Photosensitive resin composition, photosensitive element, and method for manufacturing laminate

Abstract

The present invention provides a photosensitive resin composition that is capable of producing a cured product with excellent sensitivity and excellent resistance to etching solutions. [Solution] A photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator, wherein component (B) contains a polyfunctional compound having three or more ethylenically unsaturated bonds, and when a layer (thickness 25 μm) of the photosensitive resin composition is exposed at a wavelength of 405 nm using a 41-step tablet (concentration range 0.00 to 2.00, concentration step 0.05, tablet size 20 mm × 187 mm, size of each step 3 mm × 12 mm) and then developed, an exposure amount of 30 mJ / cm² gives 15 remaining steps. 2 The following is a photosensitive resin composition.

Description

[Technical Field]

[0001] This disclosure relates to a photosensitive resin composition, a photosensitive element, a method for manufacturing a laminate, and the like. [Background technology]

[0002] In the manufacture of laminates that can be used as wiring boards, etc., a resist pattern is formed on a metal layer. After removing the exposed parts of the metal layer (parts not covered by the resist pattern) by etching, the resist pattern can be peeled off to form the desired wiring. The resist pattern can be formed by exposing and developing a layer of 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] Photosensitive resin compositions used to form cured patterns that can be used as resist patterns are required to have excellent sensitivity, from the viewpoint of shortening the exposure cycle time and improving productivity. Furthermore, such photosensitive resin compositions are required to not peel off when the cured product of the photosensitive resin composition comes into contact with an etching solution used to remove exposed metal layers. However, it is not easy to obtain a cured product with excellent etching solution resistance in a photosensitive resin composition that has excellent sensitivity.

[0005] One aspect of this disclosure aims to provide a photosensitive resin composition that is capable of producing a cured product having excellent etching resistance while also being a photosensitive resin composition with excellent sensitivity. 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 laminate using the above-mentioned photosensitive resin composition or photosensitive element. [Means for solving the problem]

[0006] To address these challenges, the inventors discovered that resin compositions that yield cured products with excellent etching resistance do not necessarily possess excellent sensitivity. They then focused on using photopolymerizable compounds having three or more ethylenically unsaturated bonds, but found that the above-mentioned problems could not be solved solely by using photopolymerizable compounds having three or more ethylenically unsaturated bonds. On the other hand, the inventors found that when a layer (thickness 25 μm) of a photosensitive resin composition is exposed at a wavelength of 405 nm using a 41-step tablet (concentration range 0.00 to 2.00, concentration step 0.05, tablet size 20 mm × 187 mm, size of each step 3 mm × 12 mm) and then developed, an exposure dose of 30 mJ / cm² yields 15 remaining steps. 2 We have found that the above-mentioned problems can be solved by using a photopolymerizable compound having three or more ethylenically unsaturated bonds in the following photosensitive resin composition (a photosensitive resin composition with excellent sensitivity).

[0007] Furthermore, the inventors have found that the above-mentioned problems can be solved by using a specific photopolymerizable compound having three or more ethylenically unsaturated bonds in combination with 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane and an acridine compound.

[0008] This disclosure relates in several respects to the following [1] to

[19] , etc. [1] A photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator, wherein component (B) comprises a polyfunctional compound having three or more ethylenically unsaturated bonds, and when a layer (thickness 25 μm) of the photosensitive resin composition is exposed at a wavelength of 405 nm using a 41-step tablet (concentration range 0.00 to 2.00, concentration step 0.05, tablet size 20 mm × 187 mm, size of each step 3 mm × 12 mm) and then developed, an exposure amount of 30 mJ / cm² is used to give 15 remaining steps. 2 The following is a photosensitive resin composition. [2] The photosensitive resin composition according to [1], wherein the component (B) comprises a polyfunctional compound having three ethylenically unsaturated bonds. [3] The photosensitive resin composition according to [1], wherein the component (B) comprises a polyfunctional compound having six ethylenically unsaturated bonds. [4] The photosensitive resin composition according to [1], wherein the component (B) comprises a polyfunctional compound having three ethylenically unsaturated bonds and a polyfunctional compound having six ethylenically unsaturated bonds. [5] A photosensitive resin composition according to any one of [1] to [4], wherein the (C) component comprises an acridine compound. [6] The photosensitive resin composition according to any one of [1] to [4], wherein the (C) component comprises an acridine compound and an N-phenylglycine compound. [7] The photosensitive resin composition according to any one of [1] to [6], wherein the content of the polyfunctional compound is 1 to 10% by mass based on the total amount of the photosensitive resin composition. [8] The photosensitive resin composition according to any one of [1] to [7], wherein the content of the polyfunctional compound is 3 to 30% by mass based on the total amount of component (B). [9] The photosensitive resin composition according to any one of [1] to [8], wherein the component (B) further comprises a bisphenol A type (meth)acrylic acid compound.

[10] A photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator, wherein component (B) comprises at least one selected from the group consisting of trimethylolpropane tri(meth)acrylate, alkylene oxide-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and alkylene oxide-modified dipentaerythritol hexa(meth)acrylate, and 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane, and component (C) comprises an acridine compound.

[11] The photosensitive resin composition according to

[10] , wherein component (B) comprises alkylene oxide-modified trimethylolpropane tri(meth)acrylate.

[12] The photosensitive resin composition according to any one of [1] to

[11] , wherein the content of component (B) is 30 to 60 parts by mass per 100 parts by mass of the total of component (A) and component (B).

[13] The photosensitive resin composition according to any one of [1] to

[12] , wherein component (A) has (meth)acrylic acid and a styrene compound as monomer units.

[14] The photosensitive resin composition according to any one of [1] to

[13] , wherein component (A) has a styrene compound as a monomer unit, and the content of the monomer unit of the styrene compound is 1 to 30% by mass based on the total amount of monomer units constituting component (A).

[15] The weight-average molecular weight of component (A) is 3.0 × 10 4 ~5.0×10 4 The photosensitive resin composition described in any one of [1] to

[14] .

[16] A photosensitive resin composition according to any one of [1] to

[15] , further comprising tribromomethylphenylsulfone.

[17] A photosensitive resin composition according to any one of [1] to

[16] , which is in the form of a film.

[18] A photosensitive element comprising a support and a photosensitive resin layer disposed on the support, wherein the photosensitive resin layer is a layer of the photosensitive resin composition described in any one of [1] to

[17] . A method for manufacturing a laminate, comprising the steps of: placing a layer of a photosensitive resin composition on a substrate using any one of

[19] [1] to

[17] or a photosensitive element described in

[18] ; photocuring a portion of the layer of the photosensitive resin composition; and removing at least a portion of the uncured portion of the layer of the photosensitive resin composition to form a cured product pattern. [Effects of the Invention]

[0009] According to one aspect of this disclosure, it is possible to provide a photosensitive resin composition that is capable of producing a cured product having excellent etching solution resistance while also being a photosensitive resin composition with excellent sensitivity. According to another aspect of this disclosure, it is possible to provide a photosensitive element using the photosensitive resin composition. According to yet another aspect of this disclosure, it is possible to provide a method for manufacturing a laminate using the above-mentioned photosensitive resin composition or photosensitive element. [Brief explanation of the drawing]

[0010] [Figure 1] This is a schematic cross-sectional view showing an example of a photosensitive element. [Modes for carrying out the invention]

[0011] The embodiments of this disclosure will be described in detail below. However, this disclosure is not limited to the embodiments described below.

[0012] 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, 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 processes that cannot be clearly distinguished from others, as long as the intended function of the process 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". The content of (meth)acrylic acid compounds means the total amount of acrylic acid compounds and methacrylic acid compounds, 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 polyoxyethylene group. "PO modified" means a compound having a polyoxypropylene group. "EO·PO modified" means a compound having both a polyoxyethylene group and a (poly)oxypropylene group.

[0013] In this specification, the solid content of a photosensitive resin composition refers to the non-volatile content of the photosensitive resin composition, excluding volatile substances (water, organic solvents, etc.). That is, the solid content refers to the components that remain without volatilizing during the drying of the photosensitive resin composition, and includes components that are liquid, syrup-like, or waxy at room temperature (25°C).

[0014] <Photosensitive resin composition> The photosensitive resin composition according to this embodiment (including the photosensitive resin compositions according to the first and second embodiments described later; the same applies hereinafter) contains (A) a binder polymer (component (A)), (B) a photopolymerizable compound (component (B)), and (C) a photopolymerization initiator (component (C)). In the photosensitive resin composition according to the first embodiment, component (B) contains a polyfunctional compound having three or more ethylenically unsaturated bonds, and when a layer (thickness 25 μm) of the photosensitive resin composition is exposed at a wavelength of 405 nm using a 41-step tablet (concentration range 0.00 to 2.00, concentration step 0.05, tablet size 20 mm × 187 mm, size of each step 3 mm × 12 mm) and then developed, the exposure amount (hereinafter, sometimes referred to as "exposure amount a") that gives a remaining number of steps (remaining step number; remaining film number) of 15 is 30 mJ / cm². 2 The following applies to the photosensitive resin composition according to the second embodiment: Component (B) comprises at least one selected from the group consisting of trimethylolpropane tri(meth)acrylate, alkylene oxide-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate and alkylene oxide-modified dipentaerythritol hexa(meth)acrylate, and 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane, and component (C) comprises an acridine compound.

[0015] The photosensitive resin composition according to this embodiment is a photosensitive resin composition that has excellent sensitivity (low exposure amount) and can produce a cured product with excellent etching solution resistance (etching chemical resistance). For example, it can produce a cured product with excellent acid resistance to acidic solutions used for etching (especially etching solutions containing hydrochloric acid).

