Photosensitive resin composition, photosensitive resin laminate, and method for forming a resist pattern

Abstract

To provide a photosensitive resin composition which exhibits excellent adhesion to copper, little development residue, and excellent plating adhesion (adhesion to plating).SOLUTION: The photosensitive resin composition contains the following components: (A) an alkali-soluble polymer; (B) a compound having an ethylenically unsaturated double bond; (C) a photopolymerization initiator; and (D) a compound that has two or more aromatic rings in which there are three or more heteroatoms in total of at least one kind selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom and that has an acidic group having an acid dissociation constant (pKa) of -5 or more and 5 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a photosensitive resin laminate, and a method for forming a resist pattern. [Background technology]

[0002] Printed circuit boards are generally manufactured by photolithography. Photolithography is a technique that forms a photosensitive resin layer on a substrate, and then exposes and develops the resin layer to form a resist pattern. Using this technique, a desired wiring pattern can be formed on the substrate by first forming a conductor pattern through etching or plating, and then removing the resist pattern from the substrate.

[0003] To manufacture printed circuit boards, a "photosensitive resin laminate" (also called a "photosensitive element" or "dry film resist") is often used, in which a photosensitive resin layer is laminated on a support. There are known examples of photosensitive resin compositions for obtaining such photosensitive resin laminates, and examples of such known examples include the following Patent Documents 1 and 2.

[0004] Patent Document 1 aims to provide a photosensitive resin composition that can form a resist film with good resolution and adhesion, and with a small curing edge after development. Patent Document 1 discloses a photosensitive resin composition containing a benzotriazole derivative having a carboxyl group.

[0005] Patent Document 2 aims to provide a photosensitive resin composition that has excellent adhesion to copper surfaces and can form a stable resist film that is not affected by changes over time after coating or lamination. Patent Document 2 discloses a photosensitive resin composition comprising one or more heteroaromatic ring compounds selected from the group consisting of triazoles, tetrazoles, and imidazoles, and a carboxylic acid compound. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Patent No. 5878040 [Patent Document 2] Patent No. 4883537 [Overview of the project] [Problems that the invention aims to solve]

[0007] In recent years, with the miniaturization and weight reduction of electronic devices, printed circuit boards have become smaller and denser. Therefore, there has been a demand for high-performance photosensitive elements in the manufacturing process that exhibit excellent adhesion to copper substrates, can form fine resist patterns after development, and produce minimal development residue, which is one of the causes of plating defects.

[0008] However, while Patent Document 1 is presumed to achieve adhesion to the copper substrate using a benzotriazole derivative having a carboxyl group, it was insufficient to meet the recent demands for miniaturization of printed circuit boards. Furthermore, while Patent Document 2 is presumed to achieve both adhesion to the copper substrate and prevention of developer residue by combining a carboxylic acid compound and a heteroaromatic ring compound, both materials exhibiting these two effects act on the surface of the copper substrate, making it difficult to obtain sufficient results.

[0009] The inventors focused on a specific compound containing a heteroatom as a compound that achieves both excellent adhesion to copper and a reduction in developing residue, which is one of the causes of plating defects. Furthermore, the inventors found that including such a compound improves various performance characteristics.

[0010] This invention was proposed in view of the above circumstances. Specifically, one of the objectives of this invention is to provide a photosensitive resin composition and a photosensitive resin laminate that have excellent adhesion to copper, produce little developing residue, and have excellent plating adhesion (adhesion to plating), as well as a method for forming a resist pattern.

Means for Solving the Problem

[0011] That is, the present invention is as follows. [1] The following components: (A) An alkali-soluble polymer, (B) A compound having an ethylenically unsaturated double bond, (C) A photopolymerization initiator, and (D) A compound having two or more aromatic rings, in which a total of three or more heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms are present in the two or more aromatic rings, and having an acidic group with an acid dissociation constant (pKa) of -5 or more and 5 or less. A photosensitive resin composition containing the above. [2] The photosensitive resin composition according to item 1, wherein the component (A) contains a monomer having an aromatic group as a copolymerization component. [3] The aromatic ring in the component (D) is At least one of an aromatic hydrocarbon ring in which ring-constituting atoms do not contain heteroatoms and A heteroaromatic ring in which ring-constituting atoms contain heteroatoms, and the photosensitive resin composition according to item 1 or 2. [4] The aromatic ring in the component (D) is A heteroaromatic ring in which three or more of the nitrogen atoms are present in the same ring, and the photosensitive resin composition according to any one of items 1 to 3. [5] In the aromatic hydrocarbon ring in the component (D), the acidic group is bonded as a substituent, and the photosensitive resin composition according to item 3 or 4. [6] The component (D) is A structure having two or more heteroaromatic rings and in which a total of three or more of the heteroatoms are present in the two or more heteroaromatic rings, and A structure including a heteroaromatic ring in which a total of three or more of the heteroatoms are present and at least one of the aromatic hydrocarbon rings, The photosensitive resin composition according to any one of Items 3 to 5, comprising a compound having at least one of the structures. [7] The component (D) is represented by the following general formulas (1) to (4):

Chemical formula

[0012] [In the formula, Y is represented by the following general formula (5):

Chemical formula

[0013] {In the formula, S 1 , S 2 , S 3 , S 4 , and S 5 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an amino group, a hydroxy group, and an organic group having 1 to 20 carbon atoms, provided that at least one of S 1 , S 2 , S 3 , S 4 , and S 5 has the acidic group.}, and R 1 and R 2 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an amino group, a hydroxy group, and an organic group having 1 to 20 carbon atoms.] The photosensitive resin composition according to any one of Items 1 to 6, comprising a compound represented by any of the above. [8] The component (D) is such that at least one of S 1 , S 2 , S 3 , S 4 , and S 5 contains a carboxy group and / or an organic group having 1 to 20 carbon atoms containing a carboxy group, and the rest contains a group selected from the group consisting of a hydrogen atom, a hydroxy group, a hydrocarbon group having 1 to 20 carbon atoms, and an organic group having 1 to 20 carbon atoms containing a hydroxy group. The photosensitive resin composition according to Item 7. [9] The aforementioned component (D) is, R 1 and R 2 The photosensitive resin composition according to item 7 or 8, wherein the composition contains a group selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxyl group, a hydrocarbon group having 1 to 20 carbon atoms, and an organic group having 1 to 20 carbon atoms containing a carboxyl group and / or a hydroxyl group.

[10] The photosensitive resin composition according to any one of items 1 to 9, wherein the (D) component comprises a compound whose common logarithm of the octanol / water partition coefficient is 0.5 or greater.

[11] The aforementioned component (A) is, It contains a monomer having a carboxyl group and a monomer having an aromatic group as copolymer components, and The photosensitive resin composition according to any one of items 1 to 10, wherein the copolymerization ratio of the monomer having the aromatic group is 10% by mass or more with respect to the total mass of the comonomers constituting component (A).

[12] A photosensitive resin composition according to any one of items 1 to 11, wherein the (D) component is contained in an amount of 0.001 to 0.5% by mass relative to the total amount of solids in the photosensitive resin composition.

[13] The (C) component is a photosensitive resin composition according to any one of items 1 to 12, comprising an anthracene derivative.

[14] The (C) component is a photosensitive resin composition according to any one of items 1 to 13, comprising a benzophenone derivative.

[15] A photosensitive resin laminate comprising a support and a photosensitive resin layer obtained from any one of the photosensitive resin compositions described in item 1 to 14.

[16] Lamination process for laminating the photosensitive resin laminate described in item 15 onto a substrate, An exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate, and A developing step in which the unexposed portion of the photosensitive resin layer is developed and removed. A method for forming a resist pattern, including [a specific component]. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a photosensitive resin composition that exhibits excellent adhesion to copper, low development residue, and excellent plating adhesion, as well as a photosensitive resin laminate obtained using the photosensitive resin composition, and a method for forming a resist pattern using the photosensitive resin laminate. Further embodiments of the present invention and their advantages will become apparent by referring to the following description. [Modes for carrying out the invention]

[0015] Embodiments of the present invention (hereinafter referred to as "these embodiments") will be described in detail below. In this specification, numerical ranges indicated using "~" include the numerical values ​​indicated before and after "~" within that range. In this specification, an upper or lower limit indicated in a numerical range described in steps may be replaced with an upper or lower limit in a numerical range described in another step. In this specification, an upper or lower limit indicated in a numerical range may also be replaced with a value described in an example. In this specification, "(meth)acrylic" means acrylic and methacrylic, and "(meth)acrylate" means "acrylate" and "methacrylate".

