Photosensitive resin composition, photosensitive element, method for producing cured product, method for producing cured product pattern, and method for producing wiring board

Abstract

To provide a photosensitive resin composition capable of reducing the time for removing an unexposed part and capable of satisfactorily forming a line part even when the line width in a linear cured product pattern is narrow.SOLUTION: A photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) a bisphenol compound having a polyoxyalkyl group located at a molecular terminal (excluding a compound corresponding to the component (B)), wherein a content of the component (D) is more than 0% by mass and 15% by mass or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a photosensitive resin composition, a photosensitive element, a method for producing a cured product, a method for producing a pattern of the cured product, a method for producing a wiring board, and the like. [Background technology]

[0002] In the manufacture of wiring boards, a resist pattern may be used to obtain desired wiring. The resist pattern can be formed by exposing and developing a photosensitive layer (photosensitive resin layer) obtained using a photosensitive resin composition. Various compositions have been studied as photosensitive resin compositions. For example, Patent Document 1 below describes a photosensitive resin composition containing a binder polymer, a photopolymerizable compound, and a specific photopolymerization initiator. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-028398 Summary of the Invention [Problem to be solved by the invention]

[0004] For photosensitive resin compositions for obtaining cured product patterns that can be used as resist patterns, it is sometimes required to reduce the time required for removing unexposed areas.

[0005] Furthermore, when forming a cured product pattern that can be used as a resist pattern, a linear cured product pattern having linear line portions and linear space portions adjacent to the line portions may be formed. Even when the line width of the linear cured product pattern is narrow, excellent adhesion may be required to ensure that the line portions are well formed.

[0006] One aspect of the present disclosure aims to provide a photosensitive resin composition that can reduce the time required to remove unexposed areas and can favorably form line portions even when the line width of a linear cured product pattern is narrow. Another aspect of the present disclosure aims to provide a photosensitive element using the photosensitive resin composition. Another aspect of the present disclosure aims to provide a method for producing a cured product, a method for producing a cured product pattern, and a method for producing a wiring board using the above-mentioned photosensitive resin composition. [Means for solving the problem]

[0007] One aspect of the present disclosure relates to a photosensitive resin composition containing (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) a bisphenol compound having a polyoxyalkyl group located at a molecular terminal (excluding compounds corresponding to the component (B)), wherein the content of the component (D) is more than 0 mass% and 15 mass% or less.

[0008] Such a photosensitive resin composition can reduce the time required to remove the unexposed areas, and can also form good line portions even when the line width of the linear cured product pattern is narrow.

[0009] Another aspect of the present disclosure relates to a photosensitive element comprising a support and a photosensitive layer disposed on the support, the photosensitive layer containing the above-described photosensitive resin composition.

[0010] Another aspect of the present disclosure relates to a method for producing a cured product, comprising an exposure step of irradiating a photosensitive layer containing the above-described photosensitive resin composition with actinic rays to obtain a cured product.

[0011] Another aspect of the present disclosure relates to a method for producing a cured product pattern, including, after the exposure step in the above-mentioned method for producing a cured product, a step of removing at least a portion of the portion of the photosensitive layer other than the cured product.

[0012] Another aspect of the present disclosure relates to a method for manufacturing a wiring board, comprising a step of performing an etching treatment or a plating treatment on a laminate having a cured product pattern obtained by the above-mentioned method for manufacturing a cured product pattern on a substrate. [Effects of the Invention]

[0013] According to one aspect of the present disclosure, it is possible to provide a photosensitive resin composition that can reduce the time required to remove unexposed portions and can favorably form line portions even when the line width of a linear cured product pattern is narrow. According to another aspect of the present disclosure, it is possible to provide a photosensitive element using the photosensitive resin composition. According to another aspect of the present disclosure, it is possible to provide a method for producing a cured product, a method for producing a cured product pattern, and a method for producing a wiring board using the above-mentioned photosensitive resin composition. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 is a schematic cross-sectional view illustrating an example of a photosensitive element. DETAILED DESCRIPTION OF THE INVENTION

[0015] Hereinafter, embodiments of the present disclosure will be described in detail, but the present disclosure is not limited to the following embodiments.

[0016] In this specification, numerical ranges indicated with "to" indicate a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. A numerical range "A or greater" means a range exceeding A and A. A numerical range "A or less" means a range less than A and A. In numerical ranges described in stages in this specification, the upper or lower limit of a numerical range in one stage can be arbitrarily combined with the upper or lower limit of a numerical range in another stage. In numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples. "A or B" may include either A or B, or may include both. Unless otherwise specified, the materials exemplified in this specification can be used alone or in combination of two or more. When multiple 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 multiple substances present in the composition, unless otherwise specified. The term "layer" encompasses structures that are formed over the entire surface as well as structures that are formed only partially when observed in a plan view. The term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as the process achieves its intended function. "(Meth)acrylic acid" refers to at least one of acrylic acid and its corresponding methacrylic acid. The same applies to other similar expressions, such as "(meth)acrylate." "(Meth)acrylic acid monomer content" refers to the total amount of acrylic acid monomer units and methacrylic acid monomer units, and similar terms. "Alkyl groups" may be linear, branched, or cyclic unless otherwise specified. "EO-modified" refers to compounds containing (poly)oxyethylene groups. "PO-modified" refers to compounds containing (poly)oxypropylene groups. "EO·PO-modified" refers to compounds containing (poly)oxyethylene groups and (poly)oxypropylene groups. "(Poly)oxyethylene groups" refers to at least one of oxyethylene groups and polyoxyethylene groups (groups in which two or more ethylene groups are linked by ether bonds).The same applies to other similar expressions such as "(poly)oxypropylene group."

[0017] In this specification, the solid content of a photosensitive resin composition refers to the non-volatile content of the photosensitive resin composition excluding volatile substances (water, solvent, etc.). In other words, the solid content refers to components (components other than the solvent) that remain without volatilizing when the photosensitive resin composition is dried, and includes components that are liquid, syrup-like, or waxy at room temperature (25°C).

[0018] <Photosensitive resin composition> The photosensitive resin composition according to this embodiment contains (A) a binder polymer (component (A)), (B) a photopolymerizable compound having an ethylenically unsaturated bond (component (B)), (C) a photopolymerization initiator (component (C)), and (D) a bisphenol compound having a polyoxyalkyl group located at a molecular terminal (component (D)). In the photosensitive resin composition according to this embodiment, the content of component (D) is greater than 0% by mass and not more than 15% by mass.

[0019] The photosensitive resin composition according to this embodiment can reduce the time required for removing the unexposed area, and the photosensitive resin composition according to this embodiment can achieve a minimum development time of, for example, less than 25 seconds (preferably 20 seconds or less) in the evaluation described in the Examples below.

[0020] The photosensitive resin composition according to this embodiment can form good line portions even when the line width of a linear cured product pattern is narrow (excellent adhesion can be obtained). Furthermore, the photosensitive resin composition according to this embodiment can form good line portions even when the line width (width of the line portion) of a linear cured product pattern is narrow, i.e., the line width (width of the line portion) is smaller than the space width (width of the space portion). The photosensitive resin composition according to this embodiment can achieve adhesion of, for example, 50 μm or less (preferably 40 μm or less) in the evaluation of adhesion described in the Examples below.