[0016] Regarding the photosensitive resin composition according to the first embodiment, the inventor speculates as follows about the factors for obtaining excellent etching liquid resistance in the cured product while obtaining excellent sensitivity. However, the factors are not limited to the following content. That is, when the exposure amount that gives 15 steps as the remaining steps when the layer of the photosensitive resin composition is exposed and developed using a 41-step tablet is 30 mJ / cm 2 In the following case (when the exposure amount is small), the number of active species generated from the photoinitiator is small. In this case, in the photosensitive resin composition according to the first embodiment, since the number of reaction points increases by using a polyfunctional compound having three or more ethylenically unsaturated bonds, even if the number of active species generated from the photoinitiator is small, the molecular weight of the polymer formed by crosslinking in the layer of the photosensitive resin composition increases, resulting in high etching liquid resistance. On the other hand, when the exposure amount is 30 mJ / cm 2 In the following case (when the exposure amount is small), if a polyfunctional compound is not used, the number of reaction points is small, so it is difficult for the molecular weight of the polymer formed by crosslinking in the layer of the photosensitive resin composition to increase, and high etching liquid resistance cannot be obtained. Also, when the exposure amount that gives 15 steps as the remaining steps when the layer of the photosensitive resin composition is exposed and developed using a 41-step tablet is 30 mJ / cm 2 Exceeding this value (when the exposure amount is large), the number of active species generated from the photoinitiator is large. In this case, if a polyfunctional compound is not used, although the number of reaction points is small, since the number of active species is large, high etching liquid resistance may be obtained by increasing the molecular weight of the polymer formed by crosslinking in the layer of the photosensitive resin composition. On the other hand, when the exposure amount is 30 mJ / cm 2 Exceeding this value (when the exposure amount is large), if a polyfunctional compound is used, the number of reaction points increases in a state where the number of active species is large, so it is difficult for the molecular weight of the polymer formed by crosslinking in the layer of the photosensitive resin composition to increase, and high etching liquid resistance cannot be obtained.

[0017] A step tablet is a light-shielded component whose optical density increases in steps. When a step tablet is placed on a layer of a photosensitive resin composition, and the layer of the photosensitive resin composition is exposed and then developed, the number of steps on which the cured product of the photosensitive resin composition peels off changes depending on the sensitivity of the photosensitive resin composition. In the first embodiment, a 41-step tablet (density range 0.00 to 2.00, density step 0.05, tablet size 20 mm × 187 mm, size of each step 3 mm × 12 mm) is used. A light-transmitting component, such as a support for a photosensitive element, may be placed between the step tablet and the layer of the photosensitive resin composition.

[0018] Exposure and development for evaluating exposure amount a can be performed under atmospheric pressure. Exposure can be performed using a direct-writing exposure machine at room temperature (25°C). Development can be performed by spray development, with a spray pressure of 0.15 MPa. A 1% by mass aqueous solution of sodium carbonate at 30°C can be used as the developer. A full-cone type nozzle can be used. The distance between the object to be processed and the nozzle tip can be 6 cm.

[0019] The exposure dose a is 30 mJ / cm². 2 The following is the result: 28 mJ / cm² 2 Below, 25mJ / cm 2 Below, 23mJ / cm 2 Below, 22mJ / cm 2 Below, 21mJ / cm 2 Below, 20mJ / cm 2 Below, 19mJ / cm 2 Below, 18mJ / cm 2 Below, 17mJ / cm 2 Below, 16mJ / cm 2 Below, 15mJ / cm 2 The following, or 14 mJ / cm² 2 The following may apply: Exposure dose a is 5 mJ / cm². 2 More than 8mJ / cm 2 More than 10mJ / cm 2 More than 12mJ / cm 2 More than 14mJ / cm 2More than 15mJ / cm 2 More than 16mJ / cm 2 More than 17mJ / cm 2 More than 18mJ / cm 2 More than 19mJ / cm 2 More than 20mJ / cm 2 More than 21mJ / cm 2 More than 22mJ / cm 2 Above, 23mJ / cm 2 More than 25mJ / cm 2 Above or above, or 28 mJ / cm² 2 The above is sufficient. From these perspectives, the exposure dose a is 5-30 mJ / cm². 2 This may be the case. The exposure amount a can be adjusted by the type or content of the photopolymerization initiator, the type or content of the polymerization inhibitor, etc.

[0020] Regarding the photosensitive resin composition according to the second embodiment, the inventors speculate that the factors for obtaining excellent etching resistance in the cured product while achieving excellent sensitivity are as follows. However, the factors are not limited to those described below. In other words, in the photosensitive resin composition according to the second embodiment, by using a specific photopolymerizable compound having three or more ethylenically unsaturated bonds, 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane, and an acridine compound in combination, an appropriate amount of active species is generated from the photopolymerization initiator, thereby obtaining excellent sensitivity, and a sufficient number of reaction sites can be secured, thus obtaining high resistance to etching solutions.

[0021] The photosensitive resin composition according to this embodiment may be liquid or may be a photosensitive film (film-like). The photosensitive resin composition according to this embodiment is photocurable, and a cured product can be obtained by photocuring the photosensitive resin composition. 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. The shape of the cured product pattern that can be obtained with the photosensitive resin composition according to this embodiment is not particularly limited. The photosensitive resin composition according to this embodiment can be used to form a resist pattern, and the resist pattern may be removed after processing using the resist pattern (for example, etching of a component such as a metal layer placed beneath the resist pattern).

[0022] The thickness of the photosensitive resin composition layer (e.g., photosensitive film) or cured product may be within the following ranges. From the viewpoint of easily obtaining excellent etching resistance in the cured product, the thickness of the photosensitive resin composition layer or cured product may be 100 μm or less, 80 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 pattern of sufficient thickness, the thickness of the photosensitive resin composition layer or cured product may be 1 μm or more, 3 μm or more, 5 μm or more, 8 μm or more, 10 μm or more, 15 μm or more, 20 μm or more, or 25 μm or more. From these viewpoints, the thickness of the photosensitive resin composition layer or cured product may be 1 to 100 μm. The thickness of the photosensitive resin composition layer or cured product may be the average thickness of 10 locations. Regarding the thickness of the photosensitive resin composition layer, although the thickness at the time of exposure a measurement is 25 μm, any thickness can be adopted in other situations in which the photosensitive resin composition is used.

[0023] 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 with (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 a phenolic hydroxyl group.

[0024] Component (A) may contain an acrylic resin, from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product. 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) substantially consists of an acrylic resin), based on the total amount of component (A).

[0025] 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), (meth)acrylamide compounds (such as diacetone acrylamide), and glycidyl (meth)acrylate esters.

[0026] Component (A) may contain (meth)acrylic acid as a monomer unit, from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product. 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), from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product. 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, 21% by mass or more, 22% by mass or more, 23% by mass or more, 24% by mass or more, 25% by mass or more, 27% by mass or more, or 30% by mass or more. The monomer content of (meth)acrylic acid may be 50% by mass or less, less than 50% by mass, 45% by mass or less, 40% by mass or less, 37% 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, 24% by mass or less, 23% by mass or less, or 22% by mass or less. From these viewpoints, the monomer content of (meth)acrylic acid may be 1 to 50% by mass.

[0027] Component (A) may contain an alkyl (meth)acrylate as a monomer unit, from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product. 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 (e.g., 2-ethylhexyl group), nonyl group, decyl group, undecyl group, dodecyl group, etc., and the alkyl group may be various structural isomers. Component (A) may contain an alkyl (meth)acrylate having 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, 1 to 2, 2 to 8, 3 to 8, 4 to 8, or 6 to 8 carbon atoms in the alkyl group, from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product.

[0028] The alkyl group of (meth)acrylate may have substituents. Examples of substituents include hydroxyl groups, carboxyl groups, carboxylic acid bases, aldehyde groups, alkoxy groups (unsubstituted alkoxy groups (structures having an unsubstituted alkyl group bonded to an oxygen atom), or substituted alkoxy groups (such as hydroxyalkoxy groups)), carbonyl groups, alkoxycarbonyl groups, alkanoyl groups (such as alkanoyl groups with 2 to 12 carbon atoms), oxycarbonyl groups, carbonyloxy groups, amino groups, epoxy groups, furyl groups, cyano groups, halogeno groups (such as fluoro groups, chloro groups, and bromo groups), nitro groups, acetyl groups, sulfonyl groups, and sulfonamide groups. Examples of alkyl (meth)acrylates include hydroxyalkyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, α-chloro(meth)acrylic acid, and α-bromo(meth)acrylic acid.

[0029] 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 obtaining excellent sensitivity while easily obtaining excellent etching solution resistance in the cured product. 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, 53% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, or 76% 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, 76% 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, 53% by mass or less, 50% by mass or less, 45% by mass or less, or 40% by mass or less. From these viewpoints, the monomer content of alkyl (meth)acrylate may be 1 to 99% by mass.

[0030] Component (A) may contain a styrene compound (excluding compounds having a (meth)acryloyl group) as a monomer unit, from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product. Examples of styrene compounds include styrene and styrene derivatives. Examples of styrene derivatives include vinyltoluene and α-methylstyrene. Component (A) may contain (meth)acrylic acid and a styrene compound as monomer units, from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product, and may contain (meth)acrylic acid, alkyl (meth)acrylate and a styrene compound as monomer units.

