WO2023188008A1

WO2023188008A1 - Photosensitive resin composition, photosensitive element, method for manufacturing cured product, method for manufacturing cured product pattern, and method for manufacturing wiring board

Info

Publication number: WO2023188008A1
Application number: PCT/JP2022/015570
Authority: WO
Inventors: 壮和粂
Original assignee: 株式会社レゾナック
Priority date: 2022-03-29
Filing date: 2022-03-29
Publication date: 2023-10-05
Also published as: JPWO2023188008A1

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

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

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 a cured product, a method for producing a wiring board, and the like.

In manufacturing wiring boards, resist patterns are sometimes 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.

JP 2019-028398 Publication

For a photosensitive resin composition for obtaining a cured product pattern that can be used as a resist pattern, it may be required to reduce the time during which unexposed areas are removed.

Furthermore, when forming a cured material pattern that can be used as a resist pattern, a linear cured material pattern having a linear line portion and a linear space portion adjacent to the line portion may be formed. be. Even when the line width in a linear cured product pattern is narrow, excellent adhesion may be required as a characteristic for forming line portions favorably.

One aspect of the present disclosure provides a photosensitive resin composition that can reduce the time it takes for unexposed areas to be removed and can form line portions favorably even when the line width in a linear cured product pattern is narrow. The purpose is to provide something. 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-described photosensitive resin composition.

One aspect of the present disclosure includes (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) a polyoxyalkyl compound located at the end of the molecule. a bisphenol compound having a group (excluding compounds corresponding to the component (B)), and the content of the component (D) is more than 0% by mass and 15% by mass or less, a photosensitive resin composition. Regarding.

According to such a photosensitive resin composition, it is possible to reduce the time for removing unexposed areas, and even when the line width in a linear cured product pattern is narrow, line portions can be formed satisfactorily.

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.

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

Another aspect of the present disclosure is a method for producing a cured product pattern, which includes a step of removing at least a portion of the photosensitive layer other than the cured product after the exposure step in the above-described method for producing a cured product. Regarding.

Another aspect of the present disclosure is manufacturing a wiring board, which includes a step of performing an etching treatment or a plating treatment on a laminate having a cured product pattern obtained by the above-described method for manufacturing a cured product pattern on a base material. Regarding the method.

According to one aspect of the present disclosure, photosensitivity allows for reducing the time for removing unexposed portions, and also enables good formation of line portions even when the line width in a linear cured material pattern is narrow. A resin composition can be provided. According to another aspect of the present disclosure, a photosensitive element using the photosensitive resin composition can be provided. According to another aspect of the present disclosure, it is possible 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.

FIG. 2 is a schematic cross-sectional view showing an example of a photosensitive element.

Hereinafter, embodiments of the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments.

In this specification, a numerical range indicated using "-" indicates a range that includes the numerical values written before and after "-" as the minimum and maximum values, respectively. The numerical range "A or more" means A and a range exceeding A. The numerical range "A or less" means a range of A and less than A. In the numerical ranges described stepwise in this specification, the upper limit or lower limit of the numerical range of one step can be arbitrarily combined with the upper limit or lower limit of the numerical range of another step. In the numerical ranges described in this specification, the upper limit or lower limit of the numerical range may be replaced with the values shown in the examples. "A or B" may include either A or B, or may include both. The materials exemplified herein can be used alone or in combination of two or more, unless otherwise specified. When a plurality of substances corresponding to each component are present in the composition, the content of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified. When observed as a plan view, the term "layer" includes a structure having a shape formed on the entire surface as well as a structure having a shape formed in a part of the layer. The term "process" is included in the term not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended effect of the process is achieved. "(Meth)acrylic acid" means at least one of acrylic acid and the corresponding methacrylic acid. The same applies to other similar expressions such as "(meth)acrylate". The "(meth)acrylic acid monomer content" means the total amount of acrylic acid monomer units and methacrylic acid monomer units, and the same applies to other similar expressions. The "alkyl group" may be linear, branched, or cyclic, unless otherwise specified. "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 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 connected through an ether bond). The same applies to other similar expressions such as "(poly)oxypropylene group".

In this specification, the solid content of the photosensitive resin composition refers to the nonvolatile content excluding volatile substances (water, solvent, etc.) in the photosensitive resin composition. That is, the solid content refers to components (components other than the solvent) that remain without being volatilized during drying of the photosensitive resin composition, and also includes components that are liquid, starch syrup-like, or wax-like at room temperature (25° C.).

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

According to the photosensitive resin composition according to the present embodiment, it is possible to reduce the time it takes for unexposed areas to be removed. According to the photosensitive resin composition according to the present embodiment, a minimum development time of, for example, less than 25 seconds (preferably 20 seconds or less) can be obtained in the evaluation described in Examples below.

According to the photosensitive resin composition according to the present embodiment, even when the line width in a linear cured product pattern is narrow, line portions can be formed satisfactorily (excellent adhesion can be obtained). Further, according to the photosensitive resin composition according to the present embodiment, the line width in the linear cured material pattern is narrower than the space width (width of the space portion). However, the line portion can be formed well. According to the photosensitive resin composition according to the present embodiment, it is possible to obtain, for example, 50 μm or less (preferably 40 μm or less) in the evaluation of adhesion described in Examples below.

