Method for manufacturing a metal mask

Abstract

The present invention provides a method for manufacturing a metal mask, the method comprising: irradiating an active light (1L) through the barrier layer (10) of a laminate (1A) comprising a metal component (150), a photosensitive layer (120) disposed on the metal component (150) and a barrier layer (110) disposed on the photosensitive layer (120) to form a patterned photocurable portion (120a) on the photosensitive layer (120); forming an exposed portion on the metal component (150) by removing the portion of the photosensitive layer (120) other than the photocurable portion (120a); and removing the exposed portion of the metal component (150).

Description

Technical Field

[0001] This invention relates to a method for manufacturing a metal mask, etc. Background Technology

[0002] In various devices such as organic EL (electroluminescent) displays, organic materials are sublimated or evaporated to deposit organic materials onto a substrate, thereby forming an organic layer. In this case, to form an organic layer at a desired location on the substrate, the organic material is deposited onto the substrate via a metal mask with openings. Various techniques are being researched regarding methods for manufacturing such metal masks (for example, see Japanese Patent Application Publication No. 2015-021179). Summary of the Invention

[0003] In various devices such as organic EL displays, the increasing resolution in recent years has led to a demand for highly precise organic layers. However, in the metal mask used to obtain the organic layer, inhomogeneity in the shape and diameter of the openings may prevent the organic layer from forming uniformly. Therefore, to obtain highly precise organic layers, the openings of the metal mask also require high precision, which may reduce the yield rate of the metal mask during manufacturing. Therefore, a new method for manufacturing a metal mask with highly precise openings is required.

[0004] One aspect of the present invention is to provide a new method for manufacturing a metal mask.

[0005] The inventors conceived of forming a photocurable portion obtained using a photosensitive layer as a resist pattern on a metal part, and using this resist pattern as a mask to remove predetermined areas of the metal part, thereby forming an opening. Furthermore, the inventors conceived of suppressing defects in the photocurable portion in order to obtain a metal mask with highly precise openings, and discovered a technique for suppressing the occurrence of defects in the photocurable portion.

[0006] One aspect of the present invention relates to a method for manufacturing a metal mask, the method comprising: irradiating an active light through the barrier layer onto a photosensitive layer comprising a metal component, a photosensitive layer disposed on the metal component, and a barrier layer disposed on the photosensitive layer, thereby forming a patterned photocurable portion on the photosensitive layer; forming an exposed portion on the metal component by removing portions of the photosensitive layer other than the photocurable portion; and removing the exposed portion.

[0007] According to one aspect of the present invention, a method for manufacturing a metal mask can be provided, which can suppress the occurrence of defects in the photocuring section, and as a new method for manufacturing a metal mask, a metal mask with a highly precise opening can be obtained. Attached Figure Description

[0008] Figure 1 This is a schematic cross-sectional view showing an example of a photosensitive element.

[0009] Figure 2 This is a schematic cross-sectional view illustrating an example of a method for manufacturing a metal mask.

[0010] Figure 3 This is a schematic cross-sectional view illustrating an example of a method for manufacturing a metal mask.

[0011] Figure 4 This is a schematic cross-sectional view illustrating an example of a method for manufacturing a metal mask. Detailed Implementation

[0012] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings, as needed. In the following embodiments, the constituent elements are not necessarily required, except where specifically stated or clearly considered essential in principle. This also applies to numerical values ​​and ranges, and should be interpreted as not unduly limiting the invention.

[0013] "Above A" in numerical ranges refers to A and the range exceeding A. "Below A" in numerical ranges refers to A and the range less than A. In the numerical ranges described hierarchically in this specification, the upper or lower limit of a certain hierarchical numerical range can be arbitrarily combined with the upper or lower limits of the numerical ranges of other hierarchical ranges. The upper or lower limit of the numerical ranges described in this specification can also be replaced with the values ​​shown in the examples. Unless otherwise specified, the materials exemplified in this specification can be used alone or in combination with two or more. When multiple substances equivalent to each component are present in the composition, unless otherwise specified, the content of each component in the composition refers to the total amount of the multiple substances present in the composition. Regarding the term "layer," when viewed in a planar view, it includes not only the structure of a shape formed on the entire surface but also the structure of a shape formed on a portion. The term "process" not only refers to an independent process but is also included in this terminology as long as the intended function of the process can be achieved, even if it cannot be clearly distinguished from other processes. "(Meth)acrylate" refers to at least one of acrylate and its corresponding methacrylate. The same applies to other similar representations such as "(meth)acrylic acid". "EO" represents ethylene oxide, and "EO-modified" compounds refer to compounds containing vinyl oxide. "PO" represents ethylene oxide, and "PO-modified" compounds refer to compounds containing propylene oxide groups. The combination of "polyoxyethylene" and "vinyl oxide" is labeled "(poly)vinyl oxide". The same applies to other representations containing "(poly)". The weight-average molecular weight in this specification is determined by gel permeation chromatography (GPC) and converted using a calibration curve prepared using standard polystyrene, allowing for the determination of the weight-average molecular weight of the adhesive polymers in the examples.

[0014] The method for manufacturing a metal mask according to this embodiment includes: an exposure step in which active light is irradiated through the barrier layer onto a photosensitive layer comprising a metal component, a photosensitive layer disposed on the metal component, and a barrier layer disposed on the photosensitive layer (hereinafter referred to as "Laminator A" as appropriate), thereby forming a patterned photocurable portion on the photosensitive layer; a development step in which exposed portions are formed on the metal component by removing portions of the photosensitive layer other than the photocurable portions; and a removal step in which the exposed portions of the metal component are removed. The metal mask obtained by the method for manufacturing a metal mask according to this embodiment can be used without being particularly limited to applications that use metal masks, and can also be used to obtain various devices such as organic EL displays.

[0015] According to the metal mask manufacturing method of this embodiment, during the exposure process, the photosensitive layer is irradiated with active light through a blocking layer, thereby suppressing exposure obstacles such as oxygen suppression in the photosensitive layer (e.g., suppressing the deterioration of the resist pattern shape). Furthermore, when a polymer film is disposed on the photosensitive layer, exposure obstacles caused by particles contained in the polymer film may occur when the photosensitive layer is irradiated with active light through the polymer film. In contrast, according to the metal mask manufacturing method of this embodiment, it is not necessary to dispose of such a polymer film on the photosensitive layer during exposure, thus suppressing exposure obstacles. Therefore, by suppressing exposure obstacles, the occurrence of defects in the photocuring section can be suppressed, and a metal mask with highly precise openings can be obtained. According to the metal mask manufacturing method of this embodiment, for example, a metal mask having a desired shape and size can be obtained, a desired shape such as a circle or polygon can be obtained as the shape of the opening, and a diameter such as 30μm or less, 25μm, 20μm or less, 15μm or less can be obtained as the diameter of the opening (e.g., the maximum diameter).

[0016] Regarding the metal mask manufacturing method according to this embodiment, there is no laminate fabrication step to obtain laminate A before the exposure step. In the laminate fabrication step, laminate A can be obtained by placing a blocking layer and a photosensitive layer of a photosensitive element on a metal component, or laminate A can be obtained by sequentially forming a photosensitive layer and a blocking layer on a metal component. Laminate A is a laminate for manufacturing a metal mask. According to this embodiment, the method for manufacturing a laminate for manufacturing a metal mask can perform a laminate fabrication step. In the metal mask manufacturing method according to this embodiment, at least one step selected from the group consisting of a laminate fabrication step, an exposure step, a development step, and a removal step can be performed using a roll-to-roll process.

[0017] As a constituent material for metal components, known materials can be used as constituent materials for metal masks. Examples of metals (metallic materials) used in metal components include iron, nickel, copper, zinc, aluminum, and chromium. Brass, stainless steel, and iron-nickel alloys can be used as constituent materials for metal components. From the viewpoint of machinability or superior composition, metal components can contain iron-nickel alloys. Metal components can be metal sheets, metal foils, etc.

