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

Abstract

The present invention is 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 the end of the molecule (excluding compounds qualifying as component (B)), wherein the content of component (D) is greater than 0 mass% and less than or equal to 15 mass%.

Description

[Technical Field]

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

[0002] In the manufacture of printed circuit boards, resist patterns are sometimes used to obtain desired wiring. Resist patterns can be formed by exposing and developing a photosensitive layer (photosensitive resin layer) obtained using a photosensitive resin composition. Various compositions have been investigated 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 Publication No. 2019-028398 [Overview of the project] [Problems that the invention aims to solve]

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

[0005] Furthermore, when forming a cured material pattern that can be used as a resist pattern, a linear cured material pattern may be formed that has linear line portions and linear space portions adjacent to the line portions. In such cases, even when the line width in the linear cured material pattern is narrow, excellent adhesion may be required as a characteristic that ensures good formation of the line portions.

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

[0007] One aspect of this disclosure relates to 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 the molecular terminal (excluding compounds corresponding to component (B)), wherein the content of component (D) is greater than 0% by mass and less than or equal to 15% by mass.

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

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

[0010] Another aspect of this 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 active light to obtain a cured product.

[0011] Another aspect of this disclosure relates to a method for manufacturing a cured product pattern, comprising a step of removing at least a portion of the photosensitive layer other than the cured product after the exposure step in the method for manufacturing a cured product described above.

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

[0013] According to one aspect of this disclosure, a photosensitive resin composition can be provided that can reduce the time required to remove unexposed areas and that can form line portions well even when the line width in a linear cured product pattern is narrow. According to another aspect of this disclosure, a photosensitive element using the photosensitive resin composition can be provided. According to yet another aspect of this disclosure, a method for manufacturing a cured product, a method for manufacturing a cured product pattern, and a method for manufacturing a wiring board using the above-mentioned photosensitive resin composition can be provided. [Brief explanation of the drawing]

[0014] [Figure 1] This is a schematic cross-sectional view showing an example of a photosensitive element. [Modes for carrying out the invention]

[0015] The embodiments of this disclosure will be described in detail below. However, this disclosure is not limited to the embodiments described below.

[0016] In this specification, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. "A or greater" in a numerical range means A and the range exceeding A. "A or less" in a numerical range means A and the range less than A. In numerical ranges described stepwise in this specification, the upper or lower limit of a numerical range in one step can be arbitrarily combined with the upper or lower limit of a numerical range in another step. In numerical ranges described in this specification, the upper or lower limit of that numerical range may be replaced with the values ​​shown in the examples. "A or B" means that either A or B is included, or both are included. Unless otherwise specified, the materials exemplified in this specification can be used individually or in combination of two or more. The content of each component in a composition means the total amount of multiple substances present in the composition if there are multiple substances corresponding to each component in the composition, unless otherwise specified. The term "layer" includes not only structures formed on the entire surface when observed as a plan view, but also structures formed on only a part of it. The term "process" includes not only independent processes but also any process that is not clearly distinguishable from other processes, as long as its intended function is achieved. "(meth)acrylic acid" means 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" means the total amount of monomeric units of acrylic acid and monomeric units of methacrylic acid, and the same applies to other similar expressions. Unless otherwise specified, "alkyl group" may be linear, branched, or cyclic. "EO modified" means a compound having a (poly)oxyethylene group. "PO modified" means a compound having a (poly)oxypropylene group. "EO·PO modified" means a compound having both a (poly)oxyethylene group and a (poly)oxypropylene group. "(Poly)oxyethylene group" means at least one of an oxyethylene group and a polyoxyethylene group (a group in which two or more ethylene groups are linked by an ether bond).The same applies to other similar expressions such as "(poly)oxypropylene group".

[0017] In this specification, the solid content of the photosensitive resin composition refers to the non-volatile content obtained by removing substances (such as water and solvents) that volatilize in the photosensitive resin composition. That is, the solid content refers to the components (components other than solvents) that do not volatilize and remain during the drying of the photosensitive resin composition, and includes components that are liquid, syrup-like, or wax-like at room temperature (25°C).

[0018] <Photosensitive resin composition> The photosensitive resin composition according to this embodiment contains (A) a binder polymer ((A) component), (B) a photopolymerizable compound having an ethylenically unsaturated bond ((B) component), (C) a photoinitiator ((C) component), and (D) a bisphenol compound having a polyoxyalkyl group located at the molecular terminal ((D) component). In the photosensitive resin composition according to this embodiment, the content of the (D) component is more than 0% by mass and 15% by mass or less.

