CN114855119A - Method for manufacturing metal mask - Google Patents

Abstract

The invention provides a manufacturing method of a metal mask, which comprises the following steps: a step in which a photosensitive layer (120) of a laminate (1A) comprising a metal member (150), a photosensitive layer (120) disposed on the metal member (150), and a barrier layer (110) disposed on the photosensitive layer (120) is irradiated with active light (1L) via a barrier layer (10), thereby forming a patterned photocured portion (120a) on the photosensitive layer (120); a step of forming an exposed portion on the metal member (150) by removing a portion of the photosensitive layer (120) other than the photocured portion (120 a); and a step of removing the exposed portion of the metal member (150).

Description

Method for manufacturing metal mask

Technical Field

The present invention relates to a method for manufacturing a metal mask.

Background

In various devices such as an organic EL (electroluminescence) display, an organic layer is formed by depositing an organic material on a substrate by sublimation, evaporation, or the like of the organic material. In this case, in order to form an organic layer at a desired position on the substrate, an organic material is vapor-deposited on the substrate through a metal mask having an opening. Various techniques have been studied for the method of manufacturing such a metal mask (see, for example, japanese patent laid-open publication No. 2015-021179).

Disclosure of Invention

In recent years, with the improvement of resolution, various devices such as organic EL displays have been required to have a high-definition organic layer. On the other hand, in a metal mask for obtaining an organic layer, if the shape, the opening diameter, and the like of the opening are not uniform, there is a possibility that the organic layer cannot be uniformly formed. Therefore, in order to obtain a high-definition organic layer, the opening of the metal mask is also required to be highly refined, and thus the yield of the metal mask may be reduced when the metal mask is manufactured. Therefore, a new metal mask manufacturing method for obtaining a metal mask having a high-definition opening is required.

An object of one aspect of the present invention is to provide a novel method for manufacturing a metal mask.

The present inventors conceived of forming a photo-cured portion obtained using a photosensitive layer having photosensitivity as a resist pattern on a metal member, and removing a predetermined portion of the metal member using the resist pattern as a mask, thereby forming an opening. Further, the present inventors conceived that in order to obtain a metal mask having a high-definition opening, the occurrence of defects in the photocured portion should be suppressed, and found a technique of suppressing the occurrence of defects in the photocured portion.

One aspect of the present invention relates to a method of manufacturing a metal mask, the method including: irradiating the photosensitive layer of a laminate comprising a metal member, a photosensitive layer disposed on the metal member, and a barrier layer disposed on the photosensitive layer with actinic rays through the barrier layer, thereby forming a patterned photocured portion on the photosensitive layer; forming an exposed portion on the metal member by removing a portion of the photosensitive layer other than the photocured portion; and removing the exposed portion.

According to an aspect of the present invention, it is possible to provide a method of manufacturing a metal mask, which can suppress occurrence of defects in a photocured portion, and as a new method of manufacturing a metal mask, can obtain a metal mask having a highly fine opening.

Drawings

Fig. 1 is a schematic cross-sectional view showing an example of a photosensitive element.

Fig. 2 is a schematic cross-sectional view for explaining an example of the method of manufacturing the metal mask.

Fig. 3 is a schematic cross-sectional view for explaining an example of the method of manufacturing the metal mask.

Fig. 4 is a schematic cross-sectional view for explaining an example of the method of manufacturing the metal mask.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the following embodiments, the constituent elements are not necessarily essential unless otherwise specified or clearly considered essential in principle. This is also true in the values and ranges, which should not be construed as unduly limiting the invention.

"A or more" in the numerical range means A and a range exceeding A. The numerical range "below A" means A and the range less than A. In the numerical ranges described in the present specification in a hierarchical manner, the upper limit or the lower limit of the numerical range of a certain hierarchical order may be arbitrarily combined with the upper limit or the lower limit of the numerical range of another hierarchical order. In the numerical ranges described in the present specification, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples. The materials exemplified in this specification can be used alone in 1 kind or in combination in 2 or more kinds, unless otherwise specified. When a plurality of substances corresponding to each component are present in the composition, the content of each component in the composition refers to the total amount of the plurality of substances present in the composition unless otherwise specified. The term "layer" includes, when viewed in a plan view, a structure having a shape formed over a part of the surface, in addition to a structure having a shape formed over the entire surface. The term "step" is not limited to an independent step, and is included in the present term as long as the intended function of the step can be achieved even when the step cannot be clearly distinguished from other steps. "(meth) acrylate" means at least one of an acrylate and a methacrylate corresponding thereto. The same applies to other similar expressions such as "(meth) acrylic acid". "EO" means ethylene oxide, and "EO-modified" compounds means compounds having an oxyethylene group. "PO" represents ethylene oxide, and a "PO-modified" compound refers to a compound having an oxypropylene group. The combination "polyoxyethylene" and "epoxy vinyl", labeled "(poly) epoxy vinyl". The same is true for other expressions involving "(poly)". The weight average molecular weight in the present specification is a value obtained by measuring by Gel Permeation Chromatography (GPC) and converting the weight average molecular weight by a calibration curve prepared using standard polystyrene, and the procedure for measuring the weight average molecular weight of the binder polymer in the examples can be employed.

The method for manufacturing a metal mask according to the present embodiment includes: an exposure step of irradiating the photosensitive layer of a laminate (hereinafter, referred to as "laminate a" in some cases) including a metal member, a photosensitive layer disposed on the metal member, and a barrier layer disposed on the photosensitive layer with active light through the barrier layer, thereby forming a patterned photocurable part on the photosensitive layer; a developing step of forming an exposed portion on the metal member by removing a portion of the photosensitive layer other than the photocured portion; and a removing step of removing the exposed portion of the metal member. The metal mask obtained by the method for manufacturing a metal mask according to the present embodiment can be used without particular limitation to applications using a metal mask, and can also be used to obtain various devices such as an organic EL display.

According to the method for manufacturing a metal mask of the present embodiment, exposure failure such as oxygen inhibition in the photosensitive layer (for example, deterioration in the shape of a resist pattern) can be suppressed by irradiating the photosensitive layer with active light via the blocking layer in the exposure step. Further, in the case where the photosensitive layer is irradiated with active light through the polymer film in a state where the polymer film is disposed on the photosensitive layer, there is a possibility that exposure failure may occur due to particles contained in the polymer film. In this way, exposure failure can be suppressed, so that defects in the photocured portion can be suppressed, and a metal mask having a highly fine opening can be obtained. According to the method of manufacturing a metal mask of the present embodiment, for example, a metal mask having a desired shape, size, or the like can be obtained, a desired shape such as a circle or polygon can be obtained as the shape of the opening, and diameters such as 30 μm or less, 25 μm or less, 20 μm or less, 15 μm or less, and 10 μm or less can be obtained as the diameter (for example, the maximum diameter) of the opening.

The method for manufacturing a metal mask according to the present embodiment does not include a laminate manufacturing step for obtaining the laminate a before the exposure step. In the laminate production step, the laminate a may be obtained by disposing the barrier layer and the photosensitive layer of the photosensitive element on the metal member, or the laminate a may be obtained by sequentially forming the photosensitive layer and the barrier layer on the metal member. The laminate a is a laminate for producing a metal mask. According to the present embodiment, the laminate manufacturing step can be performed as a method for manufacturing a laminate for manufacturing a metal mask. In the method of manufacturing a metal mask according to the present embodiment, at least one step selected from the group consisting of a laminate manufacturing step, an exposure step, a development step, and a removal step can be performed by a Roll-to-Roll process.

As the constituent material of the metal member, a known material can be used as the constituent material of the metal mask. Examples of the metal (metal material) of the metal member include iron, nickel, copper, zinc, aluminum, chromium, and the like. As a constituent material of the metal member, brass (brass), stainless steel, iron-nickel alloy, or the like can be used. The metal member may contain an iron-nickel alloy from the viewpoint of excellent workability or composition. The metal member is a metal plate, a metal foil, or the like.

The thickness of the metal member may be in the following range from the viewpoint of easily obtaining a desired opening shape at the time of etching. The thickness of the metal member may be 100 μm or less, 80 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, or 20 μm or less. The thickness of the metal member may be 1 μm or more, 5 μm or more, 10 μm or more, 15 μm or more, or 20 μm or more. From these viewpoints, the thickness of the metal member is 10 to 100 μm or 10 to 50 μm 7.