[0018] From the viewpoint of easily obtaining the desired opening shape during etching, the thickness of the metal component can be within the following ranges: The thickness of the metal component can be less than 100 μm, less than 80 μm, less than 50 μm, less than 40 μm, less than 30 μm, or less than 20 μm. The thickness of the metal component can be more than 1 μm, more than 5 μm, more than 10 μm, more than 15 μm, or more than 20 μm. From these viewpoints, the thickness of the metal component is 10–100 μm or 10–50 μm.

[0019] Regarding the absorbance of the photosensitive layer relative to light with a wavelength of 365 nm, from the viewpoint of easily suppressing the occurrence of defects in the photocurable part and easily obtaining excellent resolution and adhesion (adhesion between the photocurable part of the photosensitive layer and the metal component), it can 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. It is speculated that since the absorbance will not become too high, rapid curing on the light-receiving side of the photosensitive layer is suppressed, and the curing reaction is easily carried out uniformly throughout the entire interior of the photosensitive layer. Therefore, it is easy to suppress the occurrence of defects and easily obtain excellent resolution and adhesion. However, the main reasons for obtaining these effects are not limited to this. The absorbance of the photosensitive layer relative to light with a wavelength of 365 nm can exceed 0, or it can be 0.01 or more, 0.02 or more, or 0.03 or more. Absorbance can be adjusted by the type and content of the components of the photosensitive layer (photopolymerization initiator, photosensitizer, etc.).

[0020] The photosensitive element may also include a support layer (e.g., a support film) supporting the barrier layer. From the viewpoint of easily improving the gas barrier properties of the barrier layer and easily suppressing accidental peeling of the barrier layer from the photosensitive layer when peeling the support layer from the photosensitive element, the bond force between the support layer and the barrier layer can be less than the bond force between the barrier layer and the photosensitive layer. 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 can be disposed on the side opposite to the side of the photosensitive layer that is in contact with the barrier layer. The support layer and the protective layer can each be a single layer or multiple layers.

[0021] Figure 1 This is a schematic cross-sectional view showing an example of a photosensitive element. Figure 1 The photosensitive element 100 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 are in contact with each other.

[0022] When using a photosensitive element, after removing the protective layer, the photosensitive layer is pressed onto the metal component while heating, thereby allowing a barrier layer and a photosensitive layer to be deposited on the metal component. From the viewpoint of easily obtaining excellent adhesion and tracking performance when using a photosensitive element, the photosensitive layer can be pressed under reduced pressure. The pressing pressure can be, for example, 0.1–1.0 MPa (1–10 kgf / cm²). 2 The heating temperature during pressing can be, for example, 70–130°C. When the heating temperature is 70–130°C, it is not necessary to preheat the metal parts. However, from the viewpoint of easily obtaining better fit and conformability, it is also possible to preheat the metal parts.

[0023] In the exposure step of the metal mask manufacturing method according to this embodiment, the photosensitive layer of the laminate A is irradiated with active light through a barrier layer, thereby forming a patterned photocurable portion on the photosensitive layer. When a photosensitive element is used, in the exposure step, after removing the support layer, the photosensitive layer can be exposed with active light through a barrier layer. However, the photosensitive layer of the laminate A is irradiated with active light through a barrier layer without passing through a support layer, thereby forming a patterned photocurable portion on the photosensitive layer.

[0024] As an exposure method, known exposure techniques can be used, including: illumination of active light in an image-like manner through a mask pattern called a process pattern (mask exposure); LDI (Laser Direct Imaging) exposure; and illumination of active light in an image-like manner using a lens with an image projected onto a photomask (projection exposure). From the viewpoint of easily obtaining excellent resolution, projection exposure can be used. Projection exposure can also be referred to as an exposure method using active light with attenuated energy.

[0025] As a source of active light, known light sources can be used without particular restrictions, including gas lasers such as carbon arc lamps, mercury vapor arc lamps, ultra-high pressure mercury lamps, high pressure mercury lamps, xenon lamps, and argon lasers; solid-state lasers such as YAG lasers; and semiconductor lasers such as gallium nitride-based blue-violet lasers, which effectively emit ultraviolet light. Furthermore, light sources that effectively emit visible light, such as photographic floodlights and sunlamps, can also be used. From the viewpoint of easily and evenly improving resolution and alignment, light sources capable of emitting monochromatic I-ray light with an exposure wavelength of 365 nm, light sources capable of emitting monochromatic h-ray light with an exposure wavelength of 405 nm, or active light sources capable of emitting mixed IHG rays can be used. Ultra-high pressure mercury lamps are an example of a light source capable of emitting monochromatic I-ray light with an exposure wavelength of 365 nm.

[0026] In the developing step of the metal mask manufacturing method according to this embodiment, exposed portions are formed on the metal component by removing the portions of the photosensitive layer other than the photocurable portions (uncured portions, unexposed portions). In the developing step, the metal component is exposed by removing part or all of the portions of the photosensitive layer other than the photocurable portions. Through the developing step, a resist pattern (photocurable pattern of a photosensitive resin composition, relief pattern) composed of the photocurable portions of the photosensitive layer is formed on the metal component.

[0027] Examples of developing methods include wet development. In wet development, a developing solution can be used, and development can be performed using a known wet development method. Examples of wet development methods include immersion, paddle, high-pressure spray, and methods such as brushing, tapping, wiping, and shaking immersion. From the viewpoint of easily obtaining excellent resolution, high-pressure spray can be used. One wet development method can be used alone or in combination of two or more. The developing solution can be appropriately selected based on the composition of the photosensitive layer. Examples of developing solutions include alkaline aqueous solutions and organic solvent developing solutions. From the viewpoint of safety, stability, and good operability, alkaline aqueous solutions can be used as developing solutions.

[0028] Examples of bases that can be used in alkaline aqueous solutions include hydroxides such as lithium, sodium, or potassium hydroxides; carbonates such as lithium, sodium, potassium, or ammonium carbonates or 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; tetramethylammonium hydroxide; ethanolamine; ethylenediamine; diethylenetriamine; 2-amino-2-hydroxymethyl-1,3-propanediol; 1,3-diamino-2-propanol; morpholine, etc.

[0029] Examples of alkaline aqueous solutions include dilute solutions of 0.1–5% by mass sodium carbonate, 0.1–5% by mass potassium carbonate, 0.1–5% by mass sodium hydroxide, and 0.1–5% by mass sodium tetraborate. The pH of the alkaline aqueous solution can be 9–11. The temperature of the alkaline aqueous solution can be adjusted according to the developability of the photosensitive layer. The alkaline aqueous solution may contain surfactants, defoamers, and small amounts of organic solvents to promote development. Examples of organic solvents used in alkaline aqueous solutions include 3-propanol, acetone, ethyl acetate, alkoxyethanol (containing alkoxy groups with 1–4 carbon atoms), ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.

[0030] Organic solvents used in organic solvent developers include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. From the viewpoint of easily preventing ignition, organic solvent developers can be mixed with water, and the content of the organic solvent can be adjusted to within the range of 1–20% by mass.

[0031] When the barrier layer is water-soluble, the photosensitive layer can be removed with the developing solution after washing and removing the barrier layer. That is, during the developing process, before removing the portion of the photosensitive layer other than the photocurable portion, the barrier layer can be removed by contacting it with water. In this case, part or all of the barrier layer can be removed. When the barrier layer is dissolved in the developing solution, the barrier layer can be removed together with the photosensitive layer using the developing solution.

[0032] Regarding the method for manufacturing the metal mask according to this embodiment, after the development process, the resist pattern (the photocurable portion in the photosensitive layer) can be heated at 60 to 250°C, or exposed at an exposure rate of 0.2 to 10 J / cm. 2 The process involves exposure. This improves the curing degree of the resist pattern.

