Photosensitive resin composition and photosensitive element

Abstract

One of the objects of the present invention is to provide a photosensitive resin composition which has a reduced amount of side etching, excellent uniformity of copper line width, promotes color development of dye during exposure, and has excellent visibility of the exposed portion. According to the present invention, a photosensitive resin composition is provided, which comprises: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, (C) a photopolymerization initiator, (D) a dye, and (E) a compound represented by the following general formula, wherein R 1 and R 2 do not have an amino group and are independently selected from the group consisting of a hydrogen atom or an organic group having 1 to 20 carbon atoms, wherein R 1 and R 2 At least one of them has an acidic group with a pKa of 5 or less.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition and a photosensitive element. Background Art

[0002] Printed circuit boards are generally manufactured by photolithography, which refers to a method in which a layer of a photosensitive resin composition is formed on a substrate, the coating film is pattern-exposed and developed to form a resist pattern, then a conductor pattern is formed by etching or plating, and then the resist pattern on the substrate is removed to form a desired wiring pattern on the substrate.

[0003] In the manufacture of printed circuit boards, a photosensitive element (dry film resist) having a photosensitive resin layer laminated on a support is often used. There are many known methods for forming wiring patterns using the photosensitive element and photosensitive resin compositions suitable therefor, such as the following Patent Documents 1 to 5.

[0004] The purpose of Patent Document 1 is to provide a photosensitive resin composition which is particularly highly sensitive to ultraviolet light and visible light and can be cured by laser drawing, and has excellent storage stability after forming a film on a substrate and after drawing. As a solution, Patent Document 1 describes a photosensitive resin composition containing tetrazole or a derivative thereof, or triazole or a derivative thereof. Examples of tetrazole or a derivative thereof include 1H-1,2,3,4-tetrazole, 5-amino-1H-tetrazole, and 5-methyl-1H-tetrazole, and examples of triazole or a derivative thereof include 1,2,4-triazole or 5-chlorobenzotriazole.

[0005] Patent Document 2 aims to provide a photosensitive resin composition having excellent adhesion to a copper surface and capable of forming an extremely stable anti-corrosion film that is not affected by changes over time after coating or lamination. As a means of solving this problem, Patent Document 2 describes a photosensitive resin composition comprising one or more heterocyclic compounds selected from the group consisting of triazoles, tetrazoles, and imidazoles.

[0006] Patent Document 3 aims to provide a photosensitive resin composition that has high sensitivity, can obtain a good resist pattern shape, has a strong support film strength, and can form a high-definition and high-aspect-ratio pattern. As a means of solving this problem, Patent Document 3 describes a photosensitive resin composition containing a monocarboxylic acid compound having a molecular weight of 180 to 2,000.

[0007] The purpose of Patent Document 4 is to provide a photosensitive resin composition that can subdivide a peeling sheet (reduce the size of the resist sheet after peeling), has excellent plating resistance, and has excellent sensitivity, resolution and adhesion. As a solution, Patent Document 4 describes a photosensitive resin composition that contains a binder polymer containing at least (meth)acrylic acid and (meth) hydroxyalkyl acrylate as copolymer components, and also contains benzotriazole and a carboxybenzotriazole derivative represented by a specific general formula as an adhesion-imparting agent.

[0008] Patent Document 5 aims to provide a photosensitive resin composition having sufficiently excellent adhesion to a conductor layer and capable of forming a resist that is unlikely to cause discoloration of the conductor layer. As a means of solving the problem, Patent Document 5 describes a photosensitive resin composition comprising a binder polymer, a photopolymerizable compound having an ethylenically unsaturated group, a photopolymerization initiator, and a benzotriazole derivative represented by a specific general formula.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application Publication No. 2002-317005

[0012] Patent Document 2: Japanese Patent No. 4883537

[0013] Patent Document 3: Japanese Patent Application Publication No. 2011-81391

[0014] Patent Document 4: Japanese Patent Application Publication No. 2010-72535

[0015] Patent Document 5: Japanese Patent No. 4449983 Summary of the invention

[0016] Problem that the invention aims to solve

[0017] In recent years, with the miniaturization and lightness of electronic devices, the miniaturization and high density of printed circuit boards are being promoted. In the manufacturing process of photosensitive elements, a high-performance photosensitive element that can reduce side etching (hereinafter also referred to as "side etching") and provide a more uniform copper line width is sought. In addition, photosensitive elements generally contain dyes so that the resist pattern formed on the copper foil after development can be visually recognized with good contrast. The dye has the function of changing the color of the exposed part during DF exposure.

[0018] One object of the present invention is to provide a photosensitive resin composition which has a reduced amount of undercutting, has excellent uniformity of copper line width, promotes color development of dye during exposure, and has excellent visibility of the exposed portion.

[0019] Solutions for solving problems

[0020] The inventors of the present invention have conducted intensive studies to solve the above problems and have found that a photosensitive resin composition containing an alkali-soluble polymer, a compound having an ethylenically unsaturated double bond, a photopolymerization initiator, a dye, and a compound having a specific structure can solve the above problems, thereby completing the present invention. That is, the present invention is as follows.

[0021] [1] A photosensitive resin composition comprising:

[0022] (A) Alkali-soluble polymers,

[0023] (B) a compound having an ethylenically unsaturated double bond,

[0024] (C) a photopolymerization initiator,

[0025] (D) dyes, and

[0026] (E) a compound represented by the following general formula (3),

[0027]

[0028] {In the formula, R 1 and R 2 do not have an amino group and are independently selected from the group consisting of a hydrogen atom or an organic group having 1 to 20 carbon atoms, wherein R 1 and R 2 At least one of them has an acidic group with a pKa of 5 or less.}.

[0029] [2] The photosensitive resin composition according to item 1, wherein, in the formula, R 1 and R 2 None of them have an amino group and are independently selected from the group consisting of a hydrogen atom or an organic group having 1 to 3 carbon atoms, wherein R 1 and R 2 At least one of them has an acidic group with a pKa of 5 or less.

[0030] [3] The photosensitive resin composition according to item 2, wherein, in the formula, R 1 and R 2 None of them have amino groups, R 1 and R 2 One of them is an organic group having 1 to 3 carbon atoms and having an acidic group with a pKa of 5 or less, and the other is a hydrogen atom.

[0031] [4] The photosensitive resin composition according to any one of items 1 to 3, wherein the acidic group is any one of a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

[0032] [5] The photosensitive resin composition according to item 4, wherein the acidic group is a carboxyl group.

[0033] [6] The photosensitive resin composition according to any one of items 1 to 5, wherein the dye (D) is a leuco dye.

[0034] [7] The photosensitive resin composition according to any one of items 1 to 6, comprising 0.001 to 0.5% by mass of the compound (E) based on the total amount of solid content of the photosensitive resin composition.

[0035] [8] The photosensitive resin composition according to any one of items 1 to 7, wherein the compound (E) is solid at 25°C.

[0036] [9] The photosensitive resin composition according to any one of items 1 to 8, wherein the alkali-soluble polymer (A) contains an aromatic ring in its molecular structure.

[0037]

[10] A photosensitive element comprising: a support, and the photosensitive resin composition layer according to any one of items 1 to 9 formed on the support.

[0038] Effects of the Invention

[0039] According to the present invention, a photosensitive resin composition can be provided which has a reduced amount of side etching, excellent uniformity of copper wire width, promotes color development of dye during exposure, and excellent visibility of the exposed portion. It should be noted that the above description cannot be regarded as disclosing all embodiments of the present invention and all advantages of the present invention. Further embodiments of the present invention and their advantages will be clarified by referring to the following description. DETAILED DESCRIPTION

[0040] Hereinafter, an embodiment of the present invention (hereinafter referred to as "this embodiment") will be described in detail for the purpose of illustration, but the present invention is not limited to this embodiment. In the present specification, the upper limit and the lower limit of each numerical range can be arbitrarily combined.