The absorbance of the photosensitive layer with respect to light having a wavelength of 365nm may be 0.3 or less, 0.2 or less, 0.15 or less, 0.1 or less, 0.09 or less, 0.08 or less, 0.05 or less, 0.04 or less, or 0.03 or less from the viewpoint of easily suppressing the occurrence of defects in the photocurable portion and easily obtaining excellent resolution and adhesion (adhesion between the photocurable portion of the photosensitive layer and the metal member). It is presumed that since the absorbance does not become too high, rapid curing on the light-receiving surface side in the photosensitive layer is suppressed, and the curing reaction easily proceeds uniformly throughout the inside of the photosensitive layer, the occurrence of defects is easily suppressed, and excellent resolution and adhesion are easily obtained. However, the main reason for obtaining these effects is not limited to this. The absorbance of the photosensitive layer with respect to light having a wavelength of 365nm may exceed 0, and may be 0.01 or more and 0.02 or more or 0.03 or more. The absorbance can be adjusted by the kind, content, and the like of the constituent components (photopolymerization initiator, photosensitizer, and the like) of the photosensitive layer.

The photosensitive element may include a support layer (e.g., a support film) for supporting the barrier layer. The bonding force (bond force) between the support layer and the barrier layer may be smaller than the bonding force between the barrier layer and the photosensitive layer, from the viewpoint of easily improving the gas barrier property of the barrier layer and easily suppressing the accidental peeling of the barrier layer and the photosensitive layer when the support layer is peeled from the photosensitive element. The photosensitive element may include a protective layer (e.g., a protective film) disposed on the photosensitive layer. The protective layer covers the photosensitive layer for protection. The protective layer may be disposed on a surface opposite to a surface of the photosensitive layer in contact with the barrier layer. The support layer and the protective layer may be single-layered or multi-layered, respectively.

Fig. 1 is a schematic cross-sectional view showing an example of a photosensitive element. The photosensitive element 100 of fig. 1 includes a barrier layer 10, a photosensitive layer 20 disposed on the barrier layer 10, a support film (support layer) 30 supporting the barrier layer 10, and a protective film (protective layer) 40 disposed on the photosensitive layer 20. The barrier layer 10 and the photosensitive layer 20 are in contact with each other. The barrier layer 10 and the support film 30 are in contact with each other. The photosensitive layer 20 and the protective film 40 contact each other.

In the case of using a photosensitive element, after the protective layer is removed, the photosensitive layer is pressed against the metal member while heating, whereby the barrier layer and the photosensitive layer can be disposed on the metal member. When a photosensitive element is used, the photosensitive layer can be pressure-bonded under reduced pressure from the viewpoint that excellent adhesion and tracking properties are easily obtained. The pressure for pressure bonding may be, for example, 0.1 to 1.0MPa (1 to 10 kgf/cm) ² ). The heating temperature during the compression bonding may be, for example, 70 to 130 ℃. When the heating temperature is 70 to 130 ℃, the metal member does not need to be subjected to a preheating treatment in advance, but the metal member may be subjected to a preheating treatment from the viewpoint of easily obtaining more excellent adhesion and conformability.

In the exposure step in the method for manufacturing a metal mask according to the present embodiment, the photosensitive layer of the laminate a is irradiated with active light through the barrier layer, thereby forming a patterned photocurable part on the photosensitive layer. In the case of using a photosensitive element, in the exposure step, after the support layer is removed, the photosensitive layer can be exposed to active light via the barrier layer, and the photosensitive layer of the laminate a can be irradiated with active light via the barrier layer without via the support layer, whereby a patterned photocurable part can be formed on the photosensitive layer.

As the exposure method, a known exposure method can be used, and the following methods can be mentioned: a method of irradiating an active ray image-wise through a mask pattern called a process chart (mask exposure method); an LDI (Laser Direct Imaging) exposure mode; a method (projection exposure method) in which an image of a photomask is irradiated with actinic rays in an image form through a lens. From the viewpoint of easily obtaining excellent resolution, a projection exposure system can be used. The projection exposure method may also be referred to as an exposure method using an active ray of attenuated energy.

As the light source of the active light, known light sources can be used without particular limitation, and examples thereof include gas lasers such as carbon arc lamps, mercury vapor arc lamps, ultrahigh pressure mercury lamps, high pressure mercury lamps, xenon lamps, and argon lasers; solid laser such as YAG laser; a light source for efficiently emitting ultraviolet rays, such as a semiconductor laser, for example, a gallium nitride-based violet laser. Further, a light source that efficiently emits visible light such as a floodlight for photography or a sun lamp may be used. As the light source, from the viewpoint of easily improving the resolution and the alignment property in a well-balanced manner, a light source capable of emitting i-ray monochromatic light having an exposure wavelength of 365nm, a light source capable of emitting h-ray monochromatic light having an exposure wavelength of 405nm, or a light source capable of emitting active light having an exposure wavelength of ihg mixed rays can be used. Examples of the light source capable of emitting i-ray monochromatic light having an exposure wavelength of 365nm include an ultra-high pressure mercury lamp and the like.

In the developing step in the method for manufacturing a metal mask according to the present embodiment, the exposed portion is formed on the metal member by removing the portion (uncured portion, unexposed portion) of the photosensitive layer other than the photocured portion. In the developing step, the metal member is exposed by removing a part or all of the photosensitive layer except for the photocured portion. In the developing step, a resist pattern (a photocurable pattern or a relief pattern of the photosensitive resin composition) composed of a photocurable part of the photosensitive layer is formed on the metal member.

Examples of the developing method include wet development. In the case of wet development, development can be performed by a known wet development method using a developer. Examples of the wet developing method include a dipping method, a paddle method, a high-pressure spraying method, a method using brushing, slapping, scrubbing, shaking dipping, and the like, and the high-pressure spraying method can be used from the viewpoint of easily obtaining excellent resolution. The wet development method may be used alone in 1 kind or in combination of 2 or more kinds. The developing solution may be appropriately selected according to the composition of the photosensitive layer. Examples of the developer include an aqueous alkaline solution and an organic solvent developer. As the developer, an alkaline aqueous solution can be used from the viewpoint of safety, stability, and good workability.

Examples of the alkali of the alkaline aqueous solution include alkali hydroxides such as hydroxides of lithium, sodium, or potassium; alkali carbonates such as lithium, sodium, potassium, or ammonium carbonates and bicarbonates; alkali metal phosphates such as potassium phosphate and sodium phosphate; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; sodium borate; sodium metasilicate; tetramethyl ammonium hydroxide; ethanolamine; ethylene diamine; diethylenetriamine; 2-amino-2-hydroxymethyl-1, 3-propanediol; 1, 3-diamino-2-propanol; morpholine and the like.

Examples of the alkaline aqueous solution include a dilute solution of 0.1 to 5 mass% sodium carbonate, a dilute solution of 0.1 to 5 mass% potassium carbonate, a dilute solution of 0.1 to 5 mass% sodium hydroxide, and a dilute solution of 0.1 to 5 mass% sodium tetraborate. The pH of the alkaline aqueous solution may be 9 to 11. The temperature of the aqueous alkaline solution can be adjusted according to the developability of the photosensitive layer. The alkaline aqueous solution may contain a surfactant, a defoaming agent, a small amount of an organic solvent for promoting development, and the like. Examples of the organic solvent used in the alkaline aqueous solution include 3-acetol, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.

As the organic solvent used in the organic solvent developer, 1,1, 1-trichloroethane, N-methylpyrrolidone, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ -butyrolactone, and the like are used. In the organic solvent developer, from the viewpoint of easy prevention of ignition, the organic solvent may be mixed with water and the content of the organic solvent may be adjusted to be in the range of 1 to 20 mass%.

In the case where the barrier layer is water-soluble, the photosensitive layer can be removed by a developing solution after the barrier layer is removed by washing with water. That is, in the developing step, the blocking layer can be removed by bringing the blocking layer into contact with water before removing the photosensitive layer except for the photocured portion. In this case, a part or the whole of the barrier layer can be removed. When the barrier layer is dissolved in the developer, the barrier layer can be removed together with the photosensitive layer by the developer.

