WO2020137144A1

WO2020137144A1 - Photosensitive transfer material, laminate, touch panel, method for producing patterned substrate, method for producing circuit board, and method for producing touch panel

Info

Publication number: WO2020137144A1
Application number: PCT/JP2019/042577
Authority: WO
Inventors: 児玉　邦彦; 山田　悟; 知樹松田; 正弥鈴木; 豊岡　健太郎
Original assignee: 富士フイルム株式会社
Priority date: 2018-12-27
Filing date: 2019-10-30
Publication date: 2020-07-02
Also published as: JPWO2020137144A1; TW202027983A; CN113196891A

Abstract

Provided are: a photosensitive transfer material having a temporary support, a photosensitive resin layer, a silver nanowire-containing silver nanowire layer, and a thermosetting resin layer, in this order; a laminate; a touch panel; a method for producing a patterned substrate; a method for producing a circuit board; and a method for producing a touch panel.

Description

Photosensitive transfer material, laminate, touch panel, patterned substrate manufacturing method, circuit board manufacturing method, and touch panel manufacturing method

The present disclosure relates to a photosensitive transfer material, a laminate, a touch panel, a patterned substrate manufacturing method, a circuit board manufacturing method, and a touch panel manufacturing method.

2. Description of the Related Art In recent years, a device (hereinafter, also referred to as “touch panel”) capable of inputting information corresponding to an instruction image by touching the instruction image displayed in the image display area of a liquid crystal device with a finger or a touch pen has been widely used. There is.
In the touch panel, a conductive film made of a material such as ITO (Indium Tin Oxide) is usually used. In recent years, various techniques using a conductive film containing conductive fibers such as silver fibers have been studied as a conductive film replacing the ITO film.

For example, in WO 2010/021224, a photosensitive film including a support film, a conductive layer provided on the support film and containing conductive fibers, and a photosensitive resin layer provided on the conductive layer are provided. Conductive conductive films are disclosed.

By the way, a conductive layer containing a conductive fiber tends to have low adhesiveness to a substrate (for example, a copper substrate). Therefore, a photosensitive transfer material having a conductive layer containing conductive fibers has a problem that it is difficult to bond it to a substrate.
On the other hand, in the photosensitive conductive film described in International Publication No. 2010/021224, it is said that the problem of adhesion to the substrate can be solved by having a configuration in which the photosensitive resin layer is provided on the conductive layer.

However, according to the study by the present inventors, in a photosensitive transfer material having a temporary support, a first photosensitive resin layer, and a conductive layer containing conductive fibers in this order, the adhesiveness to a substrate is improved. For the purpose of improving, as described in WO 2010/021224, a second photosensitive resin layer is provided on the surface opposite to the surface of the conductive layer containing the conductive fibers on the side of the photosensitive resin layer. Although the problem of adhesion to the substrate can be solved by providing the first substrate, the first photosensitive resin layer or the first photosensitive resin layer or the first photosensitive resin layer formed on the surface of the conductive layer containing the conductive fiber is formed in the formation of the conductive pattern after bonding. When the pattern of the cured product of the photosensitive resin layer is removed, peeling occurs between the substrate and the second photosensitive resin layer or the cured film of the second photosensitive resin layer, and the conductive pattern is removed from the substrate. It turns out that it may come off.

An object to be solved by one embodiment of the present invention is to provide a photosensitive transfer material capable of forming a conductive pattern that is difficult to peel off from a substrate.
Another object of the present invention is to provide a laminate using the above-mentioned photosensitive transfer material, a touch panel, a method for producing a patterned substrate, a method for producing a circuit board, and a method for producing a touch panel. It is to be.

Means for solving the above problems include the following aspects.
<1> A temporary support,
A photosensitive resin layer,
A layer containing silver nanowires,
A thermosetting resin layer,
A photosensitive transfer material having in this order.
<2> The photosensitive transfer material according to <1>, wherein the thermosetting resin layer contains a blocked isocyanate compound.
<3> The photosensitive transfer material according to <2>, wherein the blocked isocyanate compound has at least one of a hydroxyl group and an acid group.
<4> The photosensitive transfer material according to <2> or <3>, wherein the thermosetting resin layer further contains a compound having at least one of a hydroxyl group and an acid group.
<5> The photosensitive transfer material according to any one of <1> to <4>, wherein the thermosetting resin layer has a thickness of 1 nm to 300 nm.
<6> The photosensitive transfer material according to any one of <1> to <5>, wherein the contact resistance of the thermosetting resin layer is 200Ω or less.
<7> substrate,
A layer containing a resin that is thermoset,
A layer containing silver nanowires,
A laminated body having in this order.
<8> The layer containing the thermosetting resin is a layer formed by curing the thermosetting resin layer that is the transfer layer, and the layer containing the silver nanowires is the transfer layer <7 The laminated body as described in >.
<9> The laminate according to <7> or <8>, in which the thermosetting resin is a crosslinked resin having a urethane bond.
<10> The laminated body according to any one of <7> to <9>, wherein the layer containing the thermosetting resin has a thickness of 1 nm to 300 nm.
<11> The laminate according to any one of <7> to <10>, in which the layer containing the thermosetting resin has a contact resistance of 200Ω or less.
<12> A touch panel having the laminate according to any one of <7> to <11>.
<13> A step of laminating the photosensitive transfer material according to any one of <1> to <6> and a substrate,
A step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material,
A step of developing the photosensitive transfer material that has undergone the pattern exposure to form a pattern,
A step of thermosetting the thermosetting resin layer,
A method of manufacturing a patterned substrate including:
<14> A step of laminating the photosensitive transfer material according to any one of <1> to <6> and a substrate,
A step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material,
A step of developing the photosensitive transfer material that has undergone the pattern exposure to form a pattern,
A step of thermosetting the thermosetting resin layer,
In the pattern, a step of removing the photosensitive resin layer or a cured product of the photosensitive resin layer,
A method for manufacturing a circuit board including:
<15> A touch panel manufacturing method including the circuit board manufacturing method according to <14>.

According to one embodiment of the present invention, there is provided a photosensitive transfer material capable of forming a conductive pattern that is difficult to peel from a substrate.
Further, according to another embodiment of the present invention, there are provided a laminate, a touch panel, a patterned substrate manufacturing method, a circuit board manufacturing method, and a touch panel manufacturing method using the above-mentioned photosensitive transfer material.

It is a schematic sectional drawing which shows an example of the layer structure of the photosensitive transfer material of this indication. It is a schematic sectional drawing which shows an example of the laminated constitution of the laminated body of this indication. It is a schematic diagram showing pattern A.

The details of the present disclosure will be described below in detail. The description of the constituent elements described below may be made based on the representative embodiment of the present disclosure, but the present disclosure is not limited to such an embodiment.

In the present disclosure, the numerical range indicated by using “to” means a range including the numerical values before and after “to” as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another stepwise described numerical range. In addition, in the numerical range described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
In the present disclosure, a combination of two or more preferable aspects is a more preferable aspect.

Regarding the notation of the group (so-called atomic group) in the present disclosure, the notation without substitution and non-substitution includes both those having no substituent and those having a substituent. For example, an “alkyl group” includes not only an alkyl group having no substituent (so-called unsubstituted alkyl group) but also an alkyl group having a substituent (so-called substituted alkyl group).

In the present disclosure, the chemical structural formula may be described as a simplified structural formula in which a hydrogen atom is omitted.

In the present disclosure, “(meth)acrylic acid” is a term used in a concept including both acrylic acid and methacrylic acid, and “(meth)acrylate” is used in a concept including both acrylate and methacrylate. The term "(meth)acryloyl" is used in a concept that includes both acryloyl and methacryloyl, and "(meth)acryloxy" is a word that is used in a concept that includes both acryloxy and methacryloxy. is there.

In the present disclosure, the amount of each component in the composition is the total amount of the plurality of substances present in the composition, unless there is a plurality of substances corresponding to each component in the composition, unless otherwise specified. Means

In the present disclosure, the term “process” is included in this term as long as the intended purpose of the process is achieved, not only when it is an independent process but also when it cannot be clearly distinguished from other processes.

In the present disclosure, the molecular weight in the case where there is a molecular weight distribution represents the weight average molecular weight (Mw; hereinafter the same) unless otherwise specified.
In the present disclosure, the ratio of the structural unit in the resin represents a molar ratio unless otherwise specified.

In the present disclosure, “transparent” means that the total light transmittance at a wavelength of 380 nm to 780 nm is 85% or more (preferably 90% or more, more preferably 95% or more). The total light transmittance is measured at a temperature of 23° C. using a spectrophotometer [for example, a spectrophotometer “U-3310 (trade name)” manufactured by Hitachi, Ltd.].

In the present disclosure, “refractive index” refers to a refractive index at a wavelength of 550 nm, unless otherwise specified. Further, the “refractive index” in the present disclosure means a value measured by an ellipsometry method with visible light having a wavelength of 550 nm at a temperature of 23° C., unless otherwise specified.

In the present disclosure, constituent elements indicated by the same reference numeral in each drawing mean the same constituent elements.

[Photosensitive transfer material]
The photosensitive transfer material of the present disclosure includes a temporary support, a photosensitive resin layer, a layer containing silver nanowires (hereinafter, also referred to as “silver nanowire layer”), and a thermosetting resin layer. Have in order.
The photosensitive transfer material of the present disclosure having the above-described configuration can form a conductive pattern that is difficult to peel from the substrate. In addition, the photosensitive transfer material of the present disclosure can form a circuit board having excellent durability, in which the sheet resistance value does not easily increase even when exposed to a humid heat environment.

FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of the photosensitive transfer material of the present disclosure.
The photosensitive transfer material 100 shown in FIG. 1 has a temporary support 10, a photosensitive resin layer 20, a silver nanowire layer 30, and a thermosetting resin layer 40A in this order. It should be noted that the scale of each element shown in the drawings of the present disclosure is not necessarily accurate.
Hereinafter, each component of the photosensitive transfer material of the present disclosure will be described.

<Temporary support>
The photosensitive transfer material of the present disclosure has a temporary support.
The temporary support is a support that supports at least the photosensitive resin layer, the silver nanowire layer, and the thermosetting resin layer, and that is removable from the adherend.

The temporary support preferably has optical transparency from the viewpoint that pattern exposure can be performed via the temporary support.
In the present disclosure, “having optical transparency” means that the transmittance of the dominant wavelength of light used for pattern exposure is 50% or more. The transmittance of the dominant wavelength of light used for pattern exposure is preferably 60% or more, and more preferably 70% or more, from the viewpoint of improving the exposure sensitivity.
Examples of the method of measuring the transmittance include a method of using a spectrophotometer [eg, MCPD-6800 manufactured by Otsuka Electronics Co., Ltd.].

Examples of the temporary support include a glass substrate, a resin film, paper and the like.
The temporary support is preferably a resin film from the viewpoint of strength and flexibility.
Examples of the resin film include polyethylene terephthalate film, cycloolefin polymer film, cellulose triacetate film, polystyrene film and polycarbonate film.
Among these, the polyethylene terephthalate film is preferable as the temporary support from the viewpoint of optical characteristics.

The thickness of the temporary support is not particularly limited and can be appropriately selected depending on the material.
The thickness of the temporary support is preferably 5 μm to 200 μm, and more preferably 10 μm to 150 μm, from the viewpoint of easy handling, versatility and the like.

A preferable embodiment of the temporary support is described in paragraphs [0017] and [0018] of JP-A-2014-85643, for example. These descriptions are incorporated herein by reference.

<Photosensitive resin layer>
The photosensitive transfer material of the present disclosure has a photosensitive resin layer.
The photosensitive resin layer is classified into a negative type in which a portion irradiated with an actinic ray remains as an image and a positive type in which a portion not irradiated with an actinic ray remains as an image, depending on the difference in the photosensitive system.
The photosensitive resin layer in the photosensitive transfer material of the present disclosure may be a positive type photosensitive resin layer or a negative type photosensitive resin layer.

(Positive photosensitive resin layer)
The positive type photosensitive resin layer is not particularly limited, and a known positive type photosensitive resin layer can be applied.
From the viewpoint of sensitivity, resolution, and removability, the positive photosensitive resin layer may include a polymer containing a structural unit having an acid group protected by an acid-decomposable group, and a photoacid generator. preferable.

The positive type photosensitive resin layer is described in paragraphs [0033] to [0130] of International Publication No. 2018/179640. These descriptions are incorporated herein by reference.

-Polymer containing a structural unit having an acid group protected by an acid-decomposable group-
The positive photosensitive resin layer is a polymer containing a structural unit having an acid group protected by an acid-decomposable group (hereinafter, also referred to as “structural unit A”) (hereinafter, also referred to as “polymer A”). ) Is preferably included.
The acid group protected by the acid-decomposable group in the polymer A becomes an acid group by the action of a catalytic amount of acid generated by exposure (that is, deprotection reaction). The acid group generated by the deprotection reaction enables the positive photosensitive resin layer to be dissolved in the developing solution.

The polymer A is preferably an addition polymerization type polymer, and more preferably a polymer containing a structural unit derived from (meth)acrylic acid or its ester.
In addition, you may contain the structural unit other than the structural unit derived from (meth)acrylic acid or its ester, for example, the structural unit derived from a styrene compound, the structural unit derived from a vinyl compound, etc.

The acid group in the structural unit A is not particularly limited, and a known acid group can be applied.
The acid group in the structural unit A is preferably a carboxy group or a phenolic hydroxyl group.

The acid-decomposable group in the structural unit A is not particularly limited, and a known acid-decomposable group can be applied.
Examples of the acid-decomposable group in the structural unit A include a group that is relatively easily decomposed by an acid (for example, an acetal-type functional group such as a 1-alkoxyalkyl group, a tetrahydropyranyl group, and a tetrahydrofuranyl group), and an acid-releasable group. Examples thereof include groups that are difficult to decompose (for example, tertiary alkyl groups such as tert-butyl group).
Among these, the acid-decomposable group in the structural unit A is preferably a group having a structure that protects the acid group in the form of acetal. Further, the acid-decomposable group is preferably an acid-decomposable group having a molecular weight of 300 or less from the viewpoint of suppressing variation in the line width of the conductive wiring when applied to the formation of a conductive pattern.

The structural unit A is a structural unit represented by the following formula A1, a structural unit represented by the following formula A2, and a following formula A3 from the viewpoint of suppressing the deformation of the pattern shape, solubility in a developing solution, and transferability. It is preferably at least one type of structural unit selected from the group consisting of structural units represented, more preferably a structural unit represented by the following formula A3, and a structure represented by the following formula A3-3. More preferably, it is a unit.
The structural unit represented by the following formula A1 and the structural unit represented by the following formula A2 are structural units having a phenolic hydroxyl group protected by an acid-decomposable group. The structural unit represented by the following formula A3 is a structural unit having a carboxy group protected by an 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, and R ¹³ is an alkyl group. Represents a group or an aryl group, R ¹¹ or R ¹² and R ¹³ may be linked to each other to form a cyclic ether, R ¹⁴ represents a hydrogen atom or a methyl group, and X ¹ represents a single bond or a divalent group. Represents a valent 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, and R ²³ is an alkyl group. Represents a group or an aryl group, and R ²¹ or R ²² and R ²³ may be linked to each other to form a cyclic ether, and R ²⁴ is independently a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, It represents 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, and R ³³ is an alkyl group. Represents a group or an aryl group, R ³¹ or R ³² and R ³³ may combine to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or a divalent group. Represents a valent linking group, and Y represents a sulfur atom or an oxygen atom.

In formula A3, when R ³¹ or R ³² is an alkyl group, the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms. When R ³¹ or R ³² is an aryl group, the aryl group is preferably a phenyl group. R ³¹ and R ³² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least one of R ³¹ and R ³² is preferably 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 for R ³¹ to R ³³ may have a substituent.

In formula A3, R ³¹ or R ³² and R ³³ are preferably linked to each other to form a cyclic ether. The number of ring members in the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.

In formula A3, X ⁰ is preferably a single bond or an arylene group, and more preferably a single bond. The arylene group may have a substituent.