[0033] In the removal step of the metal mask manufacturing method according to this embodiment, an opening (through hole) is formed on the metal part by removing the exposed portion of the metal part. This allows a metal mask in a state supporting the resist pattern (the photocurable portion in the photosensitive layer) to be obtained. In the removal step, for example, the resist pattern is used as a mask, and the exposed portion of the metal part is removed by etching. This allows an opening with a shape corresponding to the opening of the resist pattern to be formed on the metal part. The etching method can be appropriately selected depending on the metal material to be removed. Examples of etching solutions include acidic etching solutions, ferric chloride solutions, alkaline etching solutions, and hydrogen peroxide-based etching solutions. For example, an acidic etching solution can be used, or a solution containing hydrochloric acid, sulfuric acid, formic acid, acetic acid, etc., mixed with a mixture of ferric chloride and ferric perchlorate solution.

[0034] Regarding the method for manufacturing the metal mask according to this embodiment, a step of removing the resist pattern (the photocurable portion in the photosensitive layer) can be included after the removal step. This allows for the acquisition of a metal mask in a state where the resist pattern has been removed. The resist pattern can be removed, for example, by an aqueous solution that is more alkaline than the alkaline aqueous solution used in the developing step. Examples of highly alkaline aqueous solutions include 1-10% by mass sodium hydroxide aqueous solution, 1-10% by mass potassium hydroxide aqueous solution, and 1-10% by mass ammonium salt aqueous solution. Examples of methods for removing the resist pattern include immersion and spraying.

[0035] Figures 2-4 This is a schematic cross-sectional view illustrating an example of a method for manufacturing a metal mask, and it is used to illustrate the use of... Figure 1 A schematic cross-sectional view illustrating a method for manufacturing a metal mask for a photosensitive element. In one example of the metal mask manufacturing method, firstly, as... Figure 2 As shown in (a), prepare metal part 50. Next, as... Figure 2 As shown in (b), by placing the blocking layer 10 and the photosensitive layer 20 of the photosensitive element on the metal component 50, a laminate A having the metal component 50, the photosensitive layer 20 disposed on the metal component 50, and the blocking layer 10 disposed on the photosensitive layer 20 is obtained (laminate manufacturing process).

[0036] Next, as Figure 3 As shown in (a), the photosensitive layer 20 of the laminate A is irradiated with active light L through the blocking layer 10, thereby... Figure 3 As shown in (b), a patterned photocurable portion 20a (exposure process) is formed on the photosensitive layer 20.

[0037] Next, as Figure 4 As shown in (a), by removing the portion of the photosensitive layer 20 other than the photocurable portion 20a, an exposed portion 50a is formed on the metal component 50 (development process). Next, as... Figure 4 As shown in (b), by removing the exposed portion 50a of the metal component 50, a metal mask 60 supporting the photocurable portion 20a and having an opening 60a can be obtained. Furthermore, as... Figure 4 As shown in (c), by removing the photocurable part 20a, a metal mask 60 in a state where the photocurable part 20a has been removed can be obtained.

[0038] The following describes the components of a photosensitive element.

[0039] A barrier layer is a layer with gas-blocking properties that mitigate the effects of oxygen ingress during exposure of the photosensitive layer. The barrier layer can be water-soluble or soluble relative to the developer. The barrier layer can be formed using a barrier layer resin composition (a resin composition for forming a barrier layer). The barrier layer resin composition can contain barrier layer constituent materials, water, organic solvents, etc. Examples of barrier layer constituent materials include water-soluble resins, ultraviolet absorbers, leveling agents, plasticizers, surfactants, and peel accelerators. Examples of organic solvents include alcohols with three or more carbon atoms (e.g., 1-propanol).

[0040] The barrier layer and the resin composition for the barrier layer may contain a water-soluble resin. "Water-soluble resin" refers to a resin with a solubility of less than 5 g relative to 100 mL of hexane at 25°C. This solubility can be calculated by mixing hexane at 25°C and dried water-soluble resin and checking for any turbidity. Specifically, in a colorless and transparent peeling container with a frosted glass stopper, sample 1, obtained by adding a mixture of dried water-soluble resin A[g] and 100 mL of hexane, and sample 2, obtained by adding only 100 mL of hexane, were prepared. Next, the samples in the peeling container were thoroughly stirred, and it was confirmed that the bubbles disappeared. After confirmation, the two containers were immediately arranged under diffused sunlight or equivalent light, and the liquid states of sample 1 and sample 2 were compared. When comparing sample 1 and sample 2, the amount A[g] added at which sample 1 began to appear more blurred or where the solid components began to float was defined as the solubility of the water-soluble resin relative to 100 mL of hexane at 25°C.

[0041] Examples of water-soluble resins include polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), and water-soluble polyimides. From the viewpoint of easily improving the gas barrier properties of the barrier layer and easily suppressing the deactivation of free radicals generated by the active light used in exposure, the barrier layer, as a water-soluble resin, can contain PVA. For example, PVA can be obtained by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate. From the viewpoint of more easily improving the gas barrier properties of the barrier layer and easily improving the resolution of the resist pattern, the degree of saponification of PVA can be 50 mol% or more, 70 mol% or more, or 80 mol% or more. The upper limit of the degree of saponification is 100 mol%. "Degree of saponification" refers to the value measured according to JIS K 6726 (1994) (Test Method for Polyvinyl Alcohol) as specified in the Japanese Industrial Standard.

[0042] Two or more polyvinyl alcohols with different degrees of saponification, viscosity, degree of polymerization, and types of modification can be used together. The average degree of polymerization of polyvinyl alcohol can be 300–5000, 300–3500, or 300–2000. The barrier layer can contain polyvinyl alcohol and polyvinylpyrrolidone. In this case, the mass ratio of polyvinyl alcohol to polyvinylpyrrolidone (PVA:PVP) can be 40:60–90:10, 50:50–90:10, or 60:40–90:10.

[0043] From the viewpoint of easily improving gas barrier properties, the content of water-soluble resin in the barrier layer, based on the overall barrier layer, can be within the following ranges: The content of water-soluble resin can be 50% by mass or more, 60% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 99% by mass or more. The content of water-soluble resin can be less than 100% by mass or less than 99.5% by mass. From these viewpoints, the content of water-soluble resin can be 50% by mass or more and less than 100% by mass.

[0044] From the viewpoint that gas barrier properties can be easily improved, the content of water-soluble resin in the resin composition for the barrier layer can be 10-60 parts by weight, 12-50 parts by weight, 14-40 parts by weight, 16-30 parts by weight, or 16-25 parts by weight relative to 100 parts by weight of water.

[0045] The barrier layer and the resin composition for the barrier layer may or may not contain a leveling agent. The leveling agent is unevenly distributed (oriented) on the surface side of the coating film of the resin composition for the barrier layer, which can reduce the surface tension of the coating film.

[0046] When fabricating a photosensitive element with a barrier layer, for example, the barrier layer is formed by coating and drying a resin composition for the barrier layer onto a support layer. However, shrinkage is prone to occur when coating the resin composition for the barrier layer onto the support layer, which can easily lead to defects in the photocurable portion on the surface of the barrier layer. Furthermore, the barrier layer tends to have strong adhesion to the support layer, and when the support layer is peeled off, sometimes a portion of the barrier layer peels off along with the support layer while still attached, resulting in defects in the barrier layer. On the other hand, if the resin composition for the barrier layer contains a leveling agent, the uneven distribution of the leveling agent on the surface side of the coating film can suppress shrinkage and reduce the adhesion between the support layer and the barrier layer. As a result, the occurrence of defects in the photocurable portion is more easily suppressed.