The method for manufacturing a metal mask according to the present embodiment may include providing a resist pattern (photosensitive layer) after the developing stepThe light-curing part) is heated at 60 to 250 ℃ or the exposure amount is 0.2 to 10J/cm ² And (5) performing exposure. This can improve the degree of curing of the resist pattern.

In the removal step in the method for manufacturing a metal mask according to the present embodiment, the exposed portion of the metal member is removed, thereby forming an opening (through-hole) in the metal member. This makes it possible to obtain a metal mask in a state of supporting a resist pattern (a photocurable portion in a photosensitive layer). In the removal step, the exposed portion of the metal member is removed by etching using the resist pattern as a mask, for example. This enables the metal member to be provided with an opening having a shape corresponding to the opening of the resist pattern. The method of the etching treatment may be appropriately selected depending on the metal material to be removed. Examples of the etching solution include an acidic etching solution, an iron chloride solution, an alkaline etching solution, and a hydrogen peroxide etching solution. As the acidic etching solution, for example, an iron (III) perchlorate solution or a solution obtained by mixing hydrochloric acid, sulfuric acid, formic acid, acetic acid, or the like into a mixed solution of an iron (III) perchlorate solution and an iron chloride solution can be used.

The method for manufacturing a metal mask according to the present embodiment may include a step of removing the resist pattern (the photocured portion in the photosensitive layer) after the removal step. Thereby, the metal mask in a state where the resist pattern is removed can be obtained. The resist pattern can be removed, for example, by an aqueous solution having a stronger alkali than the alkaline aqueous solution used in the developing step. Examples of the strongly alkaline aqueous solution include a1 to 10 mass% aqueous sodium hydroxide solution, a1 to 10 mass% aqueous potassium hydroxide solution, and a1 to 10 mass% aqueous ammonium salt solution. Examples of the resist pattern removal method include a dip method and a spray method.

Fig. 2 to 4 are schematic cross-sectional views for explaining an example of a method for manufacturing a metal mask, and are schematic cross-sectional views for explaining a method for manufacturing a metal mask using the photosensitive element shown in fig. 1. In one example of the method of manufacturing the metal mask, first, as shown in fig. 2(a), a metal member 50 is prepared. Next, as shown in fig. 2(b), the barrier layer 10 and the photosensitive layer 20 of the photosensitive element are disposed on the metal member 50, thereby obtaining a laminate a including the metal member 50, the photosensitive layer 20 disposed on the metal member 50, and the barrier layer 10 disposed on the photosensitive layer 20 (laminate production step).

Next, as shown in fig. 3 a, the photosensitive layer 20 of the laminate a is irradiated with the active light L through the barrier layer 10, thereby forming a patterned photocurable part 20a on the photosensitive layer 20 as shown in fig. 3 b (exposure step).

Next, as shown in fig. 4 a, the photosensitive layer 20 is removed except for the photocured portion 20a, thereby forming an exposed portion 50a on the metal member 50 (developing step). Next, as shown in fig. 4(b), the exposed portion 50a of the metal member 50 is removed, whereby the metal mask 60 having the opening 60a and supporting the photocured portion 20a can be obtained. Then, as shown in fig. 4(c), by removing the photocured portion 20a, the metal mask 60 in a state where the photocured portion 20a is removed can be obtained.

Hereinafter, the constituent members of the photosensitive element will be described.

The barrier layer is a layer having gas barrier properties that reduce the effect of oxygen mixing during exposure of the photosensitive layer. The barrier layer may have water solubility or solubility in a developer. The barrier layer can be formed using a resin composition for a barrier layer (a resin composition for forming a barrier layer). The resin composition for a barrier layer may contain a constituent material of the barrier layer, water, an organic solvent, and the like. Examples of the material constituting the barrier layer include a water-soluble resin, an ultraviolet absorber, a leveling agent, a plasticizer, a surfactant, a peeling accelerator, and the like. Examples of the organic solvent include alcohols having 3 or more carbon atoms (e.g., 1-propanol).

The barrier layer and the barrier layer resin composition may contain a water-soluble resin. The term "water-soluble resin" means a resin having a solubility of 5g or less per 100mL of hexane at 25 ℃. The solubility can be calculated by mixing hexane at 25 ℃ with a dried water-soluble resin and checking the presence or absence of white turbidity. Specifically, sample 1, which was prepared by adding a mixture of dried water-soluble resin A [ g ] and 100mL hexane, and sample 2, which was prepared by adding 100mL hexane alone, were prepared in a colorless and transparent stripping container with a ground glass plug. Next, after the sample in the peeling container was sufficiently stirred, disappearance of bubbles was confirmed. Immediately after confirmation, bright containers were arranged under diffused sunlight or light equivalent thereto, and the liquid state of sample 1 and the liquid state of sample 2 were compared. In comparison between samples 1 and 2, the amount of addition A [ g ] at which the sample 1 starts to be blurred or the solid matter starts to float was set to a solubility of 100mL of hexane at 25 ℃ in the water-soluble resin.

Examples of the water-soluble resin include polyvinyl alcohol, polyvinylpyrrolidone, and water-soluble polyimides. The barrier layer may contain polyvinyl alcohol as the water-soluble resin, from the viewpoint of easily improving the gas barrier property of the barrier layer and easily suppressing the deactivation of radicals generated by active rays used in exposure. The polyvinyl alcohol can be obtained by, for example, saponifying polyvinyl acetate obtained by polymerizing vinyl acetate. The saponification degree of the polyvinyl alcohol may be 50 mol% or more, 70 mol% or more, or 80 mol% or more, from the viewpoint of more easily improving the gas barrier property of the barrier layer and easily improving the resolution of the resist pattern. The upper limit of the saponification degree is 100 mol%. The "degree of saponification" is a value measured in accordance with JIS K6726 (1994) (test method for polyvinyl alcohol) prescribed by japanese industrial standards.

It is possible to use 2 or more kinds of polyvinyl alcohols different in saponification degree, viscosity, polymerization degree, modification type, etc. in combination. The polyvinyl alcohol may have an average polymerization degree of 300 to 5000, 300 to 3500, or 300 to 2000. The barrier layer may contain polyvinyl alcohol and polyvinyl pyrrolidone. In this case, the mass ratio of polyvinyl alcohol to polyvinylpyrrolidone (PVA: PVP) may be 40:60 to 90:10, 50:50 to 90:10, or 60:40 to 90: 10.

From the viewpoint of easy improvement of the gas barrier property, the content of the water-soluble resin in the barrier layer may be in the following range based on the whole barrier layer. The content of the water-soluble resin may be 50 mass% or more, 60 mass% or more, 80 mass% or more, 90 mass% or more, 95 mass% or more, 98 mass% or more, or 99 mass% or more. The content of the water-soluble resin may be less than 100 mass% or 99.5 mass% or less. From these viewpoints, the content of the water-soluble resin may be 50% by mass or more and less than 100% by mass.

The content of the water-soluble resin in the resin composition for a barrier layer may be 10 to 60 parts by mass, 12 to 50 parts by mass, 14 to 40 parts by mass, 16 to 30 parts by mass, or 16 to 25 parts by mass with respect to 100 parts by mass of water, from the viewpoint of easily improving the gas barrier property.

The barrier layer and the barrier layer resin composition may or may not contain a leveling agent. The leveling agent is unevenly distributed (oriented) on the surface side in the coating film of the resin composition for a barrier layer, and the surface tension of the coating film can be reduced.

In the case of producing a photosensitive element having a barrier layer, the barrier layer is formed, for example, by coating and drying a resin composition for a barrier layer on a support layer. However, shrinkage easily occurs when the resin composition for a barrier layer is applied to the support layer, and thus defects that may cause defects in the photocured portion easily occur on the surface of the barrier layer. Further, the barrier layer tends to have strong adhesion to the support layer, and when the support layer is peeled off, a part of the barrier layer may be peeled off together with the support layer in a state of being attached to the support layer, resulting in a defect of the barrier layer. On the other hand, when the resin composition for a barrier layer contains the leveling agent, the leveling agent is unevenly distributed on the surface side in the coating film, so that the shrinkage can be suppressed and the adhesion force between the support layer and the barrier layer can be reduced. This makes it easy to suppress the occurrence of defects in the photocured portion.