[0031] If component (A) contains styrene compounds as monomer units, the content of monomer units of styrene compounds may be within the following ranges based on the total amount of monomer units constituting component (A), from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching solution resistance in the cured product. The content of monomer units of styrene compounds 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, more than 20% by mass, 21% by mass or more, 22% by mass or more, 23% by mass or more, 25% by mass or more, 27% by mass or more, or 30% by mass or more. The content of monomer units of styrene compounds may be 50% by mass or less, less than 50% by mass, 45% by mass or less, 40% by mass or less, 37% 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 monomeric content of the styrene compound may be 1 to 50% by mass, or 1 to 30% by mass.

[0032] 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.

[0033] In component (A), the content of monomer units of compound X1 that does not have aromatic hydrocarbon groups and alicyclic hydrocarbon groups may be within the following ranges based on the total amount of monomer units constituting component (A): The content of monomer units of compound X1 may be 80% by mass or less, less than 80% by mass, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, or 25% by mass or less. The content of monomer units of compound X1 may be 0% by mass or more, greater than 0% by mass, 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, or 25% by mass or more. From these viewpoints, the content of monomer units of compound X1 may be 0 to 80% by mass, greater than 0% by mass and 80% by mass or less, 5 to 60% by mass, or 10 to 40% by mass.

[0034] The weight-average molecular weight (Mw) of component (A) may be within the following range, from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching solution resistance in the cured product. The weight-average molecular weight of component (A) is 1.0 × 10 4 The above is 2.0 × 10 4 The above is 2.5 × 10 4 The above is 3.0 × 10 4 The above is 3.0 × 10 4 Super, 3.1×10 4 The above is 3.3 × 10 4 The above is 3.5 × 10 4 The above is 4.0 × 10 4 The above is 4.5 × 10 4 The above is 4.7 × 10 4 The above, or 5.0 × 10 4 The above is acceptable. (A) The weight-average molecular weight of component is 10 × 10 4 Below, 8.0 × 10 4 Below, 7.0 × 10 4 Below, 7.0 × 10 4 Less than 6.5 × 10 4 Below, 6.0 × 10 4 Below, 5.5 × 10 4 Below, 5.0 × 10 4 Below, 4.7 × 10 4 Below, 4.5 × 10 4 Below, 4.0 × 10 4 Below, 3.5 × 104 The following, or 3.0 × 10 4 The following may be true. From these perspectives, the weight-average molecular weight of component (A) is 1.0 × 10⁻⁶. 4 ~10×10 4 , 2.0×10 4 ~6.0×10 4 , or 3.0 × 10 4 ~5.0×10 4 That's fine.

[0035] The weight-average molecular weight can be measured, for example, by gel permeation chromatography (GPC) using a calibration curve for standard polystyrene. More specifically, it can be measured under the conditions described in the examples. For compounds with low molecular weight, if it is difficult to measure the weight-average molecular weight using the above-described method, the molecular weight can be measured by other methods and its average value can be calculated.

[0036] (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 obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product. 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, or 50% 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, or 55% by mass or less. From these viewpoints, the content of component (A) may be 10-90% by mass, 30-80% by mass, or 40-70% by mass.

[0037] From the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching solution resistance in the cured product, the content of component (A) may be in the following ranges relative to 100 parts by mass of the total of components (A) and (B): The content of component (A) may be 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, 45 parts by mass or more, 50 parts by mass or more, 54 parts by mass or more, 55 parts by mass or more, or 56 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, 60 parts by mass or less, 56 parts by mass or less, 55 parts by mass or less, or 54 parts by mass or less. From these viewpoints, the content of component (A) may be 10 to 90 parts by mass, 30 to 80 parts by mass, or 40 to 70 parts by mass.

[0038] In the photosensitive resin composition according to this embodiment, the content of the resin having phenolic hydroxyl groups may be 30% by mass or less, less than 30% by mass, 20% by mass or less, 10% by mass or less, 5% by mass or less, 1% by mass or less, or 0.1% by mass or less, based on the total amount of the photosensitive resin composition (total amount of solids). The photosensitive resin composition according to this embodiment does not need to contain the resin having phenolic hydroxyl groups (the above-mentioned content may be substantially 0% by mass).

[0039] The photosensitive resin composition according to this embodiment contains a photopolymerizable compound as component (B). The photopolymerizable compound is a compound that polymerizes upon exposure to light and may be a compound having an ethylenically unsaturated bond.

[0040] Component (B) includes a polyfunctional compound having three or more ethylenically unsaturated bonds as component (b1). Component (B) may include a (meth)acrylic acid compound having three or more (meth)acryloyl groups (trifunctional or more (meth)acrylic acid compounds: compounds in which the total number of acryloyl groups and methacryloyl groups is three or more) as component (b1) from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching solution resistance in the cured product.

[0041] Component (B) may include a polyfunctional compound as component (b1) having a number of ethylenically unsaturated bonds within the following ranges: The number of ethylenically unsaturated bonds in component (b1) is 3 or more, and may be 4 or more, 5 or more, or 6 or more, from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product. The number of ethylenically unsaturated bonds in component (b1) may be 10 or less, 8 or less, 6 or less, 5 or less, or 4 or less. From these viewpoints, the number of ethylenically unsaturated bonds in component (b1) may be 3 to 10.

[0042] Component (B) may contain a polyfunctional compound having three ethylenically unsaturated bonds as component (b1), or a polyfunctional compound having six ethylenically unsaturated bonds, from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product. Component (B) may contain two or more types of component (b1), and from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product, it may contain a polyfunctional compound having three ethylenically unsaturated bonds and a polyfunctional compound having six ethylenically unsaturated bonds.

[0043] The number of (meth)acryloyl groups in component (b1) (total of acryloyl and methacryloyl groups) may be 3 or more, 4 or more, 5 or more, or 6 or more, from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product. The number of (meth)acryloyl groups in component (b1) may be 10 or less, 8 or less, 6 or less, 5 or less, or 4 or less. From these viewpoints, the number of (meth)acryloyl groups in component (b1) may be 3 to 10.

[0044] (b1) Components include trimethylolpropane tri(meth)acrylate; alkylene oxide-modified trimethylolpropane tri(meth)acrylate such as EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO·PO-modified trimethylolpropane tri(meth)acrylate; tetramethylolmethane tri(meth)acrylate; tetramethylolmethane tetra(meth)acrylate; pentaerythritol tetra(meth)acrylate; EO-modified pentaerythritol tetra(meth)acrylate Examples include alkylene oxide-modified pentaerythritol tetra(meth)acrylate such as PO-modified pentaerythritol tetra(meth)acrylate and EO-PO-modified pentaerythritol tetra(meth)acrylate; dipentaerythritol hexa(meth)acrylate; alkylene oxide-modified dipentaerythritol hexa(meth)acrylate such as EO-modified dipentaerythritol hexa(meth)acrylate, PO-modified dipentaerythritol hexa(meth)acrylate, and EO-PO-modified dipentaerythritol hexa(meth)acrylate. In the photosensitive resin composition according to the first embodiment, component (B) may, from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching solution resistance in the cured product, contain at least one selected from the group consisting of trimethylolpropane tri(meth)acrylate, alkylene oxide-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and alkylene oxide-modified dipentaerythritol hexa(meth)acrylate, and may contain alkylene oxide-modified trimethylolpropane tri(meth)acrylate. In the photosensitive resin composition according to the second embodiment, component (B) includes at least one selected from the group consisting of trimethylolpropane tri(meth)acrylate, alkylene oxide-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and alkylene oxide-modified dipentaerythritol hexa(meth)acrylate, and may include alkylene oxide-modified trimethylolpropane tri(meth)acrylate.

[0045] Component (B) may include, from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching solution resistance in the cured product, a (meth)acrylic acid compound having a polyoxyalkylene group as component (b1), and may include at least one selected from the group consisting of alkylene oxide-modified trimethylolpropane tri(meth)acrylate and alkylene oxide-modified dipentaerythritol hexa(meth)acrylate, and may include at least one selected from the group consisting of EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO·PO-modified trimethylolpropane tri(meth)acrylate, EO-modified dipentaerythritol hexa(meth)acrylate, PO-modified dipentaerythritol hexa(meth)acrylate, and EO·PO-modified dipentaerythritol hexa(meth)acrylate.

[0046] (b1) The molecular weight of component (b1) may be within the following ranges from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching solution resistance in the cured product. The molecular weight may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 600 or more, 700 or more, 750 or more, 800 or more, 900 or more, 1000 or more, 1100 or more, or 1200 or more. The molecular weight may be 10000 or less, less than 10000, 8000 or less, 6000 or less, 5000 or less, 3000 or less, 2000 or less, 1500 or less, 1300 or less, 1200 or less, 1100 or less, 1000 or less, 900 or less, 800 or less, 750 or less, 700 or less, 600 or less, or 500 or less. From these viewpoints, the molecular weight may be between 100 and 10000.

[0047] (b1) The concentration of (meth)acryloyl groups in component (total number of (meth)acryloyl groups in one molecule / molecular weight; the same applies hereinafter) may be within the following range, from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product. The (meth)acryloyl group concentration is 1 × 10 -3 The above is 2 x 10 -3 The above is 3 x 10 -3 The above is 4 x 10-3 The above 5 x 10 -3 The above 6 x 10 -3 The above, or 7 x 10 -3 The above is acceptable. The (meth)acryloyl group concentration is 1 × 10⁻⁶ -2 Below, 9 x 10 -3 Below, 8 x 10 -3 Below, 7 x 10 -3 Below, 6 x 10 -3 Below, 5 x 10 -3 Below, 4 x 10 -3 The following, or 3 x 10 -3 The following may be the case. From these viewpoints, the (meth)acryloyl group concentration is 1 × 10 -3 ~1 × 10 -2 That's fine.