By the way, when forming a linear cured product pattern using a photosensitive resin composition, there is an excellent solution that allows the space portion to be formed well even if the space width in the cured product pattern is narrow. Image quality may be required. According to one aspect of the photosensitive resin composition according to the present embodiment, even when the space width in the linear cured product pattern is narrow, the space portion can be formed satisfactorily (excellent resolution can be obtained). . Further, according to one aspect of the photosensitive resin composition according to the present embodiment, the space width in a linear cured material pattern in which the space width (width of the space portion) and the line width (width of the line portion) are equal to each other. Even if the area is narrow, the space can be formed well. According to one aspect of the photosensitive resin composition according to the present embodiment, it is possible to obtain, for example, 40 μm or less (preferably 30 μm or less) in the evaluation of resolution described in Examples below.

According to one aspect of the photosensitive resin composition according to the present embodiment, it is also possible to obtain excellent sensitivity to actinic rays (characteristic that the amount of exposure required to obtain a predetermined cured state is small). According to one aspect of the photosensitive resin composition according to the present embodiment, it is possible to obtain, for example, 25 mJ/cm ² or less (preferably 20 mJ/cm ² or less) in the evaluation of photosensitivity described in the Examples below. .

The photosensitive resin composition according to this embodiment may be in liquid form or in 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 patterned (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 with the photosensitive resin composition according to the present embodiment is not particularly limited. .

The thickness of the film-like photosensitive resin composition or cured product is 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. It's good. The thickness of the film-like photosensitive resin composition or cured product is 300 μm or less, 200 μm or less, 100 μm or less, 80 μm or less, 70 μm or less, 60 μm or less, or 50 μm from the viewpoint of easily obtaining a resist suitable for etching treatment or plating treatment. Below, the thickness may be 40 μm or less, 30 μm or less, or 25 μm or less. From these viewpoints, the thickness of the film-like photosensitive resin composition or cured product may be 1 to 300 μm.

The photosensitive resin composition according to this embodiment contains a binder polymer as the component (A). Examples of the component (A) include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins. Acrylic resin is a resin having a compound having a (meth)acryloyl group ((meth)acrylic acid compound) as a monomer unit, and includes styrene resin, epoxy resin, amide resin, amide epoxy resin having the monomer unit. , alkyd resins and phenolic resins belong to acrylic resins. Component (A) does not need to contain a binder polymer having a phenolic hydroxyl group.

Examples of the compound having a (meth)acryloyl group include (meth)acrylic acid, (meth)acrylic acid ester, and the like. Examples of (meth)acrylic acid ester include alkyl (meth)acrylate ((meth)acrylic acid alkyl ester; excluding compounds corresponding to cycloalkyl (meth)acrylate), cycloalkyl (meth)acrylate ((meth)acrylic acid cycloalkyl acrylic acid cycloalkyl ester), (meth)acrylic acid aryl ((meth)acrylic acid aryl ester; (meth)acrylic acid benzyl, etc.), (meth)acrylamide compounds (diacetone acrylamide, etc.), (meth)acrylic acid glycidyl ester Examples include.

Component (A) is an acrylic material that is easy to obtain good alkali developability, easy to reduce the time for removing unexposed areas, and easy to obtain excellent adhesion, resolution, and sensitivity. May contain resin. From the same viewpoint, the content of the acrylic resin is 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, based on the total amount of component (A). The content may be 99% by mass or more, or substantially 100% by mass (an embodiment in which the component (A) consists essentially of an acrylic resin).

Component (A) is made from (meth)acrylic acid as a monomer unit, from the viewpoint of easily reducing the time it takes for unexposed areas to be removed, and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. may have. From the same viewpoint, when component (A) has (meth)acrylic acid as a monomer unit, the content of the monomer unit of (meth)acrylic acid is the monomer unit that constitutes component (A). It may be in the following range based on the total amount of . The content of monomer units of (meth)acrylic acid is 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, It may be 22% by mass or more, or 25% by mass or more. The content of monomer units of (meth)acrylic acid is 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, It may be 27% by mass or less, or 25% by mass or less. From these viewpoints, the content of monomer units of (meth)acrylic acid may be 1 to 50% by mass.

Component (A) is a monomer unit of alkyl (meth)acrylate, from the viewpoint of easily reducing the time for removing the unexposed area, and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. It may be used as Examples of the alkyl group of the 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, and dodecyl group. etc., and the alkyl group may be various structural isomers. Component (A) is composed of methyl (meth)acrylate as a monomer unit, from the viewpoint of easily reducing the time it takes for unexposed areas to be removed, and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. It may be used as

The alkyl group of the alkyl (meth)acrylate may have a substituent. Examples of substituents include hydroxy group, carboxyl group, carboxylic acid group, aldehyde group, alkoxy group, carbonyl group, alkoxycarbonyl group, alkanoyl group, oxycarbonyl group, carbonyloxy group, amino group, epoxy group, furyl group, and cyano group. , a halogeno group (fluoro group, chloro group, bromo group, etc.), nitro group, acetyl group, sulfonyl group, sulfonamide group, etc.