[0019] According to the photosensitive resin composition according to this embodiment, the time for removing the unexposed portion can be reduced. According to the photosensitive resin composition according to this embodiment, in the evaluation described in the examples below, a minimum development time of, for example, less than 25 seconds (preferably 20 seconds or less) can be obtained.

[0020] According to the photosensitive resin composition according to this embodiment, even when the line width in the linear cured product pattern is narrow, the line portion can be formed well (excellent adhesion can be obtained). Further, according to the photosensitive resin composition according to this embodiment, even when the line width in the linear cured product pattern is narrow and the line width is smaller than the space width (width of the space portion), the line portion can be formed well. According to the photosensitive resin composition according to this embodiment, in the evaluation of adhesion described in the examples below, for example, 50 μm or less (preferably 40 μm or less) can be obtained.

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

[0022] According to one embodiment of the photosensitive resin composition of this embodiment, excellent sensitivity to active light (the characteristic of requiring a small amount of exposure to obtain a predetermined cured state) can also be obtained. According to one embodiment of the photosensitive resin composition of this embodiment, in the evaluation of photosensitivity described in the examples below, for example, 25 mJ / cm 2 Less than or equal to (preferably 20 mJ / cm²) 2 You can obtain the following:

[0023] The photosensitive resin composition according to this embodiment may be liquid or film-like (photosensitive film). The photosensitive resin composition according to this embodiment is photocurable, 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 pattern-like (cured product pattern) or 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 with 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 having compounds having (meth)acryloyl groups ((meth)acrylic acid compounds) as monomer units, and styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenolic resins having such monomer units belong to the category of acrylic resins. Component (A) does not necessarily have to contain a binder polymer having phenolic hydroxyl groups.

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

[0027] Component (A) may contain acrylic resin from the viewpoint of easily obtaining good alkaline developability, easily reducing the time required to remove unexposed areas, and easily obtaining excellent adhesion, resolution, and sensitivity. From a similar viewpoint, the acrylic resin content 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 (a configuration in which component (A) is substantially composed of acrylic resin), based on the total amount of component (A).

[0028] Component (A) may contain (meth)acrylic acid as a monomer unit, from the viewpoint of easily reducing the time required to remove unexposed areas, and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. From a similar viewpoint, when component (A) contains (meth)acrylic acid as a monomer unit, the content of (meth)acrylic acid monomer units may be within the following ranges based on the total amount of monomer units constituting component (A). The content of (meth)acrylic acid monomer units 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 (meth)acrylic acid monomer units 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 perspectives, the monomer content of (meth)acrylic acid 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 unexposed areas, and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. Examples of alkyl groups of alkyl (meth)acrylate include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc., and the alkyl group may be 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 unexposed areas, and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity.

[0030] The alkyl group of (meth)acrylate may have substituents. Examples of substituents include hydroxyl groups, carboxyl groups, carboxylic acid bases, aldehyde groups, alkoxy groups, carbonyl groups, alkoxycarbonyl groups, alkanoyl groups, oxycarbonyl groups, carbonyloxy groups, amino groups, epoxy groups, furyl groups, cyano groups, halogeno groups (fluoro groups, chloro groups, bromo groups, etc.), nitro groups, acetyl groups, sulfonyl groups, and sulfonamide groups.

[0031] When component (A) contains alkyl (meth)acrylate as a monomer unit, the content of alkyl (meth)acrylate monomer units may be within the following ranges based on the total amount of monomer units constituting component (A), from the viewpoint of reducing the time required to remove unexposed areas and from the viewpoint of obtaining excellent adhesion, resolution, and sensitivity. The content of alkyl (meth)acrylate monomer units 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 monomer content of alkyl (meth)acrylate 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 monomer content of alkyl (meth)acrylate may be 1 to 99% by mass.

[0032] Component (A) may contain a styrene compound (excluding compounds having a (meth)acryloyl group) as a monomer unit, from the viewpoint of easily reducing the time required to remove unexposed areas and easily obtaining excellent adhesion, resolution, and sensitivity. Examples of styrene compounds include styrene and styrene derivatives. Examples of styrene derivatives include vinyltoluene and α-methylstyrene. Component (A) may contain at least one selected from the group consisting of (meth)acrylic acid and (meth)acrylic acid and a styrene compound as a monomer unit, from the viewpoint of easily reducing the time required to remove unexposed areas and easily obtaining excellent adhesion, resolution, and sensitivity, and may contain (meth)acrylic acid, alkyl (meth)acrylate and a styrene compound as monomer units.