[0016] [Photosensitive resin composition] The photosensitive resin composition of this embodiment comprises the following components: (A) Alkali-soluble polymer, (B) Compounds having an ethylenically unsaturated double bond, (C) Photopolymerization initiator, and (D) A compound having two or more aromatic rings, wherein a total of three or more heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms are present in the two or more aromatic rings, and the compound has an acidic group with an acid dissociation constant (pKa) of -5 or more and 5 or less. In this specification, "aromatic ring" is a concept that includes both "aromatic hydrocarbon rings" and "hetero-aromatic rings". "Aromatic hydrocarbon ring" means an aromatic ring whose ring constituent atoms do not contain heteroatoms, and "hetero-aromatic ring" means an aromatic ring whose ring constituent atoms include heteroatoms. According to this embodiment, by having the above configuration, it is possible to provide a photosensitive resin composition that has excellent adhesion to copper, produces little developing residue, and has excellent plating adhesion.

[0017] The reason for this is still unclear, and the present invention is not limited to theory, but the inventors speculate as follows: Heteroaromatic ring compounds containing three or more heteroatoms often have strong interactions with copper. Therefore, by including the above heteroaromatic ring compounds, it is possible to provide a photosensitive resin composition with excellent adhesion to copper surfaces. In one embodiment, compounds containing three or more heteroatoms in the same ring (compounds having a triazole skeleton, compounds having a tetrazole skeleton, etc.) have strong interactions with copper, making it easier to improve the adhesion between the resist and the copper surface.

[0018] In addition to the effects described above, the inclusion of two or more aromatic rings in one molecule of component (D) strengthens its interaction with the alkali-soluble polymer (A), thereby improving the adhesion between the resist and the copper surface. In one embodiment, the inclusion of aromatic hydrocarbon rings in component (D) tends to strengthen its interaction with the alkali-soluble polymer (A). On the other hand, due to the hydrophobicity of these ring compounds, there is a possibility that the resist will remain on the substrate after development (development residue will be generated). The inventors have found that by constituting component (D) with highly alkali-soluble acidic groups with a pKa of 5 or less, development residue can be reduced and plating adhesion can be improved.

[0019] In other words, the inventors of the present invention consider the following elements (1) to (3): (1) Having two or more aromatic rings; (2) There are a total of three or more heteroatoms in two or more aromatic rings; and, (3) Having an acidic group with a pKa of -5 or more and 5 or less; We focused on incorporating a compound that satisfies the same condition in the same compound as component (D) into the photosensitive resin composition. We found that this makes it possible to obtain a photosensitive resin composition with excellent adhesion to copper, low development residue, and excellent plating adhesion.

[0020] <(A) Component: Alkali-soluble polymer> Component (A) is preferably obtained by polymerizing at least one of the first monomers described later. Component (A) is more preferably obtained by copolymerizing at least one of the first monomers with at least one of the second monomers described later.

[0021] The first monomer is a monomer containing a carboxyl group in its molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid semi-ester. Among these, (meth)acrylic acid is preferred.

[0022] The copolymerization ratio of the first monomer in component (A) is preferably 10% by mass, 13% by mass, 15% by mass or more, and more preferably 35% by mass or less, 30% by mass or less, and 28% by mass or less, based on the total mass of the comonomers constituting component (A).

[0023] The second monomer is a non-acidic monomer that has at least one polymerizable unsaturated group in its molecule. Examples of the second monomer include: (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, etc. Vinyl alcohol esters such as vinyl acetate; (Meth)acrylonitrile, styrene, and polymerizable styrene derivatives (methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.); Examples include the following. Among them, methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, 2-ethylhexyl (meth)acrylate, and benzyl (meth)acrylate are preferred, and benzyl (meth)acrylate is particularly preferred from the viewpoint of suppressing side etching.

[0024] The copolymerization ratio of the second monomer in component (A) is preferably 65% ​​by mass or more, 70% by mass or more, and 72% by mass or more, with respect to the total mass of the comonomers constituting component (A), and preferably 90% by mass or less, 87% by mass or less, and 85% by mass or less.

[0025] In this embodiment, from the viewpoint of improving adhesion to the copper substrate and improving the resolution of the resist pattern, component (A) preferably contains an aromatic ring (in particular, an aromatic hydrocarbon ring in this case) in its molecular structure, and more preferably has an aromatic group in the side chain of its structure. In one embodiment, from the same viewpoint as above, component (A) preferably contains a monomer having an aromatic group as a copolymer component.

[0026] Component (A), which has an aromatic group in its side chain, can be prepared by using a compound having an aromatic group as at least one of the first and second monomers. Examples of monomers having an aromatic group include: Aralkyl esters of (meth)acrylic acid such as benzyl (meth)acrylate; Phenoxypolyethylene glycol (meth)acrylate; Cinnamic acid; Styrene, styrene derivatives (methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.); These are some examples. From the viewpoint of suppressing side etching, (meth)acrylate aralkyl ester and styrene are preferred, and benzyl (meth)acrylate is particularly preferred.

[0027] The copolymerization ratio of the compound having an aromatic group is preferably 10% 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, 70% by mass or more, or 80% by mass or more, relative to the total mass of the comonomers constituting component (A). From the viewpoint of maintaining alkali solubility, the copolymerization ratio of the compound having an aromatic group is preferably 95% by mass or less, or 90% by mass or less.

[0028] Component (A) preferably contains a monomer having a carboxyl group and a monomer having an aromatic group as copolymer components, and the copolymerization ratio of the monomer having an aromatic group is 10% by mass or more of the total mass of the comonomers constituting component (A). This makes it easier to achieve the effects of the present invention. From a similar viewpoint, it is more preferable that the above ratio is 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, 70% by mass or more, or 80% by mass or more.

[0029] In this embodiment, component (A) can be prepared by a known polymerization method, preferably addition polymerization, more preferably radical polymerization, by selecting one or more monomers from the first monomer and the second monomer.

[0030] The acid value of component (A) is preferably 100 mg KOH / g or more from the viewpoint of the developability of the photosensitive resin layer and the resolution and adhesion of the resist pattern, and preferably 600 mg KOH / g or less from the viewpoint of the developability and peelability of the photosensitive resin layer. (A) The acid value of component may be 60 mg KOH / g or higher, 80 mg KOH / g or higher, 500 mg KOH / g or lower, or 400 mg KOH / g or lower.

[0031] The weight-average molecular weight (hereinafter sometimes abbreviated as "Mw") of component (A) (or the total Mw when multiple components are used in combination) is preferably 5,000 or more and 10,000 or more, and also preferably 500,000 or less, 100,000 or less, and 65,000 or less. The dispersion (Mw / Mn), which is the ratio of the weight-average molecular weight to the number-average molecular weight (hereinafter sometimes abbreviated as "Mn") (or the total dispersion when multiple components of (A) are used in combination) is preferably 1.0 or more, 1.5 or more, 2.0 or more, 2.5 or more, and 3.0 or more, and also preferably 6.0 or less, 5.0 or less, 4.7 or less, 4.5 or less, and 4.2 or less. Having the weight-average molecular weight and dispersion of component (A) within the above ranges is preferable from the viewpoint of obtaining appropriate developability, high coating strength, and uniformity of resist thickness.

[0032] (A) The proportion of component used is preferably 25% by mass or more, 35% by mass or more, and preferably 85% by mass or less, and 75% by mass or less, relative to the total amount of solids in the photosensitive resin composition. Setting the proportion of component used to (A) within the above range is preferable from the viewpoint of resolution, developability, swelling of the exposed area in the developer solution, peelability of the resist pattern, and product life of the photosensitive element.

[0033] <(B) Component: Compound having an ethylenically unsaturated double bond> Component (B) is a polymerizable compound that has an ethylenically unsaturated double bond in its structure. Examples of such compounds include: Compounds obtained by adding (meth)acrylic acid to one end of a polyalkylene oxide, compounds obtained by adding (meth)acrylic acid to one end of a polyalkylene oxide and modifying the other end with an alkyl ether or allyl ether, etc. (compounds of Group 1); Compounds having (meth)acryloyl groups at both ends of an alkylene oxide chain, compounds having (meth)acryloyl groups at both ends of an alkylene oxide chain in which an ethylene oxide chain and a propylene oxide chain are randomly or block-linked, compounds modified from bisphenol A, etc. (compounds of group 2); Compounds having three or more (e.g., 3 to 6, i.e., 3, 4, 5, or 6) (meth)acryloyl groups in a single molecule, etc. (compounds of group 3); These are some examples.

