JP7743301B2 - Photosensitive transfer material for manufacturing deposition masks and method for manufacturing deposition masks - Google Patents

Description

This disclosure relates to a photosensitive transfer material for manufacturing deposition masks and a method for manufacturing deposition masks.

Vapor deposition methods using vapor deposition masks are used, for example, in the manufacture of OLEDs (organic light-emitting diodes). Vapor deposition masks are used as masters for the patterns formed by vapor deposition. Vapor deposition is a well-known example of a vapor deposition method. For example, in vacuum vapor deposition methods using a vapor deposition mask with through-holes, a substance vaporized from a vaporization source adheres to the target through the through-holes in the vapor deposition mask placed above the target, forming a pattern.

Patent Document 1 describes a method for forming a metal pattern, which includes the steps of preparing a laminate having a positive photosensitive resin layer formed from a photosensitive transfer material on a substrate, exposing and developing the positive photosensitive resin layer to form a tapered resin pattern, and forming a tapered metal pattern corresponding to the shape of the resin pattern, wherein the transmittance of the positive photosensitive resin layer at the exposure wavelength during the exposure is 50% or less.

Japanese Patent Application Laid-Open No. 2021-172879

Improving the resolution of patterns formed using deposition masks (e.g., minimizing the size of the patterns) can contribute to improving pixel density in display devices, including OLEDs, for example.

An object of one embodiment of the present disclosure is to provide a photosensitive transfer material for producing a deposition mask that has excellent resolution.
Another embodiment of the present disclosure has an object to provide a method for manufacturing a deposition mask with excellent resolution.

The present disclosure includes the following aspects.
<1> A photosensitive transfer material for producing a deposition mask, comprising a temporary support and a transfer layer having at least a photosensitive resin layer, in this order, wherein the number of foreign particles having a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50 particles/mm3 or ^less .
<2> The photosensitive transfer material for producing a deposition mask according to <1>, wherein the L ^* value of the surface of the temporary support opposite to the transfer layer side measured by an SCE method is 1.5 or less.
<3> The photosensitive transfer material for producing a deposition mask according to <1> or <2>, wherein the temporary support has a thickness of 16 μm or less.
<4> The photosensitive transfer material for producing a deposition mask according to any one of <1> to <3>, wherein the transfer layer has a melt viscosity at 25° C. of 1.0×10 ⁵ Pa·s to 1.0×10 ⁸ Pa·s.
<5> The photosensitive transfer material for producing a deposition mask according to any one of <1> to <4>, wherein the photosensitive resin layer has a thickness of 4.8 μm or less.
<6> The photosensitive transfer material for producing a deposition mask according to any one of <1> to <5>, wherein the transfer layer has, from the temporary support side, an intermediate layer and the photosensitive resin layer in this order.
<7> The photosensitive transfer material for producing a deposition mask according to <5>, wherein the intermediate layer contains a water-soluble resin.
<8> The photosensitive transfer material for producing a deposition mask according to <7>, wherein the water-soluble resin contains polyvinyl alcohol.
<9> The photosensitive transfer material for producing a deposition mask according to <7> or <8>, wherein the water-soluble resin contains polyvinylpyrrolidone.
<10> The photosensitive transfer material for producing a deposition mask according to any one of <7> to <9>, wherein the water-soluble resin contains a hydroxyalkyl cellulose compound.
<11> A method for manufacturing a vapor deposition mask, the method including, in this order: preparing a metal layer having a first surface and a second surface opposite to the first surface; bonding a photosensitive transfer material including, in this order, a temporary support and a transfer layer having at least a photosensitive resin layer, wherein the number of foreign matter particles having a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50 particles/ ^mm3 or less, to the metal layer; disposing the transfer layer and the temporary support, in this order, on the first surface of the metal layer; pattern-exposing the transfer layer; developing the transfer layer to form a resist pattern; etching the metal layer not covered by the resist pattern to form through-holes extending from the first surface of the metal layer to the second surface of the metal layer; and removing the resist pattern.
<12> The method for manufacturing a deposition mask according to <11>, wherein the first surface of the metal layer has a roughness Rmax of 0.5 μm to 5.0 μm.

According to one embodiment of the present disclosure, a photosensitive transfer material for producing a deposition mask having excellent resolution is provided.
According to another embodiment of the present disclosure, there is provided a method for manufacturing a deposition mask with excellent resolution.

FIG. 1 is a schematic plan view showing one embodiment of a deposition mask manufactured by the deposition mask manufacturing method according to the present disclosure. FIG. 2 is a schematic plan view showing an enlarged view of the through-holes of the deposition mask shown in FIG. FIG. 3 is a schematic cross-sectional view showing an enlarged view of a through-hole of the deposition mask shown in FIG. FIG. 4 is a schematic cross-sectional view illustrating a method for manufacturing a deposition mask according to an embodiment.

Embodiments of the present disclosure are described in detail below. The present disclosure is in no way limited to the following embodiments. The following embodiments may be modified as appropriate within the scope of the purpose of the present disclosure.

When describing embodiments of the present disclosure with reference to the drawings, explanations of overlapping components and reference numerals may be omitted. Components indicated with the same reference numerals in the drawings are the same components. Dimensional ratios in the drawings do not necessarily represent actual dimensional ratios.

In this disclosure, numerical ranges indicated using "to" indicate a range that includes the numerical value before "to" as the lower limit and the numerical value before "to" as the upper limit. In numerical ranges described in stages in this disclosure, the upper or lower limit stated in a certain numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described in this disclosure, the upper or lower limit stated in a certain numerical range may be replaced with a value shown in the examples.

In this disclosure, "(meth)acrylic" refers to acrylic, methacrylic, or both acrylic and methacrylic.

In this disclosure, "(meth)acrylate" refers to acrylate, methacrylate, or both acrylate and methacrylate.

In this disclosure, "(meth)acryloyl" refers to acryloyl, methacryloyl, or both acryloyl and methacryloyl.

In this disclosure, when multiple substances corresponding to each component are present in the composition, the amount of each component in the composition refers to the total amount of the multiple corresponding substances present in the composition, unless otherwise specified.

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

In this disclosure, groups (atomic groups) that are not specified as substituted or unsubstituted include groups (atomic groups) that have no substituents and groups (atomic groups) that have a substituent. For example, the term "alkyl group" includes not only alkyl groups that have no substituents (i.e., unsubstituted alkyl groups) but also alkyl groups that have a substituent (i.e., substituted alkyl groups).

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

Chemical structural formulas in this disclosure may be written as simplified structural formulas in which hydrogen atoms are omitted.

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

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

In this disclosure, "transparent" means that the average transmittance of visible light with wavelengths of 400 nm to 700 nm is 80% or more, and preferably 90% or more.

In this disclosure, the average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, the Hitachi, Ltd. U-3310 spectrophotometer.

Unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this disclosure are molecular weights measured using a gel permeation chromatography (GPC) analyzer equipped with columns TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (all product names manufactured by Tosoh Corporation) in THF (tetrahydrofuran) as the solvent, detected with a differential refractometer, and converted using polystyrene as the standard.

Unless otherwise specified, in this disclosure, the content of metal elements is a value measured using an inductively coupled plasma (ICP) spectroscopic analyzer.

Unless otherwise specified, in this disclosure, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.

Unless otherwise specified, in this disclosure, hue is a value measured using a color difference meter (CR-221, manufactured by Minolta Co., Ltd.).

In this disclosure, "alkali-soluble" means that the solubility in 100 g of a 1% by mass aqueous solution of sodium carbonate at a liquid temperature of 22°C is 0.1 g or more.

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

In this disclosure, "solids" means all components excluding solvent.

<Photosensitive transfer material for manufacturing deposition masks>
The photosensitive transfer material for producing a vapor deposition mask according to the present disclosure (hereinafter also simply referred to as "the photosensitive transfer material according to the present disclosure" or "photosensitive transfer material") has a temporary support and a transfer layer having at least a photosensitive resin layer, in this order, and the number of foreign particles having a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50 particles/ ^mm3 or less.

In the photosensitive transfer material for producing deposition masks according to the present disclosure, the number of foreign matter particles having a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50 particles/ ^mm3 or less, thereby making it possible to suppress exposure problems caused by the foreign matter blocking exposure light, and to form patterns with reduced defects even when the pattern has a small width or size, such as a thin line, and thus to provide a photosensitive transfer material for producing deposition masks with excellent resolution.

The photosensitive transfer material according to the present disclosure has a temporary support and a transfer layer having at least a photosensitive resin layer, and preferably has a temporary support, a transfer layer including at least a photosensitive resin layer, and a protective film in this order.
The photosensitive transfer material according to the present disclosure may also have other layers between the temporary support and the photosensitive resin layer, between the photosensitive resin layer and the protective film, or the like.
Furthermore, the photosensitive transfer material according to the present disclosure preferably has an intermediate layer and the photosensitive resin layer in this order from the temporary support side.
The photosensitive transfer material according to the present disclosure is preferably a roll-shaped photosensitive transfer material from the viewpoint of further exerting the effects of the present disclosure.

In the photosensitive transfer material for producing a vapor deposition mask according to the present disclosure, the number of foreign particles having a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50 particles/ ^mm3 or less, and from the viewpoints of resolution and linearity of the obtained pattern, the number is preferably 10 particles/mm3 or ^less , more preferably 5 particles/ ^mm3 or less, even more preferably 2 particles/ ^mm3 or less, and particularly preferably 1 particle/ ^mm3 or less.
The term "foreign matter" in the present disclosure refers to anything that can block exposure light, and includes particles such as dirt and dust present on the surface and inside of the temporary support, as well as aggregates and coarse powder of components contained in the temporary support.
Furthermore, the foreign matter may be other than spherical, and examples thereof include irregular particles, particle aggregates, etc., and the "diameter of the foreign matter" in this disclosure refers to the absolute maximum length of the foreign matter observed from the thickness direction of the temporary support using the measurement method described below.

In the present disclosure, the method for measuring the number of foreign particles having a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is as follows.
The temporary support is observed in an area of 1 ^cm2 from the thickness direction by transmission observation with an optical microscope, the number of foreign matter particles having a diameter of 1.0 μm to 10.0 μm is counted, and the obtained number is divided by the thickness of the temporary support to obtain the number of foreign matter particles per unit volume of the temporary support.

The L ^* value of the surface of the temporary support opposite to the transfer layer side, measured by the SCE (Specular Component Exclude: excluding specular reflected light) method, is preferably 2.0 or less, more preferably 1.5 or less, even more preferably 1.2 or less, and particularly preferably 0.9 or less, from the viewpoints of resolution and linearity of the obtained pattern.

In the present disclosure, the L ^* value of the surface to be measured (for example, the surface of the temporary support opposite to the transfer layer side) is measured by the following method.
The temporary support is peeled off from the photosensitive transfer material. Using a spectrophotometer (CM-700d, manufactured by Konica Minolta, Inc.), the L ^* value is measured at a total of 10 locations at 3 cm intervals along the width direction of the measurement surface. A D65 light source is used as the light source for the spectrophotometer. The L ^* values of the 10 locations measured by the SCE method are arithmetically averaged, and the obtained value is used as the L ^* value of the measurement surface by the SCE method.

In the photosensitive transfer material according to the present disclosure, from the viewpoints of adhesion and resolution, the melt viscosity of the transfer layer at 25°C is preferably 5.0×10 ⁴ Pa·s to 5.0×10 ⁸ Pa·s, more preferably 1.0×10 ⁵ Pa·s to 1.0×10 ⁸ Pa·s, and particularly preferably 5.0×10 ⁵ Pa·s to 1.0×10 ⁷ Pa·s.
In the present disclosure, the "melt viscosity of the transfer layer" is defined by the melt viscosity of the layer farthest from the temporary support among the one or more layers constituting the transfer layer. For example, when the transfer layer has a multi-layer structure, the melt viscosity of the layer farthest from the temporary support among the multiple layers included in the transfer layer is referred to as the "melt viscosity of the transfer layer." When the transfer layer has a single-layer structure, the melt viscosity of a single transfer layer is referred to as the "melt viscosity of the transfer layer." The melt viscosity of the transfer layer is adjusted, for example, by the composition of the transfer layer. The melt viscosity of the transfer layer is adjusted, for example, by the type of polymer, the type of polymerizable compound, the ratio of the content of the polymerizable compound to the content of the polymer, and the type of additive. For example, as the ratio of the content of the polymerizable compound to the content of the polymer increases, the melt viscosity decreases, and as the ratio of the content of the polymerizable compound to the content of the polymer decreases, the melt viscosity increases.

In the present disclosure, the melt viscosity is measured using a rheometer (for example, a DHR-2 rheometer manufactured by TA Instruments Co., Ltd.), a 20 mmφ parallel plate, and a Peltier plate (Gap: approximately 0.5 mm) under the following conditions. The melt viscosity specified in the present disclosure is the melt viscosity at 25°C.
(1) Temperature: 20℃~125℃
(2) Temperature increase rate: 5°C/min (3) Frequency: 1 Hz
(4) Distortion: 0.5%

An example of an embodiment of the photosensitive transfer material according to the present disclosure is shown below, but the present disclosure is not limited thereto.
(1) "Temporary support/photosensitive resin layer/refractive index adjusting layer/protective film"
(2) "Temporary support/photosensitive resin layer/protective film"
(3) "Temporary support/intermediate layer/photosensitive resin layer/protective film"
(4) "Temporary support/cushion layer/intermediate layer/photosensitive resin layer/protective film"
In each of the above configurations, the photosensitive resin layer may be a positive-type photosensitive resin layer or a negative-type photosensitive resin layer, and is preferably a negative-type photosensitive resin layer. It is also preferable that the photosensitive resin layer is a colored resin layer.
Among these, the photosensitive transfer material preferably has the configurations (2) to (4) described above, more preferably the configuration (3) or (4) described above, and particularly preferably the configuration (4) described above.

When the photosensitive transfer material further comprises other layers on the side of the photosensitive resin layer opposite the temporary support side, the total thickness of the other layers arranged on the side of the photosensitive resin layer opposite the temporary support side is preferably 0.1% to 30%, and more preferably 0.1% to 20%, of the thickness of the photosensitive resin layer.

Below, we will explain the photosensitive transfer material according to this disclosure by giving an example of a specific embodiment.

The following describes each element that makes up the photosensitive transfer material.

[Temporary support]
The photosensitive transfer material according to the present disclosure has a temporary support.
The temporary support is a support that supports the laminate including the transfer layer and is peelable.

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

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

The thickness (layer thickness) of the temporary support is not particularly limited, and may be selected according to the material from the viewpoints of the strength as a support, the flexibility required for bonding to the circuit wiring formation substrate, and the light transmittance required in the initial exposure step.
The thickness of the temporary support is preferably in the range of 5 μm to 100 μm, and from the viewpoint of ease of handling and versatility, more preferably in the range of 10 μm to 50 μm, still more preferably in the range of 10 μm to 20 μm, and particularly preferably in the range of 10 μm to 16 μm.
Furthermore, from the viewpoint of defect suppression, resolution, and linearity of the resist pattern, the thickness of the temporary support is preferably 50 μm or less, more preferably 25 μm or less, even more preferably 20 μm or less, and particularly preferably 16 μm or less.

