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

Abstract

A photosensitive resin composition comprising a binder polymer, a photopolymerizable compound, a photopolymerization initiator and a tetraarylbenzidine compound represented by general formula (d1). [In formula (d1): R11, R12, R13, R14, R15, R16, R17 and R18 each independently represent an alkyl group, an alkoxy group, a halogeno group, an amino group, a hydroxy group, a carboxy group or a carboxylate group; n11, n12, n13 and n14 each independently represent an integer of 0-4; and n15, n16, n17 and n18 each independently represent an integer of 0-5, provided that n15 and / or n16 represent 1 or more.]

Description

[Technical Field]

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

[0002] In the production of a laminate that can be used as a printed wiring board, a resist pattern is formed to obtain a desired wiring. The resist pattern can be formed by exposing and developing a photosensitive resin layer obtained using a photosensitive resin composition. Various compositions have been investigated as photosensitive resin compositions. For example, Patent Document 1 below describes a photosensitive resin composition containing an anthracene derivative. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2007 / 004619 Summary of the Invention [Problem to be solved by the invention]

[0004] When a photosensitive resin composition is used to form a cured product pattern that can be used as a resist pattern, a linear cured product pattern having linear line portions and linear space portions adjacent to the line portions may be formed. When forming a linear cured product pattern in which the space width (width of the space portion) is equal to or less than the line width (width of the line portion), resolution may be required as a property that allows the line portions and space portions to be formed well.

[0005] One aspect of the present disclosure is to provide a photosensitive resin composition that can reduce the space width in areas where line and space portions are well formed when forming a linear cured product pattern in which the space width is equal to or less than the line width. Another aspect of the present disclosure is to provide a photosensitive element using the photosensitive resin composition. Another aspect of the present disclosure is to provide a method for producing a laminate using the above-mentioned photosensitive resin composition or the above-mentioned photosensitive element. [Means for solving the problem]

[0006] In some aspects, the present disclosure relates to the following [1] to

[14] , etc. [1] A photosensitive resin composition containing a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a tetraarylbenzidine compound represented by the following general formula (d1): [ka] [In formula (d1), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represents an alkyl group, an alkoxy group, a halogeno group, an amino group, a hydroxy group, a carboxy group, or a carboxylate group; n11, n12, n13, and n14 each independently represent an integer of 0 to 4; n15, n16, n17, and n18 each independently represent an integer of 0 to 5; and at least one of n15 and n16 is 1 or greater. [2] The photosensitive resin composition according to [1], wherein the tetraarylbenzidine compound includes a tetraarylbenzidine compound represented by the following general formula (d2): [ka] [In formula (d2), R 11 , R 12 , R 13 , R 14 , R 15 , R16 , R 17a , R 17b , R 18a and R 18b each independently represents an alkyl group, an alkoxy group, a halogeno group, an amino group, a hydroxy group, a carboxy group, or a carboxylate group, and n11, n12, n13, and n14 each independently represents an integer of 0 to 4. [3] The photosensitive resin composition according to [1] or [2], wherein the tetraarylbenzidine compound comprises N,N'-bis[4-(2-phenylethen-1-yl)-4'-methylphenyl]-N,N'-bis(2-ethyl-6-methylphenyl)-1,1'-biphenyl-4,4'-diamine. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the content of the tetraarylbenzidine compound is 0.01 to 0.50 parts by mass per 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the binder polymer contains a polymer having benzyl (meth)acrylate as a monomer unit. [6] The photosensitive resin composition according to [5], wherein the content of the benzyl (meth)acrylate monomer unit in the polymer is 10 to 30 mass %. [7] The photosensitive resin composition according to any one of [1] to [6], wherein the binder polymer contains a polymer having a styrene compound as a monomer unit. [8] The photosensitive resin composition according to [7], wherein the content of the styrene compound monomer unit in the polymer is 40 to 60 mass %. [9] The photosensitive resin composition according to any one of [1] to [8], wherein the binder polymer has a weight average molecular weight of 10,000 to 100,000.

[10] The photosensitive resin composition according to any one of [1] to [9], wherein the photopolymerizable compound contains a bisphenol A type (meth)acrylic acid compound.

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

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

[12] The photosensitive resin composition according to

[11] , which has a thickness of 30 μm or less.

[13] A photosensitive element comprising a support and a photosensitive resin layer disposed on the support, wherein the photosensitive resin layer contains the photosensitive resin composition according to any one of [1] to

[12] .

[14] A method for manufacturing a laminate, comprising the steps of: disposing a photosensitive resin layer on a substrate using the photosensitive resin composition according to any one of [1] to

[12] or the photosensitive element according to

[13] ; photocuring a portion of the photosensitive resin layer; and removing an uncured portion of the photosensitive resin layer to form a cured product pattern. [Effects of the Invention]

[0007] According to one aspect of the present disclosure, a photosensitive resin composition can be provided that can reduce the space width in areas where line portions and space portions are well formed when forming a linear cured product pattern in which the space width is equal to or less than the line width. According to another aspect of the present disclosure, a photosensitive element using the photosensitive resin composition can be provided. According to another aspect of the present disclosure, a method for producing a laminate using the above-mentioned photosensitive resin composition or the above-mentioned photosensitive element can be provided. According to another aspect of the present disclosure, application of the photosensitive resin composition or the photosensitive element to the formation of a resist pattern can be provided. According to another aspect of the present disclosure, application of the photosensitive resin composition or the photosensitive element to the production of a printed wiring board can be provided. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic cross-sectional view illustrating an example of a photosensitive element. [Figure 2] 1A to 1C are schematic diagrams illustrating an example of a method for manufacturing a laminate. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, embodiments of the present disclosure will be described in detail.

[0010] In this specification, numerical ranges indicated with "to" indicate a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. A numerical range "A or greater" means a range exceeding A and A. A numerical range "A or less" means a range less than A and A. In numerical ranges described in stages in this specification, the upper or lower limit of a numerical range in one stage can be arbitrarily combined with the upper or lower limit of a numerical range in another stage. In numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples. "A or B" may include either A or B, or may include both. Unless otherwise specified, the materials exemplified in this specification can be used alone or in combination of two or more. When multiple substances corresponding to each component are present in the composition, the content of each component in the composition refers to the total amount of the multiple substances present in the composition, unless otherwise specified. The term "layer" encompasses structures that are formed over the entire surface as well as structures that are formed only partially when observed in a plan view. The term "process" does not only refer to an independent process, but also includes processes that cannot be clearly distinguished from other processes as long as the intended effect of the process is achieved. "(Meth)acrylic acid" means at least one of acrylic acid and its corresponding methacrylic acid, and the same applies to other similar expressions such as "(meth)acrylate." "Content of (meth)acrylic acid monomer" means the total amount of acrylic acid monomer units and methacrylic acid monomer units, and the same applies to other similar expressions. "Alkyl group" may be linear, branched, or cyclic, unless otherwise specified.

[0011] In this specification, "EO-modified" means a compound having a (poly)oxyethylene group. "PO-modified" means a compound having a (poly)oxypropylene group. "EO·PO-modified" means a compound having a (poly)oxyethylene group and a (poly)oxypropylene group. "(Poly)oxyethylene group" means at least one of an oxyethylene group and a polyoxyethylene group (a group in which two or more ethylene groups are linked by an ether bond). The same applies to other similar expressions such as "(poly)oxypropylene group."

[0012] In this specification, the term "solid content of a photosensitive resin composition" refers to the non-volatile content of the photosensitive resin composition excluding volatile components (water, solvent, etc.) that can volatilize. In other words, the term "solid content" refers to components that remain without volatilizing when the photosensitive resin composition is dried, and includes components that are liquid, syrup-like, waxy, etc. at room temperature (25°C).

[0013] <Photosensitive resin composition and cured product> The photosensitive resin composition according to this embodiment contains (A) a binder polymer (component (A)), (B) a photopolymerizable compound (component (B)), (C) a photopolymerization initiator (component (C)), and (D) a tetraarylbenzidine compound (component (D)) represented by the following general formula (d1). The photosensitive resin composition according to this embodiment can be used, for example, as a negative-type photosensitive resin composition. The photosensitive resin composition according to this embodiment may be in the form of a liquid or a film (photosensitive film).

[0014] [ka] [In formula (d1), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18each independently represents an alkyl group, an alkoxy group, a halogeno group, an amino group, a hydroxy group, a carboxy group, or a carboxylate group; n11, n12, n13, and n14 each independently represent an integer of 0 to 4; n15, n16, n17, and n18 each independently represent an integer of 0 to 5; and at least one of n15 and n16 is 1 or greater.

[0015] The photosensitive resin composition according to this embodiment has photocurability, 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 in the form of a pattern (cured product pattern) or may be a resist pattern.