In the formula A3, Y is preferably an oxygen atom from the viewpoint of exposure sensitivity.

In formula A3, R ³⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the glass transition temperature (Tg) of the polymer A can be further lowered. More specifically, the content of the structural unit in which R ³⁴ in Formula A3 is a hydrogen atom is preferably 20 mol% or more based on all the structural units represented by Formula A3 contained in the polymer A. ..
The content (unit: mol%) of the structural unit represented by Formula A3 in which R ³⁴ in Formula A3 is a hydrogen atom is determined by ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement in a conventional manner. It can be confirmed by the intensity ratio of the peak intensity calculated by.

Among the constitutional units represented by the formula A3, the constitutional unit represented by the following formula A3-3 is more preferable from the viewpoint of further increasing the sensitivity during pattern formation.

In formula A3-3, R ³⁴ represents a hydrogen atom or a methyl group, and R ³⁵ to R ⁴¹ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In formula A3-3, R ³⁴ is preferably a hydrogen atom.
In formula A3-3, R ³⁵ to R ⁴¹ are preferably hydrogen atoms.

Specific preferred examples of the structural unit represented by formula A3 include the structural units below. In addition, R ³⁴ in the following structural units represents a hydrogen atom or a methyl group.

When the polymer A contains the structural unit A, the polymer A may include only one type of structural unit A or may include two or more types.

When the polymer A contains the structural unit A, the content of the structural unit A in the polymer A is preferably 15 mol% or more, and is 15 mol% to 90 mol% with respect to all the structural units of the polymer A. More preferably, it is more preferably 20 mol% to 70 mol %.
The content of the structural unit A in the polymer A can be confirmed by the intensity ratio of the peak intensities calculated by the usual method from ¹³ C-NMR measurement.

The polymer A preferably contains a structural unit having an acid group (hereinafter, also referred to as “structural unit B”).
When the polymer A contains the structural unit B, the sensitivity during pattern formation is improved, the polymer A is easily dissolved in an alkaline developing solution in the developing step after pattern exposure, and the development time can be shortened.

The acid group in the structural unit B means a proton dissociative 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, more preferably 6 or less. The pKa of the acid group is preferably −5 or more.

Examples of the acid group in the structural unit B include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, and a sulfonylimide group.
Among these, the acid group in the structural unit B is preferably a carboxy group or a phenolic hydroxyl group.

The introduction of the structural unit having an acid group into the polymer A can be carried out by copolymerizing a monomer having an acid group.

The constituent unit B is more preferably a constituent unit in which a constituent unit derived from a styrene compound or a constituent unit derived from a vinyl compound is substituted with an acid group, or a constituent unit derived from (meth)acrylic acid.

The structural unit B is preferably at least one structural unit selected from the group consisting of a structural unit having a carboxy group and a structural unit having a phenolic hydroxyl group, from the viewpoint of better sensitivity in pattern formation. ..

When the polymer A contains the structural unit B, the structural unit B may contain only one kind or two or more kinds.

When the polymer A contains the structural unit B, the content of the structural unit B in the polymer A is 0.1 mol% to 20 mol% with respect to all the structural units of the polymer A from the viewpoint of pattern formability. The amount is preferably 0.5 mol% to 15 mol%, more preferably 1 mol% to 10 mol%.
The content of the structural unit B in the polymer A can be confirmed by the intensity ratio of the peak intensities calculated by a conventional method from ¹³ C-NMR measurement.

The polymer A contains a structural unit other than the structural unit A and the structural unit B described above (hereinafter, also referred to as “structural unit C”) as long as the effects of the photosensitive transfer material of the present disclosure are not impaired. Good.

The monomer forming the structural unit C is not particularly limited.
As the monomer forming the structural unit C, a styrene compound, (meth)acrylic acid alkyl ester, (meth)acrylic acid cyclic alkyl ester, (meth)acrylic acid aryl ester, unsaturated dicarboxylic acid diester, bicyclo unsaturated compound, maleimide Examples thereof include compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, compounds having an aliphatic cyclic skeleton, and other unsaturated compounds.

As the structural unit C, specifically, styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, (meta ) Methyl acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth ) Structural units formed by polymerizing benzyl acrylate, isobornyl (meth)acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono(meth)acrylate and the like. Further, examples of the structural unit C include the compounds described in paragraphs [0021] to [0024] of JP-A 2004-264623.

The structural unit C is at least one selected from the group consisting of a structural unit having an aromatic ring and a structural unit having an aliphatic cyclic skeleton, from the viewpoint of improving the electrical characteristics of the resulting photosensitive transfer material. It is preferably a structural unit.
Examples of the monomer forming at least one structural unit selected from the group consisting of a structural unit having an aromatic ring and a structural unit having an aliphatic cyclic skeleton include styrene, tert-butoxystyrene, methylstyrene, α-methyl. Examples thereof include styrene, dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and benzyl (meth)acrylate.
Among these, cyclohexyl (meth)acrylate is preferable as the monomer forming at least one structural unit selected from the group consisting of a structural unit having an aromatic ring and a structural unit having an aliphatic cyclic skeleton.

From the viewpoint of adhesiveness, the monomer forming the structural unit C is preferably a (meth)acrylic acid alkyl ester, and more preferably a (meth)acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms.
Specific examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylic acid. 2-ethylhexyl and the like can be mentioned.

When the polymer A includes the structural unit C, the structural unit C may include only one type or may include two or more types.

When the polymer A contains the structural unit C, the content of the structural unit C in the polymer A is preferably 70 mol% or less, and preferably 60 mol% or less, based on all the structural units of the polymer A. More preferably, it is even more preferably 50 mol% or less.
The lower limit of the content of the structural unit C in the polymer A may be 0 mol%, but it is preferably 1 mol% or more, and more preferably 5 mol% or more, based on all the structural units of the polymer A.
When the content of the structural unit C in the polymer A is within the above range, the resolution and the adhesiveness tend to be further improved.

The weight average molecular weight of the polymer A is preferably 60,000 or less.
When the weight average molecular weight of the polymer A is 60,000 or less, the melt viscosity of the photosensitive resin layer is suppressed to be low, and at the time of bonding with the substrate, bonding at low temperature (for example, 130° C. or less) is realized. be able to.
Further, the weight average molecular weight of the polymer A is more preferably 2,000 to 60,000, further preferably 3,000 to 50,000.
The weight average molecular weight of the polymer A is a polystyrene equivalent weight average molecular weight measured by the following method.

The weight average molecular weight can be measured by GPC (gel permeation chromatography). Various commercially available devices can be used as the measuring device, and the contents of the device and the measuring technique are known to those skilled in the art.
To measure the weight average molecular weight by GPC, HLC (registered trademark)-8220 GPC (manufactured by Tosoh Corporation) was used as a measuring device, and TSKgel (registered trademark) Super HZM-M (4.6 mm ID×15 cm, Tosoh Corporation) was used as a column. Co., Ltd.), Super HZ4000 (4.6 mmID×15 cm, Tosoh Corporation), Super HZ3000 (4.6 mmID×15 cm, Tosoh Corporation), and Super HZ2000 (4.6 mmID×15 cm, Tosoh Corporation). (Manufactured by K.K.), each of which is connected in series, and THF (tetrahydrofuran) can be used as an eluent. The measurement conditions are as follows: a sample concentration of 0.2 mass %, a flow rate of 0.35 ml/min, a sample injection amount of 10 μL, and a measurement temperature of 40° C., using a differential refractive index (RI) detector. be able to. The calibration curve is “standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A-5000”, It is possible to use those manufactured from 7 samples of "A-2500" and "A-1000".

When the positive photosensitive resin layer contains the polymer A, it may contain only one kind of the polymer A or may contain two or more kinds of the polymer A.

When the positive-type photosensitive resin layer contains the polymer A, the content of the polymer A in the positive-type photosensitive resin layer is such that the positive-type photosensitive resin layer exhibits good adhesion to the substrate. The amount is preferably 50% by mass to 99.9% by mass, more preferably 70% by mass to 99% by mass, and further preferably 80% by mass to 98% by mass with respect to the total mass of the conductive resin layer. More preferable.

The method for producing the polymer A (so-called synthesis method) is not particularly limited, and a known method can be applied. As the method for producing the polymer A, for example, a polymerizable monomer for forming the structural unit A, a polymerizable monomer for forming the structural unit B, and a polymerizable monomer for forming the structural unit C are A method of polymerizing using a polymerization initiator in a solvent can be mentioned.

-Photo acid generator-
The positive photosensitive resin layer preferably contains a photo-acid generator.

The photo-acid generator is a compound capable of generating an acid when irradiated with radiation such as ultraviolet rays, far ultraviolet rays, X-rays and charged particle beams.
The photoacid generator is preferably a compound which reacts with an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm to generate an acid.
Further, regarding a photo-acid generator which is not directly sensitive to an actinic ray having a wavelength of 300 nm or more, when used in combination with a sensitizer, it is a compound which is sensitive to an actinic ray having a wavelength of 300 nm or more and generates an acid. It can be preferably used in combination.

The photoacid generator is preferably a photoacid generator that generates an acid with a pKa of 4 or less, more preferably a photoacid generator that generates an acid with a pKa of 3 or less, and a light that generates an acid with a pKa of 2 or less. Acid generators are more preferred. The lower limit of pKa is not particularly limited, but is preferably -10.0 or more, for example.

Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.
From the viewpoint of sensitivity and resolution, the photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound described later and an oxime sulfonate compound described later, and contains an oxime sulfonate compound. More preferable.

Examples of the ionic photoacid generator include onium salt compounds and quaternary ammonium salt compounds. Examples of onium salt compounds include diaryl iodonium salt compounds and triaryl sulfonium salt compounds.
Among these, the ionic photoacid generator is preferably an onium salt compound, and more preferably at least one selected from the group consisting 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-A-2014-85643 can also be preferably used.

Examples of the nonionic photoacid generator include trichloromethyl-s-triazine compounds, diazomethane compounds, imide sulfonate compounds, oxime sulfonate compounds and the like.
Among these, the nonionic photoacid generator is preferably an oxime sulfonate compound from the viewpoint of sensitivity, resolution, and adhesiveness.
Specific examples of the trichloromethyl-s-triazine compound and the diazomethane compound include the compounds described in paragraphs [0083] to [0088] of JP 2011-221494A.

As the oxime sulfonate compound, a compound having an oxime sulfonate structure represented by the following formula (B1) is preferable.

In formula (B1), R ²¹ represents an alkyl group or an aryl group, and * represents a bonding site with another atom or another group.

In the compound having an oxime sulfonate structure represented by the formula (B1), any group may be substituted, and the alkyl group represented by R ²¹ may be linear and have a branched structure. And may have a ring structure. The permissible substituents are described below.

The alkyl group represented by R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group represented by R ²¹ may be substituted with an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group, or a halogen atom.

The aryl group represented by R ²¹ is preferably an aryl group having 6 to 18 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group represented by R ²¹ may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and a halogen atom.

When the positive photosensitive resin layer contains a photo-acid generator, it may contain only one photo-acid generator or two or more photo-acid generators.

When the positive photosensitive resin layer contains a photoacid generator, the content of the photoacid generator in the positive photosensitive resin layer is the total mass of the positive photosensitive resin layer from the viewpoint of sensitivity and resolution. On the other hand, it is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass to 5% by mass.

-Surfactant-
The positive photosensitive resin layer may contain a surfactant.
When the positive photosensitive resin layer contains a surfactant, the uniformity of the film thickness can be improved.

Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic (so-called nonionic) surfactants and amphoteric surfactants.
The surfactant is described in paragraph [0017] of Japanese Patent No. 4502784 and paragraphs [0060] to [0071] of Japanese Patent Laid-Open No. 2009-237362. These descriptions are incorporated herein by reference.

The surfactant is preferably a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ether compounds, polyoxyethylene higher alkyl phenyl ether compounds, higher fatty acid diester compounds of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants. ..
Among these, fluorine-based surfactants are preferable as the nonionic surfactant.

A commercially available product can be used as the nonionic surfactant.
Examples of commercially available nonionic surfactants include KP [manufactured by Shin-Etsu Chemical Co., Ltd.], Polyflow [manufactured by Kyoeisha Chemical Co., Ltd.], F-Top (manufactured by JEMCO), Megafac (registered trademark) [Product Examples: Megafac F551A, manufactured by DIC Co., Ltd., Florard [manufactured by Sumitomo 3M Co., Ltd.], Asahi Guard (registered trademark) [manufactured by AGC Co., Ltd.], Surflon (registered trademark) [manufactured by AGC Seichemical Co., Ltd.] ], PolyFox (manufactured by OMNOVA), Surfynol [manufactured by Nisshin Chemical Industry Co., Ltd.], DOWSIL (registered trademark) [Product Example: SH 8400, manufactured by Toray Dow Corning Co., Ltd.] and the like. ..

When the positive photosensitive resin layer contains a surfactant, the positive photosensitive resin layer may contain only one kind or two or more kinds of surfactants.

When the positive-type photosensitive resin layer contains a surfactant, the content of the surfactant in the positive-type photosensitive resin layer is the total mass of the positive-type photosensitive resin layer from the viewpoint of film thickness uniformity. On the other hand, it is preferably 0.05% by mass to 10% by mass, and more preferably 0.05% by mass to 5% by mass.

-Corrosion inhibitor-
The positive photosensitive resin layer may contain a corrosion inhibitor.
When the positive photosensitive resin layer contains a corrosion inhibitor, the silver nanowires are prevented from being corroded, so that durability can be improved.

The corrosion inhibitor is not particularly limited, and a known corrosion inhibitor can be applied.
Examples of the corrosion inhibitor include compounds containing at least one of nitrogen atom and sulfur atom.
From the viewpoint of durability, the corrosion inhibitor is preferably a heterocyclic aromatic compound containing at least one of a nitrogen atom and a sulfur atom, a compound having a triazole structure, a compound having a benzimidazole structure, and a thiadiazole structure. More preferably, it is at least one compound selected from the group consisting of compounds having

Specific examples of the corrosion inhibitor include benzimidazole, 1,2,4-triazole, benzotriazole, tolyltriazole, butylbenzyltriazole, alkyldithiothiadiazole, alkylthiol, 2-aminopyrimidine, 5,6-dimethylbenzimidazole, 2-Amino-5-mercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercaptopyrimidine, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto Examples thereof include benzimidazole.
Among these, at least one selected from the group consisting of benzimidazole and 1,2,4-triazole is preferable as the corrosion inhibitor.

When the positive photosensitive resin layer contains a corrosion inhibitor, it may contain only one kind of corrosion inhibitor or may contain two or more kinds thereof.

When the positive photosensitive resin layer contains a corrosion inhibitor, the content of the corrosion inhibitor in the positive photosensitive resin layer is 0.001% by mass based on the total mass of the positive photosensitive resin layer. It is preferably from 5 to 5 mass %, more preferably from 0.005 to 3 mass %.

-Other ingredients-
The positive photosensitive resin layer may contain a component other than the above components (hereinafter, also referred to as “other component”).
Other components are not particularly limited and can be appropriately selected depending on the purpose and the like.
Examples of other components include an ultraviolet absorber, a development accelerator, a colorant and the like.

(Negative type photosensitive resin layer)
The negative photosensitive resin layer is not particularly limited, and a known negative photosensitive resin layer can be applied.
The negative photosensitive resin layer preferably contains a polymerizable compound, a polymerization initiator, and a binder polymer from the viewpoint of pattern formability.

-Polymerizable compound-
The negative photosensitive resin layer preferably contains a polymerizable compound.
When the negative photosensitive resin layer contains a polymerizable compound, pattern formability can be improved.
Examples of the polymerizable compound include polymerizable compounds such as radically polymerizable compounds and cationically polymerizable compounds.
The polymerizable compound is preferably a photopolymerizable compound, and more preferably an ethylenically unsaturated compound.
An ethylenically unsaturated compound is a compound that has one or more ethylenically unsaturated groups.
As the ethylenically unsaturated group, a (meth)acryloyl group is preferable.
As the ethylenically unsaturated compound, a (meth)acrylate compound is preferable.