[0047] Examples of leveling agents include acrylic polymers, vinyl polymers, silicone polymers, and fluorinated polymers. From the viewpoint of easily improving the transferability of the barrier layer and its solubility relative to the developer, leveling agents may include acrylic polymers. From the viewpoint of easily obtaining suitable adhesion between the barrier layer and the support layer, acrylic polymers may include copolymers having at least one monomer unit selected from the group consisting of butyl methacrylate, isobutyl methacrylate, and EO-terminated methoxy-modified methacrylates; copolymers having butyl methacrylate and isobutyl methacrylate as monomer units; and copolymers having butyl methacrylate, isobutyl methacrylate, and EO-terminated methoxy-modified methacrylates as monomer units.

[0048] The content of each structural unit constituting the acrylic polymer can be based on the total amount of structural units constituting the acrylic polymer, and falls within the following ranges: The content of monomer units of butyl (meth)acrylate can be 2–20% by mass, 5–15% by mass, or 5–10% by mass. The content of monomer units of isobutyl (meth)acrylate can be 40–80% by mass, 50–70% by mass, or 55–65% by mass. The content of monomer units of terminal methoxy EO-modified (meth)acrylate can be 15–45% by mass, 20–40% by mass, or 25–35% by mass. The weight-average molecular weight of the acrylic polymer can be 10,000–40,000 or 10,000–20,000.

[0049] From the perspective of easily suppressing defects in the barrier layer when peeling off the support layer, the content of leveling agent in the barrier layer can be 0.05–1.0% by mass, 0.1–0.9% by mass, or 0.2–0.8% by mass, based on the total solid content of the barrier layer.

[0050] From the viewpoint of easy removal of the barrier layer, the thickness of the barrier layer can be less than 12 μm, less than 10 μm, less than 8 μm, less than 7 μm, less than 6 μm, or less than 5 μm. From the viewpoints of easy removal of the barrier layer, easy attainment of excellent resolution, and easy suppression of barrier layer migration, the thickness of the barrier layer can 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 these viewpoints, the thickness of the barrier layer can be 1–12 μm or 1–10 μm.

[0051] The photosensitive layer can be formed using a photosensitive resin composition. Negative photosensitive layers and photosensitive resin compositions can be used as both the photosensitive layer and the photosensitive resin composition. The photosensitive resin composition can contain constituent materials of the photosensitive layer, organic solvents, etc. Examples of constituent materials of the photosensitive layer include (A) adhesive polymers, (B) photopolymerizable compounds, (C) photopolymerization initiators, (D) photosensitizers, (E) polymerization inhibitors, and other components.

[0052] The photosensitive layer and photosensitive resin composition may contain (A) an adhesive polymer (hereinafter also referred to as "(A) component"). (A) component can be manufactured, for example, by free radical polymerization of a polymerizable monomer. Examples of such polymerizable monomers include polymerizable styrene derivatives such as styrene, vinyltoluene, and α-methylstyrene, substituted at the α-position or in an aromatic ring; acrylamides such as diacetone acrylamide; acrylonitrile; ethers of vinyl alcohol such as ethylene n-butyl ether; alkyl (meth)acrylates; benzyl methacrylates such as benzyl methacrylate; tetrahydrofurfuryl (meth)acrylate; dimethylaminoethyl (meth)acrylate; diethylaminoethyl (meth)acrylate; ( Glycidyl methacrylate; 2,2,2-trifluoroethyl methacrylate; 2,2,3,3-tetrafluoropropyl methacrylate; methacrylic acid; α-bromoacrylic acid; α-chloroacrylic acid; β-furan(meth)acrylic acid; β-styryl(meth)acrylic acid; maleic acid; maleic anhydride; monomethyl maleate, monoethyl maleate, isopropyl maleate, etc.; fumaric acid; cinnamic acid; α-cyanocinonic acid; itaconic acid; crotonic acid; propynic acid, etc.

[0053] From the viewpoint of easily improving plasticity and easily suppressing the occurrence of defects in the photocured part, component (A) can have alkyl methacrylate as a monomer unit, and can have both (meth)acrylic acid and alkyl methacrylate as monomer units. As alkyl methacrylate, compounds represented by the following general formula (I) can be cited; compounds in which the alkyl group is replaced by hydroxyl, epoxy, halogen, or other groups, etc.

[0054] H2C=C(R 11 )-COOR 12 (I)

[0055] In general formula (I), R 11 R represents a hydrogen atom or a methyl group. 12 Indicates an alkyl group having 1 to 12 carbon atoms. As R 12 Examples of alkyl groups with 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and structural isomers of these groups.

[0056] Examples of compounds represented by the above general formula (I) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, and dodecyl methacrylate.

[0057] From the viewpoint of easily obtaining excellent alkaline developability, component (A) can have a carboxyl group. A carboxyl-containing component (A) can be obtained, for example, by free radical polymerization of a polymerizable monomer having a carboxyl group with other polymerizable monomers. The polymerizable monomer with the carboxyl group can contain (meth)acrylic acid or methacrylic acid. The acid value of the carboxyl-containing component (A) can be 50–250 mg KOH / g, 50–200 mg KOH / g, or 100–200 mg KOH / g.

[0058] In component (A), from the viewpoint of easily and evenly improving alkali developability and alkali resistance, the content of the monomer unit of the polymerizable monomer having a carboxyl group can be based on the total amount of monomer units constituting component (A) and within the following ranges: From the viewpoint of easily improving alkali developability, the content of this monomer unit can be 12% by mass or more, 15% by mass or more, or 20% by mass or more. From the viewpoint of easily obtaining excellent alkali resistance, it can 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 this monomer unit can be 12 to 50% by mass, 12 to 40% by mass, 15 to 35% by mass, 15 to 30% by mass, or 20 to 30% by mass.

[0059] From the viewpoint of easily obtaining excellent adhesion and chemical resistance, component (A) may have a styrene compound selected from at least one of the group consisting of styrene and styrene derivatives as a monomer unit. When component (A) has a styrene compound monomer unit, from the viewpoint of easily obtaining even better adhesion and chemical resistance, the content of the styrene compound monomer unit may be based on the total amount of monomer units constituting component (A) and within the following ranges: From the viewpoint of easily improving adhesion, the content of the styrene compound monomer unit may be 10% by mass or more, 15% by mass or more, 30% by mass or more, 35% by mass or more, or 40% by mass or more. From the viewpoint of easily suppressing the release liner from becoming too large during development and easily suppressing the prolonged release time, the content of the styrene compound monomer unit may be 60% by mass or less or 50% by mass or less. From these viewpoints, the content of the styrene compound monomer unit may be 10–60% by mass, 15–50% by mass, 30–50% by mass, 35–50% by mass, or 40–50% by mass.

[0060] From the viewpoint of easily obtaining excellent resolution and aspect ratio, component (A) may contain monomer units of benzyl methacrylate. From the viewpoint of easily obtaining even better resolution and aspect ratio, the content of benzyl methacrylate monomer units may be based on the total amount of monomer units constituting component (A), and may be 15–50% by mass, 15–45% by mass, 15–40% by mass, 15–35% by mass, or 20–30% by mass.

[0061] (A) Component can be used alone or in combination of two or more. Examples of (A) components used in combination of two or more include two or more adhesive polymers composed of monomers with different polymerizability, two or more adhesive polymers with different weight-average molecular weights, and two or more adhesive polymers with different dispersities.

[0062] From the viewpoint of easily and evenly improving mechanical strength and alkaline developability, the weight-average molecular weight of component (A) can be within the following range. From the viewpoint of easily obtaining excellent developer resistance, the weight-average molecular weight of component (A) can be 10,000 or more, 20,000 or more, 40,000 or more, or 50,000 or more. From the viewpoint of easily suppressing the increase in development time, the weight-average molecular weight of component (A) can be 300,000 or less, 150,000 or less, 120,000 or less, or 80,000 or less. From these viewpoints, the weight-average molecular weight of component (A) can be 10,000 to 300,000, 20,000 to 300,000, 40,000 to 150,000, 40,000 to 120,000, or 50,000 to 80,000.