[0041] [Photosensitive resin composition]

[0042] The photosensitive resin composition of the present embodiment contains: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, (C) a photopolymerization initiator, (D) a dye, and (E) a compound having a specific heterocyclic structure. Compound (E) is a compound represented by the general formula (3) described later. The photosensitive resin composition of the present embodiment can provide a photosensitive resin composition having a reduced amount of side etching, excellent uniformity of copper wire width, accelerated color development of the dye during exposure, and excellent visibility of the exposed portion by having the above-mentioned structure.

[0043] The reason is unclear, and the present invention is not limited to theory, but the inventors speculate as follows.

[0044] For reducing the amount of lateral etching, the adhesion and reaction rate of the resist after curing and the copper interface are important. By etching treatment, the etching solution penetrates into the resist-copper interface, thereby producing the difference (lateral etching) between the line width of the dry film and the copper line width after etching. If the interaction of the resist-copper interface is firm, the etching solution is not easy to penetrate, and the amount of lateral etching decreases. As a compound with strong interaction with copper, it is known that there are imidazoles, triazoles, tetrazole, etc., but when the hydrophobicity of these compounds is high, there is a problem of remaining on the substrate after development and etching residues. Therefore, the inventors etc. found that by using a compound (E) with an acidic group having a high solubility in an alkaline aqueous solution and having pKa5 or less, it is possible to reduce etching residues. In addition, for reducing the amount of lateral etching, it is advantageous that the swelling amount is small, and therefore, the reaction rate of the resist after curing is also important. In particular, tetrazoles undergo radical cleavage in a short wavelength region of about 200 nm, so it is considered that the reaction rate especially at the copper interface (resist bottom) where these tetrazoles are present in large quantities increases, and the swelling rate of the resist bottom is suppressed, which contributes to reducing side etching.

[0045] On the other hand, the color development of the dye is preferred from the perspective of visibility of the exposed portion. When the inspection machine or the like reads the positioning mark for exposure, the contrast between the exposed portion and the unexposed portion is large, which is advantageous for easy identification. It is believed that the compound (E) having an acidic group with a pKa of 5 or less that reacts during exposure stabilizes the cation of the dye, preferably leuco crystal violet (DMA), thereby improving the color development and exposure contrast.

[0046] <(A) Alkali-soluble polymer>

[0047] The alkali-soluble polymer (A) is preferably obtained by polymerizing at least one of the first monomers described below. In addition, the alkali-soluble polymer (A) is more preferably obtained by copolymerizing at least one of the first monomers and at least one of the second monomers described below.

[0048] The first monomer is a monomer containing a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth)acrylic acid is particularly preferred. In this specification, "(meth)acrylic acid" refers to acrylic acid and methacrylate, and "(meth)acrylate" refers to "acrylate" and "methacrylate".

[0049] The copolymerization ratio of the first monomer in the alkali-soluble polymer (A) is preferably 10 to 35% by mass, more preferably 15 to 30% by mass, and even more preferably 16 to 28% by mass, based on the total mass of all monomers.

[0050] The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. As the second monomer, for example, (meth) acrylate 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 (meth) acrylate esters; vinyl acetate and other vinyl alcohol esters; and (meth) acrylonitrile, styrene and polymerizable styrene derivatives (such as methyl styrene, vinyl toluene, tert-butoxy styrene, acetoxy styrene, 4-vinyl benzoic acid, styrene dimer, styrene trimer, etc.) are preferred. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, 2-ethylhexyl (meth) acrylate and benzyl (meth) acrylate are preferred. From the viewpoint of suppressing side corrosion, benzyl (meth)acrylate is particularly preferred.

[0051] The copolymerization ratio of the second monomer in the alkali-soluble polymer (A) is preferably 70 to 90% by mass, more preferably 70 to 85% by mass, and even more preferably 72 to 84% by mass, based on the total mass of all monomers constituting the copolymer forming the alkali-soluble polymer (A).

[0052] In the present embodiment, from the viewpoint of improving the resolution of the resist pattern, the alkali-soluble polymer (A) preferably contains an aromatic ring in its molecular structure, and more preferably has an aromatic group in a side chain of its structure.

[0053] The alkali-soluble polymer (A) having an aromatic group in the side chain can be prepared by using a compound having an aromatic group as at least one monomer in the first monomer and the second monomer. As the monomer having an aromatic group, in addition to (meth)acrylic acid aralkyl esters such as (meth)acrylic acid benzyl ester, phenoxy polyethylene glycol (meth)acrylate, styrene, cinnamic acid, polymerizable styrene derivatives (such as methyl styrene, vinyl toluene, tert-butoxy styrene, acetoxy styrene, 4-vinyl benzoic acid, styrene dimer, styrene trimer, etc.) and the like can also be cited. From the viewpoint of suppressing side erosion, (meth)acrylic acid aralkyl esters and styrene are preferred, and (meth)acrylic acid benzyl ester is particularly preferred.

[0054] The copolymerization ratio of the compound having an aromatic group is preferably 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 all monomers. From the viewpoint of maintaining alkali solubility, the copolymerization ratio of the compound having an aromatic group is preferably 95% by mass or less, more preferably 90% by mass or less.

[0055] In the present embodiment, the alkali-soluble polymer (A) can be prepared by subjecting one or more monomers selected from the first monomer and the second monomer to a known polymerization method, preferably addition polymerization, more preferably radical polymerization.

[0056] The acid equivalent of the alkali-soluble polymer (A) (the acid equivalent of the entire mixture when containing a plurality of copolymers) is preferably 100 or more from the viewpoint of the development resistance of the photosensitive resin layer and the resolution and adhesion of the resist pattern, and is preferably 600 or less from the viewpoint of the developability and peelability of the photosensitive resin layer. The acid equivalent of the alkali-soluble polymer (A) is more preferably 200 to 500, and even more preferably 250 to 450.

[0057] The weight average molecular weight (hereinafter sometimes referred to as "Mw") of the (A) alkali-soluble polymer (when a plurality of alkali-soluble polymers are used in combination, the Mw of the whole) is preferably 5,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 65,000. The dispersity (Mw / Mn) which is the ratio of the weight average molecular weight to the number average molecular weight (hereinafter sometimes referred to as "Mn") (when a plurality of alkali-soluble polymers are used in combination, the dispersity of the whole) is preferably 1.0 to 6.0, more preferably 1.5 to 5.0, further preferably 2.0 to 5.0, further preferably 2.5 to 4.5, and particularly preferably 3.0 to 4.2.

[0058] The weight average molecular weight and the degree of dispersion of the (A) alkali-soluble polymer are preferably within the above ranges from the viewpoint of obtaining appropriate developability, high coating film strength, and uniform resist thickness.

[0059] When a plurality of alkali-soluble polymers are used in combination as (A),

[0060] Particularly preferred include:

[0061] (A-1) an alkali-soluble polymer having a Mw of less than 50,000, and

[0062] (A-2) An alkali-soluble polymer having a Mw of 50,000 or more.

[0063] The Mw of the alkali-soluble polymer (A-1) is more preferably 5000 or more and less than 50,000, further preferably 10,000 to 45,000, and particularly preferably 10,000 to 35,000. The Mw of the alkali-soluble polymer (A-1) is preferably within this range from the viewpoint of achieving both developability and resolution.

[0064] On the other hand, the Mw of the alkali-soluble polymer (A-2) is more preferably 50,000 to 100,000, further preferably 50,000 to 75,000, and particularly preferably 50,000 to 65,000. From the viewpoint of extending the product life when the photosensitive resin composition of the present embodiment is used in a photosensitive element (also referred to as a "dry film resist"), the Mw of the alkali-soluble polymer (A-2) is preferably within this range.