When the component (A) has alkyl (meth)acrylate as a monomer unit, the content of the alkyl (meth)acrylate monomer unit is determined from the viewpoint of easily reducing the time for removing the unexposed area, In addition, from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity, the following range may be used based on the total amount of monomer units constituting component (A). The content of monomer units of alkyl (meth)acrylate is 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 monomer units of alkyl (meth)acrylate is 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 monomer units of alkyl (meth)acrylate may be 1 to 99% by mass.

Component (A) is a styrene compound (a compound having a (meth)acryloyl group) from the viewpoint of easily reducing the time it takes for unexposed areas to be removed and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. ) may be included as a monomer unit. Examples of the styrene compound include styrene and styrene derivatives. Examples of styrene derivatives include vinyltoluene and α-methylstyrene. Component (A) is (meth)acrylic acid and (meth)acrylic acid, from the viewpoint of easily reducing the time for removing unexposed areas, and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. It may contain at least one selected from the group consisting of: and a styrene compound as a monomer unit, and may contain (meth)acrylic acid, an alkyl (meth)acrylate, and a styrene compound as a monomer unit.

When component (A) has a styrene compound as a monomer unit, the content of the styrene compound monomer unit is determined from the viewpoint of easily reducing the time for removing the unexposed area, as well as from the viewpoint of excellent adhesion and resolution. From the viewpoint of easily obtaining imageability and sensitivity, the following range may be used based on the total amount of monomer units constituting component (A). The content of monomer units of the styrene compound is 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 monomer units of the styrene compound is 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 The content may be below 25% by mass, below 22% by mass, below 20% by mass, below 18% by mass, or below 15% by mass. From these viewpoints, the content of monomer units of the styrene compound may be 1 to 50% by mass.

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 maleate, monoethyl maleate, maleic acid (monoisopropyl acid, etc.), fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, etc. Component (A) does not need to contain at least one of these monomers as a monomer unit.

The weight average molecular weight (Mw) of component (A) is within the following range from the viewpoint of easily reducing the time for removing unexposed areas and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. It's good to be there. 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.

The number average molecular weight (Mn) of component (A) is within the following range from the viewpoint of easily reducing the time for removing unexposed areas and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. It's good. 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 from 5,000 to 100,000.

The degree of dispersion (Mw/Mn) of component (A) is within the following range from the viewpoint of easily reducing the time for removing unexposed areas and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. It may be. The degree of dispersion 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 degree of dispersion (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 degree of dispersion of component (A) may be from 1.2 to 3.5.

The weight average molecular weight (Mw) and number average molecular weight (Mn) can be obtained, for example, by measuring by gel permeation chromatography (GPC) and converting using a standard polystyrene calibration curve. More specifically, it can be measured by the method described in Examples. If it is difficult to measure a compound with a low molecular weight using such a measuring method, it is also possible to measure the molecular weight using another method and calculate the average value.

The acid value of component (A) may be in the following range from the viewpoint of easily reducing the time for removal of unexposed areas and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. The acid value of component (A) is 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 160mgKOH/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 monomer units (for example, monomer units of (meth)acrylic acid) constituting component (A).

The content of component (A) is determined from the viewpoint of easily reducing the time during which unexposed areas are removed, and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. It may be in the following range based on the total amount of solid content. The content of component (A) is 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 It may be 55% by mass or more, or 55% by mass or more. The content of component (A) is 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.

The content of component (A) and (B) is determined from the viewpoint of easily reducing the time for removing unexposed areas, and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. It may be in the following range based on a total of 100 parts by mass of components. The content of component (A) is 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. It may be at least 56 parts by mass, at least 57 parts by mass, at least 58 parts by mass, at least 59 parts by mass, at least 60 parts by mass, or at least 63 parts by mass. The content of component (A) is 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 The amount may be less than or equal to 57 parts by mass, or less than 56 parts by mass. From these viewpoints, the content of component (A) may be 10 to 90 parts by mass.

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

Component (B) does not contain a bisphenol A type di(meth)acrylate compound from the viewpoint of easily reducing the time for removing unexposed areas and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. That's fine. The bisphenol A type di(meth)acrylate compound may be alkylene oxide modified and may have a polyoxyalkylene group (polyoxyethylene group, polyoxypropylene group, polyoxybutylene group, etc.).

Bisphenol A type 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, 2, Examples include 2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane.

Component (B) is 2,2-bis(4-((metal ) acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypoly) 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane and 2,2-bis(4-( It may contain at least one member selected from the group consisting of (meth)acryloxydiethoxy)phenyl)propane.

Component (B) is a bisphenol A-type di( The meth)acrylate compound may include 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 is 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. good. 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 points of view, the number of oxyalkylene groups may be from 1 to 20.