[0016] The thickness of the film-like photosensitive resin composition or the thickness of the cured product may be 1 μm or more, 5 μm or more, 10 μm or more, 15 μm or more, 18 μm or more, or 19 μm or more. The thickness of the film-like photosensitive resin composition or the cured product may be 100 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 25 μm or less, 20 μm or less, or 19 μm or less. From these viewpoints, the thickness of the film-like photosensitive resin composition or the cured product may be 1 to 100 μm, 5 to 50 μm, or 10 to 30 μm. The thickness of the film-like photosensitive resin composition or the cured product may be the average thickness at 10 points.

[0017] The photosensitive resin composition according to this embodiment allows for a reduction in the space width (minimum space width) in areas where line and space portions are well formed when forming a linear cured product pattern in which the space width is equal to or smaller than the line width (i.e., the space width is equal to or smaller than the line width), thereby achieving excellent resolution. The inventors speculate that this effect is due to the high light absorption efficiency of component (D) and the efficient progress of the reaction caused by component (C), which suppresses swelling of the cured product pattern due to the developer. However, the cause is not limited to this. With the recent trend toward higher density printed wiring boards, there is an increasing demand for photosensitive resin compositions with excellent resolution. In particular, photosensitive resin compositions capable of forming resist patterns with a line width / space width ratio of 10 / 10 (unit: μm) or less are needed in the production of package substrates. The photosensitive resin composition according to this embodiment allows for a resolution of, for example, 10 μm or less (preferably 8 μm or less) to be achieved, as evaluated in the Examples described below.

[0018] When a photosensitive resin composition is used to form a linear cured product pattern in which the line width is equal to or smaller than the space width (the line width is equal to or smaller than the space width), adhesion may be required as a property for favorable formation of line and space portions. According to one aspect of the photosensitive resin composition of this embodiment, when a linear cured product pattern in which the line width is equal to or smaller than the space width is formed, the line width (minimum line width) in the region in which the line and space portions are favorably formed can be reduced (superior adhesion can be obtained). With the recent trend toward higher density printed wiring boards, there is an increasing demand for photosensitive resin compositions with excellent adhesion. In particular, in the production of package substrates, there is a demand for photosensitive resin compositions capable of forming resist patterns with a line width / space width of 10 / 10 (unit: μm) or less. According to one aspect of the photosensitive resin composition of this embodiment, adhesion of, for example, 7 μm or less can be obtained in the evaluation described in the Examples below.

[0019] According to one aspect of the photosensitive resin composition of this embodiment, it is possible to obtain excellent sensitivity to actinic rays (a property in which the amount of exposure required to obtain a predetermined cured state is small), and in the evaluation described in the examples below, it is possible to obtain a cured state of, for example, 90 mJ / cm 2 or less (preferably 80 mJ / cm 2 A sensitivity (exposure amount) of 1000 nm or less can be obtained.

[0020] The photosensitive resin composition according to this embodiment contains a binder polymer (excluding compounds corresponding to the component (D)) as the component (A).

[0021] Examples of component (A) include acrylic resins, styrene resins, epoxy resins, amide resins, amide-epoxy resins, alkyd resins, phenol resins, etc. Acrylic resins are resins that have a compound having a (meth)acryloyl group (a (meth)acrylic acid compound) as a monomer unit, and styrene resins, epoxy resins, amide resins, amide-epoxy resins, alkyd resins, and phenol resins that have such monomer units are classified as acrylic resins.

[0022] From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, the component (A) may contain an acrylic resin. From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, the content of the acrylic resin may be 50% by mass or more, more than 50% by mass, 70% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, or substantially 100% by mass (an embodiment in which the component (A) is substantially composed of an acrylic resin), based on the total mass of the component (A).

[0023] Examples of compounds having a (meth)acryloyl group include (meth)acrylic acid, (meth)acrylic acid esters, etc. Examples of (meth)acrylic acid esters include alkyl (meth)acrylates (excluding compounds corresponding to alkyl (meth)acrylates; cycloalkyl (meth)acrylates), cycloalkyl (meth)acrylates (cycloalkyl (meth)acrylates), aryl (meth)acrylates (aryl (meth)acrylates), (meth)acrylamide compounds (diacetone acrylamide, etc.), glycidyl (meth)acrylates, and styryl (meth)acrylates.

[0024] From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, the component (A) may contain a polymer having aryl (meth)acrylate (aryl (meth)acrylate ester) as a monomer unit. Examples of aryl (meth)acrylate include benzyl (meth)acrylate, phenyl (meth)acrylate, and naphthyl (meth)acrylate. From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, the component (A) may contain a polymer having benzyl (meth)acrylate as a monomer unit.

[0025] The content of benzyl (meth)acrylate monomer units or the content of aryl (meth)acrylate monomer units may be within the following ranges based on the total amount of monomer units constituting the polymer having aryl (meth)acrylate (e.g., benzyl (meth)acrylate) as a monomer unit. From the viewpoint of easily obtaining excellent resolution and adhesion, the content of the above-mentioned monomer units may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more. The content of the above-mentioned monomer units may be 23% by mass or more. From the viewpoint of easily obtaining excellent resolution and adhesion, the content of the above-mentioned monomer units may be 50% by mass or less, less than 50% by mass, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, 23% by mass or less, or 20% by mass or less. From these viewpoints, the content of the above-mentioned monomer units may be 1 to 50 mass%, 10 to 50 mass%, 15 to 50 mass%, 1 to 30 mass%, 10 to 30 mass%, 15 to 30 mass%, 1 to 25 mass%, 10 to 25 mass%, or 15 to 25 mass%.

[0026] From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, the component (A) may contain a polymer having (meth)acrylic acid as a monomer unit, or may contain a polymer having aryl (meth)acrylate and (meth)acrylic acid as monomer units.

[0027] The content of (meth)acrylic acid monomer units may be within the following ranges based on the total amount of monomer units constituting the polymer having (meth)acrylic acid as a monomer unit. From the viewpoint of easily obtaining excellent resolution and adhesion, 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, 15% by mass or more, 20% by mass or more, 25% by mass or more, or 27% by mass or more. The content of (meth)acrylic acid monomer units may be 30% by mass or more. From the viewpoint of easily obtaining excellent resolution and adhesion, the content of (meth)acrylic acid monomer units may be 50% by mass or less, less than 50% by mass, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, or 27% by mass or less. From these viewpoints, the content of the (meth)acrylic acid monomer unit may be 1 to 50 mass%, 10 to 50 mass%, 20 to 50 mass%, 1 to 40 mass%, 10 to 40 mass%, 20 to 40 mass%, 1 to 30 mass%, 10 to 30 mass%, or 20 to 30 mass%.

[0028] From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, component (A) may contain a polymer having an alkyl (meth)acrylate as a monomer unit, or may contain a polymer having at least one selected from the group consisting of aryl (meth)acrylate and (meth)acrylic acid and an alkyl (meth)acrylate as a monomer unit. Examples of the alkyl group in the alkyl (meth)acrylate include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups, and the alkyl group may be various structural isomers. From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, the number of carbon atoms in the alkyl group in the alkyl (meth)acrylate may be 1 to 4, 1 to 3, 2 to 3, or 1 to 2.

[0029] The alkyl group of the alkyl (meth)acrylate may have a substituent. Examples of the substituent include a hydroxy group, an amino group, an epoxy group, a furyl group, and a halogeno group (such as a fluoro group, a chloro group, or a bromo group). Examples of the alkyl (meth)acrylate 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.

[0030] From the viewpoint of easily achieving excellent resolution, adhesion, and sensitivity, component (A) may contain a polymer having a hydroxyalkyl (meth)acrylate as a monomer unit. Examples of hydroxyalkyl (meth)acrylates include hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, and hydroxyhexyl (meth)acrylate.

[0031] The content of the alkyl (meth)acrylate monomer unit or the content of the hydroxyalkyl (meth)acrylate monomer unit may be in the following ranges based on the total amount of monomer units constituting the polymer having alkyl (meth)acrylate as a monomer unit: The content of the above-mentioned monomer unit 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, 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, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, or 70% by mass or more. From the viewpoint of easily obtaining excellent resolution and adhesion, the content of the above-mentioned monomer units may be 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, 8% by mass or less, 5% by mass or less, 4% by mass or less, or 3% by mass or less. From these viewpoints, the content of the above-mentioned monomer units may be 0.1 to 80% by mass, 0.1 to 50% by mass, 0.1 to 20% by mass, 1 to 80% by mass, 1 to 50% by mass, 1 to 20% by mass, 5 to 80% by mass, 5 to 50% by mass, or 5 to 20% by mass.

[0032] The content of (meth)acrylic acid ester monomer units (total amount of monomer units of compounds corresponding to (meth)acrylic acid ester) may be in the following ranges based on the total amount of monomer units constituting the polymer having (meth)acrylic acid ester as a monomer unit: The content of (meth)acrylic acid ester 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, 23% by mass or more, 25% by mass or more, 28% 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, more than 50% by mass, 60% by mass or more, or 70% by mass or more. From the viewpoint of easily obtaining excellent resolution and adhesion, the content of the (meth)acrylic acid ester monomer unit may be 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, less than 50% by mass, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 28% by mass or less, or 25% by mass or less. From these viewpoints, the content of the (meth)acrylic acid ester monomer unit may be 1 to 80% by mass, 1 to 50% by mass, 1 to 30% by mass, 10 to 80% by mass, 10 to 50% by mass, 10 to 30% by mass, 20 to 80% by mass, 20 to 50% by mass, or 20 to 30% by mass.