[0021] When forming a linear cured product pattern using a photosensitive resin composition, excellent resolution may be required as a property that allows space portions to be formed well even when the space width in the cured product pattern is narrow. According to one aspect of the photosensitive resin composition of this embodiment, even when the space width in the linear cured product pattern is narrow, space portions can be formed well (excellent resolution can be obtained). Furthermore, according to one aspect of the photosensitive resin composition of this embodiment, even when the space width in the linear cured product pattern is narrow, where the space width (width of the space portion) and the line width (width of the line portion) are equal to each other, space portions can be formed well. According to one aspect of the photosensitive resin composition of this embodiment, a resolution of, for example, 40 μm or less (preferably 30 μm or less) can be obtained in the resolution evaluation described in the examples below.

[0022] According to one aspect of the photosensitive resin composition of this embodiment, excellent sensitivity to actinic rays (a property in which the amount of exposure required to achieve a predetermined cured state is small) can also be obtained. According to one aspect of the photosensitive resin composition of this embodiment, in the evaluation of photosensitivity described in the examples below, for example, 25 mJ / cm 2 or less (preferably 20 mJ / cm 2 (below) can be obtained.

[0023] The photosensitive resin composition according to this embodiment may be in a liquid form or in a film form (photosensitive film). The photosensitive resin composition according to this embodiment has photocurability, and a cured product can be obtained by photocuring the photosensitive resin composition. The photosensitive resin composition according to this embodiment may have negative photosensitivity. The cured product according to this embodiment is a cured product (photocured product) of the photosensitive resin composition according to this embodiment. The cured product according to this embodiment may be in a patterned form (cured product pattern) or may be a resist pattern. Although the shape of the cured product pattern in the above-mentioned evaluation of adhesion and resolution is linear, the shape of the cured product pattern that can be obtained by the photosensitive resin composition according to this embodiment is not particularly limited.

[0024] The thickness of the film-like photosensitive resin composition or cured product may be 1 μm or more, 5 μm or more, 10 μm or more, 15 μm or more, 20 μm or more, or 25 μm or more, from the viewpoint of easily obtaining excellent adhesion and resolution. The thickness of the film-like photosensitive resin composition or cured product may be 300 μm or less, 200 μm or less, 100 μm or less, 80 μm or less, 70 μm or less, 60 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, or 25 μm or less, from the viewpoint of easily obtaining a resist suitable for etching or plating. From these viewpoints, the thickness of the film-like photosensitive resin composition or cured product may be 1 to 300 μm.

[0025] The photosensitive resin composition according to this embodiment contains a binder polymer as component (A). Examples of component (A) include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenolic resins. Acrylic resins are resins that contain a compound having a (meth)acryloyl group (a (meth)acrylic acid compound) as a monomer unit, and styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenolic resins that contain such monomer units are classified as acrylic resins. Component (A) does not need to contain a binder polymer that has a phenolic hydroxyl group.

[0026] Examples of compounds having a (meth)acryloyl group include (meth)acrylic acid, (meth)acrylic acid esters, etc. Examples of (meth)acrylic acid esters include alkyl (meth)acrylates (excluding compounds corresponding to alkyl (meth)acrylates; cycloalkyl (meth)acrylates), cycloalkyl (meth)acrylates (cycloalkyl (meth)acrylates), aryl (meth)acrylates (aryl (meth)acrylates; benzyl (meth)acrylate, etc.), (meth)acrylamide compounds (diacetone acrylamide, etc.), and glycidyl (meth)acrylates.

[0027] The component (A) may contain an acrylic resin from the viewpoints of easily achieving good alkaline developability, easily reducing the time required to remove unexposed areas, and easily achieving excellent adhesion, resolution, and sensitivity. From the same viewpoints, the content of the acrylic resin may be 50% by mass or more, more than 50% by mass, 70% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, or substantially 100% by mass (an embodiment in which the component (A) consists essentially of an acrylic resin), based on the total amount of the component (A).

[0028] Component (A) may contain (meth)acrylic acid as a monomer unit, from the viewpoint of easily reducing the time required for removal of unexposed areas and easily achieving excellent adhesion, resolution, and sensitivity. From the same viewpoint, when component (A) contains (meth)acrylic acid as a monomer unit, the content of the (meth)acrylic acid monomer unit may be within the following ranges based on the total amount of monomer units constituting component (A). The content of the (meth)acrylic acid monomer unit may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 12% by mass or more, 15% by mass or more, 18% by mass or more, 20% by mass or more, 22% by mass or more, or 25% by mass or more. The content of the (meth)acrylic acid monomer unit may be 50% by mass or less, less than 50% by mass, 45% by mass or less, 40% by mass or less, 35% by mass or less, 32% by mass or less, 30% by mass or less, 27% by mass or less, or 25% by mass or less. From these viewpoints, the content of the (meth)acrylic acid monomer unit may be 1 to 50% by mass.

[0029] Component (A) may contain alkyl (meth)acrylate as a monomer unit, from the viewpoint of easily reducing the time required to remove the unexposed portions and easily achieving excellent adhesion, resolution, and sensitivity. Examples of the alkyl group in the alkyl (meth)acrylate include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethylhexyl, nonyl, decyl, undecyl, and dodecyl groups, and the alkyl group may be any of various structural isomers. Component (A) may contain methyl (meth)acrylate as a monomer unit, from the viewpoint of easily reducing the time required to remove the unexposed portions and easily achieving excellent adhesion, resolution, and sensitivity.

[0030] The alkyl group of the alkyl (meth)acrylate may have a substituent, such as a hydroxy group, a carboxy group, a carboxylate group, an aldehyde group, an alkoxy group, a carbonyl group, an alkoxycarbonyl group, an alkanoyl group, an oxycarbonyl group, a carbonyloxy group, an amino group, an epoxy group, a furyl group, a cyano group, a halogeno group (such as a fluoro group, a chloro group, or a bromo group), a nitro group, an acetyl group, a sulfonyl group, or a sulfonamide group.

[0031] When component (A) has alkyl (meth)acrylate as a monomer unit, the content of the alkyl (meth)acrylate monomer unit may be within the following ranges based on the total amount of monomer units constituting component (A), from the viewpoint of easily reducing the time it takes to remove unexposed areas and easily obtaining excellent adhesion, resolution, and sensitivity: The content of the alkyl (meth)acrylate monomer unit may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more. The content of alkyl (meth)acrylate monomer units may be 99% by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, or 50% by mass or less. From these viewpoints, the content of alkyl (meth)acrylate monomer units may be 1 to 99% by mass.

[0032] From the viewpoint of easily reducing the time required for removal of the unexposed portions and easily obtaining excellent adhesion, resolution, and sensitivity, the component (A) may have a styrene compound (excluding compounds having a (meth)acryloyl group) as a monomer unit. Examples of the styrene compound include styrene and styrene derivatives. Examples of the styrene derivative include vinyl toluene and α-methyl styrene. From the viewpoint of easily reducing the time required for removal of the unexposed portions and easily obtaining excellent adhesion, resolution, and sensitivity, the component (A) may have, as a monomer unit, at least one selected from the group consisting of (meth)acrylic acid and (meth)acrylic acid, and a styrene compound, or may have, as monomer units, (meth)acrylic acid, an alkyl (meth)acrylate, and a styrene compound.

[0033] When component (A) has a styrene compound as a monomer unit, the content of the styrene compound monomer unit may be within the following ranges based on the total amount of monomer units constituting component (A), from the viewpoints of easily reducing the time required to remove unexposed areas and easily obtaining excellent adhesion, resolution, and sensitivity. The content of the styrene compound monomer unit may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 12% by mass or more, 15% by mass or more, 18% by mass or more, 20% by mass or more, 22% by mass or more, or 25% by mass or more. The content of the styrene compound monomer unit may be 50% by mass or less, less than 50% by mass, 45% by mass or less, 40% by mass or less, 35% by mass or less, 32% by mass or less, 30% by mass or less, 27% by mass or less, 25% by mass or less, 22% by mass or less, 20% by mass or less, 18% by mass or less, or 15% by mass or less. From these viewpoints, the content of the styrene compound monomer unit may be 1 to 50% by mass.