The content of the bisphenol A type di(meth)acrylate compound is determined from the viewpoint of easily reducing the time during which unexposed areas are removed, and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity (B) It may be in the following range based on the total amount of the components. The content of the bisphenol A type di(meth)acrylate compound is 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 It may be at least 58% by mass, at least 59% by mass, or at least 60% by mass. The content of the bisphenol A type di(meth)acrylate compound is 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 It may be 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.

The content of the bisphenol A type di(meth)acrylate compound is determined from the viewpoint of easily reducing the time for removing unexposed areas, and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. It may be within the following range based on the total solid content of the composition. The content of the bisphenol A type di(meth)acrylate compound is 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 It may be 24% by mass or more, or 24% by mass or more. The content of the bisphenol A type di(meth)acrylate compound is 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 It may be less than 22% by mass, less than 21% by mass, or less than 20% by mass. From these viewpoints, the content of the bisphenol A type di(meth)acrylate compound may be 1 to 50% by mass.

The content of the bisphenol A type di(meth)acrylate compound is determined from the viewpoint of easily reducing the time during which unexposed areas are removed, and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity (A). The content may be within the following range based on 100 parts by mass of the total amount of the components and component (B). The content of the bisphenol A type di(meth)acrylate compound is 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. The amount may be at least 25 parts by mass, or at least 26 parts by mass. The content of the bisphenol A type di(meth)acrylate compound is 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 The amount may be less than or equal to 23 parts by mass, less than 22 parts by mass, or less than 20 parts by mass. From these viewpoints, the content of the bisphenol A di(meth)acrylate compound may be 1 to 50 parts by mass.

Component (B) is trimethylolpropane tri(meth)acrylate, tetramethylol It may contain at least one compound X selected from the group consisting of methane 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.

The content of Compound From the viewpoint of easily obtaining sensitivity, the following range may be used based on the total solid content of the photosensitive resin composition. 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 is 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. It's good to be there. From these points of view, the above-mentioned content may be from 1 to 20% by weight.

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

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

The content of the compound represented by general formula (b1) is determined from the viewpoint of easily reducing the time for removing unexposed areas, and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. It may be within the following range based on the total solid content of the resin composition. 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 1 to 20% by mass.

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

The content of component (B) is determined based on the solid content of the photosensitive resin composition, from the viewpoint of easily reducing the time for removing unexposed areas, and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. It may be in the following range based on the total amount. The content of component (B) is 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 It may be at least 40% by mass, or more than 40% by mass. The content of component (B) is 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.

The content of component (B) is determined from the viewpoint of easily reducing the time for removing unexposed areas, and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. The content may be within the following range based on 100 parts by mass of the total amount of components. The content of component (B) is 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. The amount may be at least 43 parts by mass, or at least 44 parts by mass. The content of component (B) is 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 The amount may be less than or equal to 44 parts by mass, less than 43 parts by mass, less than 42 parts by mass, less than 41 parts by mass, less than 40 parts by mass, or less than 37 parts by mass. From these viewpoints, the content of component (B) may be 10 to 90 parts by mass.

The photosensitive resin composition according to this embodiment contains a photopolymerization initiator as the component (C). Component (C) includes 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, Examples include benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, and triarylamine compounds.

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

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-phenyl-3-(2,6-dimethoxy styryl)-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, Examples include 4-[[3-(4-chlorophenyl)-4,5-dihydro-1H-pyrazol]-1-yl]benzenesulfonamide.

Coumarin compounds include 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, 7-methylamino-4-methylcoumarin, and 7-ethylamino-4-methylcoumarin. Methylcoumarin, 7-aminocyclopenta[c]coumarin, 7-dimethylaminocyclopenta[c]coumarin, 7-diethylaminocyclopenta[c]coumarin, 4,6-dimethyl-7-dimethylaminocoumarin, 4,6- Dimethyl-7-ethylaminocoumarin, 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]quinolidin-11-one and the like.

Examples of anthracene compounds include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentoxyanthracene, etc. Examples include dialkoxyanthracene.

Examples of imidazole compounds include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, and 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer. fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer Examples include 2,4,5-triarylimidazole dimers such as 2,4,5-triarylimidazole dimers. Aromatic ketones include benzophenone compounds, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino- Examples include 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'- N,N,N',N'-tetraalkyl-4,4'-diaminobenzophenones such as diaminobenzophenone; dialkylaminobenzophenones such as 4-methoxy-4'-dimethylaminobenzophenone; and the like. Examples of the quinone compound include alkylanthraquinone and the like. Examples of the benzoin compound include benzoin, alkylbenzoin, and benzoin ether compounds (benzoin alkyl ether, etc.). Examples of the N-phenylglycine compound include N-phenylglycine and N-phenylglycine derivatives. Examples of benzyl derivatives include benzyl dimethyl ketal.

Component (C) is an acridine compound, a pyrazoline compound, a coumarin compound, and It may contain at least one selected from the group consisting of anthracene compounds, may contain an acridine compound, and may contain 1,7-bis(9,9'-acridinyl)heptane.

The content of component (C) may be in the following range based on the total solid content of the photosensitive resin composition. The content of component (C) is 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 from the viewpoint of easily obtaining excellent sensitivity. % 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. The content of component (C) is 20% by mass or less, and 10% by mass or less, from the viewpoint of suppressing excessive increase in light absorption on the surface of the photosensitive layer during exposure and facilitating sufficient hardening of the inside of the photosensitive layer. % 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.