Furthermore, it is preferable that the film used as the temporary support is free from deformations such as wrinkles, scratches, defects, and the like.
From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the temporary support contains as few fine particles, foreign matter, defects, precipitates, etc. The number of fine particles, foreign matter, and defects having a diameter of 1 μm or more is preferably 50/10 ^mm2 or less, more preferably 10/10 ^mm2 or less, even more preferably 3/10 ^mm2 or less, and particularly preferably 0/10 ^mm2 .

From the viewpoints of defect suppression and resolution of the resist pattern and transparency of the temporary support, it is preferable that the haze of the temporary support is small. Specifically, the haze value of the temporary support is preferably 2% or less, more preferably 1.5% or less, even more preferably less than 1.0%, and particularly preferably 0.5% or less.
The haze value in the present disclosure is measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.) according to a method in accordance with JIS K 7105:1981.

To improve handleability, a layer containing fine particles (lubricant layer) may be provided on the surface of the temporary support. The lubricant layer may be provided on one or both sides of the temporary support. The diameter of the particles contained in the lubricant layer may be, for example, 0.05 μm to 0.8 μm. The thickness of the lubricant layer may be, for example, 0.05 μm to 1.0 μm.

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

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

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

The peel strength of the temporary support in the present disclosure is measured as follows.
A copper layer having a thickness of 200 nm is formed on a polyethylene terephthalate (PET) film having a thickness of 100 μm by sputtering 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 onto the copper-layered PET substrate under lamination conditions of a laminating roll temperature of 100°C, a linear pressure of 0.6 MPa, and a linear speed (lamination speed) of 1.0 m/min. Next, tape (PRINTACK manufactured by Nitto Denko Corporation) is attached to the surface of the temporary support, and the laminate having at least the temporary support and the photosensitive resin layer on the copper-layered PET substrate is cut into a 70 mm x 10 mm sample. The PET substrate side of the sample is fixed onto a sample stage.
Using a tension and compression testing machine (SV-55, manufactured by Imada Seisakusho Co., Ltd.), the tape is pulled in a 180-degree direction at 5.5 mm/sec to peel between the photosensitive resin layer or cushion layer and the temporary support, and the force required for peeling (peeling force) or adhesion force is measured.

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

[Photosensitive resin layer]
The photosensitive transfer material according to the present disclosure has a photosensitive resin layer.
The photosensitive resin layer may be a positive photosensitive resin layer or a negative photosensitive resin layer, and is preferably a negative photosensitive resin layer.
The negative photosensitive resin layer preferably contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator, and more preferably contains, based on the total mass of the photosensitive resin layer, 10% by mass to 90% by mass of the alkali-soluble resin; 5% by mass to 70% by mass of the ethylenically unsaturated compound; and 0.01% by mass to 20% by mass of the photopolymerization initiator.
The positive photosensitive resin layer is not limited, and any known positive photosensitive resin layer can be used. The positive photosensitive resin layer preferably contains an acid-decomposable resin, i.e., a polymer having a structural unit having an acid group protected by an acid-decomposable group, and a photoacid generator. The positive photosensitive resin layer preferably contains a resin having a structural unit having a phenolic hydroxyl group, and a quinone diazide compound.
The positive photosensitive resin layer is more preferably a chemically amplified positive photosensitive resin layer containing a polymer having a structural unit having an acid group protected by an acid-decomposable group, and a photoacid generator.

Each component will be explained below in order. Note that when simply referring to a "photosensitive resin layer," this refers to both a positive-type photosensitive resin layer and a negative-type photosensitive resin layer.

<<Polymerizable compound>>
The negative photosensitive resin layer preferably contains a polymerizable compound. In this specification, the term "polymerizable compound" refers to a compound that undergoes polymerization under the action of a photopolymerization initiator, which will be described later, and is different from the alkali-soluble resin described above.

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

From the viewpoint of resolution and pattern formability, the photosensitive resin layer preferably contains a difunctional or higher functional polymerizable compound (a polyfunctional polymerizable compound), and more preferably contains a trifunctional or higher functional polymerizable compound.
Here, the bifunctional or higher functional polymerizable compound means a compound having two or more polymerizable groups in one molecule.
In terms of excellent resolution and releasability, the number of polymerizable groups that the polymerizable compound has in one molecule is preferably 6 or less.

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

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

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

In the negative-type photosensitive resin layer, the mass ratio of the content of ethylenically unsaturated compound B1 to the content of all ethylenically unsaturated compounds is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and particularly preferably 60% by mass or more, in order to achieve better resolution. There is no particular upper limit, but in order to improve releasability, it is preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less.

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

The ethylenically unsaturated compound B1 preferably has a bisphenol structure, since this suppresses swelling of the negative photosensitive resin layer due to a developer, thereby improving resolution.
Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), a bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and a bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

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

As the ethylenically unsaturated compound B1, a bifunctional ethylenically unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is more preferred.
Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 2,2-bis(4-(methacryloxydodecaethoxy)phenyl)propane. Examples of such bisphenol A diacrylates include 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)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.).

The ethylenically unsaturated compound B1 can be a compound represented by the following formula (Bis):

In formula (Bis), _R1 and _R2 each independently represent a hydrogen atom or a methyl group, _{A is C2H4 ,} B is _C3H6 , _n1 and _n3 each independently represent an integer from 1 to ₃₉ , and _n1 + _n3 is an integer from 2 to 40, _n2 and _n4 each independently represent an integer from 0 to 29, and _n2 + _n4 is an integer from 0 to 30, and the arrangement of the -(A-O)- and -(B-O)- repeating units may be random or block. In the case of a block arrangement, either -(A-O)- or -(B-O)- may be on the bisphenol structure side.
In one embodiment, n ₁ +n ₂ +n ₃ +n ₄ is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 12. Furthermore, n ₂ +n ₄ is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 2, and particularly preferably 0.

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

The negative photosensitive resin layer may contain an ethylenically unsaturated compound other than the above-mentioned ethylenically unsaturated compound B1.
The ethylenically unsaturated compound other than the ethylenically unsaturated compound B1 is not particularly limited and can be appropriately selected from known compounds, for example, a compound having one ethylenically unsaturated group in one molecule (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.
Examples of alkylene glycol di(meth)acrylates include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di(meth)acrylate.
Examples of polyalkylene glycol di(meth)acrylates include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.
Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylates and ethylene oxide and propylene oxide-modified urethane di(meth)acrylates. Commercially available products include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.).

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

Examples of alkylene oxide-modified trifunctional or higher ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., 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 (registered trademark) manufactured by Daicel-Allnex Corporation), etc. 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.).

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

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

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

The ethylenically unsaturated compounds may be used alone or in combination of two or more.
The content of the ethylenically unsaturated compound in the negative photosensitive resin layer is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and even more preferably 20% by mass to 50% by mass, relative to the total mass of the negative photosensitive resin layer.

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

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

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

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

Commercially available photoradical polymerization initiators include, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE® OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by 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, manufactured by IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, manufactured by IGM Resins B.V.), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, manufactured by IGM Resins B.V.), B.V.), 1-hydroxycyclohexyl phenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, manufactured by IGM Resins B.V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins B.V.), oxime ester-based photopolymerization initiator (trade name: Lunar 6, manufactured by DKSH Japan Co., Ltd.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, manufactured by Hampford Chemical Industry Co., Ltd.), 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 when exposed to actinic rays. The photocationic polymerization initiator is preferably a compound that responds to actinic rays with a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but the chemical structure is not limited thereto. Furthermore, even if a photocationic polymerization initiator is not directly sensitive to actinic rays with a wavelength of 300 nm or more, it can be preferably used in combination with a sensitizer, as long as it responds to actinic rays with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer.
As the cationic photopolymerization initiator, a cationic photopolymerization initiator that generates an acid having a pKa of 4 or less is preferred, a cationic photopolymerization initiator that generates an acid having a pKa of 3 or less is more preferred, and a cationic photopolymerization initiator that generates an acid having a pKa of 2 or less is particularly preferred. Although the lower limit of the pKa is not particularly limited, it is preferably −10.0 or more, for example.

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

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

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

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

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

The acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of sample.
In this specification, the unit is expressed 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 by changing the type of structural unit constituting the polymer A and the content of the structural unit containing an acid group.

The weight-average molecular weight of polymer A is preferably 5,000 to 500,000. A weight-average molecular weight of 500,000 or less is preferred from the perspective of improving resolution and developability. A weight-average molecular weight of 100,000 or less is more preferred, 60,000 or less is even more preferred, and 50,000 or less is particularly preferred. On the other hand, a weight-average molecular weight of 5,000 or more is preferred from the perspective of controlling the properties of the development aggregates and the properties of the unexposed film, such as edge fusing and cut-chip resistance. A weight-average molecular weight of 10,000 or more is more preferred, 20,000 or more is even more preferred, and 30,000 or more is particularly preferred. Edge fusing refers to the degree to which the photosensitive resin layer protrudes from the edge of a roll when the photosensitive transfer material is wound into a roll. Cut-chip resistance refers to the degree to which chips fly off when the unexposed film is cut with a cutter. If these chips adhere to the upper surface of the photosensitive resin layer, they will be transferred to a mask during a subsequent exposure process, 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 even more preferably 1.0 to 3.0. In this disclosure, molecular weight is a value measured using gel permeation chromatography. Furthermore, dispersity is the ratio of weight average molecular weight to number average molecular weight (weight average molecular weight/number average molecular weight).

In order to prevent line width thickening and resolution degradation caused by shifts in the focal position during exposure, the negative-type photosensitive resin layer preferably contains, as polymer A, a monomer component having an aromatic hydrocarbon group. 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 polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more, based on the total mass of all monomer components. While there is no particular upper limit, it is preferably 95% by mass or less, more preferably 85% by mass or less. When multiple types of polymer A are contained, the content of the monomer component having an aromatic hydrocarbon group is calculated as a weight average value.

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

Examples of aralkyl groups include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups) and substituted or unsubstituted benzyl groups, with substituted or unsubstituted benzyl groups being preferred.

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

Polymer A containing a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one first monomer described below and/or at least one second monomer described below.

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

The first monomer is a monomer having a carboxy group in the molecule. 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 polymer A is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and even more preferably 15% by mass to 30% by mass, based on the total mass of all monomer components.

The copolymerization ratio of the first monomer is preferably 10% to 50% by mass, based on the total mass of all monomer components. A copolymerization ratio of 10% by mass or more is preferred from the perspective of achieving good developability and controlling edge fusing, with 15% by mass or more being more preferred, and 20% by mass or more being even more preferred. A copolymerization ratio of 50% by mass or less is preferred from the perspective of high resolution and foot shape of the resist pattern, as well as chemical resistance of the resist pattern; from these perspectives, 35% by mass or less is more preferred, 30% by mass or less is even more preferred, and 27% by mass or less is particularly preferred.

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

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

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

Polymer A can be used singly or in a mixture of two or more types. When using a mixture of two or more types, it is preferable to use a mixture of two types of polymer A containing a monomer component having an aromatic hydrocarbon group, or to use a mixture of a polymer A containing a monomer component having an aromatic hydrocarbon group and a polymer A not containing a monomer component having an aromatic hydrocarbon group. In the latter case, the proportion of polymer A containing a monomer component having an aromatic hydrocarbon group used is preferably 50% by mass or more, more preferably 70% by mass or more, preferably 80% by mass or more, and even more preferably 90% by mass or more, based on the total amount of polymer A.

Polymer A is preferably synthesized by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution prepared by diluting one or more of the monomers described above with a solvent such as acetone, methyl ethyl ketone, or isopropanol, and then heating and stirring the mixture. Synthesis may also be carried out by adding a portion of the mixture dropwise to the reaction solution. After the reaction is complete, additional solvent may be added to adjust the concentration to the desired level. In addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may also be used as a synthesis method.

The glass transition temperature Tg of polymer A is preferably 30°C or higher and 135°C or lower. By using polymer A with a Tg of 135°C or lower in the photosensitive resin layer, it is possible to suppress line width thickening and deterioration of resolution when the focus position is shifted during exposure. From this perspective, the Tg of polymer A is more preferably 130°C or lower, even more preferably 120°C or lower, and particularly preferably 110°C or lower. Furthermore, using polymer A with a Tg of 30°C or higher is preferable from the perspective of improving edge fuse resistance. From this perspective, the Tg of polymer A is more preferably 40°C or higher, even more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

Furthermore, from the viewpoints of sensitivity and resolution, the photosensitive resin layer, preferably the negative photosensitive resin layer, preferably contains a polymer having a crosslinkable group, and more preferably contains a polymer having a crosslinkable group as the alkali-soluble resin.
From the viewpoints of developability, sensitivity, and resolution, the polymer having a crosslinkable group is preferably a polymer having a polymerizable group, more preferably a polymer having an ethylenically unsaturated group, still more preferably an acrylic resin having an ethylenically unsaturated group, and particularly preferably an acrylic resin having a structural unit having an ethylenically unsaturated group.
The polymerizable group is not particularly limited as long as it is a group that participates in a polymerization reaction, and examples thereof include groups having an ethylenically unsaturated group such as a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group; and groups having a cationically polymerizable group such as an epoxy group and an oxetane group.
Furthermore, the polymer having a crosslinkable group is preferably polymer A having a crosslinkable group from the viewpoints of developability, sensitivity, and resolution.

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

The alkali-soluble resins may be used alone or in combination of two or more.
The proportion of the alkali-soluble resin relative to the total mass of the negative photosensitive resin layer is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and even more preferably 40% by mass to 60% by mass. Setting the proportion of the alkali-soluble resin relative to the negative photosensitive resin layer to 90% by mass or less is preferred from the viewpoint of controlling the development time. On the other hand, setting the proportion of the alkali-soluble resin relative to the negative photosensitive resin layer to 10% by mass or more is preferred from the viewpoint of improving edge fuse resistance.

<<Compounds with Unshared Electron Pairs>>
From the viewpoint of adhesion to the conductive layer, the photosensitive resin layer preferably contains a compound having an unshared electron pair.
From the viewpoint of adhesion to the conductive layer, the compound having an unshared electron pair is preferably a compound having at least a nitrogen atom, an oxygen atom, or a sulfur atom, more preferably a heterocyclic compound, a thiol compound, or a disulfide compound, still more preferably a heterocyclic compound, and particularly preferably a nitrogen-containing heterocyclic compound.

The heterocyclic ring contained in the heterocyclic compound may be either a monocyclic or polycyclic heterocyclic ring.
Examples of heteroatoms contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic compound preferably contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably contains a nitrogen atom.

Preferred examples of heterocyclic compounds include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzoxazole compounds, and pyrimidine compounds. Among these, from the viewpoint of adhesion to the conductive layer, the heterocyclic compound is preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds. It is more preferred that the heterocyclic compound is at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds. It is even more preferred that the heterocyclic compound is at least one compound selected from the group consisting of triazole compounds and tetrazole compounds. A triazole compound is particularly preferred.

Specific preferred examples of heterocyclic compounds are shown below. Examples of triazole compounds and benzotriazole compounds include the following compounds:

Examples of tetrazole compounds include the following compounds:

Examples of thiadiazole compounds include the following compounds:

Examples of triazine compounds include the following compounds:

Examples of rhodanine compounds include the following compounds:

Examples of thiazole compounds include the following compounds:

Examples of benzothiazole compounds include the following compounds:

Examples of benzimidazole compounds include the following compounds:

Examples of benzoxazole compounds include the following compounds:

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

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

Furthermore, from the viewpoint of adhesion to the conductive layer, the molecular weight of the compound having an unshared electron pair is preferably less than 1,000, more preferably 50 to 500, even more preferably 50 to 200, and particularly preferably 50 to 115.

