WO2022163778A1

WO2022163778A1 - Method for manufacturing laminate, method for manufacturing circuit wiring, method for manufacturing electronic device, and photosensitive transfer material

Info

Publication number: WO2022163778A1
Application number: PCT/JP2022/003169
Authority: WO
Inventors: 隆志有冨
Original assignee: 富士フイルム株式会社
Priority date: 2021-01-28
Filing date: 2022-01-27
Publication date: 2022-08-04
Also published as: JPWO2022163778A1; CN116802558A

Abstract

The present invention provides a method for manufacturing a laminate, a method for manufacturing an electronic device and a method for manufacturing circuit wiring in which the laminate obtained by the above-described method for manufacturing a laminate is used, and a photosensitive transfer material. Said method for manufacturing a laminate comprises a bonding step in which a photosensitive transfer material having a temporary support and a transfer layer including a photosensitive layer is bonded with a substrate such that the transfer-layer side of the photosensitive transfer material is in contact with the substrate, an exposure step in which the photosensitive layer is exposed, and a developing step in which the photosensitive layer is developed to form a resin pattern. The number of particles and voids having a diameter of at least Y μm on the surface and interior of the photosensitive layer in the exposure step does not exceed 15/cm2, where X (μm) is the limiting resolution of the photosensitive layer in the exposure step and Y (μm) is the reference diameter of the particles and voids (Y=0.5×X).

Description

Laminate manufacturing method, circuit wiring manufacturing method, electronic device manufacturing method, and photosensitive transfer material

The present disclosure relates to a laminate manufacturing method, a circuit wiring manufacturing method, an electronic device manufacturing method, and a photosensitive transfer material.

In a display device with a touch panel such as a capacitive input device (organic electroluminescence (EL) display device, liquid crystal display device, etc.), the electrode pattern corresponding to the sensor in the visible part, the wiring of the peripheral wiring part and the lead-out wiring part A conductive layer pattern such as is provided inside the touch panel.
Generally, the formation of a patterned layer requires a small number of steps to obtain the required pattern shape. In contrast, a method of developing after exposure through a mask having a desired pattern is widely used.

Further, as a conventional photosensitive resin laminate roll, one described in Patent Document 1 is known.
In Patent Document 1, a photosensitive resin laminate obtained by rolling a photosensitive resin laminate including a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film The number of fine particles having a diameter of 2 μm or more contained in each small piece of the support film when a small piece of 0.75 mm × 11 mm is cut out from any 10 different locations of the support film. However, the number average of the 10 locations is 200 or less, and the back surface of the support film includes a region having an arithmetic mean roughness of 0.01 μm or more. .

Patent Document 1: JP 2019-101405

A problem to be solved by one embodiment of the present invention is to provide a method for manufacturing a laminate having a resin pattern with few pinhole defects.
A problem to be solved by another embodiment of the present invention is to provide a circuit wiring manufacturing method and an electronic device manufacturing method using the laminate obtained by the laminate manufacturing method.
Further, another object of the present invention is to provide a photosensitive transfer material with which a resin pattern with few pinhole defects can be obtained.

Means for solving the above problems include the following aspects.
<1> A bonding step of bonding the photosensitive transfer material and the substrate so that the transfer layer side of the photosensitive transfer material having the temporary support and the transfer layer including the photosensitive layer is in contact with the substrate, the photosensitive and a developing step of developing the photosensitive layer to form a resin pattern. is defined as Y μm represented by Y=0.5×X, the number of particles and voids having a diameter of Y μm or more on the surface and inside of the photosensitive layer in the exposure step is 15/cm ² or less. A method of manufacturing a laminate.
<2> The method for producing a laminate according to <1>, wherein the photosensitive layer has a thickness of 5.0 μm or less.
<3> The method for producing a laminate according to <1> or <2>, wherein the temporary support has a thickness of 16 μm or less.
<4> The method for producing a laminate according to any one of <1> to <3>, wherein the resin pattern has a line width of 10 μm or less.
<5> The method for producing a laminate according to any one of <1> to <4>, including a peeling step of peeling the temporary support between the bonding step and the exposure step.
<6> The method for producing a laminate according to any one of <1> to <5>, wherein in the exposure step, the transfer layer and the mask are brought into contact with each other.
<7> The method for producing a laminate according to any one of <1> to <6>, wherein the transfer layer further includes a thermoplastic resin layer and a water-soluble resin layer.
<8> The method for producing a laminate according to any one of <1> to <7>, wherein the photosensitive layer contains a polyfunctional polymerizable compound.
<9> The method for producing a laminate according to any one of <1> to <8>, wherein the photosensitive layer contains a trifunctional or higher polymerizable compound.
<10> The method for producing a laminate according to any one of <1> to <9>, wherein the photosensitive layer contains a polymerizable compound having a polyethylene oxide structure.
<11> A preparation step of preparing a laminate obtained by the method for producing a laminate according to any one of <1> to <10>, and removing the substrate in a region where the resin pattern is not arranged. A circuit wiring manufacturing method including an etching step of performing an etching treatment in this order.
<12> A preparation step of preparing a laminate obtained by the method for producing a laminate according to any one of <1> to <10>, and removing the substrate in a region where the resin pattern is not arranged. A method of manufacturing an electronic device including etching steps of etching in this order.
<13> Having a temporary support and a transfer layer containing a photosensitive layer, defining the limiting resolution of the photosensitive layer as X ^T μm, and expressing the reference diameter of the particles as Y ^T =0.5×X ^T a photosensitive transfer material, wherein the number of particles having a diameter of ^YT μm or more on the surface and inside of the photosensitive layer is 15 particles/cm ² or less when defined as ^YT μm.
<14> The photosensitive transfer material according to <13>, wherein the photosensitive layer has a thickness of 5.0 μm or less.
<15> The photosensitive transfer material according to <13> or <14>, wherein the temporary support has a thickness of 16 μm or less.

According to one embodiment of the present invention, it is possible to provide a method for manufacturing a laminate having a resin pattern with few pinhole defects.
According to another embodiment of the present invention, it is possible to provide a circuit wiring manufacturing method and an electronic device manufacturing method using the laminate obtained by the laminate manufacturing method described above.
Further, according to another embodiment of the present invention, it is possible to provide a photosensitive transfer material that can obtain a resin pattern with few pinhole defects.

It is a schematic diagram showing an example of the configuration of a photosensitive transfer material. 3 is a schematic plan view showing pattern A; FIG. 3 is a schematic plan view showing a pattern B; FIG.

The contents of the present disclosure will be described below. Although the description will be made with reference to the attached drawings, reference numerals may be omitted.
Further, in this specification, a numerical range represented by "to" means a range including the numerical values before and after "to" as lower and upper limits.
Further, in the present specification, "(meth)acryl" represents both or either acrylic and methacrylic, "(meth)acrylate" represents both or either acrylate and methacrylate, and "(meth) ) acryloyl” refers to either or both acryloyl and methacryloyl.
Furthermore, the amount of each component in the composition herein refers to the sum of the corresponding substances present in the composition when there are multiple substances corresponding to each component in the composition, unless otherwise specified. means quantity.
As used herein, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.
In the description of a group (atomic group) in the present specification, a description that does not describe substitution or unsubstituted includes not only those without substituents but also those with substituents. For example, the term “alkyl group” includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
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. The light used for exposure generally includes the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and active rays (active energy rays) such as electron beams. mentioned.
In addition, chemical structural formulas in this specification may be described as simplified structural formulas in which hydrogen atoms are omitted.
In the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Moreover, in the present disclosure, a combination of two or more preferred aspects is a more preferred aspect.
In addition, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation). It is a molecular weight converted using polystyrene as a standard substance, detected with a solvent THF (tetrahydrofuran) and a differential refractometer using a gel permeation chromatography (GPC) analyzer.
As used herein, "total solid content" refers to the total mass of components excluding the solvent from the total composition of the composition. Moreover, as described above, the “solid content” is the component excluding the solvent, and may be solid or liquid at 25° C., for example.

(Laminate manufacturing method)
In the method for manufacturing a laminate according to the present disclosure, the photosensitive transfer material and the substrate are attached so that the transfer layer side of the photosensitive transfer material having the temporary support and the transfer layer including the photosensitive layer is in contact with the substrate. Including a lamination step of bonding, an exposure step of exposing the photosensitive layer, and a developing step of developing the photosensitive layer to form a resin pattern, wherein the limiting resolution of the photosensitive layer in the exposure step is defined as X μm When the reference diameter of particles and voids is defined as Y μm represented by Y=0.5×X, the number of particles and voids having a diameter of Y μm or more on the surface and inside of the photosensitive layer in the above exposure step is , 15/cm ² or less.

Due to the increase in the definition of the conductive pattern, in other words, the improvement in the required resolution, foreign substances and voids (e.g., coarse particles, air bubbles, etc.) on the surface and inside of the photosensitive layer of the photosensitive layer Failures of conductive patterns (especially pinholes) are becoming apparent. Particles and voids on the surface and inside of the photosensitive layer hinder the curing of the photosensitive layer by exposure to light and cause defects (eg, pinholes) in the resin pattern. For example, when a resin pattern containing pinholes is used as a protective film in etching for forming a conductive pattern, pinholes are generated in the conductive pattern. Therefore, it is desired to reduce the number of pinholes generated in the resin pattern.

The presumed reason why the above effects are exhibited will be described below.
For example, in the technique disclosed in Patent Document 1, by limiting the number of particles having a diameter of 2 μm or more, deterioration in resolution due to foreign matter contained in the temporary support is avoided. However, the size of particles and voids that cause exposure disturbances varies depending on the required resolution. As the required resolution becomes smaller, the small particles and voids allowed in the prior art also interfere with the exposure of the photosensitive layer. Therefore, the present inventor focused on the relationship between the resolution of the photosensitive layer and the size and number of particles and voids on the surface and inside of the photosensitive layer. By examining the relationship between the resolution of the photosensitive layer and the size of particles and voids that cause exposure failure, the present inventor found that Y (Y = 0.5 x X) for the limit resolution (X μm) of the photosensitive layer It has been found that particles and voids with a diameter of .mu.m or more lead to an increased incidence of exposure disturbances. According to the reference diameter (Y μm) of particles and voids derived from the limiting resolution (X μm) of the photosensitive layer, the number of particles and voids having a diameter of Y μm or more on the surface and inside of the photosensitive layer is 15/cm ² or less. By adjusting, the incidence of exposure failure can be reduced. Therefore, according to the method for manufacturing a laminate according to the present disclosure, a method for manufacturing a laminate having a resin pattern with few pinhole defects is provided.

<Number of particles and voids having a diameter of Y μm or more on the surface and inside of the photosensitive layer>
In the method for manufacturing a laminate according to the present disclosure, the limit resolution of the photosensitive layer in the exposure step is defined as X μm, and the reference diameter of the particles and voids is Y = 0.5 × X When defined as Y μm , The number of particles having a diameter of Y μm or more and voids on the surface and inside of the photosensitive layer in the exposure step is 15 particles/cm ² or less, and from the viewpoint of suppressing pinhole defects, 10 particles/cm ² or less. It is preferably 7/cm ² or less, and particularly preferably 5/cm ² or less. The lower limit is 0/cm ² .

A method for measuring the critical resolution of the photosensitive layer in the present disclosure is shown below.
The laminate is photosensitized through a line-and-space pattern mask (the duty ratio is 1:1 and the line width is changed stepwise from 1 μm to 20 μm every 1 μm) using an ultra-high pressure mercury lamp. Expose the layer.
If necessary, the temporary support is peeled off and then developed. Development is performed by shower development for 30 seconds using a 1.0% by mass sodium carbonate aqueous solution at 25°C.
A resin pattern is formed by developing the photosensitive layer.
While adjusting the exposure amount (unit: mJ/cm ² ) each time, the above-described series of perform the steps in The minimum line width of the reference pattern is taken as the limit resolution X μm of the photosensitive layer.

When measuring from a photosensitive transfer material, a polyethylene terephthalate (PET) film having a thickness of 100 μm is placed on a vacuum laminator (manufactured by MCK Co., Ltd., roll temperature: 100 ° C., linear pressure: 1.0 MPa, linear velocity After laminating the photosensitive transfer material and the PET substrate by a roll-to-roll method using a pressure of 0.5 m/min), using an autoclave apparatus, conditions of 0.6 MPa and 60 ° C. After degassing under pressure for 30 minutes, the limiting resolution of the photosensitive layer shall be measured.

A method for measuring the number of particles having a diameter of Y μm or more and voids on the surface and inside of the photosensitive layer in the present disclosure is shown below.
If necessary, arbitrary 10 regions on the surface of the photosensitive layer in the laminate after peeling the temporary support (size of each region: 10 mm × 10 mm, total area: 1,000 mm ² ), optical Observe visually with a microscope. The number of foreign particles and voids with a diameter of Y μm or more included in each area is measured. Based on the total number of particles with a size of Y μm or larger and voids measured in 10 areas, the number of particles with a size of Y μm or larger and voids per 1 cm ² of the measurement area (particles/cm ² ) is calculated.
Particles and voids may be measured together or separately.

In the method for manufacturing a laminate according to the present disclosure, the photosensitive transfer material and the substrate are attached so that the transfer layer side of the photosensitive transfer material having the temporary support and the transfer layer including the photosensitive layer is in contact with the substrate. It includes a bonding step of bonding, an exposure step of exposing the photosensitive layer, and a developing step of developing the photosensitive layer to form a resin pattern.
Moreover, it is preferable that the method for manufacturing a laminate according to the present disclosure includes a peeling step of peeling the temporary support between the bonding step and the exposure step.
Furthermore, it is preferable that the method for manufacturing a laminate according to the present disclosure includes a protective film peeling step of peeling off the protective film before the bonding step, if necessary.

<Protective film peeling process>
The method for manufacturing a laminate according to the present disclosure preferably includes a step of peeling the protective film from the photosensitive transfer material. A method for peeling off the protective film is not limited, and a known method can be applied.

<Lamination process>
A method for manufacturing a laminate according to the present disclosure includes a bonding step.
In the lamination step, it is preferable to bring the transfer layer of the photosensitive transfer material into contact with the substrate (or the conductive layer if the substrate has a conductive layer on its surface), and press the photosensitive transfer material and the substrate together. . In the above aspect, the adhesion between the transfer layer and the substrate in the photosensitive transfer material is improved, so the patterned photosensitive layer after exposure and development is suitable as an etching resist when etching the conductive layer. can be used for
Preferred aspects of the photosensitive transfer material used in the method for producing a laminate according to the present disclosure will be collectively described later.

In addition, in the lamination step, the photosensitive transfer material further comprises a layer other than the protective film (for example, a high refractive index layer and/or a low refractive index layer) on the surface of the photosensitive layer on the side not facing the temporary support. In this case, the surface of the photosensitive layer on which the temporary support is not provided is bonded to the substrate with the layer interposed therebetween.

The method for pressure-bonding the substrate and the photosensitive transfer material is not particularly limited, and known transfer methods and lamination methods can be used.
The photosensitive transfer material is laminated to the substrate by stacking the outermost layer of the photosensitive transfer material on the side having the photosensitive layer with respect to the temporary support and the substrate, and applying pressure and heat using means such as rolls. It is preferably done by applying. A known laminator such as a laminator, a vacuum laminator, and an autocut laminator that can further improve productivity can be used for the lamination.
Although the lamination temperature is not particularly limited, it is preferably 70° C. to 130° C., for example.

The method for manufacturing a laminate according to the present disclosure is preferably performed by a roll-to-roll method.
The roll-to-roll method will be described below.
The roll-to-roll method uses a substrate that can be wound and unwound as a substrate, and before any of the steps included in the method for manufacturing a laminate according to the present disclosure, a substrate or a structure including a substrate At least any It refers to a method in which the above steps (preferably all steps or all steps other than the heating step) are performed while the substrate or a structure including the substrate is being transported.
The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and known methods may be used in manufacturing methods to which a roll-to-roll system is applied.

<Substrate>
As the substrate used in the method for producing a laminate according to the present disclosure, a known substrate may be used, but a substrate having a conductive layer is preferable, and it is more preferable to have a conductive layer on the surface of the substrate.
The substrate may have any layer other than the conductive layer, if desired.
Examples of substrates include resin substrates, glass substrates, and semiconductor substrates.
Preferred embodiments of the substrate include, for example, those described in paragraph 0140 of WO2018/155193, the contents of which are incorporated herein.

Base materials that constitute the substrate include, for example, glass, silicon, and films.
The base material constituting the substrate is preferably transparent. As used herein, "transparent" means that the transmittance of light with a wavelength of 400 nm to 700 nm is 80% or more.
Further, the refractive index of the substrate constituting the substrate is preferably 1.50 to 1.52.

Transparent glass substrates include tempered glass such as Corning's Gorilla Glass. Materials used in JP-A-2010-86684, JP-A-2010-152809, and JP-A-2010-257492 can be used as the transparent glass substrate.