[0048] The content of component (b1) is greater than 0% by mass, based on the total amount of component (B), and may be within the following ranges from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product. The content of component (b1) may be 1% by mass or more, 2% by mass or more, 3% by mass or more, 4% by mass or more, 5% by mass or more, 8% by mass or more, 10% by mass or more, 15% by mass or more, 18% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more. The content of component (b1) may be 50% by mass or less, less than 50% by mass, 40% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, 10% by mass or less, 8% by mass or less, or 5% by mass or less. From these viewpoints, the content of component (b1) may be greater than 0% by mass and 50% by mass or less, 1 to 40% by mass, or 3 to 30% by mass.

[0049] The content of component (b1) is greater than 0% by mass based on the total amount (total amount of solids) of the photosensitive resin composition and may be within the following ranges from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product. The content of component (b1) may be 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 2% by mass or more, 3% by mass or more, 5% by mass or more, 7% by mass or more, 8% by mass or more, 9% by mass or more, 10% by mass or more, 12% by mass or more, or 13% by mass or more. The content of component (b1) may be 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 13% 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% by mass or less, 5% by mass or less, 3% by mass or less, or 2% by mass or less. From these perspectives, the content of component (b1) may be greater than 0% by mass and less than or equal to 30% by mass, between 0.1% and 20% by mass, or between 1% and 10% by mass.

[0050] The content of component (b1) is greater than 0 parts by mass relative to 100 parts by mass of the total of components (A) and (B), and may be within the following ranges from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product. The content of component (b1) may be 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 4 parts by mass or more, 5 parts by mass or more, 6 parts by mass or more, 7 parts by mass or more, 8 parts by mass or more, 9 parts by mass or more, 10 parts by mass or more, 12 parts by mass or more, or 14 parts by mass or more. The content of component (b1) may be 30 parts by mass or less, 25 parts by mass or less, 20 parts by mass or less, 15 parts by mass or less, 14 parts by mass or less, 12 parts by mass or less, 10 parts by mass or less, 9 parts by mass or less, 8 parts by mass or less, 7 parts by mass or less, 6 parts by mass or less, 5 parts by mass or less, 4 parts by mass or less, 3 parts by mass or less, or 2 parts by mass or less. From these perspectives, the content of component (b1) may be greater than 0 parts by mass and less than or equal to 30 parts by mass, 0.1 to 20 parts by mass, or 1 to 10 parts by mass.

[0051] In the photosensitive resin composition according to the first embodiment, component (B) may include a photopolymerizable compound that does not correspond to component (b1) as component (b2). In the photosensitive resin composition according to the second embodiment, component (B) includes 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane as described later as component (b2), and may further include a photopolymerizable compound that does not correspond to component (b1) and 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane.

[0052] (b2) Component may be a compound having an ethylenically unsaturated bond (a monofunctional compound having one ethylenically unsaturated bond, or a compound having two ethylenically unsaturated bonds), and may be a compound having a (meth)acryloyl group ((meth)acrylic acid compound). Examples of (b2) component include bisphenol A type (meth)acrylic acid compound, EO-modified di(meth)acrylate, PO-modified di(meth)acrylate, EO·PO-modified di(meth)acrylate, polyalkylene glycol di(meth)acrylate (polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc.), EO-modified polyalkylene glycol di(meth)acrylate, PO-modified polyalkylene glycol di(meth)acrylate, EO·PO-modified polyalkylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, noni Examples include chlorophenol alkylene oxide-modified (meth)acrylates (e.g., nonylphenol EO-modified (meth)acrylate (also known as nonylphenoxypolyethylene oxy(meth)acrylate)), phthalate compounds (γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate (also known as 1-(3-chloro-2-hydroxypropyl)2-[2-((meth)acryloyloxy)ethyl phthalate])), alkyl (meth)acrylates, and photopolymerizable compounds having at least one cationically polymerizable cyclic ether group in the molecule (such as oxetane compounds). Component (B) may contain a bisphenol A type (meth)acrylic acid compound as component (b2) from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching solution resistance in the cured product.

[0053] Component (B) may contain a (meth)acrylic acid compound having a polyoxyalkylene group as component (b2) from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching solution resistance in the cured product, and may also contain a bisphenol A type (meth)acrylic acid compound having a polyoxyalkylene group. Examples of bisphenol A type (meth)acrylic acid compounds having a polyoxyalkylene group include 2,2-bis(4-((meth)acryloxypolyethoxy)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.

[0054] Component (B) may contain 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane with an ethylene oxide addition number within the following ranges, from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching solution resistance in the cured product. The number of ethylene oxide additions may be 2 mol or more, 4 mol or more, 6 mol or more, 8 mol or more, or 10 mol or more. The number of ethylene oxide additions may be 20 mol or less, 16 mol or less, 12 mol or less, 10 mol or less, 8 mol or less, 6 mol or less, or 4 mol or less. From these viewpoints, the number of ethylene oxide additions may be 2 to 20 mol, 2 to 12 mol, 2 to 10 mol, 2 to 8 mol, 6 to 20 mol, 6 to 12 mol, or 6 to 10 mol.

[0055] In the photosensitive resin composition according to the first embodiment, from the viewpoint of easily obtaining excellent etching liquid resistance in the cured product while obtaining excellent sensitivity, the component (B) may contain 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, and may contain 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, and may contain 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane. In the photosensitive resin composition according to the second embodiment, the component (B) contains 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane, and from the viewpoint of easily obtaining excellent etching liquid resistance in the cured product while obtaining excellent sensitivity, it may contain 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane and 2,2-bis(4-((meth)acryloxydiethoxy)phenyl)propane.

[0056] (b2) The molecular weight of the component (for example, bisphenol A type (meth)acrylic acid compound) may be in the following range from the viewpoint of easily obtaining excellent etching liquid resistance in the cured product while obtaining excellent sensitivity. The molecular weight may be 100 or more, 200 or more, 300 or more, 400 or more, 450 or more, 500 or more, 550 or more, 600 or more, 650 or more, 700 or more, 750 or more, or 800 or more. The molecular weight may be 10000 or less, less than 10000, 8000 or less, 6000 or less, 5000 or less, 3000 or less, 2000 or less, 1500 or less, 1000 or less, or 900 or less. From these viewpoints, the molecular weight may be 100 to 10000.

[0057] (b2) The (meth)acryloyl group concentration of the component (for example, bisphenol A type (meth)acrylic acid compound) may be in the following range from the viewpoint of easily obtaining excellent etching liquid resistance in the cured product while obtaining excellent sensitivity. The (meth)acryloyl group concentration is 1×10 -4 or more, 5×10 -4 or more, 1×10 -3 or more, 1.5×10 -32×10 or more -3 2.4×10 or more -3 It may be the above. The (meth)acryloyl group concentration is 1×10 -2 or less, 9×10 -3 or less, 8×10 -3 or less, 7×10 -3 or less, 6×10 -3 or less, 5×10 -3 or less, 4×10 -3 or less, or 3×10 -3 or less. From these viewpoints, the (meth)acryloyl group concentration may be 1×10 -4 to 1×10 -2 It may be so.

[0058] The content of the bisphenol A type (meth)acrylic acid compound is less than 100% by mass based on the total amount of the component (B), and from the viewpoint of easily obtaining excellent etching liquid resistance in the cured product while obtaining excellent sensitivity, it may be in the following range. The content of the bisphenol A type (meth)acrylic acid compound may be 50% by mass or more, more than 50% by mass, 60% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 82% by mass or more, 85% by mass or more, 90% by mass or more, 92% by mass or more, or 95% by mass or more. The content of the bisphenol A type (meth)acrylic acid compound may be 99% by mass or less, 98% by mass or less, 97% by mass or less, 96% by mass or less, 95% by mass or less, 92% by mass or less, 90% by mass or less, 85% by mass or less, 82% by mass or less, 80% by mass or less, 75% by mass or less, or 70% by mass or less. From these viewpoints, the content of the bisphenol A type (meth)acrylic acid compound may be 50% by mass or more and less than 100% by mass, 60 - 99% by mass, or 70 - 97% by mass.

[0059] The content of bisphenol A type (meth)acrylic acid compound is less than 100% by mass based on the total amount (total amount of solids) of the photosensitive resin composition, and may be within the following range from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product. The content of bisphenol A type (meth)acrylic acid 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, 25% by mass or more, 30% by mass or more, 32% by mass or more, 35% by mass or more, 36% by mass or more, 37% by mass or more, 38% by mass or more, or 40% by mass or more. The content of bisphenol A type (meth)acrylic acid compounds may be 80% by mass or less, 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, 38% by mass or less, 37% by mass or less, 36% by mass or less, 35% by mass or less, or 32% by mass or less. From these viewpoints, the content of bisphenol A type (meth)acrylic acid compounds may be 1% by mass or more and less than 100% by mass, 1 to 80% by mass, 10 to 70% by mass, or 30 to 50% by mass.

[0060] The content of the bisphenol A type (meth)acrylic acid compound may be within the following ranges relative to 100 parts by mass of the total of components (A) and (B), from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching solution resistance in the cured product. The content of the bisphenol A type (meth)acrylic acid 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, 25 parts by mass or more, 30 parts by mass or more, 32 parts by mass or more, 35 parts by mass or more, 36 parts by mass or more, 37 parts by mass or more, 38 parts by mass or more, 39 parts by mass or more, 40 parts by mass or more, 41 parts by mass or more, 42 parts by mass or more, or 44 parts by mass or more. The content of the bisphenol A type (meth)acrylic acid compound may be 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 45 parts by mass or less, 44 parts by mass or less, 42 parts by mass or less, 41 parts by mass or less, 40 parts by mass or less, 39 parts by mass or less, 38 parts by mass or less, 37 parts by mass or less, 36 parts by mass or less, 35 parts by mass or less, or 32 parts by mass or less. From these viewpoints, the content of the bisphenol A type (meth)acrylic acid compound may be 1 to 80 parts by mass, 10 to 70 parts by mass, or 30 to 50 parts by mass.

