Photosensitive transfer material for forming vapor deposition mask and method for manufacturing vapor deposition mask

Abstract

The present invention aims to provide a photosensitive transfer material for manufacturing a deposition mask with excellent resolution and a method for manufacturing a deposition mask with excellent resolution. The photosensitive transfer material for manufacturing a deposition mask and a method for manufacturing a deposition mask using the above-described photosensitive transfer material are provided. The photosensitive transfer material for manufacturing a deposition mask sequentially comprises a temporary support and a transfer layer having at least a photosensitive resin layer. The number of foreign objects with a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50 or less per mm³.

Description

[Technical Field]

[0001] This disclosure relates to a photosensitive transfer material for manufacturing a deposition mask and a method for manufacturing a deposition mask. [Previous Technology]

[0002] Deposition methods using deposition masks are used, for example, in the manufacture of OLEDs (Organic Light Emitting Diodes). The deposition mask is used as a template for patterns formed by the deposition method. Vacuum deposition is known as a representative example of a deposition method. For example, in a vacuum deposition method using a deposition mask with through-holes, material vaporized from a vaporization source adheres to the object through the through-holes of the deposition mask disposed on the object, thereby forming a pattern.

[0003] Patent Document 1 discloses a method for forming a metal pattern, which includes: a step of preparing a laminate having a positive photosensitive resin layer formed of a photosensitive transfer material on a substrate; a step of exposing and developing the positive photosensitive resin layer to form a resin pattern having a cone shape; and a step of forming a cone-shaped 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.

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2021-172879

[0005] Improving the resolution of patterns formed using deposition masks (e.g., minimizing pattern size) can, for example, contribute to increasing pixel density in display devices including OLEDs. [Summary of the Invention]

[0006] The purpose of one embodiment of this disclosure is to provide a photosensitive transfer material for manufacturing a deposition mask with excellent resolution. The purpose of another embodiment of this disclosure is to provide a method for manufacturing a deposition mask with excellent resolution.

[0007] This disclosure includes the following aspects: <1> A photosensitive transfer material for manufacturing a deposition mask, which sequentially comprises a temporary support and a transfer layer having at least a photosensitive resin layer, wherein the number of foreign objects with a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50 or less / mm³. <2> The photosensitive transfer material for manufacturing a deposition mask as described in <1>, wherein the L* value of the side of the temporary support opposite to the transfer layer side, measured by SCE method, is 1.5 or less. <3> The photosensitive transfer material for manufacturing a deposition mask as described in <1> or <2>, wherein the thickness of the temporary support is 16 μm or less. <4> The photosensitive transfer material for manufacturing a deposition mask as described in any one of <1> to <3>, wherein the melt viscosity of the transfer layer at 25°C is 1.0 × 10⁵ Pa·s to 1.0 × 10⁸ Pa·s. <5> A photosensitive transfer material for manufacturing a deposition mask as described in any one of <1> to <4>, wherein the thickness of the photosensitive resin layer is 4.8 μm or less. <6> A photosensitive transfer material for manufacturing a deposition mask as described in any one of <1> to <5>, wherein the transfer layer sequentially comprises an intermediate layer and the photosensitive resin layer from the temporary support side. <7> A photosensitive transfer material for manufacturing a deposition mask as described in <5>, wherein the intermediate layer comprises a water-soluble resin. <8> A photosensitive transfer material for manufacturing a deposition mask as described in <7>, wherein the water-soluble resin comprises polyvinyl alcohol. <9> A photosensitive transfer material for manufacturing a deposition mask as described in <7> or <8>, wherein the water-soluble resin comprises polyvinylpyrrolidone. <10> A photosensitive transfer material for manufacturing a deposition mask as described in any one of <7> to <9>, wherein the water-soluble resin comprises a hydroxyalkyl cellulose compound. <11> A method for manufacturing a deposition mask, comprising the following steps in sequence: preparing a metal layer having a first surface and a second surface at a position opposite to the first surface; bonding a photosensitive transfer material to the metal layer and sequentially disposing a transfer layer and a temporary support on the first surface of the metal layer, wherein the photosensitive transfer material sequentially includes the temporary support and the transfer layer having at least a photosensitive resin layer, and the number of foreign objects with a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50 or less per mm³; exposing the transfer layer to a pattern; performing a development process on the transfer layer to form a photoresist pattern; performing an etching process on the metal layer not covered by the photoresist pattern to form a through hole extending from the first surface of the metal layer to the second surface of the metal layer; and removing the photoresist pattern. <12> The method for manufacturing the deposition mask as described in <11>, wherein the roughness Rmax of the first surface of the aforementioned metal layer is 0.5 μm to 5.0 μm. [Effects of the Invention]

[0008] According to one embodiment of the present invention, a photosensitive transfer material for manufacturing a deposition mask with excellent resolution is provided. According to another embodiment of the present invention, a method for manufacturing a deposition mask with excellent resolution is provided.

Implementation Method

[0010] The embodiments of this disclosure will now be described in detail. This disclosure is not limited to any of the following embodiments. The following embodiments may be appropriately modified within the scope of the purpose of this disclosure.

[0011] When describing embodiments of this disclosure with reference to the drawings, explanations of repeated constituent elements and symbols in the drawings are sometimes omitted. Constituent elements represented by the same symbols in the drawings refer to the same constituent elements. The ratios of dimensions in the drawings do not necessarily represent the ratios of actual dimensions.

[0012] In this disclosure, the numerical range represented by "~" indicates a range that includes the value recorded before "~" as a lower limit and includes the value recorded before "~" as an upper limit. In the numerical ranges described in stages in this disclosure, the upper or lower limit value recorded in a certain numerical range can be replaced with the upper or lower limit value of other numerical ranges described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value recorded in a certain numerical range can also be replaced with the values ​​shown in the embodiments.

[0013] In this disclosure, “(meth)acrylate” means acrylic, methacrylate, or both acrylic and methacrylate.

[0014] In this disclosure, “(meth)acrylate” means acrylate, methacrylate, or both acrylate and methacrylate.

[0015] In this disclosure, "(meth)acryl" means acrylonitrile, methacryl, or both acrylonitrile and methacryl.

[0016] In this disclosure, the amount of each component in the composition refers to the total amount of the corresponding multiple substances present in the composition when there are multiple substances in the composition corresponding to each component, unless otherwise specified.

[0017] In this disclosure, the term “step” includes not only independent steps, but also steps that cannot be clearly distinguished from other steps when the intended purpose can be achieved.

[0018] In this disclosure, the unsubstituted and unsubstituted groups (atomic groups) include unsubstituent groups (atomic groups) and substituent groups (atomic groups). For example, "alkyl" includes not only unsubstituent alkyl groups (i.e., unsubstituent alkyl groups) but also substituent alkyl groups (i.e., substituted alkyl groups).

[0019] In this disclosure, unless otherwise specified, “exposure” includes not only exposure using light, but also the depiction using particle beams such as electron beams and ion beams. Furthermore, examples of light used for exposure include the bright-line spectrum of mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and active light rays (active energy rays) such as electron beams.

[0020] The chemical structural formulas in this disclosure are sometimes written in simplified form with the hydrogen atom omitted.

[0021] In this disclosure, "mass%" has the same meaning as "weight%", and "parts of mass" has the same meaning as "parts of weight".

[0022] In this disclosure, a combination of two or more preferred states is a better state.

[0023] In this disclosure, "transparent" means that the average transmittance of visible light with wavelengths of 400nm to 700nm is above 80%, preferably above 90%.

[0024] In this disclosure, the average transmittance of visible light is a value measured using a spectrophotometer, such as the U-3310 spectrophotometer manufactured by Hitachi, Ltd.

[0025] Unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) in this disclosure are calculated using a gel permeation chromatography (GPC) analysis apparatus with columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by TOSOH CORPORATION) and with the solvent THF (tetrahydrofuran) and a differential refractometer, and with polystyrene as a standard substance.

[0026] In this disclosure, unless otherwise specified, the content of metal elements is measured using an inductively coupled plasma (ICP) spectrophotometer.

[0027] In this disclosure, unless otherwise specified, the refractive index is the value measured using an ellipsometry at a wavelength of 550 nm.

[0028] In this disclosure, unless otherwise specified, the hue system uses values ​​measured using a colorimeter (CR-221, manufactured by Minolta Co., Ltd.).

[0029] In this disclosure, "alkali solubility" means that the solubility of 100g of a 1% by mass aqueous solution of sodium carbonate at a liquid temperature of 22°C is greater than 0.1g.

[0030] In this disclosure, "water solubility" means that the solubility of 100g of water at pH 7.0 with a liquid temperature of 22℃ is greater than 0.1g.

[0031] In this disclosure, "solid components" refers to all components other than solvents.

[0032] <Photosensitive Transfer Material for Deposition Mask Manufacturing> The photosensitive transfer material for deposition mask manufacturing disclosed herein (hereinafter also simply referred to as "the photosensitive transfer material disclosed herein" or "photosensitive transfer material") sequentially comprises a temporary support and a transfer layer having at least a photosensitive resin layer, wherein the number of foreign objects with a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50 or less per mm³.

[0033] The photosensitive transfer material for manufacturing deposition masks disclosed herein has the following characteristics: the number of foreign objects with a diameter of 1.0 μm to 10.0 μm in each unit volume of the temporary support is 50 or less per mm 3. This can suppress the exposure barrier caused by the foreign objects blocking the exposure light. Even if the pattern is a fine line or a pattern of a certain size, the generation of defects can be suppressed to form a pattern. This provides a photosensitive transfer material for manufacturing deposition masks with excellent resolution.

[0034] The photosensitive transfer material disclosed herein has a temporary support and a transfer layer having at least a photosensitive resin layer, preferably having a temporary support, a transfer layer having at least a photosensitive resin layer, and a protective film in sequence. Furthermore, the photosensitive transfer material disclosed herein may have other layers between the temporary support and the photosensitive resin layer, or between the photosensitive resin layer and the protective film. Additionally, the photosensitive transfer material disclosed herein preferably has an intermediate layer and the photosensitive resin layer in sequence from the temporary support side. From the viewpoint of further enhancing the effects of this disclosure, the photosensitive transfer material disclosed herein is preferably a roll-shaped photosensitive transfer material.

[0035] In the photosensitive transfer material for manufacturing deposition masks disclosed herein, the number of foreign objects with a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50 or less per mm³. From the viewpoint of resolution and the linearity of the obtained pattern, 10 or less per mm³ is preferred, 5 or less per mm³ is more preferred, 2 or less per mm³ is further preferred, and 1 or less per mm³ is especially preferred. As in this disclosure, "foreign objects" are those capable of blocking exposure light, and examples include dust, particles such as dust particles existing on the surface and inside the temporary support, as well as aggregates containing components and coarse powder within the temporary support. Furthermore, the aforementioned foreign objects can also be anything other than spherical, such as amorphous particles and aggregates of particles. The "diameter of the foreign object" in this disclosure refers to the absolute maximum length of the foreign object as observed from the thickness direction of the temporary support in the measurement method described later.

[0036] The method for measuring the number of foreign objects with diameters of 1.0 μm to 10.0 μm per unit volume of the temporary support in this disclosure is as follows: The temporary support is observed from its thickness direction by transmission observation of a 1 cm² area using an optical microscope, and the number of foreign objects with diameters of 1.0 μm to 10.0 μm is counted. The obtained number is divided by the thickness of the temporary support, and this number is taken as the number of foreign objects per unit volume of the temporary support.

[0037] From the viewpoint of resolution and the linearity of the obtained pattern, the L* value of the side of the temporary support opposite to the transfer layer side, measured by SCE (Specular Component Exclude: except for positive reflection), is preferably 2.0 or less, more preferably 1.5 or less, further preferably 1.2 or less, and especially preferably 0.9 or less.

[0038] In this disclosure, the L* value of the measurement object surface (e.g., the side 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 of a total of 10 locations is measured at 3 cm intervals along the width direction of the measurement object surface. A D65 light source is used as the light source for the spectrophotometer. The L* values ​​of the 10 points measured by the SCE method are arithmetically averaged, and the resulting value is used as the L* value of the measurement object surface based on the SCE method.

[0039] From the viewpoint of adhesion and resolution, the melt viscosity of the photosensitive transfer material disclosed herein is preferably 5.0 × 10⁴ Pa·s to 5.0 × 10⁸ Pa·s, more preferably 1.0 × 10⁵ Pa·s to 1.0 × 10⁸ Pa·s, and particularly preferably 5.0 × 10⁵ Pa·s to 1.0 × 10⁷ Pa·s. In this disclosure, the "melt viscosity of the transfer layer" is defined as the melt viscosity of the layer furthest from the temporary support among one or more layers constituting the transfer layer. For example, when the transfer layer has a multilayer structure, the melt viscosity of the layer furthest from the temporary support among the plurality of layers contained in the transfer layer is called 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 called the "melt viscosity of the transfer layer". The melt viscosity of the transfer layer is adjusted, for example, according to the composition of the transfer layer. The melt viscosity of the transfer layer can be adjusted, for example, based on the type of polymer, the type of polymeric compound, the ratio of the polymeric compound content to the polymer content, and the type of additives. For instance, if the ratio of the polymeric compound content to the polymer content increases, the melt viscosity decreases; conversely, if the ratio decreases, the melt viscosity increases.

[0040] In this disclosure, melt viscosity is measured using a rheometer (e.g., a DHR-2 rheometer manufactured by TA Instruments), a 20 mm Φ parallel plate, and a peltier plate (Gap: approximately 0.5 mm) under the following conditions. The melt viscosity specified in this disclosure is the melt viscosity at 25°C. (1) Temperature: 20°C to 125°C (2) Heating rate: 5°C / minute (3) Frequency: 1 Hz (4) Strain: 0.5%

[0041] The following shows an example of the state of the photosensitive transfer material disclosed herein, but is not limited thereto. (1) "Temporary support / photosensitive resin layer / refractive index adjustment layer / protective film" (2) "Temporary support / photosensitive resin layer / protective film" (3) "Temporary support / intermediate layer / photosensitive resin layer / protective film" (4) "Temporary support / buffer layer / intermediate layer / photosensitive resin layer / protective film" In addition, in each of the above configurations, the photosensitive resin layer can be a positive photosensitive resin layer or a negative photosensitive resin layer, with a negative photosensitive resin layer being preferred. Also, it is preferred that the photosensitive resin layer is a colored resin layer. Among these, as the configuration of the photosensitive transfer material, the configurations of (2) to (4) above are preferred, the configurations of (3) or (4) above are preferred, and the configuration of (4) above is particularly preferred.

[0042] In the photosensitive transfer material, when the photosensitive resin layer is further provided with other layers on the side opposite to the temporary support, the total thickness of the other layers disposed on the side opposite to the temporary support of the photosensitive resin layer is preferably 0.1% to 30% of the thickness of the photosensitive resin layer, and more preferably 0.1% to 20%.

[0043] Hereinafter, an example of a specific implementation will be given to illustrate the photosensitive transfer material disclosed herein.

[0044] The elements constituting the photosensitive transfer material will be explained below.

[0045] [Temporary Support] The photosensitive transfer material disclosed herein has a temporary support. The temporary support system supports the laminate including the transfer layer and is a peelable support.

[0046] From the viewpoint that exposure of the photosensitive resin layer through the temporary support is possible during pattern exposure of the photosensitive resin layer, it is preferable that the temporary support has light transmittance. Furthermore, in this specification, "light transmittance" means that the transmittance of light at the wavelength used in pattern exposure is 50% or more. From the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, it is preferable that the transmittance of light at the wavelength (more preferably 365 nm) used in pattern exposure of the temporary support is 60% or more, and more preferably 70% or more. Additionally, the transmittance of the layer of the photosensitive transfer material is the ratio of the intensity of the emitted light that passes 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.

[0047] Examples of materials constituting the temporary support include glass substrates, resin films, and paper. From the viewpoints of strength, flexibility, and light transmittance, resin films are preferred. Examples of resin films include polyethylene terephthalate (PET) films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among these, PET films are preferred, and biaxially stretched PET films are even more preferred.

[0048] The thickness (layer thickness) of the temporary support is not particularly limited. From the viewpoints of strength as a support, flexibility required in bonding with the substrate for circuit wiring formation, and light transmittance required in the initial exposure step, the material can be selected accordingly. A thickness of 5 μm to 100 μm is preferred for the temporary support. From the viewpoints of ease of operation and versatility, a thickness of 10 μm to 50 μm is more preferred, 10 μm to 20 μm is further preferred, and 10 μm to 16 μm is particularly preferred. Furthermore, from the viewpoints of defect suppression, resolution, and linearity of the photoresist pattern, a thickness of 50 μm or less for the temporary support is preferred, 25 μm or less is more preferred, 20 μm or less is further preferred, and 16 μm or less is particularly preferred.

[0049] Furthermore, it is preferable that the film used as the temporary support is free from deformation, scratches, defects, etc., such as wrinkles. From the viewpoint of pattern formation when the pattern is exposed through the temporary support and the transparency of the temporary support, it is preferable that the number of particles, foreign matter, defects, precipitates, etc. contained in the temporary support is low. It is preferable that the number of particles, foreign matter, or defects with a diameter of 1 μm or more is 50 or less per 10 mm², more preferably 10 or less per 10 mm², further preferably 3 or less per 10 mm², and especially preferably 0 per 10 mm².

[0050] From the viewpoints of defect suppression, resolution, and transparency of the photoresist pattern, a low haze of the temporary support is preferable. Specifically, a haze value of 2% or less is preferable, 1.5% or less is more preferable, less than 1.0% is further preferable, and 0.5% or less is particularly preferable. The haze values ​​in this disclosure were measured using a haze meter (NDH-2000, manufactured by NIPPON DENSHOKU INDUSTRIES CO.,LTD.) according to the method of JIS K 7105:1981.

[0051] From the viewpoint of providing operability, a layer containing microparticles (lubricant layer) can be provided on the surface of the temporary support. The lubricant layer can be provided on one side or both sides of the temporary support. The diameter of the particles contained in the lubricant layer can be set, for example, from 0.05 μm to 0.8 μm. Furthermore, the thickness of the lubricant layer can be set, for example, from 0.05 μm to 1.0 μm.

[0052] From the viewpoints of transportability, defect suppression of the photoresist pattern, and resolution, it is preferable that the arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive resin layer side is higher than or equal to the arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive resin layer side. From the viewpoints of transportability, defect suppression of the photoresist pattern, and resolution, it is preferable that the arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive resin layer side is 100 nm or less, more preferably 50 nm or less, further preferably 20 nm or less, and especially preferably 10 nm or less. From the viewpoints of peelability of the temporary support, defect suppression of the photoresist pattern, and resolution, it is preferable that the arithmetic mean roughness Ra of the surface of the temporary support opposite to the photosensitive resin layer side is 100 nm or less, more preferably 50 nm or less, further preferably 20 nm or less, and especially preferably 10 nm or less. Furthermore, from the viewpoints of transportability, defect suppression of photoresist patterns, and resolution, it is preferable that the arithmetic mean roughness Ra of the surface opposite to the photosensitive resin layer side of the temporary support is 0 nm to 10 nm, and even more preferable that it is 0 nm to 5 nm.

[0053] The arithmetic mean roughness Ra of the surface of the temporary support or protective film in this disclosure is measured by the following method. The surface profile of the film is obtained by measuring the surface of the temporary support or protective film using a three-dimensional optical profilometer (New View 7300, manufactured by Zygo) under the following conditions. The measurement / analysis software used is the Microscope Application of MetroPro ver8.3.2. Next, the Surface Map screen is displayed using the aforementioned analysis software, and histogram data is obtained from the Surface Map screen. The arithmetic mean roughness is calculated from the obtained histogram data to obtain the Ra value of the surface of the temporary support or protective film. When the temporary support or protective film is adhered to a photosensitive resin layer, etc., the temporary support or protective film is peeled off from the photosensitive resin layer, and the Ra value of the surface on the peeled side is measured.

[0054] When the wound laminate is transported again by roll to roll, from the viewpoint of the peel resistance of the temporary support caused by the adhesion between the upper and lower laminates, the peel force of the temporary support, specifically, the peel force between the temporary support and the photosensitive resin layer or the buffer layer is preferably 0.5 mN / mm or more, and 0.5 mN / mm to 2.0 mN / mm is more preferred.

[0055] The peel force of the temporary support in this disclosure is measured as follows. A PET substrate with a copper layer is fabricated by sputtering a 200 nm thick copper layer on a 100 μm thick polyethylene terephthalate (PET) film. A protective film is peeled off from the fabricated photosensitive transfer material and laminated onto the aforementioned PET substrate with a copper layer under lamination conditions of 100°C lamination roller temperature, 0.6 MPa linear pressure, and 1.0 m / min linear speed (lamination speed). Next, after attaching adhesive tape (PRINTACK manufactured by Nitto Denko Corporation) to the surface of the temporary support, a laminate having at least a temporary support and a photosensitive resin layer on the PET substrate with a copper layer is cut into 70 mm × 10 mm pieces to produce a sample. The PET substrate side of the sample is fixed to a sample stage. Using a tensile compression tester (manufactured by IMADA SEISAKUSHO CO.,LTD., SV-55), the tape was stretched at 5.5 mm / s in a 180-degree direction to peel it from the photosensitive resin layer or buffer layer to the temporary support, and the force required for peeling (peel force) and adhesion force were measured.

[0056] Preferred examples of temporary supports are described, for example, in paragraphs 0017 to 0018 of Japanese Patent Application Publication No. 2014-85643, paragraphs 0019 to 0026 of Japanese Patent Application Publication No. 2016-27363, paragraphs 0041 to 0057 of International Publication No. 2012 / 081680, paragraphs 0029 to 0040 of International Publication No. 2018 / 179370, and paragraphs 0012 to 0032 of Japanese Patent Application Publication No. 2019-101405, the contents of which are incorporated herein by reference.

[0057] [Photosensitive Resin Layer] The photosensitive transfer material disclosed herein has a photosensitive resin layer. The photosensitive resin layer can be a positive photosensitive resin layer or a negative photosensitive resin layer, with a negative photosensitive resin layer being preferred. The negative photosensitive resin layer preferably comprises an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator, and more preferably, based on the total mass of the aforementioned photosensitive resin layer, it comprises: alkali-soluble resin: 10% to 90% by mass; ethylene unsaturated compound: 5% to 70% by mass; and photopolymerization initiator: 0.01% to 20% by mass. As a positive photosensitive resin layer, there is no limitation, and known positive photosensitive resin layers can be used. The positive photosensitive resin layer preferably comprises an acid-degradable resin, i.e., a polymer having acid groups protected by acid-degradable groups as constituent units, and a photoacid generator. Furthermore, it is preferable that the positive photosensitive resin layer comprises a resin having phenolic hydroxyl groups as constituent units and a quinone diazide compound. It is even more preferable that the positive photosensitive resin layer is a chemically amplified positive photosensitive resin layer comprising a polymer having acid groups protected by acid-degrading groups as constituent units and a photoacid generating agent.

[0058] The components will be described in order below. In addition, when referred to simply as "photosensitive resin layer", it refers to both the positive photosensitive resin layer and the negative photosensitive resin layer.

[0059] Polymerizable Compounds It is preferable that the negative photosensitive resin layer contains polymerizable compounds. Furthermore, in this specification, "polymerizable compound" refers to a compound that polymerizes under the action of the photopolymerization initiator described later, and is different from the aforementioned alkali-soluble resin.

[0060] The polymerizable group in the polymerizable compound is not particularly limited as long as it participates in the polymerization reaction. Examples include groups with vinyl, acrylonitrile, methacrylonitrile, styrene, and maleicadiimino groups, which have vinyl unsaturated groups; and groups with cationic polymerizable groups, such as epoxy and oxybutane groups. Groups with vinyl unsaturated groups are preferred as polymerizable groups, and acrylonitrile or methacrylonitrile are even more preferred. Furthermore, it is preferred that the polymerizable compound contains vinyl unsaturated compounds, and it is even more preferred that it contains (meth)acrylate compounds.

[0061] From the viewpoint of resolution and pattern forming properties, it is preferable that the photosensitive resin layer contains a polymeric compound with two or more functions (a multifunctional polymeric compound), and it is even more preferable that it contains a polymeric compound with three or more functions. Here, a polymeric compound with two or more functions refers to a compound having two or more polymeric groups in one molecule. Furthermore, from the viewpoint of excellent resolution and peelability, it is preferable that the number of polymeric groups in one molecule of the polymeric compound is six or less.