When a film substrate is used as the substrate, it is preferable to use a film substrate with low optical distortion and/or high transparency. Such film substrates include, for example, polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetylcellulose and cycloolefin polymers.

A film substrate is preferable as the substrate when manufacturing by the roll-to-roll method. Moreover, when manufacturing the circuit wiring for touchscreens by a roll-to-roll method, it is preferable that a board|substrate is a sheet-shaped resin composition.

Examples of the conductive layer that the substrate has include conductive layers that are used for general circuit wiring or touch panel wiring.
The conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer and a conductive polymer layer, from the viewpoint of conductivity and fine line formation. A metal layer is more preferred, and a copper or silver layer is even more preferred.
The substrate may have a single conductive layer, or may have two or more layers. When it has two or more conductive layers, it is preferable to have the conductive layers made of different materials.

Materials for the conductive layer include metals and conductive metal oxides.
Metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag and Au.
Conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide) and _SiO2 .
In this specification, the term “conductivity” means that the volume resistivity is less than 1×10 ⁶ Ωcm. The volume resistivity of the conductive metal oxide is preferably less than 1×10 ⁴ Ωcm.

When manufacturing a resin pattern using a substrate having a plurality of conductive layers, at least one of the plurality of conductive layers preferably contains a conductive metal oxide.
The conductive layer is preferably an electrode pattern corresponding to a sensor in the visual recognition portion used in a capacitive touch panel or wiring in the peripheral extracting portion.
Preferred embodiments of the conductive layer are described, for example, in paragraph 0141 of WO2018/155193, the contents of which are incorporated herein.

As the substrate having a conductive layer, a substrate having at least one of a transparent electrode and lead wiring is preferable. The substrate as described above can be suitably used as a touch panel substrate.
A transparent electrode can function suitably as an electrode for touch panels. The transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), a metal mesh, and metal wires such as silver nanowires.
Fine metal wires include fine wires of silver, copper, and the like. Among them, silver conductive materials such as silver mesh and silver nanowire are preferable.

A metal is preferable as the material of the routing wiring.
Examples of metals for the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, manganese, and alloys composed of two or more of these metal elements. Copper, molybdenum, aluminum, or titanium is preferable as the material of the routing wiring, and copper is particularly preferable.

The touch panel electrode protective film formed using the photosensitive transfer material used in the present disclosure is for the purpose of protecting the electrodes and the like (that is, at least one of the touch panel electrodes and the touch panel wiring), directly or otherwise. is preferably provided so as to cover through a layer of

<Temporary support peeling step>
The method for producing a laminate according to the present disclosure preferably includes a temporary support peeling step for peeling the temporary support between the bonding step and the exposure step.
The peeling method of the temporary support is not particularly limited, and a mechanism similar to the cover film peeling mechanism described in paragraphs 0161 to 0162 of JP-A-2010-072589 can be used.

<Exposure process>
A method for manufacturing a laminate according to the present disclosure includes an exposure step.
The exposure process in the exposure process is a patterned exposure process (also referred to as “pattern exposure”), that is, an exposure process in which an exposed portion and a non-exposed portion exist.
The positional relationship between the exposed area and the unexposed area in pattern exposure is not particularly limited and is adjusted as appropriate.

The detailed arrangement and specific size of the pattern in pattern exposure are not particularly limited. For example, at least part of the pattern (preferably The electrode pattern and/or lead-out wiring portion of the touch panel) preferably includes fine lines with a width of 20 μm or less, and more preferably includes fine lines with a width of 10 μm or less.
In addition, from the viewpoint of further exerting the effects of the present disclosure, the obtained resin pattern preferably has a resin pattern with a line width of 20 μm or less, and more preferably has a resin pattern with a line width of 10 μm or less. It is more preferable to have a resin pattern with a line width of 8 μm or less, and it is particularly preferable to have a resin pattern with a line width of 5 μm or less.

The light source used for exposure can be appropriately selected and used as long as it is a light source that emits light having a wavelength (for example, 365 nm or 405 nm) capable of exposing the photosensitive layer. Specifically, ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps and LEDs (Light Emitting Diodes) are included.
The exposure dose is preferably 5 mJ/cm ² to 200 mJ/cm ² , more preferably 10 mJ/cm ² to 100 mJ/cm ² .
Preferred embodiments of the light source, exposure amount and exposure method used for exposure include, for example, paragraphs 0146 to 0147 of WO 2018/155193, the contents of which are incorporated herein.

In the exposure step, pattern exposure may be performed after peeling the temporary support from the transfer layer, and before peeling the temporary support, pattern exposure is performed through the temporary support, and then the temporary support is peeled off. good too. When the temporary support is peeled off before exposure, the mask may be exposed in contact with the transfer layer, or may be exposed in proximity without contact. When exposure is performed without peeling off the temporary support, the mask may be exposed in contact with the temporary support, or may be exposed in close proximity without contact. In order to prevent contamination of the mask due to contact between the transfer layer and the mask and to avoid the influence of foreign matter adhering to the mask on the exposure, it is preferable to carry out pattern exposure without peeling off the temporary support. The exposure method may be a contact exposure method in the case of contact exposure, a proximity exposure method in the case of a non-contact exposure method, a projection exposure method using a lens system or a mirror system, or a direct exposure method using an exposure laser or the like. It can be selected and used. In the case of projection exposure using a lens system or a mirror system, an exposure machine having an appropriate lens numerical aperture (NA) can be used according to the required resolving power and depth of focus. In the case of the direct exposure method, drawing may be performed directly on the photosensitive layer, or reduction projection exposure may be performed on the photosensitive layer via a lens. Further, the exposure may be performed not only in the air but also in a reduced pressure or a vacuum, or the exposure may be performed by interposing a liquid such as water between the light source and the transfer layer.
Moreover, in the exposure step, from the viewpoint of resolution, the transfer layer and the mask are preferably brought into contact with each other to carry out the exposure process.

<Development process>
A method for manufacturing a laminate according to the present disclosure includes a developing step.
Development of the exposed photosensitive layer in the development step can be performed using a developer.
The developer is not particularly limited as long as it can remove the non-image area of the photosensitive layer. For example, known developers such as the developer described in JP-A-5-72724 can be used.
The developer is preferably an alkaline aqueous solution containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol/L to 5 mol/L (liter). The developer may contain a water-soluble organic solvent and/or a surfactant.
Alkaline compounds that can be contained in the alkaline aqueous solution include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide).
As the developer, the developer described in paragraph 0194 of International Publication No. 2015/093271 is also preferably used. A development method that is preferably used includes, for example, the development method described in paragraph 0195 of International Publication No. 2015/093271.

The development method is not particularly limited, and may be any of puddle development, shower development, shower and spin development, and dip development. Shower development is a development process in which non-image areas are removed by spraying a developing solution onto the photosensitive layer after exposure.
After the development step, it is preferable to remove the development residue by spraying a cleaning agent with a shower and rubbing with a brush.
Although the liquid temperature of the developer is not particularly limited, it is preferably 20°C to 40°C.

<Step of removing particles adhering to surface>
In the method for producing a laminate according to the present disclosure, a surface attachment method for removing particles attached to the surface of the transfer layer or the temporary support is performed before the exposure step, preferably after the temporary support peeling step, and before the exposure step. Preferably, a particle removal step is included.
As a method for removing particles in the step of removing particles adhering to the surface, a method of contacting an adhesive roll or a cleaning roll with the surface of the transfer layer or the temporary support to remove the particles is suitably exemplified.
The material, size, contact pressure, etc. of the adhesive roll or cleaning roll can be appropriately selected as desired.

<Other processes>
The method for manufacturing a laminate according to the present disclosure may include arbitrary steps (other steps) other than the steps described above. Examples include, but are not limited to, the following steps.
Further, the exposure step, development step, and other steps applicable to the method for manufacturing a laminate according to the present disclosure include the steps described in paragraphs 0035 to 0051 of JP-A-2006-23696.

<Application>
A laminate manufactured by the method for manufacturing a laminate according to the present disclosure can be applied to various devices. Examples of the device including the laminate include an input device and the like, preferably a touch panel, and more preferably a capacitive touch panel. Moreover, the input device can be applied to display devices such as an organic electroluminescence display device and a liquid crystal display device.
When the laminate is applied to a touch panel, the formed resin pattern is preferably used as a protective film for touch panel electrodes or touch panel wiring.

<Photosensitive transfer material>
The photosensitive transfer material used in the method for producing a laminate according to the present disclosure has a temporary support and a transfer layer containing a photosensitive layer, the temporary support, a transfer layer containing a photosensitive layer, and a protective It is preferred to have a film in this order.
In addition, the photosensitive transfer material used in the present disclosure may have other layers between the temporary support and the photosensitive layer, between the photosensitive layer and the protective film, and the like.
Furthermore, the photosensitive transfer material used in the present disclosure preferably further has a thermoplastic resin layer and a water-soluble resin layer between the temporary support and the photosensitive layer.
Furthermore, the transfer layer preferably further includes a thermoplastic resin layer and a water-soluble resin layer.
The photosensitive transfer material used in the present disclosure is preferably a roll-shaped photosensitive transfer material from the viewpoint of exhibiting the effects of the present disclosure more effectively.

Examples of embodiments of the photosensitive transfer material used in the present disclosure are shown below, but are not limited thereto.
(1) "Temporary support/photosensitive layer/refractive index adjusting layer/protective film"
(2) "Temporary support/photosensitive layer/protective film"
(3) "Temporary support/water-soluble resin layer/photosensitive layer/protective film"
(4) "Temporary support/thermoplastic resin layer/water-soluble resin layer/photosensitive layer/protective film"
In addition, in each of the above structures, the photosensitive layer is preferably a negative photosensitive layer. It is also preferred that the photosensitive layer is a colored resin layer. The photosensitive transfer material used in the present disclosure is preferably used as a photosensitive transfer material for etching resist.
When it is used as a photosensitive transfer material for etching resist, the configuration of the photosensitive transfer material preferably has, for example, the configurations (2) to (4) described above.

In the photosensitive transfer material, in the case of a configuration having another layer on the side opposite to the temporary support side of the photosensitive layer, the total thickness of the other layers arranged on the side opposite to the temporary support side of the photosensitive layer is , preferably 0.1% to 30%, more preferably 0.1% to 20%, of the layer thickness of the photosensitive layer.

The photosensitive transfer material used in the present disclosure will be described below by giving an example of a specific embodiment.

An example of the photosensitive transfer material will be described below.
The photosensitive transfer material 20 shown in FIG. 1 includes a temporary support 11, a transfer layer 12 including a thermoplastic resin layer 13, a water-soluble resin layer 15, and a photosensitive layer 17, and a protective film 19 in this order. have.
Further, the photosensitive transfer material 20 shown in FIG. 1 has a form in which the thermoplastic resin layer 13 and the water-soluble resin layer 15 are arranged, but the thermoplastic resin layer 13 and the water-soluble resin layer 15 may not be arranged. .
Each element constituting the photosensitive transfer material will be described below.

[Temporary support]
The photosensitive transfer material used in the present disclosure has a temporary support.
A temporary support is a support that supports a photosensitive layer or a laminate containing a photosensitive layer and that can be peeled off.

The temporary support preferably has light transmittance from the viewpoint that the photosensitive layer can be exposed through the temporary support when patternwise exposing the photosensitive layer. In this specification, "having light transmittance" means having a transmittance of 50% or more for light having a wavelength used for pattern exposure.
From the viewpoint of improving the exposure sensitivity of the photosensitive layer, the temporary support preferably has a light transmittance of 60% or more, more preferably 70% or more, at a wavelength used for pattern exposure (more preferably a wavelength of 365 nm). is more preferred.
The transmittance of a layer included in a photosensitive transfer material is the light emitted through the layer relative to the intensity of the incident light when the light is incident in the direction perpendicular to the main surface of the layer (thickness direction). It is a ratio of intensity of incident light, and is measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.

Materials constituting the temporary support include, for example, glass substrates, resin films, and paper, with resin films being preferred from the viewpoints of strength, flexibility, and light transmittance.
Resin films include polyethylene terephthalate (PET) films, cellulose triacetate films, polystyrene films and polycarbonate films. Among them, a PET film is preferable, and a biaxially stretched PET film is more preferable.

The thickness (layer thickness) of the temporary support is not particularly limited, and the strength as a support, the flexibility required for bonding with the substrate for forming circuit wiring, and the light required in the first exposure step From the viewpoint of permeability, the material may be selected according to the material.
The thickness of the temporary support is preferably in the range of 5 μm to 100 μm, more preferably in the range of 10 μm to 50 μm, still more preferably in the range of 10 μm to 20 μm, even more preferably in the range of 10 μm to 16 μm, from the viewpoint of ease of handling and versatility. Especially preferred.
In addition, the thickness of the temporary support is preferably 50 μm or less, more preferably 25 μm or less, and more preferably 20 μm or less from the viewpoint of defect suppression, resolution and linearity of the resin pattern. More preferably, it is particularly preferably 16 μm or less.

Moreover, it is preferable that the film used as the temporary support does not have deformation such as wrinkles, flaws, or defects.
From the viewpoint of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, the number of fine particles, foreign matter, defects, precipitates, etc. contained in the temporary support is preferably as small as possible. The number of fine particles, foreign substances, and defects with a diameter of 1 μm or more is preferably 50/10 mm ² or less, more preferably 10/10 mm ² or less, and even more preferably 3/10 mm ² or less. , 0/10 mm ² .

The haze of the temporary support is preferably as small as possible from the viewpoints of the defect-suppressing property of the resin pattern, the resolution, and the transparency of the temporary support. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 1.5% or less, still more preferably less than 1.0%, and particularly preferably 0.5% or less.
The haze value in the present disclosure is measured by a method according to JIS K 7105:1981 using a haze meter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.).

A layer containing fine particles (lubricant layer) may be provided on the surface of the temporary support from the viewpoint of imparting handleability. The lubricant layer may be provided on one side or both sides of the temporary support. The diameter of the particles contained in the lubricant layer can be, for example, 0.05 μm to 0.8 μm. Further, the layer thickness of the lubricant layer can be, for example, 0.05 μm to 1.0 μm.

The arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive layer side is the photosensitive layer of the temporary support from the viewpoint of transportability, defect suppression of the resin pattern, and resolution. It is preferably equal to or greater than the arithmetic mean roughness Ra of the side surface.
The arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive layer side is preferably 100 nm or less from the viewpoints of transportability, resin pattern defect suppression, and resolution. It is more preferably 50 nm or less, still more preferably 20 nm or less, and particularly preferably 10 nm or less.
The arithmetic mean roughness Ra of the surface of the temporary support on the photosensitive layer side is preferably 100 nm or less from the viewpoints of peelability of the temporary support, defect suppression of the resin pattern, and resolution. It is more preferably 50 nm or less, still more preferably 20 nm or less, and particularly preferably 10 nm or less.
Further, the value of the arithmetic mean roughness Ra of the surface opposite to the photosensitive layer side in the temporary support - the arithmetic mean roughness Ra of the surface of the temporary support on the side of the photosensitive layer is transportability, resin pattern From the viewpoint of defect suppression and resolution, the thickness is preferably 0 nm to 10 nm, more preferably 0 nm to 5 nm.

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

The peeling force of the temporary support, specifically, the peeling force between the temporary support and the photosensitive layer or the thermoplastic resin layer, when conveying the wound laminate again by a roll-to-roll method, From the viewpoint of suppressing peeling of the temporary support due to adhesion between the vertically stacked laminate and the laminate, it is preferably 0.5 mN / mm or more, and 0.5 mN / mm to 2.0 mN / mm. It is more preferable to have

The peel strength of the temporary support in the present disclosure shall be measured as follows.
A copper layer with a thickness of 200 nm is formed on a polyethylene terephthalate (PET) film with a thickness of 100 μm by a sputtering method to prepare a PET substrate with a copper layer.
The protective film is peeled off from the prepared photosensitive transfer material, and the material is laminated on the PET substrate with the copper layer under the lamination conditions of laminating roll temperature of 100° C., linear pressure of 0.6 MPa, and linear speed (laminating speed) of 1.0 m/min. Next, after pasting a tape (PRINTACK manufactured by Nitto Denko Corporation) on the surface of the temporary support, a laminate having at least a temporary support and a photosensitive layer on a PET substrate with a copper layer is formed into a size of 70 mm × 10 mm. Make a sample by cutting. The PET substrate side of the sample is fixed on the sample table.
Using a tensile compression tester (SV-55, manufactured by Imada Seisakusho Co., Ltd.), the tape is pulled at 5.5 mm / sec in the direction of 180 degrees, and the photosensitive layer or thermoplastic resin layer and the temporary support. and measure the force required for peeling (peeling force) adhesion.

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

[Photosensitive layer]
The photosensitive transfer material used in this disclosure has a photosensitive layer.
The photosensitive layer is preferably a negative photosensitive layer.
The photosensitive layer preferably contains an alkali-soluble resin, a polymerizable compound and a photopolymerization initiator, based on the total weight of the photosensitive layer, alkali-soluble resin: 10% to 90% by weight; ethylenically unsaturated compound : 5% by mass to 70% by mass; and photopolymerization initiator: 0.01% by mass to 20% by mass.
Each component will be described in order below.