[0061] The content of monofunctional compounds having one ethylenically unsaturated bond may be within the following ranges based on the total amount of component (B). From the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product, the content of monofunctional compounds may be 20% by mass or less, 15% by mass or less, 12% by mass or less, 10% by mass or less, 5% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, 0.1% by mass or less, or 0.01% by mass or less. The content of monofunctional compounds may be 0% by mass or more, greater than 0% by mass, 0.01% by mass or more, 0.1% by mass or more, 1% by mass or more, 2% by mass or more, 3% by mass or more, 5% by mass or more, or 10% by mass or more. From these viewpoints, the content of monofunctional compounds may be 0 to 20% by mass, 0 to 10% by mass, or 5 to 20% by mass.

[0062] The content of monofunctional compounds having one ethylenically unsaturated bond may be within the following ranges based on the total amount (total solid content) of the photosensitive resin composition. From the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product, the content of monofunctional compounds may be 10% by mass or less, 8% by mass or less, 5% by mass or less, 4% by mass or less, 3% by mass or less, 1% by mass or less, less than 1% by mass, 0.1% by mass or less, or 0.01% by mass or less. The content of monofunctional compounds may be 0% by mass or more, greater than 0% by mass, 0.01% by mass or more, 0.1% by mass or more, 1% by mass or more, 3% by mass or more, or 4% by mass or more. From these viewpoints, the content of monofunctional compounds may be 0 to 10% by mass, 0 to 4% by mass, or 0% by mass or more and less than 1% by mass.

[0063] The content of the monofunctional compound having one ethylenically unsaturated bond may be within the following ranges relative to 100 parts by mass of the total of components (A) and (B). From the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product, the content of the monofunctional compound may be 10 parts by mass or less, 8 parts by mass or less, 5 parts by mass or less, 4 parts by mass or less, 3 parts by mass or less, 1 part by mass or less, less than 1 part by mass, 0.1 parts by mass or less, or 0.01 parts by mass or less. The content of the monofunctional compound may be 0 parts by mass or more, greater than 0 parts by mass, 0.01 parts by mass or more, 0.1 parts by mass or more, 1 part by mass or more, 3 parts by mass or more, 4 parts by mass or more, or 5 parts by mass or more. From these viewpoints, the content of the monofunctional compound may be 0 to 10 parts by mass, 0 to 4 parts by mass, or 0 parts by mass or more but less than 1 part by mass.

[0064] The content of component (B) may be within the following ranges based on the total amount (total amount of solids) of the photosensitive resin composition, from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product. The content of component (B) may be 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, or 43% by mass or more. The content of component (B) may be 90% by mass or less, 80% by mass or less, 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, or 45% by mass or less. From these viewpoints, the content of component (B) may be 10-90% by mass, 20-70% by mass, or 30-60% by mass.

[0065] From the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching solution resistance in the cured product, the content of component (B) may be in the following ranges relative to 100 parts by mass of the total of components (A) and (B): 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, 40 parts by mass or more, 44 parts by mass or more, 45 parts by mass or more, or 46 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, or 44 parts by mass or less. From these viewpoints, the content of component (B) may be 10 to 90 parts by mass, 20 to 70 parts by mass, or 30 to 60 parts by mass.

[0066] In the photosensitive resin composition according to this embodiment, the content of the (meth)acrylic acid compound having an isocyanuryl ring structure, or the content of the photopolymerizable compound having an ethylenically unsaturated group and an isocyanuryl ring structure, may be 1 part by mass or less, less than 1 part by mass, 0.1 parts by mass or less, 0.01 parts by mass or less, or 0.001 parts by mass or less, per 100 parts by mass of the total of components (A) and (B). The photosensitive resin composition according to this embodiment does not need to contain the (meth)acrylic acid compound having an isocyanuryl ring structure (the above-mentioned content may be substantially 0 parts by mass), and does not need to contain the photopolymerizable compound having an ethylenically unsaturated group and an isocyanuryl ring structure (the above-mentioned content may be substantially 0 parts by mass).

[0067] In the photosensitive resin composition according to this embodiment, the content of at least one selected from the group consisting of a photopolymerizable compound having a pentaerythritol-derived skeleton and a photopolymerizable compound having a dipentaerythritol-derived skeleton may be 3 parts by mass or less, less than 3 parts by mass, 1 part by mass or less, 0.1 parts by mass or less, or 0.01 parts by mass or less, per 100 parts by mass of the total of components (A) and (B). The photosensitive resin composition according to this embodiment does not have to contain at least one selected from the group consisting of a photopolymerizable compound having a pentaerythritol-derived skeleton and a photopolymerizable compound having a dipentaerythritol-derived skeleton (the content may be substantially 0 parts by mass per 100 parts by mass of the total of components (A) and (B)). In the photosensitive resin composition according to this embodiment, the content of at least one selected from the group consisting of (meth)acrylic acid compounds having a pentaerythritol-derived skeleton and (meth)acrylic acid compounds having a dipentaerythritol-derived skeleton may be 3 parts by mass or less, less than 3 parts by mass, 1 part by mass or less, 0.1 parts by mass or less, or 0.01 parts by mass or less, per 100 parts by mass of the total of components (A) and (B). The photosensitive resin composition according to this embodiment does not have to contain at least one selected from the group consisting of (meth)acrylic acid compounds having a pentaerythritol-derived skeleton and (meth)acrylic acid compounds having a dipentaerythritol-derived skeleton (the content may be substantially 0 parts by mass per 100 parts by mass of the total of components (A) and (B)).

[0068] In the photosensitive resin composition according to this embodiment, the content of the bisphenol F type (meth)acrylic acid compound may be 5% by mass or less, less than 5% by mass, 1% by mass or less, less than 1% by mass, 0.1% by mass or less, or substantially 0% by mass, based on the total amount of component (B). In the photosensitive resin composition according to this embodiment, the content of the bisphenol F type (meth)acrylic acid compound may be 0.2% by mass or less, 0.15% by mass or less, less than 0.15% by mass, 0.1% by mass or less, or 0.01% by mass or less, based on the total amount of the photosensitive resin composition (total amount of solids). The photosensitive resin composition according to this embodiment does not need to contain the bisphenol F type (meth)acrylic acid compound (the above-mentioned content may be substantially 0% by mass).

[0069] In the photosensitive resin composition according to this embodiment, the content of the epoxy compound having two or more oxirane rings may be 20 parts by mass or less, less than 20 parts by mass, 10 parts by mass or less, less than 10 parts by mass, 1 part by mass or less, or substantially 0 parts by mass, per 100 parts by mass of component (A). The photosensitive resin composition according to this embodiment does not need to contain an epoxy compound having two or more oxirane rings (the content of the epoxy compound having two or more oxirane rings may be substantially 0% by mass based on the total amount of the photosensitive resin composition (total amount of solids)).

[0070] The photosensitive resin composition according to this embodiment contains a photopolymerization initiator as component (C).

[0071] (C) Components include acridine compounds such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine compounds such as N-phenylglycine and N-phenylglycine derivatives; hexaarylbiimidazole compounds; benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, 2-methyl- Examples include aromatic ketones such as 1-[4-(methylthio)phenyl]-2-morpholino-propanone-1; quinone compounds such as alkylanthraquinones; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkylbenzoin; benzyl derivatives such as benzyldimethylketal; bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; bis(2,6-dimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide; and (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide.

[0072] The hexaarylbiimidazole compound may be a 2,4,5-triarylimidazole dimer. Examples of 2,4,5-triarylimidazole dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer. From the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product, the hexaarylbiimidazole compound may contain a 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, and may also contain 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

[0073] In the photosensitive resin composition according to the first embodiment, component (C) may contain an acridine compound, an N-phenylglycine compound, or a hexaarylbiimidazole compound. Component (C) may contain at least one selected from the group consisting of acridine compounds, N-phenylglycine compounds, and hexaarylbiimidazole compounds, or at least one selected from the group consisting of acridine compounds and N-phenylglycine compounds, or at least one acridine compound and an N-phenylglycine compound, from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching solution resistance in the cured product. By using at least one selected from the group consisting of acridine compounds and N-phenylglycine compounds, the exposure amount a can be easily reduced.

[0074] In the photosensitive resin composition according to the second embodiment, component (C) comprises an acridine compound and may further comprise a photopolymerization initiator other than the acridine compound. Component (C) may comprise an acridine compound and an N-phenylglycine compound, from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching solution resistance in the cured product.

[0075] In the photosensitive resin composition according to this embodiment, the total amount of the acridine compound and the N-phenylglycine compound 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 (in an embodiment in which component (C) substantially consists of the acridine compound and the N-phenylglycine compound), based on the total amount of component (C), from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching solution resistance in the cured product.

[0076] From the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product, the acridine compound content may be within the following ranges based on the total amount of component (C): The acridine compound content may be 50% by mass or more, more than 50% by mass, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 96% by mass or more, 97% by mass or more, 98% by mass or more, 98.5% by mass or more, or 99% by mass or more. The acridine compound content may be 100% by mass or less, less than 100% by mass, 99% by mass or less, 98% by mass or less, 97% by mass or less, 96% by mass or less, or 95% by mass or less. From these viewpoints, the acridine compound content may be 50 to 100% by mass.