[0062] From the viewpoint of achieving a better balance between photosensitivity, resolution, and peelability of the photosensitive resin layer, it is preferable that the negative photosensitive resin layer contains difunctional or trifunctional vinyl unsaturated compounds, and even more preferable that it contains difunctional vinyl unsaturated compounds. From the viewpoint of excellent peelability, it is preferable that the content of difunctional or trifunctional vinyl unsaturated compounds in the negative photosensitive resin layer is 60% by mass or more relative to the total content of vinyl unsaturated compounds, more preferably 70% by mass, and even more preferably 90% by mass or more. The upper limit is not particularly limited and can be 100% by mass. That is, all vinyl unsaturated compounds contained in the negative photosensitive resin layer can be difunctional vinyl unsaturated compounds.

[0063] From the viewpoint of resolution and pattern formation, it is preferable that the negative photosensitive resin layer contains a polymeric compound having a polyoxyalkylene structure, and even more preferable that it contains a polymeric compound having a polyoxyethylene structure. Examples of polymeric compounds having a polyoxyalkylene structure include polyalkylene glycol di(meth)acrylate, which will be described later.

[0064] - Ethylene unsaturated compound B1 - It is preferable that the negative photosensitive resin layer contains ethylene unsaturated compound B1, which has an aromatic ring and two ethylene unsaturated groups. Ethylene unsaturated compound B1 is a difunctional ethylene unsaturated compound among the above-mentioned ethylene unsaturated compounds, which has one or more aromatic rings in one molecule.

[0065] In the negative photosensitive resin layer, from the viewpoint of superior resolution, it is preferable that the mass ratio of the content of vinyl unsaturated compound B1 to the content of vinyl unsaturated compounds is 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and especially preferably 60% by mass or more. The upper limit is not particularly limited, but from the viewpoint of peelability, 99% by mass or less is preferable, 95% by mass or less is more preferably 90% by mass or less, and especially preferably 85% by mass or less.

[0066] Examples of aromatic rings in the vinyl unsaturated compound B1 include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings; aromatic heterocycles such as thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings; and condensed rings of these. Aromatic hydrocarbon rings are preferred, and benzene rings are even more preferred. Furthermore, the aforementioned aromatic rings may have substituents. The vinyl unsaturated compound B1 may have only one aromatic ring or may have two or more aromatic rings.

[0067] From the viewpoint of improving resolution by suppressing the swelling of the negative photosensitive resin layer caused by the developer, it is preferable that the vinyl unsaturated compound B1 has a bisphenol structure. Examples of bisphenol structures include the bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), the bisphenol F structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane), and the bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), with the bisphenol A structure being preferred.

[0068] As an vinyl unsaturated compound B1 having a bisphenol structure, examples include compounds having a bisphenol structure and two polymerizable groups (preferably (meth)acrylic acid) bonded to both ends of the bisphenol structure. The two polymerizable groups at both ends of the bisphenol structure can be directly bonded or bonded via one or more alkoxy groups. As the alkoxy groups added to both ends of the bisphenol structure, ethoxy or propoxy groups are preferred, with ethoxy being more preferred. The number of alkoxy groups added to the bisphenol structure is not particularly limited, but 4 to 16 per molecule is preferred, and 6 to 14 is more preferred. Regarding the vinyl unsaturated compound B1 having a bisphenol structure, it is described in paragraphs 0072 to 0080 of Japanese Patent Application Publication No. 2016-224162, the contents of which are incorporated herein by reference.

[0069] As the vinyl unsaturated compound B1, a difunctional vinyl unsaturated compound having a bisphenol A structure is preferred, and 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane is even more preferred. Examples of 2,2-bis(4-((meth)propenoxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methpropenoxydiethoxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methpropenoxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methpropenoxypentethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methpropenoxydolodecetoxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd.), and 2,2-bis(4-(methpropenoxydolodecetetoxy)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.).

[0070] As an ethylene unsaturated compound B1, it is possible to use a compound represented by the following formula (Bis).

[0071] [Chemical 1]

[0072] In formula (Bis), R1 and R2 independently represent hydrogen atoms or methyl groups, A is C2H4, B is C3H6, n1 and n3 are independent integers from 1 to 39, and n1+n3 is an integer from 2 to 40; n2 and n4 are independent integers from 0 to 29, and n2+n4 is an integer from 0 to 30; the repeating units of -(AO)- and -(BO)- can be arranged randomly or in blocks. Furthermore, in the case of blocks, either -(AO)- or -(BO)- can be on the bisphenol structure side. In a single-state sample, it is preferable that n1+n2+n3+n4 is an integer from 2 to 20, more preferably an integer from 2 to 16, and even more preferably an integer from 4 to 12. Furthermore, it is better for n 2 + n 4 to be an integer from 0 to 10, better for an integer from 0 to 4, even better for an integer from 0 to 2, and best for 0.

[0073] Vinyl unsaturated compound B1 can be used alone or in combination with two or more. From the viewpoint of superior resolution, it is preferable that the content of vinyl unsaturated compound B1 in the negative photosensitive resin layer is 10% by mass or more, and more preferably 20% by mass or more, relative to the total mass of the negative photosensitive resin layer. The upper limit is not particularly limited, but from the viewpoint of transferability and edge melting (the phenomenon of components in the negative photosensitive resin layer seeping out from the ends of the photosensitive transfer material), it is preferable that it is 70% by mass or less, and more preferably 60% by mass or less.

[0074] The negative photosensitive resin layer may contain ethylene unsaturated compounds other than the ethylene unsaturated compound B1 mentioned above. The ethylene unsaturated compounds other than ethylene unsaturated compound B1 are not particularly limited and can be appropriately selected from known compounds. For example, compounds having one ethylene unsaturated group in one molecule (monofunctional ethylene unsaturated compounds), difunctional ethylene unsaturated compounds without an aromatic ring, and ethylene unsaturated compounds with three or more functions can be cited.

[0075] Examples of monofunctional vinyl unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloxyethyl succinate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate and phenoxyethyl (meth)acrylate.

[0076] Examples of difunctional vinyl unsaturated compounds without an aromatic ring include alkyl glycol di(meth)acrylate, polyalkyl glycol di(meth)acrylate, amine ester di(meth)acrylate, and trimethylolpropane diacrylate. Examples of alkyl glycol di(meth)acrylates include tricyclodecanediethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecanediethanol 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 amine ester di(meth)acrylates include propylene oxide-modified amine ester di(meth)acrylate and ethylene oxide and propylene oxide-modified amine ester di(meth)acrylate. Examples of 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.).

[0077] Examples of trifunctional or higher ethylene unsaturated compounds include, for example, dinepentetreol (tri / tetra / penta / hexa)methacrylate, neopentetreol (tri / tetra)methacrylate, trimethylolpropane tri(methacrylate), ditrimethylolpropane tetra(methacrylate), trimethylolethane tri(methacrylate), isocyanurate tri(methacrylate), glycerol tri(methacrylate), and epoxide-modified forms thereof. The term "(tri / tetra / penta / hexa)methacrylate" encompasses the concepts of tri(methacrylate), tetra(methacrylate), penta(methacrylate), and hexa(methacrylate), while "(tri / tetra)methacrylate" encompasses the concepts of tri(methacrylate) and tetra(methacrylate). In one state, it is preferable that the negative photosensitive resin layer contains the aforementioned vinyl unsaturated compound B1 and a vinyl unsaturated compound with three or more functions; it is even more preferable that it contains the aforementioned vinyl unsaturated compound B1 and two or more vinyl unsaturated compounds with three or more functions. In this case, it is preferable that the mass ratio of vinyl unsaturated compound B1 to the vinyl unsaturated compound with three or more functions is (total mass of vinyl unsaturated compound B1) : (total mass of vinyl unsaturated compound with three or more functions) = 1:1 to 5:1, more preferably 1.2:1 to 4:1, and further preferably 1.5:1 to 3:1. Furthermore, in one state, it is preferable that the negative photosensitive resin layer contains the aforementioned vinyl unsaturated compound B1 and two or more vinyl unsaturated compounds with three or more functions.

[0078] Examples of epoxide-modified compounds that are trifunctional or higher ethylene unsaturated compounds include caprolactone-modified (meth)acrylate compounds (such as KAYARAD DPCA-20 manufactured by Nippon Kayaku Co., Ltd., and A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxide-modified (meth)acrylate compounds (such as KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL 135 manufactured by DAICEL-ALLNEX LTD.), ethoxylated glycerol triacrylates (such as A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.), and ARONIX TO-2349 (TOAGOSEI). (Manufactured by TOAGOSEI CO.,LTD.), ARONIX M-520 (manufactured by TOAGOSEI CO.,LTD.), and ARONIX M-510 (manufactured by TOAGOSEI CO.,LTD.).

[0079] Furthermore, as an ethylene unsaturated compound other than ethylene unsaturated compound B1, an ethylene unsaturated compound having an acid group as described in paragraphs 0025 to 0030 of Japanese Patent Application Publication No. 2004-239942 may be used.

[0080] From the viewpoint of resolution and linearity, the ratio of the content of the vinyl unsaturated compound Mm in the negative photosensitive resin layer to the content of the alkali-soluble resin Mb, Mm / Mb, is preferably 1.0 or less, more preferably 0.9 or less, and particularly preferably 0.5 or more and 0.9 or less. Furthermore, from the viewpoint of curability and resolution, it is preferable that the vinyl unsaturated compound in the negative photosensitive resin layer includes a (meth)acrylic acid compound. Moreover, from the viewpoint of curability, resolution, and linearity, it is preferable that the vinyl unsaturated compound in the negative photosensitive resin layer includes a (meth)acrylic acid compound, and that the content of the acrylic acid compound relative to the total mass of the aforementioned (meth)acrylic acid compound contained in the negative photosensitive resin layer is 60% by mass or less.

[0081] The molecular weight (weight average molecular weight (Mw) of the vinyl unsaturated compound containing vinyl unsaturated compound B1) is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

[0082] The vinyl unsaturated compound may be used alone or in combination with two or more. The content of the vinyl unsaturated compound in the negative photosensitive resin layer is preferably 10% to 70% by mass relative to the total mass of the negative photosensitive resin layer, more preferably 20% to 60% by mass, and even more preferably 20% to 50% by mass.

[0083] Photopolymerization Initiator: It is preferable that the negative photosensitive resin layer contains a photopolymerization initiator. A photopolymerization initiator is a compound that initiates the polymerization of ethylene unsaturated compounds upon exposure to active light such as ultraviolet light, visible light, and X-rays. There are no particular limitations on the photopolymerization initiator; known photopolymerization initiators can be used. Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators. From the viewpoint of resolution and pattern formation, it is preferable that the negative photosensitive resin layer is a photoradical polymerization initiator.

[0084] Examples of photoradical polymerization initiators include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenyl ketone structure, photopolymerization initiators having an α-hydroxyalkylphenyl ketone structure, photopolymerization initiators having a phosphine oxide structure, photopolymerization initiators having an N-phenylglycine structure, and bimidazole compounds.

[0085] As a photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of Japanese Patent Application Publication No. 2011-95716 and paragraphs 0064 to 0081 of Japanese Patent Application Publication No. 2015-14783 can be used.

[0086] Examples of photoradical polymerization initiators include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, (p,p'-dimethoxybenzyl)anisyl ester, TAZ-110 (trade name: manufactured by Midori Kagaku Co., Ltd.), benzophenone, TAZ-111 (trade name: manufactured by Midori Kagaku Co., Ltd.), Irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad 651 and 369 (trade name: manufactured by IGM Resins BV), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0087] Commercially available products that serve as photoradical polymerization initiators include, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetone-1-(O-acetylgoxime) (trade name: IRGACURE OXE-02, manufactured by BASF), IRGACURE OXE-03 (manufactured by BASF), and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-olyl)phenyl]-1-butanone (trade name: Omnirad 379EG, IGM Resins). Omnirad 907 (manufactured by IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-oxophyllylprop-1-one (trade name: Omnirad 907, manufactured by IGM Resins BV), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionic)benzyl]phenyl}-2-methylprop-1-one (trade name: Omnirad 127, manufactured by IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-oxophyllylphenyl)butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenylprop-1-one (trade name: Omnirad 1173, manufactured by IGM Resins BV), 1-hydroxycyclohexylphenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins BV). Omnirad 651 (manufactured by IGM Resins BV), 2,2-dimethoxy-1,2-diphenylethyl-1-one (trade name: Omnirad 651, manufactured by IGM Resins BV), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819, manufactured by IGM Resins BV), and oxime ester-based photopolymerization initiators (trade name: Lunar 6, manufactured by DKSH Japan). KK manufactures), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: B-CIM, manufactured by Hampford) and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.).

[0088] A photocationic polymerization initiator (photoacid generator) is a compound that generates acid upon exposure to active light. As a photocationic polymerization initiator, a compound that generates acid upon exposure to active light with a wavelength of 300 nm or higher, preferably 300–450 nm, is preferred, but its chemical structure is not limited. Furthermore, regarding photocationic polymerization initiators that do not directly react to active light with a wavelength of 300 nm or higher, as long as they are compounds that generate acid upon exposure to active light with a wavelength of 300 nm or higher by being used in conjunction with a sensitizer, they can also be used in combination with the sensitizer for better results. As a photocationic polymerization initiator, a photocationic polymerization initiator that generates acid with a pKa of 4 or lower is preferred, a photocationic polymerization initiator that generates acid with a pKa of 3 or lower is more preferred, and a photocationic polymerization initiator that generates acid with a pKa of 2 or lower is particularly preferred. The lower limit of pKa is not specifically defined, but for example, -10.0 or higher is preferred.

[0089] Examples of photocationic polymerization initiators include ionic and nonionic photocationic polymerization initiators. Examples of ionic photocationic polymerization initiators include onium salts such as diaryl monazine salts and triaryl strontium salts, as well as quaternary ammonium salts. Examples of ionic photocationic polymerization initiators include those described in paragraphs 0114 to 0133 of Japanese Patent Application Publication No. 2014-85643.

[0090] Examples of nonionic photocationic polymerization initiators include trichloromethyl-s-triazine derivatives, diazomethane compounds, amide sulfonate compounds, and oxime sulfonate compounds. As trichloromethyl-s-triazine derivatives, diazomethane compounds, and amide sulfonate compounds, compounds described in paragraphs 0083 to 0088 of Japanese Patent Application Publication No. 2011-221494 may be used. Furthermore, as oxime sulfonate compounds, compounds described in paragraphs 0084 to 0088 of International Patent Publication No. 2018 / 179640 may be used.

[0091] The negative photosensitive resin layer may contain only one photopolymerization initiator, or it may contain two or more. The content of the photopolymerization initiator in the negative photosensitive resin layer is not particularly limited, but it is preferable that it is 0.1% by mass or more relative to the total mass of the negative photosensitive resin layer, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more. The upper limit is not particularly limited, but it is preferable that it is 10% by mass or less relative to the total mass of the negative photosensitive resin layer, and more preferably 5% by mass or less.

[0092] Alkali-soluble resin: It is preferable that the negative photosensitive resin layer contains an alkali-soluble resin. Furthermore, in this specification, "alkali-soluble" means that the solubility of 100g of a 1% by mass aqueous solution of sodium carbonate at a liquid temperature of 22°C is 0.1g or more. There are no particular limitations on the alkali-soluble resin; for example, known alkali-soluble resins used as etching resists can be preferred. Also, it is preferable that the alkali-soluble resin is an adhesive polymer. As an alkali-soluble resin, an alkali-soluble resin having acid groups is preferred. Among these, polymer A, described later, is preferred as an alkali-soluble resin.

[0093] - Polymer A - As an alkali-soluble resin, it is preferable to include polymer A. From the viewpoint of improving resolution by suppressing the swelling of the photosensitive resin layer caused by the developer, it is preferable that the acid value of polymer A is 220 mg KOH / g or less, more preferably less than 200 mg KOH / g, and further preferably less than 190 mg KOH / g. The lower limit of the acid value of polymer A is not particularly limited, but from the viewpoint of improving developability, 60 mg KOH / g or more is preferable, 120 mg KOH / g or more is more preferable, 150 mg KOH / g or more is further preferable, and 170 mg KOH / g or more is particularly preferable.

[0094] Furthermore, the acid value is the mass [mg] of potassium hydroxide required to neutralize 1g of the sample; in this specification, the unit is stated 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 polymer A can be adjusted by the types of constituent units constituting polymer A and the content of constituent units containing acid groups.

[0095] It is preferable that the weight average molecular weight of polymer A is 5,000 to 500,000. From the viewpoint of improving resolution and developability, it is preferable to set the weight average molecular weight to 500,000 or less. It is even better to set the weight average molecular weight to 100,000 or less, further better to set it to 60,000 or less, and particularly better to set it to 50,000 or less. On the other hand, from the viewpoint of controlling the properties of the developed aggregates and the properties of the unexposed film such as edge melting and chipping, it is preferable to set the weight average molecular weight to 5,000 or more. It is preferable to set the weight average molecular weight to 10,000 or more, further better to set it to 20,000 or more, and particularly better to set it to 30,000 or more. Edge melting refers to the ease with which the photosensitive resin layer overflows from the end face of the roll when the photosensitive transfer material is rolled into a roll. Chipping refers to the ease with which chips scatter when the unexposed film is cut with a cutter. If the chips adhere to the upper surface of the photosensitive resin layer, they will be transferred to the mask in subsequent exposure steps, resulting in a defective product. A dispersion of polymer A of 1.0 to 6.0 is preferred, 1.0 to 5.0 is more preferred, 1.0 to 4.0 is further preferred, and 1.0 to 3.0 is even more preferred. In this disclosure, molecular weight is a value measured using gel permeation chromatography. Furthermore, dispersion is the ratio of weight-average molecular weight to number-average molecular weight (weight-average molecular weight / number-average molecular weight).

[0096] From the viewpoint of suppressing the deterioration of line width or resolution when the focus position deviates during exposure, it is preferable that the negative photosensitive resin layer contains a monomer component having an aromatic hydrocarbon group as polymer A. Furthermore, examples of such aromatic hydrocarbon groups include substituted or unsubstituted phenyl groups, or substituted or unsubstituted aralkyl groups. The content ratio 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, further 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. As an upper limit, it is not particularly limited, but preferably 95% by mass or less, more preferably 85% by mass or less. Furthermore, when multiple polymers A are contained, the content ratio of the monomer component having an aromatic hydrocarbon group is determined as a weight average.

[0097] Examples of monomers having aromatic hydrocarbon groups include monomers having aralkyl groups, styrene, and polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tributoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimers, styrene trimers, etc.). Among these, monomers having aralkyl groups or styrene are preferred. In one sample, when the monomer component having an aromatic hydrocarbon group 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, further preferably 30% to 40% by mass, and especially preferably 30% to 35% by mass, based on the total mass of all monomer components.

[0098] As an aralkyl group, examples include substituted or unsubstituted phenylalkyl groups (except benzyl), or substituted or unsubstituted benzyl groups, with substituted or unsubstituted benzyl groups being preferred.

[0099] Examples of monomers containing phenyl alkyl groups include phenyl ethyl (meth)acrylate.

[0100] Examples of monomers containing a benzyl group include (meth)acrylates such as benzyl (meth)acrylate and benzyl chloro (meth)acrylate; and vinyl monomers such as vinyl benzyl chloride and vinyl benzyl alcohol. Among these, benzyl (meth)acrylate is preferred. In one sample, when the monomer component containing an aromatic hydrocarbon group in polymer A is benzyl (meth)acrylate, the content ratio of the benzyl (meth)acrylate monomer component is preferably 50% to 95% by mass, more preferably 60% to 90% by mass, further preferably 70% to 90% by mass, and especially preferably 75% to 90% by mass, based on the total mass of all monomer components.

[0101] It is preferable that polymer A, which contains a monomer component having an aromatic hydrocarbon group, is obtained by polymerizing the monomer having an aromatic hydrocarbon group with at least one first monomer and / or at least one second monomer described later.

[0102] It is preferable to obtain polymer A, which does not contain monomer components having aromatic hydrocarbon groups, by polymerizing at least one of the first monomers described later, and even more preferable to obtain it by copolymerizing at least one of the first monomers with at least one of the second monomers described later.

[0103] The first monomer is a monomer having a carboxyl group in its 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 half-ester. Among these, (meth)acrylic acid is preferred. The content of the first monomer in polymer A is preferably 5% to 50% by mass based on the total mass of all monomer components, more preferably 10% to 40% by mass, and further preferably 15% to 30% by mass.

[0104] The copolymerization ratio of the first monomer is preferably 10% to 50% by mass, based on the total mass of all monomer components. From the viewpoints of good developability and control of edge melting, setting the above copolymerization ratio to 10% by mass or more is preferred, 15% by mass or more is more preferred, and 20% by mass or more is even more preferred. From the viewpoints of high resolution of the photoresist pattern and the shape of the hem, and further from the viewpoints of chemical resistance of the photoresist pattern, setting the above copolymerization ratio to 50% by mass or less is preferred, and from these viewpoints, 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.

[0105] The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in its molecule. Examples of the second monomer include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tributyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, etc. (meth)acrylates; vinyl acetate and other vinyl alcohol esters; and (meth)acrylonitrile, etc. Among these, methyl methacrylate, 2-ethylhexyl methacrylate, and n-butyl methacrylate are preferred, with methyl methacrylate being particularly preferred. The proportion of the second monomer in polymer A is preferably 5% to 60% by mass, more preferably 15% to 50% by mass, and even more preferably 20% to 45% by mass, based on the total mass of all monomer components.

[0106] From the viewpoint of suppressing the deterioration of linewidth or resolution when the focus position deviates during exposure, it is preferable to contain monomers having aralkyl groups and / or styrene as monomers. For example, copolymers containing methacrylic acid, benzyl methacrylate, and styrene, or copolymers containing methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene are preferred. In one sample, polymer A is preferably a polymer containing 25% to 40% by mass of monomers having aromatic hydrocarbon groups, 20% to 35% by mass of a first monomer, and 30% to 45% by mass of a second monomer. In another sample, it is preferable to contain 70% to 90% by mass of monomers having aromatic hydrocarbon groups and 10% to 25% by mass of a first monomer.

[0107] Polymer A may have any one of a straight-chain structure, a branched structure, and an alicyclic structure in its side chain. By using a monomer containing a group having a branched structure in its side chain or a monomer containing a group having an alicyclic structure in its side chain, a branched structure or an alicyclic structure can be introduced into the side chain of polymer A. The group having an alicyclic structure can be monocyclic or polycyclic. Specific examples of monomers containing a group having a branched structure in their side chains include isopropyl methacrylate, isobutyl methacrylate, butyl methacrylate, tert-butyl methacrylate, isoamyl methacrylate, pentyl methacrylate, isoamyl methacrylate, 2-octyl methacrylate, 3-octyl methacrylate, and octyl methacrylate. Among these, isopropyl methacrylate, isobutyl methacrylate, or butyl methacrylate are preferred, and isopropyl methacrylate or butyl methacrylate are even more preferred. Examples of monomers containing a group having an alicyclic structure in the side chain include monomers having a single-ring aliphatic hydrocarbon group, monomers having a multi-ring aliphatic hydrocarbon group, and (meth)acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. As more specific examples, one could cite (meth)acrylate (bicyclo[2.2.1]heptyl-2) ester, (meth)acrylate-1-adamantyl ester, (meth)acrylate-2-adamantyl ester, (meth)acrylate-3-methyl-1-adamantyl ester, (meth)acrylate-3,5-dimethyl-1-adamantyl ester, (meth)acrylate-3-ethyladamantyl ester, (meth)acrylate-3-methyl-5-ethyl-1-adamantyl ester, (meth)acrylate-3,5,8-triethyl-1-adamantyl ester, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl ester, (meth)acrylate-2-methyl-2-adamantyl ester, (meth)acrylate-2-ethyl-2-adamantyl ester. 3-hydroxy-1-adamantyl ester of (meth)acrylate, octahydro-4,7-methylindene-5-yl ester of (meth)acrylate, octahydro-4,7-methylindene-1-yl methyl ester of (meth)acrylate, 1-menthol ester of (meth)acrylate, tricyclodecane of (meth)acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl ester of (meth)acrylate, 3,7,7-trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl ester of (meth)acrylate, (nor)camphenyl ester of (meth)acrylate, isocamphenyl ester of (meth)acrylate, fumarate of (meth)acrylate, 2,2,5-trimethylcyclohexyl ester of (meth)acrylate, cyclohexyl ester of (meth)acrylate, etc.Among these (meth)acrylates, cyclohexyl (meth)acrylate, (nor)camphenyl (meth)acrylate, (isocamphenyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, fumarate, 1-mentholyl (meth)acrylate, or tricyclodecane (meth)acrylate are preferred, and cyclohexyl (meth)acrylate, (nor)camphenyl (meth)acrylate, (isocamphenyl (meth)acrylate, 2-adamantyl (meth)acrylate, or tricyclodecane (meth)acrylate are particularly preferred.