<<polymerizable compound>>
The photosensitive layer preferably contains a polymerizable compound. As used herein, the term "polymerizable compound" means a compound that polymerizes under the action of a photopolymerization initiator, which will be described later, and that is different from the alkali-soluble resin described above.

The polymerizable group possessed by the polymerizable compound is not particularly limited as long as it is a group involved in the polymerization reaction. For example, it has an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group and a maleimide group. groups; and groups having cationic polymerizable groups such as epoxy groups and oxetane groups.
As the polymerizable group, a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.
Moreover, as a polymerizable compound, it is preferable that an ethylenically unsaturated compound is included, and it is more preferable that a (meth)acrylate compound is included.

From the viewpoint of resolution and pattern formability, the photosensitive layer preferably contains a bifunctional or higher polymerizable compound (polyfunctional polymerizable compound), and more preferably contains a trifunctional or higher polymerizable compound. preferable.
Here, the bifunctional or higher polymerizable compound means a compound having two or more polymerizable groups in one molecule.
Moreover, the number of polymerizable groups in one molecule of the polymerizable compound is preferably 6 or less from the viewpoint of excellent resolution and releasability.

The photosensitive layer preferably contains a bifunctional or trifunctional ethylenically unsaturated compound in terms of better balance between the photosensitivity of the photosensitive layer and the resolution and releasability, and the bifunctional ethylenically unsaturated compound It is more preferable to include
In the photosensitive layer, the content of the bifunctional or trifunctional ethylenically unsaturated compound with respect to the total content of the ethylenically unsaturated compounds is preferably 60% by mass or more, and more than 70% by mass, from the viewpoint of excellent peelability. Preferably, 90% by mass or more is more preferable. The upper limit is not particularly limited, and may be 100% by mass. That is, all ethylenically unsaturated compounds contained in the photosensitive layer may be bifunctional ethylenically unsaturated compounds.

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

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

In the photosensitive layer, the mass ratio of the content of the ethylenically unsaturated compound B1 to the content of the ethylenically unsaturated compound is preferably 40% by mass or more, and 50% by mass, from the viewpoint of better resolution. It is more preferably 55% by mass or more, and particularly preferably 60% by mass or more. Although the upper limit is not particularly limited, it is preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less, from the viewpoint of releasability.

Examples of the aromatic ring of the ethylenically unsaturated compound B1 include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring, thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring. Aromatic heterocycles and condensed rings thereof are included, with aromatic hydrocarbon rings being preferred, and benzene rings being more preferred. In addition, the said aromatic ring may have a substituent.
Ethylenically unsaturated compound B1 may have only one aromatic ring, or may have two or more aromatic rings.

The ethylenically unsaturated compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing swelling of the photosensitive layer due to the developer.
Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane) and a bisphenol derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane). The F structure and the bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane) can be mentioned, with the bisphenol A structure being preferred.

Examples of the ethylenically unsaturated compound B1 having a bisphenol structure include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure.
Both ends of the bisphenol structure and the two polymerizable groups may be directly bonded or bonded via one or more alkyleneoxy groups. The alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, more preferably an ethyleneoxy group. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per molecule.
The ethylenically unsaturated compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the contents described in this publication are incorporated herein.

The ethylenically unsaturated compound B1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A structure, more preferably 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane.
Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical ( Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, Shin-Nakamura Chemical Industry ( Ltd.), 2,2-bis(4-(methacryloxydodecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadeca Ethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.) ), and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

A compound represented by the following formula (Bis) can be used as the ethylenically unsaturated compound B1.

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

Ethylenically unsaturated compound B1 may be used alone or in combination of two or more.
The content of the ethylenically unsaturated compound B1 in the photosensitive layer is preferably 10% by mass or more, more preferably 20% by mass or more, relative to the total mass of the photosensitive layer from the viewpoint of better resolution. Although the upper limit is not particularly limited, it is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of transferability and edge fusion (a phenomenon in which components in the photosensitive layer ooze out from the edges of the photosensitive transfer material). .

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

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

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

Examples of trifunctional or higher ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri(meth) Acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanurate tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified products thereof.
Here, "(tri/tetra/penta/hexa) (meth)acrylate" is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate. , "(tri/tetra)(meth)acrylate" is a concept including tri(meth)acrylate and tetra(meth)acrylate. In one aspect, the photosensitive layer preferably contains the above-described ethylenically unsaturated compound B1 and a trifunctional or higher ethylenically unsaturated compound, and the above-described ethylenically unsaturated compound B1 and two or more trifunctional or higher functional More preferably, it contains an ethylenically unsaturated compound. In this case, the mass ratio of the ethylenically unsaturated compound B1 and the tri- or higher functional ethylenically unsaturated compound is (total mass of the ethylenically unsaturated compound B1):(total mass of the tri- or higher functional ethylenically unsaturated compound). = 1:1 to 5:1 is preferred, 1.2:1 to 4:1 is more preferred, and 1.5:1 to 3:1 is even more preferred.
In one aspect, the photosensitive layer preferably contains the above-described ethylenically unsaturated compound B1 and two or more trifunctional ethylenically unsaturated compounds.

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

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

The ratio Mm/Mb between the content Mm of the ethylenically unsaturated compound and the content Mb of the alkali-soluble resin in the photosensitive layer is preferably 1.0 or less from the viewpoint of resolution and linearity. , is more preferably 0.9 or less, and particularly preferably 0.5 or more and 0.9 or less.
Moreover, the ethylenically unsaturated compound in the photosensitive layer preferably contains a (meth)acrylic compound from the viewpoint of curability and resolution.
Furthermore, the ethylenically unsaturated compound in the photosensitive layer contains a (meth)acrylic compound from the viewpoint of curability, resolution and linearity, and the total mass of the (meth)acrylic compound contained in the photosensitive layer It is more preferable that the content of the acrylic compound is 60% by mass or less.

The molecular weight of the ethylenically unsaturated compound containing the ethylenically unsaturated compound B1 (weight average molecular weight (Mw) when having a distribution) is preferably 200 to 3,000, more preferably 280 to 2,200, and 300 ~2,200 is more preferred.

An ethylenically unsaturated compound may be used individually by 1 type, or may use 2 or more types together.
The content of the ethylenically unsaturated compound in the photosensitive layer is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and 20% by mass to 50% by mass, based on the total mass of the photosensitive layer. % is more preferred.

<<Photoinitiator>>
The photosensitive layer preferably contains a photopolymerization initiator.
A photopolymerization initiator is a compound that initiates polymerization of an ethylenically unsaturated compound upon exposure to actinic rays such as ultraviolet rays, visible rays, and X-rays. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used.
Photopolymerization initiators include, for example, radical photopolymerization initiators and cationic photopolymerization initiators.
Among them, the photo-radical polymerization initiator is preferable for the photosensitive layer from the viewpoint of resolution and pattern formability.

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

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

Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p,p'-dimethoxybenzyl), TAZ-110 (trade name: Midori Chemical Co., Ltd.), benzophenone, TAZ-111 (trade name: Midori Chemical Co., Ltd.), IrgacureOXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade name: IGM Resins BV (manufactured by Tokyo Chemical Industry Co., Ltd.), and 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.). be done.

Commercially available photoradical polymerization initiators include, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE- 01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-02, BASF), IRGACURE OXE-03 (BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907, IGM Resins B.V.) ), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, IGM Resins B.V.). V.), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl- 1-phenylpropan-1-one (trade name: Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxycyclohexylphenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins B.V.), 2,2- Dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, IGM Resins B.V.), oxime ester-based photopolymerization initiators ( Product name: Lunar 6, manufactured by DKSH Japan Co., Ltd.), 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenylbisimidazole (2-(2-chlorophenyl)-4 ,5-diphenylimidazole dimer ) (trade name: B-CIM, manufactured by Hampford) and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.). .

A photocationic polymerization initiator (photoacid generator) is a compound that generates an acid upon receiving an actinic ray. The photocationic polymerization initiator is preferably a compound that responds to an actinic ray with a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but its chemical structure is not limited. In addition, even for photocationic polymerization initiators that do not directly react to actinic rays with a wavelength of 300 nm or more, if they are compounds that react to actinic rays with a wavelength of 300 nm or more and generate an acid by using them in combination with a sensitizer, the sensitizer can be used. It can be preferably used in combination with.
The photocationic polymerization initiator is preferably a photocationic polymerization initiator that generates an acid with a pKa of 4 or less, more preferably a photocationic polymerization initiator that generates an acid with a pKa of 3 or less, and an acid with a pKa of 2 or less. Photocationic polymerization initiators generated are particularly preferred. Although the lower limit of pKa is not particularly defined, it is preferably -10.0 or more, for example.

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

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

The photosensitive layer may contain one type of photopolymerization initiator alone, or two or more types thereof.
The content of the photopolymerization initiator in the photosensitive layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1.0% by mass, based on the total mass of the photosensitive layer. % or more is more preferable. Although the upper limit is not particularly limited, it is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the photosensitive layer.

<< Alkali-soluble resin >>
The photosensitive layer preferably contains an alkali-soluble resin.
In this specification, the term “alkali-soluble” means that the solubility in 100 g of a 1 mass % aqueous solution of sodium carbonate at a liquid temperature of 22° C. is 0.1 g or more.
Alkali-soluble resins are not particularly limited, and suitable examples include known alkali-soluble resins used in etching resists.
Also, the alkali-soluble resin is preferably a binder polymer.
The alkali-soluble resin is preferably an alkali-soluble resin having an acid group.
Among them, as the alkali-soluble resin, a polymer A described later is preferable.

-Polymer A-
It is preferable that the polymer A is included as the alkali-soluble resin.
The acid value of the polymer A is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g, more preferably less than 190 mgKOH/g, from the viewpoint of better resolution by suppressing swelling of the photosensitive layer by the developer. is more preferred.
The lower limit of the acid value of polymer A is not particularly limited, but from the viewpoint of better developability, it is preferably 60 mgKOH/g or more, more preferably 120 mgKOH/g or more, still more preferably 150 mgKOH/g or more, and 170 mgKOH/g or more. Especially preferred.

The acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample.
In this specification, the unit is described as mgKOH/g. The acid value can be calculated, for example, from the average content of acid groups in the compound.
The acid value of the polymer A may be adjusted according to the type of structural units constituting the polymer A and the content of structural units containing an acid group.

The weight average molecular weight of polymer A is preferably from 5,000 to 500,000. A weight average molecular weight of 500,000 or less is preferable from the viewpoint of improving resolution and developability. The weight average molecular weight is more preferably 100,000 or less, even more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, setting the weight-average molecular weight to 5,000 or more is from the viewpoint of controlling the properties of development aggregates and the properties of unexposed films such as edge-fuse properties and cut-chip properties when formed into photosensitive resin laminates. preferred from The weight average molecular weight is more preferably 10,000 or more, even more preferably 20,000 or more, and particularly preferably 30,000 or more. Edge fuseability refers to the degree of ease with which the photosensitive layer protrudes from the end face of the roll when the photosensitive transfer material is wound into a roll. The cut chip property refers to the degree of easiness of chip flying when the unexposed film is cut with a cutter. If this chip adheres to the upper surface of the photosensitive resin laminate, etc., it will be transferred to the mask in the subsequent exposure process or the like, resulting in defective products. The dispersity of polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and 1 .0 to 3.0 is more preferable. In the present disclosure, molecular weight is a value measured using gel permeation chromatography. The degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).

The photosensitive layer preferably contains a monomer component having an aromatic hydrocarbon group as the polymer A from the viewpoint of suppressing line width thickening and deterioration of resolution when the focus position during exposure is shifted. . Examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content of the monomer component having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, preferably 30% by mass or more, based on the total mass of all monomer components. It is more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more. Although the upper limit is not particularly limited, it is preferably 95% by mass or less, more preferably 85% by mass or less. In addition, the content rate of the monomer component which has an aromatic-hydrocarbon group in the case where the polymer A contains multiple types was calculated|required as a weight average value.

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

Aralkyl groups include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups), substituted or unsubstituted benzyl groups, and the like, with substituted or unsubstituted benzyl groups being preferred.

Examples of monomers having a phenylalkyl group include phenylethyl (meth)acrylate.

Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and chlorobenzyl (meth)acrylate; vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl. Alcohol etc. are mentioned. Among them, benzyl (meth)acrylate is preferred. In one aspect, when the monomer component having an aromatic hydrocarbon group in the polymer A is benzyl (meth) acrylate, the content of the benzyl (meth) acrylate monomer component is the total of all monomer components Based on the mass, it is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, even more preferably 70% by mass to 90% by mass, 75% by mass to 90% by mass is particularly preferred.

Polymer A containing a monomer component having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group and at least one of the first monomer described later and / or the second monomer described later. is preferably obtained by polymerizing at least one of the monomers of

Polymer A containing no monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the first monomers described later, and at least More preferably, it is obtained by copolymerizing one of the monomers with at least one of the second monomers described below.

A 1st monomer is a monomer which has a carboxy group in a molecule|numerator. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth)acrylic acid is preferred.
The content of the first monomer in the polymer A is preferably 5% by mass to 50% by mass, based on the total mass of all monomer components, and 10% by mass to 40% by mass. is more preferable, and 15% by mass to 30% by mass is even more preferable.

The copolymerization ratio of the first monomer is preferably 10% by mass to 50% by mass based on the total mass of all monomer components. The copolymerization ratio of 10% by mass or more is preferable from the viewpoint of developing good developability and controlling edge fuse properties, more preferably 15% by mass or more, and even more preferably 20% by mass or more. . Setting the copolymerization ratio to 50% by mass or less is preferable from the viewpoint of the high resolution and groove shape of the resist pattern, and further from the viewpoint of the chemical resistance of the resist pattern. The following is more preferable, 30% by mass or less is even more preferable, and 27% by mass or less is particularly preferable.

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

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

Polymer A may have any one of a linear structure, a branched structure, and an alicyclic structure in the side chain. Introducing a branched structure or an alicyclic structure to the side chain of the polymer A by using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain. can be done. A group having an alicyclic structure may be monocyclic or polycyclic.
Specific examples of the monomer containing a group having a branched structure in the side chain include i-propyl (meth)acrylate, i-butyl (meth)acrylate, s-butyl (meth)acrylate, (meth)acrylic t-butyl acid, i-amyl (meth)acrylate, t-amyl (meth)acrylate, sec-iso-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-(meth)acrylate octyl, t-octyl (meth)acrylate and the like. Among these, i-propyl (meth)acrylate, i-butyl (meth)acrylate, and t-butyl methacrylate are preferred, and i-propyl methacrylate and t-butyl methacrylate are more preferred.
Examples of the monomer containing a group having an alicyclic structure in the side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group, and the number of carbon atoms (number of carbon atoms) (Meth)acrylates having 5 to 20 alicyclic hydrocarbon groups are mentioned. More specific examples include (meth) acrylic acid (bicyclo[2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth) ) 3-methyl-1-adamantyl acrylate, 3,5-dimethyl-1-adamantyl (meth) acrylate, 3-ethyladamantyl (meth) acrylate, 3-methyl-5 (meth) acrylate -ethyl-1-adamantyl, (meth)acrylate-3,5,8-triethyl-1-adamantyl, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl, (meth)acrylic acid 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro-4,7-mentanoindene-5 (meth)acrylate -yl, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate, 3-hydroxy (meth)acrylate -2,6,6-trimethyl-bicyclo[3.1.1]heptyl, (meth)acrylate-3,7,7-trimethyl-4-hydroxybicyclo[4.1.0]heptyl, (meth)acrylic acid (nor)bornyl, isobornyl (meth)acrylate, fenchyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate and the like. Among these (meth)acrylic esters, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, -1-adamantyl (meth)acrylate, (meth)acrylate - 2-adamantyl, fenchyl (meth)acrylate, 1-menthyl (meth)acrylate, or tricyclodecane (meth)acrylate is preferred, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, Isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate are particularly preferred.

The polymer A can be used singly or in combination of two or more. When two or more types are mixed and used, two types of polymer A containing a monomer component having an aromatic hydrocarbon group are mixed and used, or a monomer component having an aromatic hydrocarbon group is used. It is preferable to use a mixture of the polymer A containing the aromatic hydrocarbon group and the polymer A containing no monomer component having an aromatic hydrocarbon group. In the latter case, the use ratio of the polymer A containing a monomer component having an aromatic hydrocarbon group is preferably 50% by mass or more, preferably 70% by mass or more, based on the total amount of the polymer A. is more preferably 80% by mass or more, and more preferably 90% by mass or more.