[0063] From the viewpoint that the coating properties of the photosensitive resin composition and the strength of the photocured part can be easily improved, the content of component (A) can be based on the total amount of solid components of component (A) and component (B), and is 30-80% by mass, 40-75% by mass, 50-70% by mass, or 50-60% by mass.

[0064] The photosensitive layer and photosensitive resin composition may contain a (B) photopolymerizable compound (hereinafter also referred to as "(B) component"). As (B) component, compounds capable of photopolymerization or photocrosslinking can be used without particular limitation. (B) component may be a compound having at least one vinyl unsaturated bond within its molecule. Examples of (B) component include bisphenol type (meth)acrylate compounds, polyalkylene glycol di(meth)acrylate having at least one (poly)epoxy vinyl and (poly)oxypropylene group within its molecule, nonylphenoxy polyoxyethylene (meth)acrylate, phthalic acid compounds (e.g., 3-chloro-2-hydroxypropyl-2-(meth)acryloyloxyethyl phthalate), (meth)acrylate polyol esters, (meth)acrylate alkyl esters, etc.

[0065] Examples of bisphenol-type (meth)acrylate compounds include 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloyloxypolyethoxypolypropoxy)phenyl)propane. From the viewpoint of easily suppressing defects in the photocured portion and easily obtaining excellent resolution and adhesion, bisphenol-type (meth)acrylate compounds may include 2,2-bis(4-((meth)acryloyloxydiethoxy)phenyl)propane and 2,2-bis(4-((meth)acryloyloxypentethoxy)phenyl)propane.

[0066] Examples of commercially available bisphenol-type (meth)acrylate compounds include 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (manufactured by SHIN-NAKAMURA CHEMICAL CO,LTD., trade name: BPE-200), 2,2-bis(4-(methacryloyloxypentaethoxy)phenyl)propane (manufactured by SHIN-NAKAMURA CHEMICAL CO,LTD., trade name: BPE-500 or Showa Denko Materials Co.,Ltd., trade name: FA-321M), 2,2-bis(4-(methacryloyloxyethoxypropoxy)phenyl)propane (manufactured by Showa Denko Materials Co.,Ltd., trade name: FA-3200MY), and 2,2-bis(4-(methacryloyloxypentadecaethoxy)phenyl)propane (SHIN-NAKAMURA CHEMICAL CO,LTD., trade name: BPE-200), 2,2-bis(4-(methacryloyloxypentadecaethoxy)phenyl)propane (manufactured by SHIN-NAKAMURA CHEMICAL CO,LTD., trade name: BPE-500 or Showa Denko Materials Co.,Ltd., trade name: FA-3200MY). (Manufactured by CO,LTD., trade name: BPE-1300), 2,2-bis(4-(methacryloyloxypolyethoxy)phenyl)propane (manufactured by Kyoisha Chemical Co.,Ltd., trade name: BP-2EM, EO group: 2.6 (average value)), etc.

[0067] From the perspective of easily improving drug resistance, the content of bisphenol type (meth)acrylate compounds can be based on the total amount of solid components (A) and (B), and can be 1-50% by mass, 3-45% by mass, 10-45% by mass, 20-45% by mass, or 30-45% by mass.

[0068] From the perspective of easily improving drug resistance, the content of bisphenol type (meth)acrylate compounds can be based on the total amount of solid components of component (B), and can be 30-99% by mass, 50-97% by mass, 60-95% by mass, 70-95% by mass, or 80-94% by mass.

[0069] A polyalkylene glycol di(meth)acrylate having at least one (poly)epoxy vinyl and (poly)oxypropylene groups within its molecule can be a polyalkylene glycol di(meth)acrylate having both (poly)epoxy ethylene and (poly)oxypropylene groups within its molecule. EOPO-modified di(meth)acrylate, dipentaerythritol hexa(meth)acrylate having EO groups, etc., can be used as polyalkylene glycol di(meth)acrylates having at least one (poly)epoxy vinyl and (poly)oxypropylene groups within its molecule.

[0070] From the viewpoint that the resolution, adhesion and inhibition of resist curling of the photosensitive resin composition can be easily improved, and from the viewpoint that good photosensitivity and coating properties can be easily obtained, the content of component (B) can be based on the total amount of solid components of components (A) and (B), and is 20-70% by mass, 25-60% by mass or 30-50% by mass.

[0071] The photosensitive layer and photosensitive resin composition may contain a photopolymerization initiator (hereinafter, “component (C)”). Component (C) may be suitably selected from compounds capable of polymerizing component (B) or from commonly used photopolymerization initiators.

[0072] Examples of components (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 alkyl anthraquinones; 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-triarylimidazolium dimers such as 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer and 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer; and acridine derivatives such as 9-phenylacridine and 1,7-(9,9'-acridinyl)heptane.

[0073] From the viewpoint of easily improving resolution, component (C) may contain a 2,4,5-triarylimidazolium dimer. Examples of 2,4,5-triarylimidazolium dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazolium dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazolium dimer. From the viewpoint of easily improving photosensitivity stability, component (C) may contain a 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer.

[0074] As a 2,4,5-triarylimidazolium dimer, for example 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbidiimidazole can be commercially available as B-CIM (manufactured by HODOGAYA CHEMICAL CO.,LTD., trade name).

[0075] From the perspective of easily improving photosensitivity and adhesion, and from the perspective of easily suppressing the light absorption of component (C), component (C) can contain either 2,4,5-triarylimidazolium dimer or 2-(2-chlorophenyl)-4,5-diphenylimidazolium dimer. The structure of the 2,4,5-triarylimidazolium dimer can be symmetrical or asymmetrical.

[0076] The content of component (C) relative to the total solid components of components (A) and (B) of 100 parts by mass can be within the following ranges. From the viewpoint of easily improving light sensitivity, resolution, and adhesion, the content of component (C) can be 0.01 parts by mass or more, 0.1 parts by mass or more, 1 part by mass or more, or 2 parts by mass or more. From the viewpoint of easily obtaining excellent resist pattern shapes, the content of component (C) can 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 these viewpoints, the content of component (C) can 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.

[0077] The photosensitive layer and photosensitive resin composition may contain a (D) photosensitizer (hereinafter also referred to as "(D) component"). By using the (D) component, there is a tendency to effectively utilize the absorption wavelength of the active light used in the exposure.

[0078] Examples of components (D) include pyrazolines, dialkylaminobenzophenones, anthracenes, coumarins, xanthones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, triazoles, stilbenesides, triazines, thiophenes, naphthimides, and triarylamines. "Pyrazolines" are compounds having a pyrazoline structure and are pyrazolines or pyrazoline derivatives. The description of other compounds described above along with pyrazolines is the same. From the viewpoint of easily and effectively utilizing the absorption wavelength of the active light used in exposure, component (D) may include at least one selected from the group consisting of pyrazolines, anthracenes, coumarins, and dialkylaminobenzophenones. Examples of pyrazolines include 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)pyrazoline.

[0079] The content of component (D) relative to the total solid components of components (A) and (B) of 100 parts by mass can be within the following range. From the viewpoints of easily suppressing defects in the photocured portion, easily obtaining excellent resolution and adhesion, easily obtaining excellent resist pattern shape, and easily suppressing resist curling, the content of component (D) can be 1.0 parts by mass or less, 0.5 parts by mass or less, 0.15 parts by mass or less, 0.12 parts by mass or less, 0.10 parts by mass or less, 0.08 parts by mass or less, 0.06 parts by mass or less, or 0.05 parts by mass or less. From the viewpoint of easily obtaining high photosensitiveness and good resolution, the content of component (D) can be 0.01 parts by mass or more.