The photosensitive resin layer may contain one kind of compound having an unshared electron pair, or may contain two or more kinds of compounds.
From the viewpoint of adhesion to the conductive layer, the content of the compound having an unshared electron pair is preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass, even more preferably 0.3% by mass to 8% by mass, and particularly preferably 0.5% by mass to 5% by mass, relative to the total mass of the photosensitive resin layer.

<<Pigment>>
From the viewpoints of visibility of exposed and unexposed areas, pattern visibility after development, and resolution, the photosensitive resin layer preferably contains a dye, and more preferably contains a dye (also simply referred to as "dye N") that has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm during color development and whose maximum absorption wavelength changes with an acid, a base, or a radical. When dye N is contained, adhesion with adjacent layers (for example, the temporary support and the first resin layer) is improved, resulting in better resolution, although the detailed mechanism is unknown.

In this specification, the expression "the maximum absorption wavelength of a dye changes in response to an acid, a base, or a radical" may mean any of an embodiment in which a dye in a colored state is decolorized by an acid, a base, or a radical, an embodiment in which a dye in a decolorized state develops color by an acid, a base, or a radical, and an embodiment in which a dye in a colored state changes to a colored state of another hue.
Specifically, the dye N may be a compound that changes from a decolorized state to develop a color upon exposure, or a compound that changes from a colored state to decolorize upon exposure. In this case, the dye may be a dye whose color-developing or decolorizing state changes when an acid, base, or radical is generated and acts within the photosensitive resin layer upon exposure, or a dye whose color-developing or decolorizing state changes when the state (e.g., pH) within the photosensitive resin layer changes due to an acid, base, or radical. Alternatively, the dye may be a dye whose color-developing or decolorizing state changes upon direct stimulation by an acid, base, or radical without exposure.

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

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

From the viewpoint of visibility of exposed and unexposed areas, dye N preferably has a maximum absorption wavelength of 550 nm or longer in the wavelength range of 400 nm to 780 nm upon color development, more preferably 550 nm to 700 nm, and even more preferably 550 nm to 650 nm.

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

Examples of dyes that develop or lose color 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 preferred from the viewpoint of visibility of exposed and unexposed areas.

Examples of leuco compounds include leuco compounds having a triarylmethane skeleton (triarylmethane-based dyes), leuco compounds having a spiropyran skeleton (spiropyran-based dyes), leuco compounds having a fluoran skeleton (fluoran-based dyes), leuco compounds having a diarylmethane skeleton (diarylmethane-based dyes), leuco compounds having a rhodamine lactam skeleton (rhodamine lactam-based dyes), leuco compounds having an indolylphthalide skeleton (indolylphthalide-based dyes), and leuco compounds having a leucoauramine skeleton (leucoauramine-based dyes).
Among these, triarylmethane dyes or fluoran dyes are preferred, and leuco compounds having a triphenylmethane skeleton (triphenylmethane dyes) or fluoran dyes are more preferred.

From the viewpoint of visibility of exposed and unexposed areas, the leuco compound preferably has a lactone ring, a sultine ring, or a sultone ring. This allows the lactone ring, sultine ring, or sultone ring of the leuco compound to react with radicals generated from a photoradical polymerization initiator or with an acid generated from a photocationic polymerization initiator, thereby converting the leuco compound into a closed ring state and discoloring, or converting the leuco compound into an open ring state and developing color. Leuco compounds are preferably compounds that have a lactone ring, a sultine ring, or a sultone ring and develop color upon ring-opening of the lactone ring, a sultine ring, or a sultone ring by radicals or an acid, and more preferably compounds that have a lactone ring and develop color upon ring-opening of the lactone ring by radicals or an acid.

Examples of the dye N include the following dyes and leuco compounds.
Specific examples of dyes among the dyes N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymolsulfophthalein, xylenol blue, methyl orange, paramethyl red, Congo red, benzopurpurin 4B, α-naphthyl red, Nile blue 2B, Nile blue A, methyl violet, malachite green, parafuchsin, Victoria Pure Blue naphthalene sulfonate, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), oil blue #603 (manufactured by Orient Chemical Industries Co., Ltd.), oil pink #312 (manufactured by Orient Chemical Industries Co., Ltd.), oil red 5B (manufactured by Orient Chemical Industries Co., Ltd.), and oil scarlet #308 (manufactured by Orient Chemical Industries Co., Ltd.). Examples of the antibacterial agents include 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

Specific examples of leuco compounds among dyes 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-(N-p-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)- 6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-diethylamino)-7-benzylaminofluoran, 3-(N,N-diethylamino)-7,8-benzofluoran, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide These include 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthen-3-one, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthen-3-one.

From the viewpoints of the visibility of exposed and unexposed areas, the pattern visibility after development, and resolution, dye N is preferably a dye whose maximum absorption wavelength changes in response to radicals, and more preferably a dye that develops color in response to radicals.
As the dye N, leuco crystal violet, crystal violet lactone, brilliant green, or Victoria Pure Blue-naphthalene sulfonate is preferred.

The dyes may be used alone or in combination of two or more.
From the viewpoints of the visibility of exposed and unexposed areas, the pattern visibility after development, and the resolution, the content of the dye is preferably 0.1% by mass or more, 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, relative to the total mass of the photosensitive resin layer.
Furthermore, from the viewpoints of the visibility of exposed and unexposed areas, the pattern visibility after development, and the resolution, the content of dye N is preferably 0.1 mass % or more, more preferably 0.1 mass % to 10 mass %, even more preferably 0.1 mass % to 5 mass %, and particularly preferably 0.1 mass % to 1 mass %, relative to the total mass of the photosensitive resin layer.

The content of dye N means the content of dye when all of the dye N contained in the photosensitive resin layer is in a color-developing 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 types of solutions were prepared by dissolving 0.001 g or 0.01 g of dye in 100 mL of methyl ethyl ketone. The photoradical polymerization initiator Irgacure OXE01 (product name, BASF Japan Co., Ltd.) was added to each of the resulting solutions, and radicals were generated by irradiating with 365 nm light, causing all of the dyes to develop color. The absorbance of each solution was then measured at 25°C using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) under atmospheric conditions, and a calibration curve was created.
Next, the absorbance of the solution in which all the dye has developed is measured in the same manner as above, except that 3 g of the photosensitive resin layer is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the photosensitive resin layer, the content of the dye contained in the photosensitive resin layer is calculated based on a calibration curve.

<<Thermal crosslinkable compound>>
From the viewpoints of the strength of the cured film obtained and the adhesiveness of the uncured film obtained, the photosensitive resin layer preferably contains a thermally crosslinkable compound. In this specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not considered to be a polymerizable compound but is considered to be a thermally crosslinkable compound.
Examples of the thermally crosslinkable compound include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoints of the strength of the resulting cured film and the adhesiveness of the resulting uncured film.
Since the blocked isocyanate compound reacts with a hydroxy group and a carboxy group, for example, when a resin and/or a polymerizable compound or the like has at least one of a hydroxy group and a carboxy group, the hydrophilicity of the formed film tends to decrease, and the functionality tends to be enhanced when the film obtained by curing the photosensitive resin layer is used as a protective film.
The blocked isocyanate compound refers to a compound having a structure in which the isocyanate group of an isocyanate is protected (so-called masked) with a blocking agent.

The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 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 accompanying the deprotection reaction of the blocked isocyanate when measured by DSC (Differential Scanning Calorimetry) analysis using a differential scanning calorimeter."
As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used. However, the differential scanning calorimeter is not limited to this.

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

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

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

As the blocked isocyanate compound, commercially available products can be used.
Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, and the like (all manufactured by Showa Denko K.K.), and the blocked Duranate series (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, and the like, manufactured by Asahi Kasei Chemicals Corporation).
Furthermore, as the blocked isocyanate compound, a compound having the following structure can also be used.

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

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

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

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

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

There are no limitations on the acid group, and any known acid group can be used. The acid group is preferably a carboxy group or a phenolic hydroxyl group.

Examples of acid-decomposable groups include groups that are relatively easily decomposable by acid and groups that are relatively resistant to decomposition by acid. Examples of groups that are relatively easily decomposable by acid include acetal-type protecting groups (e.g., 1-alkoxyalkyl groups, tetrahydropyranyl groups, and tetrahydrofuranyl groups). Examples of groups that are relatively resistant to decomposition by acid include tertiary alkyl groups (e.g., tert-butyl groups) and tertiary alkyloxycarbonyl groups (e.g., tert-butyloxycarbonyl groups). Among the above, the acid-decomposable group is preferably an acetal-type protecting group.

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

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

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

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

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

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

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

For preferred embodiments of Formulae A1 to A3, please refer to paragraphs 0044 to 0058 of WO 2018/179640.

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

Polymer X may contain a single type of structural unit A, or may contain two or more types of structural units A.

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

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

Structural unit B is a structural unit having an acid group that is not protected by an acid-decomposable group, i.e., an acid group that does not have a protecting group. The presence of structural unit B in polymer X improves sensitivity during pattern formation. Furthermore, since it is more soluble in an alkaline developer in the development step after exposure, development time can be shortened.

The acid group in structural unit B refers to a proton-dissociating group with a pKa of 12 or less. From the perspective of improving sensitivity, the pKa of the acid group is preferably 10 or less, and more preferably 6 or less. Furthermore, the pKa of the acid group is preferably -5 or more.

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

Polymer X may contain one type of structural unit B, or two or more types of structural units B.

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

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

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

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

Examples of structural unit C include structural units derived from styrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, acrylonitrile, or ethylene glycol monoacetoacetate mono(meth)acrylate. Examples of structural unit C also include structural units derived from compounds described in paragraphs 0021 to 0024 of JP 2004-264623 A.

From the viewpoint of resolution, structural unit C preferably includes a structural unit having a basic group. Examples of basic groups include groups having a nitrogen atom. Examples of groups having a nitrogen atom include aliphatic amino groups, aromatic amino groups, and nitrogen-containing heteroaromatic ring groups. The basic group is preferably an aliphatic amino group.

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

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

Furthermore, from the viewpoint of improving electrical properties, structural unit C is preferably a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton. Examples of monomers that form these structural units include styrene, α-methylstyrene, dicyclopentanyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and benzyl (meth)acrylate. Of the above, cyclohexyl (meth)acrylate is preferred.

Polymer X may contain one type of structural unit C, or two or more types of structural units C.

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

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

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

One method for adjusting the Tg of polymer X to fall within the above range is to use the FOX equation. Using the FOX equation, the Tg of the target polymer X can be adjusted based on, for example, the Tg of the homopolymer of each structural unit in the target polymer X and the mass fraction of each structural unit.

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

The Tg of the polymer can also be adjusted by adjusting the weight-average molecular weight of the polymer.

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

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

-Weight average molecular weight-
The weight-average molecular weight (Mw) of the polymer X is preferably 60,000 or less in terms of polystyrene equivalent weight-average molecular weight. When a positive-type photosensitive resin layer is formed using a transfer material described below, the weight-average molecular weight of the polymer X being 60,000 or less allows the positive-type photosensitive resin layer to be transferred at a low temperature (for example, 130° C. or less).

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

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

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

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

-Manufacturing method-
There are no limitations on the method for producing polymer X, and known methods can be used. For example, polymer X can be produced by polymerizing, in an organic solvent, a monomer for forming structural unit A, and, if necessary, a monomer for forming structural unit B and a monomer for forming structural unit C, using a polymerization initiator. Polymer X can also be produced by a so-called polymer reaction.

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

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

The positive-type photosensitive resin layer may contain one type of other polymer alone, or may contain two or more types of other polymers.

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

In this disclosure, "polymer component" is a general term for all polymers contained in a positive-type photosensitive resin layer. For example, if a positive-type photosensitive resin layer contains polymer X and another polymer, polymer X and the other polymer are collectively referred to as the "polymer component." Note that compounds that fall under the category of crosslinking agents, dispersants, and surfactants, as described below, are not included in the polymer component, even if they are high-molecular compounds.

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

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

Examples of alkali-soluble resins include resins having hydroxyl groups, carboxyl groups, or sulfo groups in the main chain or side chain. Examples of alkali-soluble resins include polyamide resins, polyhydroxystyrene, polyhydroxystyrene derivatives, styrene-maleic anhydride copolymers, polyvinyl hydroxybenzoate, carboxyl group-containing (meth)acrylic resins, and novolac resins. Preferred alkali-soluble resins include condensation polymers of m-/p-mixed cresol and formaldehyde, and condensation polymers of phenol, cresol, and formaldehyde.

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

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

Among these, preferred alkali-soluble resins are those containing structural units with phenolic hydroxyl groups, such as novolac resins.

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

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

The positive photosensitive resin layer may contain one or more alkali-soluble resins.
The content of the alkali-soluble resin is preferably 30% by mass to 99.9% by mass, more preferably 40% by mass to 99.5% by mass, and particularly preferably 70% by mass to 99% by mass, relative to the total mass of the positive-type photosensitive resin layer.

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

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

The photoacid generator is preferably a photoacid generator that generates an acid with a pKa of 4 or less, more preferably a photoacid generator that generates an acid with a pKa of 3 or less, and particularly preferably a photoacid generator that generates an acid with a pKa of 2 or less. There is no lower limit for the pKa of the acid derived from the photoacid generator. For example, the pKa of the acid derived from the photoacid generator is preferably -10.0 or greater.

Examples of photoacid generators include ionic photoacid generators and non-ionic photoacid generators.

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

Ionic photoacid generators such as those described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.

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

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

The oxime sulfonate compounds described in paragraphs 0084 to 0088 of WO 2018/179640 can be suitably used.

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

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

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

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

Quinone diazide compounds include, for example, 1,2-benzoquinone diazide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-5-sulfonic acid ester, 1,2-naphthoquinone diazide-6-sulfonic acid ester, 2,1-naphthoquinone diazide-4-sulfonic acid ester, 2,1-naphthoquinone diazide-5-sulfonic acid ester, 2,1-naphthoquinone diazide-6-sulfonic acid ester, and other quinone diazides. Examples include sulfonate esters of benzoquinone derivatives, 1,2-benzoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-naphthoquinonediazide-6-sulfonic acid chloride, 2,1-naphthoquinonediazide-4-sulfonic acid chloride, 2,1-naphthoquinonediazide-5-sulfonic acid chloride, and 2,1-naphthoquinonediazide-6-sulfonic acid chloride.

The positive photosensitive resin layer may contain one kind of photoacid generator alone, or may contain two or more kinds of photoacid generators.
From the viewpoints of sensitivity and resolution, the content of the photoacid generator is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass to 5% by mass, relative to the total mass of the positive photosensitive resin layer.

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

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

The surfactant is preferably a fluorine-based surfactant or a silicone-based surfactant.
Commercially available fluorine-based surfactants include, for example, Megafac (trade name) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, and F-55. 2, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-56 8, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41, R-41- LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Fluorard (trade name) FC430, FC431, FC171 (all manufactured by Sumitomo 3M Limited), Surflon (trade name) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox (trade name) PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Ftergent Examples include 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, and 683 (all manufactured by NEOS Corporation).
Furthermore, acrylic compounds having a molecular structure with a functional group containing a fluorine atom, which volatilizes when heated due to cleavage of the functional group containing the fluorine atom, can also be suitably used as the fluorosurfactant. Examples of such fluorosurfactants include the Megafac (trade name) DS series manufactured by DIC Corporation (The Chemical Daily, February 22, 2016; The Nikkei Business Daily, February 23, 2016), such as Megafac (trade name) DS-21.