[0108] Polymer A may be used alone or in combination with two or more polymers. When two or more polymers are used in combination, it is preferable to use two polymers A containing monomer components with aromatic hydrocarbon groups or to use a polymer A containing monomer components with aromatic hydrocarbon groups and a polymer A without monomer components with aromatic hydrocarbon groups. In the latter case, it is preferable that the proportion of polymer A containing monomer components with aromatic hydrocarbon groups is 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more relative to all polymers A.

[0109] The synthesis of polymer A is preferably carried out by adding an appropriate amount of free radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution prepared by diluting one or more of the monomers described above with solvents such as acetone, methyl ethyl ketone, or isopropanol, and heating and stirring. Sometimes, a portion of the mixture is added dropwise to the reaction solution while the synthesis is being carried out. After the reaction is completed, solvent is sometimes added further to adjust to the desired concentration. In addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization can also be used as synthesis methods.

[0110] It is preferable that the glass transition temperature (Tg) of polymer A is 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, the deterioration of linewidth or resolution when the focus position deviates during exposure can be suppressed. From this point of view, a Tg of 130°C or lower for polymer A is more preferable, 120°C or lower is further preferable, and 110°C or lower is particularly preferable. Furthermore, from the viewpoint of improving edge melt resistance, it is preferable to use polymer A with a Tg of 30°C or higher. From this point of view, a Tg of 40°C or higher for polymer A is more preferable, 50°C or higher is further preferable, 60°C or higher is particularly preferable, and 70°C or higher is optimal.

[0111] Furthermore, from the viewpoint of sensitivity and resolution, it is preferable that the photosensitive resin layer (preferably a negative photosensitive resin layer) contains a polymer with crosslinking groups, and it is even more preferable that the polymer containing crosslinking groups is an alkali-soluble resin. As for the polymer with crosslinking groups, from the viewpoint of developability, sensitivity, and resolution, a polymer with polymerizable groups is preferable, a polymer with vinyl unsaturated groups is even more preferable, an acrylic resin with vinyl unsaturated groups is further preferable, and an acrylic resin containing constituent units with vinyl unsaturated groups is particularly preferable. As for the polymerizable group, it is not particularly limited as long as it is a group that participates in the polymerization reaction, for example, groups with vinyl unsaturated groups such as vinyl, acrylonitrile, methacrylamide, styrene, and maleic anhydride; and groups with cationic polymerizable groups such as epoxy and oxybutane. Furthermore, as for the polymer with crosslinking groups, from the viewpoint of developability, sensitivity, and resolution, polymer A with crosslinking groups is preferable.

[0112] The negative photosensitive resin layer may contain resins other than alkali-soluble resins. Examples of resins other than alkali-soluble resins include acrylic resins, styrene-acrylic acid copolymers (wherein the styrene content is 40% by mass or more), polyurethane resins, polyvinyl alcohol, polyethylene formaldehyde, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0113] The alkali-soluble resin can be used alone or in combination with two or more other resins. The ratio of the alkali-soluble resin to the total mass of the negative photosensitive resin layer is preferably in the range of 10% to 90% by mass, more preferably 30% to 70% by mass, and even more preferably 40% to 60% by mass. From the viewpoint of controlling development time, it is preferable to set the ratio of the alkali-soluble resin to the negative photosensitive resin layer to 90% by mass or less. On the other hand, from the viewpoint of improving edge melting resistance, it is preferable to set the ratio of the alkali-soluble resin to the negative photosensitive resin layer to 10% by mass or more.

[0114] Compounds with Unshared Electron Pairs From the viewpoint of adhesion to the conductive layer, it is preferable that the aforementioned photosensitive resin layer contains a compound with unshared electron pairs. As compounds with unshared electron pairs, from the viewpoint of adhesion to the conductive layer, compounds containing at least nitrogen, oxygen, or sulfur atoms are preferred; heterocyclic compounds, thiols, or disulfides are more preferred; heterocyclic compounds are further preferred; and nitrogen-containing heterocyclic compounds are particularly preferred.

[0115] The heterocycle in the heterocyclic compound can be any type of heterocycle, including monocyclic and polycyclic heterocycles. Examples of heteroatoms in the heterocyclic compound include nitrogen, oxygen, and sulfur. It is preferable that the heterocyclic compound has at least one atom selected from the group consisting of nitrogen, oxygen, and sulfur atoms, and it is even more preferable that it has a nitrogen atom.

[0116] Examples of heterocyclic compounds include, for instance, triazole compounds, benzotriazole compounds, tetraazole compounds, thiadiazole compounds, triazole compounds, razotanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, benzo[a]azole compounds, or pyrimidine compounds. Among these, from the viewpoint of adhesion to the conductive layer, it is preferable that the heterocyclic compound is selected from at least one compound from the group consisting of triazole compounds, benzotriazole compounds, tetraazole compounds, thiadiazole compounds, triazole compounds, razotanine compounds, thiazole compounds, benzimidazole compounds, and benzo[a]azole compounds; it is even more preferable that it is selected from at least one compound from the group consisting of triazole compounds, benzotriazole compounds, tetraazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzo[a]azole compounds; it is further preferable that it is selected from at least one compound from the group consisting of triazole compounds and tetraazole compounds; and triazole compounds are particularly preferred.

[0117] The following are preferred examples of heterocyclic compounds. Examples of triazole and benzotriazole compounds include the following compounds.

[0118] [Chemistry 2]

[0119] [Chemistry 3]

[0120] The following compounds can be cited as examples of tetrazolium compounds.

[0121] [Chemical 4]

[0122] [Chemistry 5]

[0123] The following compounds can be cited as examples of thiadiazole compounds.

[0124] [Chemical 6]

[0125] As triterpenoid compounds, the following compounds can be cited as examples.

[0126] [Chemistry 7]

[0127] The following compounds can be cited as examples of cyclotannin compounds.

[0128] [Chemistry 8]

[0129] The following compounds can be cited as examples of thiazole compounds.

[0130] [Chemistry 9]

[0131] The following compounds can be cited as examples of benzothiazole compounds.

[0132] [Chemistry 10]

[0133] The following compounds can be cited as examples of benzimidazole compounds.

[0134] [Chemical 11]

[0135] [Chemical 12]

[0136] The following compounds can be cited as examples of benzo[a]azole compounds.

[0137] [Chemistry 13]

[0138] Aliphatic thiols are preferably used as thiols. Monofunctional or polyfunctional aliphatic thiols (i.e., aliphatic thiols with two or more functions) are preferably used as aliphatic thiols. Examples of polyfunctional aliphatic thiols include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyroxyl)butane, neopentyltetrol tetra(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyroxylethyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptobutyrate), tris[(3-mercaptopropyroxyl)ethyl]isocyanurate, and trimethylolpropane... Examples of monofunctional aliphatic thiols include alkyltris(3-mercaptopropionate), neopentyltetra(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dinepentyltetra(3-mercaptopropionate), ethylene glycol dithiopropionate, 1,4-bis(3-mercaptobutyrooxy)butane, 1,2-ethylenedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(epenylethyldithio)diethylthiol, meso-2,3-dimercaptosuccinic acid, and di(mercaptoethyl) ether. Examples of monofunctional aliphatic thiols include 1-octylthiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

[0139] As disulfide compounds, examples include 2-(4'-alkoxylinyl dithio)benzothiazole, 2,2'-benzothiazole disulfide, bis(2-benzoaminophenyl) disulfide, 1,1-thiobis(2-naphthol), bis(2,4,5-trichlorophenyl) disulfide, 4,4'-dithioalkoxylinyl, 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-isobutylthioamine disulfide, and diphenyl disulfide.

[0140] Furthermore, from the viewpoint of the close contact with the conductive layer, it is preferable that the molecular weight of the compound having unshared electron pairs is less than 1,000, more preferably 50 to 500, even more preferably 50 to 200, and especially preferably 50 to 115.

[0141] The photosensitive resin layer may contain only one compound with mispaired electron pairs, or it may contain two or more compounds. From the viewpoint of adhesion to the conductive layer, the content of the compound with mispaired electron pairs relative to the total mass of the photosensitive resin layer is preferably 0.01% to 20% by mass, more preferably 0.1% to 10% by mass, further preferably 0.3% to 8% by mass, and especially preferably 0.5% to 5% by mass.

[0142] Pigment: From the viewpoints of visibility of the exposed and unexposed areas, the visibility of the developed pattern, and resolution, it is preferable for the photosensitive resin layer to contain pigment. It is even better to contain pigments with a maximum absorption wavelength of 450 nm or higher within the wavelength range of 400 nm to 780 nm during color development, and whose maximum absorption wavelength changes with acids, alkalis, or free radicals (also simply referred to as "pigment N"). While the detailed mechanism is not yet fully understood, the presence of pigment N improves adhesion to adjacent layers (e.g., the temporary support and the first resin layer), resulting in superior resolution.

[0143] In this specification, the phrase "the maximum absorption wavelength of the pigment changes due to acid, alkali, or free radicals" can refer to any of the following states: a pigment in a chromogenic state that is decolorized by acid, alkali, or free radicals; a pigment in a decolorized state that is chromogenic by acid, alkali, or free radicals; or a pigment in a chromogenic state that changes to another hue. Specifically, pigment N can be a compound that changes from a decolorized state to a chromogenic state upon exposure, or a compound that changes from a chromogenic state to a decolorized state upon exposure. In this case, it can be a pigment whose chromogenic or decolorized state changes upon exposure to generate acid, alkali, or free radicals within the photosensitive resin layer, and these factors act. It can also be a pigment whose chromogenic or decolorized state changes upon exposure to changes in the state (e.g., pH) within the photosensitive resin layer due to acid, alkali, or free radicals. Furthermore, it can also be a pigment whose chromogenic or decolorized state changes upon direct stimulation by acid, alkali, or free radicals without exposure.

[0144] From the viewpoint of visibility and resolution of both the exposed and non-exposed areas, it is preferable that pigment N is a pigment whose maximum absorption wavelength changes due to acid or free radicals, and even more preferable that the maximum absorption wavelength changes due to free radicals. From the viewpoint of visibility and resolution of both the exposed and non-exposed areas, it is preferable that the photosensitive resin layer contains both pigment N (whose maximum absorption wavelength changes due to free radicals) and photoradical polymerization initiator. Furthermore, from the viewpoint of visibility of both the exposed and non-exposed areas, it is preferable that pigment N is a pigment that develops color through acid, alkali, or free radicals.

[0145] As an example of the color-developing mechanism of pigment N in this disclosure, a free radical reactive pigment, acid reactive pigment or base reactive pigment (e.g., colorless pigment) can be described as developing color by free radicals, acids or bases generated by the photoradical polymerization initiator, photocationic polymerization initiator (photoacid generator) or photobase generator after exposure to a photosensitive resin layer.

[0146] From the viewpoint of visibility of the exposed and unexposed parts, it is preferable that the maximum absorption wavelength of pigment N in the wavelength range of 400 nm to 780 nm is 550 nm or more, 550 nm to 700 nm is more preferable, and 550 nm to 650 nm is even more preferable.

[0147] The maximum absorption wavelength of pigment N was obtained by measuring the transmission spectrum of a solution containing pigment N (liquid temperature 25°C) in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) under atmospheric conditions and detecting the wavelength (maximum absorption wavelength) where the intensity of light becomes minimal in the above wavelength range.

[0148] Examples of pigments that develop or decolorize upon exposure include colorless compounds. Examples of pigments that decolorize upon exposure include colorless compounds, diarylmethane pigments, acetylene pigments, sigmazone pigments, iminonaphthoquinone pigments, azomethine pigments, and anthraquinone pigments. From the viewpoint of visibility of both the exposed and unexposed areas, colorless compounds are preferred as pigment N.

[0149] Examples of colorless compounds include colorless compounds having a triarylmethane skeleton (triarylmethane pigments), colorless compounds having a spiropyran skeleton (spiropyran pigments), colorless compounds having a fluorescent yellow parent skeleton (fluorescent yellow parent system pigments), colorless compounds having a diarylmethane skeleton (diarylmethane pigments), colorless compounds having a rhodamine lactone skeleton (rhodamine lactone pigments), colorless compounds having an indolephthalide skeleton (indolephthalide pigments), and colorless compounds having a colorless golden yellow amine skeleton (colorless golden yellow amine pigments). Among these, triarylmethane pigments or fluorescent yellow parent system pigments are preferred, and colorless compounds having a triphenylmethane skeleton (triphenylmethane pigments) or fluorescent yellow parent system pigments are even more preferred.

[0150] From the viewpoint of visibility of both the exposed and non-exposed areas, it is preferable for the colorless compound to have a lactone ring, a sultine ring, or a sulfonyl ring. This allows the lactone ring, sultine ring, or sulfonyl ring of the colorless compound to react with a free radical generated by a photoradical polymerization initiator or an acid generated by a photocationic polymerization initiator, thereby changing the colorless compound to a closed-ring state and thus decolorizing it, or to change the colorless compound to an open-ring state and thus making it colored. It is preferable for the colorless compound to have a lactone ring, sultine ring, or sulfonyl ring, and for the lactone ring, sultine ring, or sulfonyl ring to develop color through ring-opening by a free radical or acid; it is even more preferable for the compound to have a lactone ring, and for the lactone ring to develop color through ring-opening by a free radical or acid.

[0151] As a pigment N, examples include the following dyes and colorless compounds. Among pigments N, specific examples of dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinaldine red, rose bengal, metanil yellow, thymol sulfonphthalein, xylenol blue, methyl orange, p-methyl red, Congo red, benzopurpurine 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.), and Oil Pink #312 (manufactured by Orient Chemical Industries). Oil Red 5B (manufactured by Orient Chemical Industries Co., Ltd.), Oil Scarlet #308 (manufactured by Orient Chemical Industries Co., Ltd.), Oil Red OG (manufactured by Orient Chemical Industries Co., Ltd.), Oil Red RR (manufactured by Orient Chemical Industries Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industries Co., Ltd.), Spilon Red BEH Special (manufactured by Hodogaya Chemical Co., Ltd.) (Manufactured by Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulfonated rhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

[0152] Among pigments N, specific examples of colorless compounds include p,p',p”-hexamethyltriaminetriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), crystal violet lactone, malachite green lactone, benzoyl colorless methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)amino fluorescent yellow precursor, 2-anilino-3-methyl-6-(N-ethyl-p-tolyl) fluorescent yellow precursor, 3,6-dimethoxy fluorescent yellow precursor, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino) fluorescent yellow precursor, 3-(N-cyclohexyl-N-methylamino)-6- Methyl-7-aniline fluorescent yellow parent material, 3-(N,N-diethylamino)-6-methyl-7-aniline fluorescent yellow parent material, 3-(N,N-diethylamino)-6-methyl-7-aniline fluorescent yellow parent material, 3-(N,N-diethylamino)-6-methyl-7-chlorofluorescent yellow parent material, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorescent yellow parent material, 3-(N,N-diethylamino)-7-(4-chloroaniline)fluorescent yellow parent material, 3-(N,N-diethylamino)-7-chlorofluorescent yellow parent material 3-(N,N-diethylamino)-7-benzylamino fluorescent yellow parent compound, 3-(N,N-diethylamino)-7,8-benzofluoro yellow parent compound, 3-(N,N-dibutylamino)-6-methyl-7-aniline fluorescent yellow parent compound, 3-(N,N-dibutylamino)-6-methyl-7-aniline fluorescent yellow parent compound, 3-piperidinyl-6-methyl-7-aniline fluorescent yellow parent compound, 3-pyrrolidinyl-6-methyl-7-aniline fluorescent yellow parent compound, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalene Esters, 3,3-bis(1-n-butyl-2-methylindole-3-yl)phthalolide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalolide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindole-3-yl)-4-azaphthalolide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindole-3-yl)phthalolide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]-yamagata-3-one.

[0153] From the viewpoints of visibility of the exposed and unexposed areas, the visibility and resolution of the developed pattern, it is preferable that pigment N is a pigment whose maximum absorption wavelength changes due to free radicals, and even better that pigments develop color through free radicals. As pigment N, colorless crystal violet, crystal violet lactone, brilliant green, or Victoria blue naphthalene sulfonate are preferred.

[0154] A single pigment may be used, or two or more pigments may be used. From the viewpoint of visibility of the exposed and unexposed areas, visibility of the developed pattern, and resolution, the pigment content relative to the total mass of the photosensitive resin layer is preferably 0.1% by mass or more, more preferably 0.1% to 10% by mass, further preferably 0.1% to 5% by mass, and especially preferably 0.1% to 1% by mass. Furthermore, from the viewpoint of visibility of the exposed and unexposed areas, visibility of the developed pattern, and resolution, the pigment N content relative to the total mass of the photosensitive resin layer is preferably 0.1% by mass or more, more preferably 0.1% to 10% by mass, further preferably 0.1% to 5% by mass, and especially preferably 0.1% to 1% by mass.

[0155] The content of pigment N refers to the amount of pigment that makes all pigment N contained in the photosensitive resin layer appear in a colored state. Hereinafter, a method for quantifying the content of pigment N will be described using a pigment that appears colored by free radicals as an example. Two solutions were prepared by dissolving 0.001 g or 0.01 g of pigment in 100 mL of methyl ethyl ketone. A photoradical polymerization initiator (trade name: Irgacure OXE01, BASF Japan Ltd.) was added to each of the obtained solutions, and the solutions were irradiated with 365 nm light to generate free radicals, thereby making all pigments appear in a colored state. Subsequently, under atmospheric conditions, the absorbance of each solution at a liquid temperature of 25°C was measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation), and a calibration curve was constructed. Next, 3 g of the photosensitive resin layer was dissolved in methyl ethyl ketone instead of the pigment, and the absorbance of the solution that made all pigments appear colored was measured using the same method as described above. Based on the calibration curve, the content of pigment contained in the photosensitive resin layer is calculated from the absorbance of the obtained solution containing the photosensitive resin layer.

[0156] Thermal Crosslinking Compound From the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film, it is preferable that the photosensitive resin layer contains a thermal crosslinking compound. Furthermore, in this specification, the thermal crosslinking compound having vinyl unsaturated groups described later is treated as a thermal crosslinking compound, not a polymerizable compound. Examples of thermal crosslinking compounds include hydroxymethyl compounds and block isocyanate compounds. Among these, block isocyanate compounds are preferred from the viewpoint of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. Block isocyanate compounds react with hydroxyl and carboxyl groups; therefore, for example, when the resin and / or polymerizable compound has at least one of hydroxyl and carboxyl groups, the hydrophilicity of the formed film decreases, thereby enhancing the function of the film formed by curing the photosensitive resin layer as a protective film. In addition, capped isocyanate compounds refer to "compounds having a structure in which isocyanate groups of isocyanate are protected (so-called masked) by a capping agent".

[0157] The dissociation temperature of the terminal isocyanate compound is not particularly limited, but 100°C to 160°C is preferred, and 130°C to 150°C is even more preferred. The dissociation temperature of the terminal isocyanate refers to "the temperature of the endothermic peak accompanying the deprotection reaction of the terminal isocyanate when measured using a differential scanning calorimeter and analyzed by DSC (Differential Scanning Calorimetry)". As a differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. is preferred. However, the differential scanning calorimeter is not limited to this.

[0158] Examples of capping agents with a dissociation temperature of 100°C to 160°C include active methylene compounds (malonate esters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)) and oxime compounds (formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime, etc., compounds having a structure represented by -C (=N-OH)- in the molecule). Among these, from the viewpoint of preservation stability, it is preferable to include oxime compounds as capping agents with a dissociation temperature of 100°C to 160°C.

[0159] For example, from the viewpoint of improving the brittleness of the film and enhancing the adhesion to the substrate, it is preferable that the capping isocyanate compound has an isocyanurate structure. A capping isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanurating hexamethylene diisocyanate to protect it. Among capping isocyanate compounds having an isocyanurate structure, from the viewpoint that it is easier to set the dissociation temperature within a better range and easier to reduce development residue compared to compounds without an oxime structure, compounds with an oxime structure that use an oxime compound as a capping agent are preferable.

[0160] The capped isocyanate compound may have a polymerizable group. There are no particular limitations on the polymerizable group; known polymerizable groups can be used, with free radical polymerizable groups being preferred. Examples of polymerizable groups include vinyl unsaturated groups such as (meth)acryloxy, (meth)acrylamine, and styrene, as well as groups with epoxy groups such as glycidyl. Among these, vinyl unsaturated groups are preferred, (meth)acryloxy is more preferred, and acryloxy is even more preferred.

[0161] Commercially available products can be used as end-capped isocyanate compounds. Examples of commercially available end-capped isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (all manufactured by SHOWA DENKO KK), and end-capped Duranate series compounds (e.g., Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation). Furthermore, compounds with the following structure can also be used as end-capped isocyanate compounds.

[0162] [Chemical 14]

[0163] A single thermal crosslinking compound may be used, or two or more may be used. When the photosensitive resin layer contains a thermal crosslinking compound, the content of the thermal crosslinking compound relative to the total mass of the photosensitive resin layer is preferably 1% to 50% by mass, and more preferably 5% to 30% by mass.

[0164] "Polymer comprising a constituent unit having an acid group protected by an acid-degradable group" It is preferable that the positive photosensitive resin layer comprises a polymer (hereinafter, sometimes referred to as "polymer X") comprising a constituent unit having an acid group protected by an acid-degradable group (hereinafter, sometimes referred to as "constituent unit A"). The positive photosensitive resin layer may comprise a single polymer X, or it may comprise two or more polymers X.

[0165] In polymer X, acid groups protected by acid-degrading groups are converted into acid groups through a deprotection reaction by the action of an acidic substance (e.g., acid) generated by exposure. By generating acid groups in polymer X, the solubility of the positive photosensitive resin layer in the developer is increased.

[0166] It is preferable that polymer X is an addition polymer, and it is even more preferable that polymer has constituent units derived from (meth)acrylic acid or its esters.

[0167] -A constituent unit having an acid group protected by an acid-degradable group- It is preferable that polymer X has a constituent unit (constituent unit A) having an acid group protected by an acid-degradable group. By having constituent unit A, the sensitivity of the positive photosensitive resin layer can be improved.

[0168] As an acid group, there are no restrictions, and known acid groups can be used. It is preferred that the acid group is a carboxyl group or a phenolic hydroxyl group.

[0169] Examples of acid-degradable groups include those that are easily degraded by an acid and those that are difficult to degrade by an acid. Examples of groups that are easily degraded by an acid include acetal-type protecting groups (e.g., 1-alkoxyalkyl, tetrahydropiperanyl, and tetrahydrofuranyl). Examples of groups that are difficult to degrade by an acid include tertiary alkyl (e.g., tertiary butyl) and tertiary alkoxycarbonyl (e.g., tertiary butoxycarbonyl). Among the above, acetal-type protecting groups are preferred as acid-degradable groups.

[0170] From the viewpoint of suppressing the deviation of the linewidth of the photoresist pattern, it is preferable that the molecular weight of the acid-decomposable group is below 300.

[0171] From the viewpoint of sensitivity and resolution, it is preferable that the constituent unit A is represented by the following formula A1, formula A2, or formula A3, with the constituent unit represented by formula A3 being more preferred. The constituent unit represented by formula A3 is a constituent unit having a carboxyl group protected by an acetal-type acid decomposition group.

[0172] [Chemistry 15]

[0173] In formula A1, R11 and R12 independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R11 and R12 is an alkyl group or an aryl group, R13 represents an alkyl group or an aryl group, R11 or R12 and R13 can be linked to form a cyclic ether, R14 represents a hydrogen atom or a methyl group, X1 represents a single bond or a divalent linking group, R15 represents a substituent, and n represents an integer from 0 to 4.

[0174] In formula A2, R21 and R22 independently represent hydrogen atoms, alkyl or aryl groups, at least one of R21 and R22 is an alkyl or aryl group, R23 represents an alkyl or aryl group, R21 or R22 and R23 can be connected to form a cyclic ether, R24 independently represents hydroxyl, halogen atom, alkyl, alkoxy, alkenyl, aryl, aralkyl, alkoxycarbonyl, hydroxyalkyl, arylcarbonyl, aryloxycarbonyl or cycloalkyl, and m represents an integer from 0 to 3.

[0175] In formula A3, R31 and R32 independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R31 and R32 is an alkyl group or an aryl group, R33 represents an alkyl group or an aryl group, R31 or R32 and R33 can be linked to form a cyclic ether, R34 represents a hydrogen atom or a methyl group, and X0 represents a single bond or an extended aryl group.