[0033] If component (A) contains styrene compounds as monomer units, the content of styrene compound monomer units may be within the following ranges based on the total amount of monomer units constituting component (A), from the viewpoint of reducing the time required to remove unexposed areas and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. The content of styrene compound monomer units 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 styrene compound monomer units 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 perspectives, the monomer content of the styrene compound 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 (vinyl-n-butyl ether, etc.), (meth)acrylonitrile, maleic acid, maleic anhydride, maleic acid monoesters (monomethyl maleic acid, monoethyl maleic acid, monoisopropyl maleic acid, etc.), fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. Component (A) does not need 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 viewpoint of reducing the time required to remove unexposed areas and from the viewpoint of easily obtaining 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 between 10,000 and 200,000.

[0036] The number-average molecular weight (Mn) of component (A) may be within the following ranges, from the viewpoint of reducing the time required to remove unexposed areas and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. The number-average molecular weight of component (A) may be 5000 or more, 10000 or more, 15000 or more, 18000 or more, or 20000 or more. The number-average molecular weight of component (A) may be 100000 or less, 80000 or less, 60000 or less, 50000 or less, 45000 or less, 40000 or less, 35000 or less, 30000 or less, 28000 or less, 25000 or less, or 20000 or less. From these viewpoints, the number-average molecular weight of component (A) may be between 5000 and 100000.

[0037] The dispersion of component (A) (Mw / Mn) may be within the following ranges, from the viewpoint of reducing the time required to remove unexposed areas and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. The dispersion of component (A) may be 1.2 or higher, 1.5 or higher, 1.8 or higher, 2.0 or higher, 2.2 or higher, 2.5 or higher, or 2.7 or higher. The dispersion of component (A) (Mw / Mn) may be 3.5 or lower, 3.3 or lower, 3.0 or lower, 2.9 or lower, or 2.8 or lower. From these viewpoints, the dispersion of component (A) may be between 1.2 and 3.5.

[0038] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be obtained, for example, by measuring them using gel permeation chromatography (GPC) and converting them using a calibration curve for standard polystyrene. More specifically, they can be measured by the method described in the examples. For compounds with low molecular weight, if measurement is difficult using this method, the molecular weight can be measured by other methods and its average value can be calculated.

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

[0040] (A) The content of component (A) may be within the following ranges based on the total amount (total amount of solids) of the photosensitive resin composition, from the viewpoint of reducing the time required to remove unexposed areas and from the viewpoint of easily obtaining 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] 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), from the viewpoint of reducing the time required to remove unexposed areas and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. 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 perspectives, the content of 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 component (B).

[0043] Component (B) may contain a bisphenol A type di(meth)acrylate compound, from the viewpoint of reducing the time required to remove unexposed areas and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. The bisphenol A type di(meth)acrylate compound may be alkylene oxide modified and may have polyoxyalkylene groups (polyoxyethylene groups, polyoxypropylene groups, polyoxybutylene groups, etc.).

[0044] Examples of bisphenol A type di(meth)acrylate compounds include 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane (2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane, 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] Component (B) may contain 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, and 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, from the viewpoint of easily reducing the time required to remove unexposed areas and easily obtaining excellent adhesion, resolution, and sensitivity.

[0046] Component (B) may include a bisphenol A type di(meth)acrylate compound having polyoxyalkylene groups, where the number of oxyalkylene groups in the polyoxyalkylene chain (number of oxyalkylene groups in one molecule) is within the following ranges, from the viewpoint of easily reducing the time required to remove unexposed areas and easily obtaining excellent adhesion, resolution, and sensitivity. 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 type di(meth)acrylate compound may be within the following ranges based on the total amount of component (B), from the viewpoint of reducing the time required to remove unexposed areas and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. The content of the bisphenol A type 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 type 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 perspectives, the content of bisphenol A type di(meth)acrylate compounds may be 10 to 90% by mass.

[0048] The content of the bisphenol A type 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 reducing the time required to remove unexposed areas and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. The content of the bisphenol A type 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 type 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 type di(meth)acrylate compound may be 1 to 50% by mass.