[0065] The content of the alkali-soluble polymer (A-1) component relative to the total amount of the solid content of the photosensitive resin composition is preferably 3% by mass or more and 30% by mass or less, more preferably 5% by mass or more and 25% by mass or less, and further preferably 10% by mass or more and 20% by mass or less. From the viewpoint of balancing resolution and small side etching, it is preferred to set the usage ratio of the (A-1) component to the above range.

[0066] The content ratio of the alkali-soluble polymer (A-2) component relative to the total amount of the solid content of the photosensitive resin composition is preferably 5% by mass or more and 50% by mass or less, more preferably 15% by mass or more and 48% by mass or less, and further preferably 18% by mass or more and 45% by mass or less. From the viewpoint of extending the product life when the photosensitive resin composition of the present embodiment is used in a photosensitive element (dry film resist), it is preferred that the usage ratio of the (A-2) component be set within the above range.

[0067] The usage ratio of (A) alkali-soluble polymer in the photosensitive resin composition of the present embodiment is preferably 25% to 85% by mass, more preferably 35% to 75% by mass, relative to the total amount of solid content of the photosensitive resin composition. From the viewpoint of resolution, developability, swelling of developer of exposed part, peelability of resist pattern, and product life of photosensitive element, it is preferred to set the usage ratio of alkali-soluble polymer to the above range.

[0068] <(B) Compounds Having Ethylenically Unsaturated Double Bonds>

[0069] (B) Compounds having ethylenically unsaturated double bonds are compounds having polymerizability due to having ethylenically unsaturated double bonds in their structures. Examples of such compounds include compounds obtained by adding (meth)acrylic acid to one end of a polyoxyalkylene, compounds obtained by adding (meth)acrylic acid to one end of a polyoxyalkylene and alkyl etherifying or allyl etherifying the other end, etc. (first group of compounds); compounds having (meth)acryloyl groups at both ends of an oxyalkylene chain, compounds having (meth)acryloyl groups at both ends of an oxyalkylene chain obtained by random bonding or block bonding of an ethylene oxide chain and a propylene oxide chain, compounds obtained by modifying bisphenol A, etc. (second group of compounds); compounds having three or more (meth)acryloyl groups in one molecule, etc. (third group of compounds), etc.

[0070] As other compounds of the first group, specifically, for example, there can be mentioned: phenoxy hexaethylene glycol mono(meth)acrylate, which is a (meth)acrylate of a compound obtained by adding polyethylene glycol to a phenyl group; 4-n-nonylphenoxy heptaethylene glycol dipropylene glycol (meth)acrylate, which is a (meth)acrylate of a compound obtained by adding polypropylene glycol to an average of 2 mol of propylene oxide and polyethylene glycol to an average of 7 mol of ethylene oxide to nonylphenol; and 1 mol of (Meth)acrylate of a compound obtained by adding polypropylene glycol to propylene oxide and polyethylene glycol to which an average of 5 mol of ethylene oxide is added to nonylphenol, namely 4-n-nonylphenoxypentaethylene glycol monopropylene glycol (meth)acrylate; acrylate of a compound obtained by adding polyethylene glycol to which an average of 8 mol of ethylene oxide is added to nonylphenol, namely 4-n-nonylphenoxyoctaethylene glycol (meth)acrylate (for example, M-114 manufactured by Toagosei Co., Ltd.), etc.

[0071] As other compounds of the second group, specifically, for example, there can be mentioned: 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, and compounds having (meth)acryloyl groups at both ends of 12 mols of ethylene oxide chains; polypropylene glycol di(meth)acrylate; polybutylene glycol di(meth)acrylate, etc. Examples of the polyoxyalkylene di(meth)acrylate compound containing an oxyethylene group and an oxypropylene group include dimethacrylate of a diol obtained by further adding an average of 3 mol of ethylene oxide to each of the two ends of a polypropylene glycol obtained by adding an average of 12 mol of propylene oxide, and dimethacrylate of a diol obtained by adding an average of 15 mol of ethylene oxide to each of the two ends of a polypropylene glycol obtained by adding an average of 18 mol of propylene oxide.

[0072] Other examples include compounds having ethylenically unsaturated double bonds at both ends of a polyalkylene glycol obtained by adding an alkylene oxide to bisphenol A.

[0073] As the compound obtained by modifying bisphenol A in the above-mentioned second group of compounds, it is preferred from the viewpoint of resolution and adhesion to use a compound having ethylenically unsaturated double bonds at both ends of a polyalkylene glycol obtained by adding alkylene oxide to bisphenol A. The ethylenically unsaturated double bonds in the compound are preferably contained in the compound in the form of being contained in a (meth)acryloyl group.

[0074] For modification by adding alkylene oxide to bisphenol A, for example, ethylene oxide modification, propylene oxide modification, butylene oxide modification, pentyl oxide modification, hexyl oxide modification, etc. are known. Preferred are compounds having (meth)acryloyl groups at both ends of polyalkylene glycol obtained by adding ethylene oxide to bisphenol A.

[0075] Examples of such compounds include 2,2-bis(4-((meth)acryloyloxydiethoxy)phenyl)propane (e.g., NK ESTER BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-((meth)acryloyloxytriethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxytetraethoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloyloxypentaethoxy)phenyl)propane (e.g., NK ESTER BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.). Furthermore, compounds modified with ethylene oxide and propylene oxide are also preferred, such as di(meth)acrylate of polyalkylene glycol obtained by adding an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide to both ends of bisphenol A, or di(meth)acrylate of polyalkylene glycol obtained by adding an average of 2 mol of propylene oxide and an average of 15 mol 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 the compound having (meth)acryloyl groups at both ends by modifying bisphenol A with oxyalkylene is preferably 1 mol or more and 60 mol or less, more preferably 4 mol or more and 40 mol or less, and further preferably 5 mol or more and 20 mol or less.

[0076] The above-mentioned third group of compounds can be obtained by (meth)acrylating an alcohol obtained by adding an oxyalkylene group such as an oxyethylene group, an oxypropylene group, or an oxybutylene group to a central skeleton having 3 or more moles of a group to which an oxyalkylene group can be added in the molecule. Examples of the compound that can serve as the central skeleton include glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, and an isocyanurate ring.

[0077] More specifically, for example, trimethylolpropane triacrylate modified with 3 moles of ethylene oxide (EO), trimethylolpropane triacrylate modified with 6 moles of EO, trimethylolpropane triacrylate modified with 9 moles of EO, trimethylolpropane triacrylate modified with 12 moles of EO, etc. Examples of such compounds include triacrylate modified with 3 moles of glycerol (e.g., A-GLY-3E manufactured by Shin-Nakamura Chemical Co., Ltd.), triacrylate modified with 9 moles of glycerol (e.g., A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.), triacrylate modified with 6 moles of glycerol and 6 moles of propylene oxide (PO) (A-GLY-0606PE), and triacrylate modified with 9 moles of glycerol and 9 moles of PO (A-GLY-0909PE). Other examples include 4EO-modified tetraacrylate of pentaerythritol (for example, SR-494 manufactured by Sartomer Japan Co., Ltd.), 35EO-modified tetraacrylate of pentaerythritol (for example, NK ESTER ATM-35E manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.

[0078] As the compound having an ethylenically unsaturated double bond, an isocyanurate compound may also be mentioned.

[0079] Specific examples of such compounds include ethoxylated isocyanuric acid tri(meth)acrylate, ε-caprolactone-modified tri(2-(meth)acryloyloxyethyl)isocyanurate, triallyl isocyanurate, the compound represented by the following formula, (EO)-modified isocyanurate-derived tri(meth)acrylate (ethylene oxide average 27 mol addition product), and the like.