[0033] From the viewpoint of easily obtaining excellent resolution and adhesion, component (A) may contain a polymer having a styrene compound as a monomer unit, a polymer having at least one selected from the group consisting of a (meth)acrylic acid ester and (meth)acrylic acid and a styrene compound as a monomer unit, or a polymer having at least one selected from the group consisting of an aryl (meth)acrylate, an alkyl (meth)acrylate, and (meth)acrylic acid and a styrene compound as a monomer unit. Examples of styrene compounds include styrene and styrene derivatives. Examples of styrene derivatives include vinyltoluene and α-methylstyrene. From the viewpoint of easily obtaining excellent resolution and adhesion, component (A) may contain a polymer having benzyl (meth)acrylate, a hydroxyalkyl (meth)acrylate, and a styrene compound as a monomer unit.

[0034] The content of the styrene compound monomer unit may be in the following ranges based on the total amount of monomer units constituting the polymer having a styrene compound as a monomer unit. From the viewpoint of easily obtaining excellent resolution and adhesion, the content of the styrene compound monomer unit 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, 45% by mass or more, 48% by mass or more, or 50% by mass or more. The content of the styrene compound monomer unit may be 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, 48% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, or 30% by mass or less. From these viewpoints, the content of the monomer units of the styrene compound may be 10 to 90 mass%, 20 to 90 mass%, 30 to 90 mass%, 40 to 90 mass%, 10 to 80 mass%, 20 to 80 mass%, 30 to 80 mass%, 40 to 80 mass%, 10 to 60 mass%, 20 to 60 mass%, 30 to 60 mass%, or 40 to 60 mass%.

[0035] Component (A) may contain a polymer having other monomers as monomer units, such as vinyl alcohol ethers (e.g., vinyl n-butyl ether), (meth)acrylonitrile, maleic acid, maleic anhydride, maleic acid monoesters (e.g., monomethyl maleate, monoethyl maleate, monoisopropyl maleate), fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid.

[0036] The acid value of component (A) may be within the following ranges. The acid value of component (A) may be 80 mgKOH / g or more, 90 mgKOH / g or more, 100 mgKOH / g or more, more than 100 mgKOH / g, 120 mgKOH / g or more, 140 mgKOH / g or more, 150 mgKOH / g or more, 160 mgKOH / g or more, 170 mgKOH / g or more, 180 mgKOH / g or more, or 190 mgKOH / g or more. From the viewpoint of easily achieving excellent resolution and adhesion, the acid value of component (A) may be 250 mgKOH / g or less, 240 mgKOH / g or less, 230 mgKOH / g or less, 210 mgKOH / g or less, 200 mgKOH / g or less, 190 mgKOH / g or less, or 180 mgKOH / g or less. From these viewpoints, the acid value of component (A) may be 80 to 250 mgKOH / g, 100 to 200 mgKOH / g, or 120 to 190 mgKOH / g. The acid value of component (A) can be adjusted by the content of monomer units (e.g., monomer units of (meth)acrylic acid) constituting component (A). The acid value of component (A) can be measured by the method described in the Examples. When the measurement target is a solution obtained by mixing component (A) with volatile components such as a synthetic solvent or diluent solvent, the acid value can be calculated using the following formula. When component (A) is blended in a state where it is mixed with volatile components such as a synthetic solvent or diluent solvent, it is also possible to measure the acid value after removing the volatile components by heating for 1 to 4 hours at a temperature at least 10°C higher than the boiling point of the volatile components before precise weighing. Acid value = 0.1 × Vf × 56.1 / (Wp × I / 100) [In the formula, Vf represents the titration volume (unit: mL) of the KOH (potassium hydroxide) aqueous solution, Wp represents the mass (unit: g) of the solution containing the component (A) to be measured, and I represents the proportion of nonvolatile matter (unit: mass %) in the solution containing the component (A) to be measured.]

[0037] The weight average molecular weight (Mw) of component (A) may be within the following ranges. The weight average molecular weight of component (A) may be 10,000 or more, 20,000 or more, 25,000 or more, 30,000 or more, 35,000 or more, 40,000 or more, 45,000 or more, or 50,000 or more. From the viewpoint of easily achieving excellent resolution and adhesion, the weight average molecular weight of component (A) may be 100,000 or less, 80,000 or less, 70,000 or less, less than 70,000, 65,000 or less, 60,000 or less, 50,000 or less, 40,000 or less, or 35,000 or less. From these viewpoints, the weight average molecular weight of component (A) may be 10,000 to 100,000, 20,000 to 80,000, 25,000 to 70,000, or 30,000 to 60,000.

[0038] The number average molecular weight (Mn) of component (A) may be within the following ranges: 5,000 or more, 10,000 or more, 12,000 or more, 15,000 or more, 16,000 or more, 18,000 or more, 20,000 or more, 21,000 or more, or 22,000 or more. From the viewpoint of easily achieving excellent resolution and adhesion, the number average molecular weight of component (A) may be 50,000 or less, 40,000 or less, 35,000 or less, 30,000 or less, 25,000 or less, 22,000 or less, 21,000 or less, 20,000 or less, 18,000 or less, or 16,000 or less. From these viewpoints, the number average molecular weight of the component (A) may be 5,000 to 50,000, 10,000 to 40,000, 12,000 to 35,000, or 15,000 to 30,000.

[0039] The dispersity (weight average molecular weight / number average molecular weight) of component (A) may be in the following ranges. The dispersity of component (A) may be 1.0 or more, 1.5 or more, 1.8 or more, 2.0 or more, 2.1 or more, 2.2 or more, or 2.3 or more. From the viewpoint of easily achieving excellent resolution and adhesion, the dispersity of component (A) may be 3.0 or less, 2.8 or less, 2.5 or less, 2.3 or less, or 2.2 or less. From these viewpoints, the dispersity of component (A) may be 1.0 to 3.0, 1.5 to 2.8, or 2.0 to 2.5.

[0040] The weight average molecular weight and number average molecular weight can be measured, for example, by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene. More specifically, they can be measured under the conditions described in the Examples. For compounds with low molecular weights, if it is difficult to measure the weight average molecular weight and number average molecular weight using the above-mentioned methods, the molecular weight can be measured by another method and the average value can be calculated.

[0041] The content of component (A) may be within the following ranges based on the total solid content of the photosensitive resin composition. From the viewpoint of easily achieving excellent resolution, adhesion, and sensitivity, and from the viewpoint of excellent film formability, the content of component (A) may be 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 45% by mass or more, or 50% by mass or more. From the viewpoint of easily achieving excellent resolution, adhesion, and sensitivity, the content of component (A) may be 90% 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 to 90 mass%, 10 to 80 mass%, 10 to 60 mass%, 30 to 90 mass%, 30 to 80 mass%, 30 to 60 mass%, 50 to 90 mass%, 50 to 80 mass%, or 50 to 60 mass%.

[0042] The content of component (A) may be within the following ranges relative to 100 parts by mass of the total of components (A) and (B): From the viewpoint of easily achieving excellent resolution, adhesion, and sensitivity, and from the viewpoint of excellent film formability, 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, 40 parts by mass or more, 45 parts by mass or more, 50 parts by mass or more, or 55 parts by mass or more. From the viewpoint of easily achieving excellent resolution, adhesion, and sensitivity, 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, or 60 parts by mass or less. From these viewpoints, the content of component (A) may be 10 to 90 parts by mass, 10 to 80 parts by mass, 10 to 60 parts by mass, 30 to 90 parts by mass, 30 to 80 parts by mass, 30 to 60 parts by mass, 50 to 90 parts by mass, 50 to 80 parts by mass, or 50 to 60 parts by mass.

[0043] The photosensitive resin composition according to this embodiment contains a photopolymerizable compound (excluding compounds corresponding to component (D)) as component (B). The photopolymerizable compound is a compound that polymerizes when exposed to light, and may be, for example, a compound having an ethylenically unsaturated bond.

[0044] Examples of component (B) include bisphenol A-type (meth)acrylic acid compounds, EO-modified di(meth)acrylates, PO-modified di(meth)acrylates, EO·PO-modified di(meth)acrylates, polyalkylene glycol di(meth)acrylates (polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc.), EO-modified polyalkylene glycol di(meth)acrylates, PO-modified polyalkylene glycol di(meth)acrylates, EO·PO-modified polyalkylene glycol di(meth)acrylates, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, and EO·PO-modified trimethylolpropane. tri(meth)acrylate, compounds having a ditrimethylolpropane skeleton, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, EO-modified pentaerythritol tetra(meth)acrylate, PO-modified pentaerythritol tetra(meth)acrylate, EO·PO-modified pentaerythritol tetra(meth)acrylate, EO-modified dipentaerythritol hexa(meth)acrylate, PO-modified dipentaerythritol hexa(meth)acrylate, EO·PO-modified dipentaerythritol hexa(meth)acrylate, nonylphenoxy polyethyleneoxy acrylate, phthalic acid compounds, alkyl (meth)acrylate, and photopolymerizable compounds having at least one cationically polymerizable cyclic ether group in the molecule (such as oxetane compounds).