It is also preferable to use, as the fluorine-based surfactant, a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
The fluorine-containing surfactant may also be a block polymer. As the fluorine-containing surfactant, a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound having a fluorine atom and a structural unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups) may also be preferably used.
The fluorine-based surfactant may also be a fluorine-containing polymer having an ethylenically unsaturated group in the side chain, such as Megafac (trade name) RS-101, RS-102, RS-718K, and RS-72-K (all manufactured by DIC Corporation).

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, 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, and Pluronic (trade name) L10. , L31, L61, L62, 10R5, 17R2, 25R2 (all manufactured by BASF), Tetronic (trade name) 304, 701, 704, 901, 904, 150R1 (all manufactured by BASF), Solsperse (trade name) 20000 (all manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (all manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.), Paionin (trade name) D-6112, D-6112-W, D-6315 (all manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (all manufactured by Nissin Chemical Industry Co., Ltd.), and the like.
Furthermore, in recent years, there have been concerns about the environmental compatibility of compounds having a linear perfluoroalkyl group having seven or more carbon atoms, and therefore it is preferable to use surfactants that use alternative materials to perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS).

Examples of silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.
Specific examples of silicone surfactants include 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, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), as well as X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, and KF -945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), BYK307, BYK323, BYK330 (all manufactured by BYK-Chemie).

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

- Additives -
In addition to the above components, the photosensitive resin layer may contain known additives as needed.
Examples of the additives include a polymerization inhibitor, a sensitizer, a plasticizer, an alkoxysilane compound, and a solvent. The photosensitive resin layer may contain one kind of each additive alone or two or more kinds of each additive.
Examples of additives include metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, and organic or inorganic suspending agents. Preferred embodiments of these additives are described in paragraphs [0165] to [0184] of JP 2014-85643 A, the contents of which are incorporated herein by reference.

The photosensitive resin layer may contain a polymerization inhibitor, and the polymerization inhibitor is preferably a radical polymerization inhibitor.
Examples of the polymerization inhibitor include the thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4,502,784. Among these, phenothiazine, phenoxazine, and 4-methoxyphenol are preferred. Other polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. In order to avoid impairing the sensitivity of the photosensitive resin composition, it is preferable to use nitrosophenylhydroxyamine aluminum salt as the polymerization inhibitor.

The content of the polymerization inhibitor is preferably 0.01% by mass to 3% by mass, and more preferably 0.05% by mass to 1% by mass, relative to the total mass of the photosensitive resin layer. A content of 0.01% by mass or more is preferred from the perspective of imparting storage stability to the photosensitive resin composition. On the other hand, a content of 3% by mass or less is preferred from the perspective of maintaining sensitivity.

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

The photosensitive resin layer may contain one type of sensitizer alone or two or more types of sensitizers.
When the photosensitive resin layer contains a sensitizer, the content of the sensitizer can be appropriately selected depending on the purpose. From the viewpoints of improving the sensitivity to the light source and improving the curing rate by balancing the polymerization rate and chain transfer, the content of the sensitizer is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 1% by mass, relative to the total mass of the photosensitive resin layer.

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

The photosensitive resin layer, preferably the positive photosensitive resin layer, may contain an alkoxysilane compound.
Examples of alkoxysilane compounds include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriakoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane, and vinyltrialkoxysilane.

Of the above, the alkoxysilane compound is preferably a trialkoxysilane compound, more preferably γ-glycidoxypropyltrialkoxysilane or γ-methacryloxypropyltrialkoxysilane, even more preferably γ-glycidoxypropyltrialkoxysilane, and particularly preferably 3-glycidoxypropyltrimethoxysilane.

The photosensitive resin layer may contain one kind of alkoxysilane compound alone, or may contain two or more kinds of alkoxysilane compounds.
From the viewpoints of adhesion to the substrate and etching resistance, the content of the alkoxysilane compound is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to 40% by mass, and particularly preferably 1.0% by mass to 30% by mass, relative to the total mass of the photosensitive resin layer.

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

<<Impurities etc.>>
The photosensitive resin layer may contain a predetermined 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 these, halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, so it is preferable to set the contents to the following ranges.

The impurity content in the photosensitive resin layer is preferably 80 ppm or less by mass, more preferably 10 ppm or less, and even more preferably 2 ppm or less. The impurity content can be 1 ppb or more by mass, and may be 0.1 ppm or more.

Methods for keeping the impurity content within the above range include selecting raw materials for the composition that contain low impurities, preventing impurities from being mixed in when the photosensitive resin layer is produced, and removing them by washing. These methods make it possible to keep the impurity content within the above range.

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

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

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

<<Residual Monomer>>
The photosensitive resin layer may contain residual monomers corresponding to the respective structural units of the alkali-soluble resin described above.
From the viewpoints of patterning properties and reliability, the content of the residual monomer is preferably 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and even more preferably 500 ppm by mass or less, relative to the total mass of the alkali-soluble resin. Although there is no particular lower limit, it is preferably 1 ppm by mass or more, and more preferably 10 ppm by mass or more.
From the viewpoints of patterning ability and reliability, the residual monomer content 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, and even more preferably 100 ppm by mass or less, relative to the total mass of the photosensitive resin layer. Although there is no particular lower limit, it is preferably 0.1 ppm by mass or more, and more preferably 1 ppm by mass or more.

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

<<Physical properties etc.>>
The thickness of the photosensitive resin layer is preferably 0.1 μm to 300 μm, more preferably 0.2 μm to 100 μm, even more preferably 0.5 μm to 50 μm, still more preferably 0.5 μm to 15 μm, particularly preferably 0.5 μm to 10 μm, and most preferably 0.5 μm to 8 μm, which can improve the developability of the photosensitive resin layer and the resolution.
From the viewpoint of resolution, the thickness of the photosensitive resin layer is preferably 10 μm or less, more preferably 4.8 μm or less, even more preferably 3.0 μm or less, and particularly preferably 0.5 μm to 3.0 μm.
The thickness of each layer of the photosensitive transfer material is measured by observing a cross section of the photosensitive transfer material in a direction perpendicular to the main surface with a scanning electron microscope (SEM), measuring the thickness of each layer at 10 or more points based on the obtained observation image, and calculating the average value.

In addition, to achieve better adhesion, the transmittance of the photosensitive resin layer to light with a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and even more preferably 50% or more. There is no particular upper limit, but a value of 99.9% or less is preferred.

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

Examples of the photosensitive resin composition used to form the photosensitive resin layer include compositions containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, the above-mentioned 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 resin 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, polymerizable compound, photopolymerization initiator, and the above-mentioned optional components, and any known solvent can be used.
Examples of the solvent include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (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 preparing a photosensitive transfer material including a temporary support, a cushion layer, an intermediate layer, a photosensitive resin layer, and a protective film, the photosensitive resin composition preferably contains at least one solvent selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents. Among these, a mixed solvent containing at least one solvent selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one solvent selected from the group consisting of ketone solvents and cyclic ether solvents is more preferred, and a mixed solvent containing at least three solvents, namely, at least one solvent selected from the group consisting of alkylene glycol ether solvents and alkylene glycol ether acetate solvents, a ketone solvent, and a cyclic ether solvent, is even more preferred.

Examples of alkylene glycol ether solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, and dipropylene glycol dialkyl ethers.
Examples of alkylene glycol ether acetate solvents include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.
As the solvent, the solvents described in paragraphs 0092 to 0094 of WO 2018/179640 and the solvents described in paragraph 0014 of JP 2018-177889 A may be used, the contents of which are incorporated herein by reference.

The photosensitive resin composition may contain one solvent alone or two or more solvents.
The content of the solvent when applying the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, and more preferably 100 parts by mass to 900 parts by mass, per 100 parts by mass of the total solid content in the photosensitive resin composition.

The method for preparing the photosensitive resin composition is not particularly limited, and examples thereof include a method in which solutions of the components are dissolved in the above-mentioned solvents in advance, and the resulting solutions are mixed in a predetermined ratio to prepare the photosensitive resin composition.
From the viewpoint of particle removability, the photosensitive resin composition is preferably filtered using a filter before forming the photosensitive resin layer, more preferably using a filter having a pore size of 0.2 μm to 10 μm, even more preferably using a filter having a pore size of 0.2 μm to 7 μm, and particularly preferably using a filter having a pore size of 0.2 μm to 5 μm.
The material and shape of the filter are not particularly limited, and known materials can be used.
The filtration is preferably carried out at least once, and is also preferably carried out multiple times.

The method for applying the photosensitive resin composition is not particularly limited, and may be any known method, such as slit coating, spin coating, curtain coating, or inkjet coating.
The photosensitive resin layer may also be formed by applying a photosensitive resin composition onto a protective film described below and drying it.

In addition, from the viewpoints of resolution and releasability of the temporary support, the photosensitive transfer material in the present disclosure preferably has another layer between the temporary support and the photosensitive resin layer.
Preferred examples of the other layers include an intermediate layer, a cushion layer, and a protective film.
In particular, the transfer layer preferably has an intermediate layer, and more preferably has a cushion layer and an intermediate layer.

[Middle class]
The photosensitive transfer material preferably has an intermediate layer between the temporary support and the photosensitive resin layer, or between the cushion layer (described later) and the photosensitive resin layer when the photosensitive transfer material has a cushion layer. The intermediate layer can prevent components from mixing when forming multiple layers and during storage.

The intermediate layer is preferably a water-soluble layer from the viewpoints of developability and preventing mixing of components when applying multiple layers and during storage after application. In this disclosure, "water-soluble" means that the solubility in 100 g of water at pH 7.0 and a liquid temperature of 22°C is 0.1 g or more.

An example of the intermediate layer is an oxygen-blocking layer having an oxygen-blocking function, which is described as a "separation layer" in JP-A-5-72724. When the intermediate layer is an oxygen-blocking layer, the sensitivity during exposure is improved, and the time load on the exposure machine is reduced, resulting in improved productivity. The oxygen-blocking layer used as the intermediate layer may be appropriately selected from known layers. The oxygen-blocking layer used as the intermediate layer preferably exhibits low oxygen permeability and is dispersible or soluble in water or an alkaline aqueous solution (a 1% by mass aqueous solution of sodium carbonate at 22°C).
In addition, the intermediate layer preferably contains an inorganic layered compound from the viewpoints of oxygen blocking properties, resolution, and pattern formability.
The inorganic layered compound is a particle 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.H2O, taeniolite, montmorillonite, saponite, hectorite, and zirconium phosphate.
Examples of mica compounds include micas such as natural mica and synthetic mica represented by the formula: A(B,C) _2-5 D ₄ O ₁₀ (OH,F,O) ₂ (wherein A is K, Na, or Ca; B and C are Fe(II), Fe(III), Mn, Al, Mg, or V; and D is Si or Al).

In the mica group, natural micas include muscovite, sodalite, phlogopite, biotite, and lepidolite. Synthetic micas include non-swelling micas such as fluorphlogopite _KMg3 ( _AlSi3O10 ) _F2 and potassium _{tetrasilicate} mica _KMg2.5Si4O10 ) _F2 , and swelling micas such as Na tetrasilicic mica _{NaMg2.5 ( Si4O10} ) _F2 , Na or Li taeniolite (Na, _Li ) _Mg2Li ( _Si4O10 ) _F2 , and montmorillonite-based Na or Li hectorite (Na,Li _{) 1/} 8Mg2 _{/ 5Li1 /8} ( _{Si4O10 ) F2} . Synthetic smectite is also useful.

From the perspective of diffusion control, the shape of the inorganic layered compound should be as thin as possible, and as large as possible in terms of planar size, as long as it does not impair the smoothness of the coating surface or the transmittance of actinic rays. Therefore, the aspect ratio is preferably 20 or more, more preferably 100 or more, and particularly preferably 200 or more. The aspect ratio is the ratio of the major axis to the thickness of the particle, and can be measured, for example, from a projection view of the particle in a micrograph. The higher the aspect ratio, the greater the effect obtained.

The particle size of the inorganic layered compound is preferably 0.3 μm to 20 μm, more preferably 0.5 μm to 10 μm, and particularly preferably 1 μm to 5 μm, in terms of average major axis. The average particle thickness 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 swellable synthetic mica, a representative compound, a preferred embodiment is one in which the thickness is approximately 1 nm to 50 nm and the face size (major axis) is approximately 1 μm to 20 μm.

From the viewpoints of oxygen blocking properties, resolution, and pattern formability, the content of the inorganic layered compound is preferably 0.1% by mass to 50% by mass, and more preferably 1% by mass to 20% by mass, relative to the total mass of the intermediate layer.

The intermediate layer preferably contains a resin. Examples of resins contained in the intermediate 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. The resin contained in the intermediate layer is preferably a water-soluble resin.

From the perspective of suppressing mixing of components between multiple layers, it is preferable that the resin contained in the intermediate layer be a resin different from both the polymer A contained in the negative photosensitive resin layer and the thermoplastic resin (alkali-soluble resin) contained in the cushion layer.

From the viewpoints of oxygen blocking properties, developability, resolution, and pattern formability, the intermediate layer preferably contains a water-soluble compound, and more preferably contains a water-soluble resin.
The water-soluble compound is not particularly limited, but from the viewpoints of oxygen blocking properties, developability, resolution, and pattern formability, it is preferably one or more compounds selected from the group consisting of water-soluble cellulose derivatives, polyhydric alcohols, oxide adducts of polyhydric alcohols, polyethers, phenol derivatives, and amide compounds, and more preferably at least one water-soluble resin selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl cellulose, and hydroxypropylmethyl cellulose.
Examples of water-soluble resins include water-soluble cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide resins, (meth)acrylate resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof.
Among these, from the viewpoints of oxygen blocking properties, developability, resolution, and pattern formability, the water-soluble resin preferably contains polyvinyl alcohol, more preferably contains polyvinyl alcohol and a water-soluble cellulose derivative, even more preferably contains polyvinyl alcohol and hydroxypropyl cellulose, and particularly preferably contains polyvinyl alcohol, polyvinylpyrrolidone, and hydroxypropyl cellulose.
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.
In addition, from the viewpoints of oxygen blocking properties, developability, resolution, and pattern formability, it is preferable that the polyvinyl alcohol contains ethylene as a monomer unit.

From the viewpoints of oxygen blocking properties, developability, defect suppression of the resulting resist pattern, resolution, and sensitivity, the content of the polyvinyl alcohol is preferably 10% to 95% by mass, more preferably 30% to 90% by mass, and particularly preferably 50% to 75% by mass, relative to the total mass of the intermediate layer.

Furthermore, from the viewpoints of oxygen blocking properties, developability, defect suppression properties of the resulting resist pattern, resolution, and sensitivity, the water-soluble resin preferably contains a water-soluble cellulose derivative, more preferably contains a hydroxyalkyl cellulose compound, and particularly preferably contains hydroxypropyl cellulose.
From the viewpoints of oxygen blocking properties, developability, defect suppression properties of the resulting resist pattern, resolution, and sensitivity, the content of the hydroxypropyl cellulose is preferably 0.005% by mass to 20% by mass, more preferably 0.01% by mass to 10% by mass, even more preferably 0.1% by mass to 5% by mass, and particularly preferably 0.5% by mass to 3% by mass, relative to the total mass of the intermediate layer.