[0080]

[0081] [Where R 5 , R 6 and R 7 Each independently represents an alkylene group having 1 to 20 carbon atoms, and R 8 , R 9 and R 10 Each independently represents a hydrogen atom or a methyl group, L 1 , L 2 and L 3 Each independently represents an alkylene group having 2 to 4 carbon atoms, r3, r4 and r5 each independently represent an integer of 1 to 40, and s3, s4, s5, t3, t4 and t5 each independently represent an integer of 0 to 40. When s3, s4, s5, t3, t4 and t5 are 0, L 1 represents ethylene, and when r3, r4, r5, s3, s4, s5, t3, t4 or t5 is 2 or more, a plurality of -L 1 -O-, -L2 -O- or -L 3 The structural unit represented by -O- may exist randomly or form a block.]

[0082] As such a compound, commercially available products can be used, and examples thereof include UA-7100 and A-9300-1CL (each manufactured by Shin-Nakamura Chemical Co., Ltd.); ARONIX M-327 (manufactured by Toagosei Co., Ltd.); and the like.

[0083] Examples of compounds having a urethane bond and an ethylenically unsaturated double bond include hexamethylene diisocyanate, toluene diisocyanate, or a urethane compound of a diisocyanate compound (e.g., 2,2,4-trimethylhexamethylene diisocyanate) and a compound having a hydroxyl group and a (meth)acryloyl group in one molecule (e.g., 2-hydroxypropyl acrylate, oligopropylene glycol monomethacrylate). Specifically, it is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (e.g., Blemmer PP1000 manufactured by NOF Corporation).

[0084] Examples of the compound having a phthalic acid structure and an ethylenically unsaturated double bond include γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl phthalate and β-hydroxyalkyl-β'-(meth)acryloyloxyalkyl phthalate.

[0085] In addition, as the (B) compound having an ethylenically unsaturated double bond, tricyclodecane di(meth)acrylate, (2,2-bis{4-(methacryloyloxypentaethoxy)cyclohexyl}propane, etc. may be contained.

[0086] The photosensitive resin composition of the present embodiment preferably contains a compound obtained by modifying bisphenol A. The use ratio of the compound obtained by modifying bisphenol A in the photosensitive resin composition of the present embodiment is preferably 12% to 45% by mass, more preferably 17% to 40% by mass, and further preferably 20% to 40% by mass relative to the total mass of the solid content of the photosensitive resin composition. From the viewpoint of obtaining a photosensitive resin composition with excellent balance between resolution and developability, it is preferred to set the use ratio to this range.

[0087] (B) The ratio of the compound having an ethylenically unsaturated double bond to the total solid content of the photosensitive resin composition is preferably 5% to 70% by mass. From the viewpoints of sensitivity, resolution and adhesion, it is preferred that the ratio be 5% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more. On the other hand, from the viewpoint of suppressing edge melting and delayed peeling of the cured resist, it is preferred that the ratio be 70% by mass or less, and more preferably 60% by mass or less.

[0088] <(C) Photopolymerization Initiator>

[0089] (C) Photopolymerization initiators include, for example, hexaarylbiimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoate compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, ester compounds of N-aryl amino acids, halogen compounds, and the like.

[0090] Examples of the hexaarylbiimidazole compound include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)diphenylbiimidazole, 2,4,5-tris(o-chlorophenyl)diphenylbiimidazole, 2-(o-chlorophenyl)bis-4,5-(3,4-dimethoxyphenyl)biimidazole, 2,2'-bis(2-fluorophenyl)-4,5-(3,4-dimethoxyphenyl)biimidazole, and 2,2'-bis(2-fluorophenyl)-4,5-(3,4-dimethoxyphenyl)biimidazole. 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)-4,4',5,5'-tetrakis(3-methoxyphenyl)biimidazole, 2,2'-bis(2,6-difluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)biimidazole Bis(2,3,6-trifluorophenyl)-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(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)biimidazole, , 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(2,3,4,6-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. Among them, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred from the viewpoints of high sensitivity, resolution and adhesion.

[0091] Examples of the N-aryl-α-amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, etc. In particular, N-phenylglycine has a high sensitizing effect and is preferred.

[0092] Examples of the quinone compound 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-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0093] Examples of the aromatic ketone compound include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone.

[0094] Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1. Examples of commercially available acetophenone compounds include Irgacure-907, Irgacure-369, and Irgacure-379 manufactured by Ciba Specialty Chemicals Inc. From the viewpoint of adhesion, 4,4'-bis(diethylamino)benzophenone is preferred.

[0095] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, etc. Examples of commercially available acylphosphine oxide compounds include Lucirin TPO manufactured by BASF and Irgacure-819 manufactured by Ciba Specialty Chemicals Inc.

[0096] Examples of the benzoin compound and the benzoin ether compound include benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin.

[0097] Examples of the dialkyl ketal compound include benzyl dimethyl ketal and benzyl diethyl ketal.

[0098] Examples of the thioxanthone compound include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

[0099] Examples of the dialkylaminobenzoic acid ester compound include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl p-dimethylaminobenzoate, and 2-ethylhexyl 4-(dimethylamino)benzoate.

[0100] Examples of the oxime ester compound include 1-phenyl-1,2-propanedione-2-O-benzoyl oxime and 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime. Examples of commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 manufactured by Ciba Specialty Chemicals Inc.

[0101] As the acridine compound, 1,7-bis(9,9′-acridinyl)heptane or 9-phenylacridine is preferred from the viewpoints of sensitivity, resolution, availability, and the like.

[0102] As the pyrazoline derivative, from the viewpoint of adhesion and rectangularity of the resist pattern, 1-phenyl-3-(4-tert-butyldistyryl)-5-(4-tert-butylphenyl)pyrazoline, 1-phenyl-3-(4-biphenylyl)-5-(4-tert-butylphenyl)pyrazoline and 1-phenyl-3-(4-biphenylyl)-5-(4-tert-octylphenyl)pyrazoline are preferred.

[0103] Examples of the ester compound of an N-aryl amino acid 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.

[0104] Examples of the halogen compound include amyl bromide, isopentyl bromide, isobutylene bromide, vinyl bromide, diphenylmethyl bromide, benzyl bromide, dibromomethane, tribromomethylphenyl sulfone, 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, diallyl iodonium compounds, and the like. Among them, tribromomethylphenyl sulfone is particularly preferred.

[0105] The usage ratio of the (C) photopolymerization initiator in the photosensitive resin composition of the present embodiment is preferably 0.01% by mass to 20% by mass, and more preferably 0.5% by mass to 10% by mass, relative to the total mass of the solid content of the photosensitive resin composition. By setting the usage ratio of the (C) photopolymerization initiator to this range, sufficient sensitivity can be obtained, light can be fully transmitted to the bottom of the resist, high resolution can be obtained, and a photosensitive resin composition with excellent balance with the amount of undercut in the conductor pattern can be obtained.

[0106] (C) As the photopolymerization initiator, a hexaarylbisimidazole compound is preferably used. In this case, the usage ratio of the hexaarylbisimidazole compound is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total mass of the solid content of the photosensitive resin composition.

[0107] As (C) photopolymerization initiator, it is particularly preferred to use an aromatic ketone compound and a hexaarylbisimidazole compound in combination. In this case, the use ratio of the aromatic ketone compound is preferably 0.5% by mass or less, more preferably 0.01% by mass to 0.4% by mass, relative to the total mass of the solid content of the photosensitive resin composition. The use ratio of the hexaarylbisimidazole compound is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, relative to the total mass of the solid content of the photosensitive resin composition.

[0108] <(D) Dye>

[0109] The photosensitive resin composition of the present embodiment includes a dye (D). The photosensitive resin composition contains a dye to color the exposed portion, so it is preferred in terms of visibility. In addition, when an inspection machine or the like reads a positioning mark for exposure, the contrast between the exposed portion and the unexposed portion is large, so it is easy to identify, which is advantageous. When combined with the compound (E) in the present embodiment, the dye having a large contrast between the exposed portion and the unexposed portion is preferably a leuco dye and a fluorane dye, and more preferably a leuco dye.