[0045] From the viewpoint of easily achieving excellent resolution, adhesion, and sensitivity, component (B) may contain a bisphenol A type (meth)acrylic acid compound. Examples of bisphenol A type (meth)acrylic acid compounds include 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane (2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane, etc.), 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolybutoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane. From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, the component (B) may contain 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane or may contain 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane.

[0046] The content of the bisphenol A type (meth)acrylic acid compound is 100% by mass or less, based on the total mass of component (B). From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, the content may be within the following ranges: 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, 85% by mass or more, or 90% by mass or more. The content of the bisphenol A type (meth)acrylic acid compound may be less than 100% by mass, 99% by mass or less, 98% by mass or less, 97% by mass or less, 95% by mass or less, 92% by mass or less, or 91% by mass or less. From these viewpoints, the content of the bisphenol A type (meth)acrylic acid compound may be 50 to 100% by mass, 70 to 99% by mass, or 80 to 95% by mass.

[0047] From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, the content of the bisphenol A type (meth)acrylic acid compound may be within the following ranges based on the total solid content of the photosensitive resin composition. The content of the 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, or 35% by mass or more. The content of the bisphenol A type (meth)acrylic acid compound 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, 45% by mass or less, or 40% by mass or less. From these viewpoints, the content of the bisphenol A type (meth)acrylic acid compound may be 1 to 90 mass%, 10 to 90 mass%, 20 to 90 mass%, 1 to 70 mass%, 10 to 70 mass%, 20 to 70 mass%, 1 to 50 mass%, 10 to 50 mass%, or 20 to 50 mass%.

[0048] From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, the content of the bisphenol A type (meth)acrylic acid compound may be in the following ranges relative to 100 parts by mass of the total amount of components (A) and (B): 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, 38 parts by mass or more, or 40 parts by mass or more. The content of the bisphenol A type (meth)acrylic acid compound may be 90 parts by mass or less, 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, or 40 parts by mass or less. From these viewpoints, the content of the bisphenol A type (meth)acrylic acid compound may be 1 to 90 parts by mass, 10 to 90 parts by mass, 20 to 90 parts by mass, 1 to 70 parts by mass, 10 to 70 parts by mass, 20 to 70 parts by mass, 1 to 50 parts by mass, 10 to 50 parts by mass, or 20 to 50 parts by mass.

[0049] From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, the content of component (B) may be within the following ranges based on the total solid content of the photosensitive resin composition. 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, or 40% 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 to 90% by mass, 20 to 90% by mass, 30 to 90% by mass, 10 to 70% by mass, 20 to 70% by mass, 30 to 70% by mass, 10 to 50% by mass, 20 to 50% by mass, or 30 to 50% by mass.

[0050] From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, the content of component (B) may be within the following ranges relative to 100 parts by mass of the total amount of components (A) and (B): 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, or 40 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, 60 parts by mass or less, 55 parts by mass or less, 50 parts by mass or less, or 45 parts by mass or less. From these viewpoints, the content of component (B) may be 10 to 90 parts by mass, 20 to 90 parts by mass, 30 to 90 parts by mass, 10 to 70 parts by mass, 20 to 70 parts by mass, 30 to 70 parts by mass, 10 to 50 parts by mass, 20 to 50 parts by mass, or 30 to 50 parts by mass.

[0051] The photosensitive resin composition according to this embodiment may not contain a photopolymerizable compound having an amino group as component (B). Examples of such photopolymerizable compounds include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, dimethylaminopropyl(meth)acrylamide, diethylaminopropyl(meth)acrylamide, normal propyl(meth)acrylamide, isopropyl(meth)acrylamide, and N-(meth)acryloylmorpholine. The content of the photopolymerizable compound having an amino group may be 0.01 parts by mass or less, less than 0.01 parts by mass, 0.001 parts by mass or less, or 0.0001 parts by mass or less, or even 0% by mass, relative to 100 parts by mass of component (A).

[0052] The photosensitive resin composition according to this embodiment contains a photopolymerization initiator (excluding compounds corresponding to the component (D)) as the component (C).

[0053] Examples of the component (C) include hexaarylbiimidazole compounds; aromatic ketones such as 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, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1; quinone compounds such as alkylanthraquinone; benzoin ether compounds such as benzoin alkyl ether; benzoin compounds such as benzoin and alkylbenzoin; benzyl derivatives such as benzyl dimethyl ketal; bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; bis(2,6-dimethylbenzoyl)-2,4,4-trimethyl-pentylphosphine oxide; (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide, and the like.

[0054] From the viewpoint of easily achieving excellent resolution, adhesion, and sensitivity, component (C) may contain a hexaarylbiimidazole compound. The aryl group in the hexaarylbiimidazole compound may be a phenyl group or the like. The hydrogen atom bonded to the aryl group in the hexaarylbiimidazole compound may be substituted with a halogen atom (e.g., a chlorine atom).

[0055] The hexaarylbiimidazole compound may be a 2,4,5-triarylimidazole dimer. Examples of the 2,4,5-triarylimidazole dimer 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 easily achieving excellent resolution, adhesion, and sensitivity, the hexaarylbiimidazole compound may include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer or 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

[0056] From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, the content of the hexaarylbiimidazole 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 (an embodiment in which the component (C) consists essentially of the hexaarylbiimidazole compound), based on the total amount of the component (C).

[0057] From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, the content of component (C) may be within the following ranges based on the total solid content of the photosensitive resin composition. The content of component (C) may be 0.1 mass% or more, 0.5 mass% or more, 1 mass% or more, 2 mass% or more, 3 mass% or more, 4 mass% or more, 5 mass% or more, or 5.5 mass% or more. The content of component (C) may be 20 mass% or less, 15 mass% or less, 12 mass% or less, 10 mass% or less, 8 mass% or less, 7 mass% or less, or 6 mass% or less. From these viewpoints, the content of component (C) may be 0.1 to 20 mass%, 0.1 to 15 mass%, 0.1 to 10 mass%, 1 to 20 mass%, 1 to 15 mass%, 1 to 10 mass%, 3 to 20 mass%, 3 to 15 mass%, or 3 to 10 mass%.

[0058] From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, the content of component (C) may be within the following ranges relative to 100 parts by mass of the total amount of components (A) and (B): The content of component (C) may be 0.1 parts by mass or more, 0.5 parts by mass or more, 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, 5.5 parts by mass or more, or 6 parts by mass or more. The content of component (C) may be 20 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, 10 parts by mass or less, 8 parts by mass or less, 7 parts by mass or less, or 6 parts by mass or less. From these viewpoints, the content of component (C) may be 0.1 to 20 parts by mass, 0.1 to 15 parts by mass, 0.1 to 10 parts by mass, 1 to 20 parts by mass, 1 to 15 parts by mass, 1 to 10 parts by mass, 3 to 20 parts by mass, 3 to 15 parts by mass, or 3 to 10 parts by mass.

[0059] The photosensitive resin composition according to this embodiment contains a tetraarylbenzidine compound represented by the following general formula (d1) as component (D): Component (D) can be used as a sensitizer.

[0060] [ka] [In formula (d1), R 11 , R 12 , R 13 , R 14 , R15 , R 16 , R 17 and R 18 each independently represents an alkyl group, an alkoxy group, a halogeno group, an amino group, a hydroxy group, a carboxy group, or a carboxylate group; n11, n12, n13, and n14 each independently represent an integer of 0 to 4; n15, n16, n17, and n18 each independently represent an integer of 0 to 5; and at least one of n15 and n16 is 1 or greater.

[0061] R 11 If there are multiple, R 11 may be the same as or different from each other. 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 The same applies to the above. The number of carbon atoms in the alkyl group may be 1 to 6, 1 to 4, 1 to 3, or 1 to 2, from the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity. The number of carbon atoms in the alkoxy group may be 1 to 6, 1 to 4, 1 to 3, or 1 to 2, from the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity. Examples of the halogeno group include a fluoro group, a chloro group, a bromo group, and an iodo group. The amino group may be a primary or secondary amino group having a substituent. Examples of the carboxylate salt group include sodium salts.

[0062] From the viewpoint of easily achieving excellent resolution, adhesion, and sensitivity, the component (D) may contain a tetraarylbenzidine compound represented by the following general formula (d2). [ka] [In formula (d2), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17a , R 17b , R 18a and R 18beach independently represents an alkyl group, an alkoxy group, a halogeno group, an amino group, a hydroxy group, a carboxy group, or a carboxylate group, and n11, n12, n13, and n14 each independently represents an integer of 0 to 4.