The ethylenically unsaturated compound preferably contains a bifunctional or higher functional ethylenically unsaturated compound.
In the present disclosure, “bifunctional or higher functional ethylenically unsaturated compound” means a compound having two or more ethylenically unsaturated groups in one molecule.

Examples of the bifunctional ethylenically unsaturated compound include tricyclodecane dimethanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate.

Examples of commercially available bifunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate [trade name: NK ester A-DCP, Shin Nakamura Chemical Co., Ltd.], tricyclodecane dimethanol dimethacrylate. [Product name: NK ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.], 1,9-nonanediol diacrylate [Product name: NK ester A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.], 1, 6-hexanediol diacrylate [trade name: NK ester A-HD-N, manufactured by Shin Nakamura Chemical Co., Ltd.], ethoxylated bisphenol A dimethacrylate [trade name: BPE-500, manufactured by Shin Nakamura Chemical Co., Ltd.] ] Etc. are mentioned.

Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri/tetra/penta/hexa)(meth)acrylate, pentaerythritol (tri/tetra)(meth)acrylate, trimethylolpropane tri(meth)acrylate, Examples thereof include ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and a (meth)acrylate compound having a glycerin tri(meth)acrylate skeleton.

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

From the viewpoint of improving developability, the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an acid group.
Examples of the acid group include a phosphoric acid group, a sulfonic acid group, a carboxy group and the like.
Among these, a carboxy group is preferable as the acid group.

Examples of the ethylenically unsaturated compound having an acid group include a 3- to 4-functional ethylenically unsaturated compound having an acid group and a 5- to 6-functional ethylenically unsaturated compound having an acid group.

The ethylenically unsaturated compound having an acid group is preferably at least one selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound having a carboxy group and a carboxylic acid anhydride thereof.

Examples of preferable commercial products of a bifunctional or higher-functional ethylenically unsaturated compound having a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.) and Aronix (registered trademark) M-520 (Toagosei) Co., Ltd.], Aronix (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.) and the like.

The ethylenically unsaturated compound having an acid group is described in paragraphs [0025] to [0030] of JP-A-2004-239942. These descriptions are incorporated herein by reference.

When the negative photosensitive resin layer contains a polymerizable compound, it may contain only one kind of the polymerizable compound or may contain two or more kinds thereof.

When the negative photosensitive resin layer contains a polymerizable compound, the content of the polymerizable compound in the negative photosensitive resin layer, from the viewpoint of photosensitivity, to the total mass of the negative photosensitive resin layer. 1% by mass to 70% by mass, more preferably 10% by mass to 70% by mass, further preferably 20% by mass to 60% by mass, and 20% by mass to 50% by mass. It is particularly preferable that

-Polymerization initiator-
The negative photosensitive resin layer preferably contains a polymerization initiator.
When the negative photosensitive resin layer contains a polymerization initiator, pattern formability can be improved.
Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator.
Among these, the photopolymerization initiator is preferable as the polymerization initiator.

Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as “oxime-based photopolymerization initiator”) and a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter, “α- Aminoalkylphenone-based photopolymerization initiator"), a photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter also referred to as "α-hydroxyalkylphenone-based polymerization initiator"), an acylphosphine oxide structure. (Hereinafter, also referred to as “acylphosphine oxide-based photopolymerization initiator”) having N, and a photopolymerization initiator having an N-phenylglycine structure (hereinafter, “N-phenylglycine-based photopolymerization initiator”) Also referred to as).

The photopolymerization initiator is selected from the group consisting of oxime photopolymerization initiators, α-aminoalkylphenone photopolymerization initiators, α-hydroxyalkylphenone photopolymerization initiators, and N-phenylglycine photopolymerization initiators. It is preferable to contain at least one kind, and to contain at least one kind selected from the group consisting of an oxime photopolymerization initiator, an α-aminoalkylphenone photopolymerization initiator, and an N-phenylglycine photopolymerization initiator. More preferable.

The photopolymerization initiator is described, for example, in paragraphs [0031] to [0042] of JP2011-95716A and paragraphs [0064] to [0081] of JP2015-014783A. These descriptions are incorporated herein by reference.

Commercially available photopolymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) [trade name: IRGACURE (registered trademark) OXE-01, BASF Co., Ltd.], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) [Product name: IRGACURE (registered trademark) OXE-02] BASF Corporation], 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [trade name: IRGACURE (registered trademark) 379EG, manufactured by BASF], 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [trade name: IRGACURE (registered trademark) 907, manufactured by BASF], 2-hydroxy-1 -{4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl}-2-methylpropan-1-one [trade name: IRGACURE (registered trademark) 127, manufactured by BASF], 2-benzyl -2-Dimethylamino-1-(4-morpholinophenyl)-butanone-1 [trade name: IRGACURE (registered trademark) 369, manufactured by BASF], 2-hydroxy-2-methyl-1-phenyl-propane-1 -ON [trade name: IRGACURE (registered trademark) 1173, manufactured by BASF], 1-hydroxycyclohexyl phenyl ketone [trade name: IRGACURE (registered trademark) 184, manufactured by BASF], 2,2-dimethoxy-1,2- Examples include diphenylethane-1-one [trade name: IRGACURE 651, manufactured by BASF].

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

When the negative photosensitive resin layer contains a polymerization initiator, the content of the polymerization initiator in the negative photosensitive resin layer is 0.1% by mass based on the total mass of the negative photosensitive resin layer. It is preferably at least the above, more preferably at least 0.2% by mass, further preferably at least 0.3% by mass.
The content of the polymerization initiator in the negative photosensitive resin layer is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the negative photosensitive resin layer. More preferable.

-Binder polymer-
The negative photosensitive resin layer preferably contains a binder polymer.
The binder polymer is preferably an alkali-soluble resin from the viewpoint of developability. The alkali-soluble resin is preferably a resin having an acid value of 40 mgKOH/g or more, and is a (meth)acrylic resin having a carboxyl group and having an acid value of 40 mgKOH/g (hereinafter, also referred to as “polymer B”). Is more preferable.
In the present disclosure, “alkali-soluble” refers to being soluble in a 1 mol/L sodium hydroxide solution at 25° C. Further, “soluble” means that 0.1 g or more is dissolved in 100 mL of solvent.
In the present disclosure, the acid value is a value measured according to the method described in JIS K0070:1992.

The total content of the structural units derived from (meth)acrylic acid and the structural units derived from (meth)acrylic acid ester in polymer B is 30 mol% or more based on all the structural units of polymer B. Is preferable, and 50 mol% or more is more preferable.

The polymer B contains a structural unit having a carboxy group.
The constitutional unit having a carboxy group contained in the polymer B may be only one type, or may be two or more types.

From the viewpoint of developability, the content ratio of the structural unit having a carboxy group in the polymer B is preferably 5 mol% to 50 mol% with respect to all the structural units of the (meth)acrylic resin having a carboxy group, It is more preferably from 5 mol% to 40 mol%, further preferably from 10 mol% to 40 mol%, particularly preferably from 10 mol% to 30 mol%.

The binder polymer (particularly the polymer B) preferably contains a structural unit having an aromatic ring from the viewpoint of moisture permeability and strength after curing.
Examples of the monomer that forms the structural unit having an aromatic ring include styrene, tert-butoxystyrene, methylstyrene, styrene compounds such as α-methylstyrene, and benzyl (meth)acrylate.
Among these, styrene compounds are preferable as the monomer forming the structural unit having an aromatic ring.

The binder polymer (particularly, the (meth)acrylic resin having a carboxy group) preferably contains a structural unit having an ethylenically unsaturated group from the viewpoint of strength after curing, and has an ethylenically unsaturated group in the side chain. It is more preferable to include a structural unit.
In the present disclosure, the “side chain” means an atomic group branched from the main chain, and the “main chain” means the relatively longest binding chain in the molecules of the polymer compound constituting the resin. means.
As the ethylenically unsaturated group, a (meth)acryl group is preferable, and a (meth)acryloxy group is more preferable.

The acid value of the binder polymer is preferably 40 mgKOH/g or more, more preferably 40 mgKOH/g to 200 mgKOH/g, even more preferably 60 mgKOH/g to 150 mgKOH/g, and 60 mgKOH/g to 130 mgKOH. /G is particularly preferable.

The weight average molecular weight of the binder polymer is not particularly limited, but it is preferably more than 3,000, more preferably more than 3,000 and 60,000 or less, and 5,000 or more and 50,000 or less. Is more preferable.
The weight average molecular weight of the binder polymer is a polystyrene equivalent weight average molecular weight measured by the method described above (that is, GPC).

When the negative photosensitive resin layer contains a binder polymer, it may contain only one kind of binder polymer or two kinds or more.

When the negative photosensitive resin layer contains a binder polymer, the content of the binder polymer in the negative photosensitive resin layer is 10% by mass to 90% by mass with respect to the total mass of the negative photosensitive resin layer. Is preferable, 20% by mass to 80% by mass is more preferable, and 30% by mass to 70% by mass is further preferable.

-Sensitizer-
The negative photosensitive resin layer may contain a sensitizer.
The sensitizer has actions such as further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing polymerization inhibition of the polymerizable compound by oxygen.

Examples of the sensitizer include triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline, N-phenylglycine, tributyltin acetate and trithiane.

When the negative photosensitive resin layer contains a sensitizer, it may contain only one kind of sensitizer or two or more kinds.

When the negative photosensitive resin layer contains a sensitizer, the content of the sensitizer in the negative photosensitive resin layer is 0.01% by mass to 10% by mass based on the total mass of the photosensitive resin layer. %, more preferably 0.03% by mass to 5% by mass, and further preferably 0.05% by mass to 3% by mass.

-Corrosion inhibitor-
The negative photosensitive resin layer may contain a corrosion inhibitor.
When the negative photosensitive resin layer contains a corrosion inhibitor, the silver nanowires are prevented from being corroded, so that the durability can be improved.

The corrosion inhibitor has the same meaning as the corrosion inhibitor described in “Positive Photosensitive Resin Layer”, and the preferred examples are also the same, so the description thereof is omitted here.

When the negative photosensitive resin layer contains a corrosion inhibitor, it may contain only one kind or two or more kinds of corrosion inhibitors.

When the negative photosensitive resin layer contains a corrosion inhibitor, the content of the corrosion inhibitor in the negative photosensitive resin layer is 0.001% by mass based on the total mass of the negative photosensitive resin layer. It is preferably from 5 to 5 mass %, more preferably from 0.005 to 3 mass %.

-Surfactant-
The negative photosensitive resin layer may contain a surfactant.
When the negative photosensitive resin layer contains a surfactant, the uniformity of the film thickness can be improved.
The surfactant has the same meaning as the surfactant described in “Positive-type photosensitive resin layer”, and the preferred examples are also the same, and therefore the description thereof is omitted here.

When the negative photosensitive resin layer contains a surfactant, it may contain only one kind or two or more kinds of surfactants.

When the negative photosensitive resin layer contains a surfactant, the content of the surfactant in the negative photosensitive resin layer is the total mass of the negative photosensitive resin layer from the viewpoint of film thickness uniformity. On the other hand, it is preferably 0.05% by mass to 10% by mass, and more preferably 0.05% by mass to 5% by mass.

-Other ingredients-
The negative photosensitive resin layer may contain components other than the above components (hereinafter, also referred to as “other components”).
Other components are not particularly limited and can be appropriately selected depending on the purpose and the like.
Examples of other components include a heat-crosslinkable compound, a polymerization inhibitor, an ultraviolet absorber, a development accelerator, and a colorant.

-Thickness of photosensitive resin layer-
The thickness of the photosensitive resin layer is not particularly limited and is, for example, preferably 20 μm or less, more preferably 15 μm or less, further preferably 12 μm or less, particularly preferably 10 μm or less. Most preferably, it is 5 μm or less.
When the thickness of the photosensitive resin layer is 20 μm or less, it is advantageous in terms of thinning the entire photosensitive transfer material and improving the transmittance of the photosensitive resin layer.
The thickness of the photosensitive resin layer is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of manufacturing suitability.

The thickness of the photosensitive resin layer is measured by the following method.
In the cross-sectional observation image in the thickness direction of the photosensitive resin layer, the arithmetic mean value of the thickness of the photosensitive resin layer measured at five randomly selected points was calculated, and the obtained value was calculated as the thickness of the photosensitive resin layer. Satoshi
The cross-sectional observation image in the thickness direction of the photosensitive resin layer can be obtained using a scanning electron microscope (SEM).

-Minimum transmittance of photosensitive resin layer-
The minimum transmittance of the photosensitive resin layer at a wavelength of 400 nm to 700 nm is preferably 80% or more, more preferably 90% or more.
Examples of the method for measuring the minimum transmittance of the photosensitive resin layer include a method using a spectrophotometer [eg, MCPD-6800 manufactured by Otsuka Electronics Co., Ltd.].

(Method of forming photosensitive resin layer)
The method for forming the photosensitive resin layer is not particularly limited, and a known method can be applied.
Examples of the photosensitive resin layer include a method in which a coating solution for forming a photosensitive resin layer containing each of the above-mentioned components is applied onto an object to be coated and dried.

The coating method is not particularly limited, and a known coating method can be applied.
Examples of the coating method include slit coating, spin coating, curtain coating, inkjet coating and the like.

The drying temperature is not particularly limited and can be appropriately set depending on the type of volatile components such as a solvent.
The drying temperature can be set to, for example, 60°C to 120°C.

The photosensitive resin layer-forming coating liquid can be prepared, for example, by mixing the above-mentioned components and a solvent in an arbitrary ratio.

The solvent is not particularly limited, and a known solvent can be applied.
As the solvent, ethylene glycol monoalkyl ether compound, ethylene glycol dialkyl ether compound, ethylene glycol monoalkyl ether acetate compound, propylene glycol monoalkyl ether compound, propylene glycol dialkyl ether compound, propylene glycol monoalkyl ether acetate compound, diethylene glycol dialkyl ether compound , Diethylene glycol monoalkyl ether acetate compounds, dipropylene glycol monoalkyl ether compounds, dipropylene glycol dialkyl ether compounds, dipropylene glycol monoalkyl ether acetate compounds, ester compounds, ketone compounds, amide compounds, lactone compounds and the like.

In addition, preferred examples of the solvent include the ester compounds, ether compounds, and ketone compounds described below.
Examples of the ester compound include ethyl acetate, propyl acetate, isobutyl acetate, sec-butyl acetate, t-butyl acetate, isopropyl acetate, n-butyl acetate, 1-methoxy-2-propyl acetate and the like.
Examples of the ether compound include diisopropyl ether, 1,4-dioxane, 1,2-dimethoxyethane, 1,3-dioxolane, propylene glycol dimethyl ether, propylene glycol monoethyl ether and the like.
Examples of the ketone compound include methyl n-butyl ketone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl n-propyl ketone, and methyl isopropyl ketone.

In the photosensitive resin layer, the solvent contained in the coating liquid for forming the photosensitive resin layer does not need to be completely removed.
The photosensitive resin layer preferably contains no solvent, or more than 0% by mass and 1% by mass or less with respect to the total mass of the photosensitive resin layer, and does not contain a solvent or is photosensitive. It is more preferable that it is more than 0% by mass and 0.5% by mass or less with respect to the total mass of the functional resin layer.

The solid content concentration of the coating liquid for forming the photosensitive resin layer is not particularly limited.
The solid content concentration of the coating liquid for forming the photosensitive resin layer is preferably 1% by mass to 40% by mass, and more preferably 5% by mass to 30% by mass, from the viewpoint of coating suitability.

In the present disclosure, the “solid content concentration of the photosensitive resin layer-forming coating liquid” means a volatile component such as a solvent from the photosensitive resin layer-forming coating liquid with respect to the total mass of the photosensitive resin layer-forming coating liquid. It means the ratio of the removed residue.

<Silver nanowire layer>
The photosensitive transfer material of the present disclosure has a layer containing silver nanowires (that is, a silver nanowire layer).
The silver nanowire layer can function as a so-called conductive layer after transfer.