[0077] From the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching solution resistance in the cured product, the content of the N-phenylglycine compound may be within the following ranges based on the total amount of component (C): The content of the N-phenylglycine compound may be greater than 0% by mass, 1% or more by mass, 2% or more by mass, 3% or more by mass, 4% or more by mass, or 5% or more by mass. The content of the N-phenylglycine compound may be 50% or less by mass, less than 50% by mass, 30% or less by mass, 20% or less by mass, 10% or less by mass, 5% or less by mass, 4% or less by mass, 3% or less by mass, 2% or less by mass, or 1.5% or less by mass. From these viewpoints, the content of the N-phenylglycine compound may be greater than 0% by mass and 50% or less by mass.

[0078] The content of component (C) may be within the following ranges based on the total amount (total amount of solids) of the photosensitive resin composition, from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching solution resistance in the cured product. The content of component (C) may be 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 0.8% by mass or more, 0.9% by mass or more, 1% by mass or more, 1.1% by mass or more, 1.2% 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, or 3.5% by mass or more. The content of component (C) may be 10% by mass or less, 5% by mass or less, 3.5% by mass or less, 3% by mass or less, 2.5% by mass or less, 2% by mass or less, 1.5% by mass or less, 1.2% by mass or less, 1.1% by mass or less, 1% by mass or less, 0.9% by mass or less, 0.8% by mass or less, or 0.5% by mass or less. From these perspectives, the content of component (C) may be 0.1 to 10% by mass.

[0079] The content of component (C) may be within the following ranges relative to 100 parts by mass of the total of components (A) and (B), from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching solution resistance in the cured product. The content of component (C) may be 0.1 parts by mass or more, 0.3 parts by mass or more, 0.5 parts by mass or more, 0.8 parts by mass or more, 0.9 parts by mass or more, 1 part by mass or more, 1.1 parts by mass or more, 1.2 parts by mass or more, 1.3 parts 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, or 4 parts by mass or more. The content of component (C) may be 10 parts by mass or less, 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, 2 parts by mass or less, 1.5 parts by mass or less, 1.3 parts by mass or less, 1.2 parts by mass or less, 1.1 parts by mass or less, 1 part by mass or less, 0.9 parts by mass or less, 0.8 parts 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 10 parts by mass.

[0080] The photosensitive resin composition according to this embodiment may contain a polymerization inhibitor (excluding compounds corresponding to any of components (A) to (C)), or it may not contain a polymerization inhibitor. Examples of polymerization inhibitors include catechol compounds (e.g., tert-butylcatechol such as 4-tert-butylcatechol), hindered amines (e.g., 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl), and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl.

[0081] The photosensitive resin composition according to this embodiment may contain an organic solvent (excluding compounds corresponding to any of components (A) to (C)). Examples of organic solvents include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, and propylene glycol monomethyl ether.

[0082] The photosensitive resin composition according to this embodiment may contain other components (excluding compounds corresponding to any of components (A) to (C)). Other components include hydrogen donors (bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, leucocrystal violet, N-phenylglycine, etc.), dyes (malachite green, etc.), tribromophenylsulfone, tribromomethylphenylsulfone, vinyl polymers, oxetane compounds, anthracene compounds (9,10-dibutoxyanthracene, etc.), distylylbenzene compounds, naphthalene compounds, nitroxyl compounds, mercapto compounds (compounds having a mercapto group, such as 2-mercaptobenzimidazole), sensitizers, photochromicants, thermal color inhibitors, plasticizers (p-toluenesulfonamide, etc.), pigments, fillers, defoamers, flame retardants, stabilizers, adhesion promoters, leveling agents, peel accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, and thermal radical polymerization initiators. The photosensitive resin composition according to this embodiment may contain tribromomethylphenylsulfone, from the viewpoint of obtaining excellent sensitivity while easily obtaining excellent etching resistance in the cured product.

[0083] In the photosensitive resin composition according to this embodiment, the content of the thermal radical polymerization initiator may be 0.5% by mass or less, less than 0.5% by mass, 0.1% by mass or less, 0.01% by mass or less, or 0.001% by mass or less, based on the total amount of the photosensitive resin composition (total amount of solids). The photosensitive resin composition according to this embodiment does not need to contain a thermal radical polymerization initiator (the above-mentioned content may be substantially 0% by mass).

[0084] In the photosensitive resin composition according to this embodiment, the content of at least one selected from the group consisting of vinyl polymers (e.g., vinyl polymers containing side chains having epoxy groups) and oxetane compounds (e.g., oxetane compounds having two or more oxetane rings which may have substituents) may be 20% by mass or less, less than 20% by mass, 10% by mass or less, 1% by mass or less, 0.1% by mass or less, 0.01% by mass or less, or 0.001% by mass or less, based on the total amount of the photosensitive resin composition (total amount of solids). The photosensitive resin composition according to this embodiment does not need to contain at least one selected from the group consisting of vinyl polymers (e.g., vinyl polymers containing side chains having epoxy groups) and oxetane compounds (e.g., oxetane compounds having two or more oxetane rings which may have substituents) (the above content may be substantially 0% by mass).

[0085] In the photosensitive resin composition according to this embodiment, the content of at least one selected from the group consisting of anthracene compounds, distylylbenzene compounds, and naphthalene compounds may be 0.01% by mass or less, less than 0.01% by mass, 0.001% by mass or less, or 0.0001% by mass or less, based on the total amount of the photosensitive resin composition (total amount of solids). The photosensitive resin composition according to this embodiment does not need to contain at least one selected from the group consisting of anthracene compounds, distylylbenzene compounds, and naphthalene compounds (the above-mentioned content may be substantially 0% by mass).

[0086] In the photosensitive resin composition according to this embodiment, the content of the nitroxyl compound may be 0.005 parts by mass or less, less than 0.005 parts by mass, 0.001 parts by mass or less, or 0.0001 parts by mass or less, based on 100 parts by mass of component (A), or 100 parts by mass of the total of components (A) and (B). The photosensitive resin composition according to this embodiment does not need to contain a nitroxyl compound (the above-mentioned content may be substantially 0 parts by mass).

[0087] In the photosensitive resin composition according to this embodiment, the content of the mercapto compound may be 0.1 parts by mass or less, less than 0.1 parts by mass, 0.001 parts by mass or less, less than 0.001 parts by mass, or 0.0001 parts by mass or less, based on 100 parts by mass of the total of components (A) and (B). The photosensitive resin composition according to this embodiment does not need to contain a mercapto compound (the above-mentioned content may be substantially 0 parts by mass).

[0088] In the photosensitive resin composition according to this embodiment, the content of compound X2, which has one ethylenically unsaturated bond and at least one selected from the group consisting of an aromatic hydrocarbon group and an alicyclic hydrocarbon group, and has a weight-average molecular weight of less than 20,000, may be 1 part by mass or less, less than 1 part by mass, 0.1 parts by mass or less, or 0.01 parts by mass or less, per 100 parts by mass of the total of components (A) and (B). The photosensitive resin composition according to this embodiment does not need to contain compound X2 (the above-mentioned content may be substantially 0 parts by mass). Compound X2 has one ethylenically unsaturated bond. The weight-average molecular weight of compound X2 can be measured by the same procedure as the weight-average molecular weight of component (A).

[0089] In the photosensitive resin composition according to this embodiment, the content of the acid-modified vinyl group-containing epoxy resin may be 20% by mass or less, less than 20% by mass, 10% by mass or less, 1% by mass or less, 0.1% by mass or less, or 0.01% by mass or less, based on the total amount of the photosensitive resin composition (total amount of solids). The photosensitive resin composition according to this embodiment does not need to contain the acid-modified vinyl group-containing epoxy resin (the above-mentioned content may be substantially 0% by mass). The acid-modified vinyl group-containing epoxy resin can be obtained by modifying an epoxy resin with an acid having vinyl groups.

[0090] In the photosensitive resin composition according to this embodiment, the content of the acylphosphine oxide-based photopolymerization initiator may be 0.2% by mass or less, less than 0.2% by mass, 0.1% by mass or less, 0.01% by mass or less, or 0.001% by mass or less, based on the total amount of the photosensitive resin composition (total amount of solids). The photosensitive resin composition according to this embodiment does not need to contain the acylphosphine oxide-based photopolymerization initiator (the above-mentioned content may be substantially 0% by mass).

[0091] <Photosensitive element> The photosensitive element according to this embodiment comprises a support and a photosensitive resin layer disposed on the support, wherein the photosensitive resin layer is a layer of the photosensitive resin composition according to this embodiment. The photosensitive element according to this embodiment may include a protective layer disposed on the photosensitive resin 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 in a roll shape on a core.

[0092] Figure 1 is a schematic cross-sectional view showing an example of a photosensitive element. As shown in Figure 1, the photosensitive element 1 comprises a support (support film) 2, a photosensitive resin layer 3 disposed on the support 2, and a protective layer (protective film) 4 disposed on the photosensitive resin layer 3. The photosensitive resin layer 3 is made of a photosensitive resin composition according to this embodiment.

[0093] The photosensitive element 1 can be obtained, for example, by the following procedure. First, a photosensitive resin layer 3 is formed on the support 2. The photosensitive resin layer 3 can be formed, for example, by applying a photosensitive resin composition containing an organic solvent and drying the resulting coating layer. Next, a protective layer 4 is placed on the photosensitive resin layer 3.

[0094] 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.