[0063] R in formula (d2) 11 , R 12 , R 13 , R 14 , R 15 and R 16 is the R in equation (d1). 11 , R 12 , R 13 , R 14 , R 15 and R 16 The same applies to R in formula (d2). 17a and R 17b is the R in equation (d1). 17 The same applies to R in formula (d2). 18a and R 18b is the R in equation (d1). 18 is the same as:

[0064] R 15 and R 16 At least one selected from the group consisting of may be an alkyl group or a methyl group, from the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity. 17a and R 18a At least one selected from the group consisting of may be an alkyl group or an ethyl group, from the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity. 17b and R 18b From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, at least one selected from the group consisting of may be an alkyl group or a methyl group. From the viewpoint of easily obtaining excellent resolution, adhesion, and sensitivity, component (D) may contain N,N'-bis[4-(2-phenylethen-1-yl)-4'-methylphenyl]-N,N'-bis(2-ethyl-6-methylphenyl)-1,1'-biphenyl-4,4'-diamine.

[0065] The content of the component (D) may be in the following range based on the total solid content of the photosensitive resin composition: From the viewpoint of easily obtaining excellent sensitivity, the content of the component (D) may be 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.08% by mass or more, 0.09% by mass or more, 0.10% by mass or more, 0.13% by mass or more, 0.15% by mass or more, 0.18% by mass or more, 0.20% by mass or more, 0.23% by mass or more, 0.25% by mass or more, or 0.27% by mass or more. From the viewpoint of easily obtaining excellent resolution and adhesion, the content of the (D) component may be 5% by mass or less, 3% by mass or less, 1% by mass or less, 0.80% by mass or less, 0.60% by mass or less, 0.50% by mass or less, 0.40% by mass or less, 0.30% by mass or less, 0.28% by mass or less, 0.27% by mass or less, 0.25% by mass or less, 0.23% by mass or less, 0.20% by mass or less, 0.18% by mass or less, 0.15% by mass or less, 0.13% by mass or less, or 0.10% by mass or less. From these viewpoints, the content of component (D) may be 0.01 to 5 mass%, 0.01 to 1 mass%, 0.01 to 0.50 mass%, 0.01 to 0.20 mass%, 0.01 to 0.10 mass%, 0.05 to 5 mass%, 0.05 to 1 mass%, 0.05 to 0.50 mass%, 0.05 to 0.20 mass%, 0.05 to 0.10 mass%, 0.10 to 5 mass%, 0.10 to 1 mass%, 0.10 to 0.50 mass%, 0.10 to 0.20 mass%, 0.20 to 5 mass%, 0.20 to 1 mass%, or 0.20 to 0.50 mass%. The absorbance of the photosensitive resin composition can be adjusted by adjusting the content of component (D).

[0066] The content of component (D) may be within the following ranges relative to 100 parts by mass of the total of component (A) and component (B): From the viewpoint of easily obtaining excellent sensitivity, the content of component (D) may be 0.01 parts by mass or more, 0.03 parts by mass or more, 0.05 parts by mass or more, 0.08 parts by mass or more, 0.09 parts by mass or more, 0.10 parts by mass or more, 0.13 parts by mass or more, 0.15 parts by mass or more, 0.18 parts by mass or more, 0.20 parts by mass or more, 0.23 parts by mass or more, 0.25 parts by mass or more, 0.27 parts by mass or more, 0.28 parts by mass or more, or 0.30 parts by mass or more. From the viewpoint of easily obtaining excellent resolution and adhesion, the content of the (D) component may be 5 parts by mass or less, 3 parts by mass or less, 1 part by mass or less, 0.80 parts by mass or less, 0.60 parts by mass or less, 0.50 parts by mass or less, 0.40 parts by mass or less, 0.30 parts by mass or less, 0.28 parts by mass or less, 0.27 parts by mass or less, 0.25 parts by mass or less, 0.23 parts by mass or less, 0.20 parts by mass or less, 0.18 parts by mass or less, 0.15 parts by mass or less, 0.13 parts by mass or less, or 0.10 parts by mass or less. From these viewpoints, the content of the (D) component may be 0.01 to 5 parts by mass, 0.01 to 1 part by mass, 0.01 to 0.50 parts by mass, 0.01 to 0.25 parts by mass, 0.01 to 0.15 parts by mass, 0.05 to 5 parts by mass, 0.05 to 1 part by mass, 0.05 to 0.50 parts by mass, 0.05 to 0.25 parts by mass, 0.05 to 0.15 parts by mass, 0.15 to 5 parts by mass, 0.15 to 1 part by mass, 0.15 to 0.50 parts by mass, 0.15 to 0.25 parts by mass, 0.25 to 5 parts by mass, 0.25 to 1 part by mass, or 0.25 to 0.50 parts by mass. The absorbance of the photosensitive resin composition can be adjusted by adjusting the content of the (D) component.

[0067] The component (D) may be a compound that absorbs light in the range of 340 to 430 nm, may be a compound that efficiently absorbs light with wavelengths of 365 nm and 405 nm, may be a compound that absorbs light in the range of 395 to 415 nm, or may be a compound that efficiently absorbs light with a wavelength of 405 nm.

[0068] From the viewpoint of efficiently absorbing actinic rays, the molar absorption coefficient of component (D) at a maximum absorption wavelength in the range of 395 to 415 nm (the maximum absorption wavelength closest to 405 nm) may be 10,000 to 100,000 L / (mol cm), 20,000 to 100,000 L / (mol cm), 20,000 to 95,000 L / (mol cm), or 25,000 to 90,000 L / (mol cm). The molar absorption coefficient is an index of the ease of light absorption.

[0069] The molar extinction coefficient at the maximum absorption wavelength in the range of 395 to 415 nm (the maximum absorption wavelength closest to 405 nm) can be measured, for example, by the following procedure. First, toluene solutions of the UV absorber at four or more different concentrations (mol / L) are prepared at room temperature (25°C) using a volumetric flask and a volumetric pipette. Acetonitrile or methanol may be used as a dilution solvent, if necessary. The concentration (mol / L) can be calculated by dividing the mass (g) of the UV absorber placed in the volumetric flask by the molecular weight (g / mol) of the UV absorber, and then dividing this by the volumetric flask's capacity (L). Examples of methods for measuring the molecular weight (g / mol) of the UV absorber include mass spectrometry. The prepared toluene solution of the UV absorber is filled into a quartz cell with an optical path length of 1 cm, and the absorption spectrum of the UV absorber is measured using a UV-visible spectrophotometer (e.g., Hitachi High-Tech Corporation, product name: Hitachi Spectrophotometer U-3310). The spectrophotometer is used after stabilizing the light source. Then, a background measurement is performed in a 1 cm quartz cell filled with toluene, followed by the absorption spectrum measurement of the UV absorber. The measurement conditions are: temperature at the time of solution preparation, slit width 2 nm, scan speed 300 nm / min, sampling interval 0.50 nm, and measurement range 600 nm to 300 nm. For each measurement, ensure that the absorbance at a wavelength of 405 nm does not exceed 2.0. The vertical axis represents the absorbance of the UV absorber at a wavelength of 405 nm, and the horizontal axis represents the product of the UV absorber concentration and the optical path length. A straight line is approximated using the least-squares method. The coefficient of determination is confirmed to be 0.999 or greater. Using the Beer-Lambert law, the slope of the resulting line is calculated as the molar extinction coefficient (L / (mol·cm)) at the maximum absorption wavelength in the range of 395–415 nm (the wavelength closest to 405 nm). Note that in the above method, when the sample concentration is 1×10 -4 When the absorbance at the maximum absorption wavelength in the range of 395 to 415 nm (the maximum absorption wavelength closest to 405 nm) measured at mol / L is 0.01 or less, the molar extinction coefficient is defined as 100 or less.

[0070] The photosensitive resin composition according to this embodiment may contain other components (excluding compounds corresponding to component (A), component (B), component (C), or component (D)). Examples of other components include hydrogen donors, polymerization inhibitors, organic solvents, dyes (excluding compounds corresponding to hydrogen donors, such as malachite green), tribromophenyl sulfone, photocoloring agents, thermal color-developing inhibitors, plasticizers (such as p-toluenesulfonamide), pigments, fillers, antifoaming agents, flame retardants, stabilizers (such as light stabilizers), adhesion promoters, leveling agents, release promoters, antioxidants, fragrances, imaging agents, and thermal crosslinking agents.

[0071] Examples of the hydrogen donor include bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, leuco compounds (for example, leuco dyes such as leuco crystal violet), and N-phenylglycine.

[0072] From the viewpoint of easily achieving excellent resolution, adhesion, and sensitivity, the content of the hydrogen donor or the content of the leuco compound may be within the following ranges relative to 100 parts by mass of the total amount of the components (A) and (B): The content of the hydrogen donor or the content of the leuco compound may be more than 0 parts by mass, 0.01 parts by mass or more, 0.05 parts by mass or more, more than 0.05 parts by mass, 0.1 parts by mass or more, 0.2 parts by mass or more, 0.3 parts by mass or more, 0.4 parts by mass or more, or 0.5 parts by mass or more. The content of the hydrogen donor or the leuco compound may be 5 parts by mass or less, 3 parts by mass or less, 2 parts by mass or less, 1.5 parts by mass or less, 1 part by mass or less, 0.8 parts by mass or less, 0.7 parts by mass or less, or 0.5 parts by mass or less. From these viewpoints, the content of the hydrogen donor or the content of the leuco compound may be more than 0 parts by mass and not more than 5 parts by mass, more than 0.05 parts by mass and not more than 5 parts by mass, or 0.1 to 5 parts by mass.