(Silver nanowire)
Examples of the shape of the silver nanowire include a columnar shape, a rectangular parallelepiped shape, and a columnar shape having a polygonal cross section. In applications where high transparency is required, the silver nanowires preferably have at least one of a columnar shape and a columnar shape having a polygonal cross section.
The cross-sectional shape of the silver nanowire can be observed using, for example, a transmission electron microscope (TEM).

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

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

The diameter and length of the silver nanowire can be measured using, for example, a transmission electron microscope (TEM) or an optical microscope.
Specifically, the diameter and the length of 300 randomly selected silver nanowires are measured from the silver 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 used as the diameter and length of the silver nanowire.

The content of the silver nanowires in the silver nanowire layer is not particularly limited, but for example, from the viewpoint of transparency and conductivity, it is 1% by mass to 99% by mass with respect to the total mass of the silver nanowire layer. Is preferred, and more preferably 10% by mass to 95% by mass.

(binder)
The silver nanowire layer may include a binder (also referred to as “matrix”), if necessary.
The binder is a solid material in which silver nanowires are dispersed or embedded.
The binder can protect the silver nanowires from harmful environmental factors such as corrosion and abrasion.

Examples of the binder include polymer materials and inorganic materials.
As the binder, a light transmissive material is preferable.

Examples of the polymer material include (meth)acrylic resin [for example, poly(methyl methacrylate)], polyester [for example, polyethylene terephthalate (PET)], polycarbonate, polyimide, polyamide, polyolefin (for example, polypropylene), polynorbornene, and cellulose. A compound, polyvinyl alcohol (PVA), polyvinyl pyrrolidone, etc. are mentioned.
Examples of the cellulose compound include hydroxypropylmethyl cellulose (HPMC), hydroxyethyl cellulose (HEC), methyl cellulose (MC), hydroxypropyl cellulose (HPC), carboxymethyl cellulose (CMC) and the like.
Further, the polymer material may be a conductive polymer material.
Examples of the conductive polymer material include polyaniline and polythiophene.

Examples of inorganic materials include silica, mullite and alumina.

Further, the binder is described in paragraphs [0051] to [0052] of JP-A-2014-212117. These descriptions are incorporated herein by reference.

When the silver nanowire layer contains a binder, it may contain only one kind of binder or two or more kinds of binder.

When the silver nanowire layer contains a binder, the content of the binder in the silver nanowire layer is preferably 1% by mass to 99% by mass, and preferably 5% by mass to 80% by mass, based on the total mass of the silver nanowire layer. More preferably, it is mass %.

-Thickness of silver nanowire layer-
The thickness of the silver nanowire layer is not particularly limited, but for example, from the viewpoint of transparency and conductivity, it is preferably 1 nm to 400 nm, more preferably 10 nm to 200 nm.

The thickness of the silver nanowire layer is measured by the following method.
In the cross-sectional observation image in the thickness direction of the silver nanowire layer, the arithmetic mean value of the thickness of the silver nanowire layer measured at five randomly selected points was calculated, and the obtained value was calculated as the thickness of the silver nanowire layer. Satoshi The cross-sectional observation image in the thickness direction of the silver nanowire layer can be obtained using a scanning electron microscope (SEM).

-Minimum transmittance of silver nanowire layer-
The minimum transmittance of the silver nanowire layer at a wavelength of 400 nm to 700 nm is preferably 80% or more, and more preferably 90% or more.
Examples of the method for measuring the minimum transmittance of the silver nanowire layer include a method using a spectrophotometer [eg, MCPD-6800 manufactured by Otsuka Electronics Co., Ltd.].

(Method of manufacturing silver nanowire)
The method for producing the silver nanowire is not particularly limited, and a known method can be applied.
As a method for producing a silver nanowire, for example, in a water-based solvent containing at least a halogen compound and a reducing agent, a step of adding a silver complex solution and heating at a temperature of 150° C. or lower, and, if necessary, Examples thereof include a method including a step of desalting.

The halogen compound is not particularly limited as long as it is a compound containing bromine, chlorine or iodine.
Examples of the halogen compound include alkali halides such as sodium bromide, sodium chloride, sodium iodide, potassium iodide, potassium bromide and potassium chloride. As the halogen compound, HTAB (hexadecyl-trimethylammonium bromide), HTAC (hexadecyl-trimethylammonium chloride) or the like may be used.

As the reducing agent, metal borohydride salts such as sodium borohydride and potassium borohydride; lithium aluminum hydride, potassium aluminum hydride, cesium aluminum hydride, beryllium aluminum hydride, magnesium aluminum hydride, aluminum hydride Aluminum hydride salts such as calcium; sodium sulfite, hydrazine compound, dextrin, hydroquinone, hydroxylamine, citric acid or its salt, succinic acid or its salt, ascorbic acid or its salt, etc.; diethylaminoethanol, ethanolamine, propanolamine, tritium Alkanolamines such as ethanolamine and dimethylaminopropanol; Aliphatic amines such as propylamine, butylamine, dipropyleneamine, ethylenediamine and triethylenepentamine; Heterocyclic amines such as piperidine, pyrrolidine, N-methylpyrrolidine and morpholine; Aniline , N-methylaniline, toluidine, anisidine, phenetidine and other aromatic amines; benzylamine, xylenediamine, N-methylbenzylamine and other aralkylamines; methanol, ethanol, 2-propanol and other alcohols; ethylene glycol, glutathione, organic Examples thereof include acids (citric acid, malic acid, tartaric acid, etc.), reducing sugars (glucose, galactose, mannose, fructose, sucrose, maltose, raffinose, stachyose, etc.), sugar alcohols (sorbitol, etc.) and the like.

Examples of the ligand of the silver complex include CN-, SCN-, SO ₃ ^2- , thiourea, ammonia and the like.
As the silver complex, a silver ammonia complex is preferable.

The heating temperature is preferably 150° C. or lower, more preferably 20° C. to 130° C., further preferably 30° C. to 100° C., particularly preferably 40° C. to 90° C.

The desalting treatment can be performed by a method such as ultrafiltration, dialysis, gel filtration, decantation, and centrifugation after forming the silver nanowires.

The method for producing silver nanowires is described in paragraphs [0020] to [0031] of JP2013-167021A. These descriptions are incorporated herein by reference.

(Method of forming silver nanowire layer)
The method for forming the silver nanowire layer is not particularly limited, and a known method can be applied.
As a method of forming the silver nanowire layer, for example, a method of applying a coating solution for forming a silver nanowire layer containing silver nanowires onto an object to be coated and drying the coating solution can be mentioned.

The coating liquid for forming the silver nanowire layer can be prepared, for example, by mixing the silver nanowire and the solvent at an arbitrary ratio.
Water is mainly used as the solvent, and an organic solvent miscible with water may be used in combination at a ratio of 80% by volume or less with respect to the total amount of the solvent.

As the organic solvent, for example, an alcohol compound having a boiling point of 50° C. to 250° C., more preferably 55° C. to 200° C. is preferable.
Alcohol compounds include methanol, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol 200, polyethylene glycol 300, glycerin, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,2-butanediol, 1 1,4-butanediol, 1,5-pentanediol, 1-ethoxy-2-propanol, ethanolamine, diethanolamine, 2-(2-aminoethoxy)ethanol, 2-dimethylaminoisopropanol and the like can be mentioned.

The content of silver nanowires in the coating liquid for silver nanowire layer formation is preferably 0.1% by mass to 99% by mass, based on the total mass of the coating liquid for silver nanowire layer formation, and 0.3 It is more preferable that the content is from 95% by mass to 95% by mass.

<Thermosetting resin layer>
The photosensitive transfer material of the present disclosure has a thermosetting resin layer.
The thermosetting resin layer is soluble in a developing solution before the thermosetting and can be patterned by being selectively dissolved, and after the thermosetting, the photosensitive resin layer or a cured product of the photosensitive resin layer. It is difficult to be peeled off even after the step of removing, and has both patterning suitability and peeling resistance.
The thermosetting resin layer preferably does not have photocurability.

The thermosetting resin layer preferably contains a compound having a functional group that forms a bond by thermal reaction.
Examples of the functional group that forms a bond by thermal reaction include a (block) isocyanate group, an epoxy group, an oxetane group, a hydroxymethyl group, an alkoxymethyl group, and an oxazoline group.
In the present disclosure, the “(block)isocyanate group” is a concept that includes both an isocyanate group and a blocked isocyanate group.

The thermosetting resin layer is preferably a layer that is cured by the reaction of a functional group that forms a bond by a thermal reaction with a functional group having active hydrogen to form a crosslinked structure.
Many of the functional groups that form a bond by a thermal reaction react with each other, but from the viewpoint of curing efficiency, the thermosetting resin layer has (1) a functional group that forms a bond by a thermal reaction and active hydrogen. It is preferable to include at least one of a compound having a functional group, and (2) a combination of a compound having a functional group that forms a bond by thermal reaction and a compound having a functional group having active hydrogen.

Examples of the functional group having active hydrogen include a hydroxyl group, a carboxy group, a thiol group, an amino group and a phenol group.

As the combination of the functional group forming a bond by thermal reaction and the functional group having active hydrogen, the combinations shown in (A) to (D) below are preferable. In other words, the thermosetting resin layer preferably has the functional groups in the combinations shown in (A) to (D) below.

(A) A combination of a (block) isocyanate group and at least one functional group selected from the group consisting of a hydroxyl group, a carboxy group, and an amino group.
(B) A combination of at least one of an epoxy group and an oxetane group and a carboxy group.
(C) A combination of at least one of a hydroxymethyl group and an alkoxymethyl group and at least one of a hydroxyl group and a carboxy group.
(D) A combination of an oxazoline group and a carboxy group.

As a combination of a functional group forming a bond by a thermal reaction and a functional group having active hydrogen, from the viewpoint of stability over time and curability, a combination of a blocked isocyanate group and at least one of a hydroxyl group and a carboxy group is more preferable. A combination of a blocked isocyanate group and a hydroxyl group is more preferable.
The blocked isocyanate group and the hydroxyl group form a urethane bond by a thermal reaction.

The temperature of the thermal reaction is preferably 100°C to 180°C, more preferably 110°C to 160°C, and further preferably 120°C to 150°C.
When the temperature of the thermal reaction is within the above range, the thermosetting resin layer is cured in the step of drying the coating film of the coating liquid for forming the thermosetting resin layer, which is performed when forming the thermosetting resin layer. Without doing so, the thermosetting resin layer can be efficiently thermoset in the thermosetting step after the developing step.

The thermosetting resin layer preferably contains a blocked isocyanate compound.
The blocked isocyanate compound is a compound having a blocked isocyanate group.
In the present disclosure, the “blocked isocyanate group” is usually protected by blocking the isocyanate group with a blocking agent (so-called mask) to suppress the reactivity of the isocyanate group, but deprotects when heated, By a group is meant an active isocyanate group. Further, in the present disclosure, the “blocked isocyanate compound” means a compound having a blocked isocyanate group as described above.

The blocked isocyanate group has a partial structure represented by the following formula.

In the above formula, X represents a structure obtained by removing a hydrogen atom from the blocking agent.
Examples of the blocking agent include ketoxime compounds, amide compounds, nitrogen-containing heterocyclic compounds, active methylene compounds and the like.
The nitrogen-containing heterocyclic compound is preferably a compound having a pyrazole structure, a compound having an imidazole structure, or the like.

The blocked isocyanate group in which X is a ketoxime group (so-called ketoxime blocked isocyanate group) is preferably a group represented by the following formula.

In the above formula, R ¹⁰¹ and R ¹⁰² each independently represent an alkyl group or an aryl group. R ¹⁰¹ and R ¹⁰² may combine with each other to form a ring structure.
R ¹⁰¹ and R ¹⁰² are preferably a methyl group or an ethyl group.

As the blocked isocyanate group in which X is an amide group (so-called amide blocked isocyanate group) and the blocked isocyanate group in which X is an imide group (so-called imide blocked isocyanate group), groups represented by the following formulas are preferable.

In the above formula, R ¹⁰³ represents a substituent, R ¹⁰⁵ represents an alkyl group, and n1 represents an integer of 0 to 3.

In the above formula, the substituent represented by R ¹⁰³ is preferably an alkyl group, an alkoxy group, or a halogen atom.

As the blocked isocyanate group in which X is a nitrogen-containing heterocycle (so-called nitrogen-containing heterocycle blocked isocyanate group), a group represented by the following formula is preferable.

In the above formula, R ¹⁰³ represents a substituent, and n1 represents an integer of 0 to 3.

In the above formula, the substituent represented by R ¹⁰³ is preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms.

As the nitrogen-containing heterocyclic blocked isocyanate group, a dimethylpyrazole blocked isocyanate group is more preferable.

The blocked isocyanate group in which X is an active methylene group (so-called active methylene blocked isocyanate group) is preferably a group represented by the following formula.

In the above formula, R ¹⁰⁴ and R ¹⁰⁶ each independently represent an alkyl group or an alkoxy group. R ¹⁰⁴ and R ¹⁰⁶ may combine with each other to form a ring structure.

The blocked isocyanate compound preferably reacts at the heating temperature in the thermosetting process described below. From this point of view, the dissociation temperature of the blocked isocyanate compound is preferably 100° C. to 180° C., more preferably 110° C. to 160° C., and further preferably 120° C. to 150° C.

Representative blocked isocyanate compounds and their dissociation temperatures are shown below.
Dimethylpyrazole blocked isocyanate compound (dissociation temperature: 100°C to 120°C), active methylene blocked isocyanate compound (dissociation temperature: 100°C to 120°C), ketoxime blocked isocyanate compound (dissociation temperature: 130°C to 150°C), ε- Caprolactam-blocked isocyanate compound (dissociation temperature: 160°C to 180°C).
Among these, as the blocked isocyanate compound, from the viewpoint of thermal reactivity and stability, at least one compound selected from the group consisting of a dimethylpyrazole blocked isocyanate compound, an active methylene blocked isocyanate compound, and a ketoxime blocked isocyanate compound. Ketoxime blocked isocyanate compounds are more preferred.

The dissociation temperature of the blocked isocyanate compound in the present disclosure means "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate when measured by DSC (Differential scanning calorimetry) using a differential scanning calorimeter". To do.
As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited to this.

The number of blocked isocyanate groups in the blocked isocyanate compound is not particularly limited, but for example, from the viewpoint of curability, it is preferable to have two or more blocked isocyanate groups in one molecule, and to have three or more blocked isocyanate groups. Is more preferable.

The functional group concentration of the blocked isocyanate group in the blocked isocyanate compound is preferably 0.3 mmol/g or more, more preferably 0.5 mmol or more, further preferably 1 mmol/g or more, 2 mmol/g The above is particularly preferable.
The upper limit of the functional group concentration of the blocked isocyanate group in the blocked isocyanate compound is not particularly limited, but is preferably 6 mmol/g or less, for example.

The functional group concentration of the blocked isocyanate group in the thermosetting resin layer is preferably 0.1 mmol/g or more, more preferably 0.3 mmol/g or more, further preferably 1 mmol/g or more. , 1.5 mmol/g or more is particularly preferable.
When the functional group concentration of the blocked isocyanate group in the thermosetting resin layer is 0.1 mmol/g or more, the thermosetting property of the thermosetting resin layer is further improved, and the cured product of the thermosetting resin layer is formed. Since the resistance to peeling from the substrate is further increased, the conductive pattern tends to be more difficult to peel from the substrate.
The upper limit of the functional group concentration of the blocked isocyanate group in the thermosetting resin layer is not particularly limited, but is preferably 6 mmol/g or less from the viewpoint of developability and solvent solubility, for example.

The functional group concentration of the blocked isocyanate group in the thermosetting resin layer is represented by the product of the functional group concentration of the blocked isocyanate group of the blocked isocyanate compound and the mass content of the blocked isocyanate compound in the thermosetting resin layer. When the thermosetting resin layer contains two or more blocked isocyanate compounds, it is represented by the sum of the functional group concentrations in the thermosetting resin layer calculated from the respective blocked isocyanate compounds.