[0095] The thickness of the support may be 1 μm or more, 5 μm or more, 10 μm or more, or 15 μm or more, from the viewpoint of easily suppressing damage to the support when peeling the support from the photosensitive resin layer. The thickness of the support may be 100 μm or less, 50 μm or less, 30 μm or less, or 20 μm or less, from the viewpoint of easily exposing the support when exposure is performed through the support.

[0096] The thickness of the protective layer may be 1 μm or more, 5 μm or more, 10 μm or more, or 15 μm or more, from the viewpoint of easily suppressing damage to the protective layer when laminating the photosensitive resin layer and support onto the substrate while peeling off the protective layer. The thickness of the protective layer may be 100 μm or less, 50 μm or less, or 30 μm or less, from the viewpoint of easily improving productivity.

[0097] <Method for manufacturing laminates> The method for manufacturing a laminate according to this embodiment comprises a placement step (photosensitive resin layer placement step) in which a photosensitive resin layer (a layer of the photosensitive resin composition) is placed on a substrate using the photosensitive resin composition or the photosensitive element according to this embodiment; an exposure step in which a part of the photosensitive resin layer is photocured (exposed); and a developing step in which at least a part of the uncured portion (unexposed portion) of the photosensitive resin layer is removed to form a cured product pattern. The photosensitive resin composition in the placement step may be the photosensitive resin composition of the photosensitive element according to this embodiment. The laminate according to this embodiment is obtained by the method for manufacturing a laminate according to this embodiment and may be a wiring board (e.g., a printed circuit board). The laminate according to this embodiment may comprise a substrate and a cured product pattern (cured product according to this embodiment) placed on the substrate.

[0098] In the placement step, a photosensitive resin layer made of the photosensitive resin composition according to this embodiment is placed on the substrate. For example, the photosensitive resin layer may be formed by removing the protective layer from the photosensitive element and then pressing the photosensitive resin layer of the photosensitive element onto the substrate while heating it, or it may be formed by coating and drying the photosensitive resin composition on the substrate.

[0099] In the exposure process, an active light may be irradiated onto the photosensitive resin layer with a mask placed on it to expose and photocure the areas of the photosensitive resin layer other than the area where the mask is placed. Alternatively, without using a mask, an active light may be irradiated in a desired pattern using a direct writing exposure method such as LDI exposure or DLP exposure to expose and photocure a portion of the photosensitive resin layer. As a light source for the active light, an ultraviolet light source or a visible light source may be used, and examples include carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, xenon lamps, gas lasers (argon lasers, etc.), solid-state lasers (YAG lasers, etc.), and semiconductor lasers.

[0100] The development method in the development process may be, for example, wet development or dry development. Wet development can be performed using a developer corresponding to the photosensitive resin composition, for example, by methods such as dipping, paddle, spraying, brushing, slapping, scrubbing, or agitation immersion. The developer is appropriately selected according to the composition of the photosensitive resin composition and may be an alkaline developer or an organic solvent developer.

[0101] The alkaline developer may be an aqueous solution containing a base such as: alkali hydroxides such as lithium, sodium, or potassium hydroxide; alkali carbonates such as lithium, sodium, potassium, or ammonium carbonates or bicarbonates; alkali metal phosphates such as potassium phosphate and sodium phosphate; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; borax; sodium metasilicate; tetramethylammonium hydroxide; ethanolamine; ethylenediamine; diethylenetriamine; 2-amino-2-hydroxymethyl-1,3-propanediol; 1,3-diamino-2-propanol; or morpholine.

[0102] The organic solvent developer may contain organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

[0103] The substrate may have a metal layer, and the photosensitive resin layer may be in contact with the metal layer. In this case, the manufacturing method of the laminate according to this embodiment may include an etching step after the developing step, in which a portion of the metal layer is removed by etching the metal layer using a cured material pattern as a mask. In the etching step, portions of the metal layer where the cured material pattern has not been formed (portions that were covered with uncured portions of the metal layer) can be removed. The metal layer may contain, for example, copper. The etching solution may contain hydrochloric acid, or it may contain hydrochloric acid and cupric chloride.

[0104] The manufacturing method of the laminate according to this embodiment involves heating at 60 to 250°C or 0.2 to 10 J / cm² after the development step. 2 The system may include a step to further harden the resist pattern by exposure.

[0105] The manufacturing method of the laminate according to this embodiment may include a step of removing the cured material pattern after the etching step. The cured material pattern can be removed, for example, by developing using a strongly alkaline aqueous solution in an immersion method, spray method, or the like. [Examples]

[0106] The present disclosure will be further described below with reference to examples, but the present disclosure is not limited to these 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).

[0107] <Synthesis of binder polymers> (Binder Polymer A1) Solution (a) was prepared by mixing 22.0 parts by mass of methacrylic acid, 50.0 parts by mass of methyl methacrylate, 3.0 parts by mass of 2-ethylhexyl acrylate, 25.0 parts by mass of styrene, and 0.9 parts by mass of azobisisobutyronitrile. Solution (b) was prepared by dissolving 0.5 parts by mass of azobisisobutyronitrile in 100 parts by mass of acetone. Acetone was added to a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas inlet tube, and the flask was stirred while blowing nitrogen gas into it, raising the temperature to 80°C. Solution (a) was added to the flask dropwise at a constant dropping rate over 4 hours, and then the solution in the flask was stirred at 80°C for 2 hours. Next, solution (b) was added to the flask dropwise at a constant dropping rate over 10 minutes, and then the solution in the flask was stirred at 80°C for 3 hours. Furthermore, the solution in the flask was heated to 95°C over 1 hour, maintained at 90°C for 2 hours, then the stirring was stopped and the solution was cooled to room temperature (25°C) to obtain a binder polymer A1 solution. The non-volatile content (solids) of the binder polymer A1 solution was 49% by mass.

[0108] (Binder Polymer A2) A solution of binder polymer A2 was obtained by the same procedure as for binder polymer A1, except that solution (a) was prepared by mixing 24.0 parts by mass of methacrylic acid, 43.5 parts by mass of methyl methacrylate, 15.2 parts by mass of butyl acrylate, 17.3 parts by mass of butyl methacrylate, and 0.9 parts by mass of azobisisobutyronitrile. The non-volatile content (solids) of the binder polymer A2 solution was 49% by mass.

[0109] (Binder Polymer A3) A solution of binder polymer A3 was obtained by the same procedure as for binder polymer A1, except that solution (a) was prepared by mixing 30.0 parts by mass of methacrylic acid, 22.0 parts by mass of methyl methacrylate, 10.0 parts by mass of ethyl acrylate, 8.0 parts by mass of butyl methacrylate, 30.0 parts by mass of styrene, and 0.9 parts by mass of azobisisobutyronitrile. The non-volatile content (solids) of the binder polymer A3 solution was 49% by mass.

[0110] (Binder Polymer A4) Solution (a) was prepared by mixing 29.0 parts by mass of methacrylic acid, 26.0 parts by mass of methyl methacrylate, 45.0 parts by mass of styrene, and 0.9 parts by mass of azobisisobutyronitrile. Solution (b) was prepared by dissolving 0.5 parts by mass of azobisisobutyronitrile in 100 parts by mass of toluene. Toluene was added to a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas inlet tube, and then stirred while blowing nitrogen gas into the flask, raising the temperature to 80°C. Solution (a) was added to the flask at a constant dropping rate over 4 hours, and then the solution in the flask was stirred at 80°C for 2 hours. Next, solution (b) was added to the flask at a constant dropping rate over 10 minutes, and then the solution in the flask was stirred at 80°C for 3 hours. Furthermore, the solution in the flask was heated to 95°C over 1 hour, maintained at 90°C for 2 hours, then the stirring was stopped and the solution was cooled to room temperature (25°C) to obtain a binder polymer A4 solution. The non-volatile content (solids) of the binder polymer A4 solution was 49% by mass.

[0111] (Binder Polymer A5) A solution of binder polymer A5 was obtained by the same procedure as for binder polymer A4, except that solution (a) was prepared by mixing 27.0 parts by mass of methacrylic acid, 50.0 parts by mass of styrene, 3.0 parts by mass of 2-hydroxyethyl methacrylate, 20 parts by mass of benzyl methacrylate, and 0.9 parts by mass of azobisisobutyronitrile. The non-volatile content (solids) of the binder polymer A5 solution was 49% by mass.

[0112] <Weight-average molecular weight (Mw) of the binder polymer> The weight-average molecular weight of binder polymer A1 is 4.7 × 10⁻⁶. 4 The weight-average molecular weight of binder polymer A2 is 3.0 × 10⁻⁶. 4 The weight-average molecular weight of binder polymer A3 is 5.0 × 10⁻⁶. 4 The weight-average molecular weight of binder polymer A4 is 3.0 × 10⁻⁶. 4 The weight-average molecular weight of binder polymer A5 is 3.5 × 10⁻⁶. 4The weight-average molecular weight was measured by gel permeation chromatography (GPC) under the following conditions and derived by conversion using a calibration curve for standard polystyrene. The measurement was performed using a sample obtained by dissolving 120 mg of binder polymer solution in 5 mL of tetrahydrofuran.

[0113] (GPC conditions) Pump: Hitachi L-6000 model (manufactured by Hitachi, Ltd., product name) Columns: A total of 3 columns as listed below (manufactured by Showa Denko Materials Techno Service Co., Ltd., product name, column specifications: 10.7mmφ x 300mm) Gelpack GL-R440 Gelpack GL-R450 Gelpack GL-R400M Eluent: Tetrahydrofuran Measurement temperature: 40℃ Injection volume: 200μL Pressure: 49 kgf / cm² 2 (4.8 MPa) Flow rate: 2.05mL / min Detector: Hitachi L-2490 RI (manufactured by Hitachi, Ltd., product name)

[0114] <Preparation of photosensitive resin composition> A photosensitive resin composition was prepared by mixing each component shown in Table 1 or Table 2 with 16 parts by mass of toluene, 6 parts by mass of methanol, and 10 parts by mass of acetone. Tables 1 and 2 show 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 Tables 1 and 2 are as follows.