[0110] In order to impart appropriate color development and excellent peeling properties to the resist cured film, the above-mentioned leuco dye may be blended in the photosensitive resin composition of the present embodiment.

[0111] Specific examples of the leuco dye include leuco crystal violet (tris[4-(dimethylamino)phenyl]methane: DMA) and 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide. Among these, leuco crystal violet (DMA) is preferred.

[0112] From the perspective of the contrast between the exposed portion and the unexposed portion, the use ratio of the dye in the photosensitive resin composition of the present embodiment is preferably 0.01% by mass to 2% by mass, and more preferably 0.1% by mass to 1.5% by mass relative to the total amount of the solid content of the photosensitive resin composition. By setting the use ratio of the leuco dye to this range, good color development and sensitivity can be achieved.

[0113] In the present embodiment, the dye may include a basic dye. As a basic dye, for example, basic green 1 [CAS number (hereinafter the same): 633-03-4] (for example, Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), malachite green oxalate [2437-29-8] (for example, Aizen Malachite Green, trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), brilliant green [633-03-4], fuchsin [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, trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), rhodamine B [81-88-9], rhodamine 6G [989-38-8], basic yellow 2 [2465-27-2], etc. Among these, at least one selected from basic green 1, malachite green oxalate and basic blue 7 is preferred, and basic green 1 is particularly preferred from the viewpoint of hue stability and exposure contrast.

[0114] The basic dye used in the photosensitive resin composition of the present embodiment is preferably in the range of 0.001% to 3% by mass, more preferably in the range of 0.01% to 2% by mass, and even more preferably in the range of 0.01% to 1.2% by mass, relative to the total solid content of the photosensitive resin composition. By setting the use ratio in this range, good coloring properties can be obtained.

[0115] <(E) Compounds Having Specific Heterocyclic Structure>

[0116] In the present embodiment, the compound (E) is a compound having no amino group, an acidic group with a pKa of 5 or less, and a heterocyclic structure having 4 nitrogen atoms. The compound (E) is preferably solid at room temperature (25° C.).

[0117] The compound (E) is a compound represented by the following general formula (3).

[0118]

[0119] In the general formula (3), R 1 and R 2 None of them have an amino group, and are independently selected from the group consisting of a hydrogen atom or an organic group having 1 to 20 carbon atoms, preferably independently selected from the group consisting of a hydrogen atom and an organic group having 1 to 10 carbon atoms, and more preferably independently selected from the group consisting of a hydrogen atom and an organic group having 1 to 3 carbon atoms. 1 and R 2 At least one of the R has an acidic group with a pKa of 5 or less. 1 and / or R 2 In the case of an organic group having an acidic group with a pKa of 5 or less, the “carbon number” refers to the carbon number of the entire organic group including the carbon number of the acidic group with a pKa of 5 or less.

[0120] In the general formula (3), specific examples of the organic group having 1 to 20 carbon atoms include octadecyl, heptadecyl, hexadecyl, pentadecyl, tetradecyl, tridecyl, dodecyl, undecyl and decyl.

[0121] In the general formula (3), specific examples of the organic group having 1 to 10 carbon atoms include a nonyl group, an octyl group, a heptyl group, a hexyl group, a pentyl group, and a butyl group.

[0122] In the general formula (3), specific examples of the organic group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

[0123] In general formula (3), specific examples of the acidic group having a pKa of 5 or less include a carboxyl group, a phosphoric acid group, and a sulfonic acid group. From the viewpoint of excellent color development and low side etching, the acidic group is preferably a carboxyl group.

[0124] When the compound (E) is a compound represented by the general formula (3), excellent color development and low side etching can be obtained.

[0125] From the viewpoint of excellent color development and low side etching, the compound represented by the general formula (3) is more preferably R 1 and R 2 One of them is an organic group having 1 to 3 carbon atoms and an acidic group with a pKa of 5 or less, and the other is independently selected from the group consisting of a hydrogen atom and an organic group having 1 to 3 carbon atoms; more preferably R 1 and R 2 One of them is an organic group having 1 to 3 carbon atoms and having an acidic group with a pKa of 5 or less, and the other is a hydrogen atom.

[0126] Specific examples of the compound represented by the general formula (3) include 1H-tetrazole-1-carboxylic acid, 1H-tetrazole-5-carboxylic acid, 1H-tetrazole-1-acetic acid, 1H-tetrazole-5-acetic acid, 1H-tetrazole-1-propionic acid, 1H-tetrazole-5-propionic acid, 5-methyl-1H-tetrazole-1-carboxylic acid, 1-methyl-1H-tetrazole-5-carboxylic acid, 5-methyl-1H-tetrazole-1-acetic acid, 1-methyl-1H-tetrazole-5-acetic acid, 5-methyl-1H-tetrazole-1-propionic acid, 1-methyl-1H-tetrazole-5-propionic acid, 5-ethyl-1H-tetrazole-1-carboxylic acid, 1-ethyl-1H-tetrazole-5-carboxylic acid, 5-ethyl-1H-tetrazole-5-carboxylic acid, 1H-tetrazole-1-acetic acid, 1-ethyl-1H-tetrazole-5-acetic acid, 5-ethyl-1H-tetrazole-1-propionic acid, 1-ethyl-1H-tetrazole-5-propionic acid, 5-propyl-1H-tetrazole-1-carboxylic acid, 1-propyl-1H-tetrazole-5-carboxylic acid, 5-propyl-1H-tetrazole-1-acetic acid, 1-propyl-1H-tetrazole-5-acetic acid, 5-propyl-1H-tetrazole-1-propionic acid, 1-propyl-1H-tetrazole-5-propionic acid, 1-octadecyl-1H-tetrazole-5-acetic acid, 1-heptadecyl-1H-tetrazole-5-acetic acid, 1-hexadecyl-1H-tetrazole-5-acetic acid, 1-pentadecyl-1H-tetrazole-5 -acetic acid, 1-tetradecyl-1H-tetrazolyl-5-acetic acid, 1-tridecyl-1H-tetrazolyl-5-acetic acid, 1-dodecyl-1H-tetrazolyl-5-acetic acid, 1-undecyl-1H-tetrazolyl-5-acetic acid, 1-decyl-1H-tetrazolyl-5-acetic acid, 1-nonyl-1H-tetrazolyl-5-acetic acid, 1-octyl-1H-tetrazolyl-5-acetic acid, 1-heptyl-1H-tetrazolyl-5-acetic acid, 1-hexyl-1H-tetrazolyl-5-acetic acid, 1-pentyl-1H-tetrazolyl-5-acetic acid, 1-butyl-1H-tetrazolyl-5-acetic acid, 1-octadecyl-1H-tetrazolyl-5-propionic acid, 1-heptadecyl-1H-tetrazolyl-5-propionic acid Acid, 1-hexadecyl-1H-tetrazolyl-5-propionic acid, 1-pentadecyl-1H-tetrazolyl-5-propionic acid, 1-tetradecyl-1H-tetrazolyl-5-propionic acid, 1-tridecyl-1H-tetrazolyl-5-propionic acid, 1-dodecyl-1H-tetrazolyl-5-propionic acid, 1-undecyl-1H-tetrazolyl-5-propionic acid, 1-decyl-1H-tetrazolyl-5-propionic acid, 1-nonyl-1H-tetrazolyl-5-propionic acid, 1-octyl-1H-tetrazolyl-5-propionic acid, 1-heptyl-1H-tetrazolyl-5-propionic acid, 1-hexyl-1H-tetrazolyl-5-propionic acid, 1-pentyl-1H-tetrazolyl-5-propionic acid, 1-butyl-1H-tetrazolyl-5-propionic acid and the like. Among these, from the viewpoint of excellent color development and low side etching, the compound represented by the general formula (3) is preferably 1H-tetrazole-1-acetic acid and 1H-tetrazole-5-acetic acid, and more preferably 1H-tetrazole-5-acetic acid.