Synthesis of polymer A is carried out by adding a radical polymerization initiator such as benzoyl peroxide and azoisobutyronitrile to a solution obtained by diluting one or more of the monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol. is preferably added in an appropriate amount and heated and stirred. In some cases, the synthesis is performed while part of the mixture is added dropwise to the reaction solution. After completion of the reaction, a solvent may be further added to adjust the desired concentration. As a means of synthesis, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

The glass transition temperature Tg of polymer A is preferably 30°C or higher and 135°C or lower. By using the polymer A having a Tg of 135° C. or less in the photosensitive layer, thickening of line width and deterioration of resolution when the focal point shifts during exposure can be suppressed. From this point of view, the Tg of polymer A is more preferably 130° C. or lower, still more preferably 120° C. or lower, and particularly preferably 110° C. or lower. Moreover, it is preferable to use the polymer A having a Tg of 30° C. or more from the viewpoint of improving the edge fuse resistance. From this point of view, the Tg of the polymer A is more preferably 40° C. or higher, still more preferably 50° C. or higher, particularly preferably 60° C. or higher, and most preferably 70° C. or higher. .

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

Alkali-soluble resins may be used singly or in combination of two or more.
The ratio of the alkali-soluble resin to the total weight of the photosensitive layer is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and still more preferably 40% by mass to 60% by mass. % by mass. It is preferable from the viewpoint of controlling the developing time that the ratio of the alkali-soluble resin to the photosensitive layer is 90% by mass or less. On the other hand, it is preferable from the viewpoint of improving the edge fuse resistance that the ratio of the alkali-soluble resin to the photosensitive layer is 10% by mass or more.

<<Dye>>
The photosensitive layer preferably contains a dye from the viewpoint of the visibility of the exposed and unexposed areas, the visibility of the pattern after development, and the resolution. It is more preferable to contain a dye whose wavelength is 450 nm or more and whose maximum absorption wavelength is changed by an acid, a base, or a radical (also simply referred to as “dye N”). When the dye N is contained, although the detailed mechanism is unknown, the adhesion to the adjacent layers (for example, the temporary support and the first resin layer) is improved, and the resolution is improved.

As used herein, the term "the maximum absorption wavelength of a dye changes with an acid, a base, or a radical" means that the dye in a colored state is decolored by an acid, a base, or a radical, the dye in a decolored state is an acid, It may mean either a mode in which a color is developed by a base or a radical, or a mode in which a dye in a coloring state changes to a coloring state of another hue.
Specifically, the dye N may be a compound that changes from a decolored state to develop color upon exposure, or a compound that changes from a colored state to decolor upon exposure. In this case, it may be a dye whose coloring or decoloring state is changed by the action of an acid, a base, or a radical generated in the photosensitive layer by exposure, and the state in the photosensitive layer by the acid, the base, or the radical (for example, It may also be a dye that changes its coloring or decoloring state with a change in pH). Moreover, it may be a dye that changes its coloring or decoloring state by being directly stimulated by an acid, a base, or a radical without being exposed to light.

Among them, from the viewpoint of the visibility and resolution of the exposed and unexposed areas, the dye N is preferably a dye whose maximum absorption wavelength is changed by acid or radicals, more preferably a dye whose maximum absorption wavelength is changed by radicals.
From the viewpoint of the visibility and resolution of the exposed and unexposed areas, the photosensitive layer preferably contains both a dye whose maximum absorption wavelength is changed by radicals as the dye N and a photoradical polymerization initiator. .
From the viewpoint of the visibility of the exposed and unexposed areas, the dye N is preferably a dye that develops color with an acid, a base, or a radical.

As an example of the coloring mechanism of the dye N in the present disclosure, a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photobase generator is added to the photosensitive layer, and photoradical polymerization is initiated after exposure. A radical-reactive dye, an acid-reactive dye, or a base-reactive dye (for example, a leuco dye) develops color by radicals, acids, or bases generated from the agent, photocationic polymerization initiator, or photobase generator.

From the viewpoint of the visibility of the exposed and unexposed areas, the dye N preferably has a maximum absorption wavelength of 550 nm or more in the wavelength range of 400 nm to 780 nm during color development, more preferably 550 nm to 700 nm, and 550 nm. More preferably ~650 nm.
In addition, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development, or may have two or more. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm during color development, the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.

The maximum absorption wavelength of Dye N is measured in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) in an air atmosphere. It is obtained by measuring the spectrum and detecting the wavelength (maximum absorption wavelength) at which the intensity of light is minimal.

Examples of dyes that develop or decolorize upon exposure include leuco compounds.
Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.
As the dye N, a leuco compound is preferable from the viewpoint of the visibility of the exposed area and the non-exposed area.

Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane dyes), leuco compounds having a spiropyran skeleton (spiropyran dyes), leuco compounds having a fluorane skeleton (fluoran dyes), and diarylmethane skeletons. a leuco compound (diarylmethane dye), a leuco compound having a rhodamine lactam skeleton (rhodamine lactam dye), a leuco compound having an indolylphthalide skeleton (indolylphthalide dye), and a leuco auramine skeleton leuco compounds (leuco auramine dyes) having
Among them, triarylmethane-based dyes or fluoran-based dyes are preferable, and leuco compounds having a triphenylmethane skeleton (triphenylmethane-based dyes) or fluoran-based dyes are more preferable.

The leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring from the viewpoint of the visibility of the exposed and non-exposed areas. As a result, the lactone ring, sultine ring, or sultone ring of the leuco compound is reacted with a radical generated from a radical photopolymerization initiator or an acid generated from a photocationic polymerization initiator to change the leuco compound into a ring-closed state. It can be decolored, or it can be colored by changing the leuco compound into a ring-opened state. The leuco compound is preferably a compound that has a lactone ring, a sultine ring or a sultone ring and develops a color when the lactone ring, sultine ring or sultone ring is opened by a radical or an acid. A compound that develops color by ring-opening of the lactone ring is more preferred.

Examples of dye N include the following dyes and leuco compounds.
Specific examples of dyes among dyes N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal, methanyl yellow, thymolsulfophtalein, xylenol blue, methyl Orange, Paramethyl Red, Congo Fred, Benzopurpurin 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsin, Victoria Pure Blue-Naphthalene Sulfonate, Victoria Pure Blue BOH (protective Tsuchiya Chemical Industry Co., Ltd.), Oil Blue #603 (Orient Chemical Industry Co., Ltd.), Oil Pink #312 (Orient Chemical Industry Co., Ltd.), Oil Red 5B (Orient Chemical Industry Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red OG (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industry Co., Ltd.) ), Spiron Red BEH Special (manufactured by Hodogaya Chemical Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxy Anilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylamino phenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

Specific examples of the leuco compound of the dye N include p,p′,p″-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(Np-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p -toluidino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, 3-(N-cyclohexyl-N-methyl amino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7 -xyridinofluorane, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N ,N-diethylamino)-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-diethylamino)-7-benzylaminofluorane, 3- (N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6 -methyl-7-xyridinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl- 2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethyl aminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-zaphthalide, 3-(4-diethylaminophenyl)-3-( 1-ethyl-2-methylindol-3-yl)phthalide and 3′,6′-bis(diphenylamino)spiroisobenzofuran-1(3H),9′-[9H]xanthen-3-one be done.

Dye N is preferably a dye whose maximum absorption wavelength is changed by radicals from the viewpoint of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, and is a dye that develops color by radicals. is more preferable.
Preferred dyes N are leuco crystal violet, crystal violet lactone, brilliant green, or victoria pure blue-naphthalene sulfonate.

A dye may be used individually by 1 type, or may use 2 or more types.
The content of the dye is preferably 0.1% by mass or more based on the total mass of the photosensitive layer, from the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution. It is more preferably 0.1% by mass to 10% by mass, still more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.1% by mass to 1% by mass.
In addition, the content of the dye N is 0.1% by mass or more with respect to the total mass of the photosensitive layer from the viewpoint of the visibility of the exposed area and the non-exposed area, the pattern visibility after development, and the resolution. is preferred, 0.1% by mass to 10% by mass is more preferred, 0.1% by mass to 5% by mass is even more preferred, and 0.1% by mass to 1% by mass is particularly preferred.

The content of the dye N means the content of the dye when all the dyes N contained in the photosensitive layer are in a colored state. A method for quantifying the content of dye N will be described below using a dye that develops color by radicals as an example.
Two solutions are prepared by dissolving 0.001 g or 0.01 g of dye in 100 mL of methyl ethyl ketone. A radical photopolymerization initiator Irgacure OXE01 (trade name, BASF Japan Co., Ltd.) is added to each of the solutions obtained, and radicals are generated by irradiation with light of 365 nm to bring all the dyes into a colored state. After that, the absorbance of each solution having a liquid temperature of 25° C. is measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) in an air atmosphere to create a calibration curve.
Next, the absorbance of the solution in which all the dyes are developed is measured in the same manner as described above except that 3 g of the photosensitive layer is dissolved in methyl ethyl ketone instead of the dyes. From the absorbance of the obtained solution containing the photosensitive layer, the content of the dye contained in the photosensitive layer is calculated based on the calibration curve.

<<Thermal crosslinkable compound>>
The photosensitive layer preferably contains a thermal crosslinkable compound from the viewpoint of the strength of the resulting cured film and the adhesiveness of the resulting uncured film. In this specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not treated as a polymerizable compound, but as a thermally crosslinkable compound.
Thermally crosslinkable compounds include methylol compounds and blocked isocyanate compounds. Among them, a blocked isocyanate compound is preferable from the viewpoint of the strength of the cured film to be obtained and the adhesiveness of the uncured film to be obtained.
Since the blocked isocyanate compound reacts with the hydroxy group and the carboxy group, for example, when the resin and/or the polymerizable compound has at least one of the hydroxy group and the carboxy group, the hydrophilicity of the formed film is lowered. , there is a tendency for the function to be enhanced when a film obtained by curing the photosensitive layer is used as a protective film.
The blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent".

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

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

The blocked isocyanate compound preferably has an isocyanurate structure from the viewpoint of, for example, improving the brittleness of the film and improving the adhesion to the transferred material.
A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by converting hexamethylene diisocyanate into an isocyanurate for protection.
Among the blocked isocyanate compounds having an isocyanurate structure, compounds having an oxime structure using an oxime compound as a blocking agent tend to have a dissociation temperature within a preferred range and can reduce development residues more easily than compounds having no oxime structure. This is preferable from the viewpoint of ease of use.

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

A commercial item can be used as a blocked isocyanate compound.
Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (manufactured by Showa Denko K.K.), block type Duranate series (eg, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).
Moreover, the compound of the following structure can also be used as a blocked isocyanate compound.

The thermally crosslinkable compounds may be used singly or in combination of two or more.
When the photosensitive layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, based on the total mass of the photosensitive layer. preferable.

<<Other Ingredients>>
The photosensitive layer may contain components other than the above-described alkali-soluble resin, ethylenically unsaturated compound, photopolymerization initiator, dye, and thermally crosslinkable compound.

-Surfactant-
From the viewpoint of thickness uniformity, the photosensitive layer preferably contains a surfactant.
Examples of surfactants include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants, with nonionic surfactants being preferred.
Examples of surfactants include surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362.

As the surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferable.
Examples of commercially available fluorosurfactants include Megafac (trade name) F-171, F-172, F-173, F-176, F-177, F-141, F-142, and F-143. , F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F -556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP. MFS-578-2, EXP. MFS-579, EXP. MFS-586, EXP. MFS-587, EXP. MFS-628, EXP. MFS-631, EXP. MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (manufactured by DIC Corporation), Florard (trade names) FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited), Surflon (trade names) S-382, SC-101, SC-103 , SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Co., Ltd.), PolyFox (trade name) PF636, PF656, PF6320, PF6520 , PF7002 (manufactured by OMNOVA), Futergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (manufactured by NEOS Corporation), U-120E (manufactured by Unichem Corporation) and the like.
In addition, fluorine-based surfactants have a molecular structure with a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing a fluorine atom is cleaved and the fluorine atom volatilizes. It can be used preferably. As such a fluorosurfactant, Megafac (trade name) DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)) , for example, Megafac (trade name) DS-21.

It is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorosurfactant.
A block polymer can also be used as the fluorosurfactant. The fluorosurfactant has 2 or more (preferably 5 or more) structural units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group and a propyleneoxy group) (meta). A fluorine-containing polymer compound containing structural units derived from an acrylate compound can also be preferably used.
A fluoropolymer having an ethylenically unsaturated group in a side chain can also be used as the fluorosurfactant. Megafac (trade name) RS-101, RS-102, RS-718K, RS-72-K (manufactured by DIC Corporation) and the like.

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2 , 25R2 (manufactured by BASF), Tetronic (trade name) 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 (manufactured by BASF), Solsperse (trade name) 20000 (manufactured by Nippon Lubri Zol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Pionin (trade name) D-1105, D-6112, D-6112-W , D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), OLFINE E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like.
In recent years, compounds having linear perfluoroalkyl groups with 7 or more carbon atoms are concerned about their environmental suitability. It is preferred to use surfactants using materials.

Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into side chains or terminals.
Specific examples of silicone surfactants include EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP. S-505-2 (manufactured by DIC Corporation), DOWSIL (trade name) 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA , Toray Silicone SH8400 (manufactured by Dow Corning Toray Co., Ltd.) and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002, KP-101, KP-103, KP- 104, KP-105, KP-106, KP-109, KP-109, KP-112, KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP-369, KP-611, KP-620, KP-621, KP-626, KP-652 (Shin-Etsu Chemical ( Co.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325 , BYK330, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, BYK323 (manufactured by BYK-Chemie) and the like.

The photosensitive layer may contain one type of surfactant alone, or two or more types thereof.
The content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, relative to the total mass of the photosensitive layer.

-Additive-
The photosensitive layer may contain known additives, if necessary, in addition to the above components.
Examples of additives include polymerization inhibitors, sensitizers, plasticizers, heterocyclic compounds, benzotriazoles, carboxybenzotriazoles, pyridines (isonicotinamide, etc.), purine bases (adenine, etc.), and solvents. is mentioned. The photosensitive layer may contain each additive singly or in combination of two or more.

The photosensitive layer may contain a polymerization inhibitor. As the polymerization inhibitor, a radical polymerization inhibitor is preferred.
Examples of polymerization inhibitors include thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784 . Among them, phenothiazine, phenoxazine and 4-methoxyphenol are preferred. Other polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like. In order not to impair the sensitivity of the photosensitive resin composition, it is preferred to use a nitrosophenylhydroxyamine aluminum salt as a polymerization inhibitor.

Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole and the like.

Carboxybenzotriazoles include, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylene carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylene carboxybenzotriazole, N-(N,N-di-2-ethylhexyl)aminoethylene carboxybenzotriazole and the like. As carboxybenzotriazoles, for example, commercially available products such as CBT-1 (manufactured by Johoku Chemical Industry Co., Ltd., trade name) can be used.

The total content of the polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.01% by mass to 3% by mass, preferably 0.05%, based on the total mass of the photosensitive layer. It is more preferably from 1% by mass to 1% by mass. Setting the content to 0.01% by mass or more is preferable from the viewpoint of imparting storage stability to the photosensitive resin composition. On the other hand, setting the content to 3% by mass or less is preferable from the viewpoint of maintaining sensitivity and suppressing decolorization of the dye.

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

The photosensitive layer may contain one type of sensitizer alone, or may contain two or more types.
When the photosensitive layer contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose, but from the viewpoint of improving the sensitivity to the light source and improving the curing speed due to the balance between the polymerization speed and the chain transfer. , preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 1% by mass, based on the total mass of the photosensitive layer.

The photosensitive layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds.
Plasticizers and heterocyclic compounds include compounds described in paragraphs 0097-0103 and 0111-0118 of WO2018/179640.

The photosensitive layer may contain a solvent. When the photosensitive layer is formed from a photosensitive resin composition containing a solvent, the solvent may remain in the photosensitive layer.

The photosensitive layer contains metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, It may further contain known additives such as cross-linking agents and organic or inorganic suspending agents.
Additives contained in the photosensitive layer are described in paragraphs 0165 to 0184 of JP-A-2014-85643, and the contents of this publication are incorporated herein.

<<impurities, etc.>>
The photosensitive layer may contain a certain amount of impurities.
Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens and ions thereof. Among them, halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the following contents are preferable.

The content of impurities in the photosensitive layer is preferably 80 ppm or less, more preferably 10 ppm or less, and even more preferably 2 ppm or less on a mass basis. The content of impurities can be 1 ppb or more, and may be 0.1 ppm or more, on a mass basis.

Examples of methods for adjusting the impurity content to the above range include selecting a material with a low content of impurities as a raw material for the composition, preventing contamination with impurities during the preparation of the photosensitive layer, and removing impurities by washing. . By such a method, the amount of impurities can be made within the above range.

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

The content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive layer should be small. preferable. The content of these compounds with respect to the total mass of the photosensitive layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less, based on mass.
The lower limit can be 10 ppb or more, and can be 100 ppb or more based on the total weight of the photosensitive layer. The content of these compounds can be suppressed in the same manner as the metal impurities described above. Moreover, it can quantify by a well-known measuring method.

