comparative examples were unable to achieve both excellent lamination suitability and suppression of migration.

100: laminate, 30: substrate, 40: transparent wiring layer, 50: metal wiring layer, 60: wiring section, R1: width of metal wiring layer, R2: width of transparent wiring layer, GR: light-shielding section (non-image section), EX: exposed section (image section), DL: alignment frame

Claims (12)

A laminate having a substrate and a wiring portion in which a transparent wiring layer and a metal wiring layer are laminated in this order on the substrate,
A laminate in which a width R1 of the metal wiring layer and a width R2 of the transparent wiring layer satisfy the following formula (1).
0.1 μm≦R2−R1≦6.0 μm (1) the metal wiring layer includes at least one of a metal element and a metal alloy,
The metal element is at least one selected from the group consisting of gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese;
2. The laminate according to claim 1, wherein the metal alloy is an alloy containing two or more metal elements selected from the group consisting of gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese. The laminate according to claim 2, wherein the metal wiring layer further contains a resin. The laminate according to claim 1, wherein the transparent wiring layer contains at least one metal oxide selected from indium tin oxide and indium zinc oxide. The laminate according to claim 1, wherein the transparent wiring layer contains at least one type of metal nanowire selected from gold nanowires, silver nanowires, copper nanowires, and platinum wires, and a resin. The laminate according to claim 1, wherein the width R1 of the metal wiring layer is 8 μm to 14 μm. The laminate according to claim 1, wherein the width R2 of the transparent wiring layer is 8.1 μm to 14.5 μm. The laminate according to claim 1, wherein the thickness R3 of the metal wiring layer is 0.2 μm to 5 μm. 2. The laminate according to claim 1, wherein a width R1 of the metal wiring layer, a width R2 of the transparent wiring layer, and a thickness R3 of the metal wiring layer satisfy the following formula (2):
0.3≦(R2−R1)/R3≦4.0 (2) The laminate according to claim 1, wherein the transparent wiring layer has a thickness of 0.01 μm to 1 μm. The laminate according to claim 1, wherein the distance between adjacent patterns of the transparent wiring layer is 1 μm to 20 μm. A method for producing the laminate according to any one of claims 1 to 11, comprising the steps of:
preparing a conductive substrate having the substrate, a transparent conductive layer, and a metal layer in this order;
forming an etching resist on the metal layer;
A step of patterning the etching resist to obtain an etching resist pattern;
etching the transparent conductive layer and the metal layer using the etching resist pattern as a mask;
in that order,
A method for manufacturing a laminate, wherein a width R1 of the metal wiring layer, a width R2 of the transparent wiring layer, and a width R4 of the etching resist pattern satisfy the following formula (3):
R1<R2≦R4 (3)