[0034] Other compounds in Group 1 include: Phenoxyhexaethylene glycol mono(meth)acrylate, which is a (meth)acrylate of a compound in which polyethylene glycol is added to a phenyl group; 4-n-nonylphenoxyheptaethylene glycol dipropylene glycol (meth)acrylate is a (meth)acrylate of a compound obtained by adding polypropylene glycol with an average of 2 moles of propylene oxide and polyethylene glycol with an average of 7 moles of ethylene oxide to nonylphenol; 4-n-nonylphenoxypentaethylene glycol monopropylene glycol (meth)acrylate is a (meth)acrylate of a compound obtained by adding polypropylene glycol with an average of 1 mole of propylene oxide and polyethylene glycol with an average of 5 moles of ethylene oxide to nonylphenol; 4-n-nonylphenoxyoctaethylene glycol (meth)acrylate (e.g., M-114, manufactured by Toagosei Co., Ltd.), which is an acrylate of a compound obtained by adding polyethylene glycol with an average of 8 moles of ethylene oxide to nonylphenol. These are some examples.

[0035] Other compounds in Group 2 include: Polyethylene glycol (meth)acrylates such as tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, heptaethylene glycol di(meth)acrylate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, compounds having (meth)acryloyl groups at both ends of a 12 mole ethylene oxide chain; Polypropylene glycol di(meth)acrylate; Polybutylene glyco di(meth)acrylate; These are some examples.

[0036] Polyalkylene oxide di(meth)acrylate compounds containing ethylene oxide groups and propylene oxide groups include: A dimethacrylate of glycol obtained by adding an average of 12 moles of propylene oxide to polypropylene glycol and then adding an average of 3 moles of ethylene oxide to each end. Dimethacrylate of a glycol obtained by adding an average of 18 moles of propylene oxide to polypropylene glycol, and then adding an average of 15 moles of ethylene oxide to each end; These are some examples. Other examples include compounds having ethylenically unsaturated double bonds at both ends of a polyalkylene glycol obtained by adding alkylene oxide to bisphenol A.

[0037] From the viewpoint of resolution and adhesion, it is preferable to use a compound having ethylenically unsaturated double bonds at both ends of a polyalkylene glycol obtained by adding an alkylene oxide to bisphenol A as a modified compound of the second group of compounds described above. It is preferable that the ethylenically unsaturated double bonds in this compound are contained in the compound in the form of being contained within the (meth)acryloyl group. Known modification methods for adding alkylene oxides to bisphenol A include ethylene oxide modification, propylene oxide modification, butylene oxide modification, pentylene oxide modification, and hexylene oxide modification. Compounds having (meth)acryloyl groups at both ends of a polyalkylene glycol obtained by adding ethylene oxide to bisphenol A are preferred.

[0038] Examples of such compounds include 2,2-bis(4-((meth)acryloxydiethoxy)phenyl)propane (e.g., NK ester BPE-200 manufactured by Shin Nakamura Chemical Industry Co., Ltd.), 2,2-bis(4-((meth)acryloxytriethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxytetraethoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane (e.g., NK ester BPE-500 manufactured by Shin Nakamura Chemical Industry Co., Ltd.). Furthermore, compounds modified with ethylene oxide and propylene oxide are also preferred, such as polyalkylene glycol di(meth)acrylates obtained by adding an average of 2 moles of propylene oxide and an average of 6 moles of ethylene oxide to both ends of bisphenol A; and polyalkylene glycol di(meth)acrylates obtained by adding an average of 2 moles of propylene oxide and an average of 15 moles of ethylene oxide to both ends of bisphenol A. From the viewpoint of improving resolution, adhesion, and flexibility, the number of moles of ethylene oxide and propylene oxide in compounds having (meth)acryloyl groups at both ends by modifying bisphenol A with alkylene oxide is preferably 1 to 60 moles, more preferably 4 to 40 moles, and even more preferably 5 to 20 moles.

[0039] The compounds of the third group described above are obtained by (meth)acrylateing an alcohol obtained by adding an alkylene oxide group such as an ethylene oxide group, a propylene oxide group, or a butylene oxide group to a central skeleton having 3 moles or more of groups that can be used to add an alkylene oxide group within the molecule. Examples of compounds that can form the central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate rings. More specifically, examples include trimethylolpropane with 3 molars of ethylene oxide (EO) modified triacrylate, trimethylolpropane with 6 molars of EO modified triacrylate, trimethylolpropane with 9 molars of EO modified triacrylate, and trimethylolpropane with 12 molars of EO modified triacrylate. Examples of such compounds include glycerin EO3 molar modified triacrylate (e.g., A-GLY-3E manufactured by Shin Nakamura Chemical Industry Co., Ltd.), glycerin EO9 molar modified triacrylate (e.g., A-GLY-9E manufactured by Shin Nakamura Chemical Industry Co., Ltd.), glycerin EO6 molar and propylene oxide (PO)6 molar modified triacrylate (A-GLY-0606PE), and glycerin EO9 molar PO9 molar modified triacrylate (A-GLY-0909PE). Furthermore, examples include pentaerythritol 4EO modified tetraacrylate (e.g., SR-494 manufactured by Sartomer Japan Co., Ltd.) and pentaerythritol 35EO modified tetraacrylate (e.g., NK ester ATM-35E manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

[0040] Compounds containing ethylenically unsaturated double bonds include isocyanurate compounds. Specific examples of such compounds include ethoxylated isocyanurate tri(meth)acrylate, ε-caprolactone-modified tris(2-(meth)acryloxyethyl)isocyanurate, triallyl isocyanurate, and the following formula: [ka]

[0041] Examples include compounds represented by (EO), (EO)-modified isocyanurate-derived tri(meth)acrylate (ethylene oxide adduct with an average of 27 mol), and others. Examples of such compounds that can be used are commercially available products such as UA-7100 and A-9300-1CL (both manufactured by Shin-Nakamura Chemical Industry Co., Ltd.); and Aronics M-327 (manufactured by Toagosei Co., Ltd.).

[0042] Examples of compounds having a urethane bond and an ethylenically unsaturated double bond include urethane compounds of hexamethylene diisocyanate, tolylene diisocyanate, or diisocyanate compounds (e.g., 2,2,4-trimethylhexamethylene diisocyanate) and compounds having a hydroxyl group and a (meth)acrylic group in one molecule (e.g., 2-hydroxypropyl acrylate, oligopropylene glycol monomethacrylate). Specifically, these are reaction products of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (manufactured by Nippon Oil & Fats Co., Ltd., Bremmer PP1000).

[0043] Examples of compounds having a phthalic acid structure and an ethylenically unsaturated double bond include γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate and β-hydroxyalkyl-β'-(meth)acryloyloxyalkyl-o-phthalate.

[0044] In addition, component (B) may include tricyclodecanedi(meth)acrylate, (2,2-bis{4-(methacryloxypentaethoxy)cyclohexyl}propane, etc.

[0045] In one embodiment, an example of a usable component (B) is: A polyethylene glycol dimethacrylate obtained by adding an average of 5 moles of ethylene oxide to each end of bisphenol A; A polyethylene glycol dimethacrylate obtained by adding an average of 2 moles of ethylene oxide to each end of bisphenol A; Heptapropylene glycol dimethacrylate; Tetramethacrylate obtained by adding an average of 15 moles of ethylene oxide to pentaerythritol; Examples include the above. The component (B) exemplified herein can be used individually or in combination of two or more.

[0046] The photosensitive resin composition of this embodiment may contain a compound modified from bisphenol A. In the photosensitive resin composition of this embodiment, the proportion of the modified bisphenol A compound used is preferably 12 to 45% by mass, more preferably 17 to 40% by mass, and even more preferably 20 to 40% by mass, based on the total mass of the solids of the photosensitive resin composition. Using a proportion within this range is preferable from the viewpoint of obtaining a photosensitive resin composition with an excellent balance of resolution and developability.