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

<<Residual monomer>>
The photosensitive layer may contain residual monomers corresponding to the constituent units of the alkali-soluble resin described above.
The content of the residual monomer is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and 500 ppm by mass or less, relative to the total mass of the alkali-soluble resin, from the viewpoints of patterning properties and reliability. is more preferred. Although the lower limit is not particularly limited, it is preferably 1 mass ppm or more, more preferably 10 mass ppm or more.
The residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, relative to the total mass of the photosensitive layer, from the viewpoints of patterning properties and reliability. 100 mass ppm or less is more preferable. Although the lower limit is not particularly limited, it is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more.

It is preferable that the amount of residual monomers when synthesizing an alkali-soluble resin by a polymer reaction is also within the above range. For example, when synthesizing an alkali-soluble resin by reacting a carboxylic acid side chain with glycidyl acrylate, the content of glycidyl acrylate is preferably within the above range.
The amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.

<<physical properties>>
The layer thickness of the photosensitive layer is preferably 0.1 μm to 300 μm, more preferably 0.2 μm to 100 μm, still more preferably 0.5 μm to 50 μm, still more preferably 0.5 μm to 15 μm, and 0.5 μm to 10 μm. Particularly preferred, 0.5 μm to 8 μm is most preferred. Thereby, the developability of the photosensitive layer is improved, and the resolution can be improved.
In addition, the layer thickness (thickness) of the photosensitive layer is preferably 10 μm or less, more preferably 5.0 μm or less, from the viewpoint of exhibiting the resolution and the effects of the present disclosure. It is more preferably 0.5 μm to 4.0 μm, particularly preferably 0.5 μm to 3.0 μm.
The layer thickness of each layer provided in the photosensitive transfer material or laminate is an observation image obtained by observing a cross section in a direction perpendicular to the main surface of the photosensitive transfer material with a scanning electron microscope (SEM). It is measured by measuring the thickness of each layer at 10 or more points based on and calculating the average value.

Also, from the viewpoint of better adhesion, the transmittance of light with a wavelength of 365 nm of the photosensitive layer is preferably 10% or more, preferably 30% or more, and more preferably 50% or more. Although the upper limit is not particularly limited, 99.9% or less is preferable.

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

The photosensitive resin composition used for forming the photosensitive layer includes, for example, a composition containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, any of the above optional components, and a solvent.
The photosensitive resin composition preferably contains a solvent in order to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive layer.

-solvent-
The solvent contained in the photosensitive resin composition is not particularly limited as long as it can dissolve or disperse the alkali-soluble resin, the polymerizable compound, the photopolymerization initiator and the above optional components, and known solvents can be used.
Examples of solvents include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents. (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents, amide solvents, lactone solvents, and mixed solvents containing two or more of these.
When producing a photosensitive transfer material comprising a temporary support, a thermoplastic resin layer, a water-soluble resin layer, a photosensitive layer and a protective film, the photosensitive resin composition consists of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. It is preferable to contain at least one selected from the group. Among them, a mixed solvent containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one selected from the group consisting of ketone solvents and cyclic ether solvents is more preferable. A mixed solvent containing at least one selected from the group consisting of a glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and a cyclic ether solvent is more preferable.

Alkylene glycol ether solvents include, for example, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether. .
Alkylene glycol ether acetate solvents include, for example, ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate.
As the solvent, the solvent described in paragraphs 0092 to 0094 of WO 2018/179640, and the solvent described in paragraph 0014 of JP 2018-177889 may be used, the contents of which are herein incorporated into the book.

The photosensitive resin composition may contain one type of solvent alone, or may contain two or more types.
The content of the solvent when applying 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 with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. part is more preferred.

The method of preparing the photosensitive resin composition is not particularly limited, for example, by preparing a solution in which each component is dissolved in the solvent in advance and mixing the obtained solution in a predetermined ratio, the photosensitive resin composition and a method for preparing the
From the viewpoint of removability of particles of Y μm or more, the photosensitive resin composition is preferably filtered using a filter before forming the photosensitive layer, and filtered using a filter with a pore size of 0.2 μm to 10 μm. Filtration using a filter with a pore size of 0.2 µm to 7 µm is more preferred, and filtering using a filter with a pore size of 0.2 µm to 5 µm is particularly preferred.
The material and shape of the filter are not particularly limited, and known filters can be used.
Moreover, it is preferable to perform said filtration once or more, and it is also preferable to perform multiple times.

The method of applying the photosensitive resin composition is not particularly limited, and a known method may be used. Examples of coating methods include slit coating, spin coating, curtain coating, and inkjet coating.
Also, the photosensitive layer may be formed by applying a photosensitive resin composition onto a protective film described later and drying the composition.

In addition, the photosensitive transfer material in the present disclosure preferably has another layer between the temporary support and the photosensitive layer from the viewpoint of resolution and peelability of the temporary support.
Other layers preferably include a water-soluble resin layer, a thermoplastic resin layer, a protective film, and the like.
Among them, the transfer layer preferably has a water-soluble resin layer, and more preferably has a thermoplastic resin layer and a water-soluble resin layer.

[Water-soluble resin layer]
When the photosensitive transfer material has a thermoplastic resin layer described later between the temporary support and the photosensitive layer, it preferably has a water-soluble resin layer between the thermoplastic resin layer and the photosensitive layer. . According to the water-soluble resin layer, it is possible to suppress mixing of components when forming a plurality of layers and during storage.

The water-soluble resin layer is preferably a water-soluble layer from the viewpoint of developability and suppression of mixing of components during coating of multiple layers and storage after coating. In the present disclosure, "water-soluble" means that the solubility in 100 g of water at pH 7.0 at a liquid temperature of 22°C is 0.1 g or more.

Examples of the water-soluble resin layer include an oxygen-blocking layer having an oxygen-blocking function, which is described as a "separation layer" in JP-A-5-72724. Since the water-soluble resin layer is an oxygen-blocking layer, the sensitivity during exposure is improved and the time load of the exposure machine is reduced, resulting in improved productivity. The oxygen barrier layer used as the water-soluble resin layer may be appropriately selected from known layers. The oxygen-blocking layer used as the water-soluble resin layer is preferably an oxygen-blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22°C). .
In addition, the water-soluble resin layer preferably contains an inorganic stratiform compound from the viewpoints of oxygen blocking properties, resolution, and pattern formability.
Examples of the inorganic layered compound include particles having a thin tabular shape, and examples thereof include mica compounds such as natural mica and synthetic mica, talc represented by the formula: 3MgO.4SiO.H ₂ O, taeniolite, montmorillonite, saponite, hectorite, zirconium phosphate, and the like.
Examples of mica compounds include compounds of the formula: A(B,C) _2-5 D ₄ O ₁₀ (OH,F,O) ₂ [wherein A is any one of K, Na and Ca, and B and C are Fe(II), Fe(III), Mn, Al, Mg, or V, and D is Si or Al. ] and a group of mica such as natural mica and synthetic mica.

In the mica group, natural micas include muscovite, soda mica, phlogopite, biotite and lepidite. Synthetic mica includes non _- swelling mica such as fluorine _phlogopite _KMg3 ₍ _AlSi3O10 )F2, potash _tetrasilicon mica _KMg2.5Si4O10 )F2, and Na tetrasilic mica _NaMg2 _{. 5} (Si ₄ O ₁₀ ) F ₂ , Na or Li teniolite (Na, Li) Mg ₂ Li(Si ₄ O ₁₀ ) F ₂ , montmorillonite Na or Li hectorite (Na, Li) _1/8 Mg _2/ Swellable mica such as ₅ Li _1/8 (Si ₄ O ₁₀ )F ₂ and the like are included. Also useful are synthetic smectites.

As for the shape of the inorganic layered compound, from the viewpoint of diffusion control, the thinner the thickness, the better, and the larger the plane size, the better, as long as the smoothness of the coated surface and the transparency of actinic rays are not hindered. Therefore, the aspect ratio is preferably 20 or more, more preferably 100 or more, particularly preferably 200 or more. Aspect ratio is the ratio of the major axis to the thickness of the grain and can be determined, for example, from a micrograph projection of the grain. The larger the aspect ratio, the greater the effect that can be obtained.

As for the particle size of the inorganic layered compound, the average major axis is preferably 0.3 μm to 20 μm, more preferably 0.5 μm to 10 μm, and particularly preferably 1 μm to 5 μm. The average thickness of the particles is preferably 0.1 μm or less, more preferably 0.05 μm or less, and particularly preferably 0.01 μm or less. Specifically, for example, in the case of swelling synthetic mica, which is a representative compound, a preferred embodiment has a thickness of about 1 nm to 50 nm and a plane size (major axis) of about 1 μm to 20 μm.

The content of the inorganic layered compound is preferably 0.1% by mass to 50% by mass, or 1% by mass, based on the total mass of the water-soluble resin layer, from the viewpoints of oxygen barrier properties, resolution, and pattern formability. % to 20% by mass is more preferable.

The water-soluble resin layer preferably contains a resin. Examples of resins contained in the water-soluble resin layer include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof. coalescence is mentioned. The resin contained in the water-soluble resin layer is preferably a water-soluble resin.

From the viewpoint of suppressing mixing of components between a plurality of layers, the resin contained in the water-soluble resin layer is the polymer A contained in the negative photosensitive layer and the thermoplastic resin (alkali-soluble resin ) are preferably different resins.

In addition, the water-soluble resin layer preferably contains a water-soluble compound, and more preferably contains a water-soluble resin, from the viewpoints of oxygen barrier properties, developability, resolution, and pattern formability.
The water-soluble compound is not particularly limited, but from the viewpoint of oxygen blocking properties, developability, resolution, and pattern formation properties, water-soluble cellulose derivatives, polyhydric alcohols, and oxide adducts of polyhydric alcohols. , polyethers, phenol derivatives, and amide compounds, preferably at least one compound selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropylcellulose and hydroxypropylmethylcellulose More preferably, it is a kind of water-soluble resin.
Examples of water-soluble resins include resins such as water-soluble cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide resins, (meth)acrylate resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. mentioned.
Among them, the water-soluble compound preferably contains polyvinyl alcohol, more preferably polyvinyl alcohol, from the viewpoint of oxygen barrier properties, developability, resolution, and pattern formability.
The degree of hydrolysis of polyvinyl alcohol is not particularly limited, but is preferably 73 mol % to 99 mol % from the viewpoints of oxygen blocking properties, developability, resolution, and pattern formability.
Moreover, polyvinyl alcohol preferably contains ethylene as a monomer unit from the viewpoint of oxygen blocking properties, developability, resolution, and pattern formability.

The water-soluble resin layer preferably contains polyvinyl alcohol from the viewpoint of oxygen barrier properties and suppression of mixing of components during coating of multiple layers and storage after coating, and polyvinyl alcohol and polyvinylpyrrolidone. It is more preferable to include

The water-soluble resin layer may contain one kind of resin alone or two or more kinds of resins.

The content of the water-soluble compound in the water-soluble resin layer should be within the total weight of the water-soluble resin layer from the viewpoint of oxygen barrier properties and suppression of mixing of components during coating of multiple layers and storage after coating. On the other hand, it is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, even more preferably 80% by mass to 100% by mass, and 90% by mass to 100% by mass. % is particularly preferred.

In addition, the water-soluble resin layer may contain additives as necessary. Additives include, for example, surfactants.

The thickness of the water-soluble resin layer is not limited. The average thickness of the water-soluble resin layer is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm. When the thickness of the water-soluble resin layer is within the above range, it is possible to suppress mixing of components during formation of a plurality of layers and during storage without lowering the oxygen barrier property, and during development. An increase in the removal time of the water-soluble resin layer can be suppressed.

The method for forming the water-soluble resin layer is not limited as long as it can form a layer containing the above components. As a method for forming the water-soluble resin layer, for example, a method of applying the water-soluble resin layer composition to the surface of the thermoplastic resin layer or the photosensitive layer and then drying the coating film of the water-soluble resin layer composition. mentioned.

Examples of water-soluble resin layer compositions include compositions containing resins and optional additives. The water-soluble resin layer composition preferably contains a solvent in order to adjust the viscosity of the water-soluble resin layer composition and facilitate the formation of the water-soluble resin layer. The solvent is not limited as long as it can dissolve or disperse the resin. The solvent is preferably at least one selected from the group consisting of water and water-miscible organic solvents, more preferably water or a mixed solvent of water and a water-miscible organic solvent.

Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. The water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, more preferably methanol or ethanol.

[Thermoplastic resin layer]
The photosensitive transfer material used in the present disclosure may have a thermoplastic resin layer. The photosensitive transfer material preferably has a thermoplastic resin layer between the temporary support and the photosensitive layer. Since the photosensitive transfer material has a thermoplastic resin layer between the temporary support and the photosensitive layer, the followability to the adherend is improved, and air bubbles are not mixed between the adherend and the photosensitive transfer material. This is because the adhesion between the layers is improved as a result of the suppression of the

The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.

Examples of alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, Polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.

The alkali-soluble resin is preferably an acrylic resin from the viewpoint of developability and adhesion to the layer adjacent to the thermoplastic resin layer. Here, the "acrylic resin" is selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amides. means a resin having at least one

In the acrylic resin, the ratio of the total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid ester, and structural units derived from (meth)acrylic acid amide is It is preferably 50% by mass or more with respect to the total mass. In the acrylic resin, the ratio of the total content of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylic acid ester is 30% to 100% by mass with respect to the total mass of the acrylic resin. %, more preferably 50% by mass to 100% by mass.

Also, the alkali-soluble resin is preferably a polymer having an acid group. The acid group includes, for example, a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, with the carboxy group being preferred.

From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin with an acid value of 60 mgKOH/g or more, and more preferably a carboxy group-containing acrylic resin with an acid value of 60 mgKOH/g or more. The upper limit of the acid value is not restricted. The acid value of the alkali-soluble resin is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less.

The carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more is not limited and can be appropriately selected from known resins and used. The carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more includes, for example, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more among the polymers described in paragraph 0025 of JP-A-2011-95716, Among the polymers described in paragraphs 0033 to 0052 of JP-A-2010-237589, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more, and paragraphs 0053 to 0068 of JP-A-2016-224162. Among the binder polymers of (1), a carboxy group-containing acrylic resin having an acid value of 60 mgKOH/g or more can be mentioned.

The content of structural units having a carboxy group in the carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, based on the total mass of the carboxyl group-containing acrylic resin. 12% by mass to 30% by mass is particularly preferable.

The alkali-soluble resin is particularly preferably an acrylic resin having structural units derived from (meth)acrylic acid, from the viewpoint of developability and adhesion to the layer adjacent to the thermoplastic resin layer.

The alkali-soluble resin may have a reactive group. The reactive group may be, for example, a group capable of addition polymerization. Reactive groups include, for example, ethylenically unsaturated groups, polycondensable groups (e.g., hydroxy groups, and carboxy groups), and polyaddition-reactive groups (e.g., epoxy groups and (blocked) isocyanate groups). be done.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and particularly preferably 20,000 to 50,000.

The thermoplastic resin layer may contain one type alone or two or more types of alkali-soluble resins.

The content of the alkali-soluble resin is preferably 10% by mass to 99% by mass with respect to the total mass of the thermoplastic resin layer, from the viewpoint of developability and adhesion to layers adjacent to the thermoplastic resin layer. It is preferably from 20% by mass to 90% by mass, still more preferably from 40% by mass to 80% by mass, and particularly preferably from 50% by mass to 70% by mass.

The thermoplastic resin layer has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm during color development, and a dye whose maximum absorption wavelength changes due to acid, base, or radical (hereinafter referred to as "dye B" ) is preferably included. Preferred embodiments of the dye B are the same as the preferred embodiments of the dye N described above, except for the points described later.

Dye B is preferably a dye whose maximum absorption wavelength changes with acid or radicals from the viewpoint of visibility in exposed areas, visibility in unexposed areas, and resolution, and the maximum absorption wavelength changes with acids. It is more preferable that it is a dye that

From the viewpoint of the visibility of the exposed area, the visibility of the unexposed area, and the resolution, the thermoplastic layer contains, as the dye B, a dye whose maximum absorption wavelength is changed by an acid, and a compound that generates an acid by light, which will be described later. , is preferably included.

The thermoplastic resin layer may contain one kind of pigment B alone or two or more kinds.

From the viewpoint of the visibility of the exposed area and the visibility of the non-exposed area, the content of the dye B is preferably 0.2% by mass or more with respect to the total mass of the thermoplastic resin layer, and is preferably 0.2% by mass. % to 6% by mass, more preferably 0.2% to 5% by mass, and particularly preferably 0.25% to 3.0% by mass.