[0176] In Formula A3, when R31 or R32 is an alkyl group, it is preferred to be an alkyl group with 1 to 10 carbon atoms. In Formula A3, when R31 or R32 is an aryl group, it is preferred to be phenyl. In Formula A3, it is preferred that R31 and R32 are each independently hydrogen atoms or alkyl groups with 1 to 4 carbon atoms. In Formula A3, it is preferred that R33 is an alkyl group with 1 to 10 carbon atoms, and more preferably an alkyl group with 1 to 6 carbon atoms. In Formula A3, the alkyl and aryl groups represented by R31 to R33 may have substituents. In Formula A3, it is preferred that R31 or R32 and R33 are linked to form a cyclic ether. It is preferred that the cyclic ether has 5 or 6 ring members, and more preferably 5. In Formula A3, it is preferred that X0 is a single bond. The aryl group may have substituents. In Formula A3, from the viewpoint that the glass transition temperature (Tg) of polymer X can be further reduced, it is preferable that R 34 is a hydrogen atom.

[0177] It is preferable that the content of the hydrogen atom constituent unit R34 in Formula A3 is 20% by mass or more relative to the total mass of constituent unit A contained in polymer X. The content of the hydrogen atom constituent unit R34 in Formula A3 in constituent unit A can be confirmed by measuring the intensity ratio of peak intensities using conventional methods based on 13C nuclear magnetic resonance spectroscopy (NMR).

[0178] For preferred embodiments of formulas A1 to A3, please refer to paragraphs 0044 to 0058 of International Publication No. 2018 / 179640.

[0179] In formulas A1 to A3, from the point of view of sensitivity, it is preferable that the acid-decomposing group is a group with a cyclic structure, it is even more preferable that the group has a tetrahydrofuran ring structure or a tetrahydropyran ring structure, it is further preferable that the group has a tetrahydrofuran ring structure, and it is particularly preferable that the tetrahydrofuran group is especially preferred.

[0180] Polymer X may have a single constituent unit A, or it may have two or more constituent units A.

[0181] The content of constituent unit A relative to the total mass of polymer X is preferably 10% to 70% by mass, more preferably 15% to 50% by mass, and particularly preferably 20% to 40% by mass. With the content of constituent unit A within the above range, the resolution is further improved. When polymer X contains two or more constituent units A, the above-mentioned content of constituent unit A represents the total content of the two or more constituent units A. The content of constituent unit A can be confirmed using the intensity ratio of peak intensities calculated by conventional methods based on 13C-NMR measurements.

[0182] -Constructing unit with acid group- Polymer X may contain a constructing unit with acid group (hereinafter also referred to as "constructing unit B").

[0183] Constituent unit B is a constituent unit having an acid group that is not protected by an acid-degrading group, that is, an acid group without a protecting group. By having constituent unit B in polymer X, the sensitivity during pattern formation becomes good. Furthermore, since it is easily soluble in alkaline developer during the development step after exposure, the development time can be shortened.

[0184] The acid group in constituent unit B refers to a proton-dissociable group with a pKa of 12 or less. From the viewpoint of improving sensitivity, a pKa of 10 or less is preferred, and 6 or less is even better. Furthermore, a pKa of -5 or more is preferred.

[0185] Examples of acid groups include carboxyl, sulfonamide, phosphonic acid, sulfonic acid, phenolic hydroxyl, and sulfonylidinylimino. A carboxyl or phenolic hydroxyl group is preferred, with a carboxyl group being even more preferred.

[0186] Polymer X may have a single constituent unit B, or it may have two or more constituent units B.

[0187] The content of constituent unit B relative to the total mass of polymer X is preferably 0.01% to 20% by mass, more preferably 0.01% to 10% by mass, and particularly preferably 0.1% to 5% by mass. When the content of constituent unit B is within the above range, the resolution becomes better. When polymer X has two or more constituent units B, the above-mentioned content of constituent unit B represents the total content of the two or more constituent units B. The content of constituent unit B can be confirmed using the intensity ratio of peak intensities calculated by conventional methods based on 13C-NMR measurements.

[0188] -Other Constituent Units- It is preferable that polymer X has other constituent units besides constituent units A and B (hereinafter sometimes referred to as "constituent unit C"). By preparing at least one of the types and contents of constituent unit C, many properties of polymer X can be adjusted. By having constituent unit C, the glass transition temperature, acid value, and hydrophilicity / hydrophobicity of polymer X can be easily adjusted.

[0189] Examples of monomers forming constituent unit C include styrene, alkyl (meth)acrylate, cyclic alkyl (meth)acrylate, aryl (meth)acrylate, unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, maleic diimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated dicarboxylic acid anhydrides.

[0190] From the viewpoint of adhesion to the substrate, it is preferable that the monomer forming the constituent unit C is an alkyl methacrylate, and more preferably an alkyl methacrylate having an alkyl group having 4 to 12 carbon atoms. Examples of alkyl methacrylates include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate.

[0191] As constitutive unit C, examples include those derived from styrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, 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, isoborneol (meth)acrylate, acrylonitrile, or ethylene glycol monoacetate mono(meth)acrylate. As constitutive unit C, examples also include those derived from paragraphs 0021 to 0024 of Japanese Patent Application Publication No. 2004-264623.

[0192] From an analytical point of view, it is preferable that the constituent unit C includes a constituent unit having a basic group. Examples of basic groups include those having a nitrogen atom. Examples of nitrogen-containing groups include aliphatic amine groups, aromatic amine groups, and nitrogen-containing heteroaromatic ring groups. It is preferable that the basic group is an aliphatic amine group.

[0193] As an aliphatic amine group, it can be any of a primary amine group, a secondary amine group, or a tertiary amine group, but from the point of view of analysis, a secondary amine group or a tertiary amine group is preferred.

[0194] Examples of monomers forming constituent units having basic groups include 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, 2-(dimethylamino)ethyl methacrylate, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, 2-(diethylamino)ethyl methacrylate, 2-(dimethylamino)ethyl methacrylate, and N-(3-dimethylamino)methacrylate. The following are listed: N-(3-dimethylamino)propyl methacrylate, N-(3-diethylamino)propyl methacrylate, N-(3-diethylamino)propyl methacrylate, 2-(diisopropylamino)ethyl methacrylate, 2-methyl-3-pyridine methacrylate, 2-methyl-3-pyridine methacrylate, N-[3-(dimethylamino)propyl]acrylamide, 4-aminostyrene, 4-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine, 1-vinylimidazolium, 2-methyl-1-vinylimidazolium, 1-allylimidazolium, and 1-vinyl-1,2,4-triazole. Among the above, 1,2,2,6,6-pentamethyl-4-piperidinium methacrylate is preferred.

[0195] Furthermore, from the viewpoint of improving electrical properties, it is preferable for the constituent unit C to have an aromatic ring or an aliphatic cyclic skeleton. Examples of monomers forming such constituent units include styrene, α-methylstyrene, dicyclopentyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, isocamphenyl methacrylate, and benzyl methacrylate. Among the above, cyclohexyl methacrylate is preferred.

[0196] Polymer X may have a single constituent unit C, or it may have two or more constituent units C.

[0197] The content of constituent unit C relative to the total mass of polymer X is preferably 90% by mass or less, more preferably 85% by mass or less, and particularly preferably 80% by mass or less. The content of constituent unit C relative to the total mass of polymer X is preferably 10% by mass or more, and more preferably 20% by mass or more. By having the content of constituent unit C within the above range, the resolution and adhesion to the substrate are further improved. When polymer X has two or more constituent units C, the above-mentioned content of constituent unit C refers to the total content of the two or more constituent units C. The content of constituent unit C can be confirmed by the intensity ratio of peak intensities calculated by conventional methods based on 13C-NMR measurements.

[0198] The following shows a preferred example of polymer X. However, polymer X is not limited to the examples shown below. In addition, in order to obtain better physical properties, the ratio of each constituent unit and the weight average molecular weight of polymer X shown below can be appropriately selected respectively.

[0199] [Chemistry 16]

[0200] -Glass Transfer Temperature- The glass transfer temperature (Tg) of polymer X is preferably below 90°C, more preferably between 20°C and 60°C, and especially preferably between 30°C and 50°C. When the positive photosensitive resin layer is formed using the transfer material described later, the transferability of the positive photosensitive resin layer can be improved by ensuring that the glass transfer temperature of polymer X is within the above range.

[0201] As a method for adjusting the Tg of polymer X within the above-mentioned range, for example, the method using the FOX formula can be cited. According to the FOX formula, for example, the Tg of the target polymer X can be adjusted based on the Tg of the homopolymer of each constituent unit in the target polymer X and the mass fraction of each constituent unit.

[0202] Hereinafter, regarding the FOX formula, a copolymer having a first constituent unit and a second constituent unit will be used as an example for explanation. When the glass transition temperature of the homopolymer of the first constituent unit is set as Tg1, the mass fraction of the first constituent unit in the copolymer is set as W1, the glass transition temperature of the homopolymer of the second constituent unit is set as Tg2, and the mass fraction of the second constituent unit in the copolymer is set as W2, the glass transition temperature Tg0 (unit: K) of the copolymer having the first constituent unit and the second constituent unit can be deduced according to the following formula. FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2)

[0203] Also, the Tg of the polymer can be adjusted by adjusting the weight average molecular weight of the polymer.

[0204] -Acid Value- From a analytical point of view, the acid value of polymer X is preferably 0 mg KOH / g to 50 mg KOH / g, even better is 0 mg KOH / g to 20 mg KOH / g, and particularly good is 0 mg KOH / g to 10 mg KOH / g.

[0205] The acid value of a polymer indicates the mass of potassium hydroxide required to neutralize the acidic components in 1g of the polymer. The specific measurement method is described below. First, the sample to be measured is dissolved in a mixed solvent containing tetrahydrofuran and water (volume ratio: tetrahydrofuran / water = 9 / 1). Using a potentiometric titration apparatus (e.g., trade name: AT-510, manufactured by KYOTO ELECTRONICS MANUFACTURING CO.,LTD.), the resulting solution is titrated at 25°C with a 0.1mol / L sodium hydroxide aqueous solution. The inflection point of the titration pH curve is taken 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: Volume of 0.1mol / L sodium hydroxide aqueous solution required for titration (mL) f: Titration volume of 0.1mol / L sodium hydroxide aqueous solution w: Mass of the sample to be measured (g) (conversion to solid content)

[0206] -Weight Average Molecular Weight- The weight average molecular weight (Mw) of polymer X, converted from polystyrene, is preferably 60,000 or less. When the positive photosensitive resin layer is formed using the transfer material described later, the positive photosensitive resin layer can be transferred at low temperatures (e.g., below 130°C) by means of polymer X having a weight average molecular weight of 60,000 or less.

[0207] The weight average molecular weight of polymer X is preferably 2,000 to 60,000, and more preferably 3,000 to 50,000.

[0208] The ratio of the number average molecular weight to the weight average molecular weight (dispersion) of polymer X is preferably 1.0 to 5.0, and even more preferably 1.05 to 3.5.

[0209] The weight-average molecular weight of polymer X was measured using GPC (gel permeation chromatography). Various commercially available devices can be used as the measuring apparatus. The method for measuring the weight-average molecular weight of polymer X based on GPC is described in detail below. The measuring apparatus used was an HLC (registered trademark)-8220GPC (manufactured by TOSOH CORPORATION). The columns used were composed of one TSKgel (registered trademark) Super HZM-M (4.6mm ID × 15cm, manufactured by TOSOH CORPORATION), one Super HZ4000 (4.6mm ID × 15cm, manufactured by TOSOH CORPORATION), one Super HZ3000 (4.6mm ID × 15cm, manufactured by TOSOH CORPORATION), and one Super HZ2000 (4.6mm ID × 15cm, manufactured by TOSOH CORPORATION) connected in series. THF (tetrahydrofuran) was used as the eluent. Regarding the measurement conditions, the sample concentration was set to 0.2% by mass, the flow rate to 0.35 mL / min, the sample injection volume to 10 μL, and the measurement temperature to 40 °C. A differential refractive index (RI) detector was used. Calibration curves were constructed using any one of the following seven samples manufactured by TOSOH CORPORATION: “TSK standard, polystyrene”: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A-2500”, and “A-1000”.

[0210] -Content- From the viewpoint of high resolution, the content of polymer X relative to the total mass of the positive photosensitive resin layer is preferably 50% to 99.9% by mass, and even more preferably 70% to 98% by mass.

[0211] - Manufacturing Method- The manufacturing method for polymer X is not limited and can utilize known methods. For example, polymer X can be manufactured by using a polymerization initiator in an organic solvent, and by using monomers to form constituent unit A, and monomers to form constituent unit B and constituent unit C as needed, for polymerization. Furthermore, polymer X can also be manufactured by a so-called polymer reaction.

[0212] 《Other Polymers》 When the positive photosensitive resin layer contains a polymer having a constituent unit having an acid group protected by an acid-degradable group, in addition to the polymer having a constituent unit having an acid group protected by an acid-degradable group, it may also contain a polymer having a constituent unit not having an acid group protected by an acid-degradable group (hereinafter, sometimes referred to as "other polymers").

[0213] 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 Company, Inc.; 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.

[0214] The positive photosensitive resin layer may contain a single other polymer or two or more other polymers.

[0215] When the positive photosensitive resin layer contains other polymers, it is preferable that the content of other polymers is less than 50% by mass relative to the total mass of the polymer components, more preferably less than 30% by mass, and especially preferably less than 20% by mass.

[0216] In this disclosure, "polymer component" refers to the collective term for all polymers contained in the positive photosensitive resin layer. For example, when the positive photosensitive resin layer contains polymer X and other polymers, polymer X and other polymers are collectively referred to as "polymer component". In addition, compounds corresponding to crosslinking agents, dispersants and surfactants described later, even if they are polymeric compounds, are not included in the polymer component.

[0217] The content of polymer components relative to the total mass of the positive photosensitive resin layer is preferably 50% to 99.9% by mass, and even more preferably 70% to 98% by mass.

[0218] 《Alkali-soluble resin (positive type)》 The positive type photosensitive resin layer preferably contains an alkali-soluble resin, more preferably contains an alkali-soluble resin and a quinone diazide compound, and especially preferably contains a resin having a constituent unit with phenolic hydroxyl groups and a quinone diazide compound.

[0219] Examples of alkali-soluble resins include resins having hydroxyl, carboxyl, or sulfonic acid groups in the main chain or side chain. Examples of alkali-soluble resins include polyamide resins, polyhydroxystyrene, derivatives of polyhydroxystyrene, styrene-maleic anhydride copolymers, polyvinyl hydroxybenzoate, (meth)acrylic resins containing carboxyl groups, and phenolic varnish resins. Preferred alkali-soluble resins include, for example, condensates of meta- / p-mixed cresols and formaldehyde, and condensates of phenol, cresol, and formaldehyde.

[0220] Alkali-soluble resins may have phenolic hydroxyl groups (-Ar-OH), carboxyl groups (-CO 2H), sulfonic acid groups (-SO 3H), phosphoric acid groups (-OPO 3H), sulfonamide groups (-SO 2NH-R), or substituted sulfonamide acid groups (e.g., active amide, -SO 2NHCOR, -SO 2NHSO 2R, and -CONHSO 2R). Here, Ar represents a divalent aryl group that may have substituents, and R represents a hydrocarbon group that may have substituents.

[0221] Phenolic varnish resins are obtained, for example, by condensing phenolic compounds with aldehyde compounds 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-tert-butyl-5-methylphenol, and tert-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 using 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. Condensation reactions can be carried out in appropriate solvents.

[0222] Among them, phenolic varnish resin and other resins having constituent units with phenolic hydroxyl groups are preferred as alkali-soluble resins.

[0223] From the viewpoint of pattern formation, the weight average molecular weight of the alkali-soluble resin is preferably 5.0 × 10² to 2.0 × 10⁵. From the viewpoint of pattern formation, the number average molecular weight of the alkali-soluble resin is preferably 2.0 × 10² to 1.0 × 10⁵.

[0224] For example, condensates of phenols and formaldehyde having alkyl groups having 3 to 8 carbons, such as those described in U.S. Patent No. 4,123,279, such as condensates of tributylphenol and formaldehyde and condensates of octylphenol and formaldehyde, can also be used.

[0225] The positive photosensitive resin layer may contain one or more alkali-soluble resins. The content of alkali-soluble resin relative to the total mass of the positive photosensitive resin layer is preferably 30% to 99.9% by mass, more preferably 40% to 99.5% by mass, and particularly preferably 70% to 99% by mass.

[0226] 《Photoacid Generator》 It is preferable that the positive photosensitive resin layer contains a photoacid generator as a photosensitive compound. The photoacid generator is a compound that can generate acid by irradiation with active light (e.g., ultraviolet, far ultraviolet, X-ray and electron beam).

[0227] As a photoacid generator, a compound that generates acid by sensing active light with a wavelength of 300 nm or higher, preferably 300 nm to 450 nm, is preferred. Furthermore, regarding photoacid generators that do not directly sense active light with a wavelength of 300 nm or higher, as long as they are compounds that generate acid by sensing active light with a wavelength of 300 nm or higher in combination with a sensitizer, they can also be used in combination with a sensitizer for better results.

[0228] It is preferable for the photoacid generator to produce an acid with a pKa of 4 or less, more preferable for the photoacid generator to produce an acid with a pKa of 3 or less, and particularly preferable for the photoacid generator to produce an acid with a pKa of 2 or less. The lower limit of the pKa of the acid derived from the photoacid generator is not limited. It is preferable, for example, for the pKa of the acid derived from the photoacid generator to be -10.0 or more.

[0229] Examples of photoacid generators include ionic photoacid generators and nonionic photoacid generators.

[0230] Examples of ionic photoacid generators include onium salt compounds. Examples of onium salt compounds include diaryl monazine salt compounds, triaryl strontium salt compounds, and quaternary ammonium salt compounds. Onium salt compounds are preferred as ionic photoacid generators, and at least one of triaryl strontium salt compounds and diaryl monazine salt compounds is particularly preferred.

[0231] As an ionic photoacid generator, the ionic photoacid generator described in paragraphs 0114 to 0133 of Japanese Patent Application Publication No. 2014-85643 is also preferred.

[0232] Examples of nonionic photoacid generators include trichloromethyl-S-triazine compounds, diazomethane compounds, amide sulfonate compounds, and oxime sulfonate compounds. From the viewpoint of sensitivity, resolution, and adhesion to the substrate, oxime sulfonate compounds are preferred as nonionic photoacid generators.

[0233] As specific examples of trichloromethyl-s-trichloromethyl compounds, diazomethane compounds and aceiminosulfonate compounds, the compounds described in paragraphs 0083 to 0088 of Japanese Patent Application Publication No. 2011-221494 can be cited.

[0234] As an oxime sulfonate compound, the one described in paragraphs 0084 to 0088 of International Publication No. 2018 / 179640 is preferred.

[0235] From the viewpoint of sensitivity and resolution, it is preferable that the photoacid generator is at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, with oxime sulfonate compounds being more preferred.

[0236] As a preferred example of a photoacid generator, a photoacid generator having the following structure can be cited.

[0237] [Chemical 17]

[0238] As a photoacid generator that absorbs at a wavelength of 405 nm, for example, ADEKA ARKLS (registered trademark) SP-601 (manufactured by ADEKA CORPORATION) can be cited.

[0239] From the viewpoint of heat resistance and dimensional stability, it is preferable that the positive photosensitive resin layer contains a quinone diazide compound as an acid generator (preferably a photoacid generator). The quinone diazide compound can be synthesized, for example, by condensing a compound having phenolic hydroxyl groups with a quinone diazidesulfonate halide in the presence of a dehydrohalogenating agent.

[0240] Examples of quinone diazide compounds include 1,2-benzoquinone diazide-4-sulfonate, 1,2-naphthoquinone diazide-4-sulfonate, 1,2-naphthoquinone diazide-5-sulfonate, 1,2-naphthoquinone diazide-6-sulfonate, 2,1-naphthoquinone diazide-4-sulfonate, 2,1-naphthoquinone diazide-5-sulfonate, and 2,1-naphthoquinone diazide-6-sulfonate. Sulfonates of other quinone diazide derivatives, 1,2-benzoquinone diazide-4-sulfonic acid acechloro, 1,2-naphthoquinone diazide-4-sulfonic acid acechloro, 1,2-naphthoquinone diazide-5-sulfonic acid acechloro, 1,2-naphthoquinone diazide-6-sulfonic acid acechloro, 2,1-naphthoquinone diazide-4-sulfonic acid acechloro, 2,1-naphthoquinone diazide-5-sulfonic acid acechloro and 2,1-naphthoquinone diazide-6-sulfonic acid acechloro.

[0241] The positive photosensitive resin layer may contain a single photoacid generator or two or more photoacid generators. From the viewpoint of sensitivity and resolution, the content of the photoacid generator relative to the total mass of the positive photosensitive resin layer is preferably 0.1% to 10% by mass, and more preferably 0.5% to 5% by mass.

[0242] 《Other Ingredients》 The photosensitive resin layer may contain ingredients other than those mentioned above.

[0243] -Surfactant- From the viewpoint of thickness uniformity, it is preferable for the photosensitive resin layer to contain a surfactant. Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, with nonionic surfactants being preferred. Examples of surfactants include those described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Unexamined Patent Application Publication No. 2009-237362.

[0244] Fluorinated or silicone surfactants are preferred as surfactants. Commercially available fluorinated surfactants include, for example, MEGAFACE (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, F-552, F-554, F-555-A, F-556, F-557, and F-558. F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (the above are DIC) (Manufactured by Corporation), Fluorad (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 Solutions Inc.), Ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (all manufactured by Neos Corporation), etc. Furthermore, fluorinated surfactants can also better utilize acrylic compounds, which have a molecular structure containing functional groups with fluorine atoms. When heated, these functional groups are cleaved, causing the fluorine atoms to volatilize. Examples of such fluorinated surfactants include the MEGAFACE (trade name) DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Industrial News (February 23, 2016)), such as MEGAFACE (trade name) DS-21.

[0245] Furthermore, it is preferable to use polymers of fluorinated vinyl ether compounds having fluorinated alkyl or fluorinated alkyl ether groups and hydrophilic vinyl ether compounds as fluorinated surfactants. End-capped polymers can also be used as fluorinated surfactants. Fluorinated polymers can also preferably be used as fluorinated surfactants, which comprise units derived from (meth)acrylate compounds having fluorine atoms and units derived from (meth)acrylate compounds having two or more (preferably five or more) alkoxy groups (preferably ethoxy or propoxy). Fluorinated surfactants can also be used as fluorinated polymers having vinyl unsaturated groups in the side chain. Examples include MEGAFACE (trade name) RS-101, RS-102, RS-718K, and RS-72-K (manufactured by DIC Corporation).

[0246] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, 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), and Solsperse (trade name) 20000 (all manufactured by Lubrizol Japan). Limited), NCW-101, NCW-1001, NCW-1002 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN (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 Co., Ltd.), etc. Furthermore, in recent years, the environmental suitability of compounds with straight-chain perfluoroalkyl groups having 7 or more carbon atoms has become a concern; therefore, using surfactants that are alternatives to perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) is preferable.

[0247] Examples of silicone-based surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers with organic groups introduced into the side chains or ends. Specific examples of silicone-based 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 (the above are Dow Corning Toray). (manufactured by Shin-Etsu Chemical Co., Ltd.) and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), BYK307, BYK323, BYK330 (manufactured by BYK Chemie Co., Ltd.), etc.

[0248] The photosensitive resin layer may contain only one type of surfactant, or it may contain two or more types. The surfactant content relative to the total mass of the photosensitive resin layer is preferably 0.001% to 10% by mass, and more preferably 0.01% to 3% by mass.

[0249] -Additives- In addition to the above-mentioned components, the photosensitive resin layer may contain known additives as needed. Examples of additives include polymerization inhibitors, sensitizers, plasticizers, alkoxysilane compounds, and solvents. The photosensitive resin layer may contain one or more additives. Furthermore, examples of additives include metal oxide particles, antioxidants, dispersants, acid proliferation agents, development accelerators, conductive fibers, thermal free radical polymerization initiators, thermal acid generators, ultraviolet absorbers, tackifiers, and organic or inorganic precipitation inhibitors. Preferred forms of these additives are described in paragraphs 0165 to 0184 of Japanese Patent Application Publication No. 2014-85643, the contents of which are incorporated herein by reference.