When the thermosetting resin layer contains a blocked isocyanate compound, the blocked isocyanate compound preferably has at least one of a hydroxyl group and an acid group.

When the thermosetting resin layer contains a blocked isocyanate compound, it is preferable that the thermosetting resin layer further contains a compound having at least one of a hydroxyl group and an acid group other than the blocked isocyanate compound.

When the thermosetting resin layer has a hydroxyl group, the thermosetting property of the thermosetting resin layer is further improved, and the resistance to peeling of the cured product of the thermosetting resin layer from the substrate is further increased. Therefore, the conductive pattern tends to be more difficult to peel off.
“When the thermosetting resin layer has a hydroxyl group” means that (1) the thermosetting resin layer contains a blocked isocyanate compound having a hydroxyl group, and (2) the thermosetting resin layer does not have a hydroxyl group. Examples thereof include a case where it contains a blocked isocyanate compound and a compound having a hydroxyl group, and a case where (3) the thermosetting resin layer contains a blocked isocyanate compound having a hydroxyl group and a compound having a hydroxyl group.

When the thermosetting resin layer has an acid group, the developability of the thermosetting resin layer is further improved, so that the development residue tends to be more suppressed.
"When the thermosetting resin layer has an acid group" means that (1) the thermosetting resin layer contains a blocked isocyanate compound having an acid group, and (2) the thermosetting resin layer has an acid group. Examples thereof include a block isocyanate compound not having it and a compound having an acid group, and a case where (3) the thermosetting resin layer contains a block isocyanate compound having an acid group and a compound having an acid group.

Examples of the acid group include a carboxy group, a sulfonamide group, a sulfonimide group, a phenol group and the like.
Among these, a carboxy group is preferable as the acid group.

When the thermosetting resin layer has a hydroxyl group, the functional group concentration of the hydroxyl group in the thermosetting resin layer is preferably 0.1 mmol/g or more, more preferably 0.3 mmol/g or more, 0 More preferably, it is 0.5 mmol/g or more.
When the functional group concentration of the hydroxyl group in the thermosetting resin layer is 0.1 mmol/g or more, the thermosetting property of the thermosetting resin layer is further improved, and the cured product of the thermosetting resin layer is formed from the substrate. Since the peeling resistance of 1 is further increased, the conductive pattern tends to be more difficult to peel from the substrate.
The upper limit of the functional group concentration of hydroxyl groups in the thermosetting resin layer is not particularly limited, but is preferably 3 mmol/g or less from the viewpoint of developability and solvent solubility, for example.

The functional group concentration of the hydroxyl group in the thermosetting resin layer is represented by the product of the functional group concentration of the hydroxyl group of the compound having a hydroxyl group and the mass content of the compound having a hydroxyl group in the thermosetting resin layer. When the thermosetting resin layer contains two or more kinds of compounds having a hydroxyl group, it is represented by the sum of the functional group concentrations in the thermosetting resin layer calculated from the respective compounds having a hydroxyl group.

When the thermosetting resin layer has an acid group, the functional group concentration of the acid group in the thermosetting resin layer (also referred to as “acid value”; the same applies below) is 0.05 mmol/g to 5 mmol/g. It is preferably 0.1 mmol/g to 3 mmol/g, more preferably 0.2 mmol/g to 2 mmol/g.
When the functional group concentration of the acid group in the thermosetting resin layer is within the above range, the developability of the thermosetting resin layer is further improved, so that the development residue tends to be more suppressed.

The functional group concentration of the acid group in the thermosetting resin layer is represented by the product of the functional group concentration of the acid group of the compound having an acid group and the mass content of the compound having an acid group in the thermosetting resin layer. Be done. When the thermosetting resin layer contains two or more compounds having an acid group, it is represented by the sum of the functional group concentrations in the thermosetting resin layer calculated from the compounds having an acid group.

The blocked isocyanate compound may be a low molecular weight compound or a high molecular weight compound, but is preferably a high molecular weight compound from the viewpoint of reaction efficiency and suppression of precipitation.

When the blocked isocyanate compound is a polymer compound, the blocked isocyanate compound is preferably a polymer, more preferably a polymer having a (meth)acrylic monomer as a repeating unit, and is represented by the following formula BR-1. A polymer having a repeating unit represented by the formula: BR-2 is more preferable, and a polymer having a repeating unit represented by the following formula BR-2 is particularly preferable.
In the present disclosure, the “(meth)acrylic monomer” means a monomer having a (meth)acryloyl group.

In Formula BR-1, X represents a structure in which a hydrogen atom is removed from the blocking agent, and Z ¹ represents a hydrogen atom or a methyl group.

In formula BR-2, R ¹⁰¹ and R ¹⁰² each independently represent an alkyl group or an aryl group. R ¹⁰¹ and R ¹⁰² may combine with each other to form a ring structure. Z ¹ represents a hydrogen atom or a methyl group.
R ¹⁰¹ and R ¹⁰² are preferably a methyl group or an ethyl group.

The content of the repeating unit represented by BR-1 in the polymer having the repeating unit represented by the formula BR-1 is preferably 10 mol% to 100 mol% with respect to the total repeating units of the polymer, and 20 mol. % To 80 mol% is more preferable, and 30 mol% to 80 mol% is further preferable.

The polymer having the repeating unit represented by the formula BR-1 preferably has at least one of a hydroxyl group and an acid group.
In a more preferred embodiment, the polymer has a repeating unit having a hydroxyl group and an acid group (preferably a carboxy group) in addition to the repeating unit represented by the formula BR-1 and the repeating unit represented by the formula BR-1. And at least one repeating unit of the repeating units having.
In a further preferred embodiment, the polymer has a repeating unit having a hydroxyl group and an acid group (preferably a carboxy group) in addition to the repeating unit represented by the formula BR-1 and the repeating unit represented by the formula BR-1. And both repeating units of the repeating unit having.
In the above more preferable and still more preferable embodiments, the repeating unit having a hydroxyl group is preferably a repeating unit derived from hydroxyalkyl(meth)acrylate.
In the above more preferable and further preferable aspects, the repeating unit having an acid group (preferably a carboxy group) is preferably a repeating unit derived from (meth)acrylic acid.

The polymer having the repeating unit represented by the formula BR-1 may further have another repeating unit copolymerizable with the repeating unit represented by the formula BR-1.
The other repeating unit is not particularly limited, and examples thereof include a repeating unit derived from an alkyl(meth)acrylate, a repeating unit derived from an aralkyl(meth)acrylate, and a repeating unit derived from styrene.

When the blocked isocyanate compound is a polymer, from the viewpoint of transferability, the total content of repeating units derived from acrylic acid and repeating units derived from acrylic acid ester is 30 mol% to 100 mol% based on all repeating units of the polymer. Is preferable, and more preferably 50 mol% to 100 mol %.

When the blocked isocyanate compound is a polymer, the weight average molecular weight of the blocked isocyanate compound is not particularly limited, but is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, More preferably, it is 4,000 to 30,000.
The weight average molecular weight of the blocked isocyanate compound is a polystyrene equivalent weight average molecular weight measured by the method described above (that is, GPC).

When the blocked isocyanate compound is a polymer compound, the blocked isocyanate compound is preferably a polymer represented by the following formula.

In the above formula, Z ¹ represents a hydrogen atom or a methyl group.

When the blocked isocyanate compound is a low molecular weight compound, the blocked isocyanate compound is preferably a compound represented by the following formula.

When the number of X ¹ in the compound represented by the above formula is one, X ¹ represents a structure obtained by removing a hydrogen atom from the blocking agent.
When a plurality of X ¹ 's in the compound represented by the above formula are present, X ¹ has a structure obtained by removing a hydrogen atom from the blocking agent, or a hydrophilic group (preferably a polyalkylene glycol group). ), and at least one of a plurality of X ^{1 s} represents a structure in which a hydrogen atom is removed from the blocking agent.

The compound having at least one of a hydroxyl group and an acid group may be a low molecular weight compound or a high molecular weight compound, but is preferably a high molecular weight compound.
The polymer compound is preferably a polymer.

As the low molecular weight compound having a hydroxyl group, a compound having two or more hydroxyl groups is preferable, and a compound having 3 to 8 hydroxyl groups is more preferable.
Examples of such compounds include polyols such as trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, and ditrimethylolethane.

When the compound having at least one of a hydroxyl group and an acid group is a polymer, a preferable embodiment is that the polymer has at least one repeating unit having a repeating unit having a hydroxyl group and a repeating unit having an acid group (preferably a carboxy group). Is.
In a more preferred embodiment, the polymer has both a repeating unit having a hydroxyl group and a repeating unit having an acid group (preferably a carboxy group).
In the preferred and more preferred embodiments described above, the repeating unit having a hydroxyl group is preferably a repeating unit derived from hydroxyalkyl(meth)acrylate.
In the above preferred and more preferred embodiments, the repeating unit having an acid group (preferably a carboxy group) is preferably a repeating unit derived from (meth)acrylic acid.

The polymer having at least one of a hydroxyl group and an acid group may further have a repeating unit having a hydroxyl group or another repeating unit copolymerizable with the repeating unit having an acid group (preferably a carboxy group).
The other repeating unit is not particularly limited, and examples thereof include a repeating unit derived from an alkyl(meth)acrylate, a repeating unit derived from an aralkyl(meth)acrylate, and a repeating unit derived from styrene.

From the viewpoint of transferability, the polymer having at least one of a hydroxyl group and an acid group has a total content of repeating units derived from acrylic acid and repeating units derived from acrylic acid ester of 30 mol% with respect to all repeating units of the polymer. It is preferably ˜100 mol %, and more preferably 50 mol% to 100 mol %.

The weight average molecular weight of the polymer having at least one of a hydroxyl group and an acid group is not particularly limited, but is preferably 2,000 to 100,000, more preferably 3,000 to 80,000, and It is more preferably 000 to 50,000.
The weight average molecular weight of the polymer having at least one of a hydroxyl group and an acid group is a polystyrene equivalent weight average molecular weight measured by the method described above (that is, GPC).

The polymer having at least one of a hydroxyl group and an acid group is preferably a polymer represented by the following formula.

In the above formula, Z ¹ represents a hydrogen atom or a methyl group.

The thermosetting resin layer may have at least one of an epoxy group and an oxetane group as a functional group that forms a bond by thermal reaction.
The thermosetting resin layer preferably contains at least one of an epoxy group and an oxetane group in a mode including a compound having at least one of an epoxy group and an oxetane group.

Examples of the compound having an epoxy group include low molecular weight compounds such as glycidyl ether compounds and polycarboxylic acid glycidyl ester compounds, and polymers having a repeating unit having an epoxy group in its side chain.
The repeating unit having an epoxy group in the side chain is preferably a repeating unit derived from glycidyl (meth)acrylate.

Both the epoxy group and the oxetane group are thermally reacted alone, but it is preferable to react with the carboxy group.
In a more preferred embodiment, the thermosetting resin layer contains a polymer having both a repeating unit having an epoxy group and a repeating unit having a carboxy group.

The thermosetting resin layer may have at least one of a hydroxymethyl group and an alkoxymethyl group as a functional group that forms a bond by thermal reaction.
The thermosetting resin layer preferably contains at least one of a hydroxymethyl group and an alkoxymethyl group in a mode including a compound having at least one of a hydroxymethyl group and an alkoxymethyl group.
As the compound having at least one of a hydroxymethyl group and an alkoxymethyl group, a low-molecular compound such as hydroxymethylmelamine, alkoxymethylmelamine, alkoxymethylglycolurea, alkoxymethylbenzoguanamine, and hydroxymethyl-substituted phenol, derived from N-alkoxymethylacrylamide And a polymer having a repeating unit of.
Among these, as the compound having at least one of a hydroxymethyl group and an alkoxymethyl group, a polymer having a repeating unit derived from N-alkoxymethylacrylamide is preferable from the viewpoint of curability.

Both the hydroxymethyl group and the alkoxymethyl group are thermally reacted independently, but it is preferable to react with at least one of the hydroxyl group and the carboxy group.
In a more preferred embodiment, the thermosetting resin layer contains a polymer having a repeating unit derived from N-alkoxymethylacrylamide, a repeating unit having a hydroxyl group, and a repeating unit having a carboxy group.

-Corrosion inhibitor-
The thermosetting resin layer may contain a corrosion inhibitor.
When the thermosetting resin layer contains a corrosion inhibitor, the silver nanowires are prevented from being corroded, so that durability can be improved.

When the thermosetting resin layer contains a corrosion inhibitor, it may contain only one type of corrosion inhibitor or may contain two or more types of corrosion inhibitors.

When the thermosetting resin layer contains a corrosion inhibitor, the content of the corrosion inhibitor in the thermosetting resin layer is 0.001% by mass to 5% by mass based on the total mass of the thermosetting resin layer. It is preferably 0.005% by mass to 3% by mass.

-Surfactant-
The thermosetting resin layer may contain a surfactant.
When the thermosetting resin layer contains a surfactant, the uniformity of the film thickness can be improved.
The surfactant has the same meaning as the surfactant described in “Positive-type photosensitive resin layer”, and the preferred examples are also the same, and therefore the description thereof is omitted here.

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

When the thermosetting resin layer contains a surfactant, the content ratio of the surfactant in the thermosetting resin layer is 0. 0 with respect to the total mass of the thermosetting resin layer from the viewpoint of the film thickness uniformity. The amount is preferably 05% by mass to 10% by mass, and more preferably 0.05% by mass to 5% by mass.

-Other ingredients-
The thermosetting resin layer may contain components other than the above components (hereinafter, also referred to as “other components”).
Other components are not particularly limited and can be appropriately selected depending on the purpose and the like.
Other components include a polymerization inhibitor, an ultraviolet absorber, a development accelerator, a coloring agent and the like.

-Thickness of thermosetting resin layer-
The thickness of the thermosetting resin layer is not particularly limited and is, for example, preferably 1 nm to 10,000 nm, more preferably 1 nm to 5,000 nm, further preferably 1 nm to 1,000 nm. It is particularly preferably 1 nm to 300 nm, and most preferably 20 nm to 100 nm.
When the thickness of the thermosetting resin layer is within the above range, the cured resin layer (that is, the thermosetting resin layer) tends to be more difficult to peel from the substrate. Further, even when exposed to a moist heat environment, it is possible to form a circuit board in which the sheet resistance value is less likely to increase and the durability is superior.

The thickness of the thermosetting resin layer is measured by the following method.
In the cross-sectional observation image in the thickness direction of the thermosetting resin layer, the arithmetic mean value of the thickness of the thermosetting resin layer measured at five randomly selected points was calculated, and the obtained value was used as the thermosetting resin. The layer thickness.
The cross-sectional observation image of the thermosetting resin layer in the thickness direction can be obtained using a scanning electron microscope (SEM).

-Minimum transmittance of thermosetting resin layer-
The minimum transmittance of the thermosetting resin layer at a wavelength of 400 nm to 700 nm is preferably 80% or more, more preferably 90% or more.
Examples of the method for measuring the minimum transmittance of the thermosetting resin layer include a method using a spectrophotometer [eg, MCPD-6800 manufactured by Otsuka Electronics Co., Ltd.].

-Contact resistance of thermosetting resin layer-
The contact resistance of the thermosetting resin layer is preferably 200 Ω or less, more preferably 1 Ω to 200 Ω, and more preferably 1 Ω to, from the viewpoint of the conductivity of the cured resin layer (that is, the thermosetting resin layer). It is more preferably 100Ω, and particularly preferably 1Ω to 50Ω.

The contact resistance of the thermosetting resin layer is measured by the TLM (Transmission Line Model) method. The specific measuring method is as follows.
Seven copper electrodes (thickness: 300 nm, width: 500 μm) arranged on a substrate (for example, a cycloolefin polymer film) in parallel and independently at intervals of 2 mm, 4 mm, 6 mm, 8 mm, 12 mm, and 20 mm. ) Is formed. Next, one photosensitive transfer material was pasted on the seven copper electrodes to produce a test body having a structure in which a silver nanowire layer was laminated on the copper electrodes via a thermosetting resin layer. To do. In a plan view of the test body, the silver nanowire layer is arranged so as to cross the seven copper electrodes, and the angle formed by each copper electrode and the silver nanowire layer is 90°. After measuring the resistance between adjacent copper electrodes, the contact resistance of the thermosetting resin layer is obtained by plotting the relationship between the resistance (vertical axis) and the distance (horizontal axis) between the copper electrodes.
As a device for measuring the resistance between the copper electrodes, for example, a resistivity meter (trade name: Loresta-GP, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) can be used. However, the measuring device is not limited to this.