[0127] From the viewpoint of excellent color development and low side etching, the content of the compound (E) in the photosensitive resin composition can be in the range of 0.001% by mass to 5% by mass, preferably 0.001% by mass to 0.5% by mass, more preferably 0.001% by mass to 0.3% by mass, further preferably 0.001% by mass to 0.2% by mass, and further preferably 0.001% by mass to 0.1% by mass. The lower limit of the content of the compound (E) in the photosensitive resin composition can be 0.01% by mass, 0.02% by mass, or 0.03% by mass relative to the total amount of the solid content of the photosensitive resin composition.

[0128] <Other ingredients>

[0129] The photosensitive resin composition of the present embodiment may contain only the components (A) to (E) described above, or may contain other components together with these. Examples of other components that can be used herein include stabilizers.

[0130] The stabilizer is preferred from the viewpoint of improving the thermal stability or storage stability of the photosensitive resin composition, or both. As the stabilizer, for example, at least one compound selected from the group consisting of a free radical inhibitor, a benzotriazole compound, a carboxybenzotriazole compound, and an oxyalkylene compound having a glycidyl group can be cited. These can be used alone or in combination of two or more.

[0131] Examples of the radical polymerization inhibitor 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-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxylamine aluminum salt (for example, aluminum salt to which 3 moles of nitrosophenylhydroxylamine are added), diphenylnitrosoamine, and the like. Among these, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] and aluminum salt to which 3 moles of nitrosophenylhydroxylamine are added are preferred. In addition, these may be used alone or in combination of two or more.

[0132] Examples of the benzotriazole compound include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole, and a 1:1 mixture of 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole. Among these, a 1:1 mixture of 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole is preferred. In addition, these compounds may be used alone or in combination of two or more.

[0133] Examples of the carboxybenzotriazole compound include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole. These compounds may be used alone or in combination of two or more.

[0134] Examples of the oxyalkylene compound 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-mole 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 may be used alone or in combination of two or more.

[0135] In the present embodiment, the total content of the radical inhibitor, the benzotriazole compound, the carboxybenzotriazole compound, and the oxyalkylene compound having a glycidyl group in the photosensitive resin composition is preferably in the range of 0.001% by mass to 3% by mass, and more preferably in the range of 0.05% to 1.5% by mass. From the viewpoint of imparting good storage stability to the photosensitive resin composition, the total content is preferably 0.001% by mass or more, and from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, it is preferably 3% by mass or less.

[0136] [Photosensitive resin composition preparation liquid]

[0137] In this embodiment, a photosensitive resin composition preparation liquid can be prepared by adding a solvent to the photosensitive resin composition as described above. Suitable solvents that can be used here include ketones such as methyl ethyl ketone (MEK); alcohols such as methanol, ethanol, and isopropanol. Preferably, the preparation liquid is prepared by adding a solvent to the photosensitive resin composition in such a manner that the viscosity of the photosensitive resin composition preparation liquid is 500 mPa·second to 4,000 mPa·second at 25°C.

[0138] [Photosensitive element]

[0139] The photosensitive element (also referred to as dry film resist) of this embodiment comprises: a support and a photosensitive resin composition layer formed from the photosensitive resin composition of this embodiment on the support. The photosensitive element of this embodiment may have a protective layer on the surface of the photosensitive resin composition layer opposite to the support as needed.

[0140] [Supporting body]

[0141] 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 films, polyvinyl alcohol films, polyvinyl chloride films, vinyl chloride copolymer films, polyvinylidene chloride films, vinylidene chloride copolymer films, polymethyl methacrylate copolymer films, polystyrene films, polyacrylonitrile films, styrene copolymer films, polyamide films, and cellulose derivative films. As these films, stretched films may be used as required.

[0142] The haze of the support is preferably 0.01% to 5.0%, more preferably 0.01% to 3.5%, further preferably 0.01% to 2.5%, and further preferably 0.01% to 1.0%.

[0143] A thin support is advantageous in terms of image forming properties and economic efficiency, but strength must be maintained. Considering both, a support with a thickness of 10 to 30 μm can be preferably used.

[0144] [Photosensitive resin composition layer]

[0145] The photosensitive resin composition layer in the photosensitive element of this embodiment is a layer formed of the photosensitive resin composition of this embodiment. When the photosensitive resin composition used to form the photosensitive resin composition layer contains a solvent, the solvent is preferably removed from the photosensitive resin composition layer, but the solvent may remain.

[0146] The thickness of the photosensitive resin composition layer in the photosensitive element of this embodiment is preferably 5 to 100 μm, more preferably 5 to 50 μm. The thinner the thickness, the higher the resolution, and the thicker the thickness, the higher the film strength. Therefore, the thickness of the composition layer can be appropriately selected within the above range according to the application.

[0147] [Protective film]

[0148] The important characteristic of the protective layer in the photosensitive element of this embodiment is that the adhesion between the protective layer and the photosensitive resin composition layer is sufficiently smaller than the adhesion between the support and the photosensitive resin composition layer, and the protective layer can be easily peeled off. For example, polyethylene film, polypropylene film, etc. can be preferably used as the protective layer, and for example, a film with excellent peelability disclosed in Japanese Patent Publication No. 59-202457 can also be used.

[0149] The thickness of the protective layer is preferably 10 to 100 μm, more preferably 10 to 50 μm.

[0150] [Method for producing photosensitive element]

[0151] The photosensitive element of this embodiment can be produced by laminating a support, a photosensitive resin composition layer, and a protective layer as required in this order. As a method for laminating the support, the photosensitive resin composition layer, and the protective layer, a known method can be adopted.

[0152] For example, the photosensitive resin composition of the present embodiment is prepared as the above-mentioned photosensitive resin composition preparation liquid, first, it is coated on a support by a bar coater or a roll coater and dried to form a photosensitive resin composition layer formed of the photosensitive resin composition on the support. Then, if necessary, a protective layer is laminated on the formed photosensitive resin composition layer, thereby manufacturing a photosensitive element.

[0153] [Method for forming resist pattern]

[0154] The photosensitive element as described above can be used to form a resist pattern on a substrate. The method for forming a resist pattern includes the following steps in sequence: a lamination step of forming a photosensitive resin composition layer on a substrate using the photosensitive element of the present embodiment; an exposure step of exposing the photosensitive resin composition layer; and a development step of removing the unexposed portion of the photosensitive resin composition layer with a developer to form a resist pattern.

[0155] In the method for forming the anti-etching pattern of the present embodiment, first, a photosensitive resin composition layer is formed on a substrate using a laminator in a lamination process. Specifically, in the case where the photosensitive element has a protective layer, after peeling off the protective layer, the photosensitive resin composition layer is heated and pressed by a laminator and laminated on the surface of the substrate. As the material of the substrate used, for example, copper, stainless steel (SUS), glass, indium tin oxide (ITO), a flexible substrate laminated with a conductor film, etc. can be listed. As the above-mentioned conductor film, for example, ITO, copper, copper-nickel alloy, silver, etc. can be listed; as the material constituting the above-mentioned flexible substrate, for example, polyethylene terephthalate (PET) can be listed. The above-mentioned substrate may have a through hole corresponding to the multilayer substrate.

[0156] The photosensitive element of the present embodiment can be suitably applied to the manufacture of a touch panel sensor using an etching process. In the formation of the wiring (conductor pattern) in the touch panel sensor, an etching process is generally used. As described above, in the touch panel sensor, it is required to form wiring with a size much finer than that of a conventional printed circuit board. Here, if an etching process using a photosensitive element in the prior art is adopted, the side etching amount of the conductor pattern formed is large, so the yield rate of the product manufactured by the touch panel sensor is limited. However, the photosensitive element of the present embodiment is excellent in reducing the side etching amount, so the touch panel sensor can be manufactured with a high yield rate.