Furthermore, from the viewpoints of oxygen blocking properties, developability, defect suppression properties of the resulting resist pattern, resolution, and sensitivity, the water-soluble resin preferably contains polyvinylpyrrolidone.
From the viewpoints of oxygen blocking property, developability, defect suppression property of the obtained resist pattern, resolution, and sensitivity, the content of the polyvinylpyrrolidone is preferably 1% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, even more preferably 20% by mass to 45% by mass, and particularly preferably 25% by mass to 40% by mass, relative to the total mass of the intermediate layer.

The intermediate layer may contain one type of resin alone, or two or more types of resin.

From the viewpoints of oxygen barrier properties and preventing mixing of components when multiple layers are applied and during storage after application, the content of the water-soluble compound in the intermediate layer is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, even more preferably 80% to 100% by mass, and particularly preferably 90% to 100% by mass, relative to the total mass of the intermediate layer.

The intermediate layer may also contain additives as needed. Examples of additives include surfactants.

The thickness of the intermediate layer is not limited. The average thickness of the intermediate layer is preferably 0.1 μm to 5 μm, and more preferably 0.5 μm to 3 μm. By keeping the thickness of the intermediate layer within this range, oxygen barrier properties are not reduced, mixing of components is suppressed when forming multiple layers and during storage, and the time required to remove the intermediate layer during development is also suppressed.

There are no limitations on the method for forming the intermediate layer, as long as it is possible to form a layer containing the above components. For example, one method for forming the intermediate layer is to apply an intermediate layer composition to the surface of the cushion layer or photosensitive resin layer, and then dry the coating of the intermediate layer composition.

Examples of intermediate layer compositions include compositions containing a resin and optional additives. The intermediate layer composition preferably contains a solvent to adjust the viscosity of the intermediate layer composition and facilitate the formation of the intermediate layer. There are no restrictions on the solvent 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, and 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.

[Cushion layer]
The photosensitive transfer material according to the present disclosure preferably has a cushion layer. The photosensitive transfer material preferably has a cushion layer between the temporary support and the photosensitive resin layer or intermediate layer. By having a cushion layer between the temporary support and the photosensitive resin layer or intermediate layer, the photosensitive transfer material improves its ability to conform to the adherend, and the inclusion of air bubbles between the adherend and the photosensitive transfer material is suppressed, resulting in improved adhesion between the layers.

The cushion layer preferably contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.
As the alkali-soluble resin, polymerizable compound, and photopolymerization initiator used in the cushion layer, the alkali-soluble resin, polymerizable compound, and photopolymerization initiator used in the photosensitive resin layer can be suitably used.

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

From the viewpoints of developability and adhesion to layers adjacent to the cushion layer, the alkali-soluble resin is preferably an acrylic resin. Here, "acrylic resin" refers to a resin having at least one type 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.

In the acrylic resin, the total content 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 is preferably 50% by mass or more, based on the total mass of the acrylic resin. In the acrylic resin, the total content of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylic acid esters is preferably 30% to 100% by mass, and more preferably 50% to 100% by mass, based on the total mass of the acrylic resin.

The alkali-soluble resin is preferably a polymer having an acid group. Examples of acid groups include carboxy groups, sulfo groups, phosphate groups, and phosphonate groups, with carboxy groups being preferred.

From the standpoint 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 carboxyl group-containing acrylic resin with an acid value of 60 mgKOH/g or more. There is no upper limit to the acid value. The acid value of the alkali-soluble resin is preferably 200 mgKOH/g or less, and more preferably 150 mgKOH/g or less.

The carboxyl 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. Examples of carboxyl group-containing acrylic resins having an acid value of 60 mgKOH/g or more include the carboxyl group-containing acrylic resins having an acid value of 60 mgKOH/g or more among the polymers described in paragraph 0025 of JP 2011-95716 A, the carboxyl group-containing acrylic resins having an acid value of 60 mgKOH/g or more among the polymers described in paragraphs 0033 to 0052 of JP 2010-237589 A, and the carboxyl group-containing acrylic resins having an acid value of 60 mgKOH/g or more among the binder polymers described in paragraphs 0053 to 0068 of JP 2016-224162 A.

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

From the standpoints of developability and adhesion to layers adjacent to the cushion layer, it is particularly preferable that the alkali-soluble resin be an acrylic resin having structural units derived from (meth)acrylic acid.

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

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 cushion layer may contain one or more alkali-soluble resins.

From the viewpoints of developability and adhesion to layers adjacent to the cushion layer, the content of the alkali-soluble resin is preferably 10% to 99% by mass, more preferably 20% to 90% by mass, even more preferably 40% to 80% by mass, and particularly preferably 50% to 70% by mass, relative to the total mass of the cushion layer.

The cushion layer preferably contains a dye (hereinafter sometimes referred to as "dye B") whose maximum absorption wavelength in the color-developing wavelength range of 400 nm to 780 nm is 450 nm or greater and whose maximum absorption wavelength changes in response to an acid, base, or radical. Preferred aspects of dye B are the same as those of dye N described above, except for the points described below.

From the viewpoints of visibility of exposed areas, visibility of unexposed areas, and resolution, dye B is preferably a dye whose maximum absorption wavelength changes in response to an acid or radical, and more preferably a dye whose maximum absorption wavelength changes in response to an acid.

From the viewpoints of visibility of exposed areas, visibility of unexposed areas, and resolution, it is preferable that the cushion layer contain, as dye B, a dye whose maximum absorption wavelength changes in response to acid, and a compound that generates acid when exposed to light, as described below.

The cushion layer may contain one or more types of dye B.

From the viewpoint of visibility of exposed areas and visibility of unexposed areas, the content of dye B is preferably 0.2% by mass or more, more preferably 0.2% by mass to 6% by mass, even more preferably 0.2% by mass to 5% by mass, and particularly preferably 0.25% by mass to 3.0% by mass, relative to the total mass of the cushion layer.

Here, the content of dye B refers to the content of dye when all of the dye B contained in the cushion layer is in a colored state. Below, we will explain the method for quantifying the content of dye B using a dye that develops color through radicals as an example. Two solutions were prepared by dissolving dye (0.001 g) and dye (0.01 g) in methyl ethyl ketone (100 mL). IRGACURE OXE-01 (BASF) was added to each solution as a photoradical polymerization initiator, and then irradiated with 365 nm light to generate radicals and cause all of the dye to develop color. Next, the absorbance of each solution was measured at a liquid temperature of 25°C under ambient conditions using a spectrophotometer (UV3100, Shimadzu Corporation) to create a calibration curve. Next, the absorbance of the solution in which all of the dye had developed color was measured using the same method as above, except that the cushion layer (0.1 g) was dissolved in methyl ethyl ketone instead of the dye. The amount of dye contained in the cushion layer is calculated based on the absorbance of the resulting solution containing the cushion layer and the calibration curve.

The cushion layer may contain a compound that generates an acid, a base, or a radical when exposed to light (hereinafter, sometimes referred to as "compound C"). Compound C is preferably a compound that generates an acid, a base, or a radical when exposed to actinic rays (e.g., ultraviolet light and visible light). Examples of 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 cushion layer preferably contains a photoacid generator. Examples of photoacid generators include the cationic photopolymerization initiators that may be contained in the photosensitive resin layer described above, and preferred aspects are the same as those described below.

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

It is also preferable that the photoacid generator has the following structure:

The cushion layer may contain a photobase generator. Examples of photobase generators include 2-nitrobenzyl cyclohexyl carbamate, 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, and (4-morpholinobenzoyl)-1-benzyl-1- These include 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-dihydropyridine.

The cushion layer may contain a photoradical polymerization initiator. Examples of photoradical polymerization initiators include the photoradical polymerization initiators that may be contained in the photosensitive resin layer described above, and preferred embodiments are also the same.

The cushion layer may contain one or more types of compound C.

From the viewpoints of visibility of exposed areas, visibility of unexposed areas, and resolution, the content of compound C is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass to 5% by mass, relative to the total mass of the cushion layer.

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

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

There are no restrictions on the plasticizer, as long as it is a compound that is compatible with the alkali-soluble resin and exhibits plasticity. From the perspective of imparting plasticity, the plasticizer is preferably a compound having an alkyleneoxy group in the molecule, and more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

From the viewpoints of resolution and storage stability, it is preferable that the plasticizer contain a (meth)acrylate compound. From the viewpoints of compatibility, resolution, and adhesion to layers adjacent to the cushion 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 above in the section on ethylenically unsaturated compounds. In photosensitive transfer materials, when the cushion layer and photosensitive resin layer are disposed in direct contact with each other, it is preferable that the cushion layer and the photosensitive resin layer each contain the same (meth)acrylate compound. This is because containing the same (meth)acrylate compound in the cushion layer and the photosensitive resin layer suppresses component diffusion between the layers, improving storage stability.

If the cushion layer contains a (meth)acrylate compound as a plasticizer, it is preferable that the (meth)acrylate compound not polymerize even in the exposed areas after exposure, from the viewpoint of adhesion to layers adjacent to the cushion layer.

In one embodiment, the (meth)acrylate compound used as a plasticizer is preferably a (meth)acrylate compound having two or more (meth)acryloyl groups in one molecule, from the viewpoints of resolution, adhesion to layers adjacent to the cushion layer, and developability.

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 cushioning layer may contain one or more plasticizers.

From the viewpoints of resolution, adhesion to layers adjacent to the cushion layer, and developability, the plasticizer content is preferably 1% to 70% by weight, more preferably 10% to 60% by weight, and particularly preferably 20% to 50% by weight, relative to the total weight of the cushion layer.

From the viewpoint of thickness uniformity, it is preferable that the cushion layer contain a surfactant. Examples of surfactants include those that may be contained in the photosensitive resin layer described above, and the preferred embodiments are the same.

The cushion layer may contain one or more surfactants.

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

The cushion layer may contain a sensitizer. Examples of sensitizers include the sensitizers that may be contained in the negative-type photosensitive resin layer described above.

The cushion layer may contain one or more sensitizers.

From the viewpoints of improving sensitivity to the light source, visibility of exposed areas, and visibility of unexposed areas, the content of the sensitizer is preferably 0.01% to 5% by mass, and more preferably 0.05% to 1% by mass, relative to the total mass of the cushion layer.

In addition to the above components, the cushion layer may contain known additives as needed.

Furthermore, the cushioning layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Laid-Open No. 2014-85643. The contents of the above publication are incorporated herein by reference.

The thickness of the cushion layer is not limited. From the viewpoint of adhesion to adjacent layers, the average thickness of the cushion layer is preferably 1 μm or more, and more preferably 2 μm or more. There is no upper limit to the average thickness of the cushion layer. From the viewpoint of developability and resolution, the average thickness of the cushion layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less.

There are no limitations on the method for forming the cushion layer, as long as it is possible to form a layer containing the above components. For example, one method for forming the cushion layer includes applying a cushion layer-forming composition to the surface of a temporary support and drying the resulting coating of the cushion layer-forming composition.

Examples of the cushion layer-forming composition include compositions containing the above-mentioned components. The cushion layer-forming composition preferably contains a solvent to adjust the viscosity of the cushion layer-forming composition and facilitate the formation of the cushion layer.

There are no restrictions on the solvent contained in the cushion layer-forming composition, as long as it is a solvent that can dissolve or disperse the components contained in the cushion layer. Examples of solvents include those that may be contained in the photosensitive resin composition described above, and the preferred embodiments are also the same.

The cushion layer-forming composition may contain one solvent alone, or two or more solvents.

The solvent content in the cushion layer-forming composition is preferably 50 to 1,900 parts by mass, and more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solids in the cushion layer-forming composition.

The cushion layer-forming composition can be prepared and the cushion layer can be formed in accordance with the above-described method for preparing a photosensitive resin composition and method for forming a negative-tone photosensitive resin layer. For example, solutions of the components contained in the cushion layer can be prepared in advance by dissolving them in a solvent, and the resulting solutions can be mixed in a predetermined ratio to prepare the cushion layer-forming composition. The cushion layer can then be formed by applying the resulting cushion layer-forming composition to the surface of a temporary support and drying the coating of the cushion layer-forming composition. Alternatively, a photosensitive resin layer can be formed on a protective film, and then a cushion layer can be formed on the surface of the photosensitive resin layer.

[Protective film]
The photosensitive transfer material preferably has a protective film.
The protective film is not included in the transfer layer.
It is preferable that the photosensitive resin layer and the protective film are in direct contact with each other.

Materials constituting the protective film include resin films and paper, with resin films being preferred from the viewpoints of strength and flexibility.
Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among these, a polyethylene film, a polypropylene film, or a polyethylene terephthalate film is preferred.

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

The photosensitive transfer material may include layers other than the above-mentioned layers (hereinafter also referred to as "other layers"), such as a contrast enhancement layer.
The contrast enhancement layer is described in paragraph 0134 of WO 2018/179640. The other layers are described in paragraphs 0194 to 0196 of JP 2014-85643 A. The contents of these publications are incorporated herein by reference.

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

[Method for producing photosensitive transfer material]
The method for producing the photosensitive transfer material according to the present disclosure is not particularly limited, and known production methods, for example, known methods for forming each layer, can be used.

Examples of a method for producing the above-mentioned photosensitive transfer material include a process of applying an intermediate layer composition to the surface of a temporary support and then drying the coating of the intermediate layer composition to form an intermediate layer, and a process of applying a photosensitive resin composition to the surface of the intermediate layer and then drying the coating of the photosensitive resin composition to form a photosensitive resin layer.

A photosensitive transfer material is produced by pressing a protective film onto the photosensitive resin layer of the laminate produced by the above-mentioned production method.
The method for producing a photosensitive transfer material according to the present disclosure preferably includes a step of providing a protective film in contact with the surface of the photosensitive resin layer opposite the temporary support side, thereby producing a photosensitive transfer material comprising a temporary support, an intermediate layer, a photosensitive resin layer, and a protective film.
After producing the photosensitive transfer material by the above-described production method, the photosensitive transfer material may be wound up to produce and store a roll-shaped photosensitive transfer material. The roll-shaped photosensitive transfer material can be provided in its original form for the step of laminating the photosensitive transfer material to a substrate in a roll-to-roll system, which will be described later.

The photosensitive transfer material according to the present disclosure can be suitably used in various applications requiring precise microfabrication by photolithography. After patterning the photosensitive resin layer, the photosensitive resin layer may be used as a coating for etching, or electroforming, primarily involving electroplating, may be performed. The cured film obtained by patterning may also be used as a permanent film, such as an interlayer insulating film, a wiring protection film, or a wiring protection film having an index matching layer. The photosensitive transfer material according to the present disclosure can also be suitably used in applications such as various wiring formation applications for semiconductor packages, printed circuit boards, and sensor substrates, touch panels, electromagnetic wave shielding materials, conductive films such as film heaters, liquid crystal sealants, and the formation of structures in the fields of micromachines and microelectronics.

