JP7389071B2 - Method for forming conductive pattern, method for manufacturing metal mesh sensor, and method for manufacturing structure - Google Patents

Description

The present disclosure relates to a method for forming a conductive pattern, a method for manufacturing a metal mesh sensor, and a method for manufacturing a structure.

A conductive film in which a patterned conductive layer is formed on a flexible plastic substrate can be used in various sensors such as pressure sensors and biosensors, printed circuit boards, solar cells, capacitors, electromagnetic shielding materials, touch panels, antennas, heaters, etc. It is widely used in various fields.
Manufacturing electronic devices on flexible films allows the creation of large-area, lightweight, and thin-film devices, and has the advantage of being flexible, but continuous production using a roll-to-roll process is also an advantage. There are great expectations from the perspective of cost reduction and mass supply.
Furthermore, if fine and complex metal patterns and wiring can be made thinner to a level of several micrometers or less that is difficult to see, it is expected that the use and range of applications will expand by adding conductive functionality without compromising the design.
Research on so-called printed electronics (PE) has traditionally been carried out in which electronic devices are manufactured by applying or printing insulating ink, semiconductor ink, conductive ink, etc. onto films using printing technology or inkjet technology. It's progressing.

Further, as a conventional method for forming a conductive pattern, the method described in Patent Document 1 is known.
Specifically, in Patent Document 1, a positive photoresist layer is formed on a substrate using a positive photoresist composition containing a novolac type phenolic resin, and the positive photoresist layer is subjected to exposure and development treatment. A concave pattern is formed in the positive photoresist layer by performing the above steps, and the positive photoresist layer with the concave pattern formed thereon is exposed to light over the entire surface, and then the concave pattern is filled with a conductive paste. A method of forming a conductive layer pattern on a substrate by drying and further removing the positive photoresist layer by development is disclosed.

Japanese Patent Application Publication No. 7-94848

An object of an embodiment of the present invention is to provide a method for forming a conductive pattern that can reduce the occurrence of pattern defects.
Another problem to be solved by other embodiments of the present invention is to provide a method for manufacturing a structure that can reduce the occurrence of pattern defects.

Means for solving the above problems include the following aspects.
<1> A step of preparing a roll body by winding up a laminate having a first film, a photosensitive resin layer, and a second film, a step of unwinding the laminate from the roll body, and a step of unwinding the laminate from the roll body. a step of exposing the laminate to light; a step of developing the exposed laminate to form a resin pattern; A method for forming a conductive pattern, the method comprising the steps of: forming a conductive pattern, and removing the resin pattern.
<2> The method for forming a conductive pattern according to <1>, wherein at least one of the first film and the second film has particles.
<3> The method for forming a conductive pattern according to <1> or <2>, wherein in the step of performing the exposure, a mask is brought into contact with the second film, and the exposure is performed through the second film.
<4> The method for forming a conductive pattern according to <1> or <2>, wherein in the step of performing the exposure, a mask is brought into contact with the first film, and the exposure is performed through the first film.
<5> The method for forming a conductive pattern according to <1> or <2>, wherein in the step of exposing, the second film is peeled off, and a mask is brought into contact with the photosensitive resin layer for exposure.
<6> The method for forming a conductive pattern according to any one of <1> to <5>, wherein the first film has a thickness of 50 μm or less.
<7> The method for forming a conductive pattern according to any one of <1> to <6>, wherein the second film has a thickness of 50 μm or less.
<8> The method for forming a conductive pattern according to any one of <1> to <7>, wherein the first film has a haze value of 1.0% or less.
<9> The method for forming a conductive pattern according to any one of <1> to <8>, wherein the second film has a haze value of 1.0% or less.
<10> The conductive pattern according to any one of <1> to <9>, wherein at least one of the first film and the second film is a transparent film with a total light transmittance of 85% or more. How to form.
<11> The method for forming a conductive pattern according to any one of <1> to <10>, wherein both the first film and the second film are insulating films.
<12> The method for forming a conductive pattern according to any one of <1> to <11>, wherein the first film contains an ultraviolet absorber.
<13> The method for forming a conductive pattern according to any one of <1> to <12>, wherein the photosensitive resin layer is a positive photosensitive resin layer.
<14> The conductive pattern according to <13>, wherein the positive photosensitive resin layer contains a polymer having a polar group protected with a protecting group that is deprotected by the action of an acid, and a photoacid generator. Formation method.
<15> The method for forming a conductive pattern according to <14>, wherein the polar group protected with a protecting group that is deprotected by the action of an acid is a group in which the polar group is protected in the form of an acetal.
<16> The method for forming a conductive pattern according to <14> or <15>, wherein the polymer contains a structural unit represented by any of the following formulas A1 to A3.

In formula A1, R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, or an aryl group. However, at least one of R ¹¹ and R ¹² represents an alkyl group or an aryl group. R ¹³ represents an alkyl group or an aryl group. R ¹⁴ represents a hydrogen atom or a methyl group. X ¹ represents a single bond or a divalent linking group. R ¹⁵ represents a substituent. n represents an integer from 0 to 4. Note that R ¹¹ or R ¹² and R ¹³ may be connected to each other to form a cyclic ether.
In formula A2, R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group, or an aryl group. However, at least one of R ²¹ and R ²² represents an alkyl group or an aryl group. R ²³ represents an alkyl group or an aryl group. ^R24 each independently represents a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group, or a cyclo Represents an alkyl group. m represents an integer from 0 to 3. R ²¹ or R ²² and R ²³ may be linked to each other to form a cyclic ether.
In formula A3, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group, or an aryl group. However, at least one of R ³¹ and R ³² represents an alkyl group or an aryl group. R ³³ represents an alkyl group or an aryl group. R ³⁴ represents a hydrogen atom or a methyl group. X ⁰ represents a single bond or a divalent linking group. Note that R ³¹ or R ³² and R ³³ may be connected to each other to form a cyclic ether.

<17> The method for forming a conductive pattern according to any one of <1> to <16>, wherein the photosensitive resin layer has a layer thickness of 3 μm or less.
<18> The method for forming a conductive pattern according to any one of <1> to <17>, wherein the photosensitive resin layer has a layer thickness of 1 μm or less.
<19> The method for forming a conductive pattern according to any one of <1> to <18>, wherein the conductive pattern is formed by a sputtering method or a vapor deposition method.
<20> The method for forming a conductive pattern according to any one of <1> to <19>, wherein the conductive pattern is formed by printing or coating with a silver-containing ink or a copper-containing ink.

<21> On one side of the first film, a first photosensitive resin layer and a second film, on the other side of the first film, a second photosensitive resin layer, and a step of preparing a roll body by winding up a laminate having a third film, a step of unwinding the laminate from the roll body, and a step of rolling up the laminate having the third film, and a step of unwinding the laminate from the roll body. a step of exposing the surface to light, a step of developing the exposed laminate to form a resin pattern, and a conductive layer containing metal in at least a part of the portion of the first film where the resin pattern is not formed. A method for forming a conductive pattern, comprising a step of forming a conductive pattern and a step of removing the resin pattern.
<22> The method for forming a conductive pattern according to <21>, wherein at least one of the first film, the second film, and the third film has particles.
<23> In the step of performing the exposure, a mask is brought into contact with the second film or the third film, and the conductive pattern according to <21> or <22> is exposed through the second film. Formation method.
<24> In the step of performing the exposure, the conductive pattern according to <21> or <22>, in which the second film or the third film is peeled off, and a mask is brought into contact with the photosensitive resin layer to perform the exposure. How to form.
<25> The method for forming a conductive pattern according to any one of <21> to <24>, wherein the first film has a thickness of 50 μm or less.
<26> The conductive pattern according to any one of <21> to <25>, wherein the second film has a thickness of 50 μm or less, and the third film has a thickness of 50 μm or less. Formation method.
<27> The method for forming a conductive pattern according to any one of <21> to <26>, wherein the first film has a haze value of 1.0% or less.
<28> Any one of <21> to <27>, wherein the second film has a haze value of 1.0% or less, and the third film has a haze value of 1.0% or less. The method for forming a conductive pattern described in .
<29> Any one of <21> to <28>, wherein at least one of the first film, the second film, and the third film is a transparent film with a total light transmittance of 85% or more. The method for forming a conductive pattern described in .
<30> The method for forming a conductive pattern according to any one of <21> to <29>, wherein the first film, the second film, and the third film are all insulating films. .
<31> The method for forming a conductive pattern according to any one of <21> to <30>, wherein the first film contains an ultraviolet absorber.
<32> The conductive pattern according to any one of <21> to <31>, wherein both the first photosensitive resin layer and the second photosensitive resin layer are positive photosensitive resin layers. How to form.
<33> The conductive pattern according to <32>, wherein the positive photosensitive resin layer contains a polymer having a polar group protected with a protecting group that is deprotected by the action of an acid, and a photoacid generator. Formation method.
<34> The method for forming a conductive pattern according to <33>, wherein the polar group protected with a protecting group that is deprotected by the action of an acid is a group in which the acid group is protected in the form of an acetal.
<35> The method for forming a conductive pattern according to <33> or <34>, wherein the polymer contains a structural unit represented by any of the following formulas A1 to A3.

In formula A1, R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, or an aryl group. However, at least one of R ¹¹ and R ¹² represents an alkyl group or an aryl group. R ¹³ represents an alkyl group or an aryl group. R ¹⁴ represents a hydrogen atom or a methyl group. X ¹ represents a single bond or a divalent linking group. R ¹⁵ represents a substituent. n represents an integer from 0 to 4. Note that R ¹¹ or R ¹² and R ¹³ may be connected to each other to form a cyclic ether.
In formula A2, R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group, or an aryl group. However, at least one of R ²¹ and R ²² represents an alkyl group or an aryl group. R ²³ represents an alkyl group or an aryl group. ^R24 each independently represents a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group, or a cyclo Represents an alkyl group. m represents an integer from 0 to 3. R ²¹ or R ²² and R ²³ may be linked to each other to form a cyclic ether.
In formula A3, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group, or an aryl group. However, at least one of R ³¹ and R ³² represents an alkyl group or an aryl group. R ³³ represents an alkyl group or an aryl group. R ³⁴ represents a hydrogen atom or a methyl group. X ⁰ represents a single bond or a divalent linking group. Note that R ³¹ or R ³² and R ³³ may be connected to each other to form a cyclic ether.

<36> The method for forming a conductive pattern according to any one of <21> to <35>, wherein the first photosensitive resin layer and the second photosensitive resin layer have the same composition. .
<37> The conductive pattern according to any one of <21> to <36>, wherein the first photosensitive resin layer and the second photosensitive resin layer each have a layer thickness of 3 μm or less. Formation method.
<38> The conductive pattern according to any one of <21> to <37>, wherein the first photosensitive resin layer and the second photosensitive resin layer each have a layer thickness of 1 μm or less. Formation method.
<39> In the step of exposing, the conductive material according to any one of <21> to <38>, wherein the first photosensitive resin layer and the second photosensitive resin layer are exposed simultaneously. How sexual patterns are formed.
<40> The method for forming a conductive pattern according to any one of <21> to <39>, wherein the conductive pattern is formed by a sputtering method or a vapor deposition method.
<41> The method for forming a conductive pattern according to any one of <21> to <40>, wherein the conductive pattern is formed by printing or coating with a silver-containing ink or a copper-containing ink.

<42> A method for manufacturing a metal mesh sensor, including the method for forming a conductive pattern according to any one of <1> to <41>.
<43> With respect to the first film having the conductive pattern obtained by the method for forming a conductive pattern according to any one of <1> to <41>, the first film and the conductive pattern a step of forming a negative photosensitive resin layer on the photosensitive pattern, a step of exposing the negative photosensitive resin layer through the first film, and developing the negative photosensitive resin layer irradiated with light. A method for manufacturing a structure comprising: forming a resin pattern N on the first film; and forming a pattern M in a region defined by the conductive pattern and the resin pattern N. .

According to one embodiment of the present invention, it is possible to provide a method for forming a conductive pattern that can reduce the occurrence of pattern defects.
Further, according to another embodiment of the present invention, it is possible to provide a method for manufacturing a structure that can reduce the occurrence of pattern defects.

FIG. 2 is a schematic diagram of a conductive pattern formed by a method for forming a conductive pattern according to the present disclosure. FIG. 2 is a schematic diagram showing an example of a laminate suitable for use in the present disclosure. It is a schematic diagram which shows roughly a preferable example of the process of exposing a laminated body. It is a schematic diagram which shows a preferable example of the resin pattern formed after image development. It is a schematic diagram which shows a preferable example of the laminated body which has a conductive pattern before the resin pattern is removed. It is a schematic diagram which shows roughly a preferable example of the process of removing a resin pattern.

The contents of the present disclosure will be explained below. Note that although the description will be made with reference to the attached drawings, reference numerals may be omitted in some cases.
Furthermore, in this specification, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as lower and upper limits.
Moreover, in this specification, "(meth)acrylic" represents both or either of acrylic and methacrylic, and "(meth)acrylate" represents both or either of acrylate and methacrylate.
Furthermore, in the present specification, if there are multiple substances corresponding to each component in the composition, the amount of each component in the composition is the total amount of the corresponding substances present in the composition, unless otherwise specified. means quantity.
In this specification, the term "step" is used not only to refer to an independent step but also to include a step in which the intended purpose of the step is achieved even if the step cannot be clearly distinguished from other steps.
In the description of groups (atomic groups) in this specification, descriptions that do not indicate substituted or unsubstituted include those with no substituents as well as those with substituents. For example, the term "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. In addition, the light used for exposure generally includes active rays (active energy rays) such as the bright line spectrum of mercury lamps, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams. Can be mentioned.
Further, the chemical structural formulas in this specification may be written as simplified structural formulas in which hydrogen atoms are omitted.
In the present disclosure, "mass %" and "weight %" have the same meaning, and "mass parts" and "weight parts" have the same meaning.
Furthermore, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
In addition, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) in this disclosure are determined using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all product names manufactured by Tosoh Corporation). The molecular weight was detected using a gel permeation chromatography (GPC) analyzer using a solvent THF (tetrahydrofuran) and a differential refractometer, and was calculated using polystyrene as a standard substance.

(Method for forming conductive pattern)
A method for forming a conductive pattern according to the present disclosure includes a step of preparing a roll body by winding up a laminate having a first film, a photosensitive resin layer, and a second film, a step of exposing the unrolled laminate to light, a step of developing the exposed laminate to form a resin pattern, and forming the resin pattern on the first film. The method includes a step of forming a conductive pattern containing metal on at least a portion of the uncontained portion, and a step of removing the resin pattern.

A photolithography method using light can stably form a pattern of about several μm by projecting an optical intensity distribution through a mask onto a resist. However, even if a resist pattern can be formed, there are cases in which the resolution of the resist film decreases or the pattern transfer becomes unstable in the subsequent etching process. In particular, in the etching method, which is commonly used as a process method for forming metal patterns on flexible films and is based on a roll-to-roll process, local variations in temperature, agitation fluidity, etc. caused by the liquid process are Problems include inducing defects and increasing variation in line width linearity.
In addition, it has been found that when the conventional conductive pattern formation method described in Patent Document 1 is continuously produced using a roll-to-roll process, there is a problem in that pattern defects occur frequently. The inventor discovered this.
As a result of extensive studies, the inventors of the present invention have found that by adopting the above configuration, it is possible to provide a method for forming a conductive pattern that can reduce the occurrence of pattern defects.
In the method for forming a conductive pattern according to the present disclosure, the laminate is unwound from a roll body formed by winding up a laminate having a first film, a photosensitive resin layer, and a second film. The laminate is exposed to light and developed, and further, a conductive pattern containing metal is formed on at least a portion of the first film where the resin pattern is not formed, and the resin pattern is removed. . As described above, by using a laminate having a first film, a photosensitive resin layer, and a second film, the exposed pattern shape is stabilized and the resin pattern on the first film is formed. It is estimated that by forming a conductive pattern containing metal in the areas where the conductive pattern is not formed, the shape stability and defect suppression of the conductive pattern are excellent, and the occurrence of pattern defects can be reduced.

1 to 6 are schematic diagrams showing a preferred example of a method for forming a conductive pattern according to the present disclosure. Note that in each figure, components indicated by the same reference numerals indicate the same components. FIG. 1 is a schematic diagram of a conductive pattern formed by a method for forming a conductive pattern according to the present disclosure.
The conductive substrate 50 includes a substrate (first film) 1 and a patterned conductive layer (conductive pattern) 8A disposed on the substrate 1.
FIG. 2 is a schematic diagram showing an example of a laminate preferably used in the present disclosure.
The laminate 20 shown in FIG. 2 includes a substrate (first film) 1, a photosensitive resin layer 3 on the substrate 1, and a cover film (second film) 5.
FIG. 3 is a schematic diagram schematically showing a preferable example of the step of exposing the laminate.
In FIG. 3, a mask 6 having an opening 6a is placed in close contact with the cover film 5, and the photosensitive resin layer 3 of the laminate 20 is exposed in a pattern through the cover film 5.
After exposure, the cover film 5 is peeled off and development is performed to obtain a laminate 30 shown in FIG. 4.

FIG. 4 is a schematic diagram showing a preferable example of a resin pattern formed after development.
As shown in FIG. 4, the developed laminate 30 includes a substrate 1 and a photosensitive resin layer (resin pattern) 3A disposed on the substrate 1 and having an opening 7 passing through the layer. That is, the photosensitive resin layer 3A has an opening 7 through which the substrate 1 is exposed. When the photosensitive resin layer is positive type, the position of the opening 7 that penetrates the photosensitive resin layer 3A is the same as the position of the opening (opening 6a in FIG. 3) of the mask pattern used during exposure. Match. That is, the photosensitive resin layer 3A has an opening 7 at a position corresponding to the opening 6a of the mask used during exposure.

FIG. 5 is a schematic diagram showing a preferred example of a laminate having a conductive pattern before the resin pattern is removed.
The laminate 40 in FIG. 5 has a conductive composition layer 8A made of a conductive composition in the opening 7 of the photosensitive resin layer 3A. Note that when supplying the conductive composition to the openings 7 of the photosensitive resin layer 3A, the conductive composition does not adhere to areas other than the openings 7 (for example, the top surface of the photosensitive resin layer 3A) as shown in FIG. Good too.

FIG. 6 is a schematic diagram schematically showing a preferable example of the step of removing the resin pattern.
As shown in FIG. 6, in the step of removing the resin pattern, a preferred embodiment is exposure (preferably the entire surface exposure) from the surface of the substrate 1 opposite to the photosensitive resin layer 3A (the back surface of the substrate 1). . By the above exposure, the acid-decomposable groups in the acid-decomposable resin in the exposed photosensitive resin layer 3A are deprotected by the action of the acid, and the solubility in the alkaline stripping solution increases. That is, the polarity of the photosensitive resin layer 3A changes. By removing the exposed photosensitive resin layer 3A using, for example, a stripping solution, the conductive composition layer on the photosensitive resin layer 3A can also be removed together with the photosensitive resin layer 3A.
By the above removal, the conductive pattern shown in FIG. 1 is obtained.