[0080] The photosensitive layer and photosensitive resin composition may contain an (E) polymerization inhibitor (hereinafter also referred to as "(E) component"). By using the (E) component, the exposure amount required for photocuring the photosensitive resin composition can be easily adjusted to the most appropriate exposure amount when exposed using a projection exposure machine. Examples of (E) components include 4-tert-butylcatechol.

[0081] The photosensitive layer and photosensitive resin composition may contain additives such as silane coupling agents, dyes, photochromic agents, heat-resistant color-developing agents, plasticizers (such as p-toluenesulfonamide), pigments, fillers, defoamers, flame retardants, adhesion promoters, leveling agents, peel accelerators, antioxidants, fragrances, developers, and thermal crosslinking agents, as needed. The content of these additives may be 0.01 to 20 parts by weight relative to 100 parts by weight of the total of components (A) and (B).

[0082] Examples of silane coupling agents include 3-ureidopropyltriethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, N- Examples of silanes include 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxypropyl)tetrasulfide, and 3-isocyanate propyltriethoxysilane. Examples of silanes used as dyes include malachite green, Victoria blue, brilliant green, and methyl violet. Examples of silanes used as photochromic agents include tribromophenyl sulfone, colorless crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, o-chloroaniline, and tert-butylcatechol.

[0083] Regarding the photosensitive resin composition according to this embodiment, in order to improve the workability of the photosensitive composition, or to adjust the viscosity and storage stability, an organic solvent may be included as needed. Commonly used organic solvents can be used without particular limitation. Examples of organic solvents include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether, etc., and mixtures thereof may also be used.

[0084] From the perspectives of easily obtaining excellent resistance to etching solutions, plating solutions, etc., easily suppressing resist lifting and peeling, and facilitating industrial coating and improving productivity, the thickness of the photosensitive layer can be 1 μm or more, 2 μm or more, 3 μm or more, 5 μm or more, or 7 μm or more. From the perspectives of easily obtaining high photosensitive properties and easily forming resist patterns with excellent resolution and aspect ratio due to the excellent photocurability of the resist base, the thickness of the photosensitive layer can 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 these perspectives, the thickness of the photosensitive layer can be 1 to 200 μm.

[0085] Polymer films can be used as the support layer. Examples of polymer films include polyester films such as polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, and polyethylene-2,6-naphthalenedicarboxylate (PEN) film; and polyolefin films such as polypropylene film and polyethylene film. From the viewpoint of easily improving the mechanical strength and heat resistance of the support layer, and from the viewpoint of easily improving workability by suppressing defects such as wrinkles in the barrier layer that occur when the barrier layer is formed on the support layer, polyester films can be used as the support layer.

[0086] As a polyester film, a polyester film containing particles (lubricants, etc.) can be used. Examples of such polyester films include, for instance, a polyester film mixed with particles (lubricants, etc.), or a polyester film having a layer containing particles (lubricants, etc.) on one or both sides. Methods for manufacturing a polyester film containing particles (lubricants, etc.) include methods of mixing particles (lubricants, etc.) into a polyester film; and methods of forming a layer containing particles (lubricants, etc.) on a flow-coated polyester film using known methods such as roller coating, flow coating, spray coating, curtain flow coating, dip coating, and slot die coating.

[0087] The haze (haze value) of the support layer (e.g., support film) can be within the following ranges. From the viewpoint of ease of manufacturing the support layer itself, the haze of the support layer can be 0.01% or more. From the viewpoint of ease of detecting foreign matter in the photosensitive layer when forming the photosensitive layer of the photosensitive element, the haze of the support layer can be 5.0% or less, 1.5% or less, 1.0% or less, or 0.5% or less. From these viewpoints, the haze of the support layer can 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 turbidity. The haze in this invention refers to the value measured using a commercially available turbidimeter according to the method specified in JIS K 7105. Haze can be measured, for example, using a commercially available turbidimeter such as NDH-5000 (manufactured by NIPPON DENSHOKUINDUSTRIES Co., Ltd., trade name).

[0088] As a support layer, commercially available industrial films can also be used as support films for photosensitive elements and processed appropriately. Examples of such support films include PET films such as "FB-40", "QS69", "FS-31" (manufactured by TORAY INDUSTRIES, INC., trade name), "A4100", "A1517" (manufactured by TOYOBO CO.,LTD., trade name), "G2H" (manufactured by Teijin Dupont Film Japan Limited, trade name), and "R-705G" (manufactured by Mitsubishi Chemical Corporation, trade name).

[0089] From the viewpoint of easily suppressing support layer cracking during peeling, the thickness of the support layer can be 1 μm or more, 5 μm or more, 10 μm or more, or 15 μm or more. From the viewpoint of easily obtaining economic benefits, the thickness of the support layer can 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 support layer can be 1–200 μm, 1–100 μm, 1–60 μm, 5–60 μm, 10–60 μm, 10–50 μm, 10–40 μm, 10–30 μm, or 10–25 μm.

[0090] Examples of polymer films used as protective layers for photosensitive elements include polyethylene films and polypropylene films. As a protective layer, a polymer film identical to the aforementioned support layer can be used, or a polymer film different from the aforementioned support layer can be used.

[0091] A photosensitive element can be obtained by coating and drying a barrier layer with a resin composition on a support layer to form a barrier layer, and then coating and drying a photosensitive resin composition on the barrier layer to form a photosensitive layer.

[0092] The coating of the barrier layer resin composition and the photosensitive resin composition can be carried out by known methods such as roller coating, comma coating, gravure coating, air knife coating, mold coating, rod coating, and spray coating. The drying conditions for the barrier layer resin composition and the photosensitive resin composition are not particularly limited as long as at least a portion of the solvents such as water and organic solvents are removed; drying can be carried out at 70–150°C for 5–30 minutes. After drying, from the viewpoint of preventing solvent diffusion in subsequent processes, the residual solvent content in the barrier layer and the photosensitive layer can be less than 2% by mass.

[0093] By placing a protective layer on the photosensitive layer, a photosensitive element comprising a support layer, a barrier layer, a photosensitive layer, and a protective layer in sequence can be fabricated. Furthermore, a photosensitive element comprising a support layer, a barrier layer, a photosensitive layer, and a protective layer in sequence can also be obtained by bonding a laminate containing a barrier layer on a support layer and a photosensitive layer on a protective layer.

[0094] Example

[0095] The present invention will now be described in more detail based on embodiments, but the present invention is not limited to the following embodiments.

[0096] Synthesis of Adhesive Polymers

[0097] 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 (AIBN) as polymerizable monomers.

[0098] Solution b was prepared by dissolving 1.2 g of azobisisobutyronitrile in 100 g of a mixture of 60 g of methyl cellosolve and 40 g of toluene (mass ratio 3:2).

[0099] Add 400g of a mixture of methyl cellosolve and toluene (hereinafter also referred to as "mixture x") in a mass ratio of 3:2 to a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen inlet tube. Stir while blowing in nitrogen and heat to 80°C.

[0100] Solution a was added dropwise to mixture x in the flask at a constant rate over 4 hours, and then stirred at 80°C for 2 hours. Next, solution b was added dropwise to the same solution in the flask over 10 minutes at a constant rate, and then stirred at 80°C for 3 hours. The solution in the flask was then heated to 90°C over 30 minutes and held at 90°C for 2 hours. After cooling to room temperature, mixture x was added, and the non-volatile component (solid component) was adjusted to 50% by mass, thus obtaining a solution of adhesive polymer (A-1). The adhesive polymer (A-1) has a weight-average molecular weight of 50,000 and an acid value of 163 mg KOH / g.