[0034] Component (A) may contain other monomers as monomer units. Examples of such monomers include vinyl alcohol ethers (e.g., vinyl n-butyl ether), (meth)acrylonitrile, maleic acid, maleic anhydride, maleic acid monoesters (e.g., monomethyl maleate, monoethyl maleate, monoisopropyl maleate), fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. Component (A) does not have to contain at least one of these monomers as a monomer unit.

[0035] The weight-average molecular weight (Mw) of component (A) may be within the following ranges, from the viewpoints of easily reducing the time required to remove unexposed areas and easily achieving excellent adhesion, resolution, and sensitivity. The weight-average molecular weight of component (A) may be 10,000 or more, 20,000 or more, 25,000 or more, 30,000 or more, 35,000 or more, 40,000 or more, 45,000 or more, 50,000 or more, 53,000 or more, or 55,000 or more. The weight-average molecular weight of component (A) may be 200,000 or less, 150,000 or less, 100,000 or less, 80,000 or less, 70,000 or less, 60,000 or less, or 55,000 or less. From these viewpoints, the weight-average molecular weight of component (A) may be 10,000 to 200,000.

[0036] The number average molecular weight (Mn) of component (A) may be within the following ranges, from the viewpoints of easily reducing the time required to remove unexposed areas and easily achieving excellent adhesion, resolution, and sensitivity. The number average molecular weight of component (A) may be 5,000 or more, 10,000 or more, 15,000 or more, 18,000 or more, or 20,000 or more. The number average molecular weight of component (A) may be 100,000 or less, 80,000 or less, 60,000 or less, 50,000 or less, 45,000 or less, 40,000 or less, 35,000 or less, 30,000 or less, 28,000 or less, 25,000 or less, or 20,000 or less. From these viewpoints, the number average molecular weight of component (A) may be 5,000 to 100,000.

[0037] The dispersity (Mw / Mn) of component (A) may be within the following range, from the viewpoint of facilitating a reduction in the time required for removal of unexposed areas and facilitating the achievement of excellent adhesion, resolution, and sensitivity. The dispersity (Mw / Mn) of component (A) may be 1.2 or more, 1.5 or more, 1.8 or more, 2.0 or more, 2.2 or more, 2.5 or more, or 2.7 or more. The dispersity (Mw / Mn) of component (A) may be 3.5 or less, 3.3 or less, 3.0 or less, 2.9 or less, or 2.8 or less. From these viewpoints, the dispersity of component (A) may be 1.2 to 3.5.

[0038] The weight average molecular weight (Mw) and number average molecular weight (Mn) can be obtained by, for example, measuring by gel permeation chromatography (GPC) and converting using a calibration curve of standard polystyrene. More specifically, they can be measured by the method described in the Examples. For compounds with low molecular weights, if it is difficult to measure them using such a measurement method, the molecular weight can be measured by another method and the average value calculated.

[0039] The acid value of component (A) may be within the following ranges, from the viewpoints of easily reducing the time required to remove unexposed areas and easily achieving excellent adhesion, resolution, and sensitivity. The acid value of component (A) may be 60 mgKOH / g or more, 70 mgKOH / g or more, 80 mgKOH / g or more, 90 mgKOH / g or more, 100 mgKOH / g or more, 120 mgKOH / g or more, 130 mgKOH / g or more, 140 mgKOH / g or more, 150 mgKOH / g or more, or 160 mgKOH / g or more. The acid value of component (A) may be 250 mgKOH / g or less, 230 mgKOH / g or less, 200 mgKOH / g or less, 180 mgKOH / g or less, 170 mgKOH / g or less, or 160 mgKOH / g or less. From these viewpoints, the acid value of component (A) may be 60 to 250 mgKOH / g. The acid value of component (A) can be adjusted by the content of the monomer units (for example, monomer units of (meth)acrylic acid) that constitute component (A).

[0040] The content of component (A) may be within the following ranges based on the total amount (total solids content) of the photosensitive resin composition, from the viewpoints of easily reducing the time required to remove unexposed areas and easily achieving excellent adhesion, resolution, and sensitivity. The content of component (A) may be 10% by mass or more, 20% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 52% by mass or more, 53% by mass or more, or 55% by mass or more. The content of component (A) may be 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, or 53% by mass or less. From these viewpoints, the content of component (A) may be 10 to 90% by mass.

[0041] From the viewpoint of easily reducing the time it takes to remove the unexposed portions and easily achieving excellent adhesion, resolution, and sensitivity, the content of component (A) may be within the following ranges relative to 100 parts by mass of the total of components (A) and (B): The content of component (A) may be 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, 45 parts by mass or more, 50 parts by mass or more, 54 parts by mass or more, 55 parts by mass or more, 56 parts by mass or more, 57 parts by mass or more, 58 parts by mass or more, 59 parts by mass or more, 60 parts by mass or more, or 63 parts by mass or more. The content of component (A) may be 90 parts by mass or less, 80 parts by mass or less, 75 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, 63 parts by mass or less, 60 parts by mass or less, 59 parts by mass or less, 58 parts by mass or less, 57 parts by mass or less, or 56 parts by mass or less. From these viewpoints, the content of the component (A) may be 10 to 90 parts by mass.

[0042] The photosensitive resin composition according to this embodiment contains a photopolymerizable compound having an ethylenically unsaturated bond as the component (B).

[0043] Component (B) may contain a bisphenol A di(meth)acrylate compound, which may be alkylene oxide-modified and may have a polyoxyalkylene group (such as a polyoxyethylene group, a polyoxypropylene group, or a polyoxybutylene group), in order to facilitate a reduction in the time required for removal of unexposed areas and to facilitate obtaining excellent adhesion, resolution, and sensitivity.

[0044] Examples of bisphenol A di(meth)acrylate compounds include 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane (2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane, etc.), 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolybutoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane.

[0045] From the viewpoint of easily reducing the time required for removal of unexposed areas and easily obtaining excellent adhesion, resolution, and sensitivity, the component (B) may include at least one selected from the group consisting of 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane, or may include at least one selected from the group consisting of 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane and 2,2-bis(4-((meth)acryloxydiethoxy)phenyl)propane.

[0046] From the viewpoint of easily reducing the time required for removal of unexposed areas and easily achieving excellent adhesion, resolution, and sensitivity, component (B) may contain, as a polyoxyalkylene group-containing bisphenol A di(meth)acrylate compound, a bisphenol A di(meth)acrylate compound in which the number of oxyalkylene groups in the polyoxyalkylene chain (the number of oxyalkylene groups in one molecule) is within the following range: The number of oxyalkylene groups may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, 10 or more, 12 or more, 14 or more, or 16 or more. The number of oxyalkylene groups may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, or 4 or less. From these viewpoints, the number of oxyalkylene groups may be 1 to 20.

[0047] The content of the bisphenol A di(meth)acrylate compound may be within the following ranges based on the total amount of component (B), from the viewpoints of easily reducing the time required to remove unexposed areas and easily obtaining excellent adhesion, resolution, and sensitivity. The content of the bisphenol A di(meth)acrylate compound may be 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, 57% by mass or more, 58% by mass or more, 59% by mass or more, or 60% by mass or more. The content of the bisphenol A di(meth)acrylate compound may be 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 59% by mass or less, 58% by mass or less, 57% by mass or less, or 55% by mass or less. From these viewpoints, the content of the bisphenol A di(meth)acrylate compound may be 10 to 90% by mass.