The content of component (C) may be in the following range based on 100 parts by mass of the total amount of components (A) and (B). The content of component (C) is 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 from the viewpoint of easily obtaining excellent sensitivity. parts 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. The content of component (C) is 20 parts by mass or less, 10 parts by mass or less, from the viewpoint of suppressing excessive increase in light absorption on the surface of the photosensitive layer during exposure and facilitating sufficient hardening of the inside of the photosensitive layer. parts by weight or less, 5 parts by weight or less, 4 parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, 1 part by weight or less, or 0.5 parts by weight or less. From these viewpoints, the content of component (C) may be 0.1 to 20 parts by mass.

The photosensitive resin composition according to the present embodiment contains, as component (D), a bisphenol compound having a polyoxyalkyl group located at the end of the molecule (excluding compounds corresponding to component (B)). The polyoxyalkyl group is a group 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. A plurality of R's may be the same or different from each other.

Component (D) may include a bisphenol compound having a polyoxyalkyl group located at the end of the main chain. Component (D) may be a bisphenol compound having a polyoxyalkyl group located at the end of the molecule and having no ethylenically unsaturated bond.

Examples of the polyoxyalkyl group include a group represented by "-(CH ₂ CH ₂ O) _n H" (polyoxyethylene group), a group represented by "-(CH ₂ CH ₂ O) _n H", " Examples thereof include a group represented by "-(CH ₂ CH ₂ CH 2 CH ₂ O) _n H" and a group represented by "-(CH(CH ₃ )CH ₂ O) _n H". Component (D) has a polyoxyethylene group located at the end of the molecule, from the viewpoint of easily reducing the time it takes for unexposed areas to be removed, and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. May include bisphenol compounds.

Component (D) has a molecular weight within the following range (e.g., weight average molecular weight) from the viewpoint of easily reducing the time for removing the unexposed area, and from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. bisphenol compounds. 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 points of view, the molecular weight may be between 300 and 3000. When the molecular weight of component (D) is a weight average molecular weight, the weight average molecular weight can be measured in the same manner as for component (A).

Component (D) is a polyoxyalkyl group located at the end of the molecule (e.g. The bisphenol compound may include a bisphenol compound having two or more polyoxyalkyl groups (for example, polyoxyethylene group) located at the end of the molecule, and the may include polyoxyethylene-oxyphenyl)propane.

From the viewpoint of obtaining excellent adhesion, the content of component (D) is more than 0% by mass and not more than 15% by mass, based on the total solid content of the photosensitive resin composition. The content of component (D) may be within the following range based on the total solid content of the photosensitive resin composition. The content of component (D) is 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 1.5% by mass or more, from the viewpoint of easily reducing the time during which the unexposed area is removed. 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, more than 5% by mass, 5.5% by 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. The content of component (D) is 12% by mass or less, 10% by mass or less, 9% by mass or less, 8.5% by mass or less, and 8% by mass from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. % 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) is 0.1 to 12% by mass, 1.5 to 9% by mass, 1.5 to 7% by mass, or more than 0% by mass and 4% by mass or less. It's good to be there.

The content of component (D) exceeds 0 parts by mass based on 100 parts by mass of the total amount of components (A) and (B), and may be in the following range. The content of component (D) is 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, from the viewpoint of easily reducing the time for removing the unexposed area. 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 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. good. The content of component (D) is 15 parts by mass or less, 12 parts by mass or less, 10 parts by mass or less, 9 parts by mass or less, and 8.5 parts by mass, from the viewpoint of easily obtaining excellent adhesion, resolution, and sensitivity. parts by weight or less, 8 parts by weight or less, 7.5 parts by weight or less, 7 parts by weight or less, 6.5 parts by weight or less, 6 parts by weight or less, or 5.5 parts by weight or less. The content of component (D) is 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. It may be the following. From these viewpoints, the content of component (D) may be more than 0 parts by weight and 15 parts by weight or less, 0.1 to 12 parts by weight, 1 to 10 parts by weight, or 1 to 8 parts by weight.

The photosensitive resin composition according to the present embodiment may optionally contain a solvent, a dye (such as malachite green) as a component different from component (A), component (B), component (C), and component (D). , photochromic agents (tribromophenyl sulfone, leuco crystal violet, etc.), thermal color development inhibitors, plasticizers (p-toluenesulfonamide, etc.), polymerization inhibitors (4-t-butylcatechol, etc.), pigments, fillers, Antifoaming agents, flame retardants, stabilizers, adhesion agents, leveling agents, release promoters, antioxidants (dibutylhydroxytoluene (also known as 2,6-di-tert-butyl-p-cresol), etc.), fragrances , an imaging agent, a thermal crosslinking agent, and other additives. Examples of the solvent include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether, and the like. The photosensitive resin composition according to this embodiment does not need to contain a compound having a 1,2-naphthoquinonediazide group. The content of the compound having a 1,2-naphthoquinone diazide group is 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. It may be less than or equal to 0% by weight, and may be substantially 0% by weight.