In the method for forming a conductive pattern according to the present disclosure, the laminate has a first photosensitive resin layer and a second film on one side of the first film, and It is preferable that the laminate has a second photosensitive resin layer and a third film on the other side.
In the case of the above-mentioned laminate, the method for forming a conductive pattern according to the present disclosure includes a first photosensitive resin layer and a second film on one surface of the first film; a step of preparing a roll body by winding up a laminate having a second photosensitive resin layer and a third film on the other side of the film; a step of unwinding the laminate from the roll body; A step of exposing one or both surfaces of the unrolled laminate, a step of developing the exposed laminate to form a resin pattern, and a step of forming the resin on the first film. It is preferable to include a step of forming a conductive pattern containing metal on at least a part of the portion where no pattern is formed, and a step of removing the resin pattern.

Each step will be explained in detail below.

<Preparation process>
The method for forming a conductive pattern according to the present disclosure includes a step of preparing a roll body by winding up a laminate having a first film, a photosensitive resin layer, and a second film (also referred to as a "preparation step"). .)including.
It is preferable that the laminate has a first film, a photosensitive resin layer, and a second film in this order.
Details of the laminate including the first film, the photosensitive resin layer, and the second film will be described later.
Further, the laminate has a first photosensitive resin layer and a second film on one side of the first film, and a second photosensitive resin layer on the other side of the first film. It is preferable that the laminate is a laminate having a polyurethane resin layer and a third film.
A laminate further including a first photosensitive resin layer, a second photosensitive resin layer, and a third film will also be described later.

In the preparation step, a roll body that has already been wound up may be prepared, or a roll body may be produced by winding up the laminate.
There are no particular restrictions on the method for producing a roll body by winding up the above-mentioned laminate, and a roll body can be produced by a known winding method, such as a method applied to a roll-to-roll method. It will be done.
Moreover, the length in the longitudinal direction and the width (length in the lateral direction) of the laminate to be rolled up are not particularly limited, and can be appropriately selected as desired.
Furthermore, the roll body may be a roll body that is wound so that the first film side of the laminate is on the outside, or a roll body that is wound so that the second film side of the laminate is on the outside. It may be.

<Unwinding process>
The method for forming a conductive pattern according to the present disclosure includes a step of unwinding the laminate from the roll body (also referred to as an "unwinding step").
The method for unwinding the laminate from the roll body is not particularly limited, and the roll body can be produced by a known winding method, such as a method applied to a roll-to-roll method.
Further, the unwinding in the unwinding step may be performed continuously or intermittently, and may be selected as appropriate depending on each step after the unwinding step, such as the exposure step described later. can.
Furthermore, the unwinding speed is not particularly limited and can be performed at any desired speed.

<Exposure process>
The method for forming a conductive pattern according to the present disclosure includes a step of exposing the unrolled laminate to light (also referred to as an "exposure step").
The exposure in the exposure step is preferably patterned exposure (pattern exposure).
The detailed arrangement and specific size of the pattern in pattern exposure are not particularly limited. It is preferable that at least a part of the pattern (preferably the electrode pattern of the touch panel and/or the lead-out wiring part) includes a thin line with a width of 20 μm or less, and more preferably a thin line with a width of 10 μm or less. The display quality of a display device (for example, a touch panel) equipped with an input device having circuit wiring manufactured by the circuit wiring manufacturing method can be improved, and the area occupied by the lead wiring can be reduced.
In addition, when the photosensitive resin layer is a positive photosensitive resin layer, the unexposed part of the photosensitive resin layer becomes a resin pattern described later, and when the photosensitive resin layer is a negative photosensitive resin layer, In this case, the exposed portion of the photosensitive resin layer becomes a resin pattern to be described later.

The light source used for exposure is not particularly limited as long as it irradiates light with a wavelength that can expose the photosensitive resin layer (for example, 365 nm or 405 nm), and can be appropriately selected and used. Examples of the light source include an ultra-high-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a laser, and an LED (Light Emitting Diode).

The exposure amount is not particularly limited as long as a resin pattern can be formed, but it is preferably from 5 mJ/cm ² to 200 mJ/cm ² , more preferably from 10 mJ/cm ² to 100 mJ/cm ² .

In the exposure step, exposure may be performed from the first film side of the laminate through the first film, or exposure may be performed from the second film side of the laminate through the second film. Alternatively, exposure may be performed after peeling off the first film or the second film of the laminate.
When exposing after peeling off the first film or the second film, the mask and the photosensitive resin layer may be brought into contact with each other for exposure, or the mask and the photosensitive resin layer may be brought into close proximity without contacting each other. It may also be exposed to light.
When exposing through the first film or the second film, the mask and the first film or the second film may be brought into contact with each other, or the mask and the first film or the second film may be exposed. Exposure may be performed by bringing the film close to the film without contacting it. In order to prevent mask contamination due to contact between the photosensitive resin layer and the mask, and to avoid the influence of foreign matter adhering to the mask on exposure, pattern exposure is performed without peeling off the first film or the second film. It is preferable.

That is, in the step of performing the exposure, it is preferable to perform it in one of the following modes.
R1: In the step of performing the exposure, preferably a mask is used on the second film and the exposure is performed through the second film, more preferably a mask is brought into contact with the second film, A mode in which exposure is performed through the second film.
R2: In the step of performing the exposure, preferably a mask is used on the first film and the exposure is performed through the first film, more preferably a mask is brought into contact with the first film, A mode in which exposure is performed through the first film R3: In the step of performing the exposure, preferably, a mode in which the second film is peeled off and the photosensitive resin layer is exposed to light using a mask, more preferably , an embodiment in which the second film is peeled off and a mask is brought into contact with the photosensitive resin layer for exposure.

The laminate may have a first photosensitive resin layer and a second film on one side of the first film, and a second photosensitive resin layer on the other side of the first film. When using a laminate having a photosensitive resin layer and a third film, the first photosensitive resin layer and the second photosensitive resin layer may be exposed separately or simultaneously. However, it is preferable to perform the exposure at the same time.
That is, in the case of the above-mentioned laminate, the exposure step is preferably a step of exposing one or both surfaces of the unrolled laminate; More preferably, the step is one in which both surfaces of the substrate are exposed to light.
In addition, in the exposure step, the exposure of the first photosensitive resin layer, the second film, the second photosensitive resin layer, and the third film is performed using the photosensitive resin layer described above, and the same as the preferred embodiments of the second film.

The exposure method is a contact exposure method in the case of a contact exposure method, a proximity exposure method in the case of a non-contact exposure method, a lens-based or mirror-based projection exposure method, or a direct exposure method using an exposure laser, etc., as appropriate. It can be used selectively.
In the case of a lens-based or mirror-based projection exposure method, an exposure machine having an appropriate lens numerical aperture (NA) can be used depending on the required resolving power and depth of focus.
In the case of a direct exposure method, the photosensitive resin layer may be directly exposed to light, or the photosensitive resin layer may be subjected to reduction projection exposure through a lens.
Moreover, exposure may be performed not only under atmospheric pressure but also under reduced pressure or vacuum. Alternatively, exposure may be performed with a liquid such as water interposed between the light source and the photosensitive resin layer.

<Developing process>
The method for forming a conductive pattern according to the present disclosure includes a step (also referred to as a "developing step") of developing the exposed laminate to form a resin pattern.
The pattern shape of the resin pattern formed in the above-mentioned development step is not particularly limited and may be appropriately selected as desired.
The resin pattern is preferably a resin pattern having an opening in order to more effectively exhibit the effects of the present disclosure.
In the conductive pattern forming step described below, it is preferable that a conductive pattern is formed in at least a portion of the portion where the resin pattern is not formed, and that a conductive pattern is formed in the opening.
The shape of the opening is preferably linear, and its width is more preferably 100 μm or less, even more preferably 70 μm or less, and particularly preferably 0.5 μm or more and 20 μm or less.
Further, the resin pattern is preferably a resin pattern having a tapered shape from the viewpoint of suppressing pattern defects in the resulting conductive pattern.
The thickness of the resin pattern is preferably 30 μm or less, more preferably 10 μm or less, even more preferably 5 μm or less, and particularly preferably 3 μm or less. Further, the lower limit of the thickness of the resin pattern is preferably 0.5 μm or more, more preferably 1 μm or more.

The laminate may have a first photosensitive resin layer and a second film on one side of the first film, and a second photosensitive resin layer on the other side of the first film. When using a laminate having a photosensitive resin layer and a third film, the first photosensitive resin layer and the second photosensitive resin layer may be developed separately or simultaneously. However, it is preferable to perform development at the same time.
That is, in the case of the laminate, the exposure step is preferably a step of developing one or both surfaces of the exposed laminate to form a resin pattern; More preferably, the step is one in which both surfaces of the laminate are developed to form resin patterns.

The developing method is not particularly limited as long as the exposed photosensitive resin layer can be developed, and any known method can be used. Among these, a developing method using a developer is preferred.
The developer is not particularly limited, but an alkaline developer is preferably used.
The alkaline developer is preferably an alkaline aqueous developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol/L (liter) to 5 mol/L. The alkaline aqueous developer may further contain a water-soluble organic solvent, a surfactant, and the like.
As the alkaline aqueous developer, for example, the developer described in paragraph 0194 of International Publication No. 2015/093271 is preferable.

There is no particular restriction on the developing method, and any of paddle development, shower development, spin development, dip development, etc. may be used. Here, explaining shower development, the exposed portion can be removed by spraying an alkaline developer onto the exposed photosensitive resin layer using a shower. Further, after development, it is also preferable to spray a cleaning agent or the like in a shower and remove development residues while rubbing with a brush or the like. The temperature of the alkaline developer is preferably 20°C to 40°C.

The method for forming a conductive pattern according to the present disclosure may further include a post-bake step of heat-treating the photosensitive resin layer after development.
Post-baking is preferably carried out in an environment of 8.1 kPa to 121.6 kPa, more preferably carried out in an environment of 50.66 kPa or higher. On the other hand, it is more preferable to carry out in an environment of 111.46 kPa or less, and even more preferably to carry out in an environment of 101.3 kPa or less.
The post-bake temperature is preferably 80°C to 250°C, more preferably 110°C to 170°C, even more preferably 130°C to 150°C.
The post-bake time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, even more preferably 2 minutes to 4 minutes.
Post-baking may be performed in an air environment or in a nitrogen-substituted environment.

<Conductive pattern formation process>
The method for forming a conductive pattern according to the present disclosure includes a step of forming a conductive pattern containing metal on at least a portion of the first film where the resin pattern is not formed ("conductive pattern forming step"). ).
The material of the conductive pattern is not particularly limited as long as it contains metal at least in part, and any conductive material manufactured by Kochi can be used.
The metal is not particularly limited, but copper, silver, gold, or an alloy containing these metals is preferable, and copper, silver, or an alloy containing these metals is more preferable.
Further, the conductive pattern preferably contains at least copper, silver, or gold, and more preferably contains at least copper or silver.

The height of the conductive pattern in the conductive pattern forming step is preferably lower than the height of the resin pattern from the viewpoint of shape stability of the conductive pattern, and is 50% or less of the height of the resin pattern. It is more preferably 0.1% or more and 35% or less of the height of the resin pattern, and particularly preferably 0.5% or more and 20% or less of the height of the resin pattern.

Dry plating can be used to form the conductive pattern in the conductive pattern forming step, and metal thin film formation by sputtering can be particularly preferably used.
As a dry plating film forming method, physical film forming methods include vacuum evaporation, sputtering, etc., and chemical film forming methods include chemical vapor deposition (CVD).
The vacuum evaporation method is a method in which a film forming material is heated and evaporated by resistance heating or electron gun irradiation to form a thin film on a base material. A plasma-assisted vapor deposition method is also known in which plasma is formed between an evaporation source and a substrate during vacuum vapor deposition for the purpose of adhesion and densification of a thin film. Note that plasma can be formed by applying a DC or AC voltage to a discharge electrode installed in a vacuum film-forming device, or by irradiating microwaves to an arbitrary location using a waveguide. can do.
The sputtering method uses a target formed from a film-forming material into a plate shape, uses this target as a discharge electrode to generate plasma between the base material and the target using the plasma generation method described above, and uses a potential gradient to generate plasma between the base material and the target. An example of this method is to eject the target material by irradiating and colliding the surface with ions to form a thin film of the target material on the base material.
In the present disclosure, a known sputtering apparatus and a known sputtering target can be used. Examples include magnetron sputtering cathodes and opposed sputtering cathodes.
In order to improve the adhesion between the metal thin film formed by sputtering and the base material, the surface of the base material may be slightly roughened with Ar molecules before sputtering the metal thin film. Further, heat treatment may be performed as a preliminary treatment for the purpose of dehydration and degassing. Furthermore, when sputtering Cu as a metal thin film, Cr or Ti can be sputtered between Cu and the base material to improve adhesion.

Further, the formation of the conductive pattern in the conductive pattern forming step includes formation by printing or coating a conductive composition.
There are no particular restrictions on the printing and coating methods, and known methods can be used. Examples include an inkjet method, a roll coating method, a blade coating method, a wire bar coating method, a spray coating method, and the like.
Preferred examples of the conductive composition used in the present disclosure include the following compositions. Among these, silver-containing ink or copper-containing ink is particularly preferred.
Further, in the conductive pattern forming step, the conductive composition may be applied to the entire surface of the laminate on the photosensitive resin layer side.

-Electrically conductive composition-
The conductive composition includes a conductive material.
The electrically conductive material is intended to include both materials that exhibit electrical conductivity themselves and materials that can form a conductive layer after sintering.
The conductive material is either a conductive material that exhibits conductivity itself and can form a conductive layer with a sheet resistivity of less than 10 Ω/□ at 23°C, or a conductive material that can form a conductive layer with a sheet resistivity of less than 10Ω/□ at 23°C after a sintering process. A conductive material that can form a conductive layer with a resistivity of less than 10 Ω/□ is preferred.

The conductive composition is not particularly limited, but for example, a composition in which a conductive material is dissolved/or dispersed in a solvent, and a composition containing a conductive material and a binder polymer are preferable. A composition containing a conductive material and a binder polymer (hereinafter also referred to as "composition C2") is more preferable, and the conductive material is dispersed in a solvent. Further preferred is a composition (composition C1).
Note that, as the conductive composition, known conductive pastes and conductive inks, as well as plating-forming inks described below, etc. can also be used.
Among these, the conductive composition is preferably a silver-containing ink or a copper-containing ink. Note that in the present disclosure, metal-containing ink refers to ink containing metal particles, and for example, silver-containing ink is ink containing silver particles.

The conductive material is not particularly limited and includes, for example, those shown below, of which (a) is preferred.
(a) Metal elements or alloys in the form of particles, clusters, crystals, tubes, fibers, wires, rods, films, etc. (b) Metal oxide particles (c) Conductive organic materials such as conductive polymer particles, and superconductors (d) Organometallic compound (e) Other conductive materials other than (a) to (e) above

(a) Metal elements or alloys in the shape of particles, clusters, crystals, tubes, fibers, wires, rods, films, etc. Metal elements or alloys in the shape of particles, clusters, crystals, tubes, fibers, wires, rods, films, etc. As the alloy, it is more preferable to use a particulate metal element or an alloy (hereinafter also referred to as "conductive particles") from the viewpoint of better dispersibility. Furthermore, from the viewpoint of applicability to precision equipment such as wiring boards, these metals and alloys are more preferably nanosized. The above metals and alloys are preferably metals selected from the group consisting of gold, silver, copper, nickel, aluminum, gold, platinum, and palladium, or alloys of two or more of these metals, and the resistance value, Gold, silver, copper, or an alloy thereof is more preferable in terms of cost, sintering temperature, etc., and silver is preferable in terms of sintering temperature and oxidation suppression.
Among the metals or alloys in the form of particles, clusters, crystals, tubes, fibers, wires, rods, films, etc., gold nanoparticles, silver nanoparticles, or copper nanoparticles are preferred, and silver nanoparticles are preferable. Particles are more preferred.
In the present disclosure, "nanoparticles" refer to particles with an average particle size of 0.1 nm or more and less than 1.0 μm, preferably particles with an average particle size of 1 nm or more and 100 nm or less.

(b) Metal oxide particles A "metal oxide" is a compound that does not substantially contain unoxidized metal. Specifically, in crystal analysis by Refers to a compound for which a peak is detected and no metal-derived peak is detected. Substantially free of unoxidized metal is not particularly limited, but it means that the content of unoxidized metal is 1% by mass or less based on the metal oxide particles.
Examples of the metal oxide in the metal oxide particles include oxides of copper, silver, nickel, gold, platinum, palladium, indium, tin, and the like. The metal oxide species may be one type or a mixture of two or more types.
The metal oxide is preferably an oxide of copper, silver, nickel, or tin, more preferably an oxide of copper or silver, and even more preferably an oxide of copper. As the copper oxide, copper (I) oxide or copper (II) oxide is preferable, and copper (II) oxide is more preferable because it can be obtained at low cost.
The upper limit of the average particle diameter of the metal oxide particles is preferably less than 1 μm, more preferably less than 200 nm. Further, the lower limit thereof is preferably 1 nm or more. Note that the average particle diameter of the metal oxide particles refers to the number average value of the particle diameters of the primary particles of 100 randomly selected metal oxide particles as observed using a scanning electron microscope (SEM).

(c) Conductive organic materials such as conductive polymers and superconductors Examples of conductive organic materials such as conductive polymers and superconductors include polyaniline, polythiophene, and polyphenylene vinylene.
Examples of the conductive organic material include PEDOT (polyethylene dioxythiophene) (PEDOT/PSS) doped with PPS (polystyrene sulfonic acid).

(d) Organometallic Compound The term "organometallic compound" as used herein refers to a compound from which a metal precipitates when decomposed by heating.
Examples of the organometallic compounds include chlorotriethylphosphine gold, chlorotrimethylphosphine gold, chlorotriphenylphosphine gold, silver 2,4-pentanedionato complex, trimethylphosphine (hexafluoroacetylacetonate) silver complex, and copper hexafluoropentanedionate complex. Examples include natocyclooctadiene complex.

(e) Others Examples of conductive materials other than the above (a) to (e) include acrylic resins as resist materials and linear insulating materials, and silane compounds that become silicon when heated. These may be dispersed in the solvent as particles or may be present as a solution.
Examples of silane compounds that turn into silicon when heated include trisilane, pentasilane, cyclotrisilane, and 1,1'-biscyclobutasilane.

Further, the conductive composition preferably contains a solvent and has water as its main component, since the defect rate of the conductive substrate to be formed is further reduced.
Here, the term "main component" refers to the component with the largest amount (mass ratio) among the solvents contained in the conductive composition.
When the conductive composition contains water, the content of water is preferably more than 50% by mass, more preferably 55% by mass or more, based on the total mass of the solvent contained in the conductive composition. It is more preferably 60% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more. The upper limit of the water content is, for example, 100% by mass or less based on the total mass of the solvent contained in the composition C1.