[0048] The content of the bisphenol A di(meth)acrylate compound may be within the following ranges based on the total solid content of the photosensitive resin composition, from the viewpoint of easily reducing the time required to remove unexposed areas and easily obtaining excellent adhesion, resolution, and sensitivity. The content of the bisphenol A di(meth)acrylate compound may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 21% by mass or more, 22% by mass or more, 23% by mass or more, or 24% by mass or more. The content of the bisphenol A di(meth)acrylate compound may be 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, 24% by mass or less, 23% by mass or less, 22% by mass or less, 21% by mass or less, or 20% by mass or less. From these viewpoints, the content of the bisphenol A di(meth)acrylate compound may be 1 to 50% by mass.

[0049] The content of the bisphenol A di(meth)acrylate compound may be within the following ranges relative to 100 parts by mass of the total of components (A) and (B), from the viewpoints of easily reducing the time required to remove the unexposed areas and easily obtaining excellent adhesion, resolution, and sensitivity. The content of the bisphenol A di(meth)acrylate compound may be 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 22 parts by mass or more, 23 parts by mass or more, 24 parts by mass or more, 25 parts by mass or more, or 26 parts by mass or more. The content of the bisphenol A di(meth)acrylate compound may be 50 parts by mass or less, 45 parts by mass or less, 40 parts by mass or less, 35 parts by mass or less, 30 parts by mass or less, 26 parts by mass or less, 25 parts by mass or less, 24 parts by mass or less, 23 parts by mass or less, 22 parts by mass or less, or 20 parts by mass or less. From these viewpoints, the content of the bisphenol A di(meth)acrylate compound may be 1 to 50 parts by mass.

[0050] From the viewpoint of easily reducing the time required for removal of unexposed areas and easily obtaining excellent adhesion, resolution, and sensitivity, component (B) may contain at least one compound X selected from the group consisting of trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, and alkylene oxide modified products thereof, and may contain an alkylene oxide modified product of trimethylolpropane tri(meth)acrylate. Examples of alkylene oxide modified products of trimethylolpropane tri(meth)acrylate and tetramethylolmethane tri(meth)acrylate include EO modified products, PO modified products, and EO·PO modified products.

[0051] The content of compound X or the content of the alkylene oxide modified product of trimethylolpropane tri(meth)acrylate may be within the following ranges based on the total solid content of the photosensitive resin composition, from the viewpoint of easily reducing the time required to remove unexposed areas and easily obtaining excellent adhesion, resolution, and sensitivity. The content may be 1% by mass or more, 3% by mass or more, 5% by mass or more, 6% by mass or more, 7% by mass or more, 7.5% by mass or more, or 8% by mass or more. The content may be 20% by mass or less, 15% by mass or less, 12% by mass or less, 10% by mass or less, 9% by mass or less, 8% by mass or less, 7.5% by mass or less, or 7% by mass or less. From these viewpoints, the content may be 1 to 20% by mass.

[0052] The component (B) may contain a compound represented by the following general formula (b1), from the viewpoint of easily reducing the time required to remove the unexposed area and easily obtaining excellent adhesion, resolution, and sensitivity. Examples of the oxyalkylene group in AO include an oxyethylene group, an oxypropylene group, and an oxybutylene group. From the viewpoint of easily reducing the time required to remove the unexposed area and easily obtaining excellent adhesion, resolution, and sensitivity, the component (B) may contain a compound represented by the following general formula (b1): 12 The number of carbon atoms in the alkyl group may be 1 to 20, 1 to 12, 1 to 9, 3 to 9, 5 to 9, 9 to 20, or 9 to 12, n11 may be 1 to 10, 1 to 4, 4 to 10, or 4 to 50, and n12 may be 1 to 3 or 1 to 2.

[0053] [ka] [In formula (b1), R 11 represents a hydrogen atom or a methyl group, and R 12 represents an alkyl group, AO represents an oxyalkylene group, n11 represents the number of oxyalkylene groups and represents an integer of 1 to 50, and n12 represents an integer of 0 to 5.]

[0054] The content of the compound represented by general formula (b1) may be within the following ranges based on the total solid content of the photosensitive resin composition, from the viewpoint of easily reducing the time required to remove the unexposed areas and easily obtaining excellent adhesion, resolution, and sensitivity. The content of the compound represented by general formula (b1) may be 1 mass% or more, 3 mass% or more, 5 mass% or more, 6 mass% or more, 7 mass% or more, or 8 mass% or more. The content of the compound represented by general formula (b1) may be 20 mass% or less, 15 mass% or less, 12 mass% or less, 10 mass% or less, 9 mass% or less, or 8 mass% or less. From these viewpoints, the content of the compound represented by general formula (b1) may be 1 to 20 mass%.

[0055] Component (B) may contain a compound other than the bisphenol A di(meth)acrylate compound, compound X, and the compound represented by general formula (b1). Examples of such a compound include dimethacrylate of triethylene glycol, dodecapropylene glycol, and triethylene glycol.

[0056] The content of component (B) may be within the following ranges based on the total solid content of the photosensitive resin composition, from the viewpoints of easily reducing the time required to remove unexposed areas and easily achieving excellent adhesion, resolution, and sensitivity. The content of component (B) may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 38% by mass or more, 40% by mass or more, or more than 40% by mass. The content of component (B) may be 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, less than 40% by mass, or 38% by mass or less. From these viewpoints, the content of component (B) may be 1 to 70% by mass.

[0057] The content of component (B) may be within the following ranges relative to 100 parts by mass of the total amount of components (A) and (B), from the viewpoints of easily reducing the time required to remove the unexposed portions and easily achieving excellent adhesion, resolution, and sensitivity. The content of component (B) may be 10 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 37 parts by mass or more, 40 parts by mass or more, 41 parts by mass or more, 42 parts by mass or more, 43 parts by mass or more, or 44 parts by mass or more. The content of component (B) may be 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, 60 parts by mass or less, 55 parts by mass or less, 50 parts by mass or less, 46 parts by mass or less, 45 parts by mass or less, 44 parts by mass or less, 43 parts by mass or less, 42 parts by mass or less, 41 parts by mass or less, 40 parts by mass or less, or 37 parts by mass or less. From these viewpoints, the content of the component (B) may be 10 to 90 parts by mass.

[0058] The photosensitive resin composition according to this embodiment contains a photopolymerization initiator as component (C), such as an acridine compound, a pyrazoline compound, a coumarin compound, an anthracene compound, an imidazole compound, an aromatic ketone, a quinone compound, a benzoin compound, an N-phenylglycine compound, a benzyl derivative, a xanthone compound, a thioxanthone compound, an oxazole compound, a benzoxazole compound, a thiazole compound, a benzothiazole compound, a triazole compound, a stilbene compound, a triazine compound, a thiophene compound, a naphthalimide compound, or a triarylamine compound.

[0059] Examples of the acridine compound include acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane.

[0060] Examples of pyrazoline compounds include 1-phenyl-3-(4-isopropylstyryl)-5-(4-isopropylphenyl)-pyrazoline, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butylphenyl)-pyrazoline, 1-phenyl-3-(4-methoxystyryl)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(3,5-dimethoxystyryl)-5-(3,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3,4-dimethoxystyryl)-5-(3,4-dimethoxyphenyl)-pyrazoline, 1- Examples thereof include phenyl-3-(2,6-dimethoxystyryl)-5-(2,6-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,5-dimethoxystyryl)-5-(2,5-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,3-dimethoxystyryl)-5-(2,3-dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2,4-dimethoxystyryl)-5-(2,4-dimethoxyphenyl)-pyrazoline, and 4-[[3-(4-chlorophenyl)-4,5-dihydro-1H-pyrazol]-1-yl]benzenesulfonamide.