-Glass transition temperature of thermosetting resin layer-
The glass transition temperature of the thermosetting resin layer is preferably −50° C. to 100° C., and more preferably −30° C. to 80° C., from the viewpoint of coating properties and adhesiveness when it is bonded to a substrate. , -10°C to 50°C is more preferable.
The glass transition temperature of the thermosetting resin layer is the thermosetting resin layer formed by applying the thermosetting resin layer forming coating solution to the substrate and drying the solvent at a temperature at which the thermosetting resin layer does not cure. , DSC (Differential scanning calorimetry) analysis using a differential scanning calorimeter.
Regarding the glass transition temperature of the thermosetting resin layer, a compound having a different glass transition temperature is appropriately selected as a compound (block isocyanate compound, compound having a hydroxyl group, compound having an acid group, etc.) contained in the thermosetting resin layer. Can be adjusted.

(Method of forming thermosetting resin layer)
The method for forming the thermosetting resin layer is not particularly limited, and a known method can be applied.
Examples of the thermosetting resin layer include a method in which a coating liquid for forming a thermosetting resin layer containing each of the above-mentioned components is applied onto an object to be coated and dried.

The thermosetting resin layer-forming coating liquid can be prepared, for example, by mixing the above-mentioned components and a solvent in an arbitrary ratio.

The solvent is not particularly limited, and a known solvent can be used.
The solvent has the same meaning as the solvent described in “Method for forming photosensitive resin layer”, and the preferred examples are also the same, and therefore the description thereof is omitted here.

In the thermosetting resin layer, the solvent contained in the coating liquid for forming the thermosetting resin layer does not need to be completely removed.
The thermosetting resin layer contains no solvent, or preferably contains more than 0 mass% and 1 mass% or less of the total mass of the thermosetting resin layer and contains no solvent, or More preferably, it is more than 0% by mass and 0.5% by mass or less based on the total mass of the thermosetting resin layer.

The solid content concentration of the thermosetting resin layer-forming coating liquid is not particularly limited.
From the viewpoint of coating suitability, the solid content concentration of the thermosetting resin layer forming coating liquid is preferably 0.1% by mass to 30% by mass, and 0.5% by mass to 20% by mass. More preferable.

In the present disclosure, the “solid content concentration of the thermosetting resin layer-forming coating liquid” refers to volatilization of a solvent or the like from the thermosetting resin layer-forming coating liquid with respect to the total mass of the thermosetting resin layer-forming coating liquid. It means the ratio of the residue excluding the sex components.

<Protective film>
The photosensitive transfer material of the present disclosure may have a protective film on the surface of the thermosetting resin layer opposite to the silver nanowire layer side.
Examples of the protective film include polyethylene terephthalate film, polypropylene film, polystyrene film, polycarbonate film and the like.
The protective film is described in paragraphs [0083] to [0087] and [0093] of JP 2006-259138 A, for example. These descriptions are incorporated herein by reference.

[Method of manufacturing patterned substrate]
The method for producing a patterned substrate of the present disclosure is the above-described photosensitive transfer material and the step of attaching the substrate (hereinafter, also referred to as “attaching step”), and the photosensitive resin layer in the photosensitive transfer material. Pattern exposure (hereinafter, also referred to as "exposure step"), a step of developing the photosensitive transfer material that has undergone the pattern exposure to form a pattern (hereinafter also referred to as "developing step"), The step of thermally curing the thermosetting resin layer (hereinafter, also referred to as “thermosetting step”) is included in this order.
The method for producing a patterned substrate according to the present disclosure includes a bonding step, an exposure step, a developing step, and a thermosetting step in this order, and therefore, a patterned substrate in which the conductive pattern is difficult to peel off from the substrate is produced. You can

<Laminating process>
The method for manufacturing a patterned substrate according to the present disclosure includes the above-described photosensitive transfer material and a step of bonding the substrates (that is, a bonding step).

(Photosensitive transfer material)
The photosensitive transfer material in the method for manufacturing a patterned substrate according to the present disclosure is as described in the above-mentioned “Photosensitive transfer material”, and the preferred embodiment is also the same, and therefore the description thereof is omitted here.
The photosensitive resin layer in the photosensitive transfer material is preferably a positive photosensitive resin layer from the viewpoint of resolution.

(substrate)
The substrate may be a substrate such as glass, silicon, or a film itself, or may be a substrate provided with an optional layer such as a conductive layer on the substrate such as glass, silicon, or film, if necessary. May be. When the substrate further has a conductive layer, the substrate preferably has a conductive layer on the base material.

The base material is preferably a glass base material or a film base material, more preferably a film base material, and further preferably a resin film.

The base material is preferably transparent.
The transparent substrate is described, for example, in JP 2010-86684 A, JP 2010-152809 A and JP 2010-257492 A. These descriptions are incorporated herein by reference.
The refractive index of the base material is preferably 1.50 to 1.52.

As the glass substrate, for example, tempered glass represented by Corning's gorilla glass can be used.
When a film base material is used as the base material, it is preferable to use a base material having small optical distortion and a base material having high transparency.

The material of the resin film includes polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer and the like.

Examples of the conductive layer include general circuit wiring and any conductive layer used for touch panel wiring.
Examples of the conductive layer include a metal layer and a conductive metal oxide layer.
In the present disclosure, “conductive” means that the volume resistivity is less than 1×10 ⁶ Ωcm. The volume resistivity is preferably less than 1×10 ⁴ Ωcm.

Examples of the material of the metal layer include Al (aluminum), Zn (zinc), Cu (copper), Fe (iron), Ni (nickel), Cr (chrome), Mo (molybdenum), and the like.
The metal forming the metal layer may be a single metal consisting of one kind of metal element, a metal mixture containing two or more kinds of metal elements, or an alloy containing at least one kind of metal element. It may be.
Examples of the conductive metal oxide forming the conductive metal oxide layer include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO ₂ .

The conductive layer is preferably at least one kind of layer selected from the group consisting of a metal layer and a conductive metal oxide layer, more preferably a metal layer, from the viewpoint of conductivity and fine wire forming property, and a copper layer. More preferably, it is a layer.

The conductive layer is preferably an electrode pattern corresponding to the sensor of the visual recognition part used in the capacitive touch panel or a wiring of the peripheral extraction part.

In the bonding step, the photosensitive transfer material and the substrate are bonded by bringing the thermosetting resin layer in the photosensitive transfer material into contact with the substrate.
The lamination of the photosensitive transfer material and the substrate can be performed using a known laminator such as a vacuum laminator and an auto cut laminator.

The laminating temperature is not particularly limited.
The laminating temperature is preferably 80° C. to 150° C., more preferably 90° C. to 150° C., and further preferably 100° C. to 150° C.
When using a laminator equipped with a rubber roller, the laminating temperature refers to the temperature of the rubber roller.

The substrate temperature during lamination is not particularly limited.
The substrate temperature during lamination may be, for example, 10° C. to 150° C., preferably 20° C. to 150° C., and more preferably 30° C. to 150° C.
When a resin substrate is used as the substrate, the substrate temperature during lamination is preferably 10°C to 80°C, more preferably 20°C to 60°C, and further preferably 30°C to 50°C. preferable.

The linear pressure during lamination is not particularly limited.
The linear pressure during lamination is preferably 0.5 N/cm to 20 N/cm, more preferably 1 N/cm to 10 N/cm, and further preferably 1 N/cm to 5 N/cm.

There is no particular limitation on the conveying speed during laminating (so-called laminating speed).
The conveying speed during lamination is preferably 0.5 m/min to 5 m/min, more preferably 1.5 m/min to 3 m/min.

<Exposure process>
The method for producing a patterned substrate according to the present disclosure includes a step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material (that is, an exposure step).
In the exposure step, the photosensitive resin layer in the photosensitive transfer material is pattern-exposed to form an exposed portion and a non-exposed portion on the photosensitive resin layer.

In the exposure step, when the photosensitive resin layer in the photosensitive transfer material is a positive type, the exposed photosensitive resin layer (so-called exposed portion) has increased solubility in the developing solution due to polarity change. When the photosensitive resin layer in the photosensitive transfer material is a negative type, the exposed photosensitive resin layer (so-called unexposed portion) is cured.

The pattern exposure method may be exposure through a mask (also called “photomask”) or digital exposure using a laser or the like.

The light source for exposure is not particularly limited.
The light source for exposure can be appropriately selected depending on the components contained in the photosensitive resin layer.
When the photosensitive resin layer is of a positive type, examples of the light source include a light source capable of irradiating light (for example, 365 nm or 405 nm) in a wavelength range in which the exposed portion can be dissolved in the developing solution.
When the photosensitive resin layer is a negative type, examples of the light source include a light source capable of irradiating with light in a wavelength range in which the exposed portion can be cured (for example, 365 nm or 405 nm).
Specific examples of the light source include various lasers, light emitting diodes (LEDs), ultrahigh pressure mercury lamps, high pressure mercury lamps, metal halide lamps and the like.

Exposure ^is preferably 5mJ / cm 2 ~ 200mJ / cm 2, more preferably 10mJ / cm 2 ~ 200mJ / cm 2.

In the exposure step, the photosensitive resin layer may be pattern-exposed after the temporary support is peeled off from the photosensitive transfer material attached to the substrate, and the photosensitive resin layer may be patterned while leaving the temporary support. You may expose.

<Developing process>
The method for manufacturing a patterned substrate of the present disclosure includes a step of developing the photosensitive transfer material that has undergone the pattern exposure to form a pattern (that is, a developing step).

In the developing step, when the photosensitive resin layer in the photosensitive transfer material is a positive type, a pattern can be formed by removing the exposed portion of the photosensitive transfer material with a developing solution.
When the photosensitive resin layer in the photosensitive transfer material is a negative type, the pattern can be formed by removing the non-exposed portion of the photosensitive transfer material with a developing solution.
In the developing step, since the silver nanowire layer and the thermosetting resin layer are also developed using the pattern of the photosensitive resin layer as a mask, the silver nanowire layer and the thermosetting resin layer can be simultaneously formed with a pattern.

The developer is not particularly limited and, for example, a known developer such as the developer described in JP-A-5-72724 can be used.

The developer is preferably an alkaline aqueous solution.
As the alkaline compound that can be contained in the alkaline aqueous solution, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Examples thereof include tetrabutylammonium hydroxide and choline (2-hydroxyethyltrimethylammonium hydroxide).

The pH of the alkaline aqueous solution at 25° C. is preferably 8 to 13, more preferably 9 to 12, and even more preferably 10 to 12.

The content of the alkaline compound in the alkaline aqueous solution is preferably 0.1% by mass to 5% by mass, and more preferably 0.1% by mass to 3% by mass, based on the total mass of the alkaline aqueous solution.

The liquid temperature of the developer is preferably 20°C to 40°C.

Examples of development methods include paddle development, shower development, shower and spin development, and dip development.

Regarding pattern exposure, development, etc., for example, the description in paragraphs [0035] to [0051] of JP 2006-23696 A can be referred to.

<Thermosetting step>
The method for manufacturing a patterned substrate according to the present disclosure includes a step of thermally curing the thermosetting resin layer in the photosensitive transfer material described above (that is, a thermosetting step).

In the thermosetting process, the thermosetting resin layer is thermoset.

The heating temperature and heating time for thermosetting the thermosetting resin layer are not particularly limited as long as the thermosetting resin layer can be thermoset, and may be appropriately set according to the components contained in the thermosetting resin layer. You can
The heating temperature is preferably 100°C to 180°C, more preferably 110°C to 160°C, and further preferably 120°C to 150°C.
When the heating temperature is within the above range, the thermosetting resin layer can be thermoset more efficiently.
The heating time is preferably 0.1 minutes to 120 minutes, more preferably 0.5 minutes to 60 minutes, and further preferably 1 minute to 30 minutes.
When the heating time is within the above range, discoloration and deformation of the substrate due to heating hardly occur.

The heating method is not particularly limited, and a known heating method can be applied.
Examples of the heating method include a method of heating by contacting with a heat source such as a hot plate, a method of heating in a heating atmosphere using an oven, and a method of heating with warm air, an infrared heater or the like.

[Circuit board manufacturing method]
The method for manufacturing a circuit board according to the present disclosure includes a step of bonding the above-mentioned photosensitive transfer material and the substrate (bonding step), and a step of pattern-exposing the photosensitive resin layer in the photosensitive transfer material (exposure step). ), a step of developing the photosensitive transfer material that has undergone the pattern exposure to form a pattern (developing step), a step of thermally curing the thermosetting resin layer (thermosetting step), and The step of removing the cured product of the photosensitive resin layer or the photosensitive resin layer (hereinafter, also referred to as "removal step") is included in this order.
The method for manufacturing a circuit board according to the present disclosure includes a bonding step, an exposure step, a developing step, and a thermosetting step in this order, so that the conductive pattern is peeled off from the board even after the removal step. It is possible to manufacture a circuit board that is difficult to manufacture.

The bonding step, the exposure step, the development step, and the heat curing step in the circuit board manufacturing method of the present disclosure are the bonding step, the exposure step, the development step, and the heat curing in the above-mentioned “method for manufacturing a patterned substrate”. The steps are synonymous with each other, and the preferred embodiments are also the same, and therefore the description thereof is omitted here.

<Removal process>
The circuit board manufacturing method of the present disclosure includes a step (removing step) of removing the photosensitive resin layer or the cured product of the photosensitive resin layer in the pattern formed in the developing step.
Hereinafter, the "photosensitive resin layer or a cured product of the photosensitive resin layer in the pattern formed in the developing step" is also referred to as "removed layer".

In the development step, the photosensitive resin layer or the cured product of the photosensitive resin layer in the pattern is usually formed on the outermost layer of the pattern (that is, among the layers constituting the pattern, the layer arranged at the position farthest from the substrate). It is arranged.

As the cured product of the photosensitive resin layer, for example, a cured product of a negative photosensitive resin layer can be mentioned. The cured product of the negative photosensitive resin layer is formed, for example, by exposing the negative photosensitive resin layer in the exposure step.

As a method of removing the layer to be removed, for example, a method of removing the layer to be removed by chemical treatment can be mentioned, and a method using a removing liquid is preferable.

As a specific example of the method for removing the layer to be removed, the substrate having the layer to be removed is placed in the removal liquid under stirring at preferably 30° C. to 80° C., more preferably 50° C. to 80° C. for 1 minute to 30 minutes A method of dipping for a minute may be mentioned.

From the viewpoint of removability, the removing liquid is preferably a removing liquid containing 30% by mass or more of water, more preferably a removing liquid containing 50% by mass or more of water, and further preferably a removing liquid containing 70% by mass or more of water.

The removing liquid is an inorganic alkali component such as sodium hydroxide, potassium hydroxide or sodium carbonate, or an organic alkali such as a primary amine compound, a secondary amine compound, a tertiary amine compound or a quaternary ammonium salt compound. It is preferable to include components.

From the viewpoint of removability, the content of the alkali component is preferably 0.01% by mass to 20% by mass, and more preferably 0.1% by mass to 10% by mass, based on the total mass of the removing liquid. More preferable.

The method for manufacturing a circuit board according to the present disclosure may include steps (so-called other steps) other than the bonding step, the exposure step, the developing step, the thermosetting step, and the removing step.
As another process, a process of exposing the entire surface of the pattern formed through the developing process before the removal process (hereinafter, also referred to as “entire surface exposure process”) can be mentioned.

<Overall exposure process>
The circuit board manufacturing method of the present disclosure may include a step of exposing the entire surface of the pattern formed through the developing step (entire surface exposing step) before the removing step.