[0115] (Photopolymerizable compound) [Photopolymerizable compounds with three or more functionalities] FA-137M: EO-modified trimethylolpropane trimethacrylate (manufactured by Showa Denko Materials Co., Ltd., number of functional groups: 3, molecular weight: 1263, (meth)acryloyl group concentration: 2.38 × 10⁻⁶) -3 ) M3130: EO-modified trimethylolpropane triacrylate (manufactured by Toyo Chemicals Co., Ltd., number of functional groups: 3, molecular weight: 428, (meth)acryloyl group concentration: 7.01 × 10⁻⁶) -3 ) DPEA-12:EO-modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., number of functional groups: 6, molecular weight: 1105, (meth)acryloyl group concentration: 5.43 × 10⁻⁶) -3 ) [Bifunctional photopolymerizable compound] FA-321M(70): 2,2-Bis(4-(methacryloxypentaethoxy)phenyl)propane (ethylene oxide average 10 mol adduct, EO-modified bisphenol A dimethacrylate, manufactured by Showa Denko Materials Co., Ltd., number of functional groups: 2, molecular weight: 804, (meth)acryloyl group concentration: 2.49 × 10⁻⁶ -3 ) BP-2EM: 2,2-Bis(4-(methacryloxydiethoxy)phenyl)propane (EO-modified bisphenol A dimethacrylate, manufactured by Kyoeisha Chemical Co., Ltd.) BPE-200: Ethoxylated bisphenol A dimethacrylate (ethylene oxide adduct with an average of 4 moles, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) M2200: Ethoxylated bisphenol A dimethacrylate (ethylene oxide adduct with an average of 20 mol, manufactured by Miwon) FA-024M: EO·PO modified dimethacrylate (manufactured by Showa Denko Materials Co., Ltd., number of functional groups: 2, molecular weight: 1115, (meth)acryloyl group concentration: 1.79)

[0116] [Monofunctional photopolymerizable compounds] FA-MECH: γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate (manufactured by Showa Denko Materials Co., Ltd.)

[0117] (Photopolymerization initiator) 9-PA:9-Phenylacridine (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) N-PG: N-phenylglycine (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) BCIM: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Hampford)

[0118] (Other ingredients) LCV: Leucocrystal violet (manufactured by Yamada Chemical Industries, Ltd.) TPS: Tribromomethylphenylsulfone (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.) MKG: Malachite Green (manufactured by Osaka Organic Chemical Industry Co., Ltd.) LA-7RD: 4-Hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (manufactured by Asahi Denka Kogyo Co., Ltd.) SF-808H: A mixture of carboxybenzotriazole, 5-amino-1H-tetrazole, and methoxypropanol (manufactured by Sanwa Chemical Co., Ltd.) PTSA: p-toluenesulfonamide (manufactured by JMC) DBA: 9,10-Dibutoxyanthracene (manufactured by Kawasaki Chemical Industries, Ltd.) TBC: 4-tert-butylcatechol (manufactured by DIC Corporation, product name "DIC-TBC-5P") MBI: 2-mercaptobenzimidazole (manufactured by Sigma-Aldrich) TAGREEN2580: A mixture of a solvent blue 70 derivative and an amine salt of solvent yellow 21 (manufactured by Tokyo Aniline Dye Manufacturing Co., Ltd.) FA-711MM: Pentamethylpiperidinyl methacrylate (manufactured by Showa Denko Materials Co., Ltd.)

[0119] <Fabrication of photosensitive elements> A polyethylene terephthalate film (manufactured by Teijin Film Solutions Limited, product name "G2J", thickness: 16 μm) was prepared as a support. After applying the above-mentioned photosensitive resin composition to the support so as to be of uniform thickness, a photosensitive resin layer (photosensitive film; average thickness of 10 locations after drying: 25 μm) was formed by sequentially drying it in a hot air convection dryer at 70°C and 110°C. By laminating a polyethylene film (manufactured by Tamapoly Co., Ltd., product name "NF-13", thickness: 17 μm) as a protective layer to this photosensitive resin layer, a photosensitive element comprising a support, a photosensitive resin layer, and a protective layer in that order was obtained.

[0120] <Fabrication of laminates> A copper-clad laminate (substrate, manufactured by Showa Denko Materials Co., Ltd., product name: MCL-E-67) having copper foil (thickness: 18 μm) arranged on both sides of a glass epoxy material was pickled and washed with water, and then dried with an airflow to obtain a substrate. Next, after heating this substrate to 80°C, the above-mentioned photosensitive element was laminated so that the photosensitive resin layer was in contact with the copper surface while peeling off the protective layer, thereby obtaining a laminate comprising the substrate (copper-clad laminate), photosensitive resin layer, and support in that order. Lamination was performed using a heat roll at 110°C with a pressing pressure of 0.4 MPa and a roll speed of 1.0 m / min.

[0121] <Sensitivity> After placing a 41-step tablet (manufactured by Showa Denko Materials Co., Ltd., density range 0.00~2.00, density step 0.05, tablet size 20mm x 187mm, size of each step 3mm x 12mm) on the laminated support described above, the photosensitive resin layer was exposed through the support using a direct writing exposure machine (manufactured by Orbotec Co., Ltd., Nuvogo Fine 8, light source: 375nm (0%) + 405nm (100%)) at an exposure dose (irradiation energy amount) such that 15 steps remained after development of the 41-step tablet. The exposure dose at this time (unit: mJ / cm) 2Sensitivity (photosensitivity) was evaluated by [method / tool]. Development was performed by spray developing the unexposed photosensitive resin layer at a pressure of 0.15 MPa using a 1% by mass aqueous sodium carbonate solution at 30°C after peeling off the support (nozzle: full cone type, distance between the object to be treated and the nozzle tip: 6 cm). The results are shown in Tables 1 and 2.

[0122] <Minimum development time> After cutting the aforementioned laminate into a square shape (5cm x 5cm), test specimens were obtained by peeling off the support. Next, the unexposed photosensitive resin layer on the test specimen was spray-developed at a pressure of 0.15 MPa using a 1% by mass aqueous sodium carbonate solution at 30°C (nozzle: full cone type, distance between the object to be treated and the nozzle tip: 6cm), and the shortest time at which the removal of the unexposed photosensitive resin layer could be visually confirmed was obtained as the minimum development time (MD).

[0123] <Etching Resistance> After placing a 41-step tablet (the same tablet as used for the sensitivity evaluation described above) on the support of the laminate described above, a 3cm × 4cm pattern was exposed to the photosensitive resin layer of the laminate described above through the support using a direct-writing exposure machine (Nuvogo Fine 8, manufactured by Orbotec Co., Ltd., light source: 375nm (0%) + 405nm (100%)) with the exposure amount obtained in the sensitivity evaluation described above. Next, after peeling off the support to expose the photosensitive resin layer, spray development was performed on the unexposed photosensitive resin layer using a 1% by mass aqueous sodium carbonate solution at 30°C at a pressure of 0.15 MPa for twice the minimum development time (nozzle: full cone type, distance between the object to be treated and the nozzle tip: 6cm) to obtain a test piece having a pattern (cured photosensitive resin layer).

[0124] Next, 300 mL of etching solution (aqueous solution) containing 5.5 mol / L hydrochloric acid and 2.1 mol / L cupric chloride was placed in a 300 mL beaker, and the temperature of the etching solution was adjusted to 70°C. Subsequently, while stirring the etching solution (stirring conditions: 425-475 rpm), the test specimen was placed perpendicular to the bottom of the beaker with the patterned surface facing the center of the beaker, and the test specimen was immersed in the etching solution for 10 minutes.

[0125] After removing the test specimen from the etching solution, the specimen was washed with running water, and it was visually inspected whether peeling or lifting of the pattern occurred during washing. After washing, the test specimen was dried with air using an air duster gun, and it was visually inspected whether peeling or lifting of the pattern occurred during drying. "Lifting" is the phenomenon in which at least a part of the outer edge of the pattern separates from the substrate, and "peeling" is the phenomenon in which the center of the pattern separates from the substrate. If no peeling or lifting was observed during washing or drying, it was evaluated as "A". If no peeling or lifting was observed during washing but lifting was observed during drying, it was evaluated as "B". If no peeling or lifting was observed during washing but lifting was observed, it was evaluated as "C". If peeling was observed during washing, it was evaluated as "D". Cases "A" or "B" were judged to be good. The results are shown in Tables 1 and 2.

[0126] [Table 1]

[0127] [Table 2] [Explanation of Symbols]

[0128] 1...Photosensitive element, 2...Support, 3...Photosensitive resin layer, 4...Protective layer.

Claims

[Claim 1] A photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator, The aforementioned component (B) includes a polyfunctional compound having three or more ethylenically unsaturated bonds, When a layer (25 μm thick) of the photosensitive resin composition is exposed to a 41-step tablet (density range 0.00 to 2.00, density step 0.05, tablet size 20 mm x 187 mm, size of each step 3 mm x 12 mm) at a wavelength of 405 nm and then developed, an exposure dose of 30 mJ / cm² is required to obtain 15 remaining steps. ２ The following is a photosensitive resin composition.

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