Composition C1 and composition C2 will be explained below.
(Composition C1)
Preferably, composition C1 includes a conductive material, a solvent, and a dispersant. Moreover, the composition C1 may further contain other components such as a polymerizable compound having an ethylenically unsaturated group and a polymerization initiator.
Note that the conductive materials included in the composition C1 include the conductive materials described above.
Composition C1 preferably has a viscosity of 1 mPa·s to 20 mPa·s at 25°C.
The composition C1 is preferably a colloidal liquid in which a conductive material is dispersed in a dispersion medium.

The conductive material contained in composition C1 is preferably conductive particles, and more preferably silver nanoparticles.
The average particle diameter of the conductive particles is preferably 0.1 nm to 50 nm, more preferably 1 nm to 20 nm, from the viewpoint of stability and fusion temperature.
Note that the average particle diameter of the conductive particles refers to the number average value of the particle diameters of primary particles of 100 randomly selected conductive particles.
In Composition C1, the content of the conductive material is preferably 10% by mass to 95% by mass based on the total mass of the composition in terms of better dispersion stability and metal film forming properties. It is preferably 30% by mass to 80% by mass.

The composition C1 preferably contains colloidal silver particles in which silver nanoparticles are in a colloidal state, since the conductive layer to be formed is less likely to be oxidized and the volume resistance value is less likely to decrease.
The form of the silver colloidal particles is not particularly limited, and examples thereof include a form in which a dispersant is attached to the surface of silver nanoparticles, a form in which a silver nanoparticle is used as a core and the surface thereof is coated with a dispersant, and Examples include a configuration in which silver particles and a dispersant are uniformly mixed. Among these, preferred is a configuration in which silver nanoparticles are used as a core and the surface thereof is coated with a dispersant, or a configuration in which silver particles and a dispersant are uniformly mixed. Silver colloidal particles having each of the above-mentioned forms can be appropriately prepared by known methods.

The average particle size of the colloidal silver particles is preferably 1 nm to 400 nm, and 1 nm to 400 nm is preferable, since the stability of dispersibility in the composition over time is better, and the resistance value of the conductive layer to be formed is further reduced. ~70 nm is more preferred. Note that the average particle size of the silver colloidal particles can be measured as a median diameter (D ₅₀ ) using a particle size standard as a volume standard using a dynamic light scattering method (Doppler scattered light analysis).

In addition, when the composition C1 contains silver nanoparticles, the composition C1 contains, in addition to the silver nanoparticles, submicron-sized silver particles having a larger average particle size than the silver nanoparticles (for example, an average particle size of 1 μm or less). It may also contain submicron particles. By using nano-sized silver nanoparticles and submicron-sized silver submicron particles together, the melting point of the silver nanoparticles decreases around the silver submicron particles, making it easier to obtain a good conductive path.

Furthermore, when composition C1 contains silver nanoparticles, migration of the conductive layer can be suppressed. , and more preferably a colloidal mixture of silver nanoparticles and other metal particles.
As the metal other than silver, a metal whose ionization series is nobler than hydrogen is preferable.
The metal whose ionization series is nobler than hydrogen is preferably gold, copper, platinum, palladium, rhodium, iridium, osmium, ruthenium, or rhenium, and more preferably gold, copper, platinum, or palladium.
Metals other than silver may be used alone or in combination of two or more.
When composition C1 is a mixed colloidal liquid, silver and other metals may constitute alloy colloidal particles, or may constitute colloidal particles having a structure such as a core-shell structure or a multilayer structure. Note that the metal particles other than silver may be nano-sized particles or submicron-sized particles.

The solvent contained in composition C1 includes water and organic solvents, with water being preferred.
The organic solvent is not particularly limited, but includes, for example, hydrocarbons such as toluene, dodecane, tetradecane, cyclododecene, n-heptane, and n-undecane; saturated aliphatic monohydric alcohols such as ethanol, isopropyl alcohol, and butanol; Alkanediols such as propanediol, butanediol, and pentanediol; alkylene glycols such as ethylene glycol; diethylene glycol monoisobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol isopropyl ether, ethylene glycol monomethyl ether; and glycol monoethers such as diethylene glycol monobutyl ether: glycerin.

The composition C1 preferably contains a solvent and has water as its main component, since the defect rate of the conductive substrate to be formed is further reduced.
Here, the term "main component" refers to the component with the largest amount (mass ratio) among the solvents contained in the composition C1.
When composition C1 contains water, the content of water is preferably more than 50% by mass, more preferably 55% by mass or more, and 60% by mass based on the total mass of the solvent contained in composition C1. % or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more. The upper limit of the water content is, for example, 100% by mass or less based on the total mass of the solvent contained in the composition C1.

Further, in composition C1, the content of the solvent is preferably 2% by mass to 98% by mass, and 25% by mass based on the total mass of the composition, since the dispersion stability of the conductive material is better. % to 80% by weight, even more preferably 50% to 80% by weight, particularly preferably 55% to 80% by weight.

When composition C1 contains water, the dispersion medium other than water is selected from the group consisting of diethylene glycol monoisobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol isopropyl ether, ethylene glycol monomethyl ether, and diethylene glycol monobutyl ether. It is also preferable to use one or more selected solvents in combination. In addition to this, it is also preferable to further use one or more solvents selected from the group consisting of butanol, propanediol, butanediol, pentanediol, ethylene glycol, and glycerin.

Composition C1 may include a dispersant as described above.
The dispersant has a carboxy group and a hydroxy group, and the number of carboxy groups contained in the molecule is ≧ from the viewpoint that the dispersion stability of the conductive particles (particularly silver colloidal particles) in the composition is better. Hydroxy acids or salts thereof are preferred, which is the number of hydroxy groups contained in the molecule.

Examples of the above-mentioned hydroxy acids or salts thereof include organic acids such as citric acid, malic acid, tartaric acid, and glycolic acid; trisodium citrate, tripotassium citrate, trilithium citrate, monopotassium citrate, and hydrogen citrate. Ionic compounds such as disodium, potassium dihydrogen citrate, disodium malate, disodium tartrate, potassium tartrate, potassium sodium tartrate, potassium hydrogen tartrate, sodium hydrogen tartrate, and sodium glycolate; and hydrates thereof etc. Among these, trisodium citrate, tripotassium citrate, trilithium citrate, disodium malate, disodium tartrate, or hydrates thereof are preferred.
One type of dispersant may be used alone, or two or more types may be used in combination.

The content of the hydroxy acid or its salt in composition C1 is such that the storage stability of the conductive particles is better and the resistance value of the conductive layer to be formed is higher than the total mass of the composition. In terms of reduction, the amount is preferably 0.5% by mass to 30% by mass, more preferably 1% by mass to 20% by mass, and even more preferably 1% by mass to 10% by mass.

Composition C1 may contain a polymerizable compound having an ethylenically unsaturated group (hereinafter also referred to as "ethylenically unsaturated polymerizable compound").
The ethylenically unsaturated polymerizable compound is preferably a compound containing two or more ethylenically unsaturated groups in the molecule (polyfunctional ethylenically unsaturated compound), since it has better curability and strength. More preferably, it is a compound containing three or more ethylenically unsaturated groups.
The ethylenically unsaturated polymerizable compound is preferably a (meth)acrylate compound, a vinylbenzene compound, or a bismaleimide compound, and more preferably a polyvalent (meth)acrylate compound.
Examples of polyhydric (meth)acrylate compounds include ester compounds of polyhydric alcohol and acrylic acid or methacrylic acid. In addition, oligomers with a molecular weight of several hundred to several thousand that have several (meth)acryloyloxy groups in the molecule, etc. are called urethane (meth)acrylate, polyester (meth)acrylate, and epoxy (meth)acrylate. It may be.

Examples of the polyfunctional (meth)acrylate compound include polyfunctional (meth)acrylate compounds having 3 to 6 (meth)acryloyloxy groups in the molecule.
Examples of polyfunctional (meth)acrylate compounds having three or more (meth)acryloyloxy groups in the molecule include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and pentaerythritol tri(meth)acrylate. , polyol poly(meth)acrylates such as pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, polyisocyanate and hydroxyethyl(meth)acrylate, etc. Examples include urethane (meth)acrylates obtained by the reaction of hydroxyl group-containing (meth)acrylates.

In composition C1, the content of the ethylenically unsaturated polymerizable compound is preferably 5% by mass to 80% by mass, and preferably 10% by mass to 50% by mass, based on the total solid content of the composition. More preferred.

Composition C1 may contain a polymerization initiator.
The polymerization initiator may be either a thermal polymerization initiator or a photopolymerization initiator.
Examples of the thermal polymerization initiator include thermal radical generators. Specific examples include peroxide initiators such as benzoyl peroxide and azobisisobutyronitrile, and azo initiators.
Examples of the photopolymerization initiator include photoradical generators. Specifically, (a) aromatic ketones, (b) onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiimidazole compounds, and (f) ketoxime ester compounds. , (g) a borate compound, (h) an azinium compound, (i) an active ester compound, (j) a compound having a carbon-halogen bond, and (k) a pyridium compound.

In composition C1, the content of the polymerization initiator is preferably 0.1% by mass to 50% by mass, more preferably 1.0% by mass to 30.0% by mass, based on the total solid content of the composition. .

Composition C1 may further contain a high viscosity substance to suppress fluidity.

Composition C1 may further contain a reducing agent.
As the reducing agent, for example, tannic acid or hydroxy acid is preferable. Note that tannic acid includes, for example, gallotannic acid, pentad tannin, and the like.
One type of reducing agent may be used alone, or two or more types may be used in combination.

The content of the reducing agent is preferably 0.01 g to 6 g, more preferably 0.02 g to 1.5 g, per 1 g of conductive particles.

(Composition C2)
Preferably, composition C2 includes an electrically conductive material and a binder polymer.
Note that the conductive materials included in composition C2 include the conductive materials described above.
The conductive material contained in composition C2 is preferably conductive particles, and more preferably silver nanoparticles. Note that the above-mentioned conductive particles and silver nanoparticles that may be included in composition C2 include those similar to the conductive particles and silver nanoparticles that may be included in composition C1.

The binder polymer contained in composition C2 is not particularly limited, and any known binder polymer can be used.
Examples of the binder polymer include thermoplastic resins such as polyester resin, (meth)acrylic resin, polyethylene resin, polystyrene resin, and polyamide resin. Alternatively, thermosetting resins such as epoxy resins, amino resins, polyimide resins, and (meth)acrylic resins may be used.

The blending ratio (mass ratio) of the conductive material and the binder polymer in composition C2 is not particularly limited, and is preferably, for example, 10/90 to 90/10, more preferably 20/80 to 80/20.

Composition C2 may further contain a solvent for the purpose of adjusting viscosity.
The solvent is not particularly limited as long as it can dissolve the components of composition C2, but it is preferable that the main component is water, since it further reduces the defective rate of the conductive substrate to be formed.
Here, the term "main component" refers to the component that has the largest amount (mass ratio) among the solvents contained in composition C2.
When composition C2 contains water, the content of water is preferably more than 50% by mass, more preferably 55% by mass or more, and 60% by mass based on the total mass of the solvent contained in composition C2. % or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more. The upper limit of the water content is, for example, 100% by mass or less based on the total mass of the solvent contained in the composition C1.

A plate-forming ink may be used as the conductive composition.
Plating-forming ink is an ink consisting of a composition for forming a layer to be plated and a plating solution, and a metal layer (conductive layer) is formed by electroless plating on the layer to be plated formed from the composition for forming a layer to be plated. Intended as an ink that can form .
The composition for forming a layer to be plated contains an electroless plating catalyst or a precursor thereof, or contains an electroless plating catalyst or a precursor thereof, in order to enable electroless plating on the layer to be plated formed from the composition for forming a layer to be plated. Includes compounds containing functional groups (hereinafter also referred to as "interactive groups") that interact (for example, ionic bonds, coordinate bonds, hydrogen bonds, covalent bonds, etc.) with the plating catalyst or its precursor.
The composition for forming a layer to be plated preferably contains a compound having an interactive group and a solvent. It is preferable that the composition for forming a layer to be plated further contains a polymerization initiator and a polymerizable compound.
For the plating-forming ink and its usage mode, for example, descriptions in known documents such as International Publication No. 2016/159136 can be referred to.

In addition, in the method for forming a conductive pattern according to the present disclosure, when the above conductive composition is used, a step of sintering a layer formed of the conductive composition (also referred to as "conductive composition layer"). It is preferable to include.
As a method for sintering the conductive composition layer, thermal sintering or optical sintering is preferable since the resistance value of the conductive pattern is further reduced and manufacturing efficiency is more excellent.

When thermally sintering the conductive composition layer, the heating temperature is, for example, 90°C or higher, since the heat resistance of the base material is better and the resistance value of the conductive pattern to be formed is further reduced. , preferably 100°C or higher, more preferably 120°C or higher, even more preferably 130°C or higher. Further, the upper limit thereof is, for example, 200°C or less, preferably 180°C or less, and more preferably 160°C or less.
The heating method is not particularly limited, but includes a method using a conventionally known gear oven or the like.
In addition, the heating time is preferably 0.5 minutes to 120 minutes, and 1 minute to 80 minutes, in terms of better manufacturing efficiency and lower resistance of the formed conductive pattern. The time is more preferably 1 minute to 60 minutes, particularly preferably 10 minutes to 60 minutes, and most preferably 10 minutes to 30 minutes.

When photo-sintering the conductive composition layer, the type of light to be irradiated is not particularly limited as long as sintering is possible, but light containing ultraviolet rays is preferred. The irradiation energy is preferably 10 mJ/cm ² to 10,000 mJ/cm ² , more preferably 20 mJ/cm ² to 6,000 mJ/cm ² , and 30 mJ/cm ² to 5,000 mJ/cm 2 More preferably, it is ² . The irradiation time is not particularly limited, although it depends on the irradiation energy, and may be normal exposure or flash exposure. When performing flash exposure, the irradiation time is preferably 0.1 ms (milliseconds) to 10 ms, more preferably 0.2 ms to 5 ms, and even more preferably 0.5 ms to 4 ms.

The sintering treatment of the conductive composition layer is preferably carried out at a temperature higher than the boiling point of the organic amines contained in the stripping solution, in order to further reduce the resistance value of the conductive layer.

Among these, in the conductive pattern forming step, the conductive pattern is preferably formed by sputtering, vapor deposition, or printing or coating a conductive composition, and the adhesion and composition of the conductive pattern are From the viewpoint of uniformity, it is more preferable to form by a sputtering method or a vapor deposition method.
Further, in the conductive pattern forming step, from the viewpoint of simplicity and selectivity of the formation position, it is more preferable that the conductive pattern is formed by printing or coating with silver-containing ink or copper-containing ink.

Further, in the method for forming a conductive pattern according to the present disclosure, the conductive pattern may be formed in one step or in two or more steps.
When the conductive pattern is formed in two or more steps, the second and subsequent steps may include forming the conductive pattern by sputtering, vapor deposition, printing or coating a conductive composition, or plating. is preferred.

Moreover, the above-mentioned laminate has a first photosensitive resin layer and a second film on one side of the first film, and a second photosensitive resin layer on the other side of the first film. When using a laminate having a conductive resin layer and a third film, the conductive pattern forming step includes forming a conductive pattern on a portion of the first film on which the resin pattern is not formed. Preferably, the step is to form a conductive pattern containing metal at least in part, and the conductive pattern containing metal is preferably formed in at least a part of the parts on both sides of the first film where the resin pattern is not formed. More preferably, it is a step of forming.

<Removal process>
A method for forming a conductive pattern according to the present disclosure includes a step of removing the resin pattern.
There are no particular limitations on the method for removing the resin pattern, and the resin pattern can be removed by any known method.
For example, when the resin pattern is a positive photosensitive resin layer, a method of exposing the resin pattern to light, developing it, and removing it is preferably mentioned. As the exposure method and development method, the above-mentioned exposure method and development method can be suitably used.
Alternatively, the resin pattern may be removed using a stripping solution.
As the stripping solution, a known stripping solution can be used, and the stripping solution shown below is preferably mentioned.

Moreover, the above-mentioned laminate has a first photosensitive resin layer and a second film on one side of the first film, and a second photosensitive resin layer on the other side of the first film. When using a laminate having a synthetic resin layer and a third film, the removing step is preferably a step of removing the resin pattern on one surface or both surfaces of the first film, More preferably, the step is a step of removing the resin pattern on both sides of the first film.

-Removal liquid-
The stripping solution preferably contains water as a main component.
Here, the term "main component" refers to the component that has the largest amount (mass ratio) among the components contained in the stripping solution.
The water content in the stripping solution is preferably more than 50% by mass, more preferably 55% by mass or more, and even more preferably 60% by mass or more based on the total mass of the stripping solution. , is particularly preferably 80% by mass or more, and most preferably 90% by mass or more. The upper limit of the water content is, for example, 100% by mass or less, preferably 95% by mass or less, based on the total mass of the solvent contained in composition C1.

It is preferable that the stripping solution further contains organic amines for the purpose of promoting stripping.
Organic amines are not particularly limited, but are preferably primary to tertiary alkylamines or alkanolamines, such as diethylamine (boiling point: 55.5°C), triethylamine (boiling point: 89°C), and monoethanol. Examples include amine (boiling point: 170°C), diethanolamine (boiling point: 280°C), and N-methyl-ethanolamine (boiling point: 155°C).

The boiling point of the organic amine is, for example, 300°C or lower, and preferably 250°C or lower in order to facilitate volatilization without inhibiting the sintering of the conductive material during sintering of the conductive composition. More preferably, the temperature is 180°C or lower. Note that the lower limit of the boiling point of the organic amine is not particularly limited, but is preferably 30° C. or higher, for example.

The organic amines are preferably primary to tertiary alkylamines or alkanolamines with a boiling point of 180°C or lower, such as diethylamine (boiling point: 55.5°C), triethylamine (boiling point: 89°C), or monoethanolamine. (Boiling point: 170°C) is more preferable.

The upper limit of the content of organic amine in the stripping solution is preferably less than 50% by mass, more preferably 40% by mass or less, and even more preferably 30% by mass or less, based on the total mass of the stripping solution. The lower limit of the content of organic amine in the stripping solution is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, based on the total mass of the stripping solution.

The stripping solution may further contain a water-soluble organic solvent, a surfactant, and the like.

There is no particular restriction on the stripping method, and the same method as the above-mentioned developing method can be applied except that a stripping solution is used. Note that the temperature of the stripping solution is preferably less than 50°C, more preferably 45°C or less, and even more preferably 40°C or less, in terms of further reducing the defect rate of the conductive substrate to be formed. In addition, as a lower limit, 5 degreeC or more is preferable.