Examples of the leveling agent include acrylic polymers, vinyl polymers, silicone polymers, fluorine polymers, and the like. The leveling agent may contain an acrylic polymer from the viewpoint that transferability of the barrier layer and solubility in a developer are easily improved. From the viewpoint of easily obtaining appropriate adhesion between the barrier layer and the support layer, the acrylic polymer may include a copolymer having at least one selected from the group consisting of butyl (meth) acrylate, isobutyl (meth) acrylate, and methoxy-terminated EO-modified (meth) acrylate as a monomer unit, may include a copolymer having butyl (meth) acrylate and isobutyl (meth) acrylate as a monomer unit, and may include a copolymer having butyl (meth) acrylate, isobutyl (meth) acrylate, and methoxy-terminated EO-modified (meth) acrylate as a monomer unit.

The content of each structural unit constituting the acrylic polymer may be within the following range based on the total amount of the structural units constituting the acrylic polymer. The content of the monomer unit of butyl (meth) acrylate may be 2 to 20 mass%, 5 to 15 mass%, or 5 to 10 mass%. The content of the monomer unit of isobutyl (meth) acrylate may be 40 to 80 mass%, 50 to 70 mass%, or 55 to 65 mass%. The content of the monomer unit of the methoxy-terminated EO-modified (meth) acrylate may be 15 to 45 mass%, 20 to 40 mass%, or 25 to 35 mass%. The weight average molecular weight of the acrylic polymer may be 10000 to 40000 or 10000 to 20000.

The content of the leveling agent in the barrier layer may be 0.05 to 1.0 mass%, 0.1 to 0.9 mass%, or 0.2 to 0.8 mass% based on the total solid content of the barrier layer, from the viewpoint of easily suppressing the defect of the barrier layer when peeling off the support layer.

The thickness of the barrier layer may be 12 μm or less, 10 μm or less, 8 μm or less, 7 μm or less, 6 μm or less, or 5 μm or less from the viewpoint of easy removal of the barrier layer. The thickness of the barrier layer may be 1 μm or more, 1.5 μm or more, 2 μm or more, 3 μm or more, 4 μm or more, or 5 μm or more from the viewpoint of easy removal of the barrier layer, easy acquisition of excellent resolution, and easy suppression of migration of the barrier layer. From these viewpoints, the thickness of the barrier layer may be 1 to 12 μm or 1 to 10 μm.

The photosensitive layer can be formed using a photosensitive resin composition. As the photosensitive layer and the photosensitive resin composition, a negative photosensitive layer and a photosensitive resin composition can be used. The photosensitive resin composition may contain a constituent material of the photosensitive layer, an organic solvent, and the like. Examples of the constituent material of the photosensitive layer include (a) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a photosensitizer, (E) a polymerization inhibitor, and other components.

The photosensitive layer and the photosensitive resin composition may contain (a) a binder polymer (hereinafter, also referred to as "component (a)"). (A) The component (b) can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives substituted in the α -position or the aromatic ring, such as styrene, vinyltoluene, and α -methylstyrene; acrylamides such as diacetone acrylamide; acrylonitrile; vinyl alcohol ethers such as vinyl n-butyl ether; alkyl (meth) acrylates; benzyl (meth) acrylate such as benzyl methacrylate; tetrahydrofurfuryl (meth) acrylate; dimethylaminoethyl (meth) acrylate; diethylaminoethyl (meth) acrylate; glycidyl (meth) acrylate; 2,2, 2-trifluoroethyl (meth) acrylate; 2,2,3, 3-tetrafluoropropyl (meth) acrylate; (meth) acrylic acid; alpha-bromoacrylic acid; alpha-chloroacrylic acid; beta-furan (meth) acrylic acid; beta-styryl (meth) acrylic acid; maleic acid; maleic anhydride; maleic acid monoesters such as monomethyl maleate, monoethyl maleate, and isopropyl maleate; fumaric acid; cinnamic acid; alpha-cyanocinnamic acid; itaconic acid; crotonic acid; propiolic acid, and the like.

The component (a) may have an alkyl (meth) acrylate group as a monomer unit, and may have (meth) acrylic acid and an alkyl (meth) acrylate group as monomer units, from the viewpoint of easily improving the plasticization and easily suppressing the occurrence of defects in the photocurable portion. Examples of the alkyl (meth) acrylate include compounds represented by the following general formula (I); and compounds in which the alkyl group of the compound is substituted with a hydroxyl group, an epoxy group, a halogen group, or the like.

H ₂ C＝C(R ¹¹ )-COOR ¹² (I)

In the general formula (I), R ¹¹ Represents a hydrogen atom or a methyl group, R ¹² Represents an alkyl group having 1 to 12 carbon atoms. As R ¹² Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl groups, and the structures of these groups are differentStructures, and the like.

Examples of the compound represented by the general formula (I) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, and dodecyl (meth) acrylate.

The component (a) may have a carboxyl group from the viewpoint of easily obtaining excellent alkali developability. The component (a) having a carboxyl group can be obtained, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer. The carboxyl group-polymerizable monomer may contain (meth) acrylic acid or methacrylic acid. The component (A) having a carboxyl group may have an acid value of 50 to 250mgKOH/g, 50 to 200mgKOH/g, or 100 to 200 mgKOH/g.

In the component (a), the content of the monomer unit of the polymerizable monomer having a carboxyl group may be in the following range based on the total amount of the monomer units constituting the component (a) from the viewpoint of easily improving the alkali developability and the alkali resistance in a well-balanced manner. The content of the monomer unit may be 12% by mass or more, 15% by mass or more, or 20% by mass or more, from the viewpoint of easy improvement of alkali developability. From the viewpoint of easily obtaining excellent alkali resistance, it may be 50% by mass or less, 40% by mass or less, 35% by mass or less, or 30% by mass or less. From these viewpoints, the content of the monomer unit may be 12 to 50 mass%, 12 to 40 mass%, 15 to 35 mass%, 15 to 30 mass%, or 20 to 30 mass%.

The component (a) may have, as a monomer unit, at least one styrene compound selected from the group consisting of styrene and styrene derivatives, from the viewpoint of easily obtaining excellent adhesion and chemical resistance. When the component (a) has a monomer unit of a styrene compound, the content of the monomer unit of the styrene compound may be in the following range based on the total amount of the monomer units constituting the component (a) from the viewpoint of more excellent adhesion and chemical resistance. The content of the monomer unit of the styrene compound may be 10 mass% or more, 15 mass% or more, 30 mass% or more, 35 mass% or more, or 40 mass% or more, from the viewpoint of easily improving the adhesion. The content of the monomer unit of the styrene compound may be 60% by mass or less or 50% by mass or less from the viewpoint of easily suppressing the peeling sheet from becoming excessively large at the time of development and easily suppressing the time required for peeling from being prolonged. From these viewpoints, the content of the monomer unit of the styrene compound may be 10 to 60 mass%, 15 to 50 mass%, 30 to 50 mass%, 35 to 50 mass%, or 40 to 50 mass%.

The component (a) may have a monomer unit of benzyl (meth) acrylate from the viewpoint of easily obtaining excellent resolution and aspect ratio. The content of the monomer unit of benzyl (meth) acrylate may be 15 to 50 mass%, 15 to 45 mass%, 15 to 40 mass%, 15 to 35 mass%, or 20 to 30 mass% based on the total amount of the monomer units constituting the component (A), from the viewpoint of easily obtaining more excellent resolution and aspect ratio.

(A) The components can be used singly or in combination of two or more. When 2 or more kinds of the component (a) are used in combination, for example, 2 or more kinds of binder polymers composed of different polymerizable monomers, 2 or more kinds of binder polymers having different weight average molecular weights, and 2 or more kinds of binder polymers having different degrees of dispersion may be mentioned.