[0047] The proportion of the compound having component (B) to the total solid content of the photosensitive resin composition is preferably 5 to 70% by mass. A proportion of 5% by mass or more is preferred from the viewpoint of sensitivity, resolution and adhesion, a proportion of 15% by mass or more is more preferred, and a proportion of 20% by mass or more is even more preferred. On the other hand, a proportion of 70% by mass or less is preferred from the viewpoint of suppressing the delay of peeling of edge fuses and cured resists, and a proportion of 60% by mass or less is even more preferred.

[0048] <(C) Component: Photopolymerization initiator> (C) Examples of components include hexaarylbiimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, anthracene derivatives, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkylketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-aryl amino acid ester compounds, and halogen compounds.

[0049] Examples of hexaarylbiimidazole compounds include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, and 2,4,5-tris-(o-chlorophenyl)-diphenylbiimidazole. 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl) 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl) 2,2'-Bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-Bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-Bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-Bis-(2,Examples include 3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, rofin dimers, etc.

[0050] Examples of rophine dimers, i.e., dimers of 2,4,5-triarylimidazole, 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. Among these, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred from the viewpoint of high sensitivity, resolution, and adhesion.

[0051] Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among these, N-phenylglycine is preferred due to its high sensitizing effect.

[0052] Examples of quinone compounds include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0053] Examples of aromatic ketone compounds include benzophenone, Michla's ketone [4,4'-bis(dimethylamino)benzophenone], and 4-methoxy-4'-dimethylaminobenzophenone. 4,4'-bis(diethylamino)benzophenone is also an example of an aromatic ketone compound, given its sensitizing effect and adhesion properties.

[0054] In this specification, the term "anthracene derivative" includes both anthracene and compounds derived therefrom. Examples of anthracene derivatives include anthracene, 9,10-dialkoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, (10-phenylanthracene-9-yl)boronic acid, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, and 1-chloroanthraquinone. From the viewpoint of sensitization effect and adhesion, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and (10-phenylanthracene-9-yl)boronic acid are preferred, and 9,10-diphenylanthracene is particularly preferred.

[0055] Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, and 2,2-dimethoxy-2-phenylacetophenone. A commercially available example of an acetophenone compound is Omnirad BDK651 (manufactured by IGM RESINS).

[0056] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide. Commercially available acylphosphine oxide compounds include Lucilin TPO and Irgacure-819 (both manufactured by BASF Japan Ltd.).

[0057] Examples of benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin. Examples of dialkyl ketal compounds include benzyl dimethyl ketal and benzyl diethyl ketal. Examples of thioxanthone compounds include 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, and 2-chlorthioxanthone. Examples of dialkylaminobenzoic acid ester compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.

[0058] Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-O-benzoyl oxime and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime. Commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 (all manufactured by BASF Japan Ltd.).

[0059] As for the acridine compound, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine are preferred in terms of sensitivity, resolution, and availability.

[0060] As pyrazoline derivatives, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, and 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline are preferred from the viewpoint of adhesion and rectangularity of the resist pattern.

[0061] Examples of ester compounds of N-aryl amino acids include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.

[0062] Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, chlorinated triazine compounds, and diallylodonium compounds. Among these, tribromomethylphenylsulfone is preferred.

[0063] The content of component (C) in the photosensitive resin composition is preferably 0.01 to 20% by mass, and more preferably 0.5 to 10% by mass. By adjusting the content of component (C) within the above range, sufficient sensitivity can be easily obtained, making it easier to transmit light sufficiently to the bottom of the photosensitive resin layer, and consequently, easier to achieve high resolution.

[0064] From the viewpoint of high sensitivity, resolution, and adhesion, it is preferable that the (C) component contains a rofin dimer. In this case, the content of the rofin dimer in the photosensitive resin composition is preferably 0.1 to 15% by mass, and more preferably 0.5 to 10% by mass.

[0065] As component (C), it is preferable to use an anthracene derivative and a hexaarylbiimidazole compound in combination, or a benzophenone derivative and a hexaarylbiimidazole compound in combination. In this case, the content of component (C) (e.g., anthracene derivative) in the photosensitive resin composition is preferably 0.5% by mass or less, more preferably 0.01 to 0.4% by mass, and the content of the hexaarylbiimidazole compound in the photosensitive resin composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.

[0066] <(D) Component: Compound containing a heteroatom> In this embodiment, component (D) is a compound having two or more aromatic rings, a total of three or more heteroatoms present in the two or more aromatic rings, and an acidic group with a pKa of -5 or more and 5 or less. In this specification, nitrogen atoms, oxygen atoms, and sulfur atoms are collectively referred to as heteroatoms. In one embodiment, the aromatic rings in component (D) are A ring of aromatic hydrocarbons whose constituent atoms do not contain heteroatoms, The ring comprises at least one of the following: a heteroaromatic ring whose ring constituent atoms include heteroatoms. Furthermore, component (D) may have four or fewer aromatic rings. In addition, there may be a total of six or fewer heteroatoms in those rings.

[0067] (D) component is, A configuration in which multiple aromatic rings contain heteroatoms, and there are three or more heteroatoms; Embodiments comprising a heteroaromatic ring containing three or more heteroatoms and an aromatic hydrocarbon ring not containing heteroatoms; Either of the above is acceptable. Also, component (D) is, A structure having two to four heteroaromatic rings, and in which a total of three to six heteroatoms are present in those two or more heteroaromatic rings; A structure comprising a heteroaromatic ring having a total of 3 to 4 heteroatoms, and multiple aromatic hydrocarbon rings (for example, 1 to 3 aromatic hydrocarbon rings); It may include at least one of the structures of (D). The effects of the present invention are more easily achieved when component (D) is in the above form and includes the above structure.

[0068] Compounds containing three or more heteroatoms in a single aromatic ring include 1,2,5-oxadiazole, 1,2,3-oxadiazole, 1,3,4-thiadiazole, 1,2,5-thiadiazole, and benzothiadiazole.

[0069] Compounds in which multiple aromatic rings contain heteroatoms and the total number of heteroatoms is three or more include compounds containing multiple heteroaromatic rings listed below within a single compound. Aromatic rings containing a nitrogen atom include pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, 1H-indole, 1H-indazole, benzimidazole, 4-azaindole, 5-azaindole, 7-azaindole, quinoline, isoquinoline, quinazoline, quinoxaline, and cinnoline. Aromatic rings containing an oxygen atom include furan, 1,4-dioxin, benzofuran, and isobenzofuran. Aromatic rings containing a sulfur atom include thiophene, benzo[b]thiophene, and benzo[c]thiophene. Aromatic rings containing multiple types of heteroatoms include oxazoles, isoxazoles, thiazoles, isothiazoles, 6H-fl[2,3-b]pyrroles, 4H-fl[3,2-b]pyrroles, 6H-thieno[2,3-b]pyrroles, 4H-thieno[3,2-b]pyrroles, benzoxazoles, benzoisoxazoles, benzothiazoles, and benzoisothiazoles.

[0070] The aromatic ring in component (D) preferably includes a heteroaromatic ring containing three or more nitrogen atoms within the same ring. The effects of the present invention are more easily achieved when component (D) includes such a compound.

[0071] Examples of heterocycles containing three or more nitrogen atoms include 1,2,3-triazole, 1,2,4-triazole, tetrazole, benzotriazole, 7-azindazole, pyrazolo[1,5-a]pyrimidine, purine, 1,2,4-triazine, 1,3,5-triazine, pyrido[3,2-d]pyrimidine, pyrido[4,3-d]pyrimidine, pyrido[3,4-b]pyrazine, pyrido[2,3-b]pyrazine, pteridine, and compounds in which hydrogen atoms in these compounds are substituted with organic groups.

[0072] Examples of acidic groups with a pKa of -5 to 5 include carboxyl groups, phosphate groups, and sulfonic acid groups. In one embodiment, it is preferable that the above-mentioned acidic group is bonded as a substituent to the aromatic hydrocarbon ring in component (D). The effects of the present invention are more easily achieved when component (D) contains such compounds. However, the acidic group may be bonded as a substituent to a heteroaromatic ring, or it may be bonded to the aromatic hydrocarbon ring and / or heteroaromatic ring via any group.