Further, it is preferable that the conductive pattern obtained by the method for forming a conductive pattern according to the present disclosure has a tapered shape, and the conductive pattern on the side in contact with the first film is smaller than the conductive pattern on the side in contact with the first film. More preferably, the conductive pattern on the opposite side has a tapered shape.
The thickness of the resulting conductive pattern is not particularly limited and can be selected as desired, but from the viewpoint of the strength and durability of the resulting metal pattern, it is preferably 1 nm or more, more preferably 5 nm or more. It is preferably 10 nm or more, more preferably 15 nm or more, and particularly preferably 15 nm or more. Further, the upper limit is preferably 1 μm or less, more preferably 100 nm or less.

<Other processes>
The method for forming a conductive pattern according to the present disclosure may include any steps (other steps) other than those described above. Other steps are not particularly limited, and include known steps.
Furthermore, as examples of the resin pattern forming step and other steps in the present disclosure, the methods described in paragraphs 0035 to 0051 of JP-A No. 2006-23696 can also be suitably used in the present disclosure.
Further, the method for forming a conductive pattern according to the present disclosure may include a step of polishing the obtained conductive pattern, a step of cleaning the obtained conductive pattern, and the like.

<Application>
The conductive pattern obtained by the method for forming a conductive pattern according to the present disclosure can be applied to various uses.
Applications of the substrate having the conductive pattern include, for example, touch panels (touch sensors), antennas, electromagnetic shielding materials, semiconductor chips, various electrical wiring boards, FPCs (Flexible printed circuits), COFs (Chip on Film), TABs ( Tape Automated Bonding), multilayer wiring boards, and motherboards, and are preferably used for touch sensors, antennas, electromagnetic shielding materials, and heating elements.
When applying the substrate having the conductive pattern described above to a touch sensor, a preferred embodiment is such that the conductive pattern functions as a detection electrode or lead wiring in the touch sensor.

The touch panel is not particularly limited as long as it has the above-mentioned touch sensor, and for example, it may be a combination of the above-mentioned touch sensor and various display devices (e.g., a liquid crystal display device, an organic EL (Electro-luminescence) display device). Examples include devices.

Detection methods for touch sensors and touch panels include known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among these, capacitive touch sensors and touch panels are preferred.

Examples of the touch panel type include the so-called in-cell type (for example, those shown in FIGS. 5, 6, 7, and 8 of Japanese Patent Publication No. 2012-517051), and the so-called on-cell type (for example, those shown in Japanese Patent Application Laid-Open No. 2013-168125). 19, and those shown in FIGS. 1 and 5 of JP-A-2012-089102), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, JP-A-2012-089102) 2 of Japanese Patent Publication No. 2013-054727), various outsell types (so-called GG, G1/G2, GFF, GF2, GF1, and G1F, etc.), and other configurations (for example, those described in Japanese Patent Laid-Open No. 2013-164871 (shown in FIG. 6).
Examples of the touch panel include those described in paragraph 0229 of JP-A-2017-120345.
Further, the method for manufacturing the touch panel is not particularly limited, and any known method for manufacturing a touch panel may be referred to, except for using the touch sensor having the above-mentioned conductive substrate.

Further, the conductive pattern obtained by the method for forming a conductive pattern according to the present disclosure can be suitably applied to a sensor having a metal mesh pattern, and is referred to as a metal mesh sensor. Moreover, it can be more suitably applied to a touch sensor having a metal mesh pattern.
The metal mesh sensor according to the present disclosure may include a conductive pattern obtained by the method for forming a conductive pattern according to the present disclosure.
The method for manufacturing a metal mesh sensor according to the present disclosure preferably includes the method for forming a conductive pattern according to the present disclosure.
The material, shape, base material, etc. of the metal mesh sensor according to the present disclosure are not particularly limited and may be appropriately selected as desired.

<Laminated body>
The laminate (also referred to as "photosensitive transfer material") used in the present disclosure includes a first film, a photosensitive resin layer, and a second film.
Further, the laminate has a first photosensitive resin layer and a second film on one side of the first film, and a second photosensitive resin layer on the other side of the first film. It is preferable that the laminate is a laminate having a polyurethane resin layer and a third film.
Hereinafter, the laminate used in the present disclosure will be described in detail.

-First film and second film-
The first film and second film used in the present disclosure may be the same or different.
The first film is a film that is in contact with the conductive pattern even in the removing step, and the second film is a film that is removed before or during the developing step.
The first film and the second film are not particularly limited, but a resin film or paper is preferred, and more preferred than a resin film.
Examples of the resin constituting the resin film include cycloolefin polymer (COP), polycarbonate (PC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), polypropylene (PP), Polyethylene (PE), polyamide (PA), polyacetal (POM), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyetheretherketone (PEEK), polystyrene (PS), polymethyl methacrylate (PMMA), polyphenylene ether (PPE), polysulfone (PSF), polyethersulfone (PES), polyamideimide (PAI), polyetherimide (PEI), polyimide (PI), polyvinyl chloride (PVC), etc. The following resins are mentioned.

Among these, the first film preferably contains polyethylene terephthalate, polyimide, and cycloolefin polymer, and particularly preferably contains polyethylene terephthalate, from the viewpoints of suppressing conductive pattern defects and resolution.
In addition, from the viewpoint of suppressing conductive pattern defects and resolution, the second film preferably contains polyethylene terephthalate, polyimide, a cycloolefin polymer, polypropylene, and polyethylene; , cycloolefin polymer is more preferred, and polyethylene terephthalate is particularly preferred.

Further, from the viewpoint of suppressing conductive pattern defects and operational stability of the obtained conductive pattern, it is preferable that both the first film and the second film are insulating films.
The insulating film in the present disclosure refers to a film that does not have a conductive coating on its surface, and has a surface specific resistance value of 10 ³ Ω/□ or more.
As the insulating film, common plastic films such as polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyethylene (PE), polypropylene (PP), polystyrene, polyethylene vinyl acetate (EVA), etc. Polyolefins; vinyl resin; others include polycarbonate (PC), polyamide, polyimide, acrylic resin, triacetyl cellulose (TAC), cycloolefin polymer (COP), cyclic olefin copolymer (COC), and the like.

The surface of the first film may be subjected to surface treatment such as hydrophilic treatment for the purpose of improving adhesion to the conductive pattern.
Further, the surface of the second film may be subjected to surface treatment such as matte treatment for the purpose of improving releasability.

The first film and the second film each independently contain light in the visible range of 400 nm to 700 nm in order to facilitate exposure of the photosensitive resin layer through the first film or the second film. The transmittance is preferably 50% or more, and more preferably the transmittance of light at 400 nm to 450 nm is more than 10%. The transmittance can be measured using a spectrophotometer UV-2100 manufactured by Shimadzu Corporation.
In addition, in order to facilitate exposure of the photosensitive resin layer through the first film or the second film, at least one of the first film and the second film has a total light transmittance of 85% or more. The first film and the second film are both preferably transparent films with a total light transmittance of 85% or more.
Note that the transmittance such as the total light transmittance can be measured using a haze meter NDH4000 manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with the method specified in JIS K7375 (2008).

From the viewpoint of resolution, the thickness of the first film is preferably 100 μm or less, more preferably 50 μm or less, even more preferably 5 μm to 50 μm, and preferably 10 μm to 35 μm. Particularly preferred.
Further, from the viewpoint of resolution, the thickness of the second film is preferably 100 μm or less, more preferably 50 μm or less, even more preferably 5 μm to 50 μm, and even more preferably 10 μm to 35 μm. This is particularly preferred.

From the viewpoint of exposure sensitivity and resolution, the haze of the first film is preferably 2.0% or less, more preferably 1.5% or less, and preferably 1.0% or less. More preferably, it is particularly preferably 0.75% or less.
From the viewpoint of exposure sensitivity and resolution, the haze of the second film is preferably 2.0% or less, more preferably 1.5% or less, and preferably 1.0% or less. More preferably, it is particularly preferably 0.75% or less.
The lower limit of the haze of the first film or the second film is preferably close to 0% from the viewpoint of exposure sensitivity and resolution. The lower limit of the haze of the temporary support is preferably 0.01 or more from the viewpoint of windability during production of the temporary support.

"Haze" means cloudiness. The haze of each film refers to a value measured using a haze meter (turbidimeter) in accordance with the method specified in JIS K 7105:1981. Further, in the present disclosure, NDH-1001DP (manufactured by Nippon Denshoku Kogyo Co., Ltd.) is used as the haze meter (turbidity meter).

In addition, the first film and the second film each independently improve the wrinkle generation suppressing property during transport of the laminate, the stability over time after exposure, and the linearity of the resulting resin pattern and conductive pattern. From this point of view, it is preferable that particles are included.
Among these, it is preferable that at least one of the first film and the second film contains particles.

Examples of the particles include inorganic particles and organic particles.
Examples of the inorganic particles include silicon oxide (silica) particles, titanium oxide (titania) particles, zirconium oxide (zirconia) particles, magnesium oxide (magnesia) particles, and aluminum oxide (alumina) particles.
Examples of the organic particles include organic resin particles such as acrylic resin particles, polyester particles, polyurethane particles, polycarbonate particles, polyolefin particles, and polystyrene particles.
Among the above, inorganic particles are preferable, and silica particles are more preferable, from the viewpoint of stability over time after exposure and linearity of the obtained pattern.

The content of the particles is not particularly limited as long as it satisfies the range of the surface roughness Ra, but from the viewpoint of ease of controlling the surface roughness and suppressing the occurrence of wrinkles during transportation, the total mass of the film It is preferably 0.001% to 20% by weight, more preferably 0.01% to 10% by weight, particularly preferably 0.05% to 5% by weight.
Furthermore, the particles may be present inside the film, or a portion may be exposed on the surface of the film.
Furthermore, the first film and the second film may have a particle-containing layer containing the above particles.

The arithmetic mean particle size of the above particles is 20 nm to 300 nm from the viewpoint of ease of controlling surface roughness, suppressing wrinkle generation during transportation, stability over time after exposure, and linearity of the resulting pattern. It is preferably from 30 nm to 200 nm, even more preferably from 40 nm to 120 nm, and particularly preferably from 40 nm to 80 nm.
The arithmetic mean particle diameter of the particles in the present disclosure is determined by observing the temporary support at an accelerating voltage of 100 kV using a HT-7700 transmission electron microscope (TEM) manufactured by Hitachi High-Technologies Corporation, and arbitrarily extracting 400 particles. Find the average value of the diameters of the particles (arithmetic mean particle size). Note that clearly large aggregates (foreign matter, dust, etc.) are not counted (excluded, not extracted as particles).

The first film and the second film may contain an ultraviolet absorber, but from the viewpoint of pattern forming properties, especially pattern forming properties during double-sided exposure, the first film contains an ultraviolet absorber. It is preferable.
As the ultraviolet absorber, known ultraviolet absorbers can be used.
Examples of the ultraviolet absorber include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, and triazine compounds. For details, please refer to the compounds described in paragraphs 0052 to 0072 of JP 2012-208374, paragraphs 0317 to 0334 of JP 2013-068814, and paragraphs 0061 to 0080 of JP 2016-162946. , the contents of which are incorporated herein. Further, as the ultraviolet absorber, compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used.

Also, JP 2003-112391, JP 2008-081445, JP 2009-096973, JP 2009-096974, JP 2008-273927, JP 2009-096794, JP 2009-185217, JP 2009-096972, JP 2009-096971, JP 2009-067983, JP 2009-067984, JP 2010-132846, JP 2009-242639, 2009-263616, 2009-242642, 2009-242641, 2009-209344, 2009-209126, 2009- 209343, 2010-092842, 2010-189349, 2010-254776, 2011-088884, 2011-006517, 2011-168575 Publication, JP 2011-088885, JP 2011-068840, JP 2011-168764, JP 2011-184414, JP 2012-036359, JP 2011-225811, JP 2011-213914, JP 2012-072333, JP 2013-075841, International Publication No. 2017/122503, International Publication No. 2017/169370, JP 2018-036516, International Publication International Publication No. 2018/123267, International Publication No. 2018/180929, International Publication No. 2019/065043, International Publication No. 2019/058885, International Publication No. 2019/142538, International Publication No. 2019/146280, International Publication No. Ultraviolet absorbers described in 2019/142539, International Publication No. 2019/159570, International Publication No. 2019/198560, International Publication No. 2019/203031, JP 2019-191219, etc. may also be used. I can do it.

The ultraviolet absorbers may be used alone or in combination of two or more.
From the viewpoint of pattern formation, the content of the ultraviolet absorber is preferably 0.001% to 20% by mass, and preferably 0.005% to 5% by mass, based on the total mass of the film. The content is more preferably 0.001% by mass to 2% by mass.

-Third film-
The laminate has a first photosensitive resin layer and a second film on one side of the first film, and a second photosensitive resin layer on the other side of the first film. A laminate having a layer and a third film is preferable.
The third film may be the same film as the second film, or may be a different film.
Preferred embodiments of the third film are the same as those of the second film.

-Photosensitive resin layer-
The laminate used in the present disclosure has a photosensitive resin layer.
The photosensitive resin layer may be a positive photosensitive resin layer or a negative photosensitive resin layer, but from the viewpoint of resin pattern formation and ease of removal of the resin pattern, the positive type It is preferably a photosensitive resin layer, and more preferably a chemically amplified positive type photosensitive resin layer.
The positive photosensitive resin layer in the present disclosure preferably contains a resin and an acid generator. It is more preferable that an acid generator is included.
Further, from the viewpoint of heat resistance and dimensional stability, the positive photosensitive resin layer more preferably contains an alkali-soluble resin as the resin and a quinonediazide compound as the acid generator.
The positive photosensitive resin layer containing an acid-decomposable resin as the resin and a photoacid generator as the acid generator is a so-called chemically amplified positive photosensitive resin layer.
Photoacid generators such as onium salts and oxime sulfonate compounds described below act as catalysts for the deprotection of protected acid groups in the above polymer by the acid generated in response to active radiation (actinic rays). Therefore, the acid generated by the action of one photon contributes to multiple deprotection reactions, and the quantum yield exceeds 1, for example, a large value of several powers of 10, resulting in so-called chemical amplification. As a result, high sensitivity is obtained.
On the other hand, when a quinonediazide compound is used as a photoacid generator sensitive to actinic rays, a carboxyl group is generated by a sequential photochemical reaction, but the quantum yield is always less than 1, and it does not fall under the chemical amplification type.

The photosensitive resin composition that can be suitably used for forming the above photosensitive resin layer will be described in detail below.
In addition, unless otherwise specified, the standard for the content of each component described below is that when it is stated "based on the total solid content of the composition", it is "based on the total mass of the photosensitive resin layer". ", and when it is written as "based on 100 parts by mass of the total solid content of the composition", it shall be read as "based on 100 parts by mass of the total mass of the photosensitive resin layer".

The laminate has a first photosensitive resin layer and a second film on one side of the first film, and a second photosensitive resin layer on the other side of the first film. In the case of a laminate having a layer and a third film, preferred embodiments of the first photosensitive resin layer and the second photosensitive resin layer are independently the same as the preferred embodiments of the above photosensitive resin layer. be.
The first photosensitive resin layer and the second photosensitive resin layer may be the same photosensitive resin layer or different photosensitive resin layers, but they are photosensitive resin layers with the same composition. It is preferable that the photosensitive resin layers are the same, and it is more preferable that the photosensitive resin layers are the same.
Note that in the case of photosensitive resin layers having the same composition, the composition ratios of the components contained in the layers are the same, but the thicknesses may be different.

<<Photosensitive resin composition>>
The photosensitive resin composition will be explained below.
The photosensitive resin composition that can be used in the present disclosure is not particularly limited, and any known photosensitive resin composition can be used.
It is preferable that the photosensitive resin composition contains an acid-decomposable resin and a photoacid generator.
The photosensitive resin composition is preferably a chemically amplified photosensitive resin composition since it has better sensitivity during exposure.
In addition, when using photoacid generators such as onium salts and oxime sulfonate compounds described below, the acid generated in response to active radiation (hereinafter also referred to as "actinic rays") is generated in the acid-decomposable resin described above. Acts as a catalyst in the deprotection reaction of acid-decomposable groups. Since the acid generated by the action of one photon contributes to many deprotection reactions, the quantum yield exceeds 1 and becomes a large value, for example, a number of powers of 10, resulting in a high yield as a result of so-called chemical amplification. Sensitivity can be obtained. On the other hand, when a quinonediazide compound is used as a photoacid generator sensitive to actinic radiation, a carboxyl group is generated by a sequential photochemical reaction, but the quantum yield is always less than 1 and does not correspond to a chemical amplification type.

[Acid decomposable resin]
The photosensitive resin composition includes a polymer (acid-decomposable resin) having a polar group (acid-decomposable group) protected with a protecting group that is deprotected by the action of an acid.
The acid-decomposable resin is preferably a polymer (hereinafter also referred to as "polymer A") containing a structural unit having an acid-decomposable group (hereinafter also referred to as "constituent unit A").
Polymer A will be explained below.

≪Polymer A≫
Polymer A includes a structural unit (structural unit A) having an acid-decomposable group.
The acid-decomposable group is deprotected and converted into a polar group by the action of an acid generated by exposure to light. Therefore, the solubility of the photosensitive resin layer formed from the photosensitive resin composition in an alkaline developer increases upon exposure.

The polymer A is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth)acrylic acid or (meth)acrylic acid ester.
Polymer A does not contain any structural units other than those derived from (meth)acrylic acid or (meth)acrylic acid ester (for example, structural units derived from styrene, structural units derived from vinyl compounds, etc.). It's okay to stay.
In the following, structural units that the polymer A may contain will be explained.

・Structural unit A (structural unit having an acid-decomposable group)
Polymer A contains a structural unit having an acid-decomposable group. The acid-decomposable group can be converted into a polar group by the action of an acid, as described above.
As used herein, the term "polar group" refers to a proton dissociative group having a pKa of 12 or less.
Examples of the polar group include known acid groups such as a carboxy group and a phenolic hydroxy group. Among these, the polar group is preferably a carboxy group or a phenolic hydroxy group.

The protecting group is not particularly limited, and includes known protecting groups.
Examples of the protecting group include a protecting group that can protect a polar group in the form of an acetal (such as a tetrahydropyranyl group, a tetrahydrofuranyl group, and an ethoxyethyl group), and a protecting group that can protect a polar group in the form of an ester (for example, a protecting group that can protect a polar group in the form of an ester). For example, tert-butyl group) and the like can be mentioned.

Examples of acid-decomposable groups include groups that are relatively easily decomposed by acids (for example, acetal functional groups such as ester groups, tetrahydropyranyl ester groups, and tetrahydrofuranyl ester groups contained in the structural unit represented by formula A3 described below). ), and groups that are relatively difficult to decompose with acids (for example, tertiary alkyl ester groups such as tert-butyl ester groups, and tertiary alkyl carbonate groups such as tert-butyl carbonate groups), etc. can be used.

Among these, the acid-decomposable group is preferably a group in which a polar group is protected in the form of an acetal, and more preferably a group in which a carboxy group or a phenolic hydroxy group is protected in the form of an acetal. .