In addition, the photosensitive transfer material according to the present disclosure also preferably has an embodiment in which the photosensitive resin layer is a colored resin layer containing a pigment.
In addition to the above-mentioned applications, the colored resin layer is suitable for applications such as forming colored pixels or black matrices of color filters used in liquid crystal displays (LCDs) and solid-state imaging devices (e.g., CCDs (charge-coupled devices) and CMOSs (complementary metal oxide semiconductors)).
The aspects of the colored resin layer other than the pigment are the same as those described above.

<Pigments>
The photosensitive resin layer may be a colored resin layer containing a pigment.
In order to protect the liquid crystal display window of recent electronic devices, a cover glass having a black frame-shaped light-shielding layer formed on the periphery of the back surface of a transparent glass substrate or the like is sometimes attached. A colored resin layer can 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 pigments of chromatic colors other than black and white. In particular, when a black pattern is to be formed, a black pigment is preferably selected as the pigment.

Any known black pigment (organic pigment, inorganic pigment, etc.) can be appropriately selected as the black pigment, provided that the effects of the present disclosure are not impaired. From the standpoint of optical density, suitable black pigments include, for example, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, and graphite, with carbon black being particularly preferred. From the standpoint of surface resistance, carbon black at least partially coated with a resin is preferred.

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

As a pigment other than black pigments, the white pigments described in paragraphs 0015 and 0114 of JP-A No. 2005-007765 can be used. Specifically, among the white pigments, inorganic pigments such as titanium oxide, zinc oxide, lithopone, precipitated calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, and barium sulfate are preferred, with titanium oxide or zinc oxide being more preferred, and titanium oxide being even more preferred. As the inorganic pigment, rutile or anatase titanium oxide is more preferred, with rutile titanium oxide being particularly preferred.
The surface of titanium oxide may be subjected to a silica treatment, alumina treatment, titania treatment, zirconia treatment, or organic treatment, or may be subjected to two or more of these treatments, which suppresses the catalytic activity of titanium oxide and improves heat resistance, fading resistance, etc.
From the viewpoint of reducing the thickness of the photosensitive resin layer after heating, the surface treatment of the titanium oxide is preferably at least one of alumina treatment and zirconia treatment, and particularly preferably both alumina treatment and zirconia treatment.

In addition, when the photosensitive resin layer is a colored resin layer, it is also preferable that the photosensitive resin layer further contains a chromatic pigment other than a black pigment and a white pigment from the viewpoint of transferability. When a chromatic pigment is contained, the particle size of the chromatic pigment is preferably 0.1 μm or less, and more preferably 0.08 μm or less, in terms of better dispersibility.
Examples of chromatic pigments include Victoria Pure Blue BO (Color Index (hereinafter referred to as C.I.) 42595), Auramine (C.I. 41000), Fat Black HB (C.I. 26150), Monolight 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.I. Pigment Red 146), Hosterbalm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), Fastel Pink B Supra (C.I. Pigment Red 81), Monastral Fast Blue (C.I. Pigment Blue 15), Monolight Fast Black B (C.I. Pigment Black 1) and Carbon, C.I. Pigment Red 97, C.I. Pigment Red 122, C.I. Pigment Red 149, C.I. Pigment Red 168, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Examples of suitable pigments include C.I. Pigment Green 7, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:4, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 64, and C.I. Pigment Violet 23. Among these, C.I. Pigment Red 177 is preferred.

When the photosensitive resin layer contains a pigment, the pigment content is preferably more than 3% by mass and not more than 40% by mass, more preferably more than 3% by mass and not more than 35% by mass, even more preferably more than 5% by mass and not more than 35% by mass, and particularly preferably 10% by mass or more and not more than 35% by mass, relative to the total mass of the photosensitive resin layer.

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

In addition, when the photosensitive resin layer contains a black pigment and is formed from a photosensitive resin composition, the black pigment (preferably carbon black) is preferably introduced into the photosensitive resin composition in the form of a pigment dispersion.
The dispersion may be prepared by premixing a black pigment and a pigment dispersant, adding the resulting mixture to an organic solvent (or vehicle), and dispersing the mixture using a disperser. The pigment dispersant may be selected depending on the pigment and solvent, and for example, a commercially available dispersant may be used. The vehicle refers to the medium in which the pigment is dispersed when a pigment dispersion is prepared, and is liquid, containing a binder component that maintains the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

There are no particular limitations on the dispersing machine, and examples include known dispersing machines such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers, and sand mills. Furthermore, fine pulverization may be achieved by utilizing frictional force through mechanical grinding. For details on dispersing machines and fine pulverization, please refer to the descriptions in "Pigment Dictionary" (Kunizo Asakura, 1st Edition, Asakura Shoten, 2000, pp. 438 and 310).

<Method of manufacturing deposition mask>
The method for producing a deposition mask according to the present disclosure is a method using the photosensitive transfer material for producing a deposition mask according to the present disclosure.
A method for producing a deposition mask according to the present disclosure includes preparing a metal layer having a first surface and a second surface opposite to the first surface (hereinafter also referred to as a "preparation step"); forming a temporary support; and forming a transfer layer having at least a photosensitive resin layer in this order, and the number of foreign matters having a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50 pieces/mm It is preferable that the method includes, in this order, laminating a photosensitive transfer material having a molecular weight of ³ or less with the metal layer, and arranging the transfer layer and the temporary support on the first surface of the metal layer (hereinafter also referred to as the "laminating step"); pattern-exposing the transfer layer (hereinafter also referred to as the "exposure step"); performing a development process on the transfer layer to form a resist pattern (hereinafter also referred to as the "developing step"); performing an etching process on the metal layer that is not covered with the resist pattern to form through holes extending from the first surface of the metal layer to the second surface of the metal layer (hereinafter also referred to as the "etching step"); and removing the resist pattern (hereinafter also referred to as the "removing step").

The following describes in detail each step in the deposition mask manufacturing method according to the present disclosure.

(Preparation process)
In the preparation step, a metal layer having a first surface and a second surface opposite to the first surface is prepared. The metal layer may be a known metal substrate (including commercially available products). The metal layer may be manufactured by a known method (e.g., casting, forging, sputtering, or plating).

The metal layer may have a single-layer structure or a multi-layer structure. Examples of metal elements contained in the metal layer include Cu, Ni, Fe, Cr, Mn, and Co. A portion or all of the metal layer may be an alloy. Examples of alloys include Ni—Co alloys and Fe—Ni alloys. The metal layer preferably contains at least one metal element selected from the group consisting of Cu, Ni, Fe, Cr, Mn, and Co, more preferably at least one metal element selected from the group consisting of Cu, Fe, and Ni, even more preferably Fe, and particularly preferably Fe and Ni. The metal layer may contain elements other than metal elements. Examples of elements other than metal elements include B, C, N, O, P, S, and Cl. The metal layer may be a metal substrate.
Among these, the metal in the metal layer is preferably nickel, a Ni—Co alloy, an Fe—Ni alloy, copper, etc., and is preferably an alloy containing 30% by mass to 45% by mass of nickel, and more preferably a metal whose main component is an alloy of 36% by mass of nickel and 64% by mass of iron, i.e., Invar. When the metal in the metal layer is Invar, the thermal expansion coefficient of the metal pattern is, for example, about 1.2×10 ⁻⁶ /°C.
The metal in the metal layer may also be, for example, an Fe—Ni—Co alloy (for example, Super Invar).

From the viewpoints of adhesion and resolution, the roughness Rmax of the first surface of the metal layer is preferably 0.5 μm to 5.0 μm, more preferably 0.60 μm to 4.0 μm, and particularly preferably 0.75 μm to 3.0 μm.
The second surface of the metal layer may have a roughness Rmax of 0.5 μm to 5.0 μm. The roughness Rmax of the first surface of the metal layer may be the same as or different from the roughness Rmax of the second surface of the metal layer.

In this disclosure, the roughness Rmax of the target surface is measured using a 3D optical profiler (New View 7300, manufactured by Zygo). First, the surface profile of the target surface is obtained. The measurement and analysis software used is the Microscope Application of MetroPro version 8.3.2. Next, the measurement and analysis software is used to display the Surface Map screen, and histogram data is obtained on the Surface Map screen. The roughness Rmax of the target surface is obtained from the obtained histogram data. Note that the roughness Rmax of the target surface corresponds to the maximum height of the roughness curve over the reference length.

In the preparation step, the metal layer may be prepared in a state in which it is disposed on a substrate. In other words, the preparation step may prepare a laminate including, in this order, a substrate and a metal layer having a second surface facing the substrate and a first surface located opposite the second surface. Examples of components of the substrate include glass and polymers. Examples of polymers include polyimide, cycloolefin polymer, polyethylene, polypropylene, polyethylene terephthalate, cellulose triacetate, polystyrene, and polycarbonate. The substrate is preferably a glass substrate or a resin film, and more preferably a resin film. Examples of resin films include polyimide film, cycloolefin polymer film, polyethylene film, polypropylene film, polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film.

From the viewpoint of the resolution of the through-holes, the average thickness of the metal layer is preferably 30 μm to 500 μm, more preferably 40 μm to 400 μm, and even more preferably 50 μm to 300 μm. The average thickness of the metal layer is calculated as the arithmetic mean of the thicknesses measured at five locations by cross-sectional observation using a scanning electron microscope (SEM).

(Laminating process)
In the laminating step, a photosensitive transfer material including, in this order, a temporary support and a transfer layer having at least a photosensitive resin layer, in which the number of foreign matter particles having a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50/ ^mm3 or less, is laminated to the metal layer, and the transfer layer and the temporary support are disposed in this order on the first surface of the metal layer.
Note that preferred aspects of the photosensitive transfer material are the same as the preferred aspects of the photosensitive transfer material for manufacturing a deposition mask according to the present disclosure described above.

The photosensitive transfer material and the metal layer may be bonded together by a known method. In the bonding process, it is preferable to press the photosensitive transfer material and the metal layer together. For example, it is preferable to laminate the photosensitive transfer material and the metal layer together by overlapping them and applying pressure and heat using a roll or other means. In the bonding process, known laminators such as laminators, vacuum laminators, and auto-cut laminators, which can increase productivity, may be used. The lamination temperature is preferably, for example, 70°C to 130°C. If the photosensitive transfer material includes a protective film, the bonding process is carried out after removing the protective film.

(Pressure application process)
After laminating the photosensitive transfer material and the metal layer, a pressure application step may be carried out. For example, the laminate obtained by laminating the photosensitive transfer material and the metal layer may be pressurized. The laminate to be pressed is preferably a laminate including a metal layer, a transfer layer, and a temporary support in this order. The laminate to be pressed may also be a laminate including a metal layer and a transfer layer in this order. For example, when the temporary support is peeled off after the lamination step, a laminate including a metal layer and a transfer layer in this order is formed. In the pressure application step, the laminate obtained by laminating the photosensitive transfer material and the metal layer may be pressure-treated in an autoclave. For example, pressure application can be carried out at 50°C, 0.5 MPa, and for 60 minutes. Pressurizing the laminate can improve the adhesion between the transfer layer and the metal layer, and improve the ability of the transfer layer to follow the unevenness of the surface of the metal layer. The pressure application step is preferably carried out before the exposure step.

(Exposure process)
In the exposure step, the transfer layer is subjected to pattern exposure. "Pattern exposure of the transfer layer" means that exposed and non-exposed portions are formed in the transfer layer by irradiating the transfer layer with light. The positional relationship between the exposed and non-exposed portions is determined, for example, depending on the shape of the target resist pattern.

The light used to pattern-expose the transfer layer is preferably irradiated onto the transfer layer in a direction from the transfer layer toward the metal layer. The light used to pattern-expose the transfer layer preferably contains at least one wavelength selected from the group consisting of 365 nm and 405 nm.

Examples of light sources include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (light-emitting diodes).

The exposure dose is preferably 5 mJ/cm ² to 200 mJ/cm ² , and more preferably 10 mJ/cm ² to 100 mJ/cm ² .

Examples of exposure methods include contact exposure and non-contact exposure. Examples of contact exposure methods include methods using a photomask. Examples of non-contact exposure methods include proximity exposure, lens or mirror projection exposure, and direct exposure using an exposure laser. Lens or mirror projection exposure may use an exposure machine with an appropriate lens numerical aperture (NA) depending on the required resolution and depth of focus. In direct exposure methods, direct imaging may be performed on the transfer layer, or reduced projection exposure may be performed on the transfer layer via a lens. The exposure process may be performed under atmospheric pressure, reduced pressure, or vacuum. The exposure process may be performed with a liquid such as water interposed between the light source and the transfer layer.

The exposure step may be performed before or after the removal of the temporary support, but is preferably performed before the removal of the temporary support in order to better demonstrate the effects of the present disclosure. If the exposure step is performed before the removal of the temporary support, the transfer layer may be exposed through the temporary support. In an exposure step using a photomask, the transfer layer may be pattern-exposed with the photomask in contact with the transfer layer, or the transfer layer may be pattern-exposed with the photomask close to the transfer layer without contacting it. To prevent contamination of the photomask due to contact between the photomask and the transfer layer and to avoid the influence of foreign matter attached to the photomask on the exposure, it is preferable to pattern-expose the transfer layer without removing the temporary support. If the transfer layer is pattern-exposed through the temporary support, the temporary support is preferably removed after the exposure step and before the development step.

(Temporary support peeling step)
The method for producing a vapor deposition mask according to the present disclosure preferably includes a temporary support peeling step of peeling the temporary support between the temporary support and the transfer layer.
The temporary support peeling step is preferably carried out after the exposure step and before the development step.
The method for peeling off 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 No. 2010-072589 can be used.

(Developing process)
In the development step, the transfer layer is subjected to a development treatment to form a resist pattern. The resolution of the resist pattern formed through the development step is thought to affect the resolution of the through-holes formed through the etching step described below, and the resolution of the through-holes is thought to affect the resolution of the pattern formed using a deposition mask.

The resist pattern is formed by removing the exposed or unexposed areas of the transfer layer. When the transfer layer contains a negative-type photosensitive resin layer, the unexposed areas of the transfer layer are typically removed by development, and the exposed areas of the transfer layer form a resist pattern. When the transfer layer contains a positive-type photosensitive resin layer, the exposed areas of the transfer layer are typically removed by developer, and the unexposed areas of the transfer layer form a resist pattern.

The development process is carried out using, for example, a developer. Examples of the developer include known developers (for example, the developer described in JP-A-5-72724). A preferred developer is an aqueous alkaline developer containing a compound with a pKa of 7 to 13 at a concentration of 0.05 mol/L to 5 mol/L. Examples of alkaline compounds contained in aqueous alkaline developers include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide). The developer may contain a water-soluble organic solvent. The developer may also contain a surfactant. Examples of preferred developers include the developer described in paragraph 0194 of WO 2015/093271.

The temperature of the developer is preferably between 20°C and 40°C.

Examples of development methods include puddle development, shower development, shower and spin development, and dip development. Shower development is a development method in which the developer is sprayed onto the target object in a shower. Preferred development methods include, for example, the development method described in paragraph 0195 of WO 2015/093271.

The developer and residue remaining after the development step are preferably removed by a known method. Methods for removing developer and residue include, for example, shower treatment and air knife treatment. In shower treatment, liquids such as water and detergent are sprayed onto the object using a shower. Residue may also be removed using a brush.

(Etching process)
In the etching step, an etching process is performed on the metal layer that is not covered with the resist pattern, and a through hole extending from the first surface of the metal layer to the second surface of the metal layer is formed.