[0073] From the viewpoint of improving adhesion to the substrate, component (D) is the general formula (1) to (4) described below:

[0074] [ka]

[0075] [In the formula, Y is the following general formula (5): [ka]

[0076] {In formula, S 1 S 2 S 3 S 4 and S5 is at least one selected from the group consisting of a hydrogen atom, a halogen atom, an amino group, a hydroxyl group, and an organic group having 1 to 20 carbon atoms, provided that S 1 S 2 S 3 S 4 and S 5 At least one of them has the above-mentioned acidic group. The compound is represented by}, and R 1 and R 2 [This is at least one selected from the group consisting of hydrogen atoms, halogen atoms, amino groups, hydroxyl groups, and organic groups having 1 to 20 carbon atoms.] It is even more preferable to include a compound represented by any of the following formulas. In the formulas, "*" indicates a bonding site with a nitrogen atom (the nitrogen atom to which Y is bonded in formulas (1) to (4)).

[0077] In one embodiment, component (D) is, S in equation (5) above 1 S 2 S 3 S 4 and S 5 At least one of these includes a carboxyl group and / or an organic group having 1 to 20 carbon atoms that contains a carboxyl group. Preferably, the remaining group consists of a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 20 carbon atoms, and an organic group having 1 to 20 carbon atoms that includes a hydroxyl group. This makes it easier to achieve the effects of the present invention.

[0078] Examples of hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, and cycloalkyl groups. Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group. Examples of alkenyl groups include allyl groups, pentenyl groups, and vinyl groups. An example of an alkynyl group is the ethynyl group. Examples of alkylidene groups include methylidene groups and ethylidene groups. Examples of aryl groups include phenyl, naphthyl, benzyl, tolyl, and xylyl groups. Examples of cycloalkyl groups include adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

[0079] Organic groups having 1 to 20 carbon atoms that contain a carboxyl group or a hydroxyl group include carboxyl groups, alkyl groups in which some of the hydrogen atoms are substituted with carboxyl or hydroxyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, and cycloalkyl groups. Furthermore, as long as these compounds contain a carboxyl group or a hydroxyl group, the other hydrogen atoms may be substituted with substituents containing atoms other than carbon and hydrogen, such as halogen atoms, aldehyde groups, amino groups, imino groups, nitro groups, sulfo groups, and cyano groups, and the compounds may also have structures containing atoms other than carbon and hydrogen, such as carbonyl groups, ether bonds, ester bonds, amide bonds, and epoxy groups.

[0080] Compounds represented by general formula (1) include 4-(1H-1,2,4-triazole-4-yl)benzoic acid, 2-(4H-1,2,4-triazole-4-yl)benzoic acid, 3-(4H-1,2,4-triazole-4-yl)benzoic acid, 4-(4H-1,2,4-triazole-4-yl)benzoic acid, 2-methyl-4-(4H-1,2,4-triazole-4-yl)benzoic acid, 3-methyl-4-(4H-1,2,4-triazole-4-yl)benzoic acid, 2-hydroxy-4-(4H-1,2,4-triazole-4-yl)benzoic acid, and 3-hydroxy-4-(4H-1,2,4-triazole Examples include 2-4-yl)benzoic acid, 2-amino-4-(4H-1,2,4-triazole-4-yl)benzoic acid, 3-amino-4-(4H-1,2,4-triazole-4-yl)benzoic acid, 2-chloro-4-(4H-1,2,4-triazole-4-yl)benzoic acid, 3-chloro-4-(4H-1,2,4-triazole-4-yl)benzoic acid, 2-bromo-4-(4H-1,2,4-triazole-4-yl)benzoic acid, 3-bromo-4-(4H-1,2,4-triazole-4-yl)benzoic acid, and 2-acetylamino-4-(4H-1,2,4-triazole-4-yl)benzoic acid.

[0081] Compounds represented by general formula (2) include 2-(1H-1,2,4-triazol-1-yl)benzoic acid, 3-(1H-1,2,4-triazol-1-yl)benzoic acid, 4-(1H-1,2,4-triazol-1-yl)benzoic acid, 2-methyl-4-(1H-1,2,4-triazol-1-yl)benzoic acid, and 3-methyl-4-(1H-1,2,4-triazol (1H-1,2,4-triazole-1-yl)benzoic acid, 2-hydroxy-4-(1H-1,2,4-triazole-1-yl)benzoic acid, 3-hydroxy-4-(1H-1,2,4-triazole-1-yl)benzoic acid, 2-amino-4-(1H-1,2,4-triazole-1-yl)benzoic acid, 3-amino-4-(1H-1,2,4-triazole-1-yl)benzoic acid, 2-chloro-4-( 1H-1,2,4-triazol-1-yl)benzoic acid, 3-chloro-4-(1H-1,2,4-triazol-1-yl)benzoic acid, 2-bromo-4-(1H-1,2,4-triazol-1-yl)benzoic acid, 3-bromo-4-(1H-1,2,4-triazol-1-yl)benzoic acid, 4-(3,5-dimethyl-1H-1,2,4-triazol-4-yl) Examples include benzoic acid, 2-nitro-4-(1H-1,2,4-triazole-1-yl)benzoic acid, 3-nitro-4-(1H-1,2,4-triazole-1-yl)benzoic acid, 4,6-di-1H-1,2,4-triazole-1-yl-isophthalic acid, and 4-[3,5-bis(2-hydroxyphenyl)-1H-1,2,4-triazole-1-yl]benzoic acid.

[0082] Compounds represented by general formula (3) include 2-(2H-1,2,3-triazole-2-yl)benzoic acid, 3-(2H-1,2,3-triazole-2-yl)benzoic acid, 4-(2H-1,2,3-triazole-2-yl)benzoic acid, 5-methyl-2-(2H-1,2,3-triazole-2-yl)benzoic acid, 4-methyl-2-(2H-1,2,3-triazole-2-yl)benzoic acid, 3,5-dimethyl-2-(2H-1,2,3-triazole-2-yl)benzoic acid, 4.5-dimethyl-2-(2H-1,2,3-triazole-2-yl)benzoic acid, 2-hydroxy-6-(2H-1,2,3-triazole-2-yl)benzoic acid, and 4-amino- Examples include 2-(2H-1,2,3-triazole-2-yl)benzoic acid, 5-amino-2-(2H-1,2,3-triazole-2-yl)benzoic acid, 2-fluoro-6-(2H-1,2,3-triazole-2-yl)benzoic acid, 3-fluoro-2-(2H-1,2,3-triazole-2-yl)benzoic acid, 2-chloro-6-(2H-1,2,3-triazole-2-yl)benzoic acid, 3-chloro-2-(2H-1,2,3-triazole-2-yl)benzoic acid, 3,5-difluoro-2-(2H-1,2,3-triazole-2-yl)benzoic acid, and 4-fluoro-5-methoxy-2-(2H-1,2,3-triazole-2-yl)benzoic acid.

[0083] Compounds represented by general formula (4) include 2-(1H-1,2,3-triazole-1-yl)benzoic acid, 3-(1H-1,2,3-triazole-1-yl)benzoic acid, 4-(1H-1,2,3-triazole-1-yl)benzoic acid, 2-methyl-4-(1H-1,2,3-triazole-1-yl)benzoic acid, 3-methyl-4-(1H-1,2,3-triazole-1-yl)benzoic acid, 4-(5-methyl-1H-1,2,3-triazole-1-yl)benzoic acid, and 2-H Droxy-4-(1H-1,2,3-triazole-1-yl)benzoic acid, 3-hydroxy-4-(1H-1,2,3-triazole-1-yl)benzoic acid, 2-amino-4-(1H-1,2,3-triazole-1-yl)benzoic acid, 3-amino-4-(1H-1,2,3-triazole-1-yl)benzoic acid, 2-chloro-4-(1H-1,2,3-triazole-1-yl)benzoic acid, 3-chloro-4-1H-1,2,3-triazole-1-yl)benzoic acid, 2-methyl Lu-6-(1H-1,2,3-triazol-1-yl)benzoic acid, 3-methyl-2-(1H-1,2,3-triazol-1-yl)benzoic acid, 5-methyl-2-(1H-1,2,3-triazol-1-yl)benzoic acid, 2-hydroxy-6-(1H-1,2,3-triazol-1-yl)benzoic acid, 3-hydroxy-2-(1H-1,2,3-triazol-1-yl)benzoic acid, 5-hydroxy-2-(1H-1,2,3-triazol-1-yl)benzoic acid, 2- Examples include amino-6-(1H-1,2,3-triazole-1-yl)benzoic acid, 3-amino-2-(1H-1,2,3-triazole-1-yl)benzoic acid, 5-amino-2-(1H-1,2,3-triazole-1-yl)benzoic acid, 2-chloro-2-(1H-1,2,3-triazole-1-yl)benzoic acid, 3-chloro-2-(1H-1,2,3-triazole-1-yl)benzoic acid, and 5-chloro-2-(1H-1,2,3-triazole-1-yl)benzoic acid.