As the structural unit A, 1 is selected from the group consisting of the structural unit represented by formula A1, the structural unit represented by formula A2, and the structural unit represented by formula A3 in terms of superior sensitivity and resolution. The structural unit is preferably one or more types of structural units, more preferably one or more structural units selected from the group consisting of the structural unit represented by formula A1 and the structural unit represented by formula A3, which will be described later. More preferably, it is one or more structural units selected from the group consisting of the structural unit represented by formula A1-2 and the structural unit represented by formula A3-3 described below.
The structural unit represented by formula A1 and the structural unit represented by formula A2 are structural units having an acid-decomposable group in which a phenolic hydroxy group is protected with a protecting group that is deprotected by the action of an acid. The structural unit represented by formula A3 is a structural unit having an acid-decomposable group in which the carboxy group is protected with a protecting group that is deprotected by the action of an acid.

In formula A1, R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, or an aryl group. However, at least one of R ¹¹ and R ¹² represents an alkyl group or an aryl group. R ¹³ represents an alkyl group or an aryl group. R ¹⁴ represents a hydrogen atom or a methyl group. X ¹ represents a single bond or a divalent linking group. R ¹⁵ represents a substituent. n represents an integer from 0 to 4. Note that R ¹¹ or R ¹² and R ¹³ may be connected to each other to form a cyclic ether (if one of R ¹¹ and R ¹² is connected to R ¹³ to form a cyclic ether, R ¹¹ The other of R 11 and R ¹² may be a hydrogen atom (that is, the other of R ¹¹ and R ¹² may not be an alkyl group or an aryl group).

In formula A2, R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group, or an aryl group. However, at least one of R ²¹ and R ²² represents an alkyl group or an aryl group. R ²³ represents an alkyl group or an aryl group. ^R24 each independently represents a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group, or a cyclo Represents an alkyl group. m represents an integer from 0 to 3. R ²¹ or R ²² and R ²³ may be connected to each other to form a cyclic ether (when one of R ²¹ and R ²² is connected to R ²³ to form a cyclic ether, R ²¹ and R The other of ²² may be a hydrogen atom (that is, the other of R ²¹ and R ²² does not need to be an alkyl group or an aryl group).

In formula A3, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group, or an aryl group. However, at least one of R ³¹ and R ³² represents an alkyl group or an aryl group. R ³³ represents an alkyl group or an aryl group. R ³⁴ represents a hydrogen atom or a methyl group. X ⁰ represents a single bond or a divalent linking group. Note that R ³¹ or R ³² and R ³³ may be connected to each other to form a cyclic ether (if one of R ³¹ and R ³² is connected to R ³³ to form a cyclic ether, R ³¹ The other of R 31 and R ³² may be a hydrogen atom (that is, the other of R ³¹ and R ³² may not be an alkyl group or an aryl group).

- Preferred embodiments of the structural unit represented by formula A1 -
In formula A1, the number of carbon atoms in the alkyl group represented by R ¹¹ and R ¹² is preferably 1 to 10. The aryl group represented by R ¹¹ and R ¹² is preferably a phenyl group.
Among R ¹¹ and R ¹² , a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred.

In formula A1, the alkyl group or aryl group represented by R ¹³ includes the same alkyl groups and aryl groups represented by R ¹¹ and R ¹² . Among them, R ¹³ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

In formula A1, the alkyl group and aryl group in R ¹¹ , R ¹² , and R ¹³ may further have a substituent.

In formula A1, R ¹¹ or R ¹² and R ¹³ are preferably linked to each other to form a cyclic ether. The number of ring members in the cyclic ether is preferably 5 or 6, more preferably 5.

In formula A1, X ¹ is a single bond or a combination of one or more selected from the group consisting of an alkylene group, -C(=O)O-, -C(=O)NR ^N -, and -O- A divalent linking group is preferable, and a single bond is more preferable.
Note that the above alkylene group may be linear, branched, or cyclic, and may further have a substituent. The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 4.
When X ¹ contains -C(=O)O-, the carbon atom included in -C(=O)O- and the carbon atom to which R ¹⁴ is bonded are preferably directly bonded.
Further, when X ¹ includes -C(=O)NR ^N -, it is preferable that the carbon atom included in -C(=O)NR ^N - and the carbon atom to which R ¹⁴ is bonded directly bond. .
The above R ^N represents an alkyl group or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and more preferably a hydrogen atom.

In formula A1, the group represented by -OC(R ¹¹ )(R ¹² )-OR ¹³ specified in the formula and X ¹ are They are preferably bonded to each other at the para position on the benzene ring. That is, the structural unit represented by formula A1 is preferably a structural unit represented by formula A1-1 below.
Note that R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , X ¹ , and n in formula A1-1 are R ¹¹ , R ¹² , R 13 , R ^{14 ,} R ¹⁵ , and X in formula A1, respectively. ¹ , and has the same meaning as n.

In formula A1, R ¹⁵ is preferably an alkyl group or a halogen atom. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4.

In formula A1, n is preferably 0 or 1, more preferably 0.

In formula A1, R ¹⁴ is preferably a hydrogen atom because it can lower the glass transition temperature (Tg) of the polymer A.
More specifically, the content of the structural unit in which R ¹⁴ in formula A1 is a hydrogen atom is preferably 20% by mass or more with respect to the total content of the structural unit A contained in the polymer A. In addition, the content of the structural unit in which R ¹⁴ in formula A1 is a hydrogen atom in the structural unit A is confirmed by the intensity ratio of the peak intensities calculated by a conventional method from ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement. can.

Among the structural units represented by the formula A1, the structural units represented by the following formula A1-2 are more preferable because they are more effective in suppressing deformation of the pattern shape.

In formula A1-2, R ^B4 represents a hydrogen atom or a methyl group. R ^B5 to R ^B11 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ^B12 represents a substituent. n represents an integer from 0 to 4.

In formula A1-2, R ^B4 is preferably a hydrogen atom.
In formula A1-2, R ^B5 to R ^B11 are preferably hydrogen atoms.
Formula A1-2 and R ^B12 are preferably an alkyl group or a halogen atom. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4.
In formula A1-2, n is preferably 0 or 1, more preferably 0.

In formula A1-2, the group containing R ^B5 to R ^B11 and the carbon atom to which R ^B4 is bonded are in a parasitic relationship with each other on the benzene ring specified in the formula in terms of steric hindrance of the acid-decomposable group. It is preferable to bond at this position.

Preferred specific examples of the structural unit represented by formula A1 include the following structural units. Note that R ^B4 in the following structural units represents a hydrogen atom or a methyl group.

- Preferred embodiments of the structural unit represented by formula A2 -
In formula A2, the number of carbon atoms in the alkyl groups represented by R ²¹ and R ²² is preferably 1 to 10. The aryl group represented by R ²¹ and R ²² is preferably a phenyl group.
Of these, R ²¹ and R ²² are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably at least one of R ²¹ and R ²² is a hydrogen atom.

In formula A2, the alkyl group or aryl group represented by R ²³ includes the same alkyl groups and aryl groups represented by R ²¹ and R ²² . Among these, R ²³ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

In formula A2, the alkyl group and aryl group in R ²¹ , R ²² , and R ²³ may further have a substituent.

In formula A2, R ²⁴ is each independently preferably an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. preferable. R ²⁴ may further have a substituent. The substituent has 1 to 1 carbon atoms.
0 alkyl groups or alkoxy groups having 1 to 10 carbon atoms.

In formula A2, m is preferably 1 or 2, and more preferably 1.

Preferred specific examples of the structural unit represented by formula A2 include the following structural units.

- Preferred embodiments of the structural unit represented by formula A3 -
In formula A3, the number of carbon atoms in the alkyl group represented by R ³¹ and R ³² is preferably 1 to 10. The aryl group represented by R ³¹ and R ³² is preferably a phenyl group.
Among R ³¹ and R ³² , a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred.

In formula A3, R ³³ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

The alkyl group and aryl group in R ³¹ to R ³³ may further 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 preferably 5 or 6, 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 further have a substituent.

In formula A3, R ³⁴ is preferably a hydrogen atom because it can lower the glass transition temperature (Tg) of the polymer A.
More specifically, the content of the structural unit in which R ³⁴ in formula A3 is a hydrogen atom is 20% by mass or more with respect to the total content of structural units represented by formula A3 contained in polymer A. It is preferable.
The content of the structural unit in which R ³⁴ in formula A3 is a hydrogen atom among the structural units represented by formula A3 is determined by the peak intensity calculated by a conventional method from ¹³ C-nuclear magnetic resonance spectrum (NMR) measurement. This can be confirmed by the intensity ratio of

Among the structural units represented by the formula A3, the structural units represented by the following formula A3-3 are more preferable since the sensitivity during pattern formation is further increased.

In formula A3-3, R ³⁴ represents a hydrogen atom or a methyl group. 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.

Preferred specific examples of the structural unit represented by formula A3 include the following structural units.
Note that R ³⁴ in the following structural units represents a hydrogen atom or a methyl group.

The structural unit A contained in the polymer A may be used alone, or two or more types may be used in combination.

The content of structural unit A in polymer A is preferably 20% by mass or more, more preferably 20 to 90% by mass, and 20 to 70% by mass, based on the total mass of polymer A. It is more preferable that
The content of structural unit A in polymer A can be confirmed by the intensity ratio of peak intensities calculated by a conventional method from ¹³ C-NMR measurement.

・Structural unit B (structural unit having a polar group)
It is preferable that the polymer A includes a structural unit having a polar group (hereinafter also referred to as "constituent unit B"). When the polymer A contains the structural unit B, the sensitivity during pattern formation becomes good, and the solubility in an alkaline developer improves in the development step after pattern exposure.

The polar group in structural unit B is a proton dissociative group having a pKa of 12 or less.
In terms of further improving sensitivity, the upper limit of the pKa of the polar group is preferably 10 or less, more preferably 6 or less. Further, the lower limit value is preferably −5 or more.

Examples of the polar group in structural unit B include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxy group, and a sulfonylimide group. Among the polar groups, a carboxy group or a phenolic hydroxy group is preferable.

Examples of the method for introducing the structural unit B into the polymer A include a method of copolymerizing a monomer having a polar group, or a method of copolymerizing a monomer having an acid anhydride structure and hydrolyzing the acid anhydride. Note that examples of monomers having a carboxyl group as a polar group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene. Examples of monomers having a phenolic hydroxy group as a polar group include p-hydroxystyrene and 4-hydroxyphenyl methacrylate. Furthermore, examples of the monomer having an acid anhydride structure include maleic anhydride.

The structural unit B is preferably a structural unit derived from a styrene compound having a polar group, or a structural unit derived from a vinyl compound having a polar group, and a structural unit derived from a styrene compound having a phenolic hydroxy group. Or, it is more preferably a structural unit derived from a vinyl compound having a carboxyl group, even more preferably a structural unit derived from a vinyl compound having a carboxy group, and a structural unit derived from (meth)acrylic acid. is particularly preferred.

The structural unit B may be used alone or in combination of two or more.

The content of structural unit B in polymer A is preferably 0.1% by mass to 20% by mass, and preferably 0.5% by mass to 15% by mass, based on the total mass of polymer A. is more preferable, and even more preferably 1% by mass to 10% by mass. By adjusting the content of the structural unit B in the polymer A within the above numerical range, pattern formation properties become better.
The content of structural unit B in polymer A can be confirmed by the intensity ratio of peak intensities calculated from ¹³ C-NMR measurement using a conventional method.

- Constituent unit C: Other constituent units:
Polymer A may further contain other structural units (hereinafter also referred to as "structural units C") in addition to the above-mentioned structural units A and B. By adjusting at least one of the type and content of the structural unit C contained in the polymer A, various properties of the polymer A can be adjusted. In particular, by appropriately using the structural unit C, the glass transition temperature (Tg) of the polymer A can be easily adjusted.

Examples of monomers forming the structural unit C include styrenes, (meth)acrylic acid alkyl esters, (meth)acrylic acid cyclic alkyl esters, (meth)acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, and bicyclounsaturated compounds. , maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, unsaturated compounds having an aliphatic cyclic skeleton, and other known unsaturated compounds. Examples include saturated compounds.

Examples of the structural unit C include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, (meth)acrylic acid Methyl, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid Examples include structural units derived from benzyl, isobornyl (meth)acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono(meth)acrylate, and the like. In addition, examples of the structural unit C include structural units derived from compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623.

The structural unit C is preferably a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton from the viewpoint of further improving electrical properties.
Examples of monomers forming the above structural units include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and Examples include benzyl (meth)acrylate. The structural unit C is preferably a structural unit derived from cyclohexyl (meth)acrylate.

When step X1 is carried out by transfer as described below, the structural unit C is preferably a (meth)acrylic acid alkyl ester in terms of better adhesion, and has an alkyl group having 4 to 12 carbon atoms. (Meth)acrylic acid alkyl ester is more preferred.
Specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

Polymer A may include a structural unit having an ester of the polar group in the above structural unit B as structural unit C in order to further improve solubility in a developer and/or to optimize physical properties. is also preferable. Among these, it is preferable that the polymer A contains a structural unit having a carboxy group as the structural unit B, and further contains a structural unit C containing a carboxylic acid ester group, for example, a structural unit B derived from (meth)acrylic acid. and a structural unit C derived from a monomer selected from the group consisting of cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate.

The structural unit C may be used alone or in combination of two or more.

The upper limit of the content of structural unit C in polymer A is preferably 80% by mass or less, more preferably 75% by mass or less, and 60% by mass, based on the total mass of polymer A. % or less, more preferably 50% by mass or less. The lower limit of the content of the structural unit C in the polymer A may be 0% by mass with respect to all the structural units constituting the polymer A, but it is preferably 1% by mass or more, and 5% by mass or more. It is more preferable that By setting the content of the structural unit C in the polymer A within the above numerical range, resolution and adhesion can be further improved.

Preferred examples of polymer A will be listed below, but the invention is not limited to the following examples. In addition, the ratio of the structural units and the weight average molecular weight in the following exemplified compounds are appropriately selected in order to obtain preferable physical properties.

One type of polymer A may be used alone, or two or more types may be used in combination.

The content of polymer A in the photosensitive resin composition is based on the total solid content of the composition,
It is preferably 50% by mass to 99.9% by mass, more preferably 70% by mass to 98% by mass.

・Glass transition temperature of polymer A: Tg
When carrying out step X1 by transfer as described below, the glass transition temperature (Tg) of polymer A is preferably 90°C or less, more preferably 20°C to 60°C, from the viewpoint of transferability. The temperature is preferably 30°C to 50°C, particularly preferably.

As a method for adjusting the glass transition temperature (Tg) of polymer A to the above numerical range, for example,
A method of adjusting the type and mass fraction of each structural unit contained in the polymer A using the FOX formula as a guideline may be mentioned. By using the FOX formula, the glass transition temperature (Tg) of polymer A can be adjusted from the glass transition temperature (Tg) of the homopolymer of each structural unit contained in polymer A and the mass fraction of each structural unit. can. Further, by adjusting the weight average molecular weight of the polymer A, the glass transition temperature (Tg) of the polymer A can be adjusted.

Hereinafter, the FOX formula will be explained using a copolymer containing a first structural unit and a second structural unit as an example.
The glass transition temperature of the homopolymer of the first structural unit is Tg1, the mass fraction of the first structural unit contained in the copolymer is W1, and the glass transition temperature of the homopolymer of the second structural unit is Tg0 of the copolymer containing the first structural unit and the second structural unit, where Tg2 is the mass fraction of the second structural unit contained in the copolymer in the copolymer, and W2 is the mass fraction of the second structural unit contained in the copolymer. (Unit: K) is
It is possible to estimate according to the following formula. Therefore, by adjusting the type and mass fraction of each structural unit contained in the target polymer using the FOX formula, a polymer having a desired glass transition temperature (Tg) can be obtained.
FOX formula: 1/Tg0=(W1/Tg1)+(W2/Tg2)

- Acid value of polymer A From the viewpoint of resolution, the acid value of polymer A is preferably 0 mgKOH/g to 200 mgKOH/g, more preferably 0 mgKOH/g to 100 mgKOH/g.

The acid value of a polymer represents the mass of potassium hydroxide required to neutralize acidic components per gram of polymer. Specifically, the measurement sample was dissolved in a mixed solvent of tetrahydrofuran and water (volume ratio: tetrahydrofuran/water = 9/1), and the sample was dissolved using a potentiometric titration device (trade name: AT-510, manufactured by Kyoto Electronics Co., Ltd.). Then, the obtained solution is subjected to neutralization titration with a 0.1M aqueous sodium hydroxide solution at 25°C. Using the inflection point of the titration pH curve as the titration end point, the acid value is calculated using the following formula.
Formula: A=56.11×Vs×0.1×f/w
A: Acid value (mgKOH/g)
Vs: Amount of 0.1 mol/L sodium hydroxide aqueous solution required for titration (mL)
f: Titer of 0.1 mol/L sodium hydroxide aqueous solution w: Mass (g) of measurement sample (solid content equivalent)

・Molecular weight of polymer A: Mw
The weight average molecular weight of the polymer A is preferably 2,000 to 60,000, more preferably 3,000 to 50,000.

The weight average molecular weight of Polymer A can be measured by GPC (gel permeation chromatography), and various commercially available devices can be used as the measuring device.
The weight average molecular weight was measured by gel permeation chromatography (GPC) using HLC (registered trademark)-8220GPC (manufactured by Tosoh Corporation) as the measuring device and TSKgel (registered trademark) Super HZM-M (4. 6 mm ID x 15 cm, manufactured by Tosoh Corporation), Super HZ4000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), Super HZ3000 (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), and Super HZ2000 (4.6 mm ID x 15 cm, (manufactured by Tosoh Corporation) connected in series, and THF (tetrahydrofuran) can be used as the eluent.
In addition, the measurement conditions include a sample concentration of 0.2% by mass, a flow rate of 0.35mL/min, a sample injection amount of 10μL, and a measurement temperature of 40°C, and can be carried out using a differential refractive index (RI) detector. .
The calibration curve is based on "standard sample TSK standard, polystyrene" manufactured by Tosoh Corporation: "F-40", "F-20", "F-4", "F-1", "A-5000", " It can be created using any of the 7 samples of "A-2500" and "A-1000".

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

・Production method of polymer A The production method (synthesis method) of polymer A is not particularly limited, but to give an example, a polymerizable monomer for forming structural unit A, a polymerizable monomer for forming structural unit B The monomer and, if necessary, a polymerizable monomer for forming the structural unit C can be synthesized by polymerizing in an organic solvent using a polymerization initiator. Moreover, the polymer A can also be synthesized by a so-called polymer reaction.

[Other polymers]
In addition to the polymer A, the photosensitive resin composition may further contain a polymer (hereinafter also referred to as "other polymer") that does not contain a structural unit having an acid-decomposable group.

Examples of other polymers include polyhydroxystyrene. Examples of polyhydroxystyrene include SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (all manufactured by Sartomer), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC- 3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 (all manufactured by Toagosei Co., Ltd.), and Joncryl 690, Joncryl 678, Joncryl 67, and Joncryl 586 (all manufactured by BASF) etc. commercially available You can use the product.