The etching process may be a known method. Examples of etching processes include wet etching and dry etching (e.g., plasma etching). Examples of etching processes include the method described in paragraphs 0209 to 0210 of JP 2017-120435 A and the method described in paragraphs 0048 to 0054 of JP 2010-152155 A.

The etching process is preferably wet etching. In wet etching, an etching solution is typically used. The type of etching solution may be selected from acidic and alkaline etching solutions depending on the target to be etched. Examples of acidic etching solutions include aqueous solutions containing at least one acidic component selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid. Examples of acidic etching solutions include aqueous solutions containing the above-mentioned acidic component and at least one salt selected from the group consisting of ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a combination of multiple acidic components. Examples of alkaline etching solutions include aqueous solutions containing at least one alkaline component selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide). Examples of alkaline etching solutions include aqueous solutions containing the above-mentioned alkaline component and a salt (e.g., potassium permanganate). The alkaline component may be a combination of multiple alkaline components.
In particular, the etching solution used in the etching treatment preferably contains ferric chloride, from the viewpoint of further exerting the effects of the present disclosure.
The solubility of the resist pattern in a solution containing 40% by mass of ferric chloride at 45° C. is preferably 1 μm/min or less, and more preferably 0.5 μm/min or less. The lower limit is 0 μm/min.

The metal layer in the deposition mask manufactured by the deposition mask manufacturing method according to the present disclosure has a through hole extending from the first surface to the second surface. The metal layer may have multiple through holes. The depth of the through hole corresponds to the thickness of the metal layer. The through hole is typically defined by the inner surface of the metal layer. The through hole may be defined by one or more surfaces. The surface defining the through hole observed in cross-section may be linear or curved. The number, shape, and arrangement of the through holes are determined, for example, according to the desired pattern. The through holes extending from the first surface to the second surface form an opening in the first surface and an opening in the second surface. The diameter of the opening formed in the first surface corresponds to the diameter of the through hole in the first surface, as described below, and the diameter of the opening formed in the second surface corresponds to the diameter of the through hole in the second surface, as described below. Examples of shapes of the through holes (specifically, openings) observed in plan view include circular, elliptical, and rectangular. The shape of the through-holes observed in plan view is preferably quadrangular, and more preferably square or rectangular. When the shape of the through-holes observed in plan view is polygonal (e.g., quadrangular), some or all of the multiple corners of the polygon may be rounded.

The average diameter of the through holes on the second surface of the metal layer (hereinafter sometimes referred to as "average diameter of through holes D2") is smaller than the average diameter of the through holes on the first surface of the metal layer (hereinafter sometimes referred to as "average diameter of through holes D1"). In other words, the average diameter of the through holes D1 is larger than the average diameter of the through holes D2. For example, if the average diameter of the through holes D1 is larger than the average diameter of the through holes D2, substances that reach the first surface of the metal layer from the vaporization source can more easily enter the through holes through openings formed in the first surface of the metal layer. This results in, for example, improved productivity and pattern accuracy. The ratio of the average diameter of the through holes D2 to the average diameter of the through holes D1 (i.e., D2/D1) is preferably 0.8 or less, more preferably 0.4 or less, and even more preferably 0.3 or less. From the viewpoint of achieving high pattern resolution, the ratio of the average diameter D2 of the through holes to the average diameter D1 of the through holes (i.e., D2/D1) is preferably 0.01 or greater, more preferably 0.1 or greater, and even more preferably 0.15 or greater.

The average diameter of the through holes on the second surface of the metal layer (i.e., the average diameter D2 of the through holes) is 25 μm or less. When the average diameter D2 of the through holes is 25 μm or less, a pattern with high resolution is formed. From the perspective of achieving high pattern resolution, the average diameter D2 of the through holes is preferably 25 μm or less, more preferably 20 μm or less, and even more preferably 10 μm or less. There is no lower limit for the average diameter D2 of the through holes. The average diameter D2 of the through holes may be 5 μm, 1 μm, or 0.1 μm.

As long as the relationship "average diameter D2 of through holes" < "average diameter D1 of through holes" is satisfied, there are no restrictions on the average diameter D1 of the through holes. From the perspective of achieving high pattern resolution, the average diameter D1 of the through holes is preferably 15 μm to 100 μm, more preferably 20 μm to 50 μm, and even more preferably 20 μm to 30 μm. The lower limit of the average diameter D1 of the through holes may be 8 μm or 10 μm.

In the present disclosure, the average diameter of the through holes is calculated by taking the arithmetic mean of the diameters of 10 through holes measured based on an image obtained using a scanning electron microscope (SEM). In the present disclosure, the diameter of the through holes is defined as the maximum value of a line connecting any two points on the outline of a through hole (specifically, an opening) observed in a planar view. Because the average diameter D2 of the through holes is smaller than the average diameter D1 of the through holes, the outline of an opening formed on the second surface of the metal layer may be observed inside the outline of an opening formed on the first surface of the metal layer in a planar view of the first surface of the metal layer. The average diameter D1 of the through holes and the average diameter D2 of the through holes may be calculated based on the above observations.

As long as the relationship "average diameter D2 of the through holes" < "average diameter D1 of the through holes" is satisfied, the diameter of the through holes may change continuously or discontinuously in the direction from the first surface to the second surface. It is preferable that the diameter of the through holes gradually decrease in the direction from the first surface to the second surface.

(Removal process)
In the removing step, the resist pattern is removed. Examples of the removing method include a method of removing the resist pattern using a chemical treatment. A method of removing the resist pattern using a remover is preferred.

Examples of the removal solution include a removal solution containing an inorganic or organic alkaline component and water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solvent thereof. Examples of inorganic alkaline components include sodium hydroxide and potassium hydroxide. Examples of organic alkaline components include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

The resist pattern may be removed by immersing the laminate containing the resist pattern in a remover. The temperature of the remover is preferably 30°C to 80°C, and more preferably 50°C to 80°C. The immersion time is preferably 1 minute to 30 minutes. During the immersion method, the remover may be stirred.

The resist pattern may be removed, for example, by a spray method, shower method, or puddle method using a remover.

(Other processes)
The method for producing a deposition mask according to the present disclosure may further include other steps as necessary. When the metal layer of the deposition mask is formed on a base material, the method for producing a deposition mask according to the present disclosure may include removing the base material.

A method for manufacturing a vapor deposition mask is described with reference to FIG. 4. FIG. 4 is a schematic cross-sectional view showing a method for manufacturing a vapor deposition mask according to one embodiment. As shown in FIG. 4(a), a metal layer 10 having a first surface 10F and a second surface 10R located opposite the first surface 10F is prepared. As shown in FIG. 4(b), a photosensitive transfer material (not shown) and the metal layer 10 are bonded together, and a transfer layer 20 is placed on the first surface 10F of the metal layer 10. The average thickness of the transfer layer 20 is 50 μm or less. As shown in FIG. 4(c), the transfer layer 20 is pattern-exposed, and then a development process is performed on the transfer layer 20 to form a resist pattern 21. As shown in FIG. 4(d), a through-hole 10H is formed by etching the metal layer 10 not covered by the resist pattern 21. During the etching process, isotropic etching (i.e., etching that progresses in the depth direction of the metal layer 10 as well as in a direction perpendicular to the depth direction of the metal layer 10) occurs, forming a through-hole 10H having the cross-sectional shape shown in FIG. 4(d). As shown in FIG. 4(e), the resist pattern 21 is removed to obtain a deposition mask 100. The through-hole 10H formed in the metal layer 10 extends from the first surface 10F of the metal layer 10 to the second surface 10R of the metal layer 10. The through-hole 10H forms an opening 10FA in the first surface 10F of the metal layer 10 and an opening 10RA in the second surface 10R of the metal layer 10.

The deposition mask manufactured by the deposition mask manufacturing method according to the present disclosure may include components other than the metal layer, as necessary. Examples of components other than the metal layer include a frame. The frame can reinforce the deposition mask or improve the handleability of the deposition mask. The frame may be arranged around the through-hole in a planar view, or may be arranged on the outer periphery of the metal layer in a planar view. Examples of components of the frame include metals. Examples of metals include Fe-Ni alloys (e.g., Invar) and Fe-Ni-Co alloys (e.g., Super Invar).

The structure of a deposition mask manufactured by the deposition mask manufacturing method according to the present disclosure will be described with reference to Figures 1, 2, and 3. Figure 1 is a schematic plan view showing one embodiment of a deposition mask. Figure 2 is a schematic plan view showing an enlarged view of a through-hole in the deposition mask shown in Figure 1. Figure 3 is a schematic cross-sectional view showing an enlarged view of a through-hole in the deposition mask shown in Figure 1. The deposition mask 100 includes a metal layer 10 having a first surface 10F, a second surface 10R located opposite the first surface 10F, and through-holes 10H. The first surface of the metal layer 10 faces the viewer viewing Figures 1 and 2. The first surface 10F and the second surface 10R of the metal layer 10 face in opposite directions. As shown in Figures 1 and 2, the through-holes 10H are defined by a grid pattern formed by the metal layer 10, and the shape of the through-holes 10H observed in a plan view is rectangular. The reason why the outline of through hole 10H is observed double in Figure 2 is because the outline of an opening formed on second surface 10R of metal layer 10 (specifically, opening 10RA in Figure 3) is observed inside the outline of an opening formed on first surface 10F of metal layer 10 (specifically, opening 10FA in Figure 3). As shown in Figure 3, through hole 10H extends from first surface 10F of metal layer 10 to second surface 10R of metal layer 10. Through hole 10H forms opening 10FA on first surface 10F of metal layer 10 and opening 10RA on second surface 10R of metal layer 10. Through hole 10H is defined by the inner surface of metal layer 10, and the inner surface of metal layer 10 that defines through hole 10H is curved. The average diameter of the through holes 10H on the second surface 10R of the metal layer 10 is smaller than the average diameter of the through holes 10H on the first surface 10F of the metal layer 10. The diameter of the through holes 10H gradually decreases in the direction from the first surface 10F toward the second surface 10R.

A deposition mask manufactured by the deposition mask manufacturing method according to the present disclosure is preferably used in a pattern manufacturing method using a deposition method. In the deposition method, the deposition mask is preferably placed on the target with the second surface of the metal layer facing the target. When the second surface of the metal layer faces the target, a substance that reaches the first surface of the metal layer from the vaporization source easily enters the through-holes. The substance that enters the through-holes moves through the through-holes in the direction from the first surface to the second surface of the metal layer and adheres to the target. A pattern is formed when the substance that passes through the through-holes is deposited on the target. Examples of targets on which a pattern can be formed include glass substrates and resin films. The type of deposition method, deposition conditions, and type of substance to be deposited are determined, for example, depending on the desired pattern. A preferred deposition method is, for example, vacuum deposition. A preferred application of a deposition mask manufactured by the deposition mask manufacturing method according to the present disclosure is, for example, a method for manufacturing OLEDs.

The present disclosure will be described in detail below using examples. However, the present disclosure is not limited to the following examples. In the following description, unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass."

<Production of temporary support 1>
A temporary support including a polyester film having a thickness of 16 μm and a particle-containing layer having a thickness of 40 nm was produced by the following procedure.

(Particle-containing layer-forming composition 1)
The components were mixed according to the formulation shown below to obtain particle-containing layer-forming composition 1. After preparing particle-containing layer-forming composition 1, it was filtered through a 6 μm filter (F20, manufactured by Mahle Filter Systems Co., Ltd.) and then subjected to membrane degassing using a 2×6 Radial Flow Superphobic (manufactured by Polypore Co., Ltd.).

Acrylic polymer (AS-563A, manufactured by Daicel FineChem Co., Ltd., solid content 27.5% by mass): 167 parts by mass Nonionic surfactant (Naloracty CL95, manufactured by Sanyo Chemical Industries, Ltd., solid content 100% by mass): 0.7 parts by mass Anionic surfactant (Rapisol A-90, manufactured by NOF Corporation, diluted with water to a solid content of 1% by mass): 114.4 parts by mass Carnauba wax dispersion (Cellosol 524, manufactured by Chukyo Yushi Co., Ltd., solid content 30% by mass): 7 parts by mass Carbodiimide compound (Carbodilite V-02-L2, manufactured by Nisshinbo Chemical Co., Ltd., diluted with water to a solid content of 10% by mass) 20.9 parts by mass Matting agent (Snowtex XL, manufactured by Nissan Chemical Industries, Ltd., solid content 40% by mass, average particle size 50 nm): 2.8 parts by mass Water: 690.2 parts by mass

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

(Stretching and Coating)
The solidified unstretched film was subjected to sequential biaxial stretching by the following method to obtain a temporary support comprising a polyester film having a thickness of 16 μm and a particle-containing layer having a thickness of 40 nm.

(a) Longitudinal Stretching The unstretched film was stretched in the longitudinal direction (machine direction) by passing it between two pairs of nip rolls with different peripheral speeds. The preheating temperature was 75°C, the stretching temperature was 90°C, the stretching ratio was 3.4 times, and the stretching speed was 1300%/sec.

(b) Coating The particle-containing layer-forming composition 1 was applied to one surface of the longitudinally stretched film using a bar coater so that the thickness of the film would be 40 nm after formation.

(c) Transverse Stretching The film that had been subjected to the longitudinal stretching and coating was transversely stretched using a tenter under the following conditions.
Preheat temperature: 110°C
Stretching temperature: 120℃
Stretching ratio: 4.2 times Stretching speed: 50%/sec

(Heat Fixation and Heat Relaxation)
After the longitudinal and transverse stretching, the biaxially stretched film was heat-set under the following conditions.
Heat fixing temperature: 227℃
Heat setting time: 6 seconds

After heat setting, the tenter width was reduced and the film was heat relaxed under the following conditions.
Thermal relaxation temperature: 190℃
Thermal relaxation rate: 4%

(winding)
After heat setting and heat relaxation, both ends were trimmed, and the ends were extruded (knurled) to a width of 10 mm, and then wound up under a tension of 40 kg/m. The width was 1.5 m and the wound length was 6,300 m. The obtained film roll was designated as temporary support 1. The haze value of temporary support 1 was 0.2. The haze value was measured as the total light haze value using a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.). The thermal shrinkage rate after heating at 150°C for 30 minutes was 1.0% on the MD (machine direction) side and 0.2% on the TD (transverse direction, the direction perpendicular to the machine direction on the surface of the film). The film thickness of the particle-containing layer was measured from a cross-sectional TEM photograph and was 40 nm. The average particle size of the particles contained in the particle-containing layer was measured by the above-mentioned method using a transmission electron microscope (TEM) HT-7700 manufactured by Hitachi High-Technologies Corporation, and was found to be 50 nm.

<Temporary support 2>
The following was used as the temporary support 2.
Temporary support 2: Polyester film, 16QS62 manufactured by Toray Industries, Inc., thickness 16 μm

<Production of temporary support 3>
Temporary support 3 was produced in the same manner as in the method for producing temporary support 1, except that particle-containing layer-forming composition 1 in the method for producing temporary support 1 was changed to particle-containing layer-forming composition 2 shown below.