[0250] The photosensitive resin layer may contain a polymerization inhibitor. Free radical polymerization inhibitors are preferred as polymerization inhibitors. Examples of polymerization inhibitors include the thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. Among these, phenoxythiazolinone, phenoxythiazolinone, or 4-methoxyphenol are preferred. Other polymerization inhibitors include naphthylamine, copper(I), aluminum nitrosophenylhydroxylamine, and diphenylnitrosamine. Using aluminum nitrosophenylhydroxylamine as a polymerization inhibitor is preferred to avoid impairing the sensitivity of the photosensitive resin composition.

[0251] The content of the polymerization inhibitor relative to the total mass of the photosensitive resin layer is preferably 0.01% to 3% by mass, and more preferably 0.05% to 1% by mass. From the viewpoint of imparting storage stability to the photosensitive resin composition, it is preferable to set the above content to 0.01% by mass or more. On the other hand, from the viewpoint of maintaining sensitivity, it is preferable to set the above content to 3% by mass or less.

[0252] 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 sensitizers include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridinium compounds, succinazole compounds, benzo[a]succinazole compounds, thiazole compounds, benzo[a]thiazole compounds, triazole compounds (e.g., 1,2,4-triazole), succinate compounds, trisulfide compounds, thiophene compounds, naphthalenedimethylimine compounds, triarylamine compounds, and aminoacridine compounds.

[0253] The photosensitive resin layer may contain only one sensitizer or two or more sensitizers. When the photosensitive resin layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose. However, from the viewpoint of improving the sensitivity to light source and improving the curing speed by balancing the polymerization rate and chain transfer, a content of 0.01% to 5% by mass relative to the total mass of the photosensitive resin layer is preferred, and 0.05% to 1% by mass is even more preferred.

[0254] The photosensitive resin layer may contain at least one selected from the group consisting of plasticizers and heterocyclic compounds. Examples of plasticizers and heterocyclic compounds include those described in paragraphs 0097 to 0103 and 0111 to 0118 of International Publication No. 2018 / 179640.

[0255] The photosensitive resin layer (preferably a positive photosensitive resin layer) may contain an alkoxysilane compound. Examples of alkoxysilane compounds include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-epoxypropoxypropyltrialkoxysilane, γ-epoxypropoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane, and vinyltrialkoxysilane.

[0256] Of the above, it is preferred that the alkoxysilane compound is a trialalkoxysilane compound, more preferably γ-epoxypropoxypropyltrialkoxysilane or γ-methacryloxypropyltrialkoxysilane, further preferably γ-epoxypropoxypropyltrialkoxysilane, and especially preferably 3-epoxypropoxypropyltrimethoxysilane.

[0257] The photosensitive resin layer may contain a single alkoxysilane compound, or it may contain two or more alkoxysilane compounds. From the viewpoint of adhesion to the substrate and etching resistance, the content of the alkoxysilane compound relative to the total mass of the photosensitive resin layer is preferably 0.1% to 50% by mass, more preferably 0.5% to 40% by mass, and particularly preferably 1.0% to 30% by mass.

[0258] The photosensitive resin layer may contain a solvent. When a photosensitive resin layer is formed from a photosensitive resin composition containing a solvent, sometimes the solvent may remain in the photosensitive resin layer.

[0259] 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 easily mixed in as impurities, so the following contents are preferred.

[0260] The impurity content in the photosensitive resin layer is preferably 80 ppm or less by weight, more preferably 10 ppm or less, and even more preferably 2 ppm or less by weight. The impurity content can be set to 1 ppb or more by weight, or 0.1 ppm or more by weight.

[0261] As a method for keeping impurities within the above-mentioned range, examples include selecting raw materials with low impurity content as components, preventing impurity contamination during the fabrication of the photosensitive resin layer, and cleaning and removing impurities. By using this method, the amount of impurities can be kept within the above-mentioned range.

[0262] Impurities can be quantified using known methods such as ICP (Inductively Coupled Plasma) luminescence spectrophotometry, atomic absorption chromatography, and ion chromatography.

[0263] It is preferable that 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 low. 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 further preferably 4 ppm or less. The lower limit, relative to the total mass of the photosensitive resin layer, can be set to 10 ppb or more, or 100 ppb or more. The content of these compounds can be suppressed using the same method as for the aforementioned metal impurities. Furthermore, quantification can be performed using known measurement methods.

[0264] From the viewpoint of improving reliability and lamination, the water content in the photosensitive resin layer is preferably 0.01% to 1.0% by mass, and even more preferably 0.05% to 0.5% by mass.

[0265] Residual Monomers The photosensitive resin layer sometimes contains residual monomers corresponding to each constituent unit of the aforementioned alkali-soluble resin. From the viewpoint of patternability and reliability, it is preferable that the content of residual monomers relative to the total mass of the alkali-soluble resin is 5,000 ppm by mass or less, more preferably 2,000 ppm by mass or less, and further preferably 500 ppm by mass or less. The lower limit is not particularly limited, but 1 ppm by mass or more is preferable, and 10 ppm by mass or more is even more preferable. From the viewpoint of patternability and reliability, it is preferable that the residual monomer content of each constituent unit of the alkali-soluble resin relative to the total mass of the photosensitive resin layer is 3,000 ppm by mass or less, more preferably 600 ppm by mass or less, and further preferably 100 ppm by mass or less. The lower limit is not particularly limited, but 0.1 ppm by mass or more is preferable, and 1 ppm by mass or more is even more preferable.

[0266] It is preferable that the amount of residual monomers in the synthesis of alkali-soluble resins via polymer reactions is also within the above-mentioned range. For example, when alkali-soluble resins are synthesized by reacting glycidyl acrylate with carboxylic acid side chains, it is preferable that the content of glycidyl acrylate is within the above-mentioned range. The amount of residual monomers can be measured using known methods such as liquid chromatography and gas chromatography.

[0267] According to the "Properties, etc." standard, the thickness of the photosensitive resin layer is preferably 0.1 μm to 300 μm, more preferably 0.2 μm to 100 μm, further preferably 0.5 μm to 50 μm, even more preferably 0.5 μm to 15 μm, particularly preferably 0.5 μm to 10 μm, and optimally 0.5 μm to 8 μm. This improves the developability of the photosensitive resin layer, thereby enhancing resolution. Furthermore, from the viewpoint of resolution, a thickness of 10 μm or less is preferred, 4.8 μm or less is more preferably, 3.0 μm or less is further preferably, and 0.5 μm to 3.0 μm is particularly preferred. The thickness of each layer of the photosensitive transfer material is measured by observing the cross-section of the photosensitive transfer material in the direction perpendicular to the main surface using a scanning electron microscope (SEM), and the thickness of each layer at more than 10 points is measured based on the obtained observation image, and the average value is calculated.

[0268] Furthermore, from the viewpoint of superior adhesion, it is preferable that the transmittance of the photosensitive resin layer at a wavelength of 365 nm is 10% or more, 30% or more, and 50% or more. The upper limit is not particularly limited, but 99.9% or less is preferable.

[0269] Formation Method: The method for forming the photosensitive resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above-mentioned components. For example, when the photosensitive resin layer is a negative photosensitive resin layer, a method can be cited that involves preparing a photosensitive resin composition containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a solvent, coating the photosensitive resin composition onto the surface of a temporary support or the like, and drying the coating of the photosensitive resin composition.

[0270] Examples of photosensitive resin compositions used in the formation of the photosensitive resin layer include compositions containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, any of the above-mentioned components, and a solvent. In order to adjust the viscosity of the photosensitive resin composition so as to facilitate the formation of the photosensitive resin layer, it is preferable that the photosensitive resin composition contains a solvent.

[0271] - Solvent- As a solvent contained in the photosensitive resin composition, there are no particular limitations as long as it can dissolve or disperse the alkali-soluble resin, polymerizable compound, photopolymerization initiator, and any of the above-mentioned components; known solvents can be used. Examples of solvents include alkyl glycol ether solvents, alkyl glycol ether acetate solvents, alcohol solvents (methanol and ethanol, etc.), ketone solvents (acetone and methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents, amide solvents, lactone solvents, and mixed solvents containing two or more of these. When producing a photosensitive transfer material having a temporary support, a buffer layer, an intermediate layer, a photosensitive resin layer, and a protective film, it is preferable that the photosensitive resin composition contains at least one selected from the group including alkyl glycol ether solvents and alkyl glycol ether acetate solvents. It is more preferable to include a mixed solvent selected from at least one of the group consisting of alkyl glycol ether solvents and alkyl glycol ether acetate solvents and at least one of the group consisting of ketone solvents and cyclic ether solvents; it is further preferable to include a mixed solvent selected from at least one of the group consisting of alkyl glycol ether solvents and alkyl glycol ether acetate solvents, ketone solvents and cyclic ether solvents.

[0272] Examples of solvents for alkyl glycol ethers 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 solvents for alkyl glycol ether acetates include ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, diethylene glycol monoalkyl ether acetates, and dipropylene glycol monoalkyl ether acetates. Solvents described in paragraphs 0092 to 0094 of International Publication No. 2018 / 179640 and paragraph 0014 of Japanese Patent Application Publication No. 2018-177889 may be used, and these contents are incorporated herein by reference.

[0273] The photosensitive resin composition may contain only one solvent or two or more solvents. When coating the photosensitive resin composition, the solvent content is preferably 50 to 1,900 parts by weight, and more preferably 100 to 900 parts by weight, relative to 100 parts by weight of the total solids in the photosensitive resin composition.

[0274] The method for preparing the photosensitive resin composition is not particularly limited. For example, a method can be given by preparing a solution in which each component is dissolved in the aforementioned solvent and then mixing the resulting solution in a predetermined proportion to prepare the photosensitive resin composition. From the viewpoint of particle removal, it is preferable to filter the photosensitive resin composition using a filter before forming the photosensitive resin layer. Filtering with a filter with a pore size of 0.2 μm to 10 μm is more preferable, filtering with a filter with a pore size of 0.2 μm to 7 μm is even more preferable, and filtering with a filter with a pore size of 0.2 μm to 5 μm is particularly preferable. There are no particular limitations on the material and shape of the filter; known materials can be used. Furthermore, it is preferable to perform the above filtration once or more, and it is also preferable to perform it multiple times.

[0275] The coating method for the photosensitive resin composition is not particularly limited, and any known method may be used. Examples of coating methods include slot coating, spin coating, curtain coating, and inkjet coating. Furthermore, the photosensitive resin layer can be formed by coating the photosensitive resin composition onto the protective film described later and then drying it.

[0276] Furthermore, from the viewpoint of resolution and peelability of the temporary support, it is preferable that the photosensitive transfer material disclosed herein has other layers between the temporary support and the photosensitive resin layer. Examples of such other layers include an intermediate layer, a buffer layer, and a protective film. Among these, having an intermediate layer is preferable, and having both a buffer layer and an intermediate layer is even more preferable.

[0277] [Intermediate Layer] When the photosensitive transfer material has a buffer layer (described later) between the temporary support and the photosensitive resin layer, it is preferable to have an intermediate layer between the buffer layer and the photosensitive resin layer. The intermediate layer helps to suppress the mixing of components during the formation of multiple layers and during storage.

[0278] From the viewpoint of developability and the inhibition of mixing of components during multiple coating layers and storage after coating, it is preferable that the intermediate layer is a water-soluble layer. In this disclosure, "water-soluble" means that the solubility is 0.1g or more in 100g of water at pH 7.0 with a liquid temperature of 22°C.

[0279] As an intermediate layer, an oxygen barrier layer with oxygen barrier function, as described as a "separation layer" in Japanese Patent Application Publication No. 5-72724, can be cited as an example. By using an oxygen barrier layer as the intermediate layer, the sensitivity during exposure is improved, the time load of the exposure machine is reduced, and as a result, productivity is improved. The oxygen barrier layer used as the intermediate layer can be appropriately selected from known layers. It is preferable that the oxygen barrier layer used as the intermediate layer exhibits low oxygen permeability and is dispersed or dissolved in water or alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22°C). Furthermore, from the viewpoint of oxygen barrier properties, resolution, and pattern formation properties, it is preferable that the intermediate layer contains an inorganic layered compound. As an inorganic layered compound, it is a particle with a thin, flat plate shape, such as natural mica, synthetic mica, talc represented by the formula: 3MgO·4SiO·H2O, mica, montmorillonite, soapstone, lithium bentonite, zirconium phosphate, etc., can be cited as examples. Examples of mica compounds include natural and synthetic mica, represented by the formula: A(B,C)₂-5D₄O₁₀(OH,F,O)₂ [where A is any one of K, Na, or Ca; B and C are any one of Fe(II), Fe(III), Mn, Al, Mg, or V; and D is Si or Al].

[0280] Among the mica groups, natural mica includes muscovite, sodium mica, phlogopite, biotite, and lepidolite. Synthetic mica includes non-swellable mica such as fluorophlogopite (KMg3(AlSi3O10)F2) and potassium tetrasilicic mica (KMg2.5Si4O10)F2), as well as swelling mica such as Na tetrasilicic mica (NaMg2.5(Si4O10)F2), Na or Li banded mica (Na,Li)Mg2Li(Si4O10)F2, and montmorillonite-based Na or Li lithium bentonite (Na,Li)1 / 8Mg2 / 5Li1 / 8(Si4O10)F2. Furthermore, synthetic bentonite groups (smectite) are also useful.

[0281] From the viewpoint of controlling diffusion, the thinner the thickness, the better for the shape of inorganic layered compounds; and the larger the planar dimensions, the better, as long as they do not impede the smoothness of the coating surface or the transmissibility of active light. Therefore, the aspect ratio is preferably 20 or more, more preferably 100 or more, and especially 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 image obtained from a microscopic photograph of the particle. The larger the aspect ratio, the greater the effect obtained.

[0282] Regarding the particle size of the inorganic layered compound, its average major diameter is preferably 0.3 μm to 20 μm, more preferably 0.5 μm to 10 μm, and particularly preferably 1 μm to 5 μm. The average thickness of the particles is preferably 0.1 μm or less, more preferably 0.05 μm or less, and particularly preferably 0.01 μm or less. Specifically, for example, in the case of swellable synthetic mica as a representative compound, the preferred sample system has a thickness of about 1 nm to 50 nm and a surface size (major diameter) of about 1 μm to 20 μm.

[0283] From the viewpoints of oxygen barrier properties, resolution and pattern formation, the content of inorganic layered compounds relative to the total mass of the intermediate layer is preferably 0.1% to 50% by mass, and even more preferably 1% to 20% by mass.

[0284] It is preferable that the intermediate layer contains a resin. Examples of resins contained in the intermediate layer include polyvinyl alcohol resins, polyvinylpyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. It is preferable that the resin contained in the intermediate layer is a water-soluble resin.

[0285] From the viewpoint of suppressing the mixing of components between multiple layers, it is preferable that the resin contained in the intermediate layer is different from either the polymer A contained in the negative photosensitive resin layer or the thermoplastic resin (alkali-soluble resin) contained in the buffer layer.

[0286] Furthermore, from the viewpoint of oxygen barrier properties, developability, resolution, and pattern forming properties, it is preferable that the intermediate layer contains a water-soluble compound, and even more preferable that it contains a water-soluble resin. There are no particular limitations on the water-soluble compound, but from the viewpoint of oxygen barrier properties, developability, resolution, and pattern forming properties, it is preferable that the compound is selected from one or more of the group consisting of water-soluble cellulose derivatives, polyols, oxide adducts of polyols, polyethers, phenolic derivatives, and acetamide compounds, and even more preferable that the resin is selected from at least one of the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl cellulose, and hydroxypropyl methylcellulose. Examples of water-soluble resins include water-soluble cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide resin, (meth)acrylate resin, polyethylene oxide resin, gelatin, vinyl ether resin, polyacetamide resin, and copolymers thereof. From the viewpoints of oxygen barrier properties, developability, resolution, and pattern formation, water-soluble resins containing polyvinyl alcohol are preferred; those containing polyvinyl alcohol and water-soluble cellulose derivatives are even better; those containing polyvinyl alcohol and hydroxypropyl cellulose are further preferred; and those containing polyvinyl alcohol, polyvinylpyrrolidone, and hydroxypropyl cellulose are particularly preferred. The degree of hydrolysis of polyvinyl alcohol is not particularly limited, but from the viewpoints of oxygen barrier properties, developability, resolution, and pattern formation, 73 mol% to 99 mol% is preferred. Furthermore, from the viewpoints of oxygen barrier properties, developability, resolution, and pattern formation, polyvinyl alcohol containing ethylene as a monomer unit is preferred.

[0287] From the viewpoints of oxygen barrier properties, developability, defect suppression of the obtained photoresist pattern, resolution and sensitivity, the content of the above-mentioned polyvinyl alcohol relative to the total mass of the above-mentioned intermediate layer is preferably 10% to 95% by mass, more preferably 30% to 90% by mass, and particularly preferably 50% to 75% by mass.

[0288] Furthermore, from the viewpoints of oxygen barrier properties, developability, defect suppression of the obtained photoresist pattern, resolution, and sensitivity, it is preferable that the water-soluble resin contains a water-soluble cellulose derivative, more preferably that it contains a hydroxyalkyl cellulose compound, and especially preferably that it contains hydroxypropyl cellulose. From the viewpoints of oxygen barrier properties, developability, defect suppression of the obtained photoresist pattern, resolution, and sensitivity, it is preferable that the content of the hydroxypropyl cellulose relative to the total mass of the intermediate layer is 0.005% to 20% by mass, more preferably 0.01% to 10% by mass, further preferably 0.1% to 5% by mass, and especially preferably 0.5% to 3% by mass.

[0289] Furthermore, from the viewpoints of oxygen barrier properties, developability, defect suppression of the obtained photoresist pattern, resolution, and sensitivity, it is preferable that the water-soluble resin contains polyvinylpyrrolidone. From the viewpoints of oxygen barrier properties, developability, defect suppression of the obtained photoresist pattern, resolution, and sensitivity, it is preferable that the content of the polyvinylpyrrolidone relative to the total mass of the intermediate layer is 1% to 60% by mass, more preferably 10% to 50% by mass, further preferably 20% to 45% by mass, and especially preferably 25% to 40% by mass.

[0290] The intermediate layer may contain one or more resins.

[0291] From the viewpoint of oxygen barrier properties and the inhibition of mixing of components during the application of multiple coating layers and during storage after coating, the proportion of water-soluble compounds in the intermediate layer relative to the total mass of the intermediate layer is preferably 50% to 100% by mass, more preferably 70% to 100% by mass, further preferably 80% to 100% by mass, and especially preferably 90% to 100% by mass.

[0292] Furthermore, the intermediate layer may contain additives as needed. Examples of additives include surfactants.

[0293] The thickness of the intermediate layer is not limited. An average thickness of 0.1 μm to 5 μm is preferred, and 0.5 μm to 3 μm is even more preferred. By keeping the thickness of the intermediate layer within the above range, the oxygen barrier properties will not decrease, the mixing of components during the formation of multiple layers and during storage can be suppressed, and the increase in the removal time of the intermediate layer during development can be suppressed.

[0294] The method for forming the intermediate layer is not limited as long as it is a method capable of forming a layer containing the above-mentioned components. For example, a method for forming the intermediate layer can be described as drying the coating of the intermediate layer composition after coating the surface of the buffer layer or the photosensitive resin layer with the intermediate layer composition.

[0295] Examples of intermediate layer compositions include those comprising a resin and any additives. To adjust the viscosity of the intermediate layer composition and facilitate the formation of the intermediate layer, it is preferable that the intermediate layer composition contains a solvent. The solvent is not limited to any solvent capable of dissolving or dispersing the resin. It is preferable that the solvent is selected from at least one of the group consisting of water and water-mixed organic solvents, and water or a mixture of water and water-mixed organic solvents is more preferred.

[0296] Examples of water-mixable organic solvents include alcohols with 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerol. Alcohols with 1 to 3 carbon atoms are preferred as water-mixable organic solvents, with methanol or ethanol being even more preferred.

[0297] [Buffer Layer] It is preferable that the photosensitive transfer material disclosed herein has a buffer layer. It is preferable that the photosensitive transfer material has a buffer layer between the temporary support and the photosensitive resin layer or intermediate layer. This is because, by having a buffer layer between the temporary support and the photosensitive resin layer or intermediate layer, the conformability of the photosensitive transfer material to the substrate is improved, the incorporation of air bubbles between the substrate and the photosensitive transfer material is suppressed, and as a result, the interlayer adhesion is improved.

[0298] It is preferable that the buffer layer comprises an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator. As the alkali-soluble resin, polymerizable compound, and photopolymerization initiator used in the buffer layer, the alkali-soluble resin, polymerizable compound, and photopolymerization initiator used in the above-mentioned photosensitive resin layer can be used more preferably.

[0299] Examples of alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic acid copolymers, polyurethane resins, polyvinyl alcohol, polyethylene formaldehyde, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimine, polyallylamine, and polyalkylene glycols.

[0300] From the viewpoint of developability and adhesion to layers adjacent to the buffer layer, alkali-soluble resin is preferably acrylic resin. Here, "acrylic resin" means a resin having at least one selected from the group consisting of constituent units derived from (meth)acrylic acid, constituent units derived from (meth)acrylate, and constituent units derived from (meth)acrylamide.

[0301] In the acrylic resin, the total content of constituent units derived from (meth)acrylic acid, constituent units derived from (meth)acrylate, and constituent units derived from (meth)acrylamide is preferably 50% by mass or more relative to the total mass of the acrylic resin. In the acrylic resin, the total content of constituent units derived from (meth)acrylic acid and constituent units derived from (meth)acrylate is preferably 30% to 100% by mass relative to the total mass of the acrylic resin, and more preferably 50% to 100% by mass.

[0302] Furthermore, it is preferable that the alkali-soluble resin is a polymer having an acid group. Examples of acid groups include carboxyl groups, sulfonic acid groups, phosphoric acid groups, and phosphonic acid groups, with carboxyl groups being preferred.

[0303] From the viewpoint of developability, alkali-soluble resins with an acid value of 60 mg KOH / g or higher are preferred, and acrylic resins containing carboxyl groups with an acid value of 60 mg KOH / g or higher are even better. There is no upper limit to the acid value. An acid value of alkali-soluble resin of 200 mg KOH / g or lower is preferred, and 150 mg KOH / g or lower is even better.

[0304] There is no limitation on the use of an acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher, and it is possible to appropriately select from known resins. Examples of acrylic resins containing carboxyl groups with an acid value of 60 mg KOH / g or higher include the acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher among the polymers described in paragraph 0025 of Japanese Patent Application Publication No. 2011-95716, the acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher among the polymers described in paragraphs 0033 to 0052 of Japanese Patent Application Publication No. 2010-237589, and the acrylic resin containing carboxyl groups with an acid value of 60 mg KOH / g or higher among the adhesive polymers described in paragraphs 0053 to 0068 of Japanese Patent Application Publication No. 2016-224162.

[0305] The proportion of the carboxyl-containing unit in the acrylic resin containing carboxyl groups is preferably 5% to 50% by mass relative to the total mass of the acrylic resin containing carboxyl groups, more preferably 10% to 40% by mass, and especially preferably 12% to 30% by mass.

[0306] From the viewpoint of developability and the adhesion of the layers adjacent to the buffer layer, an alkali-soluble resin having acrylic resins with constituent units derived from (meth)acrylic acid is particularly preferred.

[0307] Alkali-soluble resins may have reactive groups. Reactive groups may be, for example, groups capable of addition polymerization. Examples of reactive groups include vinyl unsaturated groups, condensation groups (e.g., hydroxyl and carboxyl groups), and polyaddition reactive groups (e.g., epoxy and (terminated) isocyanate groups).

[0308] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or above, 10,000 to 100,000 is even better, and 20,000 to 50,000 is particularly good.

[0309] The buffer layer may contain one or more alkali-soluble resins.

[0310] From the viewpoint of developability and adhesion to the layers adjacent to the buffer layer, the content of alkali-soluble resin relative to the total mass of the buffer layer is preferably 10% to 99% by mass, more preferably 20% to 90% by mass, further preferably 40% to 80% by mass, and especially preferably 50% to 70% by mass.

[0311] Preferably, the buffer layer contains a pigment (hereinafter, sometimes referred to as "pigment B") whose maximum absorption wavelength is 450 nm or higher within the wavelength range of 400 nm to 780 nm during color development and whose maximum absorption wavelength changes with acid, base or free radical. The preferred state of pigment B is the same as that of pigment N described above, except for the points described later.

[0312] From the viewpoints of visibility of the exposed part, visibility of the unexposed part, and resolution, pigment B is better if the maximum absorption wavelength changes by acid or free radicals, and even better if the maximum absorption wavelength changes by acid.