For example, when the photosensitive resin layer in the pattern is a positive type, the solubility of the photosensitive resin layer in the removal liquid can be further improved.

In the whole surface exposure process, from the viewpoint of removability, it is preferable to use a light source containing light of the same wavelength as in the above-described exposure process.

The exposure amount in the overall exposure step, from the viewpoint of removability is ^preferably 5mJ / cm 2 ~ 1,000mJ / cm 2, more preferably 10mJ / cm 2 ~ 800mJ / cm 2, 100mJ / More preferably, it is from cm ² to 500 mJ/cm ² .

The above-mentioned removal step may be performed after the whole surface exposure step, if necessary.

[Laminate]
The laminate of the present disclosure includes a substrate, a layer containing a resin obtained by thermosetting (hereinafter, also referred to as “thermosetting resin layer”), and a layer containing silver nanowires (silver nanowire layer). Have in order.
Since the laminate of the present disclosure has the substrate, the thermosetting resin layer, and the silver nanowire layer in this order, it is difficult for the conductive pattern formed by the silver nanowire layer to be peeled from the substrate. Further, according to the laminate of the present disclosure, since it has a substrate, a thermosetting resin layer, and a silver nanowire layer in this order, the sheet resistance value increases even when exposed to a humid heat environment. It is possible to realize a circuit board that is difficult to perform and has excellent durability.

FIG. 2 is a schematic cross-sectional view showing an example of the layer structure of the laminate of the present disclosure.
The laminated body 200 illustrated in FIG. 2 includes the substrate 50, the thermosetting resin layer 40B, and the silver nanowire layer 30 in this order.

In the laminate of the present disclosure, it is preferable that the thermosetting resin layer is a layer obtained by curing the thermosetting resin layer that is the transfer layer, and the silver nanowire layer is the transfer layer.
In the present disclosure, the “transfer layer” means a layer formed by transfer.

Hereinafter, each configuration of the laminated body of the present disclosure will be described.

<Substrate>
The laminated body of the present disclosure has a substrate.
The substrate in the laminated body of the present disclosure has the same meaning as the substrate described in the above-mentioned “method for manufacturing a patterned substrate”, and the preferred embodiment is also the same, and therefore the description thereof is omitted here.

<Thermosetting resin layer>
The laminate of the present disclosure has a layer containing a resin obtained by thermosetting (that is, a thermosetting resin layer).
The thermosetting resin layer is a layer containing a resin obtained by thermosetting.
The heat-cured resin is a cured product of the components described in the above-mentioned "thermosetting resin layer". Since the thermosetting resin layer is a layer containing a resin that is thermoset, it is difficult to peel from the substrate. The conductive pattern tends to be more difficult to peel from the substrate.

The heat-cured resin is preferably a crosslinked resin having a urethane bond.
It can be confirmed by a known method [for example, IR (infrared spectroscopy) analysis] that the heat-cured resin has a urethane bond.

The thermosetting resin layer may contain only one kind of thermosetting resin, or may contain two or more kinds.

The content of the thermosetting resin in the thermosetting resin layer is preferably 50% by mass to 100% by mass, and 70% by mass to 100% by mass based on the total mass of the thermosetting resin layer. Is more preferable, and 90% by mass to 100% by mass is further preferable.
When the content of the thermosetting resin in the thermosetting resin layer is within the above range, it tends to be more difficult to peel from the substrate. Further, even when exposed to a moist heat environment, it is possible to form a circuit board in which the sheet resistance value is less likely to increase and the durability is superior.

-Thickness of thermosetting resin layer-
The thickness of the thermosetting resin layer is not particularly limited and is, for example, preferably 1 nm to 10,000 nm, more preferably 1 nm to 5,000 nm, further preferably 1 nm to 1,000 nm. Particularly preferably, it is 1 nm to 300 nm, and most preferably 20 nm to 100 nm.
When the thickness of the thermosetting resin layer is within the above range, the thermosetting resin layer tends to be more difficult to peel from the substrate. Further, even when exposed to a moist heat environment, it is possible to form a circuit board in which the sheet resistance value is less likely to increase and the durability is superior.

The thickness of the thermosetting resin layer is measured by the following method.
In the cross-section observation image in the thickness direction of the thermosetting resin layer, the arithmetic mean value of the thickness of the thermosetting resin layer measured at five randomly selected points is calculated, and the obtained value is calculated as the thickness of the thermosetting resin layer. Satoshi
The cross-sectional observation image in the thickness direction of the thermosetting resin layer can be obtained using a scanning electron microscope (SEM).

From the viewpoint of conductivity, the contact resistance of the thermosetting resin layer is preferably 200Ω or less, more preferably 1Ω to 200Ω, more preferably 1Ω to 100Ω, and more preferably 1Ω to 50Ω. More preferable.

The contact resistance of the thermosetting resin layer is measured by the TLM (Transmission Line Model) method. The specific method is as follows.
Seven copper electrodes (thickness: 300 nm, width: 500 μm) arranged on a substrate (for example, a cycloolefin polymer film) in parallel and independently at intervals of 2 mm, 4 mm, 6 mm, 8 mm, 12 mm, and 20 mm. ) Is formed. Next, after bonding one photosensitive transfer material on the seven copper electrodes, the thermosetting resin layer is thermally cured by heating, so that the silver nano-particles are formed on the copper electrodes via the thermosetting resin layer. A test body having a structure in which wire layers are laminated is produced. In a plan view of the test body, the silver nanowire layer is arranged so as to cross the seven copper electrodes, and the angle formed by each copper electrode and the silver nanowire layer is 90°. After measuring the resistance between adjacent copper electrodes, the contact resistance of the thermosetting resin layer is obtained by plotting the relationship between the resistance (vertical axis) and the distance (horizontal axis) between the copper electrodes.

<Silver nanowire layer>
The laminate of the present disclosure has a layer containing silver nanowires (that is, a silver nanowire layer).
The silver nanowire layer in the layered product of the present disclosure has the same meaning as the silver nanowire layer described in the above section “Photosensitive transfer material”, and the preferred embodiment is also the same, and therefore the description thereof is omitted here.

[Method for manufacturing laminated body]
The method for producing the laminate of the present disclosure is not particularly limited, and a known method can be applied.
As the method for manufacturing the laminated body of the present disclosure, for example, the methods described in the above-mentioned “method for manufacturing patterned substrate” and “method for manufacturing circuit board” can be applied.

[Touch panel]
The touch panel of the present disclosure has the laminated body of the present disclosure.
Since the touch panel of the present disclosure has the laminated body of the present disclosure, the conductive pattern formed by the silver nanowire layer is difficult to peel off from the substrate. Further, since the touch panel of the present disclosure has the laminated body of the present disclosure, the sheet resistance value does not easily increase even when exposed to a humid heat environment, and the durability is excellent.

The layered product in the touch panel of the present disclosure has the same meaning as the layered product described in the section “Layered product” described above, and the preferred embodiment is also the same, and thus the description thereof is omitted here.
In the touch panel of the present disclosure, when the laminated body is used as a circuit board, it is preferable that a part of the region including the thermosetting resin layer and the silver nanowire layer in the laminated body be patterned.

The detection method in the touch panel of the present disclosure includes a resistance film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, an optical method, and the like.
Among these, the capacitance method is preferable as the detection method.

As the touch panel type, a so-called in-cell type (for example, those described in FIGS. 5, 6, 7, and 8 of JP 2012-517051 A), a so-called on-cell type (for example, JP2013-168125A). 19 of Japanese Patent Laid-Open No. 2012-89102, and those of FIGS. 1 and 5 of Japanese Patent Laid-Open No. 2012-89102), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, 2 of Japanese Patent Application Laid-Open No. 2013-54727), other configurations (for example, the one shown in FIG. 6 of Japanese Patent Application Laid-Open No. 2013-164871), various out-cell types (so-called GG, G1 and G2). , GFF, GF2, GF1, G1F, etc.).
As the touch panel of the present disclosure, "Latest touch panel technology" [July 6, 2009, published by Techno Times Co., Ltd.], supervised by Yuji Mitani, "Touch Panel Technology and Development", CMC Publishing (2004, 12), The configurations disclosed in FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, and the like can be applied.

[Method of manufacturing touch panel]
The manufacturing method of the touch panel of the present disclosure includes the manufacturing method of the circuit board of the present disclosure described above. That is, the manufacturing method of the circuit board of the present disclosure can be applied to the manufacturing method of the touch panel of the present disclosure.

The method of manufacturing the circuit board in the method of manufacturing the touch panel of the present disclosure has the same meaning as the method of manufacturing the circuit board described in the above-mentioned “method of manufacturing a circuit board”, and preferable aspects are also the same. The description is omitted.

FIG. 3 shows an example of a mask pattern used in the touch panel manufacturing method of the present disclosure.
The pattern A shown in FIG. 3 can be used when pattern-exposing a positive photosensitive resin layer. In the pattern A shown in FIG. 3, the solid line portion SL and the gray portion G are light-shielding portions, and the dotted line portion DL is a virtual alignment alignment frame.
In the touch panel manufacturing method of the present disclosure, for example, the positive photosensitive resin layer is exposed through the mask having the pattern A shown in FIG. 3 to form a pattern corresponding to the solid line portion SL and the gray portion G. A touch panel on which circuit wiring is formed can be manufactured.

Hereinafter, the present disclosure will be described more specifically by way of examples.
Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present disclosure. Therefore, the scope of the present disclosure is not limited to the specific examples shown below.

In the following examples, the weight average molecular weight of the resin is the weight average molecular weight determined in terms of polystyrene by gel permeation chromatography (GPC).
Further, in the following examples, the glass transition temperature of the thermosetting resin layer is the glass transition temperature obtained by the method described above.

<Measurement of diameter and length of silver nanowire>
Diameter and length of 300 silver nanowires randomly selected from silver nanowires magnified and observed using a transmission electron microscope (TEM) [trade name: JEM-2000FX, manufactured by JEOL Ltd.] Was measured. The diameter and length of the silver nanowire were obtained by arithmetically averaging the measured values.

<Preparation of additive liquid A>
5.1 g of silver nitrate powder was dissolved in 500 mL of pure water. 1 mol/L ammonia water was added to the obtained liquid until the liquid became transparent. Next, pure water was added to the obtained liquid so that the total amount of the liquid would be 1000 mL, to prepare an additive liquid A.

<Preparation of additive liquid G>
An additive solution G was prepared by dissolving 5 g of glucose powder in 1400 mL of pure water.

<Preparation of additive liquid H>
An additive solution H was prepared by dissolving 5 g of HTAB (hexadecyl-trimethylammonium bromide) powder in 275 mL of pure water.

<Preparation of coating liquid for silver nanowire layer formation>
After adding 410 mL of pure water in the three-necked flask, the additive solution G (206 mL) and the additional solution H (82.5 mL) were added using a funnel while stirring the pure water in the three-necked flask at 20°C. .. Then, the obtained liquid was stirred at a stirring rotation speed of 800 rpm (round per minute; the same applies hereinafter), and the additive liquid A (206 mL) was added to the stirring liquid at an addition rate of 2.0 mL/min. Ten minutes after the addition was completed, the addition liquid H (82.5 mL) was added to the obtained liquid. Next, the temperature inside the flask was raised to 75° C. at a temperature raising rate of 3° C./min. After the temperature in the flask reached 75° C., the stirring rotation speed was changed to 200 rpm, and heating and stirring were continued for 5 hours. After completion of heating and stirring, the obtained liquid was cooled.

Then, for the cooled liquid, an ultrafiltration membrane [trade name: Microza (registered trademark) UF module SIP1013, molecular weight cutoff: 6,000, manufactured by Asahi Kasei Co., Ltd.], a magnet pump, and a stainless steel cup were used. Ultrafiltration was performed using an ultrafiltration device connected using a tube. Specifically, the cooled liquid was put into a stainless steel cup, and a magnet pump was operated to perform ultrafiltration. When the filtrate from the ultrafiltration membrane reached 50 mL, 950 mL of pure water was added to the stainless cup for washing. After repeating this washing 10 times, concentration was performed until the amount of the liquid became 50 mL.

The concentrated liquid was diluted with a mixed liquid of pure water and methanol (volume ratio of pure water and methanol: 60/40) to obtain a silver nanowire layer forming coating liquid.
Next, the coating liquid for forming the silver nanowire layer was applied to the cycloolefin polymer film. The coating amount of the coating liquid for forming the silver nanowire layer was such that the wet film thickness was 20 μm.
The sheet resistance of the silver nanowire layer after drying was 60 Ω/□. A non-contact type eddy current type resistance measuring instrument [trade name: EC-80P, manufactured by Napson Corporation] was used to measure the sheet resistance.
The silver nanowire contained in the coating liquid for forming the silver nanowire layer had a diameter of 17 nm and a length of 35 μm.

[Preparation of coating liquid for forming thermosetting resin layer]
<Materials A-1 to A-4>
The components were mixed so as to have the composition shown in Table 1 to prepare materials A-1 to A-4 which are coating liquids for forming a thermosetting resin layer.

<Materials A-5 to A-8>
The components were mixed so as to have the composition shown in Table 2 to prepare materials A-5 to A-8 which are coating solutions for forming a thermosetting resin layer.

[Preparation of coating liquid for forming non-thermosetting resin layer]
<Comparative material B-1>
Comparative components B-1 which is a non-thermosetting resin layer forming coating liquid (so-called resin layer forming coating liquid having no thermosetting property) were prepared by mixing the components so as to have the composition shown in Table 1. did.

<Comparative material B-2>
Each component was mixed so as to have the composition shown in Table 2 to prepare Comparative Material B-2 which is a non-thermosetting resin layer forming coating liquid (so-called resin layer forming coating liquid having no thermosetting property). did.

“-” in Tables 1 and 2 means that the corresponding component is not included.

The compounds N1 to N5, which are the binder polymers shown in Tables 1 and 2, are the compounds shown below.
In addition, the numerical value written together with each structural unit in the compounds N1 to N5 represents the content ratio (molar ratio) of each structural unit.

Compound N1: a resin having the structure shown below [weight average molecular weight: 21,000, acid value: 0.5 mmol/g, hydroxyl functional group concentration: 2.8 mmol/g, glass transition temperature: -5°C]

Compound N2: Resin having the structure shown below [weight average molecular weight: 5,500, acid value: 1.0 mmol/g, functional group concentration of blocked isocyanate group: 4.1 mmol/g, glass transition temperature: 20°C]

Compound N3: Resin having a structure shown below [weight average molecular weight: 23,000, acid value: 0.5 mmol/g, functional group concentration of blocked isocyanate group: 2.5 mmol/g, functional group concentration of hydroxyl group: 0.5 mmol /G, glass transition temperature: -1°C]

Compound N4: Resin having the structure shown below [weight average molecular weight: 12,000, acid value: 32 mgKOH/g]

Compound N5: Resin having the structure shown below [weight average molecular weight: 10,000, acid value: 47 mgKOH/g]

[Measurement of glass transition temperature of thermosetting resin layer]
The glass transition temperature of the thermosetting resin layer formed by using the materials A-5 to A-8 which are the coating liquid for forming the thermosetting resin layer was measured. The specific method is as follows.
Each of the materials A-5 to A-8 was spin-coated on a glass substrate under the conditions of 500 rpm and 20 seconds to form a coating film. Then, the formed coating film was dried at 100° C. for 1 minute using a hot plate to obtain a thermosetting resin layer. When the obtained thermosetting resin layer was scraped and analyzed by DSC (Differential scanning calorimetry), the glass transition temperature of the thermosetting resin layer was in the range of -10°C to 50°C. A differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. was used for the DSC analysis.

[Preparation of coating liquid for forming positive photosensitive resin layer]
<Material BP-1>
Each component was mixed so as to have the composition shown in Table 3 to prepare a material BP-1 which is a coating liquid for forming a positive photosensitive resin layer.

Compound D, which is a polymer shown in Table 3, is a compound shown below.
In addition, the numerical value written together with each structural unit in the compound D represents the content ratio (molar ratio) of each structural unit.