Here, the content ratio of the pigment B means the content ratio of the pigment when all the pigment B contained in the thermoplastic resin layer is in a colored state. A method for quantifying the content of the dye B will be described below using a dye that develops color by radicals as an example. Prepare two solutions of dye (0.001 g) and dye (0.01 g) in methyl ethyl ketone (100 mL). After adding IRGACURE OXE-01 (BASF Corp.) as a radical photopolymerization initiator to each solution obtained, radicals are generated by irradiation with light of 365 nm, and all dyes are brought into a colored state. Next, in an air atmosphere, using a spectrophotometer (UV3100, Shimadzu Corporation), the absorbance of each solution having a liquid temperature of 25° C. is measured to prepare a calibration curve. Next, the absorbance of the solution in which all the dyes are developed is measured in the same manner as described above except that the thermoplastic resin layer (0.1 g) is dissolved in methyl ethyl ketone instead of the dyes. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of dye contained in the thermoplastic resin layer is calculated based on the calibration curve.

The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical (hereinafter sometimes referred to as "compound C") upon exposure to light. Compound C is preferably a compound that receives actinic rays (eg, ultraviolet rays and visible rays) and generates an acid, a base, or a radical. Examples of the compound C include known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators). Compound C is preferably a photoacid generator.

From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator. Examples of the photoacid generator include photocationic polymerization initiators that may be contained in the photosensitive layer described above, and preferred embodiments are also the same except for the points described later.

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

Also, the photoacid generator is preferably a photoacid generator having the following structure.

The thermoplastic resin layer may contain a photobase generator. Examples of photobase generators include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[ [(2-Nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane , N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt (III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2,6- Dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4 - includes dihydropyridines.

The thermoplastic resin layer may contain a radical photopolymerization initiator. The radical photopolymerization initiator includes, for example, the radical photopolymerization initiator that may be contained in the photosensitive layer described above, and preferred embodiments are also the same.

The thermoplastic resin layer may contain one type of compound C alone or two or more types.

The content of compound C is 0.1% by mass to 10% by mass with respect to the total mass of the thermoplastic resin layer, from the viewpoints of visibility of exposed areas, visibility of unexposed areas, and resolution. is preferred, and 0.5% by mass to 5% by mass is more preferred.

The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion with layers adjacent to the thermoplastic resin layer, and developability.

The molecular weight of the plasticizer (weight average molecular weight (Mw) for the molecular weight of the oligomer or polymer; hereinafter the same applies in this paragraph) is preferably smaller than the molecular weight of the alkali-soluble resin. The molecular weight of the plasticizer is preferably 200-2,000.

The plasticizer is not limited as long as it is a compound that is compatible with the alkali-soluble resin and develops plasticity. From the viewpoint of imparting plasticity, the plasticizer is preferably a compound having an alkyleneoxy group in the molecule, more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

From the viewpoint of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoint of compatibility, resolution, and adhesion to the layer adjacent to the thermoplastic resin layer, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.

Examples of (meth)acrylate compounds used as plasticizers include the (meth)acrylate compounds described in the above ethylenically unsaturated compounds. In the photosensitive transfer material, when the thermoplastic resin layer and the photosensitive layer are arranged in direct contact, the thermoplastic resin layer and the photosensitive layer each preferably contain the same (meth)acrylate compound. This is because the thermoplastic resin layer and the photosensitive layer each contain the same (meth)acrylate compound, thereby suppressing the diffusion of components between layers and improving the storage stability.

When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, the (meth)acrylate compound may not be polymerized even in the exposed areas after exposure from the viewpoint of adhesion to the layer adjacent to the thermoplastic resin layer. preferable.

In one embodiment, the (meth)acrylate compound used as a plasticizer has two or more ( A (meth)acrylate compound having a meth)acryloyl group is preferred.

In one embodiment, the (meth)acrylate compound used as a plasticizer is preferably a (meth)acrylate compound having an acid group or a urethane (meth)acrylate compound.

The thermoplastic resin layer may contain one plasticizer alone or two or more plasticizers.

The content of the plasticizer is 1% by mass to 70% by mass with respect to the total mass of the thermoplastic resin layer, from the viewpoints of resolution, adhesion with a layer adjacent to the thermoplastic resin layer, and developability. preferably 10% by mass to 60% by mass, particularly preferably 20% by mass to 50% by mass.

From the viewpoint of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant. Examples of surfactants include surfactants that may be contained in the photosensitive layer described above, and preferred embodiments are also the same.

The thermoplastic resin layer may contain one kind of surfactant alone or two or more kinds of surfactants.

The content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, relative to the total mass of the thermoplastic resin layer.

The thermoplastic resin layer may contain a sensitizer. Sensitizers include, for example, the sensitizers that may be contained in the negative photosensitive layer described above.

The thermoplastic resin layer may contain one kind of sensitizer or two or more kinds of sensitizers.

The content of the sensitizer is 0.01% by mass to 5% by mass with respect to the total mass of the thermoplastic resin layer, from the viewpoint of improving the sensitivity to the light source, the visibility of the exposed area, and the visibility of the non-exposed area. %, more preferably 0.05% by mass to 1% by mass.

In addition to the above components, the thermoplastic resin layer may contain known additives as necessary.

Further, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of JP-A-2014-85643. The contents of the above publication are incorporated herein by reference.

The thickness of the thermoplastic resin layer is not limited. The average thickness of the thermoplastic resin layer is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesion to the layer adjacent to the thermoplastic resin layer. The upper limit of the average thickness of the thermoplastic resin layer is not restricted. The average thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less, from the viewpoint of developability and resolution.

The method of forming the thermoplastic resin layer is not limited as long as it is a method capable of forming a layer containing the above components. Examples of the method for forming the thermoplastic resin layer include a method of applying a thermoplastic resin composition to the surface of the temporary support and drying the coating film of the thermoplastic resin composition.

Examples of thermoplastic resin compositions include compositions containing the above components. The thermoplastic resin composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.

The solvent contained in the thermoplastic resin composition is not limited as long as it can dissolve or disperse the components contained in the thermoplastic resin layer. Examples of the solvent include solvents that may be contained in the photosensitive resin composition described above, and preferred embodiments are also the same.

The thermoplastic resin composition may contain one solvent alone or two or more solvents.

The content of the solvent in the thermoplastic resin composition is preferably 50 parts by mass to 1,900 parts by mass with respect to 100 parts by mass of the total solid content in the thermoplastic resin composition, and 100 parts by mass to 900 parts by mass. Part is more preferred.

The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out according to the method of preparing the photosensitive resin composition and the method of forming the negative photosensitive layer described above. For example, a solution in which each component contained in the thermoplastic resin layer is dissolved in a solvent is prepared in advance, and the obtained solutions are mixed in a predetermined ratio to prepare a thermoplastic resin composition. A thermoplastic resin layer can be formed by applying a thermoplastic resin composition to the surface of a temporary support and drying the coating film of the thermoplastic resin composition. Moreover, after forming a negative photosensitive layer on the protective film, a thermoplastic resin layer may be formed on the surface of the negative photosensitive layer.

〔Protective film〕
A photosensitive transfer material has a protective film.
Note that the protective film is not included in the transfer layer.
It is preferable that the photosensitive layer and the protective film are in direct contact with each other.

Materials constituting the protective film include resin films and paper, and resin films are preferable from the viewpoint of strength and flexibility.
Resin films include polyethylene films, polypropylene films, polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among them, polyethylene film, polypropylene film, or polyethylene terephthalate film is preferable.

The thickness (layer thickness) of the protective film is not particularly limited, but is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm.
The arithmetic mean roughness Ra of the surface of the protective film opposite to the photosensitive layer side is the same as that of the photosensitive layer side of the protective film, from the viewpoints of transportability, resin pattern defect suppression, and resolution. It is preferably less than the arithmetic mean roughness Ra of the surface, and more preferably smaller than the arithmetic mean roughness Ra of the surface of the protective film on the photosensitive layer side.
The arithmetic mean roughness Ra of the surface of the protective film opposite to the photosensitive layer side is preferably 300 nm or less, more preferably 100 nm or less, still more preferably 70 nm or less, and 50 nm, from the viewpoint of transportability and winding properties. The following are particularly preferred.
In addition, the arithmetic mean roughness Ra of the surface on the photosensitive layer side of the protective film is preferably 300 nm or less, more preferably 100 nm or less, even more preferably 70 nm or less, and 50 nm or less from the viewpoint of better resolution. is particularly preferred. It is considered that the thickness uniformity of the photosensitive layer and the formed resin pattern is improved when the Ra value of the surface of the protective film is within the above range.
Although the lower limit of the Ra value on the surface of the protective film is not particularly limited, it is preferably 1 nm or more, more preferably 10 nm or more, and particularly preferably 20 nm or more for both surfaces.
Moreover, the peeling force of the protective film is preferably smaller than the peeling force of the temporary support.

The photosensitive transfer material may include layers other than the layers described above (hereinafter also referred to as "other layers"). Other layers include, for example, a contrast enhancement layer.
Contrast enhancement layers are described in paragraph 0134 of WO2018/179640. Other layers are described in paragraphs 0194 to 0196 of JP-A-2014-85643. The contents of these publications are incorporated herein.

The total thickness of the photosensitive transfer material is preferably 5 μm to 55 μm, more preferably 10 μm to 50 μm, particularly preferably 20 μm to 40 μm. The total thickness of the photosensitive transfer material is measured according to the method for measuring the thickness of each layer described above.
The total thickness of each layer excluding the temporary support and the protective film in the photosensitive transfer material is preferably 20 μm or less, more preferably 10 μm or less, and 8 μm or less from the viewpoint of exhibiting the effects of the present disclosure. It is more preferable to be 2 μm or more, and particularly preferably 2 μm or more and 8 μm or less.
Further, the total thickness of the photosensitive layer, the water-soluble resin layer and the thermoplastic resin layer in the photosensitive transfer material is preferably 20 μm or less, more preferably 10 μm or less, from the viewpoint of exhibiting the effects of the present disclosure. It is more preferably 8 µm or less, and particularly preferably 2 µm or more and 8 µm or less.

[Method for producing photosensitive transfer material]
The method for producing the photosensitive transfer material used in the present disclosure is not particularly limited, and known production methods such as known methods for forming each layer can be used.
A method for manufacturing a photosensitive transfer material used in the present disclosure will be described below with reference to FIG. However, the photosensitive transfer material used in the present disclosure is not limited to those having the configuration shown in FIG.
FIG. 1 is a schematic cross-sectional view showing an example of a layer structure in one embodiment of a photosensitive transfer material used in the present disclosure. The photosensitive transfer material 20 shown in FIG. 1 has a structure in which a temporary support 11, a thermoplastic resin layer 13, a water-soluble resin layer 15, a photosensitive layer 17, and a protective film 19 are laminated in this order. . The transfer layer 12 in FIG. 1 includes the thermoplastic resin layer 13, the water-soluble resin layer 15, and the photosensitive layer 17. FIG.

As a method for producing the photosensitive transfer material 20, for example, after applying a thermoplastic resin composition to the surface of the temporary support 11, by drying the coating film of the thermoplastic resin composition, the thermoplastic resin layer 13, a step of applying a water-soluble resin layer composition to the surface of the thermoplastic resin layer 13, and then drying the coating film of the water-soluble resin layer composition to form a water-soluble resin layer 15; a step of applying a photosensitive resin composition containing an ethylenically unsaturated compound to the surface of the water-soluble resin layer 15, and then drying the coating film of the photosensitive resin composition to form a photosensitive layer 16. is mentioned.
In the above production method, a thermoplastic resin composition containing at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, and selected from the group consisting of water and water-miscible organic solvents and a binder polymer, an ethylenically unsaturated compound, and at least one selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. It is preferable to use a flexible resin composition. As a result, the water-soluble resin layer composition is applied to the surface of the thermoplastic resin layer 13 and / or contained in the thermoplastic resin layer 13 during the storage period of the laminate having the coating film of the water-soluble resin layer composition. It is possible to suppress mixing of the component contained in the water-soluble resin layer 15 with the component contained in the water-soluble resin layer 15, and the application of the photosensitive resin composition to the surface of the water-soluble resin layer 15 and / or the photosensitive resin composition mixing of the components contained in the water-soluble resin layer 15 and the components contained in the photosensitive layer 16 during the storage period of the laminate having the coating film can be suppressed.

The photosensitive transfer material 20 is manufactured by pressing the protective film 19 onto the photosensitive layer 17 of the laminate manufactured by the manufacturing method described above.
As a method for producing the photosensitive transfer material used in the present disclosure, by including the step of providing a protective film 19 so as to be in contact with the second surface of the photosensitive layer 17, the temporary support 11, the thermoplastic resin layer 13, the aqueous It is preferable to manufacture a photosensitive transfer material 20 comprising a flexible resin layer 15 , a photosensitive layer 17 and a protective film 19 .
After manufacturing the photosensitive transfer material 20 by the manufacturing method described above, the photosensitive transfer material 20 may be wound up to produce and store a roll-shaped photosensitive transfer material. The photosensitive transfer material in roll form can be provided as it is to the lamination step with a substrate in a roll-to-roll system, which will be described later.

The photosensitive transfer material used in the present disclosure can be suitably used for various applications requiring precision microfabrication by photolithography. After patterning the photosensitive layer, etching may be performed using the photosensitive layer as a film, or electroforming, which is mainly electroplating, may be performed. Moreover, the cured film obtained by patterning may be used as a permanent film, for example, as an interlayer insulating film, a wiring protective film, a wiring protective film having an index matching layer, and the like. In addition, the photosensitive transfer material used in the present disclosure includes semiconductor packages, printed circuit boards, various wiring formation applications for sensor substrates, touch panels, electromagnetic shielding materials, conductive films such as film heaters, liquid crystal sealing materials, micromachines or microelectronics. It can be suitably used for applications such as formation of structures in the field.

Moreover, in the photosensitive transfer material used in the present disclosure, an aspect in which the photosensitive layer is a colored resin layer containing a pigment is also preferred.
Applications of the colored resin layer include, in addition to those described above, for example, liquid crystal display devices (LCD), and solid-state imaging devices [e.g., CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor)]. It is suitable for use in forming colored pixels such as filters or a black matrix.
Aspects other than the pigment in the colored resin layer are the same as those described above.

<Pigment>
The photosensitive layer may be a colored resin layer containing a pigment.
In order to protect the liquid crystal display window of electronic equipment in recent years, there are cases where a cover glass with a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate or the like is attached to the liquid crystal display window. be. A colored resin layer may be used to form such a light shielding layer.
The pigment may be appropriately selected according to the desired hue, and may be selected from black pigments, white pigments, and chromatic pigments other than black and white. Among them, when forming a black pattern, a black pigment is preferably selected as the pigment.

As the black pigment, a known black pigment (organic pigment, inorganic pigment, etc.) can be appropriately selected as long as it does not impair the effects of the present disclosure. Among them, from the viewpoint of optical density, black pigments include, for example, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide and graphite, and carbon black is particularly preferred. As the carbon black, from the viewpoint of surface resistance, carbon black having at least a part of the surface coated with a resin is preferable.

From the viewpoint of dispersion stability, the number average particle size of the black pigment is preferably 0.001 μm to 0.1 μm, more preferably 0.01 μm to 0.08 μm.
Here, the particle size refers to the diameter of a circle obtained by obtaining the area of a pigment particle from a photographic image of the pigment particle taken with an electron microscope and considering a circle having the same area as the area of the pigment particle. is an average value obtained by obtaining the above particle size for 100 arbitrary particles and averaging the obtained 100 particle sizes.

White pigments described in paragraphs 0015 and 0114 of JP-A-2005-007765 can be used as pigments other than black pigments. Specifically, among white pigments, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferable as inorganic pigments, and titanium oxide or zinc oxide is more preferable. Preferred, and more preferred is titanium oxide. As the inorganic pigment, rutile-type or anatase-type titanium oxide is more preferable, and rutile-type titanium oxide is particularly preferable.
In addition, the surface of titanium oxide may be subjected to silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic substance treatment, or may be subjected to two or more treatments. As a result, the catalytic activity of titanium oxide is suppressed, and the heat resistance, fade resistance, and the like are improved.
From the viewpoint of reducing the thickness of the photosensitive layer after heating, the surface treatment of the titanium oxide surface is preferably at least one of alumina treatment and zirconia treatment, and particularly preferably both alumina treatment and zirconia treatment.

Moreover, when the photosensitive layer is a colored resin layer, from the viewpoint of transferability, the photosensitive layer preferably further contains a chromatic pigment other than the black pigment and the white pigment. When a chromatic pigment is included, the particle size of the chromatic pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of better dispersibility.
Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter C.I.) 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), and Monolite.・Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Carmine FBB (C) Pigment Red 146), Hoster Balm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), Fastel Pink B Spra (C.I. Pigment Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monolite Fast Black B (C.I. Pigment Black 1) and Carbon, C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I. Pigment Red 149, C.I. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I. Pigment Red 215, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15:1, C.I. I. Pigment Blue 15:4, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 64, and C.I. I. Pigment Violet 23 and the like. Among them, C.I. I. Pigment Red 177 is preferred.