Other polymers may be used alone or in combination of two or more.

When the photosensitive resin composition contains other polymers, the content of the other polymers in the photosensitive resin composition is 50% by mass or less based on the total content of Polymer A and other polymers. It is preferable that it is, it is more preferable that it is 30 mass % or less, and it is still more preferable that it is 20 mass % or less.

[Photoacid generator]
The photosensitive resin composition contains a photoacid generator. A photoacid generator is a compound that can generate acid when irradiated with radiation such as ultraviolet rays, deep ultraviolet rays, X-rays, and charged particle beams.

The photoacid generator is preferably a compound that generates an acid in response to actinic light having a wavelength of 300 nm or more, preferably 300 to 450 nm. Among the photoacid generators, compounds having absorption at a wavelength of 365 nm are more preferable because they have better spectral sensitivity.
In addition, even if a photoacid generator is not directly sensitive to actinic rays with a wavelength of 300 nm or more, if it is a compound that is sensitive to actinic rays with a wavelength of 300 nm or more and generates acid when used in combination with a sensitizer, it can be considered a sensitizer. They 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 photoacid generator that generates an acid with a pKa of 2 or less. A photoacid generator that generates an acid is particularly preferred. The lower limit of the pKa of the acid generated from the photoacid generator is not particularly limited, and is preferably -10 or more, for example.

Examples of the photoacid generator include ionic photoacid generators and nonionic photoacid generators. In addition, the photoacid generator preferably contains one or more compounds selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and more preferably contains oxime sulfonate compounds, in terms of better sensitivity and resolution. preferable.

Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. Among the ionic photoacid generators, onium salt compounds are preferred, and diaryliodonium salts or triarylsulfonium salts are more preferred.

As the ionic photoacid generator, the ionic photoacid generators described in paragraphs 0114 to 0133 of JP-A No. 2014-85643 can also be preferably used.

Examples of the nonionic photoacid generator include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oxime sulfonate compounds. Among the nonionic photoacid generators, oxime sulfonate compounds are preferred because they improve sensitivity, resolution, and adhesion. Specific examples of trichloromethyl-s-triazines and diazomethane derivatives include compounds described in paragraphs 0083 to 0088 of JP-A No. 2011-221494.

As the oxime sulfonate compound, that is, the compound having an oxime sulfonate structure, 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 formula (B1), any group may be substituted, and the alkyl group in R ²¹ may be linear, branched, or cyclic. . 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 includes an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a cycloalkyl group (for example, an alkyl group such as a 7,7-dimethyl-2-oxonorbornyl group). (including a bridged alicyclic group, preferably a bicycloalkyl group, etc.), or may be substituted with a halogen atom.

The aryl group for R ²¹ is preferably an aryl group having 6 to 18 carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group in 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.

The compound having an oxime sulfonate structure represented by formula (B1) is also preferably an oxime sulfonate compound described in paragraphs 0078 to 0111 of JP-A No. 2014-85643.

One type of photoacid generator may be used alone, or two or more types may be used in combination.

The content of the photoacid generator in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass, based on the total mass of the composition, from the viewpoint of better sensitivity and resolution. More preferably, the content is .2% to 5% by mass.

〔solvent〕
The photosensitive resin composition may contain a solvent.
Examples of the solvent include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl Examples include ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, and lactones. . Furthermore, examples of the solvent include the solvents described in paragraphs 0174 to 0178 of JP-A No. 2011-221494, the contents of which are incorporated into the present disclosure.

In addition to the above-mentioned solvents, the photosensitive resin composition may further contain benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, It may contain solvents such as caprylic acid, 1-octanol, 1-nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, and propylene carbonate.

The solvent is preferably a solvent with a boiling point of 130°C or more and less than 160°C, a solvent with a boiling point of 160°C or more, or a mixture thereof.
Examples of solvents with a boiling point of 130°C or higher and lower than 160°C include propylene glycol monomethyl ether acetate (boiling point 146°C), propylene glycol monoethyl ether acetate (boiling point 158°C), propylene glycol methyl-n-butyl ether (boiling point 155°C), and propylene glycol methyl-n-propyl ether (boiling point 131°C).
Examples of solvents with a boiling point of 160°C or higher include ethyl 3-ethoxypropionate (boiling point 170°C), diethylene glycol methyl ethyl ether (boiling point 176°C), propylene glycol monomethyl ether propionate (boiling point 160°C), dipropylene glycol methyl Ether acetate (boiling point 213°C), 3-methoxybutyl ether acetate (boiling point 171°C), diethylene glycol diethyl ether (boiling point 189°C), diethylene glycol dimethyl ether (boiling point 162°C), propylene glycol diacetate (boiling point 190°C), diethylene glycol monoethyl ether Examples include acetate (boiling point 220°C), dipropylene glycol dimethyl ether (boiling point 175°C), and 1,3-butylene glycol diacetate (boiling point 232°C).

Further, preferable examples of the solvent include esters, ethers, ketones, and the like.
Examples of the esters include ethyl acetate, propyl acetate, isobutyl acetate, sec-butyl acetate, t-butyl acetate, isopropyl acetate, and n-butyl acetate.
Examples of the ethers include diisopropyl ether, 1,4-dioxane, 1,2-dimethoxyethane, 1,3-dioxolane, propylene glycol dimethyl ether, and propylene glycol monoethyl ether.
Examples of ketones include methyl n-butyl ketone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl n-propyl ketone, and methyl isopropyl ketone.

Further, as the solvent, toluene, acetonitrile, isopropanol, 2-butanol, isobutyl alcohol, etc. may be used.

One type of solvent may be used alone, or two or more types may be used in combination.

The content of the solvent in the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition. It is more preferable.

[Other additives]
In addition to the polymer A and the photoacid generator, the photosensitive resin composition may further contain other additives as necessary.

- Basic compound It is preferable that the photosensitive resin composition contains a basic compound. Examples of the basic compound include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples of these include compounds described in paragraphs 0204 to 0207 of JP-A No. 2011-221494, the contents of which are incorporated into the present disclosure.

Examples of aliphatic amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine. , and dicyclohexylmethylamine.

Examples of aromatic amines include aniline, benzylamine, N,N-dimethylaniline, and diphenylamine.

Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.3.0]-7 -undecene, N-cyclohexyl-N'-[2-(4-morpholinyl)ethyl]thiourea, and 1,2,3-benzotriazole.

Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.

Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

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

The content of the basic compound in the photosensitive resin composition is preferably 0.001% by mass to 5% by mass, and 0.005% by mass to 3% by mass, based on the total mass of the composition. It is more preferable.

- Liquid repellent The photosensitive resin composition preferably contains a liquid repellent from the viewpoint of further improving the uniformity of the thickness and further reducing the defective rate of the conductive substrate to be formed.
As the liquid repellent, a compound containing one or more of a fluorine atom and a silicon atom is preferred, a fluorine atom-containing compound is more preferred, a fluorine atom-containing surfactant is even more preferred, and a fluorine atom-containing nonionic surfactant is particularly preferred.
Further, as the liquid repellent, a liquid repellent having a polymerizable group (hereinafter also referred to as a "polymerizable group-containing liquid repellent") can also be used. In addition, an epoxy group or an ethylenically unsaturated group is mentioned as a polymeric group.
Further, as the liquid repellent, a compound represented by the general formula (1) of JP-A-2013-209636 can also be used.

As the fluorine atom-containing compound, as mentioned above, a fluorine atom-containing nonionic surfactant is preferable. A preferred example of the fluorine atom-containing nonionic surfactant includes a structural unit SA and a structural unit SB represented by the following formula I-1, and is measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. Examples include copolymers having a weight average molecular weight (Mw) of 1,000 to 10,000 in terms of polystyrene.

In formula I-1, R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group. R ⁴⁰² represents a straight chain alkylene group having 1 to 4 carbon atoms. R ⁴⁰⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. L represents an alkylene group having 3 to 6 carbon atoms. p and q are mass percentages representing the polymerization ratio. p represents a numerical value of 10% by mass to 80% by mass, and q represents a numerical value of 20% by mass to 90% by mass. r represents an integer from 1 to 18. s represents an integer from 1 to 10. * represents a binding site with another structure.

L is preferably a branched alkylene group represented by the following formula I-2.

R ⁴⁰⁵ in formula I-2 represents an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms from the viewpoint of compatibility and wettability to the coated surface, and R 405 having 2 or 3 carbon atoms. Alkyl groups are more preferred.

In formula I-1, the sum of p and q (p+q) is preferably p+q=100, that is, 100% by mass.

The weight average molecular weight (Mw) of the copolymer containing the structural unit SA and the structural unit SB represented by formula I-1 is preferably 1,500 to 5,000.

Below, other specific examples of liquid repellents other than the above-mentioned copolymers will be illustrated.
Examples of the fluorine atom-containing compound include perfluoroalkyl sulfonic acid, perfluoroalkyl carboxylic acid, perfluoroalkyl alkylene oxide adduct, perfluoroalkyl trialkylammonium salt, oligomer containing a perfluoroalkyl group and a hydrophilic group, and perfluoro Examples include oligomers containing an alkyl group and a lipophilic group, oligomers containing a perfluoroalkyl group, a hydrophilic group, and a lipophilic group, urethanes containing a perfluoroalkyl and a hydrophilic group, perfluoroalkyl esters, and perfluoroalkyl phosphate esters. .

Commercially available fluorine-containing compounds include "DEFENSAMCF-300", "DEFENSAMCF-310", "DEFENSAMCF-312", "DEFENSAMCF-323", and "Megafac RS-72-K" (all manufactured by DIC Corporation). ); "Florado FC-431", "Florado FC-4430", and "Florado FC-4432" (all made by 3M Japan); "Asahi Guard AG710", "Surflon S-382", "Surflon SC" -101'', ``Surflon SC-102'', ``Surflon SC-103'', ``Surflon SC-104'', ``Surflon SC-105'', and ``Surflon SC-106'' (all manufactured by Asahi Glass Co., Ltd.); Optool DAC-HP" and "HP-650" (both manufactured by Daikin Industries, Ltd.) can be used.

In addition, commercially available fluorine atom-containing compounds include F-251, F-253, F-281, F-430, F-444, F-477, and F-251, F-253, F-281, F-430, F-444, F-477, and -551, F-552, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F-563 , F-565, F-568, F-569, F-570, F-572, F-574, F-575, F-576, F-780, EXP, MFS-330, MFS-578, MFS-579 , MFS-586, MFS-587, R-40, R-40-LM, R-41, RS-43, TF-1956, RS-90, RS-72-K, DS-21, and R-94, etc. (a fluorine atom-containing surfactant with an oligomeric structure) can also be used.
Also,

Furthermore, as commercially available fluorine atom-containing compounds, fluorine atom-containing nonionic surfactants such as Ftergent 250 and Ftergent 251 manufactured by Neos Co., Ltd. can also be used.
You can also use Futergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 212M, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 manufactured by NEOS Co., Ltd.

Furthermore, as the fluorine atom-containing compound, surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362 can also be used.

As fluorosurfactants, from the viewpoint of improving environmental suitability, compounds having a linear perfluoroalkyl group having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), are used. Surfactants derived from alternative materials are preferred.

Commercially available silicon atom-containing compounds include silicone surfactants such as the SILFOAM (registered trademark) series (eg, SD100TS, SD670, SD850, SD860, SD882) manufactured by Wacker Chemie.

The liquid repellent may be used alone or in combination of two or more.
When using a fluorine atom-containing compound as a liquid repellent, the lower limit of the content of fluorine atoms in the liquid repellent is preferably 1% by mass or more, more preferably 5% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 25% by mass or less.

The content of the liquid repellent in the photosensitive resin composition is, for example, 0.01% by mass to 10% by mass, preferably 0.05% by mass to 5% by mass, based on the total solid content of the composition. .

-Surfactant The photosensitive resin composition preferably contains a surfactant in order to further improve the uniformity of the thickness. Note that the surfactant herein does not include the above-mentioned surfactant-based liquid repellent.

As the surfactant, any of anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants can be used. Among these, nonionic surfactants are preferred.

Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, and higher fatty acid diesters of polyoxyethylene glycol. Specific examples of nonionic surfactants include, for example, the nonionic surfactants described in paragraph 0120 of International Publication No. 2018/179640.

One type of surfactant may be used alone, or two or more types may be used in combination.

The content of the surfactant in the photosensitive resin composition is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, based on the total mass of the composition. More preferably, it is 0.01% by mass to 3% by mass.

-Plasticizer The photosensitive resin composition may contain a plasticizer for the purpose of improving plasticity. The plasticizer is not particularly limited, and any known plasticizer can be used. Examples of the plasticizer include the plasticizers described in paragraphs 0097 to 0103 of International Publication No. 2018/179640.

- Sensitizer The photosensitive resin composition may contain a sensitizer. The sensitizer is not particularly limited, and any known sensitizer can be used. Examples of the sensitizer include the sensitizers described in paragraphs 0104 to 0107 of International Publication No. 2018/179640.

-Heterocyclic compound The photosensitive resin composition may contain a heterocyclic compound. The heterocyclic compound is not particularly limited, and any known heterocyclic compound can be used. As a heterocyclic compound,
Examples include the heterocyclic compounds described in paragraphs 0111 to 0118 of International Publication No. 2018/179640.

-Alkoxysilane compound The photosensitive resin composition may contain an alkoxysilane compound. The alkoxysilane compound is not particularly limited, and any known alkoxysilane compound can be used. Examples of the alkoxysilane compound include the alkoxysilane compound described in paragraph 0119 of International Publication No. 2018/179640.

・Other components The photosensitive resin composition contains metal oxide particles, antioxidant, dispersant, acid multiplying agent, development accelerator, conductive fiber, coloring agent, thermal radical polymerization initiator, thermal acid generator, ultraviolet rays. It may further contain known additives such as absorbents, thickeners, crosslinking agents, and organic or inorganic suspending agents. For preferred embodiments of other components, see paragraph 016 of JP-A-2014-85643.
5 to paragraph 0184, and the contents of this publication are incorporated into the present specification.

[Physical properties, etc.]
The thickness of the photosensitive resin layer is preferably 30 μm or less, more preferably 10 μm or less, even more preferably 5 μm or less, particularly preferably 3 μm or less, and 1 μm or less. Most preferred. When the thickness of the photosensitive resin layer is 30 μm or less, the developability of the photosensitive resin layer is improved and the resolution is improved. The lower limit of the thickness of the photosensitive resin layer is preferably 0.05 μm or more, more preferably 0.1 μm or more.

The thickness of each layer in the laminate is determined by observing a cross section perpendicular to the main surface of the photosensitive transfer material using a scanning electron microscope (SEM), and determining the thickness of each layer based on the observed image. The thickness is measured at 10 or more points and calculated as the average value.

In terms of better adhesion, the light transmittance of the photosensitive resin layer at a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and particularly preferably 50% or more. The upper limit of the light transmittance of the photosensitive resin layer at a wavelength of 365 nm is not particularly limited, but is preferably 99.9% or less.

[Method for preparing composition]
Examples of the method for preparing the photosensitive resin composition include a method in which the above components and a solvent are mixed in an arbitrary ratio, and the mixture is stirred and dissolved. Moreover, the photosensitive resin composition can be prepared by dissolving each of the above-mentioned components in a solvent in advance to form a solution, and then mixing the obtained solutions in a predetermined ratio. The prepared photosensitive resin composition may be used after being filtered using a filter having a pore size of 0.2 μm.

The laminate may include layers other than the layers described above (hereinafter also referred to as "other layers"). Examples of other layers include a contrast enhancement layer.
The contrast enhancement layer is described in paragraph 0134 of International Publication No. 2018/179640. Further, other layers are described in paragraphs 0194 to 0196 of JP-A No. 2014-85643. The contents of these publications are incorporated herein.

(Method of manufacturing structure)
The method for manufacturing a structure according to the present disclosure may be any method for manufacturing a structure including a conductive pattern obtained by the method for forming a conductive pattern according to the present disclosure, and the method for forming a conductive pattern according to the present disclosure A step of forming a negative photosensitive resin layer on the first film and the conductive pattern on the first film having the conductive pattern obtained by a step of exposing the mold photosensitive resin layer, a step of developing the negative photosensitive resin layer irradiated with light to form a resin pattern N on the first film, and a step of forming the resin pattern N on the first film; It is preferable to include a step of forming a pattern M in a region defined by the pattern and the resin pattern N.

The negative photosensitive resin layer is not particularly limited and can be formed using a known negative photosensitive resin composition.
The negative photosensitive resin layer may be in contact with the conductive pattern directly or through another layer, but it is preferably in contact with the conductive pattern. As the negative photosensitive resin layer, a known negative photosensitive resin layer can be used.
The negative photosensitive resin layer preferably contains a polymer, a polymerizable compound, and a photopolymerization initiator. The negative photosensitive resin layer contains 10% to 90% by weight of a polymer, 5% to 70% by weight of a polymerizable compound, and 0.01% by weight based on the total weight of the negative photosensitive resin layer. % to 20% by mass of a photopolymerization initiator.
Moreover, it is preferable that the negative photosensitive resin layer contains an alkali-soluble polymer, a compound having an ethylenically unsaturated bond, and a photopolymerization initiator.

A step of exposing the negative photosensitive resin layer through the first film, and developing the irradiated negative photosensitive resin layer to form a resin pattern N on the first film. Exposure and development in the forming step are not particularly limited, and can be performed using known exposure and development methods.
By performing the exposure through the first film, the conductive pattern acts as a light shielding part, and the negative photosensitive resin layer on the conductive pattern is removed by development, and the opening (the resin pattern (the part without N).
The thickness of the resin pattern N is preferably thicker than the thickness of the conductive pattern.
The ratio of the thickness of the resin pattern N to the thickness of the conductive pattern ([thickness of the resin pattern N]/[thickness of the conductive pattern]) is preferably 1.1 or more, and 1.5 or more. It is more preferable that it is, and it is especially preferable that it is 3 or more. The ratio of the thickness of the resin pattern N to the thickness of the conductive pattern is more preferably 10 or less.

The thickness of the resin pattern N is preferably 1 μm or more, more preferably 5 μm or more, and particularly preferably 10 μm or more. The upper limit of the thickness of the resin pattern N is not limited. The average thickness of the resin pattern N may be determined, for example, within a range of 100 μm or less.

<Pattern M formation process>
The method for manufacturing a structure according to the present disclosure preferably includes a step of forming a pattern M in a region defined by the conductive pattern and the resin pattern N (also referred to as a "pattern M forming step").
It is preferable that the pattern M has electrical conductivity from the viewpoint of further exerting the effects of the present disclosure.
Further, from the viewpoint of pattern formability and dimensional stability of the resulting pattern M, it is preferable that the average thickness of the pattern M is thicker than the average thickness of the conductive pattern.