[0313] From the viewpoints of visibility of the exposed part, visibility of the unexposed part, and resolution, it is preferable that the buffer layer contains a pigment B, which has a maximum absorption wavelength that changes with acid, and a compound that produces acid with light described later.

[0314] The buffer layer may contain one or more pigments B.

[0315] From the viewpoint of visibility of the exposed part and visibility of the unexposed part, it is preferable that the content of pigment B is 0.2% by mass or more relative to the total mass of the buffer layer, 0.2% to 6% by mass is more preferable, 0.2% to 5% by mass is even more preferable, and 0.25% to 3.0% by mass is particularly preferable.

[0316] Here, the content ratio of pigment B refers to the proportion of pigment that makes all pigment B contained in the buffer layer in a colored state. The following describes a quantitative method for the content ratio of pigment B, using a pigment that develops color via free radicals as an example. Two solutions were prepared by dissolving pigment (0.001 g) and pigment (0.01 g) separately in methyl ethyl ketone (100 mL). IRGACURE OXE-01 (BASF Corporation), a photoradical polymerization initiator, was added to each of the obtained solutions. Free radicals were generated by irradiating the solutions with 365 nm light, causing all pigments to develop color. Next, under atmospheric conditions, the absorbance of each solution at a liquid temperature of 25°C was measured using a spectrophotometer (UV3100, Shimadzu Corporation), and calibration curves were constructed. Then, instead of pigment, the buffer layer (0.1 g) was dissolved in methyl ethyl ketone, and the absorbance of the solution that made all pigments colored was measured using the same method as described above. Based on the calibration curve, the amount of pigment contained in the buffer layer is calculated from the absorbance of the obtained solution containing the buffer layer.

[0317] The buffer layer may contain a compound that generates acids, bases, or free radicals upon exposure to light (hereinafter, sometimes referred to as "Compound C"). It is preferable that Compound C is a compound that generates acids, bases, or free radicals upon exposure to active light (e.g., ultraviolet and visible light). Known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators) can be cited as Compound C. It is preferable that Compound C is a photoacid generator.

[0318] From a analytical point of view, it is preferable that the buffer layer contains a photoacid generator. As a photoacid generator, photocationic polymerization initiators that can be contained in the aforementioned photosensitive resin layer can be cited, and the preferred form is the same, except for the points described later.

[0319] From the viewpoint of sensitivity and resolution, it is preferable that the photoacid generator includes at least one selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and from the viewpoint of sensitivity, resolution and adhesion, it is even more preferable that it includes oxime sulfonate compounds.

[0320] Furthermore, it is also preferable for the photoacid generator to have the following structure.

[0321] [Chemistry 18]

[0322] The buffer layer may contain a photoalkali generating agent. Examples of photoalkali generating agents include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-aminomethylhydroxylamine, O-aminomethyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-oxophyllylethane, (4-oxophyllylbenzoyl)-1-benzyl-1- Dimethylaminopropane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaminecobalt(III)tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-oxo-porphyrin-phenyl)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.

[0323] The buffer layer may contain a photoradical polymerization initiator. Examples of photoradical polymerization initiators include those contained in the photosensitive resin layer described above, and the preferred embodiment is also the same.

[0324] The buffer layer may contain one or more compounds C.

[0325] From the viewpoints of visibility of the exposed part, visibility of the non-exposed part and resolution, the content of compound C relative to the total mass of the buffer layer is preferably 0.1% to 10% by mass, and even more preferably 0.5% to 5% by mass.

[0326] From the viewpoints of resolution, adhesion to layers adjacent to the buffer layer, and developability, it is preferable that the buffer layer contains a plasticizer.

[0327] It is preferable that the molecular weight of the plasticizer (for oligomers or polymers, the molecular weight refers to the weight average molecular weight (Mw). The same applies below in this paragraph.) is less than that of the alkali-soluble resin. It is preferable that the molecular weight of the plasticizer is 200 to 2,000.

[0328] Plasticizers are not limited to compounds that exhibit plasticity as long as they are compatible with alkali-soluble resins. From the viewpoint of imparting plasticity, plasticizers containing alkoxy groups in the molecule are preferred, and polyalkylene glycol compounds are even more preferred. It is preferable that the alkoxy groups contained in the plasticizer have a polyalkylene ethoxy structure or a polyalkylene propoxy structure.

[0329] From the viewpoint of resolution and storage stability, it is preferable that the plasticizer contains a (meth)acrylate compound. From the viewpoint of compatibility, resolution, and adhesion to layers adjacent to the buffer layer, it is even better that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth)acrylate compound.

[0330] Examples of (meth)acrylate compounds used as plasticizers include those described in the above-mentioned vinyl unsaturated compounds. When a buffer layer and a photosensitive resin layer are disposed in direct contact in a photosensitive transfer material, it is preferable that both the buffer layer and the photosensitive resin layer contain the same (meth)acrylate compound. This is because, by having both the buffer layer and the photosensitive resin layer contain the same (meth)acrylate compound, interlayer diffusion is suppressed, and storage stability is improved.

[0331] When the buffer layer contains a (meth)acrylate compound as a plasticizer, it is preferable that the (meth)acrylate compound does not polymerize in the exposed portion after exposure, from the viewpoint of the adhesion between the buffer layer and the adjacent layer.

[0332] In a certain embodiment, from the viewpoints of resolution, adhesion to the layers adjacent to the buffer layer, and developability, the (meth)acrylate compound used as a plasticizer is preferably a (meth)acrylate compound having two or more (meth)acrylic groups in one molecule.

[0333] In one embodiment, it is preferred that the (meth)acrylate compound used as a plasticizer is a (meth)acrylate compound having an acid group or a carbamate (meth)acrylate compound.

[0334] The buffer layer may contain one or more plasticizers.

[0335] From the viewpoints of resolution, adhesion to the layers adjacent to the buffer layer, and developability, the content of plasticizer relative to the total mass of the buffer layer is preferably 1% to 70% by mass, more preferably 10% to 60% by mass, and especially preferably 20% to 50% by mass.

[0336] From the viewpoint of thickness uniformity, it is preferable that the buffer layer contains a surfactant. Examples of surfactants that can be contained in the aforementioned photosensitive resin layer are also preferred.

[0337] The buffer layer may contain one or more surfactants.

[0338] The content of surfactant relative to the total mass of the buffer layer is preferably 0.001% to 10% by mass, and even more preferably 0.01% to 3% by mass.

[0339] The buffer layer may contain a sensitizer. Examples of sensitizers include those that can be contained in the negative photosensitive resin layer described above.

[0340] The buffer layer may contain one or more sensitizers.

[0341] From the viewpoint of improving the sensitivity to light source, the visibility of the exposed part and the visibility of the unexposed part, the content of the sensitizer relative to the total mass of the buffer layer is preferably 0.01% to 5% by mass, and even more preferably 0.05% to 1% by mass.

[0342] In addition to the above-mentioned components, the buffer layer may contain known additives as needed.

[0343] Furthermore, regarding the buffer layer, it is described in paragraphs 0189 to 0193 of Japanese Patent Application Publication No. 2014-85643. The contents of the aforementioned publication are incorporated herein by reference.

[0344] The thickness of the buffer layer is not limited. From the viewpoint of the adhesion between the buffer layer and the layers adjacent to it, an average thickness of 1 μm or more is preferred, and 2 μm or more is even better. There is no upper limit to the average thickness of the buffer layer. From the viewpoint of developability and resolution, an average thickness of 20 μm or less is preferred, 10 μm or less is even better, and 5 μm or less is particularly preferred.

[0345] The method for forming the buffer layer is not limited as long as it is a method capable of forming a layer containing the above-mentioned components. For example, a method for forming a buffer layer can be described by coating a buffer layer forming composition on the surface of a temporary support and drying the coating of the buffer layer forming composition.

[0346] Examples of compositions for forming a buffer layer include compositions containing the above-mentioned components. In order to adjust the viscosity of the composition for forming a buffer layer so as to facilitate the formation of a buffer layer, it is preferable that the composition for forming a buffer layer contains a solvent.

[0347] The solvent contained in the composition for forming the buffer layer is not limited as long as it is a solvent capable of dissolving or dispersing the components contained in the buffer layer. Examples of solvents that can be contained in the above-mentioned photosensitive resin composition are as follows, and the preferred embodiment is the same.

[0348] The composition for forming the buffer layer may contain one or more solvents.

[0349] The proportion of solvent in the composition for forming the buffer layer is preferably 50 to 1,900 parts by mass relative to 100 parts by mass of the total solids in the composition for forming the buffer layer, and more preferably 100 to 900 parts by mass.

[0350] The preparation of the buffer layer composition and the formation of the buffer layer can be carried out according to the above-described methods for preparing the photosensitive resin composition and forming the negative photosensitive resin layer. For example, by preparing a buffer layer composition by dissolving each component contained in the buffer layer in a solvent and mixing the solutions in a predetermined ratio, the obtained buffer layer composition is coated onto the surface of a temporary support and the coating is dried, thereby forming a buffer layer. Alternatively, a buffer layer can be formed on the surface of the photosensitive resin layer after a photosensitive resin layer is formed on a protective film.

[0351] [Protective Film] It is preferable that the photosensitive transfer material has a protective film. Alternatively, the protective film is not included in the transfer layer described above. It is preferable that the photosensitive resin layer and the protective film are in direct contact.

[0352] As materials constituting the protective film, resin films and paper can be cited as examples. From the viewpoint of strength and flexibility, resin films are preferred. As resin films, polyethylene films, polypropylene films, polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films can be cited as examples. Among these, polyethylene films, polypropylene films, or polyethylene terephthalate films are preferred.

[0353] The thickness (layer thickness) of the protective film is not particularly limited, but 5 μm to 100 μm is preferred, and 10 μm to 50 μm is even better. From the viewpoints of transportability, defect suppression of photoresist pattern, and resolution, it is preferable that the arithmetic mean roughness Ra of the surface of the protective film opposite to the photosensitive resin layer side is less than or equal to the arithmetic mean roughness Ra of the surface of the protective film opposite to the photosensitive resin layer side, and even better that it is less than or equal to the arithmetic mean roughness Ra of the surface of the protective film opposite to the photosensitive resin layer side. From the viewpoints of transportability and winding performance, it is preferable that the arithmetic mean roughness Ra of the surface of the protective film opposite to the photosensitive resin layer side is 300 nm or less, even better that it is 100 nm or less, further preferred that it is 70 nm or less, and particularly preferred that it is 50 nm or less. Furthermore, from the viewpoint of superior resolution, it is preferable that the arithmetic mean roughness Ra of the surface of the photosensitive resin layer in the protective film is 300 nm or less, more preferably 100 nm or less, further preferably 70 nm or less, and especially preferably 50 nm or less. This is believed to be because, by having the Ra value of the protective film surface within the above-mentioned range, the uniformity of the thickness of the photosensitive resin layer and the formed photoresist pattern is improved. The lower limit of the Ra value of the protective film surface is not particularly limited, but it is preferable that both sides have a Ra value of 1 nm or more, more preferably 10 nm or more, and especially preferably 20 nm or more. Additionally, it is preferable that the peel force of the protective film is less than that of the temporary support.

[0354] Photosensitive transfer materials may have layers other than those described above (hereinafter also referred to as "other layers"). Examples of other layers include, for instance, a contrast enhancement layer. Contrast enhancement layers are described in paragraph 0134 of International Publication No. 2018 / 179640. Other layers are described in paragraphs 0194 to 0196 of Japanese Patent Application Publication No. 2014-85643. The contents of these publications are incorporated herein by reference.

[0355] 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 the method described above for measuring the thickness of each layer. From the viewpoint of further enhancing the effects of this 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, further preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less. Furthermore, from the viewpoint of further enhancing the effects of this disclosure, the total thickness of the photosensitive resin layer, intermediate layer, and buffer layer in the photosensitive transfer material is preferably 20 μm or less, more preferably 10 μm or less, further preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.

[0356] [Manufacturing method of photosensitive transfer material] The manufacturing method of the photosensitive transfer material disclosed herein is not particularly limited and can use known manufacturing methods, such as known methods for forming layers.

[0357] As a method for manufacturing the above-mentioned photosensitive transfer material, a method including the following steps can be cited: after coating an intermediate layer composition on the surface of a temporary support, drying the coating of the intermediate layer composition to form an intermediate layer; and after coating a photosensitive resin composition on the surface of the intermediate layer, drying the coating of the photosensitive resin composition to form a photosensitive resin layer.

[0358] A photosensitive transfer material is manufactured by pressing a protective film onto the photosensitive resin layer of a laminate manufactured using the above-described manufacturing method. As a method for manufacturing the photosensitive transfer material disclosed herein, it is preferable to manufacture a photosensitive transfer material comprising a temporary support, an intermediate layer, a photosensitive resin layer, and a protective film by including a step of setting a protective film in contact with the side of the photosensitive resin layer opposite to the temporary support side. After manufacturing the photosensitive transfer material by the above-described manufacturing method, a roll-shaped photosensitive transfer material can be produced and stored by winding the photosensitive transfer material. The roll-shaped photosensitive transfer material can be directly provided in this form to the roll-to-roll bonding step with a substrate described later.

[0359] The photosensitive transfer material disclosed herein is preferably used in various applications requiring precision microfabrication based on photolithography. After patterning the photosensitive resin layer, the photosensitive resin layer can be etched as a film, or electroforming, primarily electroplating, can be performed. Furthermore, the hardened film obtained by patterning can be used as a permanent film, for example, as an interlayer insulating film, a wiring protection film, or a wiring protection film with a refractive index matching layer. Moreover, the photosensitive transfer material disclosed herein is preferably used in various wiring formation applications in semiconductor packaging, printed circuit boards, and sensor substrates, as well as in touch panels, electromagnetic wave shielding materials, conductive films such as thin-film heaters, liquid crystal sealing materials, and the formation of structures in the fields of micromechanics or microelectronics.

[0360] Furthermore, the photosensitive transfer material disclosed herein is preferably exemplified as a coloring resin layer containing pigment. In addition to the above-described uses, the coloring resin layer is suitable for, for example, forming color pixels or black matrices in color filters used in liquid crystal display devices (LCDs) and solid-state imaging elements (e.g., CCDs and CMOS). The forms of the coloring resin layer other than pigment are the same as those described above.

[0361] <Pigment> The photosensitive resin layer can be a colored resin layer containing pigment. In recent years, cover glass, in order to protect the liquid crystal display window of electronic devices, is sometimes installed with a black frame-shaped light-shielding layer formed on the back periphery of a transparent glass substrate, etc. To form this light-shielding layer, a colored resin layer can be used. As for the pigment, it can be appropriately selected according to the desired hue, and can be selected from black pigment, white pigment, and colored pigments other than black and white. Among them, when forming a black pattern, black pigment is preferred as the pigment.

[0362] As a black pigment, any known black pigment (organic pigment or inorganic pigment, etc.) can be appropriately selected, provided it does not impair the effects disclosed herein. From the viewpoint of optical concentration, carbon black, titanium oxide, titanium carbide, iron oxide, titanium oxide, and graphite are preferred examples of black pigments, with carbon black being particularly preferred. From the viewpoint of surface resistivity, carbon black with at least a portion of its surface coated with resin is preferred.

[0363] From the viewpoint of dispersion stability, the particle size of black pigment is preferably 0.001 μm to 0.1 μm, and more preferably 0.01 μm to 0.08 μm, based on the number average particle size. Here, particle size refers to the diameter of a circle whose area is calculated from a photographic image of the pigment particles taken with an electron microscope and considering a circle with the same area as the pigment particles. The number average particle size is the average value obtained by calculating the above particle size for any 100 particles and averaging the 100 particle sizes.

[0364] Regarding white pigments other than black pigments, the white pigments described in paragraphs 0015 and 0114 of Japanese Patent Application Publication No. 2005-007765 can be used. Specifically, among white pigments, titanium dioxide, zinc oxide, zinc barium white, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferred as inorganic pigments, with titanium dioxide or zinc oxide being more preferred, and titanium dioxide being even more preferred. As inorganic pigments, rutile or anatase titanium dioxide is even more preferred, with rutile titanium dioxide being particularly preferred. Furthermore, the surface of titanium dioxide can be treated with silicon dioxide, aluminum oxide, titanium dioxide, zirconium dioxide, or organic matter, and two or more treatments can also be performed. In this way, the catalytic activity of titanium dioxide is suppressed, and its heat resistance and fading properties are improved. From the viewpoint of reducing the thickness of the heated photosensitive resin layer, at least one of aluminum oxide treatment and zirconium dioxide treatment is preferred as a surface treatment for titanium oxide, and both aluminum oxide treatment and zirconium dioxide treatment are particularly preferred.

[0365] Furthermore, when the photosensitive resin layer is a colored resin layer, from the viewpoint of transferability, it is preferable that the photosensitive resin layer further includes colored pigments other than black and white pigments. When colored pigments are included, from the viewpoint of better dispersibility, a particle size of 0.1 μm or less is preferable, and 0.08 μm or less is even more preferable. As colored pigments, examples include Victoria Blue BO (Color Index 42595), Golden Ammonium (CI 41000), Fat Black HB (CI 26150), Monolight Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hostaperm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Pastel Pink B Supura (CI Pigment Red 81), and Monastral Fast. Blue (CI Pigment Blue 15), Monolight Black B (CI Pigment Black 1), and carbon, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Blue 15:1, CI Pigment Blue 15:4, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, and CI Pigment Violet 23, etc. Among them, CI Pigment Red 177 is considered superior.

[0366] When the photosensitive resin layer contains pigment, the pigment content relative to the total mass of the photosensitive resin layer is preferably more than 3% by mass and less than 40% by mass, more than 3% by mass and less than 35% by mass is even better, more than 5% by mass and less than 35% by mass is further better, and more than 10% by mass and less than 35% by mass is particularly better.

[0367] When the photosensitive resin layer contains pigments other than black pigment (white pigments and colored pigments), it is preferable that the content of pigments other than black pigment is less than 30% by mass relative to black pigment, more preferably 1% to 20% by mass, and even more preferably 3% to 15% by mass.

[0368] Furthermore, when the photosensitive resin layer contains a black pigment and the photosensitive resin layer is formed from a photosensitive resin composition, it is preferable that the black pigment (preferably carbon black) is introduced into the photosensitive resin composition in the form of a pigment dispersion. The dispersion can be prepared by adding a mixture obtained by pre-mixing a black pigment and a pigment dispersant to an organic solvent (or vehicle) and dispersing it using a disperser. The pigment dispersant can be selected based on the pigment and solvent; for example, a commercially available dispersant can be used. The vehicle refers to the medium that disperses the pigment when preparing the pigment dispersion; it is liquid and contains a binder component that holds the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component.

[0369] There are no particular limitations on the type of dispersing machine. Examples include known dispersing machines such as kneaders, roller mills, attritors, super mills, dissolvers, homogenizers, and sand mills. Furthermore, mechanical grinding can be used to achieve micronization through friction. For information on dispersing machines and micronization, please refer to the "Dictionary of Pigments" (Kunizo Asakura, 1st edition, Asakura Shoten, 2000, pp. 438, 310).

[0370] <Method for Manufacturing a Deposition Mask> The method for manufacturing a deposition mask disclosed herein uses the photosensitive transfer material for manufacturing a deposition mask disclosed herein. Furthermore, the method for manufacturing a deposition mask disclosed herein preferably includes the following steps in sequence: preparing a metal layer having a first surface and a second surface at a position opposite to the first surface (hereinafter also referred to as the "preparation step"); bonding the photosensitive transfer material to the metal layer, and sequentially disposing a transfer layer and a temporary support on the first surface of the metal layer (hereinafter also referred to as the "bonding step"). The photosensitive transfer material sequentially includes the temporary support and the transfer layer having at least a photosensitive resin layer, and the number of foreign objects with a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50 per mm. 3. The above-mentioned transfer layer is patterned and exposed (hereinafter also referred to as the "exposure step"). The above-mentioned transfer layer is developed to form a photoresist pattern (hereinafter also referred to as the "development step"). The above-mentioned metal layer not covered by the above-mentioned photoresist pattern is etched to form a through hole extending from the above-mentioned first surface of the above-mentioned metal layer to the above-mentioned second surface of the above-mentioned metal layer (hereinafter also referred to as the "etching step"). The above-mentioned photoresist pattern is removed (hereinafter also referred to as the "removal step").

[0371] The following describes in detail the steps of the method for manufacturing the deposition mask disclosed herein.

[0372] (Preparation Step) In the preparation step, a metal layer having a first surface and a second surface at a position opposite to the first surface is prepared. The metal layer can be a known metal substrate (including commercially available products). The metal layer can also be manufactured by known methods (e.g., casting, forging, sputtering, and electroplating).

[0373] The structure of the metal layer can be a single-layer structure or a multi-layer structure. Examples of metallic elements included in the metal layer include Cu, Ni, Fe, Cr, Mn, and Co. Part or all of the metal layer can also be an alloy. Examples of alloys include Ni-Co alloys and Fe-Ni alloys. It is preferable that the metal layer includes at least one metallic element selected from the group consisting of Cu, Ni, Fe, Cr, Mn, and Co; it is more preferable that it includes at least one metallic element selected from the group consisting of Cu, Fe, and Ni; it is further preferable that it includes Fe; and it is particularly preferable that it includes both Fe and Ni. The metal layer can include elements other than metallic elements. Examples of elements other than metallic elements include B, C, N, O, P, S, and Cl. The metal layer can also be a metal substrate. Among the metals used in the metal layer, nickel, Ni-Co alloys, Fe-Ni alloys, and copper are preferred. Alloys containing 30% to 45% nickel by mass are particularly desirable, and metals with an alloy of 36% nickel and 64% iron as the main components, i.e., inert steel, are even more desirable. When the metal in the metal layer is inert steel, the coefficient of thermal expansion of the metal pattern is, for example, approximately 1.2 × 10⁻⁶ / ℃. Furthermore, Fe-Ni-Co alloys (e.g., super inert steel) can also be used as metals in the metal layer.

[0374] From the viewpoint of adhesion and resolution, it is preferable that the roughness Rmax of the first surface of the metal layer is 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 roughness Rmax of the second surface of the metal layer can be 0.5 μm to 5.0 μm. The roughness Rmax of the first surface of the metal layer can be the same as or different from the roughness Rmax of the second surface of the metal layer.

[0375] In this disclosure, a three-dimensional optical profilometer (New View 7300, manufactured by Zygo Corporation) is used to measure the surface roughness Rmax of an object. First, the surface profile of the object is obtained. The Microscope Application of MetroPro ver8.3.2 is used as the measurement / analysis software. Next, the Surface Map screen is displayed using the measurement / analysis software, and histogram data is obtained from the Surface Map screen. The surface roughness Rmax of the object is obtained from the obtained histogram data. Furthermore, the surface roughness Rmax corresponds to the maximum height of the roughness curve at the reference length.

[0376] In the preparation step, the metal layer can be prepared in a state disposed on a substrate. In other words, in the preparation step, a laminate comprising a substrate and a metal layer having a second surface facing the substrate and a first surface located opposite to the second surface can be prepared. Examples of components of the substrate include glass and polymers. Examples of polymers include polyimide, cyclic olefin polymers, polyethylene, polypropylene, polyethylene terephthalate, cellulose triacetate, polystyrene, and polycarbonate. A glass substrate or a resin film is preferred as the substrate, with a resin film being more preferred. Examples of resin films include polyimide films, cyclic olefin polymer films, polyethylene films, polypropylene films, polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films.

[0377] From the point of view of the resolution of the through-hole, an average thickness of 30 μm to 500 μm is preferred, 40 μm to 400 μm is more preferred, and 50 μm to 300 μm is even more preferred. The average thickness of the metal layer is calculated by the arithmetic mean of the thicknesses measured at five locations during cross-sectional observation using a scanning electron microscope (SEM).

[0378] (Lamination Step) In the bonding step, a photosensitive transfer material is bonded to the aforementioned metal layer, and a transfer layer and a temporary support are sequentially disposed on the first surface of the aforementioned metal layer. The photosensitive transfer material sequentially includes the aforementioned temporary support and the aforementioned transfer layer having at least a photosensitive resin layer, and the number of foreign objects with a diameter of 1.0 μm to 10.0 μm per unit volume of the aforementioned temporary support is 50 or less per mm³. Furthermore, the preferred embodiment of the photosensitive transfer material is the same as the preferred embodiment of the photosensitive transfer material for manufacturing a deposition mask disclosed herein.