[0084] Component (D) is R in the above formulas (1) to (4). 1 and R 2However, it is preferable to include a group selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxyl group, a hydrocarbon group having 1 to 20 carbon atoms, and an organic group having 1 to 20 carbon atoms that includes a carboxyl group and / or a hydroxyl group. This makes it easier to achieve the effects of the present invention.

[0085] (D) The above compound included as component (D) may have a common logarithm of octanol / water partition coefficient of 0 or greater, and is preferably 0.5 or greater, from the viewpoint of preventing development residue on the copper substrate.

[0086] The content of component (D) in the photosensitive resin composition may be in the range of 0.0010 to 1.000% by mass, preferably 0.0010 to 0.5000% by mass, and more preferably 0.0100 to 0.5000% by mass, based on the total amount of solids in the photosensitive resin composition, from the viewpoint of adhesion to the copper substrate.

[0087] <Other ingredients> The photosensitive resin composition of this embodiment may contain only the components (A) to (D) described above, or it may contain other components along with them. Examples of other components include dyes and stabilizers.

[0088] The photosensitive resin composition contains a dye, which causes the exposed area to change color, making it preferable in terms of visibility. Furthermore, when an inspection machine or the like reads the alignment marker for exposure, a greater contrast between the exposed and unexposed areas is advantageous as it makes recognition easier.

[0089] Examples of dyes include leucocrystal violet (tris[4-(dimethylamino)phenyl]methane: DMA), 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, Basic Green 1 [CAS number (same below): 633-03-4] (e.g., Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), and malachite green oxalate [2437-29-8] (e.g., Aizen Malachite). Examples include Green (product name, manufactured by Hodogaya Chemical Co., Ltd.), Brilliant Green [633-03-4], Fuchsine [632-99-5], Methyl Violet [603-47-4], Methyl Violet 2B [8004-87-3], Crystal Violet [548-62-9], Methyl Green [82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390-60-5] (for example, Aizen Victoria Pure Blue BOH, product name, manufactured by Hodogaya Chemical Co., Ltd.), Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], Basic Yellow 2 [2465-27-2], etc.

[0090] Stabilizers are preferred from the viewpoint of improving the thermal stability, storage stability, or both of the photosensitive resin composition. Examples of stabilizers include at least one compound selected from the group consisting of radical polymerization inhibitors and alkylene oxide compounds having a glycidyl group. These can be used individually or in combination of two or more.

[0091] Examples of radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxyamine aluminum salts (such as aluminum salts with 3 moles of nitrosophenylhydroxylamine added), and diphenylnitrosamines. Among these, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate] and aluminum salts with 3 moles of nitrosophenylhydroxylamine added are preferred. These can be used individually or in combination of two or more.

[0092] Examples of alkylene oxide compounds having a glycidyl group include neopentyl glycol diglycidyl ether (e.g., Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (e.g., Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2 molar adduct diglycidyl ether (e.g., Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), and 1,6-hexanediol diglycidyl ether (e.g., Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.). These can be used individually or in combination of two or more.

[0093] In this embodiment, the total content of the dye, radical polymerization inhibitor, and alkylene oxide compound having a glycidyl group in the photosensitive resin composition is preferably in the range of 0.001 to 3% by mass, and more preferably in the range of 0.05 to 1.5% by mass. From the viewpoint of imparting visibility of the exposed area and good storage stability to the photosensitive resin composition, this total content is preferably 0.001% by mass or more, while from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, it is preferably 3% by mass or less.

[0094] [Photosensitive resin composition solution] In this embodiment, a photosensitive resin composition solution can be prepared by adding a solvent to the photosensitive resin composition described above. Suitable solvents used here include ketones such as methyl ethyl ketone (MEK); and alcohols such as methanol, ethanol, and isopropyl alcohol. It is preferable to prepare the solution by adding a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition solution is 500 to 4,000 mPa·sec at 25°C.

[0095] [Photosensitive element] The photosensitive element in this embodiment comprises a support and a photosensitive resin layer formed on the support from the photosensitive resin composition of this embodiment described above. The photosensitive element in this embodiment may optionally have a protective layer on the surface of the photosensitive resin layer opposite to the support.

[0096] [Support] As the support, a transparent substrate (film substrate, hereinafter also referred to as "support film") that transmits light emitted from an exposure light source is preferred. Examples of such support films include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films can also be stretched as needed. The haze of the support is preferably 0.01 to 5.0%, more preferably 0.01 to 3.5%, even more preferably 0.01 to 2.5%, and even more preferably 0.01 to 1.0%.

[0097] While a thinner support is advantageous in terms of image formation and cost-effectiveness, it is necessary to maintain strength. Considering both of these factors, a support of 10 to 30 μm is preferably used.

[0098] [Photosensitive resin layer] The photosensitive resin layer in the photosensitive element of this embodiment is a layer made of the photosensitive resin composition of this embodiment described above. If the photosensitive resin composition used to form the photosensitive resin layer contains a solvent, it is preferable that the solvent be removed from the photosensitive resin layer, but it is acceptable for the solvent to remain. The thickness of the photosensitive resin layer in the photosensitive element of this embodiment is preferably 5 to 100 μm, and more preferably 5 to 50 μm. The thinner the layer, the better the resolution, and the thicker the layer, the better the film strength. Therefore, the thickness of the layer can be appropriately selected within the above range depending on the application.

[0099] [Protective film] An important characteristic of the protective layer in the photosensitive element of this embodiment is that its adhesion force to the photosensitive resin layer is sufficiently smaller than the adhesion force between the support and the photosensitive resin layer, allowing for easy peeling. As the protective layer, polyethylene film, polypropylene film, etc., are preferably used, as well as a film with excellent peelability disclosed in, for example, Japanese Patent Publication No. 59-202457. The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 10 to 50 μm.

[0100] [Method for manufacturing a photosensitive element] The photosensitive element of this embodiment can be manufactured by sequentially laminating a support, a photosensitive resin layer, and, if necessary, a protective layer. Known methods can be used for laminating the support, the photosensitive resin layer, and the protective layer. For example, the photosensitive resin composition of this embodiment can be prepared as the aforementioned photosensitive resin composition preparation liquid, first applied to a support using a bar coater or roll coater and dried to form a photosensitive resin layer made of the photosensitive resin composition on the support. Then, if necessary, a protective layer can be laminated on the formed photosensitive resin layer to manufacture the photosensitive element.

[0101] [Method for forming a resist pattern] A resist pattern can be formed on a substrate using the photosensitive element described above. The method for forming a resist pattern includes, in the order described above, a laminating step of forming a photosensitive resin layer on a substrate using the photosensitive element of this embodiment, an exposure step of exposing the photosensitive resin layer to light, and a developing step of forming a resist pattern by removing the unexposed parts of the photosensitive resin layer with a developer.

[0102] In the resist pattern formation method of this embodiment, first, in the lamination process, a photosensitive resin layer is formed on the substrate using a laminator. Specifically, if the photosensitive element has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed and laminated onto the substrate surface using a laminator. Examples of substrate materials used include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and flexible substrates with laminated conductive thin films. Examples of conductive thin films include ITO, copper, copper-nickel alloy, and silver; examples of flexible substrate materials include polyethylene terephthalate (PET); Each of these can be listed. The above substrate may have through-holes to accommodate multilayer substrates.

[0103] Here, the photosensitive resin layer may be laminated to only one side of the substrate surface, or it may be laminated to both sides of the substrate as needed. The heating temperature at this time is preferably 40 to 160°C. By performing the heat pressing process two or more times, the adhesion of the resulting resist pattern to the substrate is further improved. When performing pressing two or more times, a two-stage laminator equipped with two rolls may be used, or the laminate of the substrate and the photosensitive resin layer may be passed through the rolls several times and pressed.

[0104] Next, in the exposure process, the photosensitive resin layer is exposed using an exposure machine. This exposure may be performed through the support without removing it, or, if necessary, after removing the support. By performing this exposure in a patterned manner, a resist film (resist pattern) with the desired pattern can be obtained after going through the development process described later. Patterned exposure may be performed by either exposure via a photomask or maskless exposure. When exposure via a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time. The exposure amount may also be measured using a light meter. In maskless exposure, a photomask is not used; exposure is performed directly onto the substrate using a drawing device. Light sources include semiconductor lasers with wavelengths of 350-500 nm, ultra-high pressure mercury lamps, etc. In maskless exposure, the drawing pattern is controlled by a computer, and the exposure amount is determined by the illuminance of the exposure light source and the substrate's movement speed. From the viewpoint of improving the resolution of the resist pattern and the yield of the resist or wiring pattern, exposure via a photomask is preferable.