The weight average molecular weight of the component (a) may be in the following range from the viewpoint of easily improving the mechanical strength and the alkali developability in a well-balanced manner. The weight average molecular weight of the component (a) may be 10000 or more, 20000 or more, 40000 or more, or 50000 or more from the viewpoint of easily obtaining excellent developing solution resistance. From the viewpoint of easily suppressing the development time from becoming longer, the weight average molecular weight of the component (a) may be 300000 or less, 150000 or less, 120000 or less, or 80000 or less. From these viewpoints, the weight average molecular weight of the component (A) may be 10000 to 300000, 20000 to 300000, 40000 to 150000, 40000 to 120000, or 50000 to 80000.

The content of the component (A) may be 30 to 80 mass%, 40 to 75 mass%, 50 to 70 mass%, or 50 to 60 mass% based on the total amount of the solid components of the component (A) and the component (B), from the viewpoint of easily improving the film coatability of the photosensitive resin composition and the strength of the photocured part.

The photosensitive layer and the photosensitive resin composition may contain (B) a photopolymerizable compound (hereinafter, also referred to as "component (B)"). As the component (B), a compound capable of photopolymerization or a compound capable of photocrosslinking can be used without particular limitation. (B) As the component (B), a compound having at least 1 ethylenically unsaturated bond in the molecule can be used. Examples of the component (B) include bisphenol type (meth) acrylate compounds, polyalkylene glycol di (meth) acrylate having at least one of a (poly) epoxy vinyl group and a (poly) oxypropylene group in the molecule, nonylphenoxypolyoxyethylene (meth) acrylate, phthalic acid compounds (for example, 3-chloro-2-hydroxypropyl-2- (meth) acryloyloxyethyl phthalate), polyhydric alcohols of (meth) acrylic acid, alkyl (meth) acrylates, and the like.

Examples of the bisphenol-type (meth) acrylate compound include 2, 2-bis (4- ((meth) acryloyloxypolyethoxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxypolyethoxy polypropoxy) phenyl) propane, and the like. The bisphenol-type (meth) acrylate compound may include 2, 2-bis (4- ((meth) acryloyloxydiethoxy) phenyl) propane and 2, 2-bis (4- ((meth) acryloyloxypentaethoxy) phenyl) propane, from the viewpoint of easily suppressing the occurrence of defects in the photocured portion and from the viewpoint of easily obtaining excellent resolution and adhesion.

As the commercially available bisphenol type (meth) acrylate compound, there may be mentioned 2, 2-bis (4- (methacryloyloxydiethoxy) phenyl) propane (SHIN-NAKAMURA CHEMICAL CO, manufactured by LTD, trade name: BPE-200), 2-bis (4- (methacryloyloxypentaethoxy) phenyl) propane (SHIN-NAKAMURA CHEMICAL CO, manufactured by LTD, trade name: BPE-500 or Showa Denko Materials Co., manufactured by Ltd, trade name: FA-321M), 2-bis (4- (methacryloyloxyethoxypropoxy) phenyl) propane (Showa Denko Materials Co., manufactured by Ltd, trade name: FA-3200MY), 2-bis (4- (methacryloyloxypentadecyloxy) phenyl) propane (SHIN-KAMURA CHEMICAL CO, ltd, trade name: BPE-1300), 2-bis (4- (methacryloxypolyethoxy) phenyl) propane (Kyoeisha Chemical co., ltd., product name: BP-2EM, EO group: 2.6 (average)), etc.

The content of the bisphenol (meth) acrylate compound may be 1 to 50 mass%, 3 to 45 mass%, 10 to 45 mass%, 20 to 45 mass%, or 30 to 45 mass% based on the total amount of the solid components of the component (a) and the component (B) from the viewpoint of easy improvement of chemical resistance.

The content of the bisphenol (meth) acrylate compound may be 30 to 99 mass%, 50 to 97 mass%, 60 to 95 mass%, 70 to 95 mass%, or 80 to 94 mass% based on the total amount of the solid components of the component (B), from the viewpoint of facilitating improvement of chemical resistance.

The polyalkylene glycol di (meth) acrylate having at least one of a (poly) ethylene oxide group and a (poly) propylene oxide group in a molecule may be a polyalkylene glycol di (meth) acrylate having a (poly) ethylene oxide group and a (poly) propylene oxide group in a molecule. As the polyalkylene glycol di (meth) acrylate having at least one of a (poly) epoxy vinyl group and a (poly) oxypropylene group in a molecule, EOPO-modified di (meth) acrylate, dipentaerythritol hexa (meth) acrylate having an EO group, or the like can be used.

The content of the component (B) may be 20 to 70% by mass, 25 to 60% by mass, or 30 to 50% by mass based on the total amount of the solid components of the component (a) and the component (B), from the viewpoint that the resolution, the adhesiveness, and the resistance to resist curling of the photosensitive resin composition are easily improved, and that good photosensitivity and coating properties are easily obtained.

The photosensitive layer and the photosensitive resin composition may contain (C) a photopolymerization initiator (hereinafter, "(C) component"). (C) The component (B) can be appropriately selected from compounds capable of polymerizing the component (B), and can also be appropriately selected from generally used photopolymerization initiators.

Examples of the component (C) include aromatic ketones such as 2-benzyl ester-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-acetone-1; quinones such as alkylanthraquinone; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkyl benzoin; benzyl ester derivatives such as benzyl ester dimethyl ketal; 2,4, 5-triarylimidazole dimers such as 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer and 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer; acridine derivatives such as 9-phenylacridine (acridine) and 1,7- (9, 9' -acridinyl) heptane, and the like.

The component (C) may contain a 2,4, 5-triarylimidazole dimer from the viewpoint of easy improvement in resolution. Examples of the 2,4, 5-triarylimidazole dimer include a 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, a 2- (o-chlorophenyl) -4, 5-bis- (m-methoxyphenyl) imidazole dimer, and a 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer. The component (C) may contain 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer from the viewpoint that the photosensitivity stability is easily improved.

As the 2,4, 5-triarylimidazole dimer, for example, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenylbiimidazole can be commercially introduced as B-CIM (trade name, manufactured by rodogaya chemcal co., ltd).

The component (C) may contain a 2,4, 5-triarylimidazole dimer or a 2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer, from the viewpoint of easy improvement in photosensitivity and adhesion, and from the viewpoint of easy suppression of light absorption of the component (C). The structure of the 2,4, 5-triaryl imidazole dimer may be symmetrical or asymmetrical.

(C) The content of the component (B) may be in the following range with respect to 100 parts by mass of the total of the solid components of the components (a) and (B). The content of the component (C) may be 0.01 parts by mass or more, 0.1 parts by mass or more, 1 parts by mass or more, or 2 parts by mass or more, from the viewpoint of easily improving the photosensitivity, the resolution, and the adhesion. The content of the component (C) may be 30 parts by mass or less, 10 parts by mass or less, 7 parts by mass or less, 6 parts by mass or less, 5 parts by mass or less, or 4 parts by mass or less, from the viewpoint of easily obtaining an excellent resist pattern shape. From these viewpoints, the content of the component (C) may be 0.01 to 30 parts by mass, 0.1 to 10 parts by mass, 1 to 6 parts by mass, 1 to 5 parts by mass, 1 to 4 parts by mass, or 2 to 4 parts by mass.

The photosensitive layer and the photosensitive resin composition may contain (D) a photosensitizer (hereinafter, also referred to as a "(D) component"). By using the component (D), there is a tendency that the absorption wavelength of the active light used in the exposure can be effectively utilized.

Examples of the component (D) include pyrazolines, dialkylaminobenzophenones, anthracenes, coumarins, xanthones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, triazoles, stilbenes, triazines, thiophenes, naphthalimides, and triarylamines. "pyrazolines" are compounds having a pyrazoline structure, and are pyrazolines or pyrazoline derivatives. The same applies to the other compounds described above together with pyrazolines. The component (D) may contain at least one selected from the group consisting of pyrazolines, anthracenes, coumarins, and dialkylaminobenzophenones, from the viewpoint of facilitating and effectively utilizing the absorption wavelength of the active light used for exposure. Examples of pyrazolines include 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) pyrazoline.

(D) The content of the component (B) may be in the following range with respect to 100 parts by mass of the total of the solid components of the components (a) and (B). The content of the component (D) may be 1.0 part by mass or less, 0.5 part by mass or less, 0.15 part by mass or less, 0.12 part by mass or less, 0.10 part by mass or less, 0.08 part by mass or less, 0.06 part by mass or less, or 0.05 part by mass or less from the viewpoint of easily suppressing the occurrence of defects in the photocurable portion, easily obtaining excellent resolution and adhesion, easily obtaining an excellent resist pattern shape, and easily suppressing the occurrence of resist curling. The content of the component (D) may be 0.01 parts by mass or more from the viewpoint of easily obtaining high photosensitivity and good resolution.