As a method for forming the pattern M, a known method can be used. As the material of the pattern M having conductivity, a material having conductivity suitable for the purpose can be used. The conductive material of the pattern M preferably contains Cu or a Cu alloy. The alloy of Cu is preferably an alloy of Cu and at least one member selected from the group consisting of Ni, Mo, Ta, Ti, V, Cr, Fe, Mn, Co, and W. The pattern M formed using the above-mentioned material contains the above-mentioned metal element. The pattern M obtained in the pattern M forming step may be a conductive pattern made of Cu.
Further, from the viewpoint of pattern formability and dimensional stability of the resulting pattern M, it is preferable that the conductive pattern and the pattern M contain the same kind of material. For example, it is more preferable that they contain the same metal element, and it is particularly preferable that they are the same metal or an alloy that contains the same metal element.

A known method can be used to form the pattern M on the conductive pattern. The pattern M is preferably a pattern formed by a plating method. As the plating, known plating can be used. Examples of plating include electroplating and electroless plating. The plating is preferably electroplating, more preferably electrolytic copper plating.

In electroplating, for example, a conductive pattern that can function as a seed layer is used as a cathode, and metal is stacked on top of the light-shielding pattern, thereby forming a conductive pattern M on the conductive pattern. I can do it.

Components of the plating solution used in electroplating include, for example, water-soluble copper salts. As the water-soluble copper salt, water-soluble copper salts commonly used as components of plating solutions can be used. The water-soluble copper salt is preferably at least one selected from the group consisting of, for example, an inorganic copper salt, an alkanesulfonic acid copper salt, an alkanolsulfonic acid copper salt, and an organic acid copper salt. Examples of inorganic copper salts include copper sulfate, copper oxide, copper chloride, and copper carbonate. Examples of copper alkanesulfonate include copper methanesulfonate and copper propanesulfonate. Examples of copper alkanolsulfonate salts include copper isethionate and copper propanolsulfonate. Examples of organic acid copper salts include copper acetate, copper citrate, and copper tartrate.

The plating solution may contain sulfuric acid. By including sulfuric acid in the plating solution, the pH and sulfate ion concentration of the plating solution can be adjusted.

The electroplating method and conditions are not limited. For example, a conductive pattern M can be formed on a conductive pattern by supplying the transparent base material after the development process to a plating tank to which a plating solution is added. In electroplating, for example, a conductive pattern M can be formed by controlling the current density and the transport speed of the transparent base material.

The temperature of the plating solution used for electroplating is preferably 70°C or lower, more preferably 10°C to 40°C. The current density in electroplating is preferably 0.1 A/dm ² to 100 A/dm ² , more preferably 0.5 A/dm ² to 20 A/dm ² . The productivity of conductive patterns can be improved by increasing the current density. By lowering the current density, the uniformity of the thickness of the conductive pattern can be improved.

In the method of forming the conductive pattern M by plating, a plurality of metals may be plated in succession. For example, in the pattern M formed of metal such as copper, visibility or aesthetics may be degraded due to reflection. Examples of methods for reducing the reflectance of the surface of the pattern M include oxidation treatment, sulfidation treatment, nitridation treatment, chlorination treatment, formation of a blackened layer, and black plating. For example, by performing chromium plating after copper plating, a layer containing a black material can be formed on the surface of the pattern M. The method for reducing the reflectance of the surface of the pattern M is preferably oxidation treatment or sulfurization treatment. Oxidation treatment is preferable from the viewpoints of obtaining a better anti-glare effect, and also from the viewpoint of ease of waste liquid treatment and environmental safety.

After forming the pattern M, a post-bake process may be performed. The post-bake step can improve insulation reliability, curing properties, or plating adhesion by completely thermosetting unreacted thermosetting components. The heating temperature is preferably 80°C to 240°C. The heating time is preferably 5 minutes to 120 minutes.

After forming the pattern M, the surface of the pattern M may be protected with a resin layer. For example, after forming the pattern M, the surface of the pattern M can be protected by forming a resin layer on the conductive pattern. Examples of the components of the resin layer include acrylic resin, polyester resin, polyvinyl acetal resin layer, polyimide resin, and epoxy resin. Examples of methods for forming the resin layer include coating and thermocompression bonding.

The structure of the pattern M may be a single layer structure or a multilayer structure. The components of each layer of pattern M having a multilayer structure may be the same or different.

The thickness of pattern M is not limited. The thickness of the pattern M may be determined depending on the application, for example. When the pattern M is used as a wiring, the average thickness of the pattern M may be determined depending on, for example, the magnitude of the current supplied to the wiring and the width of the wiring. From the viewpoint of conductivity, the average thickness of the pattern M is preferably 0.5 μm or more, more preferably 1 μm or more, and particularly preferably 2 μm or more. Further, the average thickness of the pattern M is preferably 3 μm or more, more preferably 5 μm or more, and particularly preferably 10 μm or more. The average thickness of the pattern M is measured by a method similar to the method for measuring the average thickness of the transparent substrate described above.

The width of the pattern M is preferably narrow. Specifically, the average width of the pattern M is preferably 50 μm or less, more preferably 10 μm or less, even more preferably 5 μm or less, and particularly preferably 2 μm or less. When the average width of the pattern M is 5 μm or less, the visibility of the pattern M in a device sensitive to visibility, such as a touch panel, can be reduced, for example. From the viewpoint of conductivity, the average width of the pattern M is preferably 0.1 μm or more, more preferably 0.5 μm or more, and particularly preferably 0.8 μm or more. The average width of the pattern M is measured by a method similar to the method for measuring the average width of the conductive pattern described above.

The surface resistance value of the conductive pattern M is preferably less than 0.2 Ω/□, more preferably less than 0.15 Ω/□. The surface resistance value of the conductive pattern M is measured by a four-probe method. If the pattern size is so small that measurement is difficult, the surface resistance value of a conductive layer having the same composition and thickness may be measured.

In the pattern M forming process, the interface between the pattern M and the conductive pattern may not be clearly observed. For example, when the conductive pattern is used as a seed layer and the pattern M is formed by plating, the interface between the conductive pattern and the pattern M may not be clearly observed. However, the fact that the interface between the pattern M and the conductive pattern is not clearly observed does not impede the purpose of the present disclosure.

The method for manufacturing a structure according to the present disclosure further includes the step of subjecting the resin pattern N to at least one of post-exposure and post-heating, from the viewpoint of improving the strength and durability of the resin pattern N, which is a permanent film. It is preferable.

The method for manufacturing a structure according to the present disclosure may include any steps (other steps) other than those described above. Other steps are not particularly limited, and include known steps.
Furthermore, as examples of the resin pattern forming step and other steps in the present disclosure, the methods described in paragraphs 0035 to 0051 of JP-A No. 2006-23696 can also be suitably used in the present disclosure.
Further, the method for manufacturing a structure according to the present disclosure may include a step of polishing the obtained pattern, a step of cleaning the obtained pattern, and the like.
Furthermore, the method for manufacturing a structure according to the present disclosure may include a step of providing members corresponding to each use described later.

A structure obtained by the method for manufacturing a structure according to the present disclosure can be applied to various uses. Preferred uses of the structure obtained by the method for manufacturing a structure according to the present disclosure include those similar to the uses of the conductive pattern obtained by the method for forming a conductive pattern according to the present disclosure described above.

Embodiments of the present invention will be described in more detail with reference to Examples below. The materials, amounts used, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the embodiments of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. Note that unless otherwise specified, "parts" and "%" are based on mass.

"AA": Acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
"ATHF": 2-tetrahydrofuranyl acrylate (synthetic product)
"CHA": cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
"EA": Ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
"MAA": Methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
"PGMEA": Propylene glycol monomethyl ether acetate (manufactured by Showa Denko K.K.)
"TBA": tert-butyl acrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
"BMA": Benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
"PMPMA": 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
"MMA": Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
"V-601": Dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

<Preparation of positive photosensitive resin composition 1>
The components shown below were mixed to obtain a mixed solution. Next, the above mixture was filtered using a polytetrafluoroethylene filter with a pore size of 0.2 μm to obtain a positive photosensitive resin composition 1.
・Acid-decomposable resin (polymer 1 below): 9.64 parts ・Photoacid generator (compound A-1 below): 0.25 parts ・Surfactant (surfactant C below): 0.01 part ・Additive (compound D below (basic compound)): 0.1 part, PGMEA: 90.00 parts

Polymer 1: In the resin shown below and the above-mentioned Polymer 1, the numerical values written for each structural unit are intended to be mass %. Moreover, the weight average molecular weight of the polymer 1 is 25,000. The glass transition temperature of the polymer 1 is 25°C.

Compound A-1: The following compound

Surfactant C: the following compound

Compound D: The following compound

<Preparation of positive photosensitive resin composition 2>
The components shown below were mixed to obtain a mixed solution. Next, the above mixture was filtered using a polytetrafluoroethylene filter with a pore size of 0.2 μm to obtain a positive photosensitive resin composition 2.
・Acid-decomposable resin (polymer 2 below): 9.64 parts ・Photoacid generator (compound A-2 below): 0.25 parts ・Surfactant (surfactant C above): 0.01 part ・Additive (Compound D above): 0.1 part PGMEA: 90.00 parts

Polymer 2: Compound having the structure shown below (glass transition temperature is 90°C. Weight average molecular weight is 20,000. The numerical values described in each of the structural units below mean % by mass.

Compound A-2: Compound with the structure shown below

<Preparation of positive photosensitive resin composition 3>
-Synthesis of acid-decomposable resin (polymer 3)-
<<Synthesis of ATHF>>
Acrylic acid (72.1 g, 1.0 mol) and hexane (72.1 g) were added to a three-necked flask, and the mixture was cooled to 20°C. After dropping camphorsulfonic acid (7.0 mg, 0.03 mmol) and 2-dihydrofuran (77.9 g, 1.0 mol), stirring at 20°C ± 2°C for 1.5 hours, the temperature was raised to 35°C. The mixture was stirred for 2 hours. After spreading Kyoward 200 (filter material, aluminum hydroxide powder, manufactured by Kyowa Chemical Industry Co., Ltd.) and Kyoward 1000 (filter material, hydrotalcite powder, manufactured by Kyowa Chemical Industry Co., Ltd.) in the order of Nutsche, the reaction solution was A filtrate was obtained by filtering. After adding hydroquinone monomethyl ether (MEHQ, 1.2 mg) to the obtained filtrate, it was concentrated under reduced pressure at 40°C to obtain 140.8 g of tetrahydrofuran-2-yl acrylate (ATHF) as a colorless oil. (Yield 99.0%).

<<Synthesis of acid-decomposable resin (polymer 3)>>
PGMEA (75.0 g) was placed in a three-necked flask, and the temperature was raised to 90° C. under a nitrogen atmosphere. ATHF (40.0g), AA (2.0g), EA (20.0g), MMA (22.0g), CHA (16.0g), V-601 (4.0g), and PGMEA (75.0g) ) was added dropwise over 2 hours into a three-necked flask solution maintained at 90°C±2°C. After the dropwise addition was completed, the mixture was stirred at 90°C±2°C for 2 hours to obtain Polymer 3 (solid content concentration: 40.0% by mass).
The content of each structural unit in Polymer 3 (mass%: ATHF/AA/EA/MMA/CHA) is 40/2/20/22/16. Note that ATHF corresponds to a structural unit containing an acid-decomposable group, and AA corresponds to a structural unit containing an acid group.
The weight average molecular weight of Polymer 3 is 25,000.
Polymer 3 has a glass transition temperature (Tg) of 34° C. and an acid value of 15.6 mgKOH/g.

-Preparation of positive photosensitive resin composition 3-
The components shown below were mixed to obtain a mixture with a solid content concentration of 10% by mass. Next, the above mixture was filtered using a polytetrafluoroethylene filter with a pore size of 0.2 μm to obtain a positive photosensitive resin composition 3.
・Acid-decomposable resin (above polymer 3): 100 parts ・Photoacid generator (above compound A-1): 3 parts ・Additive (above compound D (basic compound)): 1.6 parts ・Surface active Agent (surfactant C above): 0.1 part / Additive (compound E below): 4.5 parts / PGMEA: Amount (parts) for a solid content concentration of 10% by mass

Compound E: 9,10-dibutoxyanthracene

<Preparation of positive photosensitive resin composition 4>
The components shown below were mixed to obtain a mixed solution. Next, the above mixture was filtered using a polytetrafluoroethylene filter with a pore size of 0.2 μm to obtain a positive photosensitive resin composition 4.
- Acid decomposable resin (above polymer 1): 9.64 parts - Photo acid generator (above compound A-1): 0.25 part - Surfactant (above surfactant C): 0.01 part - Additive (Compound D above): 0.09 part Additive (Compound F below): 0.01 part PGMEA: 90.00 part

Compound F: 1,2,3-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Preparation of positive photosensitive resin composition 5>
-Synthesis of acid-decomposable resin (polymer 4)-
PGMEA (75.0 g) was placed in a three-necked flask, and the temperature was raised to 90° C. under a nitrogen atmosphere. TBA (30.0g), PMPMA (1.0g), AA (3.0g), MMA (26.0g), BMA (5.0g), EA (25.0g), CHA (10.0g), V A solution containing -601 (4.0 g) and PGMEA (75.0 g) was dropped over 2 hours into a three-necked flask solution maintained at 90°C ± 2°C. After the dropwise addition was completed, the mixture was stirred at 90°C±2°C for 2 hours to obtain Polymer 4 (solid content concentration: 40.0% by mass).
The content of each structural unit in polymer 4 (mass %: TBA/PMPMA/AA/MMA/BMA/EA/CHA) is 30/1/3/26/5/25/10. Note that TBA corresponds to a structural unit containing an acid-decomposable group, and AA corresponds to a structural unit containing an acid group.
The weight average molecular weight of Polymer 4 is 25,000.
The glass transition temperature (Tg) of Polymer 4 is 28°C.

-Preparation of positive photosensitive resin composition 5-
The components shown below were mixed to obtain a mixture with a solid content concentration of 10% by mass. Next, the pore size is 0.
A positive photosensitive resin composition 5 was obtained by filtering the above mixture using a 2 μm polytetrafluoroethylene filter.
・Acid-decomposable resin (above polymer 4): 100 parts ・Photoacid generator (above compound A-1): 3 parts ・Additive (above compound D (basic compound)): 1.6 parts ・Surface active Agent (surfactant W-2 below): 0.1 part PGMEA: Amount (part) that makes the solid content concentration 10% by mass

W-2: Megafac R08 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) (fluorine and silicone surfactant)

(Example 1)
A PET film (Lumirror 16KS40 manufactured by Toray Industries, Inc., thickness: 16 μm, arithmetic mean roughness Ra: 0.02 μm, haze value: 0.7%) was prepared as a support (first film). 3 m of positive photosensitive resin composition 1 was applied onto the surface of the support using a slit-shaped nozzle so that the coating width was 1.0 m and the thickness after drying was the value listed in Table 1. Coated. A resist layer (photosensitive resin layer) was formed by drying the formed coating film of positive photosensitive resin composition 1 at 90° C. for 100 seconds. A PET film (Lumirror 16KS40 manufactured by Toray Industries, Inc., thickness: 16 μm, arithmetic mean roughness Ra: 0.02 μm, haze value: 0.7) was applied to the surface of the formed resist layer as a cover film (second film). %) and then winding it up to produce a roll-shaped photosensitive composition material.
Next, after unrolling the photosensitive composition material in roll form, the cover film side is brought into contact with an exposure mask, and a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Dainihon Kaken Co., Ltd., dominant wavelength: 365 nm) is used. irradiated with light. The exposure amount was 100 mJ/cm ² . Next, after separating the exposure mask and cover film, the film was moved so that the exposed areas did not overlap, and the mask and film were brought into contact to perform a second exposure. This operation was performed 10 times in succession. Next, after peeling off the cover film, the positive photosensitive resin layer was subjected to shower development for 30 seconds using a sodium carbonate aqueous solution at a liquid temperature of 25° C., thereby forming a resin pattern on the support.

Subsequently, the film cut out to a size of 10 cm was placed inside a sputtering film forming apparatus, and after reducing the pressure inside the apparatus, argon gas was introduced, and sputtering was performed using Cu as a target. The discharge power and sputtering time required for sputtering were adjusted as appropriate, and a copper layer with a thickness of 50 nm was formed between and on the resin patterns.
Next, using an ultra-high pressure mercury lamp (including a wavelength of 365 nm), energy of 500 mJ/cm ² is irradiated onto the entire surface of the substrate from the back surface of the substrate (i.e., the surface opposite to the surface of the substrate with the copper layer). did. Thereafter, the substrate was immersed in a 5% by mass triethylamine aqueous solution adjusted to 50°C for 5 minutes, the photosensitive resin layer and the copper layer on the photosensitive resin layer were peeled off, and a patterned conductive composition layer (conductive composition layer) was placed on the substrate. sexual patterns).

(Example 2 to Example 16)
The support (first film), positive photosensitive resin composition, and cover film (second film) used were changed to those listed in Table 1 to form a positive photosensitive resin composition. A conductive pattern was formed in the same manner as in Example 1, except that the thickness of the coating film after drying was as shown in Table 1.
In addition, in Example 15, instead of performing Cu sputtering, water-based silver nano ink SW-1020 manufactured by Bando Chemical Co., Ltd. was diluted 5 times with pure water, and then applied with a bar coater (#1) for 10 minutes at 90°C. It was dried in an oven to form a silver nano ink layer with a thickness of about 500 nm between and on the resin patterns.

(Comparative Example 1: This is an embodiment in which the film is transferred to another PET film, and both the first and second films are peeled off.)
A PET film (Lumirror 16KS40 manufactured by Toray Industries, Inc., thickness: 16 μm, arithmetic mean roughness Ra: 0.02 μm) was prepared as a temporary support. Positive photosensitive resin composition 1 was applied onto the surface of the temporary support using a slit-shaped nozzle so that the coating width was 1.0 m and the thickness after drying was the value listed in Table 1. 3m was applied. A resist layer was formed by drying the formed coating film of positive photosensitive resin composition 1 at 90° C. for 100 seconds. A PET film (Lumirror 16KS40 manufactured by Toray Industries, Inc., thickness: 16 μm, arithmetic mean roughness Ra: 0.02 μm) is crimped onto the surface of the formed resist layer as a cover film, and then rolled up to form a roll. A photosensitive composition material was prepared.

Next, after unwinding the photosensitive composition material in the roll form, the cover film was peeled off from the laminate, and a PET film (Lumirror 16KS40 manufactured by Toray Industries, Inc., manufactured by Toray Industries, Inc., thickness: 16 μm) was separately prepared as a support. : Arithmetic mean roughness Ra: 0.02 μm). The bonding process was performed under the conditions of a roll temperature of 100° C., a linear pressure of 1.0 MPa, and a linear speed of 4.0 m/min. It was confirmed that sporadic bubbles were mixed between the laminate and the support. Next, light was irradiated through a photomask using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm), and the subsequent steps were repeated in the same manner.
In Comparative Example 1, in the bonding step, "bubbles" in which air bubbles entered between the laminate and the PET film occurred, resulting in pattern defects in the resulting conductive pattern.