[0157] Here, the photosensitive resin composition layer can be laminated only on one side of the substrate surface, or can be laminated on both sides of the substrate as needed. The heating temperature at this time is preferably set to 40°C to 160°C. By performing heating and pressing more than 2 times, the adhesion of the obtained anti-etching pattern to the substrate is further improved. In the case of pressing more than 2 times, a two-stage laminator with a double roller can be used, or the laminate of the substrate and the photosensitive resin composition layer can be repeatedly pressed by the roller.

[0158] Next, in the exposure step, the photosensitive resin composition layer is exposed using an exposure machine. The exposure may be performed with the support without peeling the support, or after peeling the support as necessary.

[0159] By performing the exposure in a pattern, a resist film (resist pattern) having a desired pattern can be obtained after the development step described later. The patterned exposure can be performed by any method of exposure with the aid of a photomask and maskless exposure. When the exposure is performed with the aid of a photomask, the exposure amount is determined by the light source illumination and the exposure time. The exposure amount can be measured using a light meter.

[0160] In maskless exposure, exposure is performed on the substrate using a direct drawing device without using a photomask. As a light source, a semiconductor laser with a wavelength of 350nm to 410nm, an ultra-high pressure mercury lamp, etc. can be used. In maskless exposure, the drawing pattern is controlled by a computer, and the exposure amount is determined by the illumination of the exposure light source and the moving speed of the substrate.

[0161] The photosensitive element of this embodiment is preferably used in a method of performing exposure via a photomask in that the effect of improving resolution and reducing the amount of undercut is maximized.

[0162] Next, in the development step, the unexposed portion of the photosensitive resin composition layer is removed with a developer. When a support is present on the photosensitive resin composition layer after exposure, it is preferably removed before subjecting the layer to the development step.

[0163] In the development process, a developer formed of an alkaline aqueous solution is used to develop and remove the unexposed portion to obtain a resist image. As the alkaline aqueous solution, for example, an aqueous solution such as Na2CO3 or K2CO3 is preferably used. The alkaline aqueous solution is selected according to the characteristics of the photosensitive resin composition layer, and preferably a Na2CO3 aqueous solution with a concentration of 0.2% to 2% by mass is used. The alkaline aqueous solution may be mixed with a surfactant, a defoaming agent, a small amount of an organic solvent for promoting development, and the like.

[0164] The temperature of the developer in the development step is preferably kept constant within a range of 18°C ​​to 40°C.

[0165] The above process can obtain a resist pattern. Depending on the situation, a heating process at 100°C to 300°C can be further performed. By implementing this heating process, chemical resistance can be further improved. Heating can be performed using a heating furnace using a suitable method such as hot air, infrared rays, or far infrared rays.

[0166] [Method for forming wiring board]

[0167] The method for forming a wiring board in the present embodiment includes the following steps in sequence: a lamination step, which forms a photosensitive resin composition layer on a substrate using the photosensitive element of the present embodiment; an exposure step, which exposes the photosensitive resin composition layer; a development step, which forms an anti-etching pattern by removing the unexposed portion of the photosensitive resin composition layer with a developer; a conductor pattern forming step, which etches or plates the substrate on which the anti-etching pattern is formed; and a stripping step, which strips the anti-etching pattern. By the above method, a wiring board formed with a desired conductor pattern on a substrate can be obtained.

[0168] The lamination process, exposure process and development process are the same as those of the above-mentioned [resist pattern forming method]. After the resist pattern is formed by the above-mentioned resist pattern forming method, the following conductor pattern forming process and stripping process are performed to obtain a wiring board having a conductor pattern formed on a substrate.

[0169] In the conductor pattern forming step, on the substrate on which the resist pattern is formed, a conductor pattern can be formed on the substrate surface (eg, copper surface) exposed by the development step using a known etching method or plating method.

[0170] The amount of side etching of the resist pattern obtained using the photosensitive resin composition of the present embodiment is preferably 5.5 μm or less, more preferably 5.4 μm or less, and further preferably 5.3 μm or less.

[0171] The top width of the copper line pattern is preferably 4.2 μm or more, more preferably 4.5 μm or more, and even more preferably 4.8 μm or more.

[0172] This is preferable because it is possible to obtain an advantage of being able to form fine wiring.

[0173] The photosensitive resin composition, photosensitive element, and conductive pattern forming method of the present embodiment are extremely suitable for use in the production of, for example, printed wiring boards, lead frames, substrates having concavo-convex patterns, semiconductor packages, touch panel sensors, and the like.

[0174] [Touch panel sensor]

[0175] The photosensitive resin composition, photosensitive element, and method for forming a conductor pattern of the present embodiment are particularly suitable for manufacturing a touch panel sensor. The touch panel sensor is manufactured by forming a lead wiring formed by the conductor pattern formed by the above method on a flexible substrate having a sputtered copper layer. In addition, a touch panel can be obtained by sequentially stacking a liquid crystal display element, the above touch panel sensor, and glass.

[0176] Unless otherwise specified, the evaluation values ​​of the above-mentioned various parameters are measured according to the measurement methods in the examples described later.

[0177] Example

[0178] Hereinafter, the present embodiment will be specifically described using Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

[0179] <Weight Average Molecular Weight and Dispersity>

[0180] The sample was measured by gel permeation chromatography (GPC), and the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion degree (Mw / Mn) were calculated using a polystyrene (ShodexSTANDARD SM-105 manufactured by Showa Denko K.K.).

[0181] Specifically, the measurement was performed under the following conditions using a gel permeation chromatograph manufactured by JASCO Corporation.

[0182] Differential refractometer: RI-1530

[0183] Pump: PU-1580

[0184] Degassing device: DG-980-50

[0185] Column thermostat: CO-1560

[0186] Column: KF-8025, KF-806M×2 and KF-807 connected in series

[0187] Eluent: THF

[0188] <Acid equivalent>

[0189] The acid equivalent refers to the mass (g) of a polymer having one equivalent of a carboxyl group in the molecule. The acid equivalent was measured by potentiometric titration using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd. using a 0.1 mol / L sodium hydroxide aqueous solution.

[0190] <Glass transition temperature>

[0191] The glass transition temperature of the alkali-soluble polymer was calculated using the above literature value as the Tg of each comonomer. i , calculated according to the above Fox formula (I).

[0192] <Production of Photosensitive Element>

[0193] The components shown in Table 1 were mixed, and methyl ethyl ketone (MEK) was further added to prepare a photosensitive resin composition having a solid content concentration of 61% by mass. Table 2 shows the explanation of the components shown in Table 1.

[0194] The obtained photosensitive resin composition was uniformly coated on a 16 μm thick polyethylene terephthalate film (manufactured by Toray Industries, Ltd., product name "FB40") as a support film using a bar coater, and then heated and dried in a dryer adjusted to 95° C. for 5 minutes to form a 5 μm thick photosensitive resin composition layer on the support film.

[0195] Next, a polyethylene film (manufactured by TAMAPOLY CORPORATION, product name "GF-858") having a thickness of 33 μm was attached as a protective layer to the surface of the photosensitive resin composition layer opposite to the support film, thereby obtaining a photosensitive element.

[0196] <Substrates used in evaluation>

[0197] As the evaluation substrate, a flexible base material was used in which ITO and a thin-film copper with a thickness of 5 μm or less were sequentially deposited on PET.

[0198] <Lamination>

[0199] On the above substrate, while peeling off the polyethylene film of the photosensitive element obtained in each example or comparative example, lamination was carried out using a hot roll laminator (AL-70 manufactured by Asahi Kasei Corporation) at a roll temperature of 105°C, an air pressure of 0.35 MPa and a lamination speed of 1.5 m / min.