[0061] Coumarin compounds include 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, 7-methylamino-4-methylcoumarin, 7-ethylamino-4-methylcoumarin, 7-aminocyclopenta[c]coumarin, 7-dimethylaminocyclopenta[c]coumarin, 7-diethylaminocyclopenta[c]coumarin, 4,6-dimethyl-7-dimethylaminocoumarin, and 4,6-dimethyl-7-ethylaminocoumarin. coumarin, 4,6-dimethyl-7-diethylaminocoumarin, 4,6-diethyl-7-dimethylaminocoumarin, 4,6-diethyl-7-ethylaminocoumarin, 4,6-diethyl-7-dimethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3,3'-carbonylbis(7-diethylaminocoumarin), 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizin-11-one, and the like.

[0062] Examples of the anthracene compound include 9,10-dialkoxyanthracenes such as 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-dipentoxyanthracene.

[0063] Examples of the imidazole compound include 2,4,5-triarylimidazole dimers such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer. Examples of the aromatic ketone include benzophenone compounds, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1. Examples of benzophenone compounds include benzophenone; N,N,N',N'-tetraalkyl-4,4'-diaminobenzophenones such as N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (also known as Michler's ketone) and N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone; and dialkylaminobenzophenones such as 4-methoxy-4'-dimethylaminobenzophenone. Examples of quinone compounds include alkylanthraquinones. Examples of benzoin compounds include benzoin, alkylbenzoin, and benzoin ether compounds (benzoin alkyl ethers, etc.). Examples of N-phenylglycine compounds include N-phenylglycine and N-phenylglycine derivatives. Examples of benzyl derivatives include benzyl dimethyl ketal.

[0064] From the viewpoint of easily reducing the time required for removal of the unexposed areas and easily obtaining excellent adhesion, resolution, and sensitivity, the component (C) may include at least one selected from the group consisting of an acridine compound, a pyrazoline compound, a coumarin compound, and anthracene compound, or may include an acridine compound or 1,7-bis(9,9'-acridinyl)heptane.

[0065] The content of component (C) may be within the following ranges based on the total solid content of the photosensitive resin composition. From the viewpoint of easily achieving excellent sensitivity, the content of component (C) may be 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.2% by mass or more, 0.3% by mass or more, 0.4% by mass or more, 0.5% by mass or more, 1% by mass or more, 2% by mass or more, or 3% by mass or more. From the viewpoint of suppressing excessive increase in light absorption at the surface of the photosensitive layer during exposure and facilitating sufficient curing of the interior of the photosensitive layer, the content of component (C) may be 20% by mass or less, 10% by mass or less, 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, or 0.5% by mass or less. From these viewpoints, the content of component (C) may be 0.1 to 20% by mass.

[0066] The content of component (C) may be within the following ranges relative to 100 parts by mass of the total of components (A) and (B). From the viewpoint of easily achieving excellent sensitivity, the content of component (C) may be 0.01 parts by mass or more, 0.05 parts by mass or more, 0.1 parts by mass or more, 0.2 parts by mass or more, 0.3 parts by mass or more, 0.4 parts by mass or more, 0.5 parts by mass or more, 1 part by mass or more, 2 parts by mass or more, or 3 parts by mass or more. From the viewpoint of suppressing excessive increase in light absorption at the surface of the photosensitive layer during exposure and facilitating sufficient curing of the interior of the photosensitive layer, the content of component (C) may be 20 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, 4 parts by mass or less, 3 parts by mass or less, 2 parts by mass or less, 1 part by mass or less, or 0.5 parts by mass or less. From these viewpoints, the content of component (C) may be 0.1 to 20 parts by mass.

[0067] The photosensitive resin composition according to this embodiment contains, as component (D), a bisphenol compound (excluding compounds corresponding to component (B)) having a polyoxyalkyl group located at the molecular terminal. The polyoxyalkyl group is represented by "-(RO) n H" (n is an integer of 2 or more), and R represents an alkylene group. The alkylene group may be linear or branched. Multiple Rs may be the same or different from one another.

[0068] Component (D) may include a bisphenol compound having a polyoxyalkyl group located at the end of the main chain, or may be a bisphenol compound having a polyoxyalkyl group located at the molecular end and having no ethylenically unsaturated bond.

[0069] The polyoxyalkyl group is "-(CH2CH2O) n H" (polyoxyethylene group), "-(CH2CH2O) n H" and the group represented by "-(CH2CH2CH2O) n H" and the group represented by "-(CH(CH3)CH2O) n The component (D) may contain a bisphenol compound having a polyoxyethylene group located at a molecular terminal, from the viewpoint of easily reducing the time required to remove the unexposed areas and easily obtaining excellent adhesion, resolution, and sensitivity.

[0070] From the viewpoint of easily reducing the time required for removal of unexposed areas and easily obtaining excellent adhesion, resolution, and sensitivity, component (D) may contain a bisphenol compound having a molecular weight (e.g., weight-average molecular weight) within the following ranges. The molecular weight may be 300 or more, 400 or more, 500 or more, 600 or more, 650 or more, or 700 or more. The molecular weight may be 3000 or less, 2000 or less, 1500 or less, 1200 or less, 1000 or less, 900 or less, 800 or less, or 700 or less. From these viewpoints, the molecular weight may be 300 to 3000. When the molecular weight of component (D) is a weight-average molecular weight, the weight-average molecular weight can be measured using the same method as for component (A).

[0071] From the viewpoint of easily reducing the time required for removal of unexposed areas and easily obtaining excellent adhesion, resolution, and sensitivity, component (D) may contain a bisphenol compound having multiple polyoxyalkyl groups (e.g., polyoxyethylene groups) located at the molecular terminals, may contain a bisphenol compound having two polyoxyalkyl groups (e.g., polyoxyethylene groups) located at the molecular terminals, or may contain 2,2-bis(4-polyoxyethylene-oxyphenyl)propane.

[0072] From the viewpoint of obtaining excellent adhesion, the content of the component (D) is more than 0 mass% and 15 mass% or less, based on the total solid content of the photosensitive resin composition. The content of the component (D) may be in the following ranges, based on the total solid content of the photosensitive resin composition. From the viewpoint of easily reducing the time it takes to remove the unexposed portions, the content of the component (D) may be 0.1 mass% or more, 0.5 mass% or more, 1 mass% or more, 1.5 mass% or more, 2 mass% or more, 2.5 mass% or more, 3 mass% or more, 3.5 mass% or more, 4 mass% or more, 4.5 mass% or more, 5 mass% or more, more than 5 mass%, 5.5 mass% or more, 6 mass% or more, 6.5 mass% or more, 7 mass% or more, 7.5 mass% or more, 8 mass% or more, or 8.5 mass% or more. From the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity, the content of component (D) may be 12% by mass or less, 10% by mass or less, 9% by mass or less, 8.5% by mass or less, 8% by mass or less, 7.5% by mass or less, 7% by mass or less, 6.5% by mass or less, 6% by mass or less, 5.5% by mass or less, 5% by mass or less, or less than 5% by mass. The content of component (D) may be 4.5% by mass or less, 4% by mass or less, 3.5% by mass or less, 3% by mass or less, 2.5% by mass or less, or 2% by mass or less. From these viewpoints, the content of component (D) may be 0.1 to 12% by mass, 1.5 to 9% by mass, 1.5 to 7% by mass, or more than 0% by mass but not more than 4% by mass.