The photosensitive layer and the photosensitive resin composition may contain (E) a polymerization inhibitor (hereinafter, also referred to as "component (E)"). By using the component (E), the exposure amount required for photocuring the photosensitive resin composition can be easily adjusted to the optimum exposure amount for exposure by a projection exposure machine. Examples of the component (E) include 4-tert-butylcatechol and the like.

The photosensitive layer and the photosensitive resin composition may contain additives such as a silane coupling agent, a dye, a photo-developer, a thermal development inhibitor, a plasticizer (e.g., p-toluenesulfonamide), a pigment, a filler, an antifoaming agent, a flame retardant, an adhesion imparting agent, a leveling agent, a peeling accelerator, an antioxidant, a perfume, a developer, and a thermal crosslinking agent, as required. The content of these additives may be 0.01 to 20 parts by mass per 100 parts by mass of the total of the components (A) and (B).

Examples of the silane coupling agent include 3-ureidopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-vinyltrimethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-glycidoxypropyltrimethoxysilane, N-glycidoxypropyltriethoxysilane, N-glycidoxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-methyldimethoxysilane, N-2- (aminopropyltriethoxysilane, N-glycidyloxy) and the like, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxypropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, and the like. Examples of the dye include malachite green, victoria pure blue, brilliant green, and methyl violet. Examples of the optical developer include tribromophenylsulfone, leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, o-chloroaniline, and tert-butylcatechol.

The photosensitive resin composition according to the present embodiment may contain an organic solvent as needed in order to improve the handling properties of the photosensitive composition or to adjust the viscosity and the storage stability. As the organic solvent, a commonly used organic solvent can be used without particular limitation. Examples of the organic solvent include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N-dimethylformamide, and propylene glycol monomethyl ether, and a mixed solvent thereof may be used.

The photosensitive layer may have a thickness of 1 μm or more, 2 μm or more, 3 μm or more, 5 μm or more, or 7 μm or more, from the viewpoint of easily obtaining excellent chemical resistance to an etching solution, a plating solution, or the like, from the viewpoint of easily suppressing the occurrence of resist lifting, peeling, or the like, and from the viewpoint of easily achieving industrial coating and easily improving productivity. The thickness of the photosensitive layer may be 200 μm or less, 100 μm or less, 50 μm or less, 30 μm or less, 20 μm or less, less than 20 μm, 15 μm or less, 12 μm or less, 10 μm or less, 8 μm or less, or 7 μm or less, from the viewpoint of easily obtaining high photosensitivity, and easily forming a resist pattern excellent in resolution and aspect ratio due to easily obtaining excellent photocurability of the resist base. From these viewpoints, the thickness of the photosensitive layer may be 1 to 200 μm.

As the support layer, a polymer film can be used. Examples of the polymer film include polyester films such as polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, and polyethylene-2, 6-naphthalate (PEN) film; polyolefin films such as polypropylene films and polyethylene films. The support layer may be a polyester film, from the viewpoint of easily improving the mechanical strength and heat resistance of the support layer, and from the viewpoint of easily improving performance by suppressing defects such as wrinkles of the barrier layer occurring when the barrier layer is formed on the support layer.

As the polyester film, a polyester film having particles (lubricant, etc.) can be used. Examples of such a polyester film include a polyester film mixed with particles (such as a lubricant), a polyester film having a layer containing particles (such as a lubricant) on one surface or both surfaces, and the like. Examples of the method for producing a polyester film having particles (lubricant, etc.) include a method using a polyester film mixed with particles (lubricant, etc.); examples of the method include known methods such as roll coating, flow coating, spray coating, curtain flow coating, dip coating, and slit die coating, and a method of forming a layer containing particles (lubricant and the like) on a flow-coated polyester film.

The Haze (Haze, Haze value) of the support layer (e.g., support film) may be in the range described below. The haze of the support layer may be 0.01% or more from the viewpoint of ease of manufacturing the support layer itself. The haze of the support layer may be 5.0% or less, 1.5% or less, 1.0% or less, or 0.5% or less, from the viewpoint of easily detecting foreign matter in the photosensitive layer when the photosensitive layer of the photosensitive element is formed. From these viewpoints, the haze of the supporting layer may be 0.01 to 5.0%, 0.01 to 1.5%, 0.01 to 1.0%, or 0.01 to 0.5%. "haze" refers to haze. The haze in the present invention is a value measured by a commercially available haze meter (turbidimeter) according to the method defined in JIS K7105. The haze can be measured, for example, by a commercially available haze meter such as NDH-5000(NIPPON DENSHOKU INDUSTRIES Co., Ltd., trade name).

As the support layer, a film that can be used starting from commercially available general industrial films can be used as a support film for the photosensitive element, and can be appropriately processed and used. Examples of such a support Film include "FB-40", "QS 69", "FS-31" (trade name, manufactured by TORAY INDUSTRIES, INC.), "A4100", "A1517" (trade name, manufactured by TOYOBO CO., LTD.), "G2H" (trade name, manufactured by Teijin Dupont Film Japan Limited), and "R-705G" (trade name, manufactured by Mitsubishi Chemical Corporation) as PET films.

The thickness of the support layer may be 1 μm or more, 5 μm or more, 10 μm or more, or 15 μm or more, from the viewpoint of easily suppressing the breakage of the support layer when peeling off the support layer. From the viewpoint of easy availability of economical enna , the thickness of the support layer may be 200 μm or less, 100 μm or less, 60 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 25 μm or less, 20 μm or less, or 15 μm or less. The thickness of the supporting layer may be 1 to 200 μm, 1 to 100 μm, 1 to 60 μm, 5 to 60 μm, 10 to 50 μm, 10 to 40 μm, 10 to 30 μm, or 10 to 25 μm.

Examples of the protective layer of the photosensitive element include polymer films such as a polyethylene film and a polypropylene film. As the protective layer, the same polymer film as the support layer described above may be used, or a polymer film different from the support layer described above may be used.

The photosensitive element can be obtained by: after the barrier layer is formed by coating and drying the resin composition for the barrier layer on the support layer, the photosensitive layer is formed by coating and drying the photosensitive resin composition on the barrier layer.

The coating of the resin composition for a barrier layer and the photosensitive resin composition can be carried out by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, bar coating, or spray coating. The conditions for drying the resin composition for a barrier layer and the photosensitive resin composition are not particularly limited as long as at least a part of the solvent such as water and an organic solvent can be removed, and the drying may be performed at 70 to 150 ℃ for 5 to 30 minutes. After drying, the amount of the residual solvent in the barrier layer and the photosensitive layer may be 2 mass% or less from the viewpoint of preventing diffusion of the solvent in the subsequent step.

By disposing the protective layer on the photosensitive layer, a photosensitive element including the supporting layer, the barrier layer, the photosensitive layer, and the protective layer in this order can be manufactured. Further, a photosensitive element including a support layer, a barrier layer, a photosensitive layer, and a protective layer in this order can also be obtained by bonding a laminate including a barrier layer on a support layer and a laminate including a photosensitive layer on a protective layer.

Examples

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples.

< Synthesis of adhesive Polymer >

Solution a was prepared by mixing 125g of methacrylic acid, 25g of methyl methacrylate, 125g of benzyl methacrylate, 225g of styrene, and 1.5g of azobisisobutyronitrile as polymerizable monomers.

Solution b was prepared by dissolving azobisisobutyronitrile (1.2 g) in 100g of a mixed solution (mass ratio: 3: 2) of methyl cellosolve (60 g) and toluene (40 g).

400g of a mixed solution of methyl cellosolve and toluene (hereinafter, also referred to as "mixed solution x") in a mass ratio of 3:2 was added to a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel, and a nitrogen introduction tube, and then the mixture was stirred while blowing nitrogen and heated to 80 ℃.

