TWI770578B - Photosensitive resin composition, and photosensitive element - Google Patents

Abstract

One of the objects of the present invention is to provide a photosensitive resin composition, the photosensitive resin composition can reduce the amount of side etching, the uniformity of the copper line width is excellent, the color development of the dye can be promoted during exposure, and the visual recognition of the exposed part Excellent sex. According to the present invention, there is provided a photosensitive resin composition comprising: (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 {in the formula, both R ¹ and R ² do not have an amine group, and are independently selected from the group consisting of a hydrogen atom or an organic group having 1 to 20 carbon atoms, wherein, At least one of R ¹ and R ² has an acidic group with pKa5 or less}.

Description

Photosensitive resin composition, and photosensitive element

The present invention relates to a photosensitive resin composition and a photosensitive element.

Printed wiring boards are usually fabricated by photolithography. The so-called photolithography method refers to the following method: forming a layer containing a photosensitive resin composition on a substrate, pattern exposure and development of the coating film to form a photoresist pattern thereon, followed by etching or plating The conductor pattern is formed by processing, and then the photoresist pattern on the substrate is removed, thereby forming the desired wiring pattern on the substrate.

When manufacturing a printed wiring board, a photosensitive element (dry film resist) in which a photosensitive resin layer is laminated on a support is often used. As a method of forming a wiring pattern using this photosensitive element, and a photosensitive resin composition suitable for the method, there are many well-known examples, and the following Patent Documents 1 to 5 are mentioned, for example.

The purpose of Patent Document 1 is to provide a photosensitive resin composition which has a high sensitivity to ultraviolet light or visible light in particular, can be cured by laser drawing, and can be drawn after forming a film on a substrate Excellent storage stability thereafter. As a solution for this, Patent Document 1 describes a photosensitive resin composition containing a tetrazole or a derivative thereof, or a triazole or a derivative thereof. Examples of tetrazole or derivatives thereof include 1H-1,2,3,4-tetrazole, 5-amino-1H-tetrazole, and 5-methyl-1H-tetrazole; as triazole or its derivatives Derivatives include 1,2,4-triazole and 5-chlorobenzotriazole.

Patent Document 2 aims to provide a photosensitive resin composition capable of forming a photoresist film which is excellent in adhesion to the copper surface, is not affected by changes over time after coating or lamination, and is extremely stable. As a solution for this, Patent Document 2 describes a photosensitive resin composition containing one or two or more heterocyclic compounds selected from the group consisting of triazoles, tetrazoles, and imidazoles.

The purpose of Patent Document 3 is to provide a photosensitive resin composition, which has high sensitivity, can obtain a good photoresist pattern shape, and has high shielding film strength, and can form a pattern with high definition and high aspect ratio. . As a solution for this, Patent Document 3 describes a photosensitive resin composition containing a monocarboxylic acid compound having a molecular weight of 180 to 2,000.

The purpose of Patent Document 4 is to provide a photosensitive resin composition that can subdivide the peeling sheet (reduce the size of the photoresist sheet after peeling), and has excellent plating resistance, sensitivity, resolution and Excellent adhesion. As a solution to this, Patent Document 4 describes a photosensitive resin composition containing a binder polymer containing at least (meth)acrylic acid and hydroxyalkyl (meth)acrylate as copolymerization components, and further containing benzene Triazole and carboxybenzotriazole derivatives represented by a specific general formula are used as an adhesion-imparting agent.

An object of Patent Document 5 is to provide a photosensitive resin composition capable of forming a photoresist which has sufficiently excellent adhesion to a conductor layer, and which does not easily cause discoloration of the conductor layer. As a solution to this, 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 compound represented by a specific general formula Benzotriazole derivatives. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2002-317005 [Patent Document 2] Japanese Patent No. 4883537 [Patent Document 3] Japanese Patent Laid-Open No. 2011-81391 [Patent Document 4] Japanese Patent Laid-Open No. 2010-72535 [Patent Document 5] Japanese Patent No. 4449983

[Problems to be Solved by Invention]

In recent years, with the miniaturization and weight reduction of electronic equipment, the miniaturization and high density of printed wiring boards have been progressing, and a high-performance photosensitive element is required in the process of manufacturing photosensitive elements, which can reduce side etching (the following Also referred to as "undercut") to provide a more uniform copper line width. In addition, the photosensitive element usually contains a dye so that the photoresist pattern formed on the copper foil after development can be visually recognized with a better contrast ratio. The dye has the function of changing the color of the exposed part after the DF (dry film, dry film) is exposed.

One of the objects of the present invention is to provide a photosensitive resin composition, the photosensitive resin composition can reduce the amount of side etching, the uniformity of the copper line width is excellent, the color development of the dye can be promoted during exposure, and the visual recognition of the exposed part Excellent sex. [Technical means to solve problems]