[0073] The content of component (D), relative to 100 parts by mass of the total of component (A) and component (B), exceeds 0 parts by mass and may be within the following ranges: From the viewpoint of easily reducing the time it takes to remove the unexposed portions, the content of component (D) may be 0.1 parts by mass or more, 0.5 parts by mass or more, 1 part by mass or more, 1.5 parts by mass or more, 2 parts by mass or more, 2.5 parts by mass or more, 3 parts by mass or more, 3.5 parts by mass or more, 4 parts by mass or more, 4.5 parts by mass or more, 5 parts by mass or more, 5.5 parts by mass or more, 6 parts by mass or more, 6.5 parts by mass or more, 7 parts by mass or more, 7.5 parts by mass or more, 8 parts by mass or more, 8.5 parts by mass or more, 9 parts by mass or more, or 9.5 parts by mass or more. From the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity, the content of component (D) may be 15 parts by mass or less, 12 parts by mass or less, 10 parts by mass or less, 9 parts by mass or less, 8.5 parts by mass or less, 8 parts by mass or less, 7.5 parts by mass or less, 7 parts by mass or less, 6.5 parts by mass or less, 6 parts by mass or less, or 5.5 parts by mass or less. The content of component (D) may be 5 parts by mass or less, 4.5 parts by mass or less, 4 parts by mass or less, 3.5 parts by mass or less, 3 parts by mass or less, 2.5 parts by mass or less, or 2 parts by mass or less. From these viewpoints, the content of component (D) may be more than 0 parts by mass but 15 parts by mass or less, 0.1 to 12 parts by mass, 1 to 10 parts by mass, or 1 to 8 parts by mass.

[0074] The photosensitive resin composition according to this embodiment may contain, as necessary, additives other than components (A), (B), (C), and (D), such as solvents, dyes (e.g., malachite green), photocoloring agents (e.g., tribromophenyl sulfone, leuco crystal violet), thermal color-developing inhibitors, plasticizers (e.g., p-toluenesulfonamide), polymerization inhibitors (e.g., 4-t-butylcatechol), pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion promoters, leveling agents, release promoters, antioxidants (e.g., dibutylhydroxytoluene (also known as 2,6-di-tert-butyl-p-cresol)), fragrances, imaging agents, and thermal crosslinkers. Examples of solvents include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, and propylene glycol monomethyl ether. The photosensitive resin composition according to this embodiment may not contain a compound having a 1,2-naphthoquinone diazide group. The content of the compound having a 1,2-naphthoquinone diazide group may be 1% by mass or less, less than 1% by mass, 0.1% by mass or less, or 0.01% by mass or less, or may be substantially 0% by mass, based on the total solid content of the photosensitive resin composition.

[0075] <Photosensitive element> The photosensitive element according to this embodiment includes a support and a photosensitive layer (e.g., a photosensitive film) disposed on the support, and the photosensitive layer contains the photosensitive resin composition according to this embodiment. The photosensitive element according to this embodiment may include a protective layer disposed on the photosensitive layer. The photosensitive element according to this embodiment may include a cushion layer, an adhesive layer, a light-absorbing layer, a gas barrier layer, or the like. The photosensitive element may be in the form of a sheet, or may be in the form of a photosensitive element roll wound around a core.

[0076] Fig. 1 is a schematic cross-sectional view showing an example of a photosensitive element. The photosensitive element 1 shown in Fig. 1 includes a support film (support) 10 and a photosensitive layer 20. The photosensitive layer 20 is provided on a first main surface 10a of the support film 10. The support film 10 has a second main surface 10b on the side opposite to the first main surface 10a.

[0077] The support and the protective layer may each be a polymer film having heat resistance and solvent resistance, such as a polyester film (polyethylene terephthalate film, etc.), a polyolefin film (polyethylene film, polypropylene film, etc.), a hydrocarbon polymer (excluding polyolefin films), etc. The type of film constituting the protective layer and the type of film constituting the support may be the same or different from each other.

[0078] The thickness of the support layer may be 1 μm or more, 5 μm or more, 10 μm or more, 11 μm or more, 12 μm or more, 15 μm or more, or 16 μm or more, from the viewpoint of preventing the support from tearing when peeled off from the photosensitive element. The thickness of the support layer may be 200 μm or less, 100 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, or 18 μm or less, from the viewpoint of easily ensuring focus latitude during exposure. From these viewpoints, the thickness of the support layer may be 1 to 200 μm.

[0079] <Method of manufacturing a cured product and a method of manufacturing a cured product pattern> The method for producing a cured product according to this embodiment includes an exposure step in which a photosensitive layer containing the photosensitive resin composition according to this embodiment is irradiated with actinic rays to obtain a cured product (photocured product). In the exposure step, the photosensitive layer may be irradiated with actinic rays through the support in a state in which the photosensitive element is laminated on a base material (e.g., a substrate), to obtain a cured product. In this case, the photosensitive element may be laminated on the base material so that the photosensitive layer is located closer to the base material than the support.

[0080] In the exposure step, for example, a photomask having a negative or positive mask pattern may be attached to a support, and the photosensitive layer may be irradiated with actinic rays through the support (e.g., imagewise) to obtain a cured product. Examples of light sources for actinic rays include light sources that emit ultraviolet light, visible light, etc. (carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, xenon lamps, etc.). In the exposure step, a laser direct writing exposure method may also be used.

[0081] The method for producing a cured product according to this embodiment may include a lamination step of laminating the photosensitive element on the substrate prior to the exposure step. In the lamination step, the photosensitive element can be laminated on the substrate so that the photosensitive layer is located closer to the substrate than the support.

[0082] The method for producing a cured product pattern (method for forming a resist pattern) according to this embodiment includes, after the exposure step in the method for producing a cured product according to this embodiment, a development step of removing at least a portion of the portion of the photosensitive layer other than the cured product (unexposed portion) to obtain a cured product pattern (resist pattern).

[0083] In the development step, the photomask is peeled off from the support, and the support is peeled off from the photosensitive layer. In the development step, the unexposed areas (uncured areas) of the photosensitive layer are removed by wet development using a developer (an alkaline aqueous solution, a water-based developer, an organic solvent, etc.), dry development, or the like, to obtain a cured product pattern.

[0084] Examples of the alkaline aqueous solution include a 0.1 to 5% by mass sodium carbonate solution, a 0.1 to 5% by mass potassium carbonate solution, and a 0.1 to 5% by mass sodium hydroxide solution. The pH of the alkaline aqueous solution may be 9 to 11. The temperature of the alkaline aqueous solution can be adjusted depending on the developability of the photosensitive layer. The alkaline aqueous solution may contain a surfactant, an antifoaming agent, an organic solvent, etc. Examples of the development method include a dipping method, a spraying method, a brushing method, and a slapping method.

[0085] The method for producing a cured product pattern according to this embodiment may further include a step of further curing the cured product pattern by heating and / or exposure to light, as necessary, after the development step, from the viewpoint of improving solder heat resistance, chemical resistance, etc. Heating may be carried out, for example, at 60 to 250°C or 100 to 170°C for 15 to 90 minutes. Exposure can be performed by irradiating with ultraviolet light from a high-pressure mercury lamp. The exposure dose is, for example, 0.2 to 10 J / cm. 2Heating and exposure (e.g., ultraviolet irradiation) may be carried out simultaneously, or one of heating and exposure may be carried out after the other. When heating and exposure are carried out simultaneously, heating can be carried out at 60 to 150°C from the viewpoint of effectively imparting solder heat resistance, chemical resistance, etc.