After the solution a was added dropwise at a constant dropping rate over 4 hours to the mixed solution x in the flask, the mixture was stirred at 80 ℃ for 2 hours. Then, after the solution b was added dropwise to the solution in the flask over 10 minutes at a constant dropping rate, the solution in the flask was stirred at 80 ℃ for 3 hours. Further, the solution in the flask was heated to 90 ℃ over 30 minutes, and then kept at 90 ℃ for 2 hours. After that, the mixture was cooled to room temperature, and then the nonvolatile content (solid content) was adjusted to 50 mass% by adding the mixture solution x, thereby obtaining a solution of the binder polymer (a-1). The weight-average molecular weight of the binder polymer (A-1) was 50000, and the acid value was 163 mgKOH/g.

The weight average molecular weight was measured by Gel Permeation Chromatography (GPC) under the following conditions, and was derived by conversion using a calibration curve of standard polystyrene.

[ GPC conditions ]

A pump: HITACHI L-6000 type (manufactured by HITACHI LTD.)

Pipe column: gelpack GL-R420, Gelpack GL-R430 and Gelpack GL-R440 are all 3 (pipe column specification:

are all Showa Denko Materials Co., Ltd., manufactured by Ltd.)

Eluent: tetrahydrofuran (THF)

Sample concentration: 120mg of a binder polymer solution having a solid content of 50 mass% was collected and dissolved in 5mL of tetrahydrofuran to prepare a sample.

Measuring temperature: 25 deg.C

Flow rate: 2.05 mL/min

A detector: HITACHI RI model L-3300 (HITACHI, manufactured by LTD., trade name)

The acid number is determined by neutralization titration. Specifically, first, 30g of acetone was added to 1g of a solution of the binder polymer, and then the solution was uniformly dissolved. Next, an appropriate amount of phenolphthalein as an indicator was added to the solution of the binder polymer (a-1), and then the solution was titrated with a 0.1N KOH aqueous solution, thereby measuring the acid value.

< preparation of photosensitive resin composition >

(photosensitive resin composition A)

A binder polymer (A-1) was compounded with 57 parts by mass of a binder polymer (A-1), 31 parts by mass of 2, 2-bis (4- (methacryloxypentaethoxy) phenyl) propane (Showa Denko Materials Co., product of Ltd., trade name: FA-321M) and 3 parts by mass of EOPO-modified dimethylacrylic acid (Showa Denko Materials Co., product of Ltd., trade name: FA-024M) and 2, 2-bis (4- (methacryloxydiethoxy) phenyl) propane (SHIN-NAKAMURA CHEMICAL CO., product of LTD, trade name: BPE-200)10 parts by mass of 2,2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -biphenylbiimidazole (photopolymerization initiator, HOGAGACHEMICAL CO., product of YAD, trade name: B-CIM)2.9 parts by mass and 1-phenyl-3- (4-methoxystyryl) -5- (4-tetraphenylpyrazine) pyridine (1-4-methoxyphenylethylene-4-tetraphenylpyrazine) 5A photosensitive resin composition A was obtained by mixing 0.05 parts by mass of oxazoline (Nippon CHEMICAL works Co., Ltd., trade name: PZ-501D), 0.05 parts by mass of 4-t-butylcatechol (polymerization inhibitor, manufactured by TBC, DIC Corporation), 0.05 parts by mass of MKG (malachite green, manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), 0.05 parts by mass of LCV (leuco crystal violet, YAMADA CHEMICAL CO., manufactured by LTD., Ltd.), 0.05 parts by mass of 3-mercaptopropyltrimethoxysilane (Shin-Etsu CHEMICAL Co., LTD., manufactured by KBM-803), 10 parts by mass of methanol, 10 parts by mass of toluene, and 10 parts by mass of acetone. The above-mentioned amounts except the solvent are amounts of solid components.

(photosensitive resin composition B)

A binder polymer (A-1) was compounded with 51 parts by mass of a binder polymer, 28 parts by mass of 2, 2-bis (4- (methacryloxypentaethoxy) phenyl) propane (Showa Denko Materials Co., product of Ltd., trade name: FA-321M), 10 parts by mass of 3-chloro-2-hydroxypropyl-2-acryloyloxyethyl phthalate (Showa Denko Materials Co., product of Ltd., trade name: FA-MECH), 4 parts by mass of 2, 2-bis (4- (methacryloyloxyethoxypropoxy) phenyl) propane (Showa Denko Materials Co., product of Ltd., product of trade name: FA-3200MY), 7 parts by mass of dipentaerythritol hexaacrylate having an EO group (Nippon Kayaku Co., product of Ltd., trade name: DPEA-12), and 2, 2' -bis (2-chlorophenyl) -4,4 ', 5, 5' -tetraphenylbiimidazole (photopolymerization initiator, HODOGAYA CHEMICAL CO., LTD. product, trade name: B-CIM)2.9 parts by mass, 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) pyrazoline (Nippon CHEMICAL works Co., manufactured by Ltd., trade name: PZ-501D)0.1 part by mass, 4-t-butylcatechol (polymerization inhibitor, TBC, DIC Corporation) 0.05 part by mass, MKG (malachite green, OSAKA ORGANIC CHEMICAL INDLY LTD. product) 0.1 part by mass, LCV (leuco crystal violet, YAMADA CHEMICAL CO., manufactured by LTD. product), 3-methacryloxypropyltrimethoxysilane (CorDow Dow Tor.Co., manufactured by Ltd. product, trade name: SZ6030)0.5 part by mass, Shin-mercaptopropyltrimethoxysilane (Etsu Co., EtD Co., manufactured by CHEMICAL Co., Etsu CHEMICAL Co., product, Shi, and so as the like, ltd, trade name: KBM-803)0.5 part by mass, 3-ureidopropyltriethoxysilane (Dow Corning Toray co., ltd. product name: AY43-031), 0.5 part by mass, 10 parts by mass of methanol, 10 parts by mass of toluene, and 10 parts by mass of acetone, thereby obtaining a photosensitive resin composition B. The above-mentioned amounts except the solvent are amounts of solid components.

< measurement of Absorbance >

The absorbance of light having a wavelength of 365nm in the photosensitive layers obtained using the photosensitive resin compositions A and B was measured using a UV spectrophotometer (manufactured by Hitachi, LTD., trade name: U-3310). Specifically, first, a photosensitive resin composition was coated on a PET film (product name: R-705G, thickness: 16 μm, manufactured by Mitsubishi Chemical Corporation) so as to have a uniform thickness, and then dried for 10 minutes by a hot air convection dryer at 100 ℃ to obtain an evaluation sample having a photosensitive layer having a thickness of 7 μm after drying. After setting the evaluation sample in a UV spectrophotometer, continuous measurement of a wavelength of 550 to 300nm is performed by an absorbance mode to obtain a UV absorption spectrum, thereby obtaining absorbance with respect to light having a wavelength of 365 nm. In the measurement, the above-mentioned PET film was used as a reference. The absorbance of the photosensitive layer obtained using photosensitive resin composition a was 0.03, and the absorbance of the photosensitive layer obtained using photosensitive resin composition B was 0.09.

< preparation of resin composition for Barrier layer >

(resin composition for Barrier layer A)

A resin composition A for a barrier layer was obtained by mixing 65 parts by mass of polyvinyl alcohol (water-soluble resin, The Nippon Synthetic Chemical Industry Co., Ltd., trade name: EG-05, saponification degree: 88 mol%), 40 parts by mass of polyvinylpyrrolidone (water-soluble resin, Nippon Shokubai Co., Ltd., trade name: K-30), 0.8 part by mass of an acrylic polymer (leveling agent, Kyoeisha Chemical Co., Ltd., trade name: WS-314), 250 parts by mass of 1-propanol, and 500 parts by mass of water. Specifically, the water-soluble resin was slowly added to 1-propanol and water at room temperature, and the mixture was heated to 90 ℃. After 90 ℃ had been reached, stirring was carried out for 1 hour. Next, the leveling agent was mixed and uniformly dissolved, and then cooled to room temperature, thereby obtaining a resin composition a for a barrier layer. The amounts of the components other than the solvent are the amounts of the solid components.

(resin composition for Barrier layer B)

The same procedure as for the resin composition a for a barrier layer was carried out except that the leveling agent was not mixed and cooled to room temperature, thereby obtaining a resin composition B for a barrier layer.