[0073] The polymerization inhibitor suppresses polymerization in unexposed areas during resist pattern formation, and thus improves resolution. Examples of the polymerization inhibitor include t-butylcatechol (e.g., 4-t-butylcatechol), hindered amine (e.g., 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl), and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl.

[0074] From the viewpoint of facilitating improvement in resolution, the content of the polymerization inhibitor may be in the following ranges relative to 100 parts by mass of the total amount of the (A) and (B) components. The content of the polymerization inhibitor may be 0.001 parts by mass or more, 0.003 parts by mass or more, 0.005 parts by mass or more, 0.01 parts by mass or more, 0.015 parts by mass or more, 0.02 parts by mass or more, or 0.025 parts by mass or more. The content of the polymerization inhibitor may be 0.1 parts by mass or less, 0.05 parts by mass or less, 0.04 parts by mass or less, or 0.03 parts by mass or less. From these viewpoints, the content of the polymerization inhibitor may be 0.001 to 0.1 parts by mass.

[0075] Examples of the organic solvent include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, and propylene glycol monomethyl ether.

[0076] The photosensitive resin composition according to this embodiment may be free of an anthracene compound. Examples of anthracene compounds include 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 9,10-diethoxyanthracene, and 9,10-dipropoxyanthracene. The content of the anthracene compound may be 0.5 parts by mass or less, 0.2 parts by mass or less, less than 0.2 parts by mass, 0.1 parts by mass or less, less than 0.1 parts by mass, 0.01 parts by mass or less, or 0.001 parts by mass or less, or even 0% by mass, relative to 100 parts by mass of the total amount of components (A) and (B).

[0077] The photosensitive resin composition according to this embodiment may be free of an aminobenzenesulfonamide compound. Examples of the aminobenzenesulfonamide compound include 3-amino-4-methoxy-N,N'-diethylaminobenzenesulfonamide. The content of the aminobenzenesulfonamide compound may be 0.5 parts by mass or less, 0.3 parts by mass or less, less than 0.3 parts by mass, 0.1 parts by mass or less, less than 0.1 parts by mass, 0.01 parts by mass or less, or 0.001 parts by mass or less, relative to 100 parts by mass of the total amount of the components (A) and (B). It may even be 0% by mass.

[0078] <Photosensitive element> The photosensitive element according to this embodiment includes a support and a photosensitive resin layer disposed on the support, and the photosensitive resin layer contains the photosensitive resin composition according to this embodiment. The photosensitive element according to this embodiment may include a protective layer disposed on the photosensitive 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, or the like. The photosensitive element may be in the form of a sheet, or may be in the form of a photosensitive element roll wound around a core.

[0079] Fig. 1 is a schematic cross-sectional view showing an example of a photosensitive element. As shown in Fig. 1, the photosensitive element 1 includes 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 the photosensitive resin composition according to this embodiment.

[0080] The photosensitive element 1 can be obtained, for example, by the following procedure. First, a photosensitive resin layer 3 is formed on a 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 disposed on the photosensitive resin layer 3.

[0081] The support and the protective layer may each be a polymer film having heat resistance and solvent resistance, such as a polyester film (polyethylene terephthalate film, etc.), a polyolefin film (polyethylene film, polypropylene film, etc.), a hydrocarbon polymer (excluding polyolefin films), etc. The type of film constituting the protective layer and the type of film constituting the support may be the same or different from each other.

[0082] 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 preventing 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 and suitably exposing when exposing through the support. The thickness of the photosensitive resin layer (thickness after drying; if the photosensitive resin composition contains an organic solvent, thickness after volatilizing the organic solvent) may be the thickness of the above-mentioned film-like photosensitive resin composition.

[0083] <Method of manufacturing laminate> The method for producing a laminate according to this embodiment includes a photosensitive resin layer disposing step of disposing a photosensitive resin layer on a substrate (e.g., a substrate) using the photosensitive resin composition or photosensitive element according to this embodiment, an exposure step of photocuring (exposing) a portion of the photosensitive resin layer, and a development step of removing an uncured portion (unexposed portion) of the photosensitive resin layer to form a cured product pattern. The laminate according to this embodiment is obtained by the method for producing a laminate according to this embodiment and may be a printed wiring board. The laminate according to this embodiment may also include a substrate and a cured product pattern (the cured product according to this embodiment) disposed on the substrate.

[0084] In the photosensitive resin layer disposing step, a photosensitive resin layer made of the photosensitive resin composition according to this embodiment is disposed on a substrate. For example, the photosensitive resin layer may be formed by applying the photosensitive resin composition to the substrate and drying it, or by removing a protective layer from the photosensitive element and then pressing the photosensitive resin layer of the photosensitive element onto the substrate while heating.

[0085] In the exposure step, the photosensitive resin layer may be irradiated with actinic rays while a mask is placed on it, thereby exposing and photocuring regions of the photosensitive resin layer other than the region where the mask is placed, or may be irradiated with actinic rays in a desired pattern by a direct writing exposure method such as LDI exposure or DLP exposure without using a mask, thereby exposing and photocuring a portion of the photosensitive resin layer. The light source for the actinic rays may be an ultraviolet light source or a visible light source, such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a gas laser (such as an argon laser), a solid-state laser (such as a YAG laser), or a semiconductor laser.

[0086] The development method in the development step may be, for example, wet development or dry development. Wet development can be carried out using a developer suitable for the photosensitive resin composition by, for example, a dipping method, a puddle method, a spray method, brushing, scrubbing, or swing immersion. The developer is appropriately selected depending on the composition of the photosensitive resin composition, and may be an alkaline developer or an organic solvent developer.

[0087] The alkaline developer may be an aqueous solution containing a base such as an alkali hydroxide such as lithium, sodium, or potassium hydroxide; an alkali carbonate such as lithium, sodium, potassium, or ammonium carbonate or bicarbonate; an alkali metal phosphate such as potassium phosphate or sodium phosphate; an alkali metal pyrophosphate such as sodium pyrophosphate or potassium pyrophosphate; borax; sodium metasilicate; tetramethylammonium hydroxide; ethanolamine; ethylenediamine; diethylenetriamine; 2-amino-2-hydroxymethyl-1,3-propanediol; 1,3-diamino-2-propanol; morpholine, etc.

[0088] The organic solvent developer may contain an organic solvent such as 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, or γ-butyrolactone.

[0089] The method for producing a laminate according to this embodiment includes heating at 60 to 250°C or applying 0.2 to 10 J / cm after the exposure step and / or the development step. 2 The method may further include a step of further curing the cured portion of the photosensitive resin layer by exposing the cured portion to light.

[0090] The method for producing a laminate according to this embodiment may include, after the development step, a metal layer forming step of forming a metal layer on at least a portion of the portion of the substrate where the cured product pattern is not formed. The metal layer may be, for example, a metallic copper layer. The metal layer may be formed, for example, by plating. The plating may be one or both of an electrolytic plating process and an electroless plating process. The laminate according to this embodiment may include a substrate, a cured product pattern disposed on the substrate, and a metal layer disposed on at least a portion of the portion of the substrate where the cured product pattern is not formed.

[0091] The method for producing a laminate according to this embodiment may include a step of removing the cured product pattern after the metal layer formation step. The cured product pattern can be removed by, for example, developing using a strong alkaline aqueous solution by a dipping method, a spray method, or the like.

[0092] 2A and 2B are schematic diagrams showing an example of a method for manufacturing a laminate (a method for manufacturing a printed wiring board). In this example of a method for manufacturing a laminate, first, as shown in FIG. 2A, a substrate (e.g., a circuit-forming substrate) 10 is prepared, which includes an insulating layer 10a and a conductor layer 10b disposed on the insulating layer 10a. The conductor layer 10b may be, for example, a metallic copper layer.

[0093] 2(b), a photosensitive resin layer 12 is disposed on the conductor layer 10b of the substrate 10 (photosensitive resin layer disposing step). In the photosensitive resin layer disposing step, the photosensitive resin layer 12 is disposed on the conductor layer 10b of the substrate 10 using the photosensitive resin composition or photosensitive element according to this embodiment.

[0094] Next, as shown in FIG. 2(c), a mask 14 is placed on the photosensitive resin layer 12 and actinic rays L are irradiated to expose and photo-cure areas of the photosensitive resin layer 12 other than the area where the mask 14 is placed.

[0095] Next, after removing the mask 14, the areas of the photosensitive resin layer other than the photocured portions (uncured portions) are removed from the substrate 10 by development, as shown in FIG. 2(d), to form a resist pattern 12a consisting of the photocured portions (cured product of the photosensitive resin layer).