{式中，R¹ 及R² 均不具有胺基，且獨立地選自由氫原子或碳數1～20之有機基所組成之群，其中，R¹ 及R² 中之至少一者具有pKa5以下之酸性基}。 [2] 如項目1記載之感光性樹脂組合物，其中式中之R¹ 及R² 均不具有胺基，且獨立地選自由氫原子或碳數1～3之有機基所組成之群，其中，R¹ 及R² 中之至少一者具有pKa5以下之酸性基。 [3] 如項目2記載之感光性樹脂組合物，其中式中之R¹ 及R² 均不具有胺基，R¹ 及R² 中之其中一者係具有pKa5以下之酸性基之碳數1～3之有機基，另一者係氫原子。 [4] 如項目1至3中任一項之感光性樹脂組合物，其中上述酸性基係羧基、磷酸基、或磺酸基中之任一者。 [5] 如項目4記載之感光性樹脂組合物，其中上述酸性基為羧基。 [6] 如項目1至5中任一項之感光性樹脂組合物，其中上述染料(D)為隱色染料。 [7] 如項目1至6中任一項記載之感光性樹脂組合物，其中相對於上述感光性樹脂組合物之固形物成分之總量，含有0.001～0.5質量%之上述化合物(E)。 [8] 如項目1至7中任一項之感光性樹脂組合物，其中上述化合物(E)於25℃下為固體。 [9] 如項目1至8中任一項之感光性樹脂組合物，其中上述鹼溶性高分子(A)於其分子結構中包含芳香環。 [10] 一種感光性元件，其具備：支持體、及形成於上述支持體上之如項目1至9中任一項之感光性樹脂組合物層。 [發明之效果]The inventors of the present application have repeatedly conducted intensive studies to solve the above-mentioned problems, and found that the above-mentioned problems can be solved by a photosensitive resin composition containing an alkali-soluble polymer and having ethylenically unsaturated bis A bond compound, a photopolymerization initiator, a dye, and a compound having a specific structure are used to complete the present invention. That is, the present invention is as follows. [1] A photosensitive resin composition comprising: (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 (3): [Chemical 1]

{In the formula, R ¹ and R ² do not have an amine group, and are independently selected from the group consisting of hydrogen atoms or organic groups with 1 to 20 carbon atoms, wherein at least one of R ¹ and R ² has pKa5 The following acidic groups}. [2] The photosensitive resin composition according to item 1, wherein R ¹ and R ² in the formula do not have an amine group, and are independently selected from the group consisting of a hydrogen atom or an organic group having 1 to 3 carbon atoms, However, at least one of R ¹ and R ² has an acidic group with pKa5 or less. [3] The photosensitive resin composition as described in item 2, wherein neither R ¹ and R ² in the formula have an amine group, and one of R ¹ and R ² is a carbon number 1 having an acidic group with pKa5 or less ~3 is an organic group, and the other is a hydrogen atom. [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, or a sulfonic acid group. [5] The photosensitive resin composition according to item 4, wherein the acidic group is a carboxyl group. [6] The photosensitive resin composition according to any one of items 1 to 5, wherein the dye (D) is a leuco dye. [7] The photosensitive resin composition according to any one of Items 1 to 6, wherein the compound (E) is contained in an amount of 0.001 to 0.5 mass % with respect to the total amount of the solid content of the photosensitive resin composition. [8] The photosensitive resin composition according to any one of items 1 to 7, wherein the compound (E) is solid at 25°C. [9] The photosensitive resin composition according to any one of items 1 to 8, wherein the alkali-soluble polymer (A) includes an aromatic ring in its molecular structure. [10] A photosensitive element comprising: a support and the photosensitive resin composition layer as any one of items 1 to 9 formed on the above-mentioned support. [Effect of invention]

According to the present invention, it is possible to provide a photosensitive resin composition that can reduce the amount of side etching, has excellent uniformity of copper line width, promotes color development of dyes during exposure, and has excellent visibility of exposed parts. . Furthermore, the above description should not be considered as revealing all the embodiments of the present invention and all the advantages of the present invention. Further embodiments of the present invention and advantages thereof will be known with reference to the following description.

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

[Photosensitive resin composition] 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) Compounds with specific heterocyclic structures. Compound (E) is a compound represented by the following general formula (3). By having the above-mentioned constitution, the photosensitive resin composition of the present embodiment can provide a photosensitive resin composition with reduced side etching, excellent uniformity of copper line width, and accelerated exposure during exposure. The color development of the dye is excellent, and the visibility of the exposed part is excellent. The reason for this has not been clarified, and the present invention is not limited by theory, but the inventors and the like conjecture as follows. In order to reduce the amount of undercut, the adhesion and reactivity of the hardened photoresist and the copper interface are more important. The etching solution penetrates into the photoresist-copper interface due to the etching process, so the difference between the line width of the dry film and the copper line width after etching (side etching) is generated. If the interaction between the photoresist and the copper interface is strong, the etching solution will be difficult to penetrate, and the amount of side etching will be reduced. As compounds with strong interaction with copper, imidazole, triazole, tetrazole, etc. are known. However, if these compounds have high hydrophobicity, they may remain on the substrate after development, resulting in etching residues. . On the other hand, the inventors discovered that the etching residue can be reduced by using the compound (E) which has high solubility in an alkaline aqueous solution and has an acidic group of pKa5 or less. In addition, in order to reduce the amount of side etching, a smaller amount of swelling is more favorable, so the reaction rate of the photoresist after hardening is also more important. It is considered that tetrazole, in particular, undergoes radical cleavage in the short wavelength region of about 200 nm, so the interface with many such interfaces, especially the copper interface (the bottom of the photoresist), has an increased reaction rate, and the swelling rate of the bottom of the photoresist is suppressed. , thereby contributing to low side erosion. On the other hand, the color development of the dye is better in view of the