[0086] The method for producing a cured product pattern according to this embodiment allows a cured product pattern (resist pattern) to be formed on a conductor layer (wiring). The cured product pattern can be used as a solder resist to prevent solder from adhering to unnecessary portions of the conductor layer when mounting components are joined. The cured product pattern obtained by the method for producing a cured product pattern according to this embodiment may be used as a permanent mask for semiconductor packages, or may be used as a permanent mask formed on a rigid substrate.

[0087] <Method of manufacturing a wiring board> The method for producing a wiring board (e.g., a printed wiring board) according to this embodiment includes a step of etching or plating a laminate having a cured product pattern formed on a substrate (e.g., a board) and the cured product pattern obtained by the method for producing a cured product pattern according to this embodiment. In this case, the laminate can be etched or plated by a known method using the cured product pattern as a mask. The wiring board may be a multilayer printed wiring board and may have small-diameter through-holes.

[0088] Examples of etching solutions used in the etching treatment include cupric chloride solution, ferric chloride solution, alkaline etching solution, etc. Examples of plating treatment include copper plating, solder plating, nickel plating, gold plating, etc.

[0089] After etching or plating, the cured pattern can be peeled off with, for example, an aqueous solution that is more alkaline than the aqueous solution used for development. Examples of such an aqueous solution include a 1 to 10% by mass sodium hydroxide solution and a 1 to 10% by mass potassium hydroxide solution. Methods for peeling off the cured pattern include immersion and spraying.

[0090] When a plating process is performed on a substrate having an insulating layer and a conductor layer disposed on the insulating layer, the conductor layer can be removed from areas other than the patterned portion. Methods for removing the conductor layer include a method of peeling off the cured pattern and then lightly etching it, and a method of masking the wiring portion with solder by peeling off the cured pattern after plating or the like, followed by treatment with an etching solution that can etch only the conductor layer. [Example]

[0091] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to the following examples. Various operations such as exposure and development described below were carried out under atmospheric pressure at room temperature (25°C) unless otherwise specified.

[0092] <Preparation of binder polymer> (Binder Polymer A1) A solution a (monomer mass ratio=methacrylic acid / methyl methacrylate / styrene=25 / 50 / 25) was obtained by mixing 150 g of methacrylic acid, 300 g of methyl methacrylate, 150 g of styrene, and 5.4 g of azobisisobutyronitrile.

[0093] 420 g of a mixture b of toluene and methyl cellosolve (mass ratio = 6:4 (toluene:methyl cellosolve)) was added to a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas inlet tube. Next, mixture b was heated to 80°C with stirring while blowing in nitrogen gas. Subsequently, the above solution a was added dropwise to mixture b using the dropping funnel over 4 hours. Then, the inside of the dropping funnel was washed with 40 g of a mixture of toluene and methyl cellosolve (mass ratio = 6:4) as a washing liquid, and this washing liquid was then added to the flask to obtain mixture c.

[0094] Next, mixture c was kept at 80°C for 2 hours while stirring. Subsequently, using a dropping funnel, solution d obtained by dissolving 1.0 g of azobisisobutyronitrile in 40 g of a mixture of methyl cellosolve and toluene (mass ratio = 6:4) was dropped into the flask over 30 minutes. Subsequently, the inside of the dropping funnel was washed with 120 g of a mixture of toluene and methyl cellosolve (mass ratio = 6:4) as a washing liquid, and this washing liquid was then added to the flask to obtain mixture e.

[0095] Next, the mixture e was kept at 80°C for 3 hours while stirring. Subsequently, it was heated to 90°C over 30 minutes. After keeping it at 90°C for 2 hours, it was cooled to obtain a binder polymer solution containing binder polymer A1. Toluene was added to this binder polymer solution to adjust the non-volatile component concentration (solid content concentration) to 40 mass%.

[0096] The binder polymer A1 had a weight-average molecular weight of 55,000, a number-average molecular weight of 20,000, and a molecular weight dispersity of 2.7. Measurements were performed by gel permeation chromatography (GPC) under the following conditions, and the weight-average molecular weight and number-average molecular weight were calculated by conversion using a calibration curve of standard polystyrene.

[0097] Pump: L-2130 type [manufactured by Hitachi High-Technologies Corporation] Detector: L-2490 RI [Hitachi High-Technologies Corporation] Column oven: L-2350 [Hitachi High-Technologies Corporation] Column: Gelpack GL-R440 + Gelpack GL-R450 + Gelpack GL-R400M (total of 3 columns) [product name, manufactured by Showa Denko Materials Co., Ltd.] Column size: 10.7mm ID x 300mm Eluent: tetrahydrofuran Sample concentration: 10 mg / 2 mL Injection volume: 200μL Flow rate: 2.05mL / min Measurement temperature: 25℃

[0098] The acid value of binder polymer A1 was 160 mgKOH / g. The acid value was measured using the following procedure. First, the binder polymer was weighed into an Erlenmeyer flask. Next, a mixed solvent (mass ratio: toluene / methanol = 70 / 30) was added to dissolve the binder polymer, and then a phenolphthalein solution was added as an indicator. The acid value was then obtained by titration using a 0.1 mol / L (N / 10) potassium hydroxide solution (alcohol solution).

[0099] (Binder polymer A2) A solution of binder polymer A2 was obtained by performing the same operation as for binder polymer A1, except that 150 g of methacrylic acid, 60 g of methyl acrylate, 300 g of methyl methacrylate, 90 g of styrene, and 5.4 g of azobisisobutyronitrile were mixed to obtain solution a (monomer mass ratio = methacrylic acid / methyl acrylate / methyl methacrylate / styrene = 25 / 10 / 50 / 15). The non-volatile content (solid content) of the binder polymer solution of binder polymer A2 was 40 mass%. The weight average molecular weight of binder polymer A2 was 80,000, the number average molecular weight was 28,000, and the molecular weight dispersity was 2.9. The acid value of binder polymer A2 was 160 mgKOH / g.

[0100] <Preparation of Photosensitive Resin Composition> Photosensitive resin compositions were prepared by mixing the components shown in Table 1. Table 1 shows the amount (parts by mass) of each component, and the amount of binder polymer is the mass of the nonvolatile content (solid content). Details of each component shown in Table 1 are as follows.

[0101] (Photopolymerizable compound) FA-321M: 2,2-bis(4-(methacryloxypolyethoxy)phenyl)propane (EO-modified bisphenol A dimethacrylate, average 10 mol ethylene oxide adduct, number of methacryloyl groups: 2, molecular weight: 804, manufactured by Showa Denko Materials Co., Ltd.) BPE-200: 2,2-bis(4-(methacryloxypolyethoxy)phenyl)propane (EO-modified bisphenol A dimethacrylate, average 4 mol ethylene oxide adduct, number of methacryloyl groups: 2, molecular weight: 540, Shin-Nakamura Chemical Co., Ltd.) FA-137M: Trimethylolpropane EO-modified trimethacrylate (average 21 mol ethylene oxide adduct, number of methacryloyl groups: 3, molecular weight: 1263, manufactured by Showa Denko Materials Co., Ltd.) FA-314A: nonylphenyl EO-modified monoacrylate (compound represented by the above formula (b1), average 4 mol ethylene oxide adduct, number of methacryloyl groups: 1, molecular weight: 454, manufactured by Showa Denko Materials Co., Ltd.) B-1: Triethylene glycol dodecapropylene glycol triethylene glycol α,ω-dimethacrylate B-2: A monomer obtained by reacting bisphenol A with 8 mol of ethylene oxide and 8 mol of propylene oxide, followed by esterification of methacrylic acid.