[0049] The content of the bisphenol A type di(meth)acrylate compound may be within the following ranges relative to 100 parts by mass of the total amount of component (A) and component (B), from the viewpoint of reducing the time required to remove unexposed areas and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. The content of the bisphenol A type 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 type 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 perspectives, the content of the bisphenol A type di(meth)acrylate compound may be 1 to 50 parts by mass.

[0050] 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 forms thereof, from the viewpoint of easily reducing the time required to remove unexposed areas and easily obtaining excellent adhesion, resolution, and sensitivity, and may contain an alkylene oxide modified form of trimethylolpropane tri(meth)acrylate. Examples of alkylene oxide modified forms of trimethylolpropane tri(meth)acrylate and tetramethylolmethane tri(meth)acrylate include EO modified forms, PO modified forms, EO·PO modified forms, etc.

[0051] The content of compound X, or the content of the alkylene oxide modified form 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 reducing the time required to remove unexposed areas and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. The above 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 above 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 above content may be 1 to 20% by mass.

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

[0053] [ka] [In formula (b1), R 11 R represents a hydrogen atom or a methyl group. 12 n11 represents an alkyl group, AO represents an oxyalkylene group, n11 represents the number of oxyalkylene groups (an integer from 1 to 50), and n12 represents an integer from 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 reducing the time required to remove unexposed areas and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. The content of the compound represented by general formula (b1) 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, or 8% by mass or more. The content of the compound represented by general formula (b1) 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, or 8% by mass or less. From these viewpoints, the content of the compound represented by general formula (b1) may be between 1 and 20% by mass.

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

[0056] (B) The content of component (B) may be within the following ranges based on the total solid content of the photosensitive resin composition, from the viewpoint of reducing the time required to remove unexposed areas and from the viewpoint of easily obtaining 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 between 1 and 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 viewpoint of reducing the time required to remove unexposed areas and from the viewpoint of easily obtaining 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 perspectives, the content of 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). Examples of component (C) include acridine compounds, pyrazoline compounds, coumarin compounds, anthracene compounds, imidazole compounds, aromatic ketones, quinone compounds, benzoin compounds, N-phenylglycine compounds, benzyl derivatives, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and the like.

[0059] Examples of acridine compounds include 9-phenylacridine and acridine derivatives such as 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-butylstyryl)-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- Examples 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-pyrazole]-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. Examples include phosphorus, 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]quinoridine-11-one, etc.

[0062] Examples of anthracene compounds include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentoxyanthracene, and other 9,10-dialkoxyanthracenes.

[0063] Examples of imidazole compounds 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 aromatic ketones 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'-tetramethyl-4,4'-diaminobenzophenone (also known as Michler's ketone), N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone, and other N,N,N',N'-tetraalkyl-4,4'-diaminobenzophenones; 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 (such as benzoin alkyl ethers). Examples of N-phenylglycine compounds include N-phenylglycine and N-phenylglycine derivatives. Examples of benzyl derivatives include benzyldimethylketal.

[0064] Component (C) may contain at least one selected from the group consisting of acridine compounds, pyrazoline compounds, coumarin compounds, and anthracene compounds, from the viewpoint of reducing the time required to remove unexposed areas and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity, and may contain an acridine compound, and may contain 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 obtaining 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 an excessive increase in light absorption on the surface of the photosensitive layer during exposure and allowing the inside of the photosensitive layer to harden sufficiently, 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 amount of components (A) and (B). From the viewpoint of easily obtaining 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 an excessive increase in light absorption on the surface of the photosensitive layer during exposure and making it easier for the inside of the photosensitive layer to harden sufficiently, 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 having a polyoxyalkyl group located at the molecular terminal (excluding the compound corresponding to component (B)). The polyoxyalkyl group is "-(RO) n The group is represented by H (where n is an integer greater than or equal to 2), and R indicates an alkylene group. The alkylene group may be linear or branched. Multiple Rs may be the same or different from one another.

[0068] The component (D) may contain a bisphenol compound having a polyoxyalkyl group located at the terminal of the main chain. The component (D) may be a bisphenol compound having a polyoxyalkyl group located at the molecular terminal and not having an ethylenically unsaturated bond.