Compound D: Resin having the structure shown below [weight average molecular weight: 25,000]

Compound E, which is a photoacid generator shown in Table 3, is the compound shown below.

[Preparation of coating liquid for forming negative photosensitive resin layer]
<Material BN-1>
Each component was mixed so as to have the composition shown in Table 4 to prepare a material BN-1 which is a coating liquid for forming a negative photosensitive resin layer.

Compound B, which is the binder polymer described in Table 4, is the compound shown below.
In addition, the numerical value written together with each structural unit in the compound B represents the content ratio (molar ratio) of each structural unit.

Compound B: Resin having the structure shown below [weight average molecular weight: 20,000, acid value: 95 mgKOH/g]

The details of the following components shown in Table 4 are as shown below.
"Carboxyl group-containing monomer" [trade name: Aronix (registered trademark) TO-2349, manufactured by Toagosei Co., Ltd.]: mixture of pentafunctional ethylenically unsaturated compound and hexafunctional ethylenically unsaturated compound "Megafuck F551A [Product name: Megafac (registered trademark) F551A, manufactured by DIC Corporation]: Fluorine-based surfactant

[Preparation of photosensitive transfer material]
<Examples 1 to 4 and Examples 9 to 12, and Comparative Examples 1 and 3>
Coating liquid for forming a positive photosensitive resin layer using a slit-shaped nozzle on a temporary support (trade name: Lumirror (registered trademark) 16KS40, polyethylene terephthalate film, thickness: 16 μm, manufactured by Toray Industries, Inc.) Then, the material BP-1 was applied to form a coating film. The coating amount of the material BP-1 was such that the thickness of the layer after drying was 3 μm. The coating film was dried at a drying temperature of 100° C. to form a positive photosensitive resin layer.
Next, the coating liquid for forming the silver nanowire layer was applied onto the positive photosensitive resin layer using a slit-shaped nozzle at an application amount such that the wet film thickness was 20 μm to form a coating film. The coating film was dried at a drying temperature of 100° C. to form a silver nanowire layer (that is, a layer containing silver nanowires). The formed silver nanowire layer had a thickness of 100 nm.
Next, on the silver nanowire layer, a material which is a coating liquid for forming a thermosetting resin layer (that is, any of materials A-1 to A-8) or non-thermosetting selected according to the description in Table 5 A comparative material (that is, comparative material B-1 or B-2) which is a coating liquid for forming a functional resin layer was applied to form a coating film. The coating amounts of the materials A-1 to A-8 and the comparative materials B-1 and B-2 were such that the thickness of the layer after drying was the thickness shown in Table 5. The coating film was dried at a drying temperature of 100° C. to form a thermosetting resin layer or a non-thermosetting resin layer.
Next, a protective film [trade name: Lumirror (registered trademark) 16KS40, polyethylene terephthalate film, thickness: 16 μm, manufactured by Toray Industries, Inc.] was pressure-bonded onto the thermosetting resin layer or the non-thermosetting resin layer. ..
As described above, the photosensitive transfer materials of Examples 1 to 4 and Examples 9 to 12 and Comparative Examples 1 and 3 were prepared.

<Examples 5 to 8 and Examples 13 to 16 and Comparative Examples 2 and 4>
On the protective film [trade name: Lumirror (registered trademark) 16KS40, polyethylene terephthalate film, thickness: 16 μm, manufactured by Toray Industries, Inc.], a thermosetting property selected according to the description in Table 5 using a slit nozzle. A material that is a coating liquid for forming a resin layer (that is, any of materials A-1 to A-8) or a comparative material that is a coating liquid for forming a non-thermosetting resin layer (that is, comparative material B-1 or B- 2) was applied to form a coating film. The coating amounts of the materials A-1 to A-8 and the comparative materials B-1 and B-2 were such that the thickness of the layer after drying was the thickness shown in Table 5. The coating film was dried at a drying temperature of 100° C. to form a thermosetting resin layer or a non-thermosetting resin layer.
Next, a coating liquid for forming a silver nanowire layer is applied onto the thermosetting resin layer or the non-thermosetting resin layer using a slit-shaped nozzle in an application amount such that a wet film thickness is 20 μm, and then applied. A film was formed. The coating film was dried at a drying temperature of 100° C. to form a silver nanowire layer (that is, a layer containing silver nanowires). The formed silver nanowire layer had a thickness of 100 nm.
Next, the material BN-1 which is a coating liquid for forming a negative photosensitive resin layer was coated on the silver nanowire layer to form a coating film. The coating amount of the material BN-1 was such that the thickness of the layer after drying was 3 μm. The coating film was dried at a drying temperature of 100° C. to form a negative photosensitive resin layer.
Next, a temporary support [trade name: Lumirror (registered trademark) 16KS40, polyethylene terephthalate film, thickness: 16 μm, manufactured by Toray Industries, Inc.] was pressure-bonded onto the negative photosensitive resin layer to form Example 5. 8 to Examples 13 to 16 and Comparative Examples 2 and 4 were prepared.

[Preparation of multilayer body]
Using the photosensitive transfer materials of Examples 1 to 16 and Comparative Examples 1 to 4, a multilayer body was prepared according to the following procedure.
The photosensitive transfer material from which the protective film has been peeled off is attached to a transparent film substrate (cycloolefin polymer film, thickness: 38 μm, refractive index: 1.53) (hereinafter referred to as “laminating” in this paragraph). A multi-layer body was obtained.
The lamination process was performed using a vacuum laminator manufactured by MCK Co., Ltd. under the conditions of the transparent film substrate temperature: 40° C., the rubber roller temperature: 100° C., the linear pressure: 3 N/cm, and the conveying speed: 2 m/min. went. In the laminating process, the surface exposed by peeling the protective film from the photosensitive transfer material was brought into contact with the surface of the transparent film substrate.

[Preparation of transparent electrode pattern film (1)]
A transparent electrode pattern film was produced according to the following procedure using the above-mentioned multilayer bodies produced by using the photosensitive transfer materials of Examples 1 to 4 and Examples 9 to 12 and Comparative Examples 1 and 3.
Using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, the exposure mask (quartz exposure mask having a transparent electrode forming pattern) surface and the temporary support are brought into close contact with each other, and the temporary support is provided. The positive photosensitive resin layer was pattern-exposed through the body with an exposure amount of 100 mJ/cm ² (i-line).
After the temporary support was peeled off, development treatment was carried out at 32° C. for 60 seconds using a 1% by mass aqueous solution of sodium carbonate. After the development treatment, ultrapure water was sprayed from the ultrahigh pressure cleaning nozzle onto the transparent film substrate on which the pattern was formed to remove the residue on the transparent film substrate.
By the above operation, the thermosetting resin layer or the non-thermosetting resin layer, the silver nanowire layer, and the photosensitive resin layer were patterned.
Next, air was blown to the transparent film substrate from which the residue was removed to remove the moisture on the transparent film substrate, and then heat treatment was performed at 145° C. for 10 minutes to obtain a patterned substrate.
Next, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having a high pressure mercury lamp, the exposure amount of 400 mJ/cm ² (i-line) was applied to the positive type photosensitivity remaining on the patterned substrate. After exposing the resin layer, the positive photosensitive resin layer is removed by treatment with a 1% by mass aqueous solution of sodium carbonate at 32° C. for 60 seconds, and a transparent electrode having a patterned silver nanowire layer A pattern film (so-called circuit board) was produced.

[Preparation of transparent electrode pattern film (2)]
In the production of a transparent electrode pattern film using the above-mentioned multilayer body produced by using each of the photosensitive transfer materials of Examples 5 to 8 and Examples 13 to 16 and Comparative Examples 2 and 4, exposure was performed after heat treatment. Without using the negative resist removing solution [trade name: SH-303, manufactured by Kanto Kagaku Co., Ltd.], the cured product of the negative photosensitive resin layer is treated at 30° C. for 60 seconds. A transparent electrode pattern film (so-called circuit board) having a patterned silver nanowire layer was produced by the same procedure as in Example 1 except that the film was removed.

<Evaluation>
1. Peeling resistance The line and space pattern after removing the cured product of the positive type photosensitive resin layer or the negative type photosensitive resin layer was observed using an optical microscope to confirm the presence or absence of peeling of the pattern. The evaluation criteria are shown below.
If the evaluation result was "A" or "B", it was judged to be within the practically acceptable range.
In the following evaluation criteria, “A” indicates the case where the peel resistance of the pattern is the best, and “C” indicates the case where the peel resistance of the pattern is the poorest.

-Evaluation criteria-
A: A line and space pattern of 50 μm was resolved, and no peeling of the pattern was confirmed.
B: A line and space pattern of 50 μm was resolved, but peeling was confirmed in some patterns.
C: Most of the 50 μm line-and-space pattern was peeled off.

2. Change in sheet resistance value before and after the wet heat test The sheet resistance of the transparent electrode pattern film prepared above was measured using a non-contact type eddy current resistance measuring instrument [trade name: EC-80P, manufactured by Napson Corporation]. Was measured. The obtained measured value was defined as "sheet resistance value before wet heat test".
Next, the transparent electrode pattern film whose sheet resistance value was measured was allowed to stand for 300 hours in an environment of an atmospheric temperature of 65° C. and 90% RH. Then, the sheet resistance of the transparent electrode pattern film after standing was measured in the same manner as above. The obtained measured value was defined as "sheet resistance value after wet heat test".
Using the “sheet resistance value before the wet heat test” and the “sheet resistance value after the wet heat test”, the rate of increase in the sheet resistance value before and after the wet heat test was calculated based on the following calculation formula.
Increase rate of sheet resistance before and after the wet heat test (unit: %) = [[Sheet resistance value after wet heat test (unit: Ω/□)]-[Sheet resistance value before wet heat test (unit: Ω/□)] ]/[Sheet resistance value before wet heat test (unit: Ω/□)]×100

Then, based on the rate of increase in sheet resistance, the change in sheet resistance before and after the wet heat test was evaluated according to the following evaluation criteria.
If the evaluation result was "A" or "B", it was judged to be within the practically acceptable range.
In the following evaluation criteria, “A” indicates the case where the durability is the best, and “C” indicates the case where the durability is the worst.

-Evaluation criteria-
A: The rate of increase is less than 20%.
B: The rate of increase is 20% or more and less than 50%.
C: The rate of increase is 50% or more.

3. Contact Resistance of Thermosetting Resin Layer The contact resistance of the thermosetting resin layer was measured by the TLM (Transmission Line Model) method. The specific method is as follows.
Seven coppers arranged on the substrate (cycloolefin polymer film, thickness: 38 μm, refractive index: 1.53) at intervals of 2 mm, 4 mm, 6 mm, 8 mm, 12 mm, and 20 mm in parallel and independently of each other. An electrode (thickness: 300 nm, width: 500 μm) was formed.
Next, the photosensitive transfer materials of Examples 1 to 8 from which the protective film was peeled off were adhered to the seven copper electrodes, respectively, to form a silver nanowire layer on the copper electrodes via a thermosetting resin layer. A test body having a laminated structure was prepared.
In a plan view of each of the test bodies, the silver nanowire layer was arranged so as to cross the seven copper electrodes, and the angle formed by each copper electrode and the silver nanowire layer was 90°.
After measuring the resistance between adjacent copper electrodes, the contact resistance of the thermosetting resin layer was obtained by plotting the relationship between the resistance (vertical axis) and the distance (horizontal axis) between the copper electrodes. A resistivity meter [trade name: Loresta GP, manufactured by Mitsubishi Chemical Analytech Co., Ltd.] was used to measure the resistance between the copper electrodes.
As a result, the contact resistance of the thermosetting resin layer of each of the photosensitive transfer materials of Examples 1 to 8 was 200Ω or less.
The sample was subjected to a heat treatment at 145° C. for 10 minutes to cure the thermosetting resin layer, and the contact resistance was measured in the same manner. The contact resistance of each of the layers containing the resin was 200 Ω or less.

4. Sensor operation confirmation Using the photosensitive transfer materials of Examples 1 to 16 on the cycloolefin polymer film (thickness: 38 μm, refractive index: 1.53) having a copper electrode on the surface as a takeout wiring, the method described above According to the procedure, a transparent electrode pattern was formed to manufacture a capacitance type touch sensor. The touch sensor was manufactured by a method similar to the method described in Japanese Patent No. 6173831. When the sensor operation was confirmed for the manufactured touch sensors, they all operated normally.

As shown in Table 5, according to the photosensitive transfer materials of Examples 1 to 16 having a temporary support, a photosensitive resin layer, a silver nanowire layer, and a thermosetting resin layer in this order, It was revealed from the above that a conductive pattern that is difficult to peel off can be formed. It was also confirmed that the photosensitive transfer materials of Examples 1 to 16 were capable of producing transparent electrode pattern films having excellent durability, in which the sheet resistance value did not easily increase even when exposed to a humid heat environment.

On the other hand, the photosensitive materials of Comparative Examples 1 to 4 having a temporary support, a photosensitive resin layer, a silver nanowire layer, and a non-thermosetting resin layer (that is, a resin layer having no thermosetting property) in this order. It was confirmed that the conductive pattern formed by using the conductive transfer material was more easily peeled from the substrate than the conductive patterns formed by using the photosensitive transfer materials of Examples 1 to 16. In addition, the transparent electrode pattern films produced using the photosensitive transfer materials of Comparative Examples 1 to 4 were more durable than the transparent electrode pattern films produced using the photosensitive transfer materials of Examples 1 to 16. It was confirmed that it was inferior in sex.

The disclosure of Japanese Patent Application No. 2018-246221 filed on Dec. 27, 2018 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards mentioned in this specification are specifically and individually referred to as if each individual document, patent application, and technical standard were incorporated by reference. To the extent, incorporated herein by reference.

Claims

A temporary support,
A photosensitive resin layer,
A layer containing silver nanowires,
A thermosetting resin layer,
A photosensitive transfer material having in this order.
The photosensitive transfer material according to claim 1, wherein the thermosetting resin layer contains a blocked isocyanate compound.
The photosensitive transfer material according to claim 2, wherein the blocked isocyanate compound has at least one of a hydroxyl group and an acid group.
The photosensitive transfer material according to claim 2 or 3, wherein the thermosetting resin layer further contains a compound having at least one of a hydroxyl group and an acid group.
The photosensitive transfer material according to any one of claims 1 to 4, wherein the thickness of the thermosetting resin layer is 1 nm to 300 nm.
The photosensitive transfer material according to any one of claims 1 to 5, wherein the thermosetting resin layer has a contact resistance of 200Ω or less.
Board,
A layer containing a resin that is thermoset,
A layer containing silver nanowires,
A laminated body having in this order.
The layer containing the thermosetting resin is a layer formed by curing a thermosetting resin layer that is a transfer layer, and the layer containing the silver nanowires is a transfer layer. Stack of.
The laminate according to claim 7 or 8, wherein the thermosetting resin is a crosslinked resin having a urethane bond.
The layered product according to any one of claims 7 to 9, wherein a thickness of the layer containing the thermosetting resin is 1 nm to 300 nm.
The layered product according to any one of claims 7 to 10, wherein the layer containing the thermosetting resin has a contact resistance of 200Ω or less.
A touch panel having the laminate according to any one of claims 7 to 11.
A step of bonding the photosensitive transfer material according to any one of claims 1 to 6 and a substrate;
Pattern-exposing a photosensitive resin layer in the photosensitive transfer material,
Developing the photosensitive transfer material that has undergone the pattern exposure to form a pattern,
A step of thermosetting the thermosetting resin layer,
A method of manufacturing a patterned substrate including:
A step of bonding the photosensitive transfer material according to any one of claims 1 to 6 and a substrate;
Pattern-exposing a photosensitive resin layer in the photosensitive transfer material,
Developing the photosensitive transfer material that has undergone the pattern exposure to form a pattern,
A step of thermosetting the thermosetting resin layer,
In the pattern, a step of removing the photosensitive resin layer or a cured product of the photosensitive resin layer,
A method for manufacturing a circuit board including:
A method for manufacturing a touch panel including the method for manufacturing a circuit board according to claim 14.