<Photosensitive element>
The photosensitive element according to the present embodiment includes a support and a photosensitive layer (for example, a photosensitive film) disposed on the support, and the photosensitive layer contains the photosensitive resin composition according to the present embodiment. include. 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 absorption layer, a gas barrier layer, and 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.

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 the first main surface 10a of the support film 10. The support film 10 has a second main surface 10b on the opposite side to the first main surface 10a.

Each of the support and the protective layer may be a polymer film having heat resistance and solvent resistance. (excluding films), etc. The type of film constituting the protective layer and the type of film constituting the support may be the same or different.

The thickness of the support layer is 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 that the support is difficult to tear when peeling the support from the photosensitive element. It's fine. 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 points of view, the thickness of the support layer may be 1 to 200 μm.

<Method for manufacturing cured product and method for manufacturing cured product pattern>
The method for producing a cured product according to the present embodiment includes an exposure step of irradiating a photosensitive layer containing the photosensitive resin composition according to the present embodiment with actinic rays to obtain a cured product (photocured product). In the exposure step, a cured product may be obtained by irradiating the photosensitive layer with actinic rays through the support while the photosensitive element is laminated on a base material (for example, a substrate). In this case, the photosensitive element may be laminated on the substrate such that the photosensitive layer is located closer to the substrate than the support.

In the exposure step, for example, with a photomask having a negative or positive mask pattern in close contact with the support, the photosensitive layer is irradiated with actinic rays (for example, irradiated in an imagewise manner) through the support to cure the photosensitive layer. You can get things. Examples of the active light source include light sources that emit ultraviolet rays, visible light, etc. (carbon arc lamps, mercury vapor arc lamps, high pressure mercury lamps, xenon lamps, etc.). A laser direct writing exposure method can also be used in the exposure step.

The method for producing a cured product according to the present embodiment may include a lamination step of laminating a photosensitive element on a base material before the exposure step. In the lamination step, the photosensitive element can be laminated on the substrate such that the photosensitive layer is located closer to the substrate than the support.

The method for producing a cured product pattern (method for forming a resist pattern) according to the present embodiment is to remove a portion of the photosensitive layer other than the cured product (unexposed portion) after the exposure step in the method for producing a cured product according to the present embodiment. A developing step is provided to obtain a cured product pattern (resist pattern) by removing at least a portion of the resist.

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 process, wet development with a developer (alkaline aqueous solution, aqueous developer, organic solvent, etc.); dry development, etc. is used to remove the unexposed areas (unphotocured areas) of the photosensitive layer and develop the cured product pattern. Obtainable.

Examples of the alkaline aqueous solution include 0.1 to 5% by mass sodium carbonate solution, 0.1 to 5% by mass potassium carbonate solution, and 0.1 to 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 depending on the developability of the photosensitive layer. The alkaline aqueous solution may contain a surfactant, an antifoaming agent, an organic solvent, and the like. Examples of the developing method include a dipping method, a spray method, brushing, and slapping.

In the method for producing a cured product pattern according to the present embodiment, from the viewpoint of improving solder heat resistance, chemical resistance, etc., the cured product pattern is further heated and/or exposed as necessary after the development step. It may include a curing step. Heating may be performed, for example, at 60-250°C or 100-170°C for 15-90 minutes. For exposure, ultraviolet rays can be irradiated using a high-pressure mercury lamp. The exposure amount may be, for example, 0.2 to 10 J/cm ² . Heating and exposure (for example, ultraviolet irradiation) may be performed simultaneously, or one of heating and exposure may be performed before the other. When heating and exposure are performed simultaneously, heating can be performed at 60 to 150° C. from the viewpoint of effectively imparting solder heat resistance, chemical resistance, etc.

By the method for manufacturing a cured product pattern according to the present embodiment, a cured product pattern (resist pattern) can 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 joining mounted components. The cured product pattern obtained by the method for manufacturing a cured product pattern according to the present embodiment may be used as a permanent mask for a semiconductor package, or may be used as a permanent mask formed on a rigid substrate.

<Method for manufacturing wiring board>
The method for manufacturing a wiring board (for example, a printed wiring board) according to the present embodiment is directed to a laminate having a cured product pattern obtained by the method for manufacturing a cured product pattern according to the present embodiment on a base material (for example, a substrate). The method includes a step of performing an etching treatment or a plating treatment. 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.

Etching solutions used in the etching process include cupric chloride solutions, ferric chloride solutions, alkaline etching solutions, and the like. Examples of the plating treatment include copper plating, solder plating, nickel plating, gold plating, and the like.

After performing the etching treatment or the plating treatment, the cured product pattern can be peeled off using an aqueous solution that is more strongly alkaline than the alkaline aqueous solution used for development, for example. Examples of the strongly alkaline aqueous solution include a 1 to 10% by mass aqueous sodium hydroxide solution, a 1 to 10% by mass aqueous potassium hydroxide solution, and the like. Methods for peeling off the cured product pattern include a dipping method, a spray method, and the like.