< production of photosensitive element >

(photosensitive element A)

As the support film, a PET film (a 2-layer biaxially oriented PET film having an antistatic layer on the opposite side to the side coated with the resin composition for a barrier layer, a PET film containing a lubricant on both sides, product name: R-705G manufactured by Mitsubishi Chemical Corporation, thickness: 16 μm) was prepared. Next, the resin composition for barrier layers shown in table 1 was applied to a support film (a surface with less lubricant) so as to have a uniform thickness, and then dried for 10 minutes by a hot air convection dryer at 95 ℃. Next, the photosensitive resin composition of table 1 was coated on the barrier layer so as to have a uniform thickness, and then dried for 10 minutes by a hot air convection dryer at 100 ℃. Next, a protective film (polyethylene film, tamapol co., ltd., product name: NF-15A) was laminated on the photosensitive layer, thereby obtaining a photosensitive element a having a structure in which a support film, a barrier layer, a photosensitive layer, and a protective film were laminated in this order.

(photosensitive element B)

As the support film, a PET film (a 2-layer biaxially oriented PET film having an antistatic layer on the opposite side to the side to which the photosensitive resin composition was applied, a PET film containing a lubricant on both sides, product name: R-705G manufactured by Mitsubishi Chemical Corporation, thickness: 16 μm) was prepared. Next, the photosensitive resin composition of table 1 was applied to a support film (a surface with less lubricant) so as to have a uniform thickness, and then dried for 10 minutes by a hot air convection dryer at 100 ℃. Next, a protective film (polyethylene film, tamapol co., ltd., product name: NF-15A) was laminated on the photosensitive layer, thereby obtaining a photosensitive element B having a structure in which a support film, a photosensitive layer, and a protective film were laminated in this order.

< production of laminate >

The photosensitive layer was brought into contact with a metal member (sheet of invar, thickness: 20 μm) while peeling off the protective film, and the photosensitive element a was pressure-bonded to the metal member, using a Laminator (product name: HLM-3000 manufactured by Taisei developer co. The crimping was carried out using a 110 ℃ hot roll at a roll speed of 1.0 m/min under a pressure of 0.40 MPa. Thus, a laminate a having the metal member, the photosensitive layer, the barrier layer, and the support film in this order in the lamination direction was obtained. A laminate B having a metal member, a photosensitive layer, and a support film in this order in the lamination direction was obtained in the same manner as above except that the photosensitive element B was used instead of the photosensitive element a.

< evaluation >

(number of defects)

After the support film was peeled off from the laminate a, 41-step ladder plates were disposed on the barrier layer. As the pattern for evaluation, the photosensitive layer was exposed to light using a projection exposure machine (product name: UX-2240SM-XJ01, manufactured by Ushio Inc.) having a high-pressure mercury lamp with a wavelength of 365nm using a lift-off mask having a wiring pattern with a line width/space width of 10 μm/10 μm. The irradiation energy was adjusted so that the number of residual steps after the development of the 41-step ladder plate became 11-step irradiation energy. After the exposure, the barrier layer was removed by washing with water at room temperature, thereby obtaining a laminate a.

Further, 41 steps of stepped plates were disposed on the support film of the laminate B. As the pattern for evaluation, the photosensitive layer was exposed to light using a projection exposure machine (product name: UX-2240SM-XJ01, manufactured by Ushio Inc.) having a high-pressure mercury lamp with a wavelength of 365nm using a lift-off mask having a wiring pattern with a line width/space width of 10 μm/10 μm. The irradiation energy was adjusted so that the number of residual steps after the development of the 41-step ladder plate became 11-step irradiation energy. After the exposure, the support film was peeled off to obtain a laminate b.

The photosensitive layer was subjected to spray development (30 ℃) for 2 times the shortest development time using a1 mass% aqueous solution of sodium carbonate, thereby removing unexposed portions from the laminate a and the laminate b. The shortest development time is adjusted to a time at which the unexposed portion is completely removed by the above-described development process. In conclusion, the resist pattern X1 having a line width/space width of 10 μm/10 μm and a line length of 18mm was produced.

As a result of observing the cross section of the resist pattern X1 with a Scanning Electron Microscope (SEM), it was confirmed that a rectangular cross-sectional shape was obtained as a resist shape in all of the examples and comparative examples.

The entire of 3 resist patterns X1 described above was observed with a Scanning Electron Microscope (SEM), and the number of defects was confirmed. The portion of the resist pattern X1 missing by 3 μm or more was judged as defective. The results are shown in table 1. The number of defects was determined to be 10 or less.

(analysis ability)

A resist pattern X2 was produced in the same manner as the resist pattern X1 described above, except that a lift-off mask having a wiring pattern with a line width/space width of 3X/X (X is 1 to 30 μm.1 μm intervals) was used as the evaluation pattern. After the development, the minimum value (unit: μm) of the space width in the resist pattern formed by removing the space portion (unexposed portion) without leaving any residue and the line portion (exposed portion) without meandering and missing was obtained as an index of the resolution. The evaluation results are shown in table 1. The smaller the value, the better the resolution.

(Adhesivity)

A resist pattern X3 was produced in the same manner as the resist pattern X1 described above, except that a lift-off mask having a wiring pattern with a line width/space width of X/3X (X is 1 to 30 μm.1 μm intervals) was used as the evaluation pattern. After the development, the minimum value (unit: μm) of the line widths in the resist pattern formed without the space portion (unexposed portion) being removed and the line portion (exposed portion) being meandering and missing was obtained as an index of the adhesion. The evaluation results are shown in table 1. The smaller the numerical value, the better the adhesion.

[ Table 1]

Description of the symbols

10-barrier layer, 20-photosensitive layer, 20 a-photocured part, 30-support film, 40-protective film, 50-metal part, 50 a-exposed part, 60-metal mask, 60 a-opening, 100-photosensitive element, a-laminate, L-active ray.

Claims (12)

1. A method of manufacturing a metal mask, the method comprising:

irradiating the photosensitive layer of a laminate comprising a metal member, a photosensitive layer disposed on the metal member, and a barrier layer disposed on the photosensitive layer with actinic rays through the barrier layer, thereby forming a patterned photocured portion on the photosensitive layer;

forming an exposed portion on the metal member by removing a portion of the photosensitive layer other than the photocured portion; and

and removing the exposed portion.

2. The method for manufacturing a metal mask according to claim 1,

removing the blocking layer by bringing water into contact with the blocking layer before removing a portion of the photosensitive layer other than the photocured portion.

3. The method for manufacturing a metal mask according to claim 1 or 2, wherein,

the metal part comprises an iron-nickel alloy.

4. The method for manufacturing a metal mask according to any one of claims 1 to 3, wherein,

the photosensitive layer has an absorbance of 0.05 or less with respect to light having a wavelength of 365 nm.

5. The method for manufacturing a metal mask according to any one of claims 1 to 4, wherein,

the photosensitive layer contains a binder polymer and a binder polymer,

the binder polymer has (meth) acrylic acid and an alkyl (meth) acrylate group as monomer units.

6. The method for manufacturing a metal mask according to any one of claims 1 to 5, wherein,

the photosensitive layer contains a photopolymerizable compound,

the photopolymerizable compound comprises a bisphenol-type (meth) acrylate compound.

7. The method for manufacturing a metal mask according to claim 6, wherein,

the photopolymerizable compounds include 2, 2-bis (4- ((meth) acryloyloxydiethoxy) phenyl) propane and 2, 2-bis (4- ((meth) acryloyloxypentaethoxy) phenyl) propane.

8. The method for manufacturing a metal mask according to any one of claims 1 to 7, wherein,

the photosensitive layer contains a photosensitizer.

9. The method for manufacturing a metal mask according to any one of claims 1 to 8, wherein,

the barrier layer contains polyvinyl alcohol.

10. The method for manufacturing a metal mask according to any one of claims 1 to 9,

the barrier layer contains a leveling agent.

11. The method for manufacturing a metal mask according to claim 10, wherein,

the leveling agent includes an acrylic polymer.

12. The method for manufacturing a metal mask according to any one of claims 1 to 11,

the thickness of the barrier layer is 1-12 mu m.

Images