[0096] 2(e), a wiring layer (metal layer) 16 is formed on the portion of the conductor layer 10b of the substrate 10 where the resist pattern 12a is not formed. The wiring layer 16 may be formed of the same material as the conductor layer 10b, or may be formed of a different material.

[0097] 2(f), the resist pattern 12a is removed, and the conductor layer 10b provided at a position corresponding to the resist pattern 12a is removed to form the conductor layer 10c. This results in a printed wiring board 18 including the conductor layer 10c and the wiring layer 16 disposed on the insulating layer 10a. The conductor layer 10b can be removed by etching. The etching solution is appropriately selected depending on the type of conductor layer 10b, and may be, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, a hydrogen peroxide etching solution, or the like. [Example]

[0098] The present disclosure will be explained in more detail below using examples, but the present disclosure is not limited to these examples.

[0099] <Synthesis of binder polymer> (Binder Polymer A1) Solution (a) was prepared by mixing 27 parts by weight of methacrylic acid, 3 parts by weight of 2-hydroxyethyl methacrylate, 20 parts by weight of benzyl methacrylate, 50 parts by weight of styrene, and 0.9 parts by weight of azobisisobutyronitrile. Solution (b) was prepared by dissolving 0.5 parts by weight of azobisisobutyronitrile in 50 parts by weight of a mixture of 30 parts by weight of methyl cellosolve and 20 parts by weight of toluene. 500 g of a mixture of 30 parts by weight of methyl cellosolve and 20 parts by weight of toluene was placed in a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas inlet tube. The mixture was stirred while blowing nitrogen gas into the flask and heated to 80°C. Solution (a) was added dropwise to the flask at a constant rate over 4 hours, and the solution in the flask was stirred at 80°C for 2 hours. Next, solution (b) was added dropwise to the flask at a constant rate over 10 minutes, and the solution in the flask was stirred at 80°C for 3 hours. The solution in the flask was then heated to 90°C over 30 minutes and maintained at 90°C for 2 hours. After that, stirring was stopped and the solution was cooled to room temperature (25°C), yielding a solution of binder polymer A1. The non-volatile content (solid content) of the binder polymer A1 solution was 49% by mass.

[0100] (Binder polymer A2) A solution of binder polymer A2 was obtained in the same manner as for binder polymer A1, except that solution (a) was prepared by mixing 27 parts by mass of methacrylic acid, 5 parts by mass of methyl methacrylate, 23 parts by mass of benzyl methacrylate, 45 parts by mass of styrene, and 0.9 parts by mass of azobisisobutyronitrile. The non-volatile content (solid content) of the solution of binder polymer A2 was 47% by mass.

[0101] (Binder polymer A3) A solution of binder polymer A3 was obtained in the same manner as for binder polymer A1, except that solution (a) was prepared by mixing 30 parts by mass of methacrylic acid, 35 parts by mass of methyl methacrylate, 35 parts by mass of butyl methacrylate, and 0.5 parts by mass of azobisisobutyronitrile. The non-volatile content (solid content) of the solution of binder polymer A3 was 44% by mass.

[0102] (Binder polymer A4) A solution of binder polymer A4 was obtained in the same manner as for binder polymer A1, except that solution (a) was prepared by mixing 30 parts by mass of methacrylic acid, 22 parts by mass of methyl methacrylate, 8 parts by mass of butyl methacrylate, 10 parts by mass of ethyl acrylate, 30 parts by mass of styrene, and 0.5 parts by mass of azobisisobutyronitrile. The non-volatile content (solid content) of the solution of binder polymer A4 was 43% by mass.

[0103] <Acid value of binder polymer> The acid value of binder polymer A1 was 176 mg KOH / g, the acid value of binder polymer A2 was 176 mg KOH / g, the acid value of binder polymer A3 was 196 mg KOH / g, and the acid value of binder polymer A4 was 196 mg KOH / g. The acid values ​​were measured using the following procedure. First, 1 g of the binder polymer to be measured for acid value was precisely weighed, and then 30 g of acetone was added to the binder polymer to uniformly dissolve it, obtaining a solution. Next, an appropriate amount of phenolphthalein as an indicator was added to the solution, and then titration was performed using a 0.1 N aqueous solution of potassium hydroxide (KOH). The acid value was determined by calculating the mass (unit: mg) of KOH required to neutralize the acetone solution of the binder polymer.

[0104] <Molecular weight of binder polymer> The weight average molecular weight (Mw) of binder polymer A1 was 35,000, and the number average molecular weight (Mn) was 16,000. The weight average molecular weight (Mw) of binder polymer A2 was 50,000, and the number average molecular weight (Mn) was 21,000. The weight average molecular weight (Mw) of binder polymer A3 was 50,000, and the number average molecular weight (Mn) was 22,000. The weight average molecular weight (Mw) of binder polymer A4 was 50,000, and the number average molecular weight (Mn) was 21,000. The weight average molecular weight and number average molecular weight were measured by gel permeation chromatography (GPC) under the following conditions, and calculated using a calibration curve of standard polystyrene.

[0105] (GPC conditions) Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd., product name) Columns: Three of the following (product names, manufactured by Showa Denko Materials Co., Ltd.) Gelpack GL-R440 Gelpack GL-R450 Gelpack GL-R400M Eluent: tetrahydrofuran Measurement temperature: 40℃ Flow rate: 2.05mL / min Detector: Hitachi L-3300 RI (Hitachi, Ltd., product name)

[0106] <Preparation of Photosensitive Resin Composition> Example 1 A solution of binder polymer A1 (amount equivalent to 56 parts by mass of binder polymer (non-volatile content)), 35 parts by mass of 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (EO average 10 mol adduct, molecular weight: 804) (manufactured by Showa Denko Materials Co., Ltd., product name: FA-321M(70)), 5 parts by mass of 2,2-bis(4-(methacryloxypolyethoxy)phenyl)propane (EO average 2.6 mol adduct, molecular weight: 478, manufactured by Kyoeisha Chemical Co., Ltd., product name: BP-2EM), and (PO)(EO)( PO)-modified dimethacrylate (an adduct of an average of 6 mol of EO and an average of 12 mol of PO (total value), molecular weight: 1114, manufactured by Showa Denko Materials Co., Ltd., product name: FA-024M), 4 parts by mass, a photopolymerization initiator (2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, BCIM, manufactured by Hampford), and a sensitizer D1 (N,N'-bis[4-(2-phenylethen-1-yl)-4'-methylphenyl]-N,N'-bis(2-ethyl-6-methylphenyl) 0.10 parts by mass of 1,1'-biphenyl-4,4'-diamine (TRONLY (Changzhou Strong) Co., Ltd., trade name: PSS-402, maximum absorption wavelength: 397 nm, molar absorption coefficient at maximum absorption wavelength: 85000 L / (mol cm)), 0.5 parts by mass of hydrogen donor (leuco crystal violet, LCV, Yamada Chemical Co., Ltd.), 0.015 parts by mass of polymerization inhibitor A (4-t-butylcatechol, DIC Corporation, trade name: DIC-TBC-5P), and 0.015 parts by mass of polymerization inhibitor B (Asahi Denka Kogyo Co., Ltd., trade name: LA-7RD). A photosensitive resin composition was prepared by mixing 0.01 parts by mass of toluene, 0.02 parts by mass of dye (Malachite Green, MKG, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 1 part by mass of additive A (light stabilizer, manufactured by Showa Denko Materials Co., Ltd., product name: FA-711MM), 0.5 parts by mass of additive B (mixture of carboxybenzotriazole, 5-amino-1H-tetrazole and methoxypropanol, manufactured by Sanwa Chemical Co., Ltd., product name: SF-808H), 8 parts by mass of methanol, 18 parts by mass of toluene, and 10 parts by mass of acetone.

[0107] Example 2 A photosensitive resin composition was prepared in the same manner as in Example 1, except that the amount of sensitizer D1 used was changed to 0.20 parts by mass.

[0108] Example 3 A photosensitive resin composition was prepared in the same manner as in Example 1, except that the amount of sensitizer D1 used was changed to 0.30 parts by mass.

[0109] Example 4 A photosensitive resin composition was prepared in the same manner as in Example 1, except that a solution of binder polymer A2 (56 parts by mass of binder polymer (non-volatile content)) was used instead of the solution of binder polymer A1 (56 parts by mass of binder polymer (non-volatile content)).

[0110] Example 5 A photosensitive resin composition was prepared in the same manner as in Example 1, except that a solution of binder polymer A3 (56 parts by mass of binder polymer (non-volatile content)) was used instead of the solution of binder polymer A1 (56 parts by mass of binder polymer (non-volatile content)).

[0111] Example 6 A photosensitive resin composition was prepared in the same manner as in Example 1, except that a solution of binder polymer A4 (56 parts by mass of binder polymer (non-volatile content)) was used instead of the solution of binder polymer A1 (56 parts by mass of binder polymer (non-volatile content)).