[0069] Examples of the polyoxyalkyl group include a group represented by "-(CH2CH2O) n H" (polyoxyethylene group), a group represented by "-(CH2CH2O) n H", a group represented by "-(CH2CH2CH2O) n H", a group represented by "-(CH(CH3)CH2O) n H", and the like. From the viewpoint of easily reducing the time for removing the unexposed portion and the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity, the component (D) may contain a bisphenol compound having a polyoxyethylene group located at the molecular terminal.

[0070] From the viewpoint of easily reducing the time for removing the unexposed portion and the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity, the component (D) may contain a bisphenol compound having a molecular weight (for example, weight average molecular weight) within the following range. 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 the component (D) is the weight average molecular weight, the weight average molecular weight can be measured in the same manner as the component (A).

[0071] Component (D) may contain a bisphenol compound having multiple polyoxyalkyl groups (e.g., polyoxyethylene groups) located at the molecular terminals, or 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, from the viewpoint of easily reducing the time required to remove unexposed areas and easily obtaining excellent adhesion, resolution, and sensitivity.

[0072] (D) The content of component (D) is greater than 0% by mass and less than or equal to 15% by mass, based on the total solid content of the photosensitive resin composition, from the viewpoint of obtaining excellent adhesion. The content of component (D) may be within the following ranges based on the total solid content of the photosensitive resin composition. The content of component (D) may be 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 1.5% by mass or more, 2% by mass or more, 2.5% by mass or more, 3% by mass or more, 3.5% by mass or more, 4% by mass or more, 4.5% by mass or more, 5% by mass or more, greater than 5% by mass, 5.5% by mass or more, 6% by mass or more, 6.5% by mass or more, 7% by mass or more, 7.5% by mass or more, 8% by mass or more, or 8.5% by mass or more, from the viewpoint of easily reducing the time required to remove unexposed areas. 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, from the viewpoint of easily obtaining excellent adhesion, resolution and sensitivity. 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 greater than 0% by mass and 4% by mass or less.

[0073] The content of component (D) is greater than 0 parts by mass per 100 parts by mass of the total amount of components (A) and (B), and may be within the following ranges: From the viewpoint of reducing the time required to remove the unexposed portion, 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. 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, from the viewpoint of easily obtaining excellent adhesion, resolution and sensitivity. 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 greater than 0 parts by mass and 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 additives such as solvents, dyes (malachite green, etc.), photochromicants (tribromophenylsulfone, leucocrystal violet, etc.), thermal color inhibitors, plasticizers (p-toluenesulfonamide, etc.), polymerization inhibitors (4-t-butylcatechol, etc.), pigments, fillers, defoamers, flame retardants, stabilizers, adhesion promoters, leveling agents, release accelerators, antioxidants (dibutylhydroxytoluene (also known as 2,6-di-tert-butyl-p-cresol), etc.), fragrances, imaging agents, and thermal crosslinking agents, as components different from components (A), (B), (C), and (D), as needed. The photosensitive resin composition according to this embodiment does not need to 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, based on the total solid content of the photosensitive resin composition, and may be substantially 0% by mass.

[0075] <Photosensitive element> The photosensitive element according to this embodiment comprises a support and a photosensitive layer (e.g., a photosensitive film) disposed on the support, wherein 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, etc. The photosensitive element may be in the form of a sheet, or it may be in the form of a photosensitive element roll wound on a core.

[0076] Figure 1 is a schematic cross-sectional view showing an example of a photosensitive element. The photosensitive element 1 shown in Figure 1 comprises a support film (support) 10 and a photosensitive layer 20. The photosensitive layer 20 is provided on the 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 protective layer may each be a polymer film having heat resistance and solvent resistance, and may be polyester film (polyethylene terephthalate film, etc.), polyolefin film (polyethylene film, polypropylene film, etc.), hydrocarbon polymer (excluding polyolefin film), etc. The type of film constituting the protective layer and the type of film constituting the support may be the same or different.

[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 peeling it 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 a margin of focus during exposure. From these viewpoints, the thickness of the support layer may be between 1 and 200 μm.

[0079] <Method for manufacturing cured products and method for manufacturing cured product patterns> The method for producing a cured product according to this embodiment includes an exposure step of irradiating a photosensitive layer containing the photosensitive resin composition according to this embodiment with active light to obtain a cured product (photocured product). In the exposure step, with the photosensitive elements laminated on a substrate (e.g., a substrate), the photosensitive layer may be irradiated with active light through a support to obtain a cured product. In this case, the photosensitive elements may be laminated on the substrate such that the photosensitive layer is located on the substrate side of the support.