[0101] The weight-average molecular weight was determined by gel permeation chromatography (GPC) under the following conditions, using a calibration curve of standard polystyrene and derived by conversion.

[0102] [GPC Conditions]

[0103] Pump: HITACHI L-6000 model (manufactured by Hitachi, LTD.)

[0104] Tube Columns: 3 in total: Gelpack GL-R420, Gelpack GL-R430, and Gelpack GL-R440 (Tube Column Specifications: (All manufactured by Showa Denko Materials Co., Ltd.)

[0105] Eluent: Tetrahydrofuran

[0106] Sample concentration: 120 mg of a solution of 50% by mass of the adhesive polymer was dissolved in 5 mL of tetrahydrofuran to prepare the sample.

[0107] Measurement temperature: 25℃

[0108] Flow rate: 2.05 mL / min

[0109] Detector: HITACHI L-3300 RI (manufactured by Hitachi, LTD., trade name)

[0110] The acid value was determined by neutralization titration. Specifically, firstly, 30g of acetone was added to 1g of the adhesive polymer solution and allowed to dissolve uniformly. Then, an appropriate amount of phenolphthalein as an indicator was added to the adhesive polymer (A-1) solution, and the acid value was determined by titration with a 0.1N KOH aqueous solution.

[0111] <Preparation of Photosensitive Resin Compositions>

[0112] (Photosensitive resin composition A)

[0113] The adhesive polymer (A-1) consisted of 57 parts by weight, 2,2-bis(4-(methacryloyloxypentethoxy)phenyl)propane (manufactured by Showa Denko Materials Co., Ltd., trade name: FA-321M) 31 parts by weight, EOPO-modified dimethacrylate (manufactured by Showa Denko Materials Co., Ltd., trade name: FA-024M) 3 parts by weight, 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (manufactured by SHIN-NAKAMURA CHEMICAL CO,LTD., trade name: BPE-200) 10 parts by weight, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (photopolymerization initiator, HODOGAYACHEMICAL) 2.9 parts by weight of B-CIM (manufactured by Nippon Chemical Works Co., Ltd., trade name: B-CIM), 0.05 parts by weight of 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)pyrazoline (manufactured by Nippon Chemical Works Co., Ltd., trade name: PZ-501D), 0.05 parts by weight of 4-tert-butylcatechol (polymerization inhibitor, TBC, manufactured by DIC Corporation), 0.05 parts by weight of MKG (malachite green, manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), 0.05 parts by weight of LCV (colorless crystal violet, manufactured by YAMADACHEMICAL CO.,LTD.), and 0.05 parts by weight of 3-mercaptopropyltrimethoxysilane (Shin-Etsu Chemical). Co.,LTD. (trade name: KBM-803) 0.05 parts by weight, 10 parts by weight of methanol, 10 parts by weight of toluene, and 10 parts by weight of acetone were mixed to obtain photosensitive resin composition A. Except for the solvent, the above amounts are all amounts of solid components.

[0114] (Photosensitive resin composition B)

[0115] The adhesive polymer (A-1) consisted of 51 parts by weight, 28 parts by weight of 2,2-bis(4-(methacryloyloxypentethoxy)phenyl)propane (manufactured by Showa Denko Materials Co., Ltd., trade name: FA-321M), 10 parts by weight of 3-chloro-2-hydroxypropyl-2-acryloyloxyethyl phthalate (manufactured by Showa Denko Materials Co., Ltd., trade name: FA-MECH), 4 parts by weight of 2,2-bis(4-(methacryloyloxyethoxypropoxy)phenyl)propane (manufactured by Showa Denko Materials Co., Ltd., trade name: FA-3200MY), and dipentaerythritol hexaacrylate with an EO group (Nippon Kayaku). 7 parts by weight of DPEA-12 (manufactured by Co., Ltd., trade name: HODOGAYA CHEMICAL CO.,LTD.), 2.9 parts by weight of 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbidiimidazole (photopolymerization initiator, manufactured by HODOGAYA CHEMICAL CO.,LTD., trade name: B-CIM), 0.1 parts by weight of 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)pyrazoline (manufactured by Nippon Chemical Works Co., Ltd., trade name: PZ-501D), 0.05 parts by weight of 4-tert-butylcatechol (polymerization inhibitor, manufactured by DICCO Corporation), 0.1 parts by weight of MKG (malachite green, manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), and 0.1 parts by weight of LCV (colorless crystal violet, manufactured by YAMADA CHEMICAL). 0.3 parts by weight of 3-methacryloyloxypropyltrimethoxysilane (manufactured by Dow Corning Toray Co., Ltd., trade name: SZ6030), 0.5 parts by weight of 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803), 0.5 parts by weight of 3-ureopropyltriethoxysilane (manufactured by Dow Corning Toray Co., Ltd., trade name: AY43-031), 10 parts by weight of methanol, 10 parts by weight of toluene, and 10 parts by weight of acetone were mixed to obtain photosensitive resin composition B. Except for the solvent, all the above proportions refer to the proportions of solid components.

[0116] <Determination of absorbance>

[0117] The absorbance of the photosensitive layers obtained using photosensitive resin compositions A and B relative to a wavelength of 365 nm was measured using a UV spectrophotometer (Hitachi, LTD., trade name: U-3310). Specifically, firstly, the photosensitive resin composition was coated onto a PET film (Mitsubishi Chemical Corporation, trade name: R-705G, thickness: 16 μm) in a uniform thickness manner, and then dried in a hot air convection dryer at 100°C for 10 minutes, thereby obtaining an evaluation sample with a photosensitive layer having a dried thickness of 7 μm. The evaluation sample was placed after being placed in the UV spectrophotometer, and the UV absorption spectrum was obtained by continuously measuring the wavelength from 550 to 300 nm in absorbance mode, thereby obtaining the absorbance relative to a wavelength of 365 nm. The aforementioned PET film was used as a reference in the measurement. 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.

[0118] <Preparation of Resin Compositions for Barrier Layers>

[0119] (Resin composition A for barrier layer)

[0120] A barrier layer resin composition A was obtained by mixing 65 parts by weight of polyvinyl alcohol (water-soluble resin, manufactured by The Nippon Synthetic Chemical Industry Co., Ltd., trade name: EG-05, saponification degree: 88 mol%), 40 parts by weight of polyvinylpyrrolidone (water-soluble resin, manufactured by Nippon Shokubai Co., Ltd., trade name: K-30), 0.8 parts by weight of acrylic polymer (leveling agent, manufactured by Kyoisha Chemical Co., Ltd., trade name: WS-314), 250 parts by weight of 1-propanol, and 500 parts by weight of water. Specifically, the water-soluble resin was slowly added to 1-propanol and water at room temperature, and after all the resin was added, the mixture was heated to 90°C. After reaching 90°C, the mixture was stirred for 1 hour. Then, the leveling agent was mixed and dissolved uniformly, and the mixture was cooled to room temperature to obtain the barrier layer resin composition A. All the above-mentioned amounts, except for the solvent, are amounts of solid components.

[0121] (Resin composition B for barrier layer)

[0122] Except for not mixing the leveling agent and cooling to room temperature, the process was carried out in the same manner as that of the barrier layer resin composition A, thereby obtaining the barrier layer resin composition B.

[0123] <Fabrication of Photosensitive Elements>

[0124] (Photosensitive element A)

[0125] As a support film, a PET film (a biaxially oriented PET film with an antistatic layer on the opposite side of the side coated with the barrier layer resin composition, a PET film containing lubricant on both sides, manufactured by Mitsubishi Chemical Corporation, trade name: R-705G, thickness: 16 μm) was prepared. Next, to ensure uniform thickness, the barrier layer resin composition from Table 1 was coated onto the support film (the side with less lubricant), and then dried in a hot air convection dryer at 95°C for 10 minutes, thereby forming a barrier layer with a dried thickness of 5 μm. Next, to ensure uniform thickness, the photosensitive resin composition from Table 1 was coated onto the barrier layer, and then dried in a hot air convection dryer at 100°C for 10 minutes, thereby forming a photosensitive layer with a dried thickness of 7 μm. Next, by bonding a protective film (polyethylene film, manufactured by Tamapoly Co., Ltd., trade name: NF-15A) to a photosensitive layer, a photosensitive element A with a structure having a support film, a barrier layer, a photosensitive layer and a protective film stacked in sequence was obtained.