When the photosensitive layer contains a pigment, the content of the pigment is preferably more than 3% by mass and 40% by mass or less, more preferably more than 3% by mass and 35% by mass or less, based on the total mass of the photosensitive layer. More than 35% by mass is more preferable, and 10% by mass or more and 35% by mass or less is particularly preferable.

When the photosensitive layer contains pigments other than black pigments (white pigments and chromatic pigments), the content of pigments other than black pigments is preferably 30% by mass or less, and 1% to 20% by mass, based on the black pigment. % by mass is more preferred, and 3 to 15% by mass is even more preferred.

In addition, when the photosensitive layer contains a black pigment and the photosensitive layer is formed of a photosensitive resin composition, the black pigment (preferably carbon black) is added to the photosensitive resin composition in the form of a pigment dispersion. preferably introduced.
The dispersion liquid may be prepared by adding a mixture obtained by previously mixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing the mixture with a dispersing machine. A pigment dispersant may be selected according to the pigment and solvent, and for example, a commercially available dispersant can be used. In addition, the vehicle refers to the part of the medium in which the pigment is dispersed when it is made into a pigment dispersion, and is a liquid binder component that holds the black pigment in a dispersed state, and a solvent component that dissolves and dilutes the binder component. (Organic solvent) and.

The disperser is not particularly limited, and includes known dispersers such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Furthermore, it may be finely pulverized using frictional force by mechanical grinding. Regarding the dispersing machine and the fine pulverization, reference can be made to the description in "Encyclopedia of Pigment" (Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pp. 438, 310).

(Method for manufacturing circuit wiring)
The method for producing circuit wiring according to the present disclosure is not particularly limited as long as it is a method using a laminate produced by the method for producing a laminate according to the present disclosure or a photosensitive transfer material according to the present disclosure, which will be described later.
Further, the method for manufacturing a circuit wiring according to the present disclosure includes a preparation step of preparing a laminate obtained by the method for manufacturing a laminate according to the present disclosure, and etching the substrate in a region where the resin pattern is not arranged. A method including etching steps for processing in this order is preferred.
Hereinafter, each step included in the circuit wiring manufacturing method will be described. shall also apply.

<Preparation process>
The circuit wiring manufacturing method according to the present disclosure preferably includes a preparation step of preparing the laminate obtained by the laminate manufacturing method according to the present disclosure.
Preferred aspects of the laminate in the preparation step are the same as the preferred aspects of the laminate manufacturing method according to the present disclosure.

<Etching process>
It is preferable that the circuit wiring manufacturing method includes a step of etching the substrate in a region where the resin pattern is not arranged (etching step).

In the etching step, the conductive layer is etched using the resin pattern formed from the photosensitive layer as an etching resist.
As the etching method, a known method can be applied, for example, the method described in paragraphs 0209 to 0210 of JP-A-2017-120435, and the method described in paragraphs 0048 to 0054 of JP-A-2010-152155. method, a wet etching method in which the substrate is immersed in an etching solution, and a dry etching method such as plasma etching.

As the etchant used for wet etching, an acidic or alkaline etchant may be appropriately selected according to the object to be etched.
Examples of acidic etching solutions include aqueous solutions of acidic components alone selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid and phosphoric acid, and acidic components, ferric chloride, ammonium fluoride and A mixed aqueous solution with a salt selected from potassium permanganate can be mentioned. The acidic component may be a combination of multiple acidic components.
Alkaline etching solutions include aqueous solutions of alkali components alone selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (tetramethylammonium hydroxide, etc.), and alkali components and salts. (potassium permanganate, etc.). The alkaline component may be a component obtained by combining a plurality of alkaline components.

<Removal process>
In the circuit wiring manufacturing method, it is preferable to perform a step of removing the remaining resin pattern (removing step).
The removal step is not particularly limited and can be performed as necessary, but is preferably performed after the etching step.
A method for removing the remaining resin pattern is not particularly limited, but a method of removing by chemical treatment is mentioned, and a method of removing using a removing liquid is preferable.
As a method for removing the photosensitive layer, the substrate having the remaining resin pattern is placed in a stirring removal liquid whose liquid temperature is preferably 30° C. to 80° C., more preferably 50° C. to 80° C., for 1 minute to 30° C. A method of immersing for a minute can be mentioned.

Examples of the remover include a remover obtained by dissolving an inorganic alkaline component or an organic alkaline component in water, dimethylsulfoxide, N-methylpyrrolidone, or a mixed solution thereof. Examples of inorganic alkaline components include sodium hydroxide and potassium hydroxide. Organic alkaline components include primary amine compounds, secondary amine compounds, tertiary amine compounds and quaternary ammonium salt compounds.
Alternatively, it may be removed by a known method such as a spray method, a shower method, or a paddle method using a remover.

<Other processes>
The circuit wiring manufacturing method may include arbitrary steps (other steps) other than the steps described above. Examples include, but are not limited to, the following steps.
Further, the exposure process, the development process, and other processes applicable to the circuit wiring manufacturing method include the processes described in paragraphs 0035 to 0051 of JP-A-2006-23696.
Furthermore, other steps include, for example, a step of reducing the visible light reflectance described in paragraph 0172 of WO 2019/022089, and a new step on the insulating film described in paragraph 0172 of WO 2019/022089. Examples include a step of forming a conductive layer, but the present invention is not limited to these steps.

- Step of reducing visible light reflectance -
The circuit wiring manufacturing method may include a step of performing a process for reducing the visible light reflectance of a part or all of the plurality of conductive layers of the substrate.
The treatment for reducing the visible light reflectance includes oxidation treatment. When the substrate has a conductive layer containing copper, the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to form copper oxide and blackening the conductive layer.
The treatment for reducing the visible light reflectance is described in paragraphs 0017 to 0025 of JP-A-2014-150118, and paragraphs 0041, 0042, 0048 and 0058 of JP-A-2013-206315. , the contents of which are incorporated herein.

-Step of Forming Insulating Film, Step of Forming New Conductive Layer on Surface of Insulating Film-
It is also preferable that the circuit wiring manufacturing method includes a step of forming an insulating film on the surface of the circuit wiring, and a step of forming a new conductive layer on the surface of the insulating film.
Through the above steps, a second electrode pattern insulated from the first electrode pattern can be formed.
The process of forming the insulating film is not particularly limited, and a known method of forming a permanent film can be used. Alternatively, an insulating film having a desired pattern may be formed by photolithography using an insulating photosensitive material.
The step of forming a new conductive layer on the insulating film is not particularly limited. For example, a conductive photosensitive material may be used to form a new conductive layer in a desired pattern by photolithography.

It is also preferable that the circuit wiring manufacturing method uses a substrate having a plurality of conductive layers on both surfaces of the substrate, and sequentially or simultaneously forms circuits on the conductive layers formed on both surfaces of the substrate. With such a configuration, it is possible to form a circuit wiring for a touch panel in which the first conductive pattern is formed on one surface of the substrate and the second conductive pattern is formed on the other surface of the substrate. It is also preferable to form the touch panel circuit wiring having such a configuration from both sides of the substrate by roll-to-roll.

<Application>
The resin pattern manufactured by the resin pattern manufacturing method according to the present disclosure, the laminate manufactured by the laminate manufacturing method according to the present disclosure, and the circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure , can be applied to various devices. Examples of the device provided with the laminate include an input device and the like, preferably a touch panel, and more preferably a capacitive touch panel. Further, the input device can be applied to display devices such as an organic electroluminescence display device and a liquid crystal display device.
When the laminate is applied to a touch panel, the formed resin pattern is preferably used as a protective film for touch panel electrodes or touch panel wiring. That is, the photosensitive transfer material according to the present disclosure is preferably used for forming a touch panel electrode protective film or a touch panel wiring.

(Method for manufacturing electronic device)
The method for producing an electronic device according to the present disclosure is not particularly limited as long as it is a method using a laminate produced by the method for producing a laminate according to the present disclosure or a photosensitive transfer material according to the present disclosure, which will be described later.
Further, a method for manufacturing an electronic device according to the present disclosure includes a preparation step of preparing a laminate obtained by the method for manufacturing a laminate according to the present disclosure, and etching the substrate in a region where the resin pattern is not arranged. A method including etching steps for processing in this order is preferred.
An electronic device manufactured by the method for manufacturing an electronic device according to the present disclosure preferably has the resin pattern as a permanent film.

The specific aspects of each step and the order of performing each step in the method of manufacturing an electronic device are described in the above sections of "Method for manufacturing laminate" and "Method for manufacturing circuit wiring". and preferred embodiments are also the same.
As for the method for manufacturing an electronic device, a known method for manufacturing an electronic device may be referred to, except that the electronic device wiring is formed by the method described above.
Moreover, the method for manufacturing an electronic device may include arbitrary steps (other steps) other than those described above.

Electronic devices are not particularly limited, but semiconductor packages, printed circuit boards, various wiring formation applications for sensor substrates, touch panels, electromagnetic wave shielding materials, conductive films such as film heaters, liquid crystal sealing materials, micromachines or in the field of microelectronics Structures are preferred.
In the electronic device, the resin pattern is preferably used as a permanent film, such as an interlayer insulating film, a wiring protective film, or a wiring protective film having an index matching layer.
Among them, a touch panel is particularly suitable as an electronic device.

An example of a mask pattern used for manufacturing a touch panel is shown in FIGS. 2 and 3. FIG.
In pattern A shown in FIG. 2 and pattern B shown in FIG. It is shown In the touch panel manufacturing method, for example, by exposing the photosensitive layer through a mask having pattern A shown in FIG. 2, a touch panel having circuit wiring having pattern A corresponding to EX formed thereon can be manufactured. Specifically, it can be produced by the method described in FIG. 1 of International Publication No. 2016/190405. In one example of the manufactured touch panel, the central portion of the exposed portion EX (the pattern portion where the qualifications are connected) is the portion where the transparent electrode (touch panel electrode) is formed, and the peripheral portion (thin line portion) of the exposed portion EX is This is the portion where the wiring of the peripheral extracting portion is formed.

By the method for manufacturing an electronic device, an electronic device having at least electronic device wiring is manufactured, and preferably, a touch panel having at least touch panel wiring is manufactured, for example.
The touch panel preferably has a transparent substrate, electrodes, and an insulating layer or protective layer.
As a detection method for a touch panel, known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method can be used. Among them, the capacitance method is preferable.

As the touch panel type, the so-called in-cell type (for example, those described in FIGS. 5, 6, 7 and 8 of JP-A-2012-517051), the so-called on-cell type (for example, JP 2013-168125) Those described in FIG. 19, and those described in FIGS. 1 and 5 of JP-A-2012-89102), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, JP-A 2013-54727), various out-cell types (so-called GG, G1 G2, GFF, GF2, GF1 and G1F, etc.) and other configurations (for example, Japanese Patent Application Laid-Open No. 2013-164871 6).
Examples of touch panels include those described in paragraph 0229 of JP-A-2017-120435.

(Photosensitive transfer material)
A photosensitive transfer material according to the present disclosure has a temporary support and a transfer layer including a photosensitive layer, wherein the limiting resolution of the photosensitive layer is defined as X ^T μm, and the reference diameter of the particles is Y ^T =0 When defined as Y ^T μm represented by .5×X ^T , the number of particles having a diameter of Y ^T μm or more on the surface and inside of the photosensitive layer is 15 particles/cm ² or less.
In addition, the preferred aspects of the photosensitive transfer material according to the present disclosure are the same as the preferred aspects of the photosensitive transfer material used in the above-described method for producing a laminate according to the present disclosure, except as described later.

<The critical resolution of the photosensitive layer is X ^T μm, and the number of particles having a diameter of Y ^T μm or more on the surface and inside of the photosensitive layer>
In the photosensitive transfer material according to the present disclosure, when the critical resolution of the photosensitive layer is defined as X ^T μm and the reference diameter of the particles is defined as Y ^T μm represented by Y ^T =0.5×X ^T , the number of particles having a diameter of Y ^T μm or more on the surface and inside of the photosensitive layer is 15 particles/cm ² or less, and from the viewpoint of suppressing pinhole defects, it is preferably 10 particles/cm ² or less. It is preferably 7/cm ² or less, and particularly preferably 5/cm ² or less. The lower limit is 0/cm ² .

Measurement of the limiting resolution ^XT of the photosensitive layer in the photosensitive transfer material according to the present disclosure, and measurement of the number of particles having a diameter of ^YT μm or more on the surface and inside of the photosensitive layer are described in the present disclosure. It can be measured in the same manner as the limit resolution X μm and the number of particles having a diameter of Y μm or more in the manufacturing method of the laminate.

The embodiments of the present invention will be described more specifically below with reference to examples. Materials, usage amounts, proportions, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the gist of the embodiments of the present invention. Accordingly, the scope of embodiments of the present invention is not limited to the specific examples shown below. "Parts" and "%" are based on mass unless otherwise specified.

<Production of temporary support A>
A temporary support A was produced by the following method.

[Preparation of Particle-Containing Layer-Forming Composition 1]
A particle-containing layer-forming composition 1 was obtained by mixing each component according to the formulation shown below. After preparing the particle-containing layer-forming composition 1, it was filtered with a 6 μm filter (F20, manufactured by Mahle Filter Systems Co., Ltd.), and then a membrane was filtered using a 2×6 radial flow superphobic (manufactured by Polypore Co., Ltd.). Degassed.
・Acrylic polymer (AS-563A, manufactured by Daicel Finechem Co., Ltd., solid content 27.5% by mass) 167 parts ・Nonionic surfactant (Naroacty CL95, manufactured by Sanyo Chemical Industries, Ltd., solid content 100% by mass) 0.7 parts Anionic surfactant (Rapisol A-90, manufactured by NOF Corporation, diluted with water to a solid content of 1% by mass) 114.4 parts Carnauba wax dispersion (Cerosol 524, Chukyo Yushi Co., Ltd. ), solid content 30% by mass) 7 parts Carbodiimide compound (Carbodilite V-02-L2, manufactured by Nisshinbo Co., Ltd., diluted with water to a solid content of 10% by mass) 20.9 parts Matting agent (Snowtex XL, Nissan Chemical Co., Ltd., solid content 40 mass%, average particle diameter 50 nm) 2.8 parts, water 690.2 parts

[Extrusion]
Pellets of polyethylene terephthalate (PET) produced using the citric acid chelate organotitanium complex described in Japanese Patent No. 5575671 as a polymerization catalyst were dried to reduce the moisture content of the pellets to 50 ppm or less. The dried pellets were put into the hopper of a single-screw kneading extruder with a diameter of 30 mm and melted at 280°C. This melt was passed through a filter (pore size of 2 μm) and then extruded from a die onto a cooling roll at 25° C. to obtain an unstretched film. In the above method, the melt was brought into close contact with the cooling roll using an electrostatic application method.

[Stretching and coating]
The solidified unstretched film was sequentially biaxially stretched by the following method to form a particle-containing layer with a thickness of 40 nm on a polyethylene terephthalate film with a thickness of 16 μm.

(a) Longitudinal Stretching An unstretched film was passed between two pairs of nip rolls with different peripheral speeds and stretched in the longitudinal direction (conveyance direction). The conditions for longitudinal stretching are shown below.
・Preheating temperature: 75℃
・Stretching temperature: 90°C
・Stretching ratio: 3.4 times ・Stretching speed: 1,300%/sec

(b) Coating Using a bar coater, the particle-containing layer-forming composition 1 was coated on one side of the longitudinally stretched film so that the thickness after forming the film was 40 nm.

(c) Lateral Stretching The film coated with the particle-containing layer-forming composition 1 was laterally stretched using a tenter under the following conditions.
・Preheating temperature: 110℃
・Stretching temperature: 120°C
・Stretching ratio: 4.2 times ・Stretching speed: 50%/sec

[Heat setting and heat relaxation]
A biaxially stretched film that had undergone longitudinal stretching and transverse stretching was heat set under the following conditions.
・Heat setting temperature: 227°C
・Heat fixation time: 6 seconds

After heat setting, the width of the tenter was reduced and the biaxially stretched film was thermally relaxed under the following conditions.
・Thermal relaxation temperature: 190°C
・Thermal relaxation rate: 4%

〔Take-up〕
After heat setting and heat relaxation, both ends of the film were trimmed, the ends of the film were extruded (knurled) with a width of 10 mm, and the film was wound under a tension of 40 kg/m. The width of the film was 1.5 m and the roll length of the film was 6,300 m. The resulting film roll was used as a temporary support A.

Temporary support A has a polyethylene terephthalate film (substrate) and a particle-containing layer in this order.
The haze of the temporary support A was 0.2%. Haze was measured as total light haze using a haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.).
The thickness of the particle-containing layer measured from a cross-sectional TEM photograph of the temporary support A was 40 nm. The average particle diameter of the particles contained in the particle-containing layer measured by the method described above using a HT-7700 transmission electron microscope (TEM) manufactured by Hitachi High-Technologies Corporation was 50 nm.