(Comparative example 2)
A PET film (Lumirror 16KS40 manufactured by Toray Industries, Inc., thickness: 16 μm, arithmetic mean roughness Ra: 0.02 μm) was prepared as a support. 3 m of positive photosensitive resin composition 1 was applied onto the surface of the support using a slit-shaped nozzle so that the coating width was 1.0 m and the thickness after drying was the value listed in Table 1. Coated. The formed coating film of positive photosensitive resin composition 1 was dried at 90° C. for 100 seconds to form a resist layer, and then wound up into a roll.
After being left at 30°C and 80% relative humidity for 24 hours, when the laminate was sent out from the roll, part of the resist layer peeled off from the surface of the support and adhered to the back surface of the support that had been in contact with it in roll form. Therefore, it was difficult to continue the process after the exposure process.

<Pattern defect rate (pattern defect suppression ability) evaluation>
In the exposed area formed in the first exposure, a pattern in which 10 consecutive lines and spaces (L/S) = 15 (μm)/15 (μm) were formed was observed with an optical microscope, and pattern defects were detected. The rate was calculated. Specifically, 100 fields of 200 μm×200 μm were arbitrarily extracted from a range of 30 mm in the longitudinal direction, and patterns were observed. The frequency with which abnormalities corresponding to any of the following are observed in the conductive pattern: disconnections, peeling of the conductive layer from the substrate, short circuits at openings (in other words, short circuits between line parts), and adhesion of peeled objects. It was measured and evaluated according to the following evaluation criteria.
"A": Pattern defect rate is less than 2 fields of view.
"B": Pattern defect rate is 2 fields or more and less than 10 fields.
"C": Pattern defect rate is 10 or more and less than 20 fields.
"D": Pattern defect rate is 20 fields or more and less than 40 fields.
"E": Pattern defect rate is 40 fields of view or more.

<Evaluation of pattern defect rate during continuous exposure (pattern defect suppression ability during continuous exposure)>
In the exposed area formed in the 10th exposure, a pattern in which 10 L/S = 15 (μm)/15 (μm) were continuously formed was observed with an optical microscope to determine the pattern defect rate. Specifically, 100 fields of 200 μm×200 μm were arbitrarily extracted from a range of 30 mm in the longitudinal direction, and patterns were observed. Frequency in which abnormalities corresponding to any of the following are observed in conductive patterns: disconnections, peeling of the conductive layer from the substrate, short circuits at openings (in other words, short circuits between line parts), and adhesion of peeled objects. was measured and evaluated according to the following evaluation criteria.
"A": Pattern defect rate is less than 2 fields of view.
"B": Pattern defect rate is 2 fields or more and less than 10 fields.
"C": Pattern defect rate is 10 or more and less than 20 fields.
"D": Pattern defect rate is 20 fields or more and less than 40 fields.
"E": Pattern defect rate is 40 fields of view or more.

<Resolution evaluation>
In the exposed area formed in the first exposure, the state of the formed conductive pattern (copper wiring) having a width of L/S (to be described later) was observed at a magnification of 1,000 times using an electron microscope SEM. Since a pattern with good resolution has excellent linearity in a pattern with a finer line width, this was used as an index of resolution and evaluated according to the following criteria.
The line width was measured at 20 randomly selected locations from the copper wiring patterned into a line-and-space shape. The standard deviation σ was determined from the obtained line width data, and the value obtained by multiplying the standard deviation σ by 3 was defined as LWR (Line Width Roughness), and was used as an index of pattern linearity. If LWR<250 nm or less, there is no problem in practical use.
-Resolution evaluation criteria-
"A": LWR<250nm at L/S=5μm/5μm
“B”: LWR≧250nm at L/S=5μm/5μm, and LWR<250nm at L/S=6μm/6μm
“C”: LWR≧250nm at L/S=6μm/6μm, and LWR<250nm at L/S=8μm/8μm
“D”: LWR≧250nm at L/S=8μm/8μm

The evaluation results are summarized in Table 1.

The details of the films used in Table 1 other than those mentioned above are shown below.

-First film-
PI of Example 5: polyimide film, thickness: 16 μm, haze value: 0.8%, produced according to the method described in Example 1 of JP-A-2017-49596, except that the thickness was adjusted.
COP of Example 8: cycloolefin polymer film, thickness: 16 μm, haze value: 0.5%, produced according to the method described in paragraph 0069 of JP-A No. 2009-227932.
PI of Example 11: polyimide film, thickness: 38 μm, haze value: 0.8%, produced according to the method described in Example 1 of JP-A-2017-49596, except that the thickness was adjusted.
PET: polyethylene terephthalate film of Example 12, thickness: 50 μm, haze value: 0.7%, produced according to the method described in the example of JP 2015-21119, except that the thickness was adjusted.
PET: polyethylene terephthalate film of Example 13, thickness: 75 μm, haze value: 0.7%, produced according to the method described in the example of JP 2015-21119, except that the thickness was adjusted.
PET: polyethylene terephthalate film of Example 14, thickness: 16 μm, haze value: 1.4%, produced according to the method described in the example of JP 2015-21119, except that the thickness was adjusted.

-Second film-
The PET: polyethylene terephthalate film of Example 3, thickness: 38 μm, haze value: 0.7%, was produced according to the method described in the example of JP 2015-21119, except that the thickness was adjusted.
PI of Example 4: polyimide film, thickness: 50 μm, haze value: 0.7%, produced according to the method described in Example 1 of JP-A-2017-49596, except that the thickness was adjusted.
The PET: polyethylene terephthalate film of Example 5, thickness: 75 μm, haze value: 0.7%, was produced according to the method described in the example of JP 2015-21119, except that the thickness was adjusted.
PET of Example 6: polyethylene terephthalate film, thickness: 16 μm, haze value: 1.4%, produced by adjusting the thickness and silica sol particle size according to the method described in the example of JP 2015-21119. .
PP of Example 13: Polypropylene film, manufactured by Oji F-Tex Co., Ltd., thickness: 12 μm, haze value: 0.4%
PE of Example 14: polyethylene film, manufactured by Tamapoly Co., Ltd., thickness: 30 μm, haze value: 2.1%

As shown in Table 1 above, the method for forming a conductive pattern according to the example can reduce the occurrence of pattern defects in the resulting conductive pattern compared to the method for forming a conductive pattern according to the comparative example.
In addition, as shown in Table 1 above, the method for forming a conductive pattern of the example can reduce the occurrence of pattern defects in the resulting conductive pattern even during continuous exposure, and also improves resolution. Also excellent.

(Example 17)
A PET film (thickness: 100 μm, haze value: 1.0%) containing a UV absorber (Tinuvin 326 (manufactured by BASF Japan Ltd.)) was prepared as a support (first film).
3 m of positive photosensitive resin composition 1 was applied onto the surface of the support using a slit-shaped nozzle so that the coating width was 1.0 m and the thickness after drying was 1 μm.
A resist layer (photosensitive resin layer) was formed by drying the formed coating film of positive photosensitive resin composition 1 at 90° C. for 100 seconds.
A PET film (Lumirror 16KS40 manufactured by Toray Industries, Inc., thickness: 16 μm, arithmetic mean roughness Ra: 0.02 μm, haze value: 0.7) was applied to the surface of the formed resist layer as a cover film (second film). %), then turn the film over and use a slit-shaped nozzle to apply a positive coating onto the opposite side of the support so that the coating width is 1.0 m and the thickness after drying is 1 μm. After applying 3 m of photosensitive resin composition 1, it was dried at 90° C. for 100 seconds.
After that, a PET film (Lumirror 16KS40 manufactured by Toray Industries, Inc., thickness: 16 μm, arithmetic mean roughness Ra: 0.02 μm, haze value: 0.7%) was crimped as a cover film (third film). By winding it up, a roll-shaped photosensitive composition material was produced.
Next, after unrolling the photosensitive composition material in roll form and peeling off the cover film sides on both sides, an exposure mask is brought into contact with each side while maintaining alignment on the photosensitive resin composition on both sides. The front and back photosensitive resin layers were simultaneously exposed using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm).
The exposure amount was 100 mJ/cm ² .
Next, the film was moved by a predetermined amount so that the exposed areas did not overlap, and a second exposure was performed. This operation was performed 10 times in succession. Next, a resin pattern was formed on the support by subjecting the positive photosensitive resin layer to shower development from both sides for 30 seconds using a sodium carbonate aqueous solution at a liquid temperature of 25°C.
Next, the film cut out to a size of 10 cm was placed inside a sputtering film forming apparatus, the inside of the apparatus was depressurized, argon gas was introduced, sputtering was performed using Ti as a target, and then Cu was used as a target for sputtering. Sputtering was performed. The discharge power and sputtering time required for sputtering were adjusted as appropriate, and a Ti layer with a thickness of 10 nm or less and a copper layer with a thickness of 50 nm were formed between and on the resin patterns. Subsequently, the film was reversed, and sputtering was similarly performed using Cu.
Next, using an ultra-high pressure mercury lamp (including a wavelength of 365 nm), energy of 500 mJ/cm ² was irradiated onto the entire surface of the substrate from both sides of the substrate. Thereafter, the substrate was immersed in a 5% by mass aqueous triethylamine solution adjusted to 50°C for 5 minutes to peel off the photosensitive resin layer, the Ti layer and the copper layer on the photosensitive resin layer, and form a patterned conductive layer ( A conductive pattern) was formed.
The patterns on the front and back sides were evaluated, and the patterns on both sides had a pattern failure rate of A, a pattern failure rate of A during continuous exposure, and linearity of A.

1: Substrate (first film), 2: Conductive pattern, 3, 3A: Photosensitive resin layer, 5: Cover film (second film), 6: Mask, 6a: Mask opening, 7: Opening part, 8A, 8B: conductive composition layer, 20, 30, 40, 50: laminate

Claims (41)

preparing a roll body by winding up a laminate having a first film, a photosensitive resin layer, and a second film;
unwinding the laminate from the roll body;
a step of exposing the unrolled laminate to light;
a step of developing the exposed laminate to form a resin pattern;
forming a conductive pattern containing metal on at least a portion of the first film where the resin pattern is not formed;
including the step of removing the resin pattern,
forming the conductive pattern by a sputtering method;
Method for forming conductive patterns. The method for forming a conductive pattern according to claim 1, wherein at least one of the first film and the second film has particles. 3. The method for forming a conductive pattern according to claim 1, wherein in the step of exposing, a mask is brought into contact with the second film, and the exposure is performed through the second film. 3. The method for forming a conductive pattern according to claim 1, wherein in the step of exposing, a mask is brought into contact with the first film, and the exposure is performed through the first film. 3. The method for forming a conductive pattern according to claim 1, wherein in the step of exposing, the second film is peeled off, and a mask is brought into contact with the photosensitive resin layer for exposure. The method for forming a conductive pattern according to any one of claims 1 to 5, wherein the first film has a thickness of 50 μm or less. The method for forming a conductive pattern according to any one of claims 1 to 6, wherein the second film has a thickness of 50 μm or less. The method for forming a conductive pattern according to any one of claims 1 to 7, wherein the first film has a haze value of 1.0% or less. The method for forming a conductive pattern according to any one of claims 1 to 8, wherein the second film has a haze value of 1.0% or less. The method for forming a conductive pattern according to any one of claims 1 to 9, wherein at least one of the first film and the second film is a transparent film with a total light transmittance of 85% or more. . The method for forming a conductive pattern according to any one of claims 1 to 10, wherein both the first film and the second film are insulating films. The method for forming a conductive pattern according to any one of claims 1 to 11, wherein the first film contains an ultraviolet absorber. The method for forming a conductive pattern according to any one of claims 1 to 12, wherein the photosensitive resin layer is a positive photosensitive resin layer. 14. The method for forming a conductive pattern according to claim 13, wherein the positive photosensitive resin layer contains a polymer having a polar group protected with a protecting group that is deprotected by the action of an acid, and a photoacid generator. 15. The method for forming a conductive pattern according to claim 14, wherein the polar group protected with a protecting group that is deprotected by the action of an acid is a group in which the polar group is protected in the form of an acetal. The method for forming a conductive pattern according to claim 14 or 15, wherein the polymer contains a structural unit represented by any one of the following formulas A1 to A3.


In formula A1, R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, or an aryl group. However, at least one of R ¹¹ and R ¹² represents an alkyl group or an aryl group. R ¹³ represents an alkyl group or an aryl group. R ¹⁴ represents a hydrogen atom or a methyl group. X ¹ represents a single bond or a divalent linking group. R ¹⁵ represents a substituent. n represents an integer from 0 to 4. Note that R ¹¹ or R ¹² and R ¹³ may be connected to each other to form a cyclic ether.
In formula A2, R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group, or an aryl group. However, at least one of R ²¹ and R ²² represents an alkyl group or an aryl group. R ²³ represents an alkyl group or an aryl group. ^R24 each independently represents a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group, or a cyclo Represents an alkyl group. m represents an integer from 0 to 3. R ²¹ or R ²² and R ²³ may be linked to each other to form a cyclic ether.
In formula A3, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group, or an aryl group. However, at least one of R ³¹ and R ³² represents an alkyl group or an aryl group. R ³³ represents an alkyl group or an aryl group. R ³⁴ represents a hydrogen atom or a methyl group. X ⁰ represents a single bond or a divalent linking group. Note that R ³¹ or R ³² and R ³³ may be connected to each other to form a cyclic ether. The method for forming a conductive pattern according to any one of claims 1 to 16, wherein the photosensitive resin layer has a layer thickness of 3 μm or less. The method for forming a conductive pattern according to any one of claims 1 to 17, wherein the photosensitive resin layer has a layer thickness of 1 μm or less. The method for forming a conductive pattern according to any one of claims 1 to 18 , wherein the conductive pattern is formed by printing or coating with a silver-containing ink or a copper-containing ink. A first photosensitive resin layer and a second film are provided on one surface of the first film, and a second photosensitive resin layer and a second film are provided on the other surface of the first film. a step of preparing a roll body by winding up a laminate having three films;
unwinding the laminate from the roll body;
a step of exposing one or both surfaces of the unrolled laminate;
a step of developing the exposed laminate to form a resin pattern;
forming a conductive pattern containing metal on at least a portion of the first film where the resin pattern is not formed, and
including the step of removing the resin pattern,
forming the conductive pattern by a sputtering method;
Method for forming conductive patterns. The method for forming a conductive pattern according to claim 20 , wherein at least one of the first film, the second film, and the third film has particles. 22. The method for forming a conductive pattern according to claim 20 , wherein in the step of exposing, a mask is brought into contact with the second film or the third film, and the exposure is performed through the second film. The method for forming a conductive pattern according to claim 20 or 21 , wherein in the step of exposing, the second film or the third film is peeled off, and the photosensitive resin layer is brought into contact with a mask and exposed. . The method for forming a conductive pattern according to any one of claims 20 to 23 , wherein the first film has a thickness of 50 μm or less. The method for forming a conductive pattern according to any one of claims 20 to 24, wherein the second film has a thickness of 50 μm or less, and the third film has a thickness of 50 μm or less. The method for forming a conductive pattern according to any one of claims 20 to 25 , wherein the first film has a haze value of 1.0% or less. The haze value of the second film is 1.0% or less, and the haze value of the third film is 1.0% or less, according to any one of claims 20 to 26 . A method for forming a conductive pattern. 28. At least one of the first film, the second film, and the third film is a transparent film with a total light transmittance of 85 % or more. Method for forming conductive patterns. The method for forming a conductive pattern according to any one of claims 20 to 28 , wherein the first film, the second film, and the third film are all insulating films. The method for forming a conductive pattern according to any one of claims 20 to 29 , wherein the first film contains an ultraviolet absorber. The method for forming a conductive pattern according to any one of claims 20 to 30 , wherein both the first photosensitive resin layer and the second photosensitive resin layer are positive photosensitive resin layers. . 32. The method for forming a conductive pattern according to claim 31 , wherein the positive photosensitive resin layer contains a polymer having a polar group protected with a protecting group that is deprotected by the action of an acid, and a photoacid generator. 33. The method for forming a conductive pattern according to claim 32 , wherein the polar group protected with a protecting group that is deprotected by the action of an acid is a group in which an acid group is protected in the form of an acetal. 34. The method for forming a conductive pattern according to claim 32 or 33 , wherein the polymer contains a structural unit represented by any one of the following formulas A1 to A3.


In formula A1, R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, or an aryl group. However, at least one of R ¹¹ and R ¹² represents an alkyl group or an aryl group. R ¹³ represents an alkyl group or an aryl group. R ¹⁴ represents a hydrogen atom or a methyl group. X ¹ represents a single bond or a divalent linking group. R ¹⁵ represents a substituent. n represents an integer from 0 to 4. Note that R ¹¹ or R ¹² and R ¹³ may be connected to each other to form a cyclic ether.
In formula A2, R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group, or an aryl group. However, at least one of R ²¹ and R ²² represents an alkyl group or an aryl group. R ²³ represents an alkyl group or an aryl group. ^R24 each independently represents a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group, or a cyclo Represents an alkyl group. m represents an integer from 0 to 3. R ²¹ or R ²² and R ²³ may be linked to each other to form a cyclic ether.
In formula A3, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group, or an aryl group. However, at least one of R ³¹ and R ³² represents an alkyl group or an aryl group. R ³³ represents an alkyl group or an aryl group. R ³⁴ represents a hydrogen atom or a methyl group. X ⁰ represents a single bond or a divalent linking group. Note that R ³¹ or R ³² and R ³³ may be connected to each other to form a cyclic ether. The method for forming a conductive pattern according to any one of claims 20 to 34 , wherein the first photosensitive resin layer and the second photosensitive resin layer have the same composition. The method for forming a conductive pattern according to any one of claims 20 to 35 , wherein the first photosensitive resin layer and the second photosensitive resin layer each have a layer thickness of 3 μm or less. The method for forming a conductive pattern according to any one of claims 20 to 36 , wherein the first photosensitive resin layer and the second photosensitive resin layer each have a layer thickness of 1 μm or less. The conductive pattern according to any one of claims 20 to 37 , wherein in the step of exposing, the first photosensitive resin layer and the second photosensitive resin layer are exposed simultaneously. Formation method. The method for forming a conductive pattern according to any one of claims 20 to 38 , wherein the conductive pattern is formed by printing or coating with a silver-containing ink or a copper-containing ink. A method for manufacturing a metal mesh sensor, comprising the method for forming a conductive pattern according to any one of claims 1 to 39 . With respect to the first film having the conductive pattern obtained by the method for forming a conductive pattern according to any one of claims 1 to 39 , on the first film and the conductive pattern, a step of forming a negative photosensitive resin layer on the
a step of exposing the negative photosensitive resin layer through the first film;
forming a resin pattern N on the first film by developing the negative photosensitive resin layer irradiated with light, and
A method for manufacturing a structure, including a step of forming a pattern M in a region defined by the conductive pattern and the resin pattern N.