When plating is performed on a base material that includes an insulating layer and a conductor layer disposed on the insulating layer, the conductor layer other than the pattern portion can be removed. The method for removing the conductor layer is to peel off the cured product pattern and then lightly etch it; following the plating process, perform solder plating, etc., then peel off the cured product pattern to mask the wiring part with solder, and then, Examples include a method of processing using an etching solution that can etch only the conductor layer.

Hereinafter, the content of the present disclosure will be explained in more detail 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 performed at room temperature (25° C.) under atmospheric pressure unless otherwise specified.

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

420 g of 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 introduction tube. Next, mixture b was heated to 80° C. while stirring while blowing nitrogen gas. Subsequently, the above solution a was added dropwise to mixture b using a dropping funnel over 4 hours. Then, after cleaning the inside of the dropping funnel using 40 g of a mixture of toluene and methyl cellosolve (mass ratio = 6:4) as a cleaning liquid, the mixture c was obtained by adding this cleaning liquid to the flask.

Next, mixture c was kept at 80° C. for 2 hours while stirring. Next, 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 poured into the flask over 30 minutes. dripped into. Subsequently, the inside of the dropping funnel was washed using 120 g of a mixture of toluene and methyl cellosolve (mass ratio = 6:4) as a washing liquid, and then this washing liquid was added to the flask to obtain a mixture e.

Next, mixture e was kept at 80° C. for 3 hours while stirring. Subsequently, it was heated to 90°C over 30 minutes. A binder polymer solution containing binder polymer A1 was obtained by keeping the temperature at 90° C. for 2 hours and then cooling it. Toluene was added to this binder polymer solution to adjust the nonvolatile component concentration (solid content concentration) to 40% by mass.

The weight average molecular weight of the 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 by gel permeation chromatography (GPC) under the following conditions and converting using a standard polystyrene calibration curve.

Pump: L-2130 type [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]
Column: Gelpack GL-R440 + Gelpack GL-R450 + Gelpack GL-R400M (3 columns in total) [manufactured by Showa Denko Materials Co., Ltd., product name]
Column size: 10.7mmI. D×300mm
Eluent: Tetrahydrofuran Sample concentration: 10mg/2mL
Injection volume: 200μL
Flow rate: 2.05mL/min Measurement temperature: 25℃

The acid value of binder polymer A1 was 160 mgKOH/g. The acid value was measured by the following procedure. First, a 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. Then, the acid value was obtained by titration using a 0.1 mol/L (N/10) potassium hydroxide solution (alcohol solution).

(Binder polymer A2)
Solution a (mass ratio of monomers = methacrylic acid/methyl acrylate/ A solution of binder polymer A2 was obtained by performing the same operation as binder polymer A1, except that methyl methacrylate/styrene = 25/10/50/15) was obtained. The nonvolatile content concentration (solid content concentration) of the binder polymer solution of binder polymer A2 was 40% by mass. The weight average molecular weight of the binder polymer A2 was 80,000, the number average molecular weight was 28,000, and the degree of molecular weight dispersion was 2.9. The acid value of binder polymer A2 was 160 mgKOH/g.

<Preparation of photosensitive resin composition>
A photosensitive resin composition was prepared by mixing each component shown in Table 1. Table 1 shows the blending amount (parts by mass) of each component, and the blending amount of the binder polymer is the mass of nonvolatile components (solid content). Details of each component shown in Table 1 are as follows.

(Photopolymerizable compound)
FA-321M: 2,2-bis(4-(methacryloxypolyethoxy)phenyl)propane (EO-modified bisphenol A dimethacrylate, ethylene oxide average 10 mol adduct, number of methacryloyl groups: 2, molecular weight: 804, Showa Denko Materials) (manufactured by Zuzu Co., Ltd.)
BPE-200: 2,2-bis(4-(methacryloxypolyethoxy)phenyl)propane (EO-modified bisphenol A dimethacrylate, ethylene oxide average 4 mol adduct, number of methacryloyl groups: 2, molecular weight: 540, Shin Nakamura Chemical) Industrial Co., Ltd.)
FA-137M: Trimethylolpropane EO modified trimethacrylate (ethylene oxide average 21 mol 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), ethylene oxide average 4 mol adduct, number of methacryloyl groups: 1, molecular weight: 454, manufactured by Showa Denko Materials Co., Ltd.)
B-1: Triethylene glycol decapropylene glycol α,ω-dimethacrylate of triethylene glycol B-2: Monomer in which bisphenol A is reacted with 8 mol of ethylene oxide and 8 mol of propylene oxide and then ester-bonded with methacrylic acid.

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

(Bisphenol compound having polyoxyalkyl group)
BA-10: 2,2-bis(4-polyoxyethylene-oxyphenyl)propane (manufactured by Nippon Nyukazai Co., Ltd., product name: BA-10, weight average molecular weight: 700)

(Other ingredients)
LCV: Leuco Crystal Violet (manufactured by Yamada Chemical Industry Co., 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.)