[0379] The bonding of the photosensitive transfer material to the metal layer can be performed using known methods. In the bonding step, it is preferable to press the photosensitive transfer material and the metal layer together. For example, it is preferable to bond the photosensitive transfer material and the metal layer by overlapping them and applying pressure and heat using a mechanism such as rollers. In the bonding step, known laminators such as laminators, vacuum laminators, and automated cutting laminators that improve productivity can be used. A lamination temperature of, for example, 70°C to 130°C is preferable. When the photosensitive transfer material includes a protective film, the bonding step is performed after removing the protective film.

[0380] (Pressure Step) After bonding the photosensitive transfer material to the metal layer, a pressure step can be performed. For example, the laminate obtained by bonding the photosensitive transfer material to the metal layer can be pressurized. It is preferable that the laminate being pressurized consists of a metal layer, a transfer layer, and a temporary support in sequence. Alternatively, the laminate being pressurized can consist of a metal layer and a transfer layer in sequence. For example, if the temporary support is peeled off after the bonding step, a laminate consisting of a metal layer and a transfer layer in sequence can be formed. In the pressure step, the laminate obtained by bonding the photosensitive transfer material to the metal layer can be pressurized using an autoclave. For example, a pressure treatment at 50°C, 0.5 MPa, and 60 minutes can be performed. By pressurizing the laminate, the adhesion between the transfer layer and the metal layer can be improved, and the conformability of the transfer layer to the surface irregularities of the metal layer is improved. It is better to apply the pressure before the exposure step.

[0381] (Exposure Step) In the exposure step, the transfer layer is pattern-exposed. "Pattern-exposed transfer layer" means that exposed and unexposed areas are formed on the transfer layer by irradiating the transfer layer with light. The positional relationship between the exposed and unexposed areas can be determined, for example, based on the shape of the target photoresist pattern.

[0382] It is preferable that the light used for patterning the transfer layer illuminates the transfer layer in a direction from the transfer layer toward the metal layer. It is also preferable that the light used for patterning the transfer layer includes at least one wavelength selected from the group consisting of 365 nm and 405 nm.

[0383] As a light source, examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps and LEDs (Light Emitting Diodes).

[0384] An exposure of 5 mJ / cm² to 200 mJ / cm² is preferred, and 10 mJ / cm² to 100 mJ / cm² is even better.

[0385] Examples of exposure methods include contact exposure and non-contact exposure. Examples of contact exposure methods include using a photomask. Examples of non-contact exposure methods include proximity exposure, projection exposure using a lens system or mirror system, and direct exposure using an exposure laser. In projection exposure using a lens system or mirror system, an exposure machine with an appropriate aperture number (NA) can be used depending on the required resolution and depth of focus. In direct exposure, the transfer layer can be directly drawn, or the transfer layer can be subjected to reduced projection exposure via a lens. The exposure process can be performed under atmospheric conditions, under reduced pressure, or under vacuum. Alternatively, a liquid such as water can be placed between the light source and the transfer layer to perform the exposure process.

[0386] The exposure step can be performed before or after the temporary support is removed, but from the viewpoint of further maximizing the effects disclosed herein, it is preferable to perform it before the temporary support is removed. When the exposure step is performed before the temporary support is removed, the transfer layer can be exposed via the temporary support. In the exposure step using a photomask, the transfer layer can be patterned and exposed while the photomask is in contact with the transfer layer, or the transfer layer can be patterned and exposed while the photomask is close to the transfer layer without contacting it. To prevent photomask contamination caused by 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. When patterning the transfer layer via the temporary support, it is preferable to remove the temporary support after the exposure step and before the development step.

[0387] (Temporary Support Stripping Step) The method for manufacturing the deposition mask disclosed herein preferably includes a temporary support stripping step, in which the temporary support is stripped between the temporary support and the transfer layer. Furthermore, it is preferable that the temporary support stripping step is performed after the exposure step and before the development step. The method for stripping the temporary support is not particularly limited, and a mechanism identical to the cover film stripping mechanism described in paragraphs 0161-0162 of Japanese Patent Application Publication No. 2010-072589 can be used.

[0388] (Developing Step) In the developing step, the transfer layer is developed to form a photoresist pattern. It is believed that the resolution of the photoresist pattern formed after the developing step affects the resolution of the through-holes formed after the etching step described later, and further, the resolution of the through-holes affects the resolution of the pattern formed using a deposition mask.

[0389] Photoresist patterns are formed by removing the exposed or non-exposed portions of the transfer layer. When the transfer layer includes a negative photosensitive resin layer, the non-exposed portions of the transfer layer are usually removed by developing, and the photoresist pattern is formed from the exposed portions of the transfer layer. When the transfer layer includes a positive photosensitive resin layer, the exposed portions of the transfer layer are usually removed using a developing solution, and the photoresist pattern is formed from the non-exposed portions of the transfer layer.

[0390] The developing process is carried out, for example, using a developing solution. Examples of known developing solutions include (e.g., the developing solution described in Japanese Patent Application Publication No. 5-72724). An alkaline aqueous solution containing a compound with a pKa of 7 to 13 at a concentration of 0.05 mol / L to 5 mol / L is preferred. Examples of alkaline compounds contained in the alkaline aqueous solution 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 developing solution may contain a water-soluble organic solvent. The developing solution may contain a surfactant. Examples of preferred developing solutions include the developing solution described in paragraph 0194 of International Publication No. 2015 / 093271.

[0391] The optimal temperature for the developer is 20℃~40℃.

[0392] Examples of developing methods include, for example, immersion development, shower development, shower and spin development, and immersion development. Shower development refers to a developing method in which developing solution is sprayed onto an object by a shower. As a preferred developing method, for example, the developing method described in paragraph 0195 of International Publication No. 2015 / 093271 may be cited.

[0393] It is preferable to remove the developer and residue remaining after the developing step using known methods. Examples of methods for removing developer and residue include spray treatment and AirKnife treatment. In spray treatment, liquids such as water and cleaning agents are sprayed onto the object. Residue can also be removed using a brush.

[0394] (Etching Step) In the etching step, an etching process is performed on the metal layer not covered by the photoresist pattern to form a through hole extending from the first side of the metal layer to the second side of the metal layer.

[0395] The etching process can be a known method. Examples of etching processes include wet etching and dry etching (e.g., plasma etching). Examples of etching processes include the methods described in paragraphs 0209 to 0210 of Japanese Patent Application Publication No. 2017-120435 and the methods described in paragraphs 0048 to 0054 of Japanese Patent Application Publication No. 2010-152155.

[0396] Wet etching is preferred. In wet etching, an etching solution is typically used. The type of etching solution can be selected from acidic or alkaline etching solutions depending on the object being etched. Examples of acidic etching solutions include an aqueous solution 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 a mixed aqueous solution of the aforementioned acidic component and at least one salt selected from the group consisting of ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component can also be a combination of multiple acidic components. Examples of alkaline etching solutions include an aqueous solution containing at least one alkaline component selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (such as tetramethylammonium hydroxide). Examples of alkaline etching solutions include a mixed aqueous solution of the aforementioned alkaline component and a salt (e.g., potassium permanganate). The alkaline component can also be a combination of multiple alkaline components. From the viewpoint of further enhancing the effects disclosed herein, it is preferable that the etching solution used in the above etching process contains ferric chloride. Furthermore, it is preferable that the solubility of the photoresist pattern in a solution containing 40% by mass of ferric chloride at 45°C is 1 μm / min or less, and more preferably 0.5 μm / min or less. The lower limit is 0 μm / min.

[0397] In the method for manufacturing the deposition mask disclosed herein, the metal layer in the deposition mask has through holes extending from a first surface to a second surface. The metal layer may have a plurality of through holes. The depth of the through holes corresponds to the thickness of the metal layer. The through holes are typically defined by the inner surface of the metal layer. The through holes may be defined by one or more surfaces. The surfaces defining the through holes as seen in cross-section may be straight lines or curves. The number, shape, and arrangement of the through holes are determined, for example, according to the target pattern. The through holes extending from the first surface to the second surface form openings on the first surface and also on the second surface. The diameter of the opening formed on the first surface corresponds to the diameter of the through holes on the first surface, as described later, and the diameter of the opening formed on the second surface corresponds to the diameter of the through holes on the second surface, as described later. Examples of the shape of the through holes (specifically, the openings) as seen in top view include circles, ellipses, and quadrilaterals. When viewed from above, the through-hole is preferably quadrilateral, and even better if it is square or rectangular. When the through-hole is viewed from above and is polygonal (e.g., quadrilateral), some or all of the multiple corners of the polygon may be rounded.

[0398] The average diameter of the through-hole in the second surface of the metal layer (hereinafter, sometimes referred to as "the average diameter D2 of the through-hole") is smaller than the average diameter of the through-hole in the first surface of the metal layer (hereinafter, sometimes referred to as "the average diameter D1 of the through-hole"). In other words, the average diameter D1 of the through-hole is greater than the average diameter D2 of the through-hole. For example, if the average diameter D1 of the through-hole is greater than the average diameter D2 of the through-hole, then material arriving at the first surface of the metal layer from the vaporization source can easily enter the through-hole through the opening formed on the first surface of the metal layer. As a result, for example, productivity and pattern accuracy are improved. It is preferable that the ratio of the average diameter D2 of the through-hole to the average diameter D1 of the through-hole (i.e., D2 / D1) is 0.8 or less, more preferably 0.4 or less, and further preferably 0.3 or less. From the perspective of high-resolution patterning, it is preferable for the ratio of the average diameter D2 of the through hole to the average diameter D1 of the through hole (i.e., D2 / D1) to be 0.01 or higher, even better if it is 0.1 or higher, and further preferred if it is 0.15 or higher.

[0399] The average diameter of the through-holes in the second surface of the metal layer (i.e., the average diameter D2 of the through-holes) is 25 μm or less. If the average diameter D2 of the through-holes is 25 μm or less, a pattern can be formed with high resolution. From the viewpoint of high-resolution patterning, it is preferable that the average diameter D2 of the through-holes is 25 μm or less, more preferably 20 μm or less, and further preferably 10 μm or less. The lower limit of the average diameter D2 of the through-holes is not limited. The average diameter D2 of the through-holes can also be 5 μm, 1 μm, or 0.1 μm.

[0400] As long as the relationship "average diameter D2 of the through hole" < "average diameter D1 of the through hole" is satisfied, the average diameter D1 of the through hole is not limited. From the viewpoint of high-resolution patterning, an average diameter D1 of 15μm to 100μm is preferred, 20μm to 50μm is more preferred, and 20μm to 30μm is even more preferred. The lower limit of the average diameter D1 of the through hole can be 8μm or 10μm.

[0401] In this disclosure, the average diameter of the through-hole is calculated by the arithmetic mean of the diameters of 10 through-holes measured using images obtained using a scanning electron microscope (SEM). In this disclosure, the diameter of the through-hole is defined by the maximum value of the straight line connecting any two points on the outline of the through-hole (specifically, the opening) as observed from above. The average diameter D2 of the through-hole is smaller than the average diameter D1 of the through-hole; therefore, when viewing the first surface of the metal layer from above, the outline of the opening formed on the second surface of the metal layer can sometimes be observed inside the outline of the opening formed on the first surface of the metal layer. The average diameters D1 and D2 of the through-hole can be calculated based on the observations described above.

[0402] As long as the relationship "average diameter D2 of the through hole" < "average diameter D1 of the through hole" is satisfied, the diameter of the through hole can vary continuously or discontinuously along the direction from the first surface to the second surface. It is preferable that the diameter of the through hole gradually decreases along the direction from the first surface to the second surface.

[0403] (Removal Step) In the removal step, the photoresist pattern is removed. For example, a method of removing the photoresist pattern using chemical treatment can be cited. Using a removal solution to remove the photoresist pattern is preferred.

[0404] Examples of removal solutions include those comprising an inorganic base or an organic base and a mixed solvent of water, dimethyl sulfoxide, N-methylpyrrolidone, or the like. Examples of inorganic bases include sodium hydroxide and potassium hydroxide. Examples of organic bases include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

[0405] Photoresist patterns can also be removed by immersing the laminate containing the photoresist pattern in a removal solution. The temperature of the removal solution 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. The removal solution can be stirred during the immersion method.

[0406] Photoresist patterns can be removed, for example, by spraying, spraying or immersion using a removal liquid.

[0407] (Other Steps) The method for manufacturing the deposition mask disclosed herein may further include other steps as needed. When the metal layer of the deposition mask is formed on a substrate, the method for manufacturing the deposition mask disclosed herein may include a step of removing the substrate.

[0408] The manufacturing method of the deposition mask will be described with reference to FIG4. FIG4 is a schematic cross-sectional view showing the manufacturing method of a deposition mask in a certain embodiment. As shown in FIG4(a), a metal layer 10 having a first surface 10F and a second surface 10R located opposite to the first surface 10F is prepared. As shown in FIG4(b), a photosensitive transfer material (not shown) is bonded to the metal layer 10 to form a transfer layer 20 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 FIG4(c), the transfer layer 20 is patterned by exposure, and then the transfer layer 20 is developed to form a photoresist pattern 21. As shown in FIG4(d), a through hole 10H is formed by etching the metal layer 10 not covered by the photoresist pattern 21. It is assumed that during the etching process, isotropic etching (i.e., etching in a direction orthogonal to the depth direction of the metal layer 10, in addition to etching in the depth direction of the metal layer 10) occurs, forming a through-hole 10H with the cross-sectional shape shown in FIG4(d). As shown in FIG4(e), a deposition mask 100 is obtained by removing the photoresist pattern 21. 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 on the first surface 10F of the metal layer 10, and an opening 10RA on the second surface 10R of the metal layer 10.

[0409] The deposition mask manufactured by the method disclosed herein may, as needed, include components other than a metal layer. Examples of components other than a metal layer include, for example, a frame. The frame can enhance the deposition mask or improve its operability. The frame can be disposed around a through-hole in plan view, or disposed on the outer periphery of the metal layer in plan view. Examples of components of the frame include, for example, metals. Examples of metals include, for example, Fe-Ni alloys (e.g., Indium) and Fe-Ni-Co alloys (e.g., Super Indium).

[0410] The structure of a deposition mask manufactured by the method disclosed herein will be described with reference to Figures 1, 2, and 3. Figure 1 is a schematic top view showing an embodiment of the deposition mask. Figure 2 is an enlarged schematic top view showing the through-hole of the deposition mask shown in Figure 1. Figure 3 is an enlarged schematic cross-sectional view showing the through-hole of 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 to the first surface 10F, and through-holes 10H. The first surface of the metal layer 10 faces the observer looking at Figures 1 and 2. The first surface 10F and the second surface 10R of the metal layer 10 face opposite directions. As shown in Figures 1 and 2, the through-holes 10H are defined by a grid-like pattern formed by the metal layer 10, and the through-holes 10H are quadrilateral in shape when viewed from above. In Figure 2, the contour line of the through-hole 10H is observed twice because the contour line of the opening formed on the first surface 10F of the metal layer 10 (specifically, the opening 10FA in Figure 3) is observed inside the contour line of the opening formed on the second surface 10R of the metal layer 10 (specifically, the opening 10RA in Figure 3). As shown in Figure 3, the through-hole 10H 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 the opening 10FA on the first surface 10F of the metal layer 10, and the opening 10RA forms on the second surface 10R of the metal layer 10. The through-hole 10H is defined by the inner surface of the metal layer 10, and the inner surface of the metal layer 10 defining the through-hole 10H is curved. The average diameter of the through-hole 10H on the second surface 10R of the metal layer 10 is smaller than the average diameter of the through-hole 10H on the first surface 10F of the metal layer 10. The diameter of the through hole 10H gradually decreases along the direction from the first surface 10F toward the second surface 10R.

[0411] The deposition mask manufactured by the method of manufacturing the deposition mask disclosed herein is preferably applicable to the method of manufacturing patterns using deposition. In the deposition method, it is preferable that the deposition mask is disposed on the object with the second surface of the metal layer facing the object. If the second surface of the metal layer faces the object, the material reaching the first surface of the metal layer from the vaporization source can easily enter the through-hole. The material entering the through-hole moves in the through-hole along the direction from the first surface of the metal layer toward the second surface and adheres to the object. The material passing through the through-hole accumulates on the object, thereby forming a pattern. Examples of objects for forming patterns include glass substrates and resin films. The type of deposition method, the conditions of the deposition method, and the type of material to be deposited can be determined, for example, according to the target pattern. As a preferred deposition method, vacuum deposition can be cited as an example. As a preferred application of the deposition mask manufactured by the method of manufacturing the deposition mask disclosed herein, an example is an OLED manufacturing method. [Example]

[0412] Hereinafter, the present disclosure will be described in detail with reference to embodiments. However, the present disclosure is not limited to the following embodiments. In the following description, unless otherwise specified, "%" refers to "mass %" and "parts" refers to "parts by mass".

[0413] <Manufacturing of Temporary Support 1> A temporary support consisting of a 16μm thick polyester film and a 40nm thick particle-containing layer is manufactured in the following order.

[0414] (Particle layer forming composition 1) Particle layer forming composition 1 was obtained by mixing the components as shown below. After preparing particle layer forming composition 1, it was filtered using a 6 μm filter (F20, manufactured by MAHLE Japan Ltd.), and then degassed using a 2×6 Radial Flow Super Phobic membrane (manufactured by Polypore Co., Ltd.).

[0415] · Acrylic polymer (AS-563A, manufactured by Daicel FineChem Ltd., solids content 27.5% by mass): 167 parts by mass· Nonionic surfactant (NAROACTY CL95, manufactured by Sanyo Chemical Industries, Ltd., solids content 100% by mass): 0.7 parts by mass· Anionic surfactant (RAPISOL A-90, manufactured by NOF CORPORATION, diluted with water to 1% by mass): 114.4 parts by mass· Carnauba wax dispersion (Selosol 524, manufactured by CHUKYO YUSHI CO.,LTD., solids content 30% by mass): 7 parts by mass· Carbodiimide compound (CARBODILITE V-02-L2, manufactured by Nisshinbo Chemical Inc., diluted with water to 10% by mass): 20.9 parts· Matting agent (SNOWTEX XL, Nissan Chemical) Manufactured by Corporation, solid content 40% by mass (average particle size 50 nm): 2.8 parts by mass; water: 690.2 parts by mass.

[0416] (Extrusion Molding) Particles of polyethylene terephthalate (PET), which uses citric acid chelated organotitanium complex as a polymerization catalyst as described in Japanese Patent No. 5575671, are dried to a moisture content of less than 50 ppm, fed into the hopper of a 30 mm diameter uniaxial compounding extruder, and melted and extruded at 280°C. The melt is then passed through a filter (2 μm pore size) and extruded from a die onto a cooling roller at 25°C to obtain an unstretched film. Furthermore, an electrostatic application method is used to ensure close contact between the extruded melt and the cooling roller.

[0417] (Stretching and Coating) A temporary support consisting of a 16 μm thick polyester film and a 40 nm thick particle-containing layer was obtained by successively biaxial stretching a cured unstretched film using the following method.

[0418] (a) Longitudinal stretching involves passing the unstretched film between two pairs of clamping rollers with different circumferential speeds and stretching it longitudinally (in the conveying direction). The preheating temperature was set to 75°C, the stretching temperature to 90°C, the stretching ratio to 3.4 times, and the stretching speed to 1300% / second.

[0419] (b) A particle layer forming composition 1 was coated on one side of a longitudinally stretched film using a bar coater in such a way that the film thickness was 40 nm after coating.

[0420] (c) Transverse stretching: The film that has undergone the above longitudinal stretching and coating was transversely stretched using a tenter frame under the following conditions: Preheating temperature: 110°C; Stretching temperature: 120°C; Stretching ratio: 4.2 times; Stretching speed: 50% / second

[0421] (Heat Curing and Heat Relaxation) The biaxially stretched film after longitudinal and transverse stretching was heat-cured under the following conditions: Heat curing temperature: 227°C; Heat curing time: 6 seconds.

[0422] After heat setting, the width of the tenter frame was reduced, and heat relaxation was performed under the following conditions: Heat relaxation temperature: 190℃; Heat relaxation rate: 4%.

[0423] (Rolling) After heat fixation and heat relaxation, the ends were trimmed, and the ends were extruded (knurled) with a width of 10 mm. The roll was then wound with a tension of 40 kg / m. The width was 1.5 m, and the roll length was 6300 m. The resulting film roll was used as a temporary support 1. The haze value of the temporary support 1 was 0.2. The haze value was measured as the total light haze value using a haze meter (manufactured by NIPPON DENSHOKU INDUSTRIES CO.,LTD., NDH2000). Furthermore, the heat shrinkage rate based on heating at 150°C for 30 minutes was 1.0% on the MD (Machine Direction) side and 0.2% on the TD (Transverse Direction) side. The film thickness containing the particle layer was measured to be 40 nm based on a cross-sectional TEM image. The average particle size of the particles contained in the particle-containing layer was measured using the above method with a Hitachi High-Technologies HT-7700 transmission electron microscope (TEM), and the result was 50 nm.

[0424] <Temporary Support 2> The following was used as temporary support 2: Temporary support 2: Polyester film, 16QS62 manufactured by TORAY INDUSTRIES, INC., with a thickness of 16μm.

[0425] <Manufacturing of Temporary Support 3> In the method of manufacturing temporary support 1, the particle layer forming composition 1 is changed to the particle layer forming composition 2 as shown below, and the temporary support 3 is manufactured in the same manner as the method of manufacturing temporary support 1.

[0426] (Contains total particle formation composition 2) • Acrylic polymer (AS-563A, Daicel Miraizu Ltd., solids content: 27.5% by mass): 167 parts by mass • Nonionic surfactant (NAROACTY CL95, Sanyo Chemical Industries, Ltd., solids content: 100% by mass): 0.7 parts by mass • Anionic surfactant (RAPISOL A-90, NOF CORPORATION, water dilution with solids content of 1% by mass): 55.7 parts by mass • Carnauba wax dispersion (Selosol 524, CHUKYO YUSHI CO.,LTD., solids content: 30% by mass): 7 parts by mass • Carbodiimide compound (CARBODILITE V-02-L2, Nisshinbo Chemical Inc., water dilution with solids content of 10% by mass): 20.9 parts by mass • Matting agent (SNOWTEX XL, Nissan Chemical) Corporation, solids content: 40% by mass, average particle size: 50 nm): 2.8 parts by mass; matting agent (AEROSIL OX50, NIPPON AEROSIL CO.,LTD., solids content: 10% by mass, water dispersion, median particle size: 0.2 μm): 3.5 parts by mass; water: 743 parts by mass.

[0427] <Manufacturing of Temporary Support 4> The thickness of the temporary support is changed to 25μm. Otherwise, the temporary support 4 is manufactured in the same manner as the temporary support 1.

[0428] <Manufacturing of Temporary Support 5> The following was used as temporary support 5: Temporary support 5: Polyethylene terephthalate film, A1517 manufactured by Toyobo Co., Ltd., with a thickness of 16 μm.

[0429] <Example 1> (Manufacturing of Photosensitive Transfer Material) A photosensitive transfer material comprising a temporary support 1, a buffer layer, an intermediate layer, a photosensitive resin layer, and a protective film is manufactured in the following order. The transfer layer 1 has a buffer layer, an intermediate layer, and a photosensitive resin layer, and the photosensitive resin layer is a negative photosensitive resin layer.

[0430] Composition A, containing the components listed in the "Buffer Layer" column of Table 1, was prepared. After applying composition A to the temporary support 1 using a slit nozzle, composition A was dried at 80°C for 2 minutes, thereby forming a buffer layer. The thickness of the buffer layer is shown in Table 1.

[0431] Composition B, containing the components listed in the "Intermediate Layer" column of Table 1, was prepared. After applying composition B to the buffer layer using a slit nozzle, composition B was dried at 90°C for 2 minutes to form an intermediate layer. The thickness of the intermediate layer is shown in Table 1.

[0432] A composition C containing the components listed in the "Photosensitive Resin Layer" column of Table 1 was prepared. After applying composition C to the intermediate layer using a slit nozzle, composition C was dried at 80°C for 2 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer is shown in Table 1.

[0433] Finally, a protective film (16KS40, manufactured by TORAY INDUSTRIES, INC., thickness: 16μm) was placed on the photosensitive resin layer to obtain the photosensitive transfer material 1.

[0434] Subsequently, a deposition mask was manufactured using the obtained photosensitive transfer material 1 in the following order. An inductor substrate was prepared as a metal layer having a first surface and a second surface at a position opposite to the first surface. The first and second surfaces face opposite directions. The roughness Rmax of the first surface of the inductor substrate is 0.80 μm. The roughness Rmax of the second surface of the inductor substrate is 0.90 μm. The average thickness of the inductor substrate is 50 μm. A protective film was peeled off from the transfer layer 1. Using a roll-to-roll laminator, the photosensitive transfer material was bonded to the inductor substrate at a temperature of 100°C, a linear pressure of 0.5 MPa, and a linear speed (lamination speed) of 4 m / min. The transfer layer 1 (i.e., the photosensitive resin layer, intermediate layer, and buffer layer) and a temporary support 1 were sequentially disposed on the first surface of the inductor substrate. The first surface of the inductor substrate was in contact with the photosensitive resin layer.