(Particle-containing total composition 2)
Acrylic polymer (AS-563A, Daicel Miraize Co., Ltd., solid content: 27.5% by mass): 167 parts by mass Nonionic surfactant (Naroacty CL95, Sanyo Chemical Industries, Ltd., solid content: 100% by mass): 0.7 parts by mass Anionic surfactant (Rapisol A-90, NOF Corporation, water dilution solution with a solid content concentration of 1% by mass): 55.7 parts by mass Carnauba wax dispersion (Cellosol 524, Chukyo Yushi Co., Ltd., solid content: 30% by mass) % by weight): 7 parts by weight; Carbodiimide compound (Carbodilite V-02-L2, Nisshinbo Chemical Inc., diluted with water to a solids concentration of 10% by weight): 20.9 parts by weight; Matting agent (Snowtex XL, Nissan Chemical Industries, Ltd., solids content: 40% by weight, average particle size: 50 nm): 2.8 parts by weight; Matting agent (Aerosil OX50, Nippon Aerosil Co., Ltd., solids content: 10% by weight, water dispersion, median diameter: 0.2 μm): 3.5 parts by weight; Water: 743 parts by weight

<Production of temporary support 4>
Temporary support 4 was produced in the same manner as temporary support 1, except that the thickness of the temporary support was changed to 25 μm.

<Production of temporary support 5>
The following was used as the temporary support 5.
Temporary support 5: polyethylene terephthalate film, A1517 manufactured by Toyobo Co., Ltd., thickness 16 μm

Example 1
(Production of photosensitive transfer material)
A photosensitive transfer material including, in this order, a temporary support 1, a cushion layer, an intermediate layer, a photosensitive resin layer, and a protective film was produced by the following procedure: The transfer layer 1 has a cushion layer, an intermediate layer, and a photosensitive resin layer, and the photosensitive resin layer is a negative photosensitive resin layer.

Composition A was prepared, containing the components listed in the "Cushion Layer" column in Table 1. Composition A was applied to temporary support 1 using a slit nozzle, and then dried at 80°C for 2 minutes to form a cushion layer. The thickness of the cushion layer is listed in Table 1.

Composition B containing the ingredients listed in the "Intermediate Layer" column in Table 1 was prepared. Composition B was applied onto the cushion layer using a slit nozzle, and then dried at 90°C for 2 minutes to form an intermediate layer. The thickness of the intermediate layer is listed in Table 1.

Composition C was prepared, containing the components listed in the "Photosensitive Resin Layer" column in Table 1. Composition C was applied onto the intermediate layer using a slit nozzle, and then dried at 80°C for 2 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer is listed in Table 1.

Finally, a protective film (16KS40, manufactured by Toray Industries, Inc., thickness: 16 μm) was placed on top of the photosensitive resin layer to obtain Photosensitive Transfer Material 1.

Subsequently, a deposition mask was produced using the obtained photosensitive transfer material 1 according to the following procedure.
An Invar substrate was prepared as a metal layer having a first surface and a second surface opposite the first surface. The first surface and the second surface face in opposite directions. The roughness Rmax of the first surface of the Invar substrate was 0.80 μm. The roughness Rmax of the second surface of the Invar substrate was 0.90 μm. The average thickness of the Invar substrate was 50 μm.
The protective film was peeled off from the transfer layer 1. Using a roll laminator, the photosensitive transfer material and the Invar substrate were bonded together under conditions of a temperature of 100°C, a linear pressure of 0.5 MPa, and a linear speed (lamination speed) of 4 m/min, and the transfer layer 1 (i.e., the photosensitive resin layer, intermediate layer, and cushion layer) and temporary support 1 were placed in this order on the first surface of the Invar substrate. The first surface of the Invar substrate was in contact with the photosensitive resin layer.

An exposure mask was placed in close contact with the exposed surface of the transfer layer. The exposure mask had multiple square light-shielding areas. The dimensions of each light-shielding area varied in 5 μm increments, ranging from 5 μm long x 5 μm wide to 100 μm long x 100 μm wide. The transfer layer was irradiated with light using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Nippon Kaken Co., Ltd., dominant wavelength: 365 nm). The exposure dose was adjusted so that the resist pattern shape obtained after development would reproduce the pattern shape of the photomask.

After peeling the temporary support 1 from the transfer layer 1, development was performed using a 1.0% by weight aqueous sodium carbonate solution at 28°C as the developer, yielding a resist pattern. Specifically, development consisted of showering for 30 seconds, removing the developer using an air knife, then showering with pure water for 30 seconds, and then performing an air knife treatment.

The Invar layer not covered by the resist pattern was etched using an etching solution containing ferric chloride at 45°C for 60 seconds, forming through-holes in the Invar substrate. The through-holes extended from the first surface of the Invar substrate toward the second surface of the Invar substrate. The resist pattern was removed using a 4% by weight sodium hydroxide solution to obtain a deposition mask. In the resulting deposition mask, the average diameter of the through-holes on the first surface of the Invar substrate was 28.0 μm, and the average diameter of the through-holes on the second surface of the Invar substrate was 7.0 μm.

<Examples 2 to 21 and Comparative Example 1>
In the production of the photosensitive transfer material, a photosensitive transfer material and a deposition mask were produced by the same procedure as in Example 1, except that the type of temporary support and the configuration of the transfer layer were changed according to the descriptions in Tables 1 to 5.

<Counting foreign matter>
The temporary support was peeled off from the obtained photosensitive transfer material. The peeled temporary support was observed in the thickness direction by transmission observation with an optical microscope over an area of 1 ^cm2 , and the number of foreign particles having a diameter of 1.0 μm to 10.0 μm was counted. The obtained number was divided by the thickness of the temporary support to obtain the number of foreign particles per unit volume of the temporary support.

<Evaluation>
The photosensitive transfer materials or deposition masks produced in the examples and comparative examples were used to evaluate the following items.

(Resolution)
The hole pattern obtained in the obtained deposition mask was observed with an optical microscope, and the smallest size of the pattern resolved in the deposition mask size was taken as the resolution. The smaller the smallest resolved pattern size, the better the resolution.

(linearity)
Of the obtained resist patterns, the resist pattern with the minimum resolution line width was observed using a scanning electron microscope (SEM), and the maximum value minus the minimum value of the line width (hereinafter referred to as "line width variation") was measured within a length range of 100 μm. Based on the line width variation, the linearity of the resist pattern was evaluated according to the following criteria.
A: The line width fluctuation value is less than 0.4 μm.
B: The line width fluctuation value is 0.4 μm or more and less than 0.7 μm.
C: The line width fluctuation value is 0.7 μm or more and less than 1.0 μm.
D: The fluctuation value of the line width is 1.0 μm or more and less than 1.5 μm.
E: The line width fluctuation value is 1.5 μm or more.

(Lamination properties)
The obtained photosensitive transfer material was laminated on a metal substrate having a surface roughness Rmax of 0.5 μm to 5.0 μm, and then the laminated laminate was observed from the temporary support side with an optical microscope to count the number of bubbles in an area of 25 ^mm2 .
A: 10 or less B: More than 10 and up to 20 C: More than 20

The evaluation results are summarized in Tables 4 and 5.

The following abbreviations shown in Tables 1 to 3 have the following meanings:
"M/B": ratio of the total mass of polymerizable compounds to the total mass of the polymer "Compound B1": benzyl methacrylate (BzMA)/methacrylic acid (MAA)/acrylic acid (AA) = 78/14.5/7.5 (mass ratio), Mw: 12,500, acid value: 187 mg KOH/g, glass transition temperature: 75°C, solid content: 30 mass%
"A-DCP": Tricyclodecane dimethanol diacrylate, NK ester A-DCP manufactured by Shin-Nakamura Chemical Co., Ltd.
"8UX-015A": UV-curable urethane acrylate, 8UX-015A manufactured by Taisei Fine Chemical Co., Ltd.
"TO-2349": Aronix TO-2349 manufactured by Toagosei Co., Ltd.
"Phenothiazinepril": Phenothiazine powder, manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd. "CBT-1": Carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.
"F-552": Fluorine-based surfactant, Megafac F-552 manufactured by DIC Corporation, solid content: 30% by mass (methyl ethyl ketone solution)
"MEK": methyl ethyl ketone "PVA": polyvinyl alcohol, PVA205 manufactured by Kuraray Co., Ltd.
"PVP": Polyvinylpyrrolidone, K-30 manufactured by Nippon Shokubai Co., Ltd.
"HPMC": Hydroxypropyl cellulose, Metrose 60SH-03 manufactured by Shin-Etsu Chemical Co., Ltd.
"F-444": Megafac F-444 manufactured by DIC Corporation, a fluorosurfactant. "MeOH": methanol. "Compound B2": styrene (St) / methyl methacrylate (MMA) / methacrylic acid (MAA) / methacrylic acid-glycidyl methacrylate (GMA-MAA) = 47.7/1.3/19/32, Mw: 20,000, acid value: 124 mg KOH/g, glass transition temperature: 76°C, solid content: 30% by mass.
It should be noted that "methacrylic acid-glycidyl methacrylate" refers to a structural unit obtained by reacting the carboxy group of a structural unit derived from methacrylic acid with the epoxy group of glycidyl methacrylate.
"Compound B3": styrene (St)/methyl methacrylate (MMA)/methacrylic acid (MAA) = 52/19/29, Mw: 50,000, acid value: 148 mg KOH/g, glass transition temperature: 131°C, solid content: 30% by mass
"Compound B4": styrene (St)/methyl methacrylate (MMA)/methacrylic acid (MAA)=45/19/36, Mw: 47,000, acid value: 183 mg KOH/g, glass transition temperature: 122°C, solid content: 30% by mass
"Compound B5": styrene (St)/methyl methacrylate (MMA)/methacrylic acid (MAA)=57/11/32, Mw: 49,000, acid value: 163 mg KOH/g, glass transition temperature: 140°C, solid content: 30% by mass
"BPE-500": (2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane, NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.
"Aronix M-270": Polypropylene glycol diacrylate, Aronix M-270 manufactured by Toagosei Co., Ltd.
"B-IMD": (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, B-CIM manufactured by Kurogane Kasei Co., Ltd.
"EAB-F": 4,4'-bis(diethylamino)benzophenone obtained from Sanyo Trading Co., Ltd. "Phenothiazine": manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. "Phenidone 1% MEK solution": methyl ethyl ketone solution containing 1% by mass of phenidone "Compound A": N-phenylcarbamoylmethyl-N-carboxymethylaniline, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. "LCV": leuco crystal violet, a dye that develops color in response to radicals, manufactured by Tokyo Chemical Industry Co., Ltd. "CBT-1": carboxybenzotriazole, CBT-1 manufactured by Johoku Chemical Industry Co., Ltd.
"MMPGAc": 1-methoxy-2-propyl acetate "MFG": 1-methoxy-2-propanol

Tables 4 and 5 show that the resolution of the deposition masks manufactured using the deposition mask manufacturing method of the example is superior to the resolution of the deposition masks manufactured using the deposition mask manufacturing method of the comparative example.

10: Metal layer 10F: First surface of metal layer 10FA: Opening formed in first surface of metal layer 10H: Through hole 10R: Second surface of metal layer 10RA: Opening formed in second surface of metal layer 20: Transfer layer 21: Resist pattern 100: Vapor deposition mask

Claims (14)

A temporary support and a transfer layer having at least a photosensitive resin layer in this order,
the number of foreign matters having a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50/ ^mm3 or less ;
the number of foreign matters having a diameter exceeding 10.0 μm per unit volume of the temporary support is 0/ ^mm3 ;
the photosensitive resin layer contains a photopolymerization initiator,
the thickness of the temporary support is 10 μm to 50 μm;
The thickness of the photosensitive resin layer is 0.5 μm to 10 μm.
Photosensitive transfer material for manufacturing deposition masks. A temporary support and a transfer layer having at least a photosensitive resin layer in this order,
The number of foreign particles having a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50/mm ³ is as follows:
the temporary support is a temporary support prepared by filtering,
the photosensitive resin layer contains a photopolymerization initiator,
the thickness of the temporary support is 10 μm to 50 μm;
The thickness of the photosensitive resin layer is 0.5 μm to 10 μm.
Photosensitive transfer material for manufacturing deposition masks. 3. The photosensitive transfer material for producing a deposition mask according to claim 1, wherein the L ^* value of the surface of the temporary support opposite to the transfer layer side measured by the SCE method is 1.5 or less. 4. The photosensitive transfer material for producing a deposition mask according to claim 1, wherein the temporary support has a thickness of 16 μm or less. 5. The photosensitive transfer material for producing a deposition mask according to claim 1 , wherein the transfer layer has a melt viscosity at 25° C. of 1.0×10 ⁵ Pa·s to 1.0×10 ⁸ Pa·s. 6. The photosensitive transfer material for producing a deposition mask according to claim 1 , wherein the photosensitive resin layer has a thickness of 4.8 μm or less. 7. The photosensitive transfer material for manufacturing a deposition mask according to claim 1 , wherein the transfer layer has, from the temporary support side, an intermediate layer and the photosensitive resin layer in this order. The photosensitive transfer material for manufacturing a deposition mask according to claim 7 , wherein the intermediate layer contains a water-soluble resin. 9. The photosensitive transfer material for manufacturing a deposition mask according to claim 8 , wherein the water-soluble resin contains polyvinyl alcohol. 10. The photosensitive transfer material for producing a deposition mask according to claim 8 , wherein the water-soluble resin contains polyvinylpyrrolidone. The photosensitive transfer material for producing a deposition mask according to any one of claims 8 to 10 , wherein the water-soluble resin contains a hydroxyalkyl cellulose compound. providing a metal layer having a first surface and a second surface opposite the first surface;
a photosensitive transfer material including a temporary support and a transfer layer having at least a photosensitive resin layer in this order, wherein the number of foreign matter particles having a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50/ ^mm3 or less, and the metal layer is bonded to the photosensitive transfer material, and the transfer layer and the temporary support are disposed in this order on the first surface of the metal layer;
patternwise exposing the transfer layer;
performing a development process on the transfer layer to form a resist pattern;
performing an etching process on the metal layer that is not covered with the resist pattern to form a through hole that extends from the first surface of the metal layer to the second surface of the metal layer;
removing the resist pattern ,
the number of foreign matters having a diameter exceeding 10.0 μm per unit volume of the temporary support is 0/ ^mm3 ;
the photosensitive resin layer contains a photopolymerization initiator,
the thickness of the temporary support is 10 μm to 50 μm;
The thickness of the photosensitive resin layer is 0.5 μm to 10 μm.
A method for manufacturing a deposition mask. providing a metal layer having a first surface and a second surface opposite the first surface;
A substrate including a temporary support and a transfer layer having at least a photosensitive resin layer in this order, and the number of foreign particles having a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50/mm ³ laminating the metal layer to a photosensitive transfer material having the following structure, and disposing the transfer layer and the temporary support in this order on the first surface of the metal layer;
patternwise exposing the transfer layer;
performing a development process on the transfer layer to form a resist pattern;
performing an etching process on the metal layer that is not covered with the resist pattern to form a through hole that extends from the first surface of the metal layer to the second surface of the metal layer;
removing the resist pattern,
the temporary support is a temporary support prepared by filtering,
the photosensitive resin layer contains a photopolymerization initiator,
the thickness of the temporary support is 10 μm to 50 μm;
The thickness of the photosensitive resin layer is 0.5 μm to 10 μm.
A method for manufacturing a deposition mask. 14. The method for manufacturing a deposition mask according to claim 12 , wherein the first surface of the metal layer has a roughness Rmax of 0.5 μm to 5.0 μm.