<Preparation of photosensitive element>
After applying the above-mentioned photosensitive resin composition onto a support film (PET film, manufactured by Teijin DuPont Films Ltd., trade name "G2") so that the thickness was uniform, it was dried in a hot air convection dryer at 100°C for 2 hours. A photosensitive layer (thickness: 25 μm) was formed by removing the solvent by drying for minutes. Thereafter, the photosensitive layer was covered with a polyethylene protective film (manufactured by Tamapori Co., Ltd., trade name: NF-15, thickness: 18 μm) to obtain a photosensitive element.

<Evaluation>
(Preparation of laminate)
After forming a copper layer (electroless copper, thickness: 500 nm) on both sides of an interlayer insulation material (manufactured by Ajinomoto Fine-Techno Co., Inc., product name: GX-T31), the surface of the copper layer is coated with acid. Substrate a was obtained by washing, washing with water, and drying (air flow). After heating this 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. Thereby, a laminate including the substrate a, the photosensitive layer, and the support film in this order in the lamination direction was obtained. Lamination was performed using a 110° C. heat roll at a pressure of 0.4 MPa and a roll speed of 1.5 m/min.

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

(light sensitivity)
The above-described laminate was allowed to cool to 23°C. Next, a photo tool having a step tablet was brought into close contact with the support film on the surface of the laminate. As a step tablet, 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 a size of each step of 3 mm x 12 mm was used. . Exposure of the photosensitive layer was then carried out via a phototool with a step tablet and a support film. Exposure was performed at an exposure dose of 17 mJ/cm ² using an exposure machine using a semiconductor-excited solid-state laser as a light source (manufactured by Nippon Orbotech Co., Ltd., trade name "Paragon-9000m").

After exposure, the support film was peeled off from the laminate to expose the photosensitive layer. The exposed photosensitive layer was sprayed with a 1.0% by mass sodium carbonate aqueous solution at 30° C. for 50 seconds (development treatment) to remove the unexposed portion. 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 (light sensitivity) of this cured film was evaluated by measuring the number of step tablets. The results are shown in Table 1. The higher the number of steps on the step tablet, the higher the sensitivity.

(Adhesion and resolution)
Evaluation pattern (for adhesion evaluation) with a line width/space width of n/3n (unit: μm, 1 μm interval for n = 5 to 40 μm, 5 μm interval for 40 to 60 μm), and a line width/space width of 3n /n (unit: μm, 1 μm intervals for n = 5 to 30 μm, 5 μm intervals for 30 to 60 μm) using a photo tool having an evaluation pattern (for resolution evaluation) to expose the photosensitive layer of the above-mentioned laminate. went. Exposure was performed at an exposure dose of 17 mJ/cm ² using an exposure machine (manufactured by Nippon Orbotech Co., Ltd., trade name "Paragon-9000m") using a semiconductor-excited solid-state laser as a light source. Next, the unexposed areas were removed by developing under the same conditions as in the above-mentioned evaluation of photosensitivity. Adhesion was evaluated by the minimum width (unit: μm) of the line area where the cured film remained after the development process. The resolution was evaluated based on the minimum width (unit: μm) of the space between the line areas from which the non-photocured portion could be clearly removed by the development process. The results are shown in Table 1. In the evaluation of adhesion and resolution, the smaller the numerical value, the better.

1... Photosensitive element, 10... Support film (support), 10a... First main surface, 10b... Second main surface, 20... Photosensitive layer.

Claims

(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 (the (Excluding compounds corresponding to component (B));
A photosensitive resin composition in which the content of the component (D) is more than 0% by mass and 15% by mass or less.
The photosensitive resin composition according to claim 1, wherein the component (D) contains a bisphenol compound having two polyoxyalkyl groups located at the ends of the molecule.
The photosensitive resin composition according to claim 1 or 2, wherein the component (D) contains 2,2-bis(4-polyoxyethylene-oxyphenyl)propane.
The photosensitive resin composition according to any one of claims 1 to 3, wherein the content of the component (D) is more than 0% by mass and 4% by mass or less.
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.
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 the component (A).
The photosensitive resin composition according to any one of claims 1 to 6, wherein the component (B) contains a bisphenol A di(meth)acrylate compound.
The photosensitive resin composition according to any one of claims 1 to 7, wherein the component (B) contains an alkylene oxide modified product of trimethylolpropane tri(meth)acrylate.
The photosensitive resin composition according to any one of claims 1 to 8, wherein the component (C) contains at least one selected from the group consisting of an acridine compound, a pyrazoline compound, a coumarin compound, and an anthracene compound.
The photosensitive resin composition according to any one of claims 1 to 8, wherein the component (C) contains an acridine compound.
The photosensitive resin composition according to any one of claims 1 to 10, which is in the form of a film.
comprising a support and a photosensitive layer disposed on the support,
A photosensitive element, wherein the photosensitive layer comprises the photosensitive resin composition according to any one of claims 1 to 11.
A method for producing a cured product, comprising an exposure step of irradiating a photosensitive layer containing the photosensitive resin composition according to any one of claims 1 to 11 with actinic rays to obtain a cured product.
A method for producing 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 producing a cured product according to claim 13.
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 method for manufacturing a cured product pattern according to claim 14 on a base material.