[0105] Next, in the development process, the unexposed portion of the photosensitive resin layer is removed with a developer. If there is a support on the photosensitive resin layer after exposure, it is preferable to remove it before subjecting the material to the development process. In the development process, an alkaline aqueous solution is used to develop and remove unexposed areas to obtain a resist image. It is preferable to use an aqueous solution of Na2CO3, K2CO3, etc., as the alkaline aqueous solution. The alkaline aqueous solution is selected according to the characteristics of the photosensitive resin layer, but it is preferable to use an aqueous solution of Na2CO3 with a concentration of 0.2 to 2% by mass. A surfactant, an antifoaming agent, and a small amount of organic solvent to accelerate development may be added to the alkaline aqueous solution. It is preferable to maintain a constant temperature of the developer solution within the range of 18 to 40°C during the developing process.

[0106] A resist pattern is obtained through the process described above. In some cases, a further heating step of 100 to 300°C may be performed. By performing this heating step, further improvement in chemical resistance is possible. For heating, a suitable heating furnace can be used, such as one using hot air, infrared radiation, or far-infrared radiation.

[0107] [Method for forming a wiring board] The method for forming a wiring board in this embodiment includes, in the order described above, a laminating step of forming a photosensitive resin layer on a substrate using the photosensitive element of this embodiment, an exposure step of exposing the photosensitive resin layer to light, a developing step of forming a resist pattern by removing the unexposed portion of the photosensitive resin layer with a developer, a conductor pattern forming step of etching or plating the substrate on which the resist pattern has been formed, and a peeling step of peeling off the resist pattern. By the above method, a wiring board can be obtained in which a desired conductor pattern is formed on a substrate.

[0108] The lamination process, exposure process, and development process are the same as in the [Method for Forming a Resist Pattern] described above. After forming a resist pattern using the resist pattern formation method described above, a wiring board with a conductor pattern formed on the substrate can be obtained by going through the following conductor pattern formation process and peeling process. In the conductor pattern formation process, a conductor pattern can be formed on the substrate surface (e.g., the copper surface) exposed by the development process on the substrate on which the resist pattern has been formed, using a known etching method or plating method.

[0109] [Etching process] By forming a resist pattern using the resist pattern formation method described above, and then performing a plating treatment as necessary, a wiring pattern corresponding to the resist pattern can be formed on the substrate by etching the substrate.

[0110] The etching process can employ, for example, a method of spraying an etching solution onto the resist pattern. Etching methods include acid etching and alkaline etching. Etching solutions include aqueous hydrochloric acid solution, aqueous ferric chloride solution, or mixtures thereof.

[0111] [Plating process] Plating can be performed by applying metallic plating (e.g., metallic plating with copper sulfate solution) or solder plating to the parts exposed by development, according to known plating methods.

[0112] If plating is performed, the resist pattern can be removed after the plating process; if plating is omitted, the resist pattern can be removed after the etching process using an aqueous solution (stripping solution) that is more alkaline than the developer. The stripping solution is preferably an aqueous solution of NaOH or KOH with a concentration of about 2 to 5% by mass and a temperature of about 40 to 70°C.

[0113] The photosensitive resin composition, photosensitive element, and method for forming a conductive pattern of this embodiment can be suitably applied to the manufacture of printed circuit boards, lead frames, substrates having uneven patterns, semiconductor packages, touch panel sensors, and the like.

[0114] Unless otherwise specified, the values ​​of each of the parameters mentioned above are measured and calculated according to the methods described later.

[0115] <Weight-average molecular weight and degree of dispersion> The samples were measured by gel permeation chromatography (GPC), and the weight-average molecular weight (Mw), number-average molecular weight (Mn), and degree of dispersion (Mw / Mn) were calculated using a calibration curve for polystyrene (Shodex STANDARD SM-105, manufactured by Showa Denko K.K.). Specifically, measurements were taken using a gel permeation chromatography system manufactured by JASCO Corporation under the following conditions. Differential refractometer: RI-1530 Pump: PU-1580 Degasser: DG-980-50 Column oven: CO-1560 Columns: KF-8025, KF-806M x 2, and KF-807 are connected in series in that order. Eluent:THF

[0116] <Acid dissociation constant (pKa)> The values ​​for the acid dissociation constant were obtained using SciFinder®, a registered trademark provided by CAS (Chemical Abstract Service).

[0117] <Distribution coefficient (P)> The partition coefficient (P) is defined in liquid-liquid partitioning as the ratio of the total concentrations of the solute in both phases. It is a numerical value that represents the properties of a chemical substance, serving as an indicator of its hydrophobicity and migration properties, and is temperature-dependent. It is expressed as the concentration ratio of each phase or its common logarithm (logP) when the substance in question is in equilibrium in a system of two adjacent phases. The partition coefficient when octanol and water are used as solvents is given by , and is more commonly expressed in terms of the common logarithm (LogPow or logP) than in terms of Octanol / Water. When determining the octanol / water partition coefficient, the values ​​shown in "Scott A. Wildman and Gordon M. Crippen, J. Chem. Inf. Comput. Sci. 39, 868 (1999), Prediction of Physicochemical Parameters by Atomic Contributions" should be used, and the values ​​calculated based on the contribution of each atom should be used. [Examples]

[0118] <Fabrication of photosensitive elements> A photosensitive resin composition with a solid content of 60% by mass was prepared by mixing the components shown in the table below and adding methyl ethyl ketone (MEK). The obtained photosensitive resin composition was uniformly applied to a 16 μm thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., product name "QS73"), which served as a support film, using a bar coater. The film was then heated and dried in a dryer heated to 95°C for 2.5 minutes to form a 25 μm thick photosensitive resin layer on the support film. Next, a 19 μm thick polyethylene film (manufactured by Tamapoly Co., Ltd., product name "GF-818"), which served as a protective layer, was attached to the side of the photosensitive resin layer opposite to the support film to obtain a photosensitive element.

[0119] <Circuit board used for evaluation> A 0.4 mm thick copper-clad laminate, constructed by laminating 35 μm rolled copper foil, was cleaned on its surface with a 10 mass% sulfuric acid (H2SO4) aqueous solution. The cleaned substrate was then used as an evaluation substrate.

[0120] <Laminate> On evaluation substrates, the photosensitive elements obtained in each example or comparative example were laminated using a hot roll laminator (Asahi Kasei Corporation, AL-70) while peeling off the polyethylene film, under the conditions of a roll temperature of 105°C, an air pressure of 0.35 MPa, and a lamination speed of 1.5 m / min.

[0121] <Exposure> The evaluation substrates were exposed to light two hours after lamination. For the photosensitive resin elements obtained from experimental compositions 1-14 and comparative compositions 1-7, exposure was performed using a direct writing exposure machine (FDi-3, manufactured by Oak Manufacturing Co., Ltd.) with a predetermined mask pattern for direct imaging (DI) exposure. For the photosensitive resin elements obtained from experimental compositions 15-24 and comparative compositions 8-12, exposure was performed through a glass mask using a projection exposure machine (UX-44101SM, manufactured by Ushio Inc.). The exposure level was determined to be such that independent nanolines with a length of 30 mm and a thickness of 10 μm were formed within a range of 10.0 ± 0.1 μm in thickness.

[0122] <Heating> The evaluation substrate, one minute after exposure, was heated for 30 seconds in a forced-air constant-temperature incubator (DKM600, manufactured by Yamato Scientific Co., Ltd.) set to 70°C.

[0123] <Developing> After peeling the support film from the photosensitive resin layer after exposure, an alkaline developer (manufactured by Fuji Kiko, for dry film) was used to spray a 1% by mass Na2CO3 aqueous solution at 30°C for twice the minimum development time to dissolve and remove the unexposed portions of the photosensitive resin layer. After development, a substrate with an evaluation cured film was obtained by washing with water. The minimum development time refers to the minimum time required for the unexposed portions of the photosensitive resin layer to be completely dissolved and removed.