[0112] (Comparative Example 1) A photosensitive resin composition was prepared in the same manner as in Example 4, except that 0.65 parts by mass of sensitizer D2 (9,10-dibutoxyanthracene, DBA, manufactured by Kawasaki Chemical Industries, Ltd., maximum absorption wavelength: 408 nm, molar absorption coefficient at the maximum absorption wavelength: 7800 L / (mol cm)) was used instead of 0.10 parts by mass of sensitizer D1.

[0113] (Comparative Example 2) A photosensitive resin composition was prepared in the same manner as in Example 4, except that 0.10 parts by mass of sensitizer D3 (N,N'-bis[4-(2-phenylethen-1-yl)-phenyl]-N,N'-bis(2-ethyl-6-methylphenyl)-1,1'-biphenyl-4,4'-diamine, maximum absorption wavelength: 392 nm, molar absorption coefficient at the maximum absorption wavelength: 68,000 L / (mol cm)) was used instead of 0.10 parts by mass of sensitizer D1.

[0114] <Preparation of Photosensitive Element> A 16 μm-thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., product name "FS-31") was prepared as a support. The above-mentioned photosensitive resin composition was applied to the support so as to have a uniform thickness, and then dried sequentially in a hot air convection dryer at 80°C and 120°C to form a photosensitive resin layer (photosensitive film, average thickness at 10 points after drying: 19 μm). A polyethylene film (manufactured by Tamapoly Corporation, product name "NF-15") was laminated to this photosensitive resin layer as a protective layer, thereby obtaining a photosensitive element having a support, a photosensitive resin layer, and a protective layer in that order.

[0115] <Preparation of laminate> A copper-clad laminate (substrate, Showa Denko Materials Co., Ltd., product name: MCL-E-67) with copper foil (thickness: 35 μm) arranged on both sides of a glass epoxy material was pickled, rinsed with water, and then dried in an air stream. The copper-clad laminate was then heated to 80°C, and the protective layer was peeled off. The photosensitive element described above was then laminated onto the copper surface, with the photosensitive resin layer in contact with the copper surface, to obtain a laminate comprising, in order, the copper-clad laminate, the photosensitive resin layer, and the support. Lamination was performed using a 110°C heat roll at a pressure of 0.4 MPa and a roll speed of 1.0 m / min.

[0116] <Evaluation> (minimum development time) The laminate was cut into a square (5 cm x 5 cm) and the support was peeled off to obtain a test piece. Next, the unexposed photosensitive resin layer of the test piece was spray-developed at a pressure of 0.18 MPa using a 1% by mass aqueous sodium carbonate solution at 30°C. The minimum development time (MD) was determined as the shortest time required for visual confirmation that the unexposed photosensitive resin layer had been removed. A full-cone type nozzle was used. The distance between the test piece and the nozzle tip was 6 cm, and the test piece was positioned so that the center of the nozzle coincided with the center of the test piece.

[0117] (sensitivity) A 41-step tablet (manufactured by Showa Denko Materials Co., Ltd.) was placed on the support of the above-mentioned laminate, and then the photosensitive resin layer was exposed through the support using a direct imaging exposure machine (manufactured by Via Mechanics Co., Ltd., product name: DE-1UH) with a blue-violet laser diode having a wavelength of 405 nm as a light source, at an exposure dose (amount of irradiation energy) such that the number of remaining steps after development of the 41-step tablet was 15. The exposure dose at this time (unit: mJ / cm 2 The sensitivity (photosensitivity) was evaluated by the following method. The results are shown in Table 1. The lower the exposure amount, the better the sensitivity.

[0118] (resolution) A 41-step tablet (Showa Denko Materials) was placed on the support of the laminate. A direct imaging exposure system (Via Mechanics, DE-1UH) using a 405 nm blue-violet laser diode as a light source was used to expose (draw) the photosensitive resin layer through the support without offset, using a pattern with a line width (L) / space width (S) ratio of 3x / x (x = 1-20 μm, 1 μm intervals) to the 41-step tablet. The exposure dose (irradiation energy) was adjusted so that 15 steps remained after development. Within 3 minutes of exposure, a post-exposure bake (PEB) was performed in a heating oven at 80°C for 30 seconds.

[0119] After exposure, the support was peeled off from the laminate to expose the photosensitive resin layer, and the unexposed areas were removed by spraying a 1% by mass aqueous solution of sodium carbonate at 30°C for twice the minimum development time mentioned above. After development, the space areas (unexposed areas) were removed without residue, and the line areas (exposed areas) were formed without meandering or chipping. The resolution was evaluated based on the minimum space width (unit: μm) in the resist pattern. The results are shown in Table 1. The smaller this value, the better the resolution.

[0120] (adhesion) A 41-step tablet (manufactured by Showa Denko Materials Co., Ltd.) was placed on the support of the above-mentioned laminate, and then a direct imaging exposure machine (manufactured by Via Mechanics Co., Ltd., product name: DE-1UH) using a 405 nm blue-violet laser diode as a light source was used to expose (image) the photosensitive resin layer through the support without offset, using an imaging pattern with an L / S of x / 3x (x = 1 to 20, unit: μm, 1 μm intervals) at an exposure dose (irradiation energy amount) such that the number of remaining steps after development of the 41-step tablet was 15. Within 3 minutes after exposure, a post-exposure bake (PEB) was performed in a heating oven at 80°C for 30 seconds.

[0121] After exposure, the support was peeled off from the laminate to expose the photosensitive resin layer, and the unexposed areas were removed by spraying a 1% by mass aqueous solution of sodium carbonate at 30°C for twice the minimum development time mentioned above. After development, the space areas (unexposed areas) were removed without residue, and the line areas (exposed areas) were formed without meandering or chipping. Adhesion was evaluated based on the minimum line width (unit: μm) in the resist pattern. The results are shown in Table 1. The smaller this value, the better the adhesion.

[0122] [Table 1] [Explanation of symbols]

[0123] 1...photosensitive element, 2...support, 3, 12...photosensitive resin layer, 4...protective layer, 10...base material, 10a...insulating layer, 10b, 10c...conductor layer, 12a...resist pattern, 14...mask, 16...wiring layer, 18...printed wiring board, L...actinic light.

Claims

1. The composition contains a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a tetraarylbenzidine compound represented by the following general formula (d1): the binder polymer includes a polymer having a styrene compound as a monomer unit, the content of the styrene compound monomer unit in the polymer is 35 mass % or more. 【Chemistry 1】 [In formula (d1), R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ each independently represents an alkyl group, an alkoxy group, a halogeno group, an amino group, a hydroxy group, a carboxy group, or a carboxylate group; n11, n12, n13, and n14 each independently represent an integer of 0 to 4; n15, n16, n17, and n18 each independently represent an integer of 0 to 5; and at least one of n15 and n16 is 1 or greater.

2. The photosensitive resin composition according to claim 1 , wherein the tetraarylbenzidine compound comprises a tetraarylbenzidine compound represented by the following general formula (d2): 【Chemistry 2】 [In formula (d2), R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ａ , R １７ｂ , R １８ａ and R １８ｂ each independently represents an alkyl group, an alkoxy group, a halogeno group, an amino group, a hydroxy group, a carboxy group, or a carboxylate group, and n11, n12, n13, and n14 each independently represents an integer of 0 to 4.

3. 2. The photosensitive resin composition according to claim 1, wherein the tetraarylbenzidine compound comprises N,N'-bis[4-(2-phenylethen-1-yl)-4'-methylphenyl]-N,N'-bis(2-ethyl-6-methylphenyl)-1,1'-biphenyl-4,4'-diamine.

4. 2. The photosensitive resin composition according to claim 1, wherein the content of the tetraarylbenzidine compound is 0.01 to 0.50 parts by mass per 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound.

5. The photosensitive resin composition according to claim 1 , wherein the polymer further comprises benzyl (meth)acrylate as a monomer unit.

6. 6. The photosensitive resin composition according to claim 5, wherein the content of the benzyl (meth)acrylate monomer unit in the polymer is 10 to 30% by mass.

7. 2. The photosensitive resin composition according to claim 1, wherein the content of the styrene compound monomer unit in the polymer is 40 to 60 mass %.

8. 2. The photosensitive resin composition according to claim 1, wherein the binder polymer has a weight average molecular weight of 10,000 to 100,000.

9. The photosensitive resin composition according to claim 1 , wherein the photopolymerizable compound comprises a bisphenol A (meth)acrylic acid compound.

10. The photosensitive resin composition according to claim 1 , which is in the form of a film.

11. The photosensitive resin composition according to claim 10, which has a thickness of 30 μm or less.

12. A support and a photosensitive resin layer disposed on the support, A photosensitive element, wherein the photosensitive resin layer comprises the photosensitive resin composition according to any one of claims 1 to 11.

13. A step of disposing a photosensitive resin layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 11; photocuring a portion of the photosensitive resin layer; and removing uncured portions of the photosensitive resin layer to form a cured pattern.

14. disposing a photosensitive resin layer on a substrate using the photosensitive element of claim 12; photocuring a portion of the photosensitive resin layer; and removing uncured portions of the photosensitive resin layer to form a cured pattern.

Images