[0080] In the exposure process, for example, a photomask having a negative or positive mask pattern may be placed in close contact with a support, and an active light beam may be irradiated onto the photosensitive layer through the support (for example, irradiated in an image pattern) to obtain a cured product. Examples of light sources for the active light beam include light sources that emit ultraviolet light, visible light, etc. (carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, xenon lamps, etc.). Laser direct writing exposure can also be used in the exposure process.

[0081] The method for manufacturing a cured product according to this embodiment may include a lamination step of laminating photosensitive elements onto a substrate before the exposure step. In the lamination step, the photosensitive elements can be laminated onto the substrate such that the photosensitive layer is located on the substrate side of the support.

[0082] The method for manufacturing a cured material pattern (method for forming a resist pattern) according to this embodiment includes a developing step after the exposure step in the method for manufacturing a cured material according to this embodiment, in which at least a portion of the parts other than the cured material (unexposed parts) in the photosensitive layer is removed to obtain a cured material pattern (resist pattern).

[0083] In the development process, the photomask is peeled off the support, and the support is peeled off the photosensitive layer. In the development process, the unexposed areas (unphotocured areas) of the photosensitive layer are removed by wet development or dry development using a developer (alkaline aqueous solution, aqueous developer, organic solvent, etc.) to obtain a cured pattern.

[0084] Examples of alkaline aqueous solutions include 0.1-5% by mass sodium carbonate solution, 0.1-5% by mass potassium carbonate solution, and 0.1-5% by mass sodium hydroxide solution. The pH of the alkaline aqueous solution may 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, organic solvents, etc. Examples of developing methods include the dip method, spray method, brushing, and slapping.

[0085] The method for manufacturing a cured pattern according to this embodiment may include a step of further curing the cured pattern by heating and / or exposure after the development step, if necessary, from the viewpoint of improving solder heat resistance, chemical resistance, etc. Heating may be performed, 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 using a high-pressure mercury lamp. The exposure amount may be, for example, 0.2 to 10 J / cm². 2This may be the case. Heating and exposure (e.g., ultraviolet irradiation) may be performed simultaneously, or one of heating and exposure may be performed first, followed by the other. When heating and exposure are performed simultaneously, heating can be done at 60 to 150°C from the viewpoint of effectively imparting solder heat resistance, chemical resistance, etc.

[0086] The method for manufacturing a cured material pattern according to this embodiment allows for the formation of a cured material pattern (resist pattern) on a conductor layer (wiring). The cured material pattern can be used as a solder resist to prevent solder from adhering to unwanted parts of the conductor layer during the joining of mounted components. The cured material pattern obtained by the method for manufacturing a cured material pattern according to this embodiment may be used as a permanent mask for semiconductor packages, or as a permanent mask formed on a rigid substrate.

[0087] <Manufacturing method for wiring boards> The method for manufacturing a wiring board (e.g., a printed circuit board) according to this embodiment includes a step of performing an etching or plating treatment on a laminate on which a cured material pattern obtained by the method for manufacturing a cured material pattern according to this embodiment is placed on a substrate (e.g., a circuit board). In this case, the cured material pattern can be used as a mask to perform the etching or plating treatment on the laminate by a known method. The wiring board may be a multilayer printed circuit board and may have small-diameter through-holes.

[0088] Etching solutions used in etching processes include cupric chloride solution, ferric chloride solution, and alkaline etching solution. Plating processes include copper plating, solder plating, nickel plating, and gold plating.

[0089] After etching or plating, the cured pattern can be removed using, for example, an aqueous solution that is even more strongly alkaline than the alkaline aqueous solution used for developing. Examples of such strongly alkaline aqueous solutions include 1-10% by mass sodium hydroxide aqueous solution and 1-10% by mass potassium hydroxide aqueous solution. Methods for removing the cured pattern include immersion methods and spray methods.

[0090] When a plating treatment is performed on a substrate comprising an insulating layer and a conductive layer disposed on the insulating layer, the conductive layer other than the pattern portion can be removed. Methods for removing the conductive layer include light etching after peeling off the cured pattern, and masking the wiring portion with solder by peeling off the cured pattern after the plating treatment, and then treating only the conductive layer with an etching solution capable of etching. [Examples]

[0091] The contents of this disclosure will be further explained below with reference to examples, but this disclosure is not limited to the following examples. Unless otherwise specified, the various operations such as exposure and development described later were performed under atmospheric pressure and at room temperature (25°C).