[0124] <plating> The developed substrate was surface-treated by immersing it in 10% sulfuric acid at 40°C for 5 minutes. Next, it was washed with deionized water at room temperature and dried. The surface-treated substrate was connected to the cathode, and a phosphorus-containing copper plate was connected to the anode. The substrate was then immersed in a plating solution at 25°C at 0.5 A / dm². 2 By applying the current for 45 minutes, a substrate coated with copper plating 20 μm thick was obtained. The patterned copper plating formed in this process consisted of independent fine lines 30 mm in length. The plating solution was prepared as an aqueous solution containing 75 g / L of copper sulfate pentahydrate, 200 g / L of sulfuric acid, 40 mg / L of hydrochloric acid, 1 mL / L of brightener (Caparaside Universal, manufactured by Attec Japan), and 20 mL / L of additive (Caparaside G-40, manufactured by Attec Japan).

[0125] <Peeling> After plating, the substrate was washed with deionized water at room temperature, and then immersed in a 40 g / L aqueous sodium hydroxide solution at 50°C until the exposed areas of the photosensitive resin layer peeled off. Next, the substrate was washed with deionized water, then immersed in 10% sulfuric acid at 25°C for 1 minute, and then immersed in a rust inhibitor at 25°C for 1 minute to perform surface treatment of the substrate. Finally, the substrate was washed with deionized water at room temperature and dried to obtain a copper-plated substrate. The rust inhibitor was prepared as an aqueous solution containing 5 g / L of 1,2,3-benzotriazole and 100 g / L of ethanol.

[0126] <Adhesion to copper> When measuring independent fine lines with a length of 30 mm under the above development conditions, the minimum line width in which the pattern remained was defined as the adhesion strength value, and the results were ranked as follows. The minimum mask width that was formed normally, without any deformation of the cured resist pattern or adhesion between cured resists, was evaluated. Excellent: The adhesion value is 5 μm or less. Good: The adhesion value is greater than 5 μm and less than or equal to 5.5 μm. Acceptable: The adhesion value is greater than 5.5 μm and 6 μm or less. Not acceptable: The adhesion value exceeds 6 μm.

[0127] <Prevention of developing residue> After developing under the above development conditions, the presence or absence of discoloration due to development residue on the evaluation substrate was visually checked. None: No discoloration was observed. Yes: Discoloration is observed.

[0128] <Plating adhesion> After copper plating and resist stripping were performed under the above plating and stripping conditions, peel tests were conducted on 10 30mm long plated fine wires on an evaluation substrate using a tape test in accordance with JIS H8504. Excellent: No peeling of the 6μm plating on the fine wires was observed. Good: No peeling of the 7μm plating on the fine wires is observed. Acceptable: No peeling of the 8μm plating on the fine wires is observed. Unacceptable: Peeling was observed in 8μm plated fine wires.

[0129] <Examples 1-24 and Comparative Examples 1-14> The composition and details of each component name of the photosensitive resin compositions used in the examples and comparative examples are shown in the tables below. The amounts of each component in Tables 1 and 2 are all parts by mass on a solid content basis. The evaluation results of adhesion, developer residue prevention, and plating adhesion performed using each photosensitive resin composition are summarized in the table below. See Table 4. Along with component (D), the number of nitrogen atoms contained in the ring, the acid dissociation constant (pKa), and the octanol / water partition coefficient (logP) are shown. However, for carboxylic acids D-5 to D-8, the acid dissociation constant (pKa) and octanol / water partition coefficient (logP) are shown, and for heteroaromatic ring compounds D-9 to D-12, only the number of nitrogen atoms contained in the compound is indicated.

[0130] [Table 1]

[0131] [Table 2]

[0132] [Table 3]

[0133] [Table 4]

[0134] As is clear from the table above, the examples showed excellent adhesion and prevented discoloration due to developing residue. Furthermore, the low amount of developing residue resulted in excellent plating adhesion. In particular, it was confirmed that adhesion was even better when component (D) was in the range of 0.0010 to 0.5000% by mass and the copolymerization ratio of the aromatic compound in component (A) was 20% by mass or more.

[0135] On the other hand, in Comparative Examples 1 to 4, a mixture of aromatic carboxylic acids and heterocyclic compounds was added as component (D), but adhesion, prevention of developer residue, and plating adhesion were not achieved simultaneously. Therefore, the effects of the Examples (for example, the effect of having multiple rings in the structure and containing acidic groups with a pKa of 5 or less) were confirmed.

[0136] In Comparative Examples 5, 6, and 8, a benzotriazole derivative or triazole derivative having a carboxyl group was added as component (D), but the adhesion was not as good as in the Examples. Therefore, the effect in the Examples (for example, the effect of having multiple rings independently present in the compound) was confirmed.

[0137] In Comparative Examples 9-11, a compound containing two or fewer nitrogen atoms in the ring, or a compound without an acidic group with a pKa of 5 or less, was added as component (D). However, when there were two or fewer nitrogen atoms, the coating on the copper substrate surface deteriorated, and when there was no acidic group with a pKa of 5 or less, the solubility in the alkaline developer deteriorated. As a result, neither method provided an effect of reducing development residue, leading to plating defects. [Industrial applicability]

[0138] The photosensitive resin composition of this embodiment exhibits excellent adhesion to substrates and has the effect of preventing development residue, and therefore can be used, for example, in dry films for wiring formation.

Claims

1. The following ingredients: (A) Alkali-soluble polymer, (B) Compounds having an ethylenically unsaturated double bond, (C) Photopolymerization initiator, and (D) A compound having two to four aromatic rings, wherein a total of three to six nitrogen atoms are present in the two to four aromatic rings, and the compound has a carboxyl group as an acidic group with an acid dissociation constant (pKa) of -5 or more and 5 or less. Includes, The aforementioned component (D) is given by the following general formulas (1) to (4): 【Chemistry 1】 [In the formula, Y is given by the following general formula (5): 【Chemistry 2】 The compound is represented by the formula {wherein S1, S2, S3, S4, and S5 are at least one selected from the group consisting of a hydrogen atom, a halogen atom, an amino group, a hydroxyl group, and an organic group having 1 to 20 carbon atoms, provided that at least one of S1, S2, S3, S4, and S5 has the aforementioned acidic group}, where R1 and R2 are at least one selected from the group consisting of a hydrogen atom, a halogen atom, an amino group, a hydroxyl group, and an organic group having 1 to 20 carbon atoms. A photosensitive resin composition comprising a compound represented by any of the following.

2. The photosensitive resin composition according to claim 1, wherein component (A) comprises a monomer having an aromatic group as a copolymer component.

3. The aforementioned component (D) is, S １ S ２ S ３ S ４ and S ５ At least one of these includes a carboxyl group and / or an organic group having 1 to 20 carbon atoms that contains a carboxyl group. The photosensitive resin composition according to claim 1 or 2, wherein the remainder comprises a group selected from the group consisting of a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 20 carbon atoms, and an organic group having 1 to 20 carbon atoms containing a hydroxyl group.

4. The aforementioned component (D) is, R １ and R ２ The photosensitive resin composition according to any one of claims 1 to 3, wherein the photosensitive resin composition comprises a group selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxyl group, a hydrocarbon group having 1 to 20 carbon atoms, and an organic group having 1 to 20 carbon atoms containing a carboxyl group and / or a hydroxyl group.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the (D) component comprises a compound having a common logarithm of 0.5 or more for its octanol / water partition coefficient.

6. The aforementioned component (A) is, It contains a monomer having a carboxyl group and a monomer having an aromatic group as copolymer components, and The photosensitive resin composition according to any one of claims 1 to 5, wherein the copolymerization ratio of the monomer having the aromatic group is 10% by mass or more with respect to the total mass of the comonomers constituting component (A).

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the (D) component is contained in an amount of 0.001 to 0.5% by mass relative to the total amount of solids in the photosensitive resin composition.

8. The photosensitive resin composition according to any one of claims 1 to 7, wherein the (C) component comprises an anthracene derivative.

9. The photosensitive resin composition according to any one of claims 1 to 8, wherein the (C) component comprises a benzophenone derivative.

10. A photosensitive resin laminate comprising a support and a photosensitive resin layer obtained from a photosensitive resin composition according to any one of claims 1 to 9.

11. A lamination step of laminating the photosensitive resin laminate according to claim 10 onto a substrate, An exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate, and A developing step in which the unexposed portion of the photosensitive resin layer is developed and removed. A method for forming a resist pattern, including [a specific component].

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