[0435] The exposure mask is brought into close contact with the surface of the exposed transfer layer. The exposure mask has a plurality of square light-shielding portions. The size of each light-shielding portion varies in 5μm units from 5μm long × 5μm wide to 100μm long × 100μm wide. The transfer layer is irradiated with light using a high-pressure mercury lamp exposure machine (MAP-1200L, manufactured by Japan Science Engineering Co., Ltd., main wavelength: 365nm). The exposure amount is adjusted to the exposure amount required to reproduce the pattern shape of the photoresist pattern obtained after development.

[0436] After the temporary support 1 is peeled off from the transfer layer 1, a photoresist pattern is obtained by developing the sample using a 1.0% by mass sodium carbonate aqueous solution at 28°C as the developer. Specifically, during development, after removing the developer by performing an AirKnife treatment with a 30-second spray treatment, the sample is further treated by performing an AirKnife treatment with pure water for 30 seconds.

[0437] Through-holes were formed on the inductor substrate by etching the inductor layer not covered by the photoresist pattern at 45°C for 60 seconds using an etchant containing ferric chloride. The through-holes extended from the first surface of the inductor substrate toward the second surface. The photoresist pattern was removed using a 4% by mass sodium hydroxide solution to obtain a deposition mask. In the obtained deposition mask, the average diameter of the through-holes in the first surface of the inductor substrate was 28.0 μm, and the average diameter of the through-holes in the second surface of the inductor substrate was 7.0 μm.

[0438] <Examples 2-21 and Comparative Example 1> In the manufacture of photosensitive transfer material, the type of temporary support and the composition of the transfer layer were changed according to the description in Tables 1-5. Otherwise, the photosensitive transfer material and the deposition mask were manufactured in the order of Example 1.

[0439] <Measurement of the number of foreign objects> A temporary support was peeled off from the obtained photosensitive transfer material. The area of ​​the peeled temporary support was observed in 1 cm² by transmission optical microscopy along its thickness direction. The number of foreign objects with diameters of 1.0 μm to 10.0 μm was counted. The number obtained was divided by the thickness of the temporary support to obtain the number of foreign objects per unit volume of the temporary support.

[0440] <Evaluation> The following items were evaluated using the photosensitive transfer materials or deposition masks manufactured in the Examples and Comparative Examples.

[0441] (Resolution) In the obtained deposition mask, the obtained hole pattern is observed with an optical microscope, and the smallest pattern size that can be resolved with respect to the size of the deposition mask is taken as the resolution. The smaller the smallest pattern size that can be resolved, the better the resolution.

[0442] (Linearity) The photoresist pattern with the minimum resolving linewidth was observed using a scanning electron microscope (SEM). The maximum-minimum linewidth values ​​(hereinafter referred to as "linewidth variation") were measured over a length of 100 μm. Based on the linewidth variation, the linearity of the photoresist pattern was evaluated according to the following criteria: A: Linewidth variation less than 0.4 μm. B: Linewidth variation greater than or equal to 0.4 μm but less than 0.7 μm. C: Linewidth variation greater than or equal to 0.7 μm but less than 1.0 μm. D: Linewidth variation greater than or equal to 1.0 μm but less than 1.5 μm. E: Linewidth variation greater than or equal to 1.5 μm.

[0443] (Lamination) After laminating a photosensitive transfer material onto a metal substrate with a surface roughness Rmax of 0.5 μm to 5.0 μm, the number of air bubbles in a 25 mm² area was observed using an optical microscope from the temporary support side of the laminated layer. A: Less than 10 B: More than 10 but less than 20 C: More than 20

[0444] The evaluation results are summarized in Tables 4 and 5.

[0445] [Table 1] Transfer layer 1 Transfer layer 2 Transfer layer 3 Transfer layer 4 Transfer layer 5 Transfer layer 6 Buffer layer Layer thickness (μm) 6.0 - - - 6.0 6.0 Alkali-soluble resins Compound B1 39.8 - - - 39.8 39.8 Aggregation compound A-DCP 5.8 - - - 5.8 5.8 8UX-015A 2.9 - - - 2.9 2.9 TO-2349 1.3 - - - 1.3 1.3 additive Prill 0.69 - - - 0.69 0.69 CBT-1 0.04 - - - 0.04 0.04 surfactants F-552 0.05 - - - 0.05 0.05 solvent MEK 49.4 - - - 49.4 49.4 Total (parts by weight) 100.0 - - - 100.0 100.0 middle between layer Layer thickness (μm) 1.0 1.0 - - 1.0 1.0 Water-soluble resin PVA 2.7 2.7 - - 2.7 2.7 PVP 1.3 1.3 - - 1.3 1.3 HPMC - 0.041 - - - - surfactants F-444 0.004 0.004 - - 0.004 0.004 solvent MeOH 70 70 - - 70 70 pure water 26 26 - - 26 26 Total (parts by weight) 100.0 100.0 - - 100.0 100.0 feel Light sex Tree fat layer Layer thickness (μm) 2.0 3.0 3.0 6.0 2.0 2.0 M / B 1.0 1.0 1.0 1.0 0.72 0.72 Adhesive Compound B1 - - - - - - Compound B2 - - - - 23.2 - Compound B3 19.9 19.9 19.9 19.9 - 23.2 Compound B4 - - - - - - Compound B5 - - - - - - Aggregation compound BPE-500 5.4 5.4 5.4 5.4 - 5.0 BPE-100 - - - - 5.0 - ARONIX M-270 0.59 0.59 0.59 0.59 0.45 0.45 Photopolymerization Initiator B-IMD 0.89 0.89 0.89 0.89 0.89 0.89 sensitizer EAB-F 0.04 0.04 0.04 0.04 0.04 0.04 Polymer inhibitors Coffee 0.03 0.03 0.03 0.03 0.03 0.03 phenidone 1% MEK solution 0.14 0.14 0.14 0.14 0.14 0.14 Chain transfer agent Compound A 0.02 0.02 0.02 0.02 0.02 0.02 color developer LCV 0.05 0.05 0.05 0.05 0.05 0.05 Rust inhibitor CBT-1 0.01 0.01 0.01 0.01 0.01 0.01 surfactants F-552 0.14 0.14 0.14 0.14 0.14 0.14 solvent MMPGAc 21.51 21.51 21.51 21.51 18.70 18.70 MEK 46.52 46.52 46.52 46.52 46.52 46.52 MFG 2.23 2.23 2.23 2.23 2.23 2.23 MeOH 2.61 2.61 2.61 2.61 2.61 2.61 Total (parts by weight) 100.0 100.0 100.0 100.0 100.0 100.0 Melt viscosity (Pa) of the transfer layer at 25°C 2.0×10 6 2.0×10 6 2.0×10 6 2.0×106 9.0×10 5 3.0×10 7

[0446] [Table 2] Transfer layer 7 Transfer layer 8 Transfer layer 9 Transfer layer 10 Transfer layer 11 Transfer layer 12 slow rush layer Layer thickness (μm) 6.0 6.0 6.0 6.0 6.0 6.0 Alkali soluble resin Compound B1 39.8 39.8 39.8 39.8 39.8 39.8 Aggregation compound A-DCP 5.8 5.8 5.8 5.8 5.8 5.8 8UX-015A 2.9 2.9 2.9 2.9 2.9 2.9 TO-2349 1.3 1.3 1.3 1.3 1.3 1.3 additive Prill 0.69 0.69 0.69 0.69 0.69 0.69 CBT-1 0.04 0.04 0.04 0.04 0.04 0.04 surfactants F-552 0.05 0.05 0.05 0.05 0.05 0.05 solvent MEK 49.4 49.4 49.4 49.4 49.4 49.4 Total (parts by weight) 100.0 100.0 100.0 100.0 100.0 100.0 middle between layer Layer thickness (μm) 1.0 1.0 1.0 1.0 1.0 1.0 Water-soluble resin PVA 2.7 2.7 2.7 2.7 2.7 2.7 PVP 1.3 1.3 1.3 1.3 1.3 1.3 HPMC - - - - - - surfactants F-444 0.004 0.004 0.004 0.004 0.004 0.004 solvent MeOH 70 70 70 70 70 70 pure water 26 26 26 26 26 26 Total (parts by weight) 100.0 100.0 100.0 100.0 100.0 100.0 feel Light sex Tree fat layer Layer thickness (μm) 2.0 2.0 2.0 2.0 2.0 2.0 M / B 1.00 1.00 1.00 1.00 0.82 1.00 Adhesive Compound B1 - - - 19.9 - - Compound B2 - - - - 21.9 24.9 Compound B3 24.9 - - - - - Compound B4 - - 19.9 - - - Compound B5 - 19.9 - - - - Aggregation compound BPE-500 4.00 5.4 5.4 5.4 - - BPE-100 - - - - 4.9 4.04 ARONIX M-270 0.45 0.59 0.59 0.59 0.54 0.45 Photopolymerization Initiator B-IMD 0.89 0.89 0.89 0.89 0.89 0.89 sensitizer EAB-F 0.04 0.04 0.04 0.04 0.04 0.04 Polymer inhibitors Coffee 0.03 0.03 0.03 0.03 0.03 0.03 phenidone 1% MEK solution 0.14 0.14 0.14 0.14 0.14 0.14 Chain transfer agent Compound A 0.02 0.02 0.02 0.02 0.02 0.02 color developer LCV 0.05 0.05 0.05 0.05 0.05 0.05 Rust inhibitor CBT-1 0.01 0.01 0.01 0.01 0.01 0.01 surfactants F-552 0.14 0.14 0.14 0.14 0.14 0.14 solvent MMPGAc 18.00 21.51 21.51 21.51 21.51 21.51 MEK 46.52 46.52 46.52 46.52 46.52 46.52 MFG 2.23 2.23 2.23 2.23 2.23 2.23 MeOH 2.61 2.61 2.61 2.61 2.61 2.61 Total (parts by weight) 100.0 100.1 100.1 100.1 101.5 103.6 Melt viscosity (Pa) of the transfer layer at 25°C 2.4×10 8 6.5×10 8 2.0×10 5 4.0×10 7 0.9×10 5 0.9×10 7

[0447] [Table 3] Transfer layer 13 Transfer layer 14 Transfer layer 15 Transfer layer 16 Transfer layer 17 Transfer layer 18 slow rush layer Layer thickness (μm) 6.0 6.0 6.0 6.0 6.0 6.0 Alkali soluble resin Compound B1 39.8 39.8 39.8 39.8 39.8 39.8 Aggregation compound A-DCP 5.8 5.8 5.8 5.8 5.8 5.8 8UX-015A 2.9 2.9 2.9 2.9 2.9 2.9 TO-2349 1.3 1.3 1.3 1.3 1.3 1.3 additive Prill 0.69 0.69 0.69 0.69 0.69 0.69 CBT-1 0.04 0.04 0.04 0.04 0.04 0.04 surfactants F-552 0.05 0.05 0.05 0.05 0.05 0.05 solvent MEK 49.4 49.4 49.4 49.4 49.4 49.4 Total (parts by weight) 100.0 100.0 100.0 100.0 100.0 100.0 middle between layer Layer thickness (μm) 1.0 1.0 0.5 2.0 1.0 1.0 Water-soluble resin PVA 2.7 2.7 2.7 2.7 3.7 0.7 PVP 1.3 1.3 1.3 1.3 0.3 3.3 HPMC - - - - - - surfactants F-444 0.004 0.004 0.004 0.004 0.004 0.004 solvent MeOH 70 70 70 70 70 70 pure water 26 26 26 26 26 26 Total (parts by weight) 100.0 100.0 100.0 100.0 100.0 100.0 feel Light sex Tree fat layer Layer thickness (μm) 4.8 8.0 2.0 2.0 2.0 2.0 M / B 1.00 1.00 1.0 1.0 1.0 1.0 Adhesive Compound B1 - - - - - - Compound B2 - - - - - - Compound B3 19.9 19.9 19.9 19.9 19.9 19.9 Compound B4 - - - - - - Compound B5 - - - - - - Aggregation compound BPE-500 5.4 5.4 5.4 5.4 5.4 5.4 BPE-100 - - - - - - ARONIX M-270 0.59 0.59 0.59 0.59 0.59 0.59 Photopolymerization Initiator B-IMD 0.89 0.89 0.89 0.89 0.89 0.89 Sensitive agent EAB-F 0.04 0.04 0.04 0.04 0.04 0.04 Polymer inhibitors Coffee 0.03 0.03 0.03 0.03 0.03 0.03 phenidone 1% MEK solution 0.14 0.14 0.14 0.14 0.14 0.14 Chain transfer agent Compound A 0.02 0.02 0.02 0.02 0.02 0.02 color developer LCV 0.05 0.05 0.05 0.05 0.05 0.05 Rust inhibitor CBT-1 0.01 0.01 0.01 0.01 0.01 0.01 surfactants F-552 0.14 0.14 0.14 0.14 0.14 0.14 solvent MMPGAc 21.51 21.51 21.51 21.51 21.51 21.51 MEK 46.52 46.52 46.52 46.52 46.52 46.52 MFG 2.23 2.23 2.23 2.23 2.23 2.23 MeOH 2.61 2.61 2.61 2.61 2.61 2.61 Total (parts by weight) 100.1 100.1 100.0 100.0 100.0 100.0 Melt viscosity (Pa) of the transfer layer at 25°C 3.0×10 6 4.0×10 6 2.0×10 6 2.0×10 6 2.0×10 6 2.0×10 6

[0448] The following abbreviations shown in Tables 1 to 3 have the following meanings respectively. "M / B": The ratio of the total mass of the polymeric compound 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 transfer temperature: 75℃, Solid content: 30% by mass. "A-DCP": Tricyclodecanedimethylethanol diacrylate, NK Ester A-DCP manufactured by Shin-Nakamura Chemical Co., Ltd. "8UX-015A": UV-curable amine acrylate, 8UX-015A manufactured by Taisei Fine Chemical Co., Ltd. "TO-2349": ARONIX TO-2349 manufactured by TOAGOSEI CO.,LTD. "Pill": Powder of pyrithione, FUJIFILM Wako Pure Chemical. "CBT-1": Carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO.,LTD. "F-552": Fluorinated surfactant, MEGAFACE 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, METOLOSE 60SH-03 manufactured by Shin-Etsu Chemical Co.,Ltd. "F-444": MEGAFACE manufactured by DIC Corporation. F-444, Fluorine-based surfactant "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 transfer temperature: 76℃, Solid content: 30% by mass. Additionally, "Methacrylic acid-glycidyl methacrylate" indicates a constituent unit formed by reacting the epoxy group of glycidyl methacrylate with the carboxyl group derived from the constituent unit of methacrylic acid.Compound B3: Styrene (St) / Methyl methacrylate (MMA) / Methacrylamide (MAA) = 52 / 19 / 29, Mw: 50,000, Acid value: 148 mg KOH / g, Glass transfer temperature: 131℃, Solid content: 30% by mass. Compound B4: Styrene (St) / Methyl methacrylate (MMA) / Methacrylamide (MAA) = 45 / 19 / 36, Mw: 47,000, Acid value: 183 mg KOH / g, Glass transfer temperature: 122℃, Solid content: 30% by mass. Compound B5: Styrene (St) / Methyl methacrylate (MMA) / Methacrylamide (MAA) = 57 / 11 / 32, Mw: 49,000, Acid value: 163 mg KOH / g, Glass transfer temperature: 140℃, Solid content: 30% by mass. "BPE-500": (2,2-bis(4-(methacryloxypentethoxy)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-diphenylimidazolium dimer, B-CIMD manufactured by KUROGANE KASEI Co.,Ltd. "EAB-F": 4,4'-bis(diethylamino)benzophenone obtained from Sanyo Trading Co.,Ltd. "Phenythiazoline": FUJIFILM Wako Pure Chemical Corporation manufactures "Phenylidene 1% MEK Solution": a methyl ethyl ketone solution containing 1% by mass of phenylidene; "Compound A": N-phenylaminomethylmethyl-N-carboxymethylaniline; FUJIFILM Wako Pure Chemical Corporation manufactures "LCV": colorless crystal violet, a pigment that develops color via free radicals; Tokyo Chemical Industry Co., Ltd. manufactures "CBT-1": carboxybenzotriazole; JOHOKU CHEMICAL CO.,LTD. manufactures CBT-1; "MMPGAc": 1-methoxy-2-propyl acetate; "MFG": 1-methoxy-2-propanol.

[0449] [Table 4] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Types of transfer layers Transfer layer 1 Transfer layer 1 Transfer layer 1 Transfer layer 1 Transfer layer 2 Transfer layer 3 Transfer layer 4 Transfer layer 5 Transfer layer 6 Transfer layer 7 Transfer layer 8 The thickness of the transfer layer 9μm 9μm 9μm 9μm 4μm 3μm 6μm 9μm 9μm 9μm 9μm Melt viscosity (Pa) of the transfer layer at 25°C 2.0×10 6 2.0×10 6 2.0×10 6 2.0×10 6 2.0×10 6 2.0×10 6 2.0×10 6 9.0×10 5 3.0×10 7 2.4×10 8 6.5×10 8 temporary support Support type temporary support 1 temporary support 2 temporary support 3 temporary support 4 temporary support 1 temporary support 1 temporary support 1 temporary support 1 temporary support 1 temporary support 1 temporary support 1 thickness 16μm 16μm 16μm 25μm 16μm 16μm 16μm 16μm 16μm 16μm 16μm Haze 0.2 0.5 0.5 0.9 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Number of foreign objects (pieces / mm) 3 ) 0 1 1 3 0 0 0 0 0 0 0 L * value 0.6 0.8 1.6 1.0 0.6 0.6 0.6 0.6 0.6 0.6 0.6 evaluate result Analytical 10μm 10μm 15μm 20μm 5μm 5μm 15μm 10μm 10μm 15μm 20μm linearity A A C B A B B A A A B lamination A A A A C C B A B B C

[0450] [Table 5] Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example twenty one Comparative example 1 Types of transfer layers Transfer layer 9 Transfer layer 10 Transfer layer 11 Transfer layer 12 Transfer layer 13 Transfer layer 14 Transfer layer 15 Transfer layer 16 Transfer layer 17 Transfer layer 18 Transfer layer 1 The thickness of the transfer layer 9μm 9μm 9μm 9μm 11.8μm 15μm 8.5μm 10μm 9μm 9μm 9μm Melt viscosity (Pa) of the transfer layer at 25°C 2.0×10 5 4.0×10 7 0.9×105 0.9×10 7 3.0×10 6 4.0×10 6 2.0×10 6 2.0×10 6 2.0×10 6 2.0×10 6 2.0×10 6 temporary support Support type temporary support 1 temporary support 1 temporary support 1 temporary support 1 temporary support 1 temporary support 1 temporary support 1 temporary support 1 temporary support 1 temporary support 1 temporary support 5 thickness 16μm 16μm 16μm 16μm 16μm 16μm 16μm 16μm 16μm 16μm 16μm Haze 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Number of foreign objects (pieces / mm) 3 ) 0 0 0 0 0 0 0 0 0 0 105 L * value 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.8 evaluate result Analytical 10μm 15μm 15μm 10μm 15μm 20μm 10μm 15μm 25μm 25μm 35μm linearity A B B A A B A B C C D lamination A A A A A A B A A A A

[0451] Tables 4 and 5 show that the resolution of the deposition mask manufactured by the deposition mask manufacturing method of the embodiment is better than that of the deposition mask manufactured by the deposition mask manufacturing method of the comparative example. [Simplified Explanation of the Diagram]

[0009] Figure 1 is a schematic top view showing an embodiment of a deposition mask manufactured by the method disclosed herein. Figure 2 is an enlarged schematic top view showing the through-hole of the deposition mask shown in Figure 1. Figure 3 is an enlarged schematic cross-sectional view showing the through-hole of the deposition mask shown in Figure 1. Figure 4 is a schematic cross-sectional view showing a method for manufacturing a deposition mask in a certain embodiment.

Claims

1. A photosensitive transfer material for manufacturing a deposition mask, comprising a temporary support and a transfer layer having at least a photosensitive resin layer, wherein the number of foreign objects with a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is less than 50 per mm3, the number of foreign objects with a diameter greater than 10.0 μm per unit volume of the temporary support is 0 per mm3, the temporary support is a glass substrate or a resin film, and the thickness of the temporary support is 10 μm to 50 μm.

2. The photosensitive transfer material for manufacturing a deposition mask as described in claim 1, wherein the L* value of the side of the temporary support opposite to the aforementioned transfer layer side, measured by SCE method, is 1.5 or less.

3. The photosensitive transfer material for manufacturing a deposition mask as described in claim 1, wherein the thickness of the aforementioned temporary support is 16 μm or less.

4. The photosensitive transfer material for manufacturing a deposition mask as described in claim 1, wherein the melt viscosity of the aforementioned transfer layer at 25°C is 1.0×10⁵ Pa·s to 1.0×10⁸ Pa·s.

5. The photosensitive transfer material for manufacturing a deposition mask as described in claim 1, wherein the thickness of the aforementioned photosensitive resin layer is 4.8 μm or less.

6. The photosensitive transfer material for manufacturing a deposition mask as described in any one of claims 1 to 5, wherein the transfer layer has an intermediate layer and the photosensitive resin layer sequentially from the temporary support side.

7. The photosensitive transfer material for manufacturing a deposition mask as described in claim 6, wherein the aforementioned intermediate layer comprises a water-soluble resin.

8. The photosensitive transfer material for manufacturing a deposition mask as described in claim 7, wherein the aforementioned water-soluble resin comprises polyvinyl alcohol.

9. The photosensitive transfer material for manufacturing a deposition mask as described in claim 7, wherein the aforementioned water-soluble resin comprises polyvinylpyrrolidone.

10. The photosensitive transfer material for manufacturing a deposition mask as described in claim 7, wherein the aforementioned water-soluble resin comprises a hydroxyalkyl cellulose compound.

11. A photosensitive transfer material for manufacturing a deposition mask, comprising a temporary support and a transfer layer having at least a photosensitive resin layer, wherein the number of foreign objects with a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50 or less per mm3, the temporary support is a temporary support obtained by filter treatment, the temporary support is a glass substrate or a resin film, and the thickness of the temporary support is 10 μm to 50 μm.

12. A method for manufacturing a deposition mask, comprising the following steps in sequence: preparing a metal layer having a first surface and a second surface at a position opposite to the first surface; bonding a photosensitive transfer material to the metal layer and sequentially disposing a transfer layer and a temporary support on the first surface of the metal layer, wherein the photosensitive transfer material sequentially includes the temporary support and the transfer layer having at least a photosensitive resin layer, and the number of foreign objects with a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50 or less per mm3; exposing the transfer layer to a pattern; performing a development process on the transfer layer to form a photoresist pattern; performing an etching process on the metal layer not covered by the photoresist pattern to form a through-hole extending from the first surface of the metal layer to the second surface of the metal layer; and removing the photoresist pattern, wherein the number of foreign objects with a diameter exceeding 10.0 μm per unit volume of the temporary support is 0 per mm3. The aforementioned temporary support is a glass substrate or a resin film, and the thickness of the aforementioned temporary support is 10μm to 50μm.

13. The method for manufacturing a deposition mask as described in claim 12, wherein the roughness Rmax of the first surface of the aforementioned metal layer is 0.5 μm to 5.0 μm.

14. A method for manufacturing a deposition mask, comprising the following steps in sequence: preparing a metal layer having a first surface and a second surface at a position opposite to the first surface; bonding a photosensitive transfer material to the metal layer and sequentially disposing a transfer layer and a temporary support on the first surface of the metal layer, wherein the photosensitive transfer material sequentially includes the temporary support and the transfer layer having at least a photosensitive resin layer, and the number of foreign objects with a diameter of 1.0 μm to 10.0 μm per unit volume of the temporary support is 50 or less per mm³; exposing the transfer layer to a pattern; performing a development process on the transfer layer to form a photoresist pattern; performing an etching process on the metal layer not covered by the photoresist pattern to form a through-hole extending from the first surface of the metal layer to the second surface of the metal layer; and removing the photoresist pattern, wherein the temporary support is a temporary support obtained by filter treatment, and the temporary support is a glass substrate or a resin film. The thickness of the aforementioned temporary support is 10μm to 50μm.

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