[0102] (Photopolymerization initiator) N-1717: 1,7-bis(9,9'-acridinyl)heptane (ADEKA Corporation) BCIM: 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole), manufactured by Hodogaya Chemical Co., Ltd. EAB: N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone

[0103] (bisphenol compounds having polyoxyalkyl groups) BA-10: 2,2-bis(4-polyoxyethylene-oxyphenyl)propane (manufactured by Nippon Nyukazai Co., Ltd., trade name: BA-10, weight-average molecular weight: 700)

[0104] (Other ingredients) LCV: Leuco Crystal Violet (Yamada Chemical Industry Co., Ltd.) MKG: Malachite Green (Osaka Organic Chemical Industry Co., Ltd.) TPS: Tribromomethylphenyl sulfone (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) PTSA: p-toluenesulfonamide (JMC) N-PHLGL: Phenylaminoacetic acid (Mitsubishi Fine Chemical Co., Ltd.)

[0105] <Preparation of Photosensitive Element> The above-mentioned photosensitive resin composition was applied to a support film (PET film, manufactured by Teijin DuPont Films Co., Ltd., product name "G2") so as to have a uniform thickness, and then dried in a hot air convection dryer at 100°C for 2 minutes to remove the solvent, forming a photosensitive layer (thickness: 25 μm). The photosensitive layer was then covered with a polyethylene protective film (manufactured by Tamapoly Co., Ltd., product name: NF-15, thickness: 18 μm) to obtain a photosensitive element.

[0106] <Evaluation> (Preparation of laminate) Electroless plating was applied to both sides of an interlayer insulating material (Ajinomoto Fine-Techno Co., Ltd., product name: GX-T31) to form a copper layer (electroless copper, thickness: 500 nm). The surface of the copper layer was then pickled, washed with water, and dried (air flow) to obtain substrate a. After heating this substrate a to 80°C, the photosensitive element was laminated onto the substrate a so that the photosensitive layer was in contact with the copper layer while peeling off the protective film of the photosensitive element. This resulted in a laminate comprising substrate a, a photosensitive layer, and a support film in this order in the stacking direction. Lamination was performed using a heat roll at 110°C, with a pressure of 0.4 MPa and a roll speed of 1.5 m / min.

[0107] (Minimum development time) After peeling off the support film, the photosensitive layer was spray-developed using a 1% by weight aqueous solution of sodium carbonate at 30°C, and the time required for the unexposed area to be completely removed was determined as the minimum development time (unit: seconds). The results are shown in Table 1.

[0108] (light sensitivity) The above-mentioned laminate was allowed to cool to 23°C. Next, a phototool having a step tablet was attached to the support film on the surface of the laminate. The step tablet used was a 41-step step tablet with a density range of 0.00 to 2.00, a density step of 0.05, a tablet size of 20 mm x 187 mm, and each step size of 3 mm x 12 mm. Next, the photosensitive layer was exposed via the phototool having the step tablet and the support film. The exposure was performed using an exposure machine (manufactured by Orbotech Japan Co., Ltd., product name "Paragon-9000m") with a semiconductor-pumped solid-state laser as a light source, at 17 mJ / cm. 2 The exposure was carried out at an exposure amount of .

[0109] After exposure, the support film was peeled off from the laminate to expose the photosensitive layer. The unexposed portions of the exposed photosensitive layer were removed by spraying a 1.0% by mass aqueous solution of sodium carbonate at 30°C for 50 seconds (development treatment). In this way, a cured film made of a cured product of the photosensitive resin composition was formed on the copper surface of the laminate. The sensitivity (photosensitivity) of this cured film was evaluated by measuring the number of steps on the step tablet. The results are shown in Table 1. The higher the number of steps on the step tablet, the higher the sensitivity.

[0110] (Adhesion and resolution) The photosensitive layer of the laminate was exposed using a phototool having an evaluation pattern (for adhesion evaluation) with a line width / space width of n / 3n (unit: μm, n = 5 to 40 μm at 1 μm intervals, 40 to 60 μm at 5 μm intervals) and an evaluation pattern (for resolution evaluation) with a line width / space width of 3n / n (unit: μm, n = 5 to 30 μm at 1 μm intervals, 30 to 60 μm at 5 μm intervals). The exposure was performed using an exposure machine (manufactured by Orbotech Japan Co., Ltd., product name "Paragon-9000m") with a semiconductor-pumped solid-state laser as a light source at 17 mJ / cm. 2The exposure was carried out at an exposure dose of 1000 sq. m. The unexposed areas were then removed by developing under the same conditions as in the evaluation of photosensitivity described above. Adhesion was evaluated based on the minimum width (unit: μm) of the line area where the cured film remained after the development process. Resolution was evaluated based on the minimum width (unit: μm) of the space between the line areas where the uncured part was successfully removed after the development process. The results are shown in Table 1. The smaller the numerical values ​​for adhesion and resolution, the better the results.

[0111] [Table 1] [Explanation of symbols]

[0112] 1...photosensitive element, 10...support film (support), 10a...first main surface, 10b...second main surface, 20...photosensitive layer.

Claims

1. (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) a bisphenol compound having a polyoxyalkyl group located at the molecular terminal (excluding the compound corresponding to component (B) above), The above component (B) contains a bisphenol A type di(meth)acrylate compound, The content of the bisphenol A type di(meth)acrylate compound is 40% by mass or more based on the total amount of component (B), A photosensitive resin composition in which the content of component (D) is greater than 0% by mass and 7% by mass or less, based on the total amount of solids in the photosensitive resin composition.

2. The photosensitive resin composition according to claim 1, wherein component (D) comprises a bisphenol compound having two polyoxyalkyl groups located at the molecular terminals.

3. The photosensitive resin composition according to claim 1 or 2, wherein the (D) component comprises 2,2-bis(4-polyoxyethylene-oxyphenyl)propane.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the content of component (D) is greater than 0% by mass and 4% by mass or less, based on the total amount of solids in the photosensitive resin composition.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the component (A) has a styrene compound as a monomer unit.

6. The photosensitive resin composition according to claim 5, wherein the content of monomer units of the styrene compound is 20% by mass or more based on the total amount of monomer units constituting component (A).

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the weight-average molecular weight of component (A) is 60,000 or less.

8. The photosensitive resin composition according to any one of claims 1 to 7, wherein the (B) component further comprises an alkylene oxide modified product of trimethylolpropane tri(meth)acrylate.

9. The photosensitive resin composition according to any one of claims 1 to 8, wherein the (C) component comprises at least one selected from the group consisting of acridine compounds, pyrazoline compounds, coumarin compounds, and anthracene compounds.

10. A photosensitive resin composition according to any one of claims 1 to 9, which is in the form of a film.

11. It comprises a support and a photosensitive layer disposed on the support, A photosensitive element wherein the photosensitive layer comprises the photosensitive resin composition described in any one of claims 1 to 10.

12. A method for producing a cured product, comprising an exposure step of irradiating a photosensitive layer containing a photosensitive resin composition according to any one of claims 1 to 10 with an active light to obtain a cured product.

13. A method for manufacturing a cured product pattern, comprising the step of removing at least a portion of the part of the photosensitive layer other than the cured product after the exposure step in the method for manufacturing a cured product according to claim 12.

14. A method for manufacturing a wiring board, comprising the step of applying an etching or plating treatment to a laminate having a cured pattern obtained by the method for manufacturing a cured pattern according to claim 13 on a substrate.