[0126] (Photosensitive element B)

[0127] As a support film, a PET film (a biaxially oriented PET film with an antistatic layer on the opposite side of the side coated with the photosensitive resin composition, a PET film containing lubricant on both sides, manufactured by Mitsubishi Chemical Corporation, trade name: R-705G, thickness: 16 μm) was prepared. Next, to ensure uniform thickness, the photosensitive resin composition from Table 1 was coated onto the support film (the side with less lubricant), and then dried in a hot air convection dryer at 100°C for 10 minutes, thereby forming a photosensitive layer with a dried thickness of 7 μm. Then, by laminating a protective film (polyethylene film, manufactured by Tamapoly Co., Ltd., trade name: NF-15A) to the photosensitive layer, a photosensitive element B having a structure in which a support film, a photosensitive layer, and a protective film are sequentially stacked was obtained.

[0128] <Creating Layered Bodies>

[0129] Using a laminator (manufactured by Taisei Laminator Co., LTD., trade name: HLM-3000), while peeling off the protective film, the photosensitive layer is brought into contact with a metal component (Invar sheet, thickness: 20 μm), and the aforementioned photosensitive element A is simultaneously pressed onto the metal component. The pressing is performed using a 110°C hot roller at a pressure of 0.40 MPa and a roller speed of 1.0 m / min. This yields a laminate A having a metal component, a photosensitive layer, a barrier layer, and a support film sequentially in the lamination direction. Furthermore, a photosensitive element B is used instead of photosensitive element A, and the process is repeated in the same manner, thereby obtaining a laminate B having a metal component, a photosensitive layer, and a support film sequentially in the lamination direction.

[0130] <Evaluation>

[0131] (Number of defects)

[0132] After the support film was peeled off from the aforementioned laminate A, a 41-step trapezoidal plate was arranged on the barrier layer. As an evaluation pattern, a release mask with a wiring pattern having a linewidth / space width of 10 μm / 10 μm was used, and the photosensitive layer was exposed using a projection exposure machine (manufactured by Ushio Inc., trade name: UX-2240SM-XJ01) with a high-pressure mercury lamp at a wavelength of 365 nm. The irradiation energy was adjusted so that the number of residual steps after development of the 41-step trapezoidal plate was 11. After exposure, the barrier layer was removed by washing with water at room temperature, thereby obtaining laminate a.

[0133] Furthermore, a 41-step trapezoidal plate was disposed on the support film of the aforementioned laminate B. As an evaluation pattern, a release mask with a wiring pattern having a line width / space width of 10 μm / 10 μm was used, and the photosensitive layer was exposed using a projection exposure machine (manufactured by Ushio Inc., trade name: UX-2240SM-XJ01) with a high-pressure mercury lamp having a wavelength of 365 nm. The irradiation energy was adjusted so that the residual stage number after development of the 41-step trapezoidal plate was 11 stages. After exposure, laminate b was obtained by peeling off the support film.

[0134] Regarding the aforementioned laminates a and b, the photosensitive layer was spray-developed (30°C) using a 1% (w / w) sodium carbonate aqueous solution for twice the minimum development time, thereby removing the unexposed areas. The minimum development time was adjusted to the time required for the unexposed areas to be completely removed through the aforementioned development process. In summary, a resist pattern X1 with a linewidth / space width of 10 μm / 10 μm and a line length of 18 mm was fabricated.

[0135] The results of observing the cross-section of the resist pattern X1 by scanning electron microscopy (SEM) confirmed that a rectangular cross-sectional shape was obtained as the resist shape in all embodiments and comparative examples.

[0136] The three resist patterns X1 described above were observed using a scanning electron microscope (SEM) to confirm the number of defects. Areas with a missing resist pattern X1 of 3 μm or more were identified as defects. The results are shown in Table 1. Cases with fewer than 10 defects were considered good.

[0137] (Analytical)

[0138] As the evaluation pattern, a stripping mask with a line width / space width of 3x / x (x = 1~30μm, 1μm interval) was used. Otherwise, a resist pattern X2 was fabricated in the same manner as the resist pattern X1 described above. After development, the minimum value (unit: μm) of the space width in the resist pattern, where the unexposed portion (space portion) was removed without residue and the exposed portion (line portion) showed no bending or loss, was used as an indicator of resolution. The evaluation results are shown in Table 1. A smaller value indicates better resolution.

[0139] (Seamless fit)

[0140] As the evaluation pattern, a stripping mask with a line width / space width of x / 3x (x = 1 to 30 μm, 1 μm interval) was used. Otherwise, a resist pattern X3 was fabricated in the same manner as the resist pattern X1 described above. After development, the minimum line width (unit: μm) of the resist pattern formed where the unexposed space portion (unexposed portion) was removed without residue and the line portion (exposed portion) showed no bending or loss was used as an indicator of adhesion. The evaluation results are shown in Table 1. The smaller the value, the better the adhesion.

[0141] [Table 1]

[0142]

[0143] Symbol Explanation

[0144] 10-Blocking layer, 20-Photosensitive layer, 20a-Cureable part, 30-Support film, 40-Protective film, 50-Metal component, 50a-Exposed part, 60-Metal mask, 60a-Opening, 100-Photosensitive element, A-Laminated body, L-Active light ray.

Claims

1. A method for manufacturing a metal mask, the method comprising: A process in which active light is irradiated through the barrier layer of a laminate comprising a metal component, a photosensitive layer disposed on the metal component, and a barrier layer disposed on the photosensitive layer, thereby forming a patterned photocurable portion on the photosensitive layer; The process of forming an exposed portion on the metal component by removing the portion of the photosensitive layer other than the photocurable portion; and The process of removing the exposed portion, The barrier layer contains a leveling agent comprising an acrylic polymer.

2. The method for manufacturing a metal mask according to claim 1, wherein, Before removing the portion of the photosensitive layer other than the photocurable portion, the barrier layer is removed by contacting water with the barrier layer.

3. The method for manufacturing a metal mask according to claim 1 or 2, wherein, The metal component contains an iron-nickel alloy.

4. The method for manufacturing a metal mask according to claim 1 or 2, wherein, The absorbance of the photosensitive layer relative to light with a wavelength of 365 nm is less than 0.

05.

5. The method for manufacturing a metal mask according to claim 1 or 2, wherein, The photosensitive layer contains an adhesive polymer. The adhesive polymer has (meth)acrylic acid and (meth)acrylic acid alkyl esters as monomer units.

6. The method for manufacturing a metal mask according to claim 1 or 2, wherein, The photosensitive layer contains a photopolymerizable compound. The photopolymerizable compound contains bisphenol-type (meth)acrylate compounds.

7. The method for manufacturing a metal mask according to claim 6, wherein, The photopolymerizable compound comprises 2,2-bis(4-((meth)acryloyloxydiethoxy)phenyl)propane and 2,2-bis(4-((meth)acryloyloxypentethoxy)phenyl)propane.

8. The method for manufacturing a metal mask according to claim 1 or 2, wherein, The photosensitive layer contains a photosensitizer.

9. The method for manufacturing a metal mask according to claim 1 or 2, wherein, The barrier layer contains polyvinyl alcohol.

10. The method for manufacturing a metal mask according to claim 1 or 2, wherein, The thickness of the barrier layer is 1–12 μm.

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