[0200] <Exposure>

[0201] Exposure was performed using a chrome glass mask with a parallel light exposure machine (HMW-801, manufactured by Oak Corporation) at an exposure amount such that the top width of the resist obtained after exposure and development was 0 μm to +1 μm higher than the mask design value.

[0202] <Contrast>

[0203] The polyethylene film was peeled off from the photosensitive element and exposed to the above exposure amount. Then, 15 minutes later, the contrast between the exposed area and the unexposed area was measured from the polyethylene terephthalate side using a spectrometer (NF333, manufactured by Nippon Denshoku Industries).

[0204] Contrast ratio = Transmittance of exposed part (%) / Transmittance of unexposed part (%)

[0205] <Development>

[0206] After peeling off the support film from the exposed photosensitive resin composition layer, an alkali developer (manufactured by Fuji Kiko Co., Ltd., a developer for dry films) 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 portion of the photosensitive resin composition layer. After development, the substrate was washed with water to obtain a substrate having a cured film for evaluation.

[0207] The minimum development time is the minimum time required until the unexposed portion of the photosensitive resin composition layer is completely dissolved and removed.

[0208] <Adhesion>

[0209] When independent thin lines of 30 mm in length were measured under the above-mentioned development conditions, the minimum line width at which the pattern remained was defined as the adhesion.

[0210] <Amount of side erosion>

[0211] In the evaluation of the side etching amount, the laminated substrate after 15 minutes from the above-mentioned <Lamination> was used.

[0212] This laminated substrate was exposed to light in a pattern of line / space=10 μm / 10 μm, and then developed by the method described in the above <Development>.

[0213] First, the resist bottom width Wb of the pattern is measured using an optical microscope.

[0214] Next, the substrate having the line / space pattern was etched by dipping at a hydrochloric acid concentration of 2 mass %, ferric chloride of 2 mass % and a temperature of 30° C. for 70 seconds (condition I) or 30 seconds (condition II).

[0215] After the etching, the cured film on the substrate was stripped off at 50° C. using a 3 mass % NaOH aqueous solution as a stripping solution, and the top width Wt of the obtained copper line pattern was measured using an optical microscope.

[0216] Then, the side erosion amount was calculated according to the following mathematical formula.

[0217] Side erosion (μm) = Wb-Wt

[0218] <Uniformity of copper wire width>

[0219] After development was performed by the method described in the above <Development>, the copper wire was measured within a length of 100 mm, and the outermost end and the innermost end of the copper wire were determined and evaluated according to the following criteria.

[0220] ◎: The distance from the outermost end of the line to the innermost end of the line is less than 0.2μm

[0221] ○: The distance from the outermost end of the line to the innermost end of the line is 0.2 μm or more and less than 0.5 μm

[0222] △: The distance from the outermost end of the line to the innermost end of the line is 0.5μm or more

[0223] <Examples 1 to 5 and Comparative Examples 1 to 5>

[0224] The compositions of the photosensitive resin compositions used in the examples and comparative examples are shown in Table 1, respectively, and the details of the names of the components described in Table 1 are shown in Table 2. The amounts of the components in Table 1 are all in parts by mass in terms of solid content. The evaluation results of adhesion, side etching, uniformity of copper wire width, and contrast using the various photosensitive resin compositions are summarized in Table 1. In Table 1, Examples 1 to 5 all obtained good results in terms of the balance of the evaluation items "side etching", "uniformity of copper wire width", and "contrast", and good results in each evaluation result. In particular, despite the small amount of compound (E) in the photosensitive resin compositions of Examples 2 and 4, good results were obtained.

[0225] [Table 1]

[0226]

[0227] [Table 2]

[0228]

[0229] Industrial Applicability

[0230] The photosensitive resin composition of the present embodiment is not limited, and can be used, for example, as a dry film for forming wiring, a color development aid for a dye, or a formulation for preventing an etching solution from penetrating between a resist and a substrate.

Claims

1. A photosensitive resin composition comprising: (A) Alkali-soluble polymers, (B) a compound having an ethylenically unsaturated double bond, (C) a photopolymerization initiator, (D) dyes, and (E) a compound represented by the following general formula (3), In formula (3), R 1 and R 2 None of them have an amino group, and are independently selected from the group consisting of a hydrogen atom or an organic group having 1 to 20 carbon atoms, wherein: R 1 and R 2 At least one of the compounds has an acidic group with a pKa of 5 or less, The dye (D) is a leuco dye.

2. The photosensitive resin composition according to claim 1, wherein In formula (3), R 1 and R 2 do not have an amino group and are independently selected from the group consisting of a hydrogen atom or an organic group having 1 to 10 carbon atoms, wherein R 1 and R 2 At least one of them has an acidic group with a pKa of 5 or less.

3. The photosensitive resin composition according to claim 1, wherein In formula (3), R 1 and R 2 None of them have an amino group and are independently selected from the group consisting of a hydrogen atom or an organic group having 1 to 3 carbon atoms, wherein R 1 and R 2 At least one of them has an acidic group with a pKa of 5 or less.

4. The photosensitive resin composition according to claim 3, wherein In formula (3), R 1 and R 2 None of them have amino groups, R 1 and R 2 One of them is an organic group having 1 to 3 carbon atoms and having an acidic group with a pKa of 5 or less, and the other is a hydrogen atom.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein The acidic group is any one of a carboxyl group, a phosphoric acid group or a sulfonic acid group.

6. The photosensitive resin composition according to claim 5, wherein The acidic group is a carboxyl group.

7. The photosensitive resin composition according to claim 6, wherein The compound (E) is selected from 1H-tetrazolyl-1-acetic acid and 1H-tetrazolyl-5-acetic acid.

8. The photosensitive resin composition according to any one of claims 1 to 4, wherein The compound (E) is contained in an amount of 0.001 to 0.5% by mass based on the total amount of solid content of the photosensitive resin composition.

9. The photosensitive resin composition according to any one of claims 1 to 4, wherein The compound (E) is contained in an amount of 0.001 to 0.3% by mass based on the total amount of solid content of the photosensitive resin composition.

10. The photosensitive resin composition according to any one of claims 1 to 4, wherein The compound (E) is contained in an amount of 0.001 to 0.2% by mass based on the total amount of solid content of the photosensitive resin composition.

11. The photosensitive resin composition according to any one of claims 1 to 4, wherein The compound (E) is contained in an amount of 0.001 to 0.1% by mass based on the total amount of solid content of the photosensitive resin composition.

12. The photosensitive resin composition according to any one of claims 1 to 4, wherein The compound (E) is solid at 25°C.

13. The photosensitive resin composition according to any one of claims 1 to 4, wherein The alkali-soluble polymer (A) contains an aromatic ring in its molecular structure.

14. The photosensitive resin composition according to claim 13, wherein The alkali-soluble polymer (A) is a combination of an alkali-soluble polymer (A-1) having a Mw of less than 50,000 and an alkali-soluble polymer (A-2) having a Mw of 50,000 or more.

15. The photosensitive resin composition according to claim 14, wherein The content ratio of the alkali-soluble polymer (A-1) relative to the total amount of solid content of the photosensitive resin composition is 3% by mass or more and 30% by mass or less.

16. The photosensitive resin composition according to claim 14, wherein The content ratio of the alkali-soluble polymer (A-1) relative to the total amount of solid content of the photosensitive resin composition is 5 mass % or more and 25 mass % or less.

17. The photosensitive resin composition according to claim 14, wherein The content ratio of the alkali-soluble polymer (A-2) relative to the total amount of solid content of the photosensitive resin composition is 5 mass % or more and 50 mass % or less.

18. The photosensitive resin composition according to claim 13, wherein The copolymerization ratio of the compound having an aromatic group in the alkali-soluble polymer (A) is 20% by mass or more based on the total mass of all monomers. 19 . A photosensitive element comprising: a support, and the photosensitive resin composition layer according to claim 1 formed on the support.

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