[0092] <Preparation of binder polymer> (Binder Polymer A1) 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] A flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas inlet tube contained 420 g of a mixture b (mass ratio = 6:4 (toluene:methyl cellosolve)) of toluene and methyl cellosolve. Mixture b was then heated to 80°C while stirring and blowing in nitrogen gas. Subsequently, solution a, as described above, was added dropwise to mixture b using the dropping funnel over a period of 4 hours. The inside of the dropping funnel was then washed with 40 g of a mixture of toluene and methyl cellosolve (mass ratio = 6:4) as a washing solution, and this washing solution was added to the flask to obtain mixture c.

[0094] Next, mixture c was kept warm at 80°C for 2 hours while stirring. Then, 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 added dropwise to 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 solution, and this washing solution was added to the flask to obtain mixture e.

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

[0096] The weight-average molecular weight of binder polymer A1 was 55,000, the number-average molecular weight was 20,000, and the degree of molecular weight dispersion was 2.7. The weight-average molecular weight and number-average molecular weight were calculated by measuring using gel permeation chromatography (GPC) under the following conditions and converting using a calibration curve for standard polystyrene.

[0097] Pump: L-2130 model [manufactured by Hitachi High-Technologies Corporation] Detector: L-2490 type RI [manufactured by Hitachi High-Technologies Corporation] Column Oven: L-2350 [Manufactured by Hitachi High-Technologies Corporation] Columns: Gelpack GL-R440 + Gelpack GL-R450 + Gelpack GL-R400M (3 in total) [Manufactured by Showa Denko Materials Co., Ltd., product name] Column size: 10.7mm I.D × 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 mg KOH / 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 phenolphthalein solution was added as an indicator. The acid value was then obtained by titration with 0.1 mol / L (N / 10) potassium hydroxide solution (alcohol solution).

[0099] (Binder Polymer A2) A solution of binder polymer A2 was obtained by the same procedure as for binder polymer A1, except that solution a (monomer mass ratio = methacrylic acid / methyl acrylate / methyl methacrylate / styrene = 25 / 10 / 50 / 15) was obtained by mixing 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. The non-volatile content concentration (solid content concentration) of the binder polymer A2 solution was 40% by 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 dispersion was 2.9. The acid value of binder polymer A2 was 160 mg KOH / g.

[0100] <Preparation of photosensitive resin composition> A photosensitive resin composition was 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 nonvolatile content (solids). 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, ethylene oxide adduct with an average of 10 mol, 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, ethylene oxide average 4mol adduct, number of methacryloyl groups: 2, molecular weight: 540, Shin Nakamura Chemical Industry Co., Ltd.) FA-137M: Trimethylolpropane EO-modified trimethacrylate (ethylene oxide adduct with an average of 21 mol, number of methacryloyl groups: 3, molecular weight: 1263, manufactured by Showa Denko Materials Co., Ltd.) FA-314A: Nonylphenyl EO-modified monoacrylate (a compound represented by formula (b1) above, an average of 4 moles of ethylene oxide adduct, number of methacryloyl groups: 1, molecular weight: 454, manufactured by Showa Denko Materials Co., Ltd.) B-1: Triethylene glycol, dodecapropylene glycol, α,ω-dimethacrylate of triethylene glycol B-2: Bisphenol A was reacted with 8 moles of ethylene oxide and 8 moles of propylene oxide, and then methacrylic acid was esterified to form a monomer.

[0102] (Photopolymerization initiator) N-1717: 1,7-Bis(9,9'-Acridinyl)heptane (manufactured by 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 containing polyoxyalkyl groups) BA-10: 2,2-bis(4-polyoxyethylene-oxyphenyl)propane (manufactured by Nippon Emulsifier Co., Ltd., product name: BA-10, weight-average molecular weight: 700)

[0104] (Other ingredients) LCV: Leucocrystal violet (manufactured by Yamada Chemical Industries, Ltd.) MKG: Malachite Green (manufactured by Osaka Organic Chemical Industry Co., Ltd.) TPS: Tribromomethylphenylsulfone (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.) PTSA: p-toluenesulfonamide (manufactured by JMC) N-PHLGL: Phenylaminoacetic acid (manufactured by Mitsubishi Chemical Fine Co., Ltd.)