<Preparation of temporary support B>
A temporary support B was obtained in the same manner as the temporary support A except that the thickness was adjusted to 25 μm by adjusting the melt flow rate and stretching conditions.

<Preparation of Photosensitive Compositions 1 to 4>
Each component shown in Table 1 and a mixed solvent of methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.) (60 parts) and propylene glycol monomethyl ether acetate (manufactured by Showa Denko Co., Ltd.) (40 parts) were subjected to exposure. A mixed solvent was added to obtain a mixed liquid so that the solid content concentration of the liquid composition was 13% by mass. Thereafter, the resulting mixed solution was filtered using a polytetrafluoroethylene filter having a pore size shown in Table 4, which will be described later, the number of times shown in Table 4, thereby preparing photosensitive compositions 1 to 4, respectively. .

Further, the details of the compounds listed in Table 1 are shown below.
BPE-500: 2,2-bis (4-(methacryloxypentaethoxy) phenyl) propane, manufactured by Shin-Nakamura Chemical Co., Ltd. M-270: polypropylene glycol diacrylate, manufactured by Toagosei Co., Ltd. A-TMPT: Tri Methylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. SR-454: Ethoxylated (3) trimethylolpropane triacrylate, manufactured by Sartomer A-9300-CL1: ε-caprolactone-modified tris(2-acryloxyethyl) isocyanate Nurate, manufactured by Shin-Nakamura Chemical Co., Ltd. B-CIM: photoradical generator (photopolymerization initiator), manufactured by Hampford, 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer SB-PI 701 : Sensitizer, 4,4'-bis(diethylamino)benzophenone, available from Sanyo Boeki Co., Ltd. CBT-1: Antirust agent, carboxybenzotriazole, Johoku Chemical Industry Co., Ltd. TDP-G: polymerization inhibitor, Phenothiazine, manufactured by Kawaguchi Chemical Industry Co., Ltd. Irganox245: Hindered phenol-based polymerization inhibitor, manufactured by BASF F-552: Fluorine-based surfactant, Megafac F552, manufactured by DIC Corporation

<Preparation of thermoplastic resin composition>
Each component shown in Table 2 was mixed to prepare a thermoplastic resin composition.

In addition, the unit of the numerical value of each component of Table 2 is a mass part.
The meanings of the abbreviations described in Table 2 are shown below.
A-2: benzyl methacrylate/methacrylic acid/acrylic acid copolymer (75% by mass/10% by mass/15% by mass, weight average molecular weight: 30,000, Tg: 75°C, acid value: 186 mgKOH/g)
・B-1: A compound having the structure shown below (a dye that develops color with an acid)

· C-1: A compound having the structure shown below (photoacid generator, compound described in paragraph 0227 of JP-A-2013-47765, synthesized according to the method described in paragraph 0227.)

・ D-3: NK Ester A-DCP (tricyclodecanedimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
・ D-4: 8UX-015A (polyfunctional urethane acrylate compound, Taisei Fine Chemical Co., Ltd.)
・ D-5: Aronix TO-2349 (polyfunctional acrylate compound having a carboxy group, manufactured by Toagosei Co., Ltd.)
・ E-1: Megaface F552 (manufactured by DIC Corporation)
・ F-1: Phenothiazine (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
・ F-2: CBT-1 (manufactured by Johoku Chemical Industry Co., Ltd.)
・MEK: Methyl ethyl ketone ・PGME: Propylene glycol monomethyl ether ・PGMEA: Propylene glycol monomethyl ether acetate

<Preparation of water-soluble resin composition>
A water-soluble resin composition was prepared by mixing the following components. In addition, the unit of the quantity of each component is a mass part.
Ion-exchanged water: 38.12 parts Methanol (manufactured by Mitsubishi Gas Chemical Co., Ltd.): 57.17 parts Kuraray Poval 4-88LA (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts Polyvinylpyrrolidone K-30 (Japan Catalyst Co., Ltd.): 1.49 parts Megafac F-444 (fluorosurfactant, manufactured by DIC Corporation): 0.0035 parts

(Examples 1 to 5)
A thermoplastic resin composition was applied onto the base material (polyethylene terephthalate film) of the temporary support using a slit nozzle. The applied thermoplastic resin composition was dried at 100° C. for 120 seconds to form a thermoplastic resin layer having the thickness shown in Table 3.

A water-soluble resin composition was applied onto the thermoplastic resin layer using a slit nozzle. The applied water-soluble resin composition was dried at 120° C. for 120 seconds to form a water-soluble resin layer having the thickness shown in Table 3.

The photosensitive composition shown in Table 3 was applied onto the water-soluble resin layer using a slit nozzle. The coated photosensitive composition was dried at 100° C. for 120 seconds to form a photosensitive layer having a thickness shown in Table 3 (layer structure: coating layer 1 shown in Table 3), and photosensitive transfer. got the material.

The photosensitive transfer material obtained by the above procedure includes a temporary support, a thermoplastic resin layer, a water-soluble resin layer, and a photosensitive layer in this order. Table 3 shows the layer structures (coating layers 1 to 5) of the thermoplastic resin layer, the water-soluble resin layer and the photosensitive layer.

(Examples 6 to 18 and Comparative Example 1)
A photosensitive transfer material was obtained in the same manner as in Example 1, except that the contents were appropriately changed according to the descriptions in Tables 3 and 4.

<Resolution>
(1) A PET substrate with a copper layer was produced by forming a copper layer with a thickness of 200 nm on a polyethylene terephthalate (PET) film with a thickness of 100 μm by sputtering. By a roll-to-roll method using a vacuum laminator (manufactured by MCK Co., Ltd., roll temperature: 100 ° C., linear pressure: 1.0 MPa, linear speed: 0.5 m / min), the photosensitive transfer material and the PET substrate with a copper layer were laminated to obtain a laminate. The obtained laminate includes at least a PET film, a copper layer, a photosensitive layer, and a temporary support in this order.
(2) The obtained laminate was pressurized and defoamed under conditions of 0.6 MPa and 60° C. for 30 minutes using an autoclave. After that, using a cleaning roll (manufactured by Osada Corporation, DCH-12H2LS), the surface of the temporary support was manually rubbed 10 times to remove foreign matters on the temporary support.
(3) Using an ultra-high pressure mercury lamp, a line and space pattern mask without peeling off the temporary support (the duty ratio is 1: 1, the line width is changed step by step from 1 μm to 20 μm every 1 μm .) to expose the photosensitive layer.
(4) After peeling off the temporary support, development was carried out. Development was performed by shower development for 30 seconds using a 1.0% by mass sodium carbonate aqueous solution at 25°C.
A resin pattern was formed by developing the photosensitive layer.
While adjusting the exposure amount (unit: mJ/cm ² ) each time, the above-described series of Procedures (1) to (4) were performed. The minimum line width of the reference pattern was taken as the limiting resolution X μm of the photosensitive layer.
Table 4 shows the measurement results.

<Total number of foreign substances and voids on the surface and inside of the photosensitive layer>
(1) Use a vacuum laminator (manufactured by MCK Co., Ltd., roll temperature: 100 ° C., linear pressure: 1.0 MPa, linear speed: 0.5 m / min) on a polyethylene terephthalate (PET) film with a thickness of 100 μm. The photosensitive transfer material and the PET substrate were bonded together by a roll-to-roll method. The obtained laminate includes at least a PET film, a photosensitive layer, and a temporary support in this order.
(2) The obtained laminate was pressurized and defoamed under conditions of 0.6 MPa and 60° C. for 30 minutes using an autoclave.
Ten arbitrary regions (size of each region: 10 mm×10 mm, total area: 1,000 mm ² ) on the surface after peeling the temporary support were visually observed using an optical microscope. The number of foreign particles and voids with a diameter of Y μm or more included in each region was measured. Based on the total number of foreign matter and voids of Y μm or more measured in 10 regions, the number of foreign matter and voids of Y μm or more per 1 cm ² of the measurement region (pieces/cm ² ) was calculated. Table 4 shows the measurement results.

<Pinhole in wiring pattern>
Wiring formation mask (Duty ratio is 1:1, line width is changed step by step from 1 μm to 20 μm every 1 μm. The length of the wiring pattern is 50 mm. The number of wiring is 10. ), except that the wiring pattern ( That is, a resin pattern) was formed. The wiring pattern was visually observed using an optical microscope, and the pinholes in the wiring pattern were evaluated according to the following criteria based on the maximum size and number of pinholes. Table 4 shows the evaluation results.
A: No pinhole was observed, or a pinhole having a size of 1/4 or less of the wiring width was confirmed.
B: A pinhole having a size exceeding 1/4 and not more than 1/2 of the wiring width was confirmed.
C: A pinhole having a size exceeding 1/2 and 3/4 or less of the wiring width was confirmed.
D: A pinhole having a size exceeding 3/4 of the wiring width was confirmed.

<Defective Wiring Pattern>
With respect to the sample used for the pinhole evaluation of the wiring pattern, the state of pattern defects (so-called bite) was visually observed using an optical microscope, and evaluated according to the following criteria.
A: No pattern defects were observed, or pattern defects with a maximum diameter of less than 1 μm were confirmed.
B: Pattern defects with a maximum diameter of 1 μm or more and 2 μm or less were confirmed.
C: Pattern defects with a maximum diameter exceeding 2 μm were confirmed.

<Linearity of Wiring Pattern>
A 10 μm pattern of the pattern for which resolution was evaluated was observed with a scanning electron microscope (SEM), and the maximum value − minimum value of the line width (also referred to as “variation value of line width”) within a length range of 100 μm. ) was evaluated, and the linearity of the resin pattern was evaluated according to the following criteria.
A: Line width fluctuation value is less than 0.4 μm.
B: Line width fluctuation value is 0.4 μm or more and less than 0.7 μm.
C: Line width fluctuation value is 0.7 μm or more and less than 1.0 μm.
D: Line width fluctuation value is 1.0 μm or more and less than 1.5 μm.
E: Line width fluctuation value is 1.5 μm or more.

In the laminates obtained in Examples 1 to 18, the number of voids having a diameter of Y μm or more was 0/cm ² . It is presumed that the pressure defoaming treatment using an autoclave suppressed the generation of voids.

As shown in Table 4 above, the photosensitive transfer materials and the laminate manufacturing methods of Examples 1 to 18 had fewer pinhole defects than the photosensitive transfer materials and laminate manufacturing methods of Comparative Example 1. was obtained, and a resin pattern with few pinhole defects corresponding to the wiring pattern was obtained.

(Example 101: Contact exposure)
The photosensitive transfer material prepared in Example 1 was laminated on the PET substrate with the copper layer under lamination conditions of a roll temperature of 100° C., a linear pressure of 1.0 MPa, and a linear velocity of 4.0 m/min. The temporary support was peeled off, and after exposure with an ultra-high pressure mercury lamp through a line-and-space pattern mask (Duty ratio 1:1, line width changed stepwise from 1 μm to 10 μm at intervals of 1 μm), the film was developed.
Development was carried out by shower development using a 1.0% sodium carbonate aqueous solution at 25° C. for 30 seconds.
When the obtained patterned substrate was observed with a microscope, the pattern had good resolution and pattern shape.

(Example 102: Laser direct drawing)
The photosensitive transfer material prepared in Example 1 was laminated on the PET substrate with the copper layer under lamination conditions of a roll temperature of 100° C., a linear pressure of 1.0 MPa, and a linear velocity of 4.0 m/min. Direct writing exposure machine (DE-1DH, manufactured by Hitachi Via Mechanics Co., Ltd., light source: GaN blue-violet diode (dominant wavelength 405 nm ± 5 nm)) using a Stofer 21-step step tablet or a predetermined mask pattern for DI exposure. , and an illuminance of 80 mW/cm ² . This exposure was carried out with an exposure amount such that the maximum number of remaining film steps was 6 when exposure and development were performed using the Stouffer 21 step tablet as a mask. Development was carried out by shower development using a 1.0% sodium carbonate aqueous solution at 25° C. for 30 seconds.
When the obtained patterned substrate was observed with a microscope, the pattern had good resolution and pattern shape.

(Example 103)
On a 100 μm-thick PET substrate, a second conductive layer of ITO was formed by sputtering to a thickness of 150 nm, and a first conductive layer of copper was formed thereon by a vacuum deposition method to a thickness of 200 nm. and used as a substrate for forming a circuit.
The photosensitive transfer material obtained in Example 1 was laminated on the copper layer after peeling off the cover film (laminating roll temperature: 100° C., linear pressure: 0.8 MPa, linear velocity: 3.0 m/min.). ) to form a laminate. The resulting laminate was subjected to contact pattern exposure using a photomask having a pattern A shown in FIG. A high-pressure mercury lamp with i-line (365 nm) as the main exposure wavelength was used for exposure.
Then, the pattern A was obtained by developing and washing with water. Then, after etching the copper layer using a copper etching solution (manufactured by Kanto Chemical Co., Ltd. Cu-02), by etching the ITO layer using an ITO etching solution (manufactured by Kanto Chemical Co., Ltd. ITO-02), A substrate on which pattern A was drawn for both copper and ITO was obtained.
Next, the photosensitive transfer material obtained in Example 1 was laminated on the remaining resist (cured negative photosensitive layer) under the same conditions as in Example 101 after peeling off the cover film. rice field. In the aligned state, the temporary support was peeled off, pattern exposure was performed using a photomask having a pattern B shown in FIG. Then, the copper wiring was etched using Cu-02, and the remaining cured negative photosensitive layer was peeled off using a peeling solution (KP-301 manufactured by Kanto Kagaku Co., Ltd.) to obtain a circuit wiring board.
Observation of the resulting circuit wiring board with a microscope revealed that there was no peeling or chipping, and the pattern was clean.

The disclosure of Japanese Patent Application No. 2021-011932 filed on January 28, 2021 is incorporated herein by reference in its entirety.
All publications, patent applications and technical standards mentioned herein are to the same extent as if each individual publication, patent application or technical standard were specifically and individually noted to be incorporated by reference. , incorporated herein by reference.

11: temporary support, 12: transfer layer, 13: thermoplastic resin layer, 15: water-soluble resin layer, 17: photosensitive layer, 19: protective film, 20: photosensitive transfer material, GR: light shielding portion (non-image part), EX: exposure part (image part), DL: frame for alignment

Claims

A bonding step of bonding the photosensitive transfer material and the substrate so that the transfer layer side of the photosensitive transfer material having the temporary support and the transfer layer containing the photosensitive layer is in contact with the substrate;
An exposure step of exposing the photosensitive layer, and
including a developing step of developing the photosensitive layer to form a resin pattern;
When the critical resolution of the photosensitive layer in the exposure step is defined as X μm, and the reference diameter of the particles and voids is defined as Y μm represented by Y=0.5×X, the surface of the photosensitive layer in the exposure step and A method for producing a laminate, wherein the number of particles having a diameter of Y μm or more and voids therein is 15/cm 2 or less.
The method for producing a laminate according to claim 1, wherein the thickness of the photosensitive layer is 5.0 µm or less.
The method for producing a laminate according to claim 1 or claim 2, wherein the temporary support has a thickness of 16 µm or less.
The method for producing a laminate according to any one of claims 1 to 3, wherein the resin pattern has a line width of 10 µm or less.
The method for producing a laminate according to any one of claims 1 to 4, comprising a peeling step of peeling off the temporary support between the bonding step and the exposure step.
The method for manufacturing a laminate according to any one of claims 1 to 5, wherein in the exposure step, the transfer layer and the mask are brought into contact with each other for exposure processing.
The method for producing a laminate according to any one of claims 1 to 6, wherein the transfer layer further includes a thermoplastic resin layer and a water-soluble resin layer.
The method for producing a laminate according to any one of claims 1 to 7, wherein the photosensitive layer contains a polyfunctional polymerizable compound.
The method for producing a laminate according to any one of claims 1 to 8, wherein the photosensitive layer contains a trifunctional or higher polymerizable compound.
The method for producing a laminate according to any one of claims 1 to 9, wherein the photosensitive layer contains a polymerizable compound having a polyethylene oxide structure.
A preparation step of preparing a laminate obtained by the method for producing a laminate according to any one of claims 1 to 10, and
A method of manufacturing a circuit wiring, comprising, in this order, an etching step of etching the substrate in a region where the resin pattern is not arranged.
A preparation step of preparing a laminate obtained by the method for producing a laminate according to any one of claims 1 to 10, and
A method of manufacturing an electronic device, comprising, in this order, an etching step of etching the substrate in a region where the resin pattern is not arranged.
Having a temporary support and a transfer layer containing a photosensitive layer,
If the limiting resolution of the photosensitive layer is defined as X T μm and the reference diameter of the particles is defined as Y T μm expressed by Y T =0.5×X T , then A photosensitive transfer material, wherein the number of particles having a diameter of Y T μm or more is 15/cm 2 or less.
The photosensitive transfer material according to claim 13, wherein the photosensitive layer has a thickness of 5.0 µm or less.
The photosensitive transfer material according to claim 13 or 14, wherein the temporary support has a thickness of 16 µm or less.