[0105] <Fabrication of photosensitive elements> The above-mentioned photosensitive resin composition was applied to a support film (PET film, manufactured by Teijin DuPont Films Ltd., product name "G2") to ensure uniform thickness. A photosensitive layer (thickness: 25 μm) was formed by removing the solvent by drying in a 100°C hot air convection dryer for 2 minutes. Subsequently, a photosensitive element was obtained by covering the photosensitive layer with a polyethylene protective film (manufactured by Tamapoly Co., Ltd., product name: NF-15, thickness: 18 μm).

[0106] <Rating> (Fabrication of laminates) A copper layer (electroless copper, thickness: 500 nm) was formed by electroless plating on both sides of an interlayer insulating material (manufactured by Ajinomoto Fine Techno Co., Ltd., product name: GX-T31). Then, the surface of the copper layer was pickled, washed with water, and dried (with airflow) to obtain substrate a. After heating substrate a to 80°C, the photosensitive element was laminated so that the photosensitive layer was in contact with the copper layer, while peeling off the protective film of the photosensitive element as described above. This resulted in a laminate having substrate a, photosensitive layer, and support film in this order in the lamination direction. Lamination was performed using a 110°C heat roll with a pressure of 0.4 MPa and a roll speed of 1.5 m / min.

[0107] (Minimum development time) After removing the support film, the photosensitive layer was spray-developed using a 1% by mass sodium carbonate aqueous solution at 30°C. The minimum development time (in seconds) was determined by the time it took for the unexposed areas to be completely removed. The results are shown in Table 1.

[0108] (Light sensitivity) The laminate described above was allowed to cool to 23°C. Next, a phototool with step tablets was placed in close contact with the support film on the surface of the laminate. A 41-step tablet was used, with a density range of 0.00 to 2.00, a density step of 0.05, a tablet size of 20 mm × 187 mm, and a step size of 3 mm × 12 mm. Then, the photosensitive layer was exposed through the phototool with step tablets and the support film. Exposure was performed using an exposure machine (manufactured by Nippon Orbotech Co., Ltd., product name "Paragon-9000m") with a semiconductor-excited solid-state laser as the light source, at a rate of 17 mJ / cm². 2 This was done with the following exposure settings.

[0109] After exposure, the photosensitive layer was exposed by peeling the support film from the laminate. The unexposed areas were removed by spraying a 1.0% by mass aqueous sodium carbonate solution 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 step tablets. The results are shown in Table 1. A higher number of step tablets indicates higher sensitivity.

[0110] (Adhesion and resolution) The photosensitive layer of the aforementioned laminate was exposed using a phototool having evaluation patterns (for adhesion evaluation) with a line width / space width of n / 3n (unit: μm, 1 μm spacing for n=5~40 μm, 5 μm spacing for n=40~60 μm) and evaluation patterns (for resolution evaluation) with a line width / space width of 3n / n (unit: μm, 1 μm spacing for n=5~30 μm, 5 μm spacing for n=30~60 μm). Exposure was performed using an exposure machine (manufactured by Nippon Orbotech Co., Ltd., product name "Paragon-9000m") that uses a semiconductor-excited solid-state laser as a light source at a rate of 17 mJ / cm². 2The exposure was set to the specified exposure level. Next, the unexposed areas were removed by developing the material under the same conditions as the light sensitivity evaluation described above. Adhesion was evaluated by the minimum width (in μm) of the line region where the hardened film remained after development. Resolution was evaluated by the minimum width (in μm) of the space between line regions where the non-photocured areas could be cleanly removed after development. The results are shown in Table 1. For adhesion and resolution, smaller values ​​indicate better performance.

[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) includes an alkylene oxide modified form of trimethylolpropane tri(meth)acrylate, The content of the alkylene oxide modified trimethylolpropane tri(meth)acrylate is 1 to 20% by mass based on the total solid content of the photosensitive resin composition. 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 (B) component comprises a bisphenol A type di(meth)acrylate compound.

8. The photosensitive resin composition according to any one of claims 1 to 7, wherein the (C) component comprises at least one selected from the group consisting of acridine compounds, pyrazoline compounds, coumarin compounds, and anthracene compounds.

9. The photosensitive resin composition according to any one of claims 1 to 7, wherein the (C) component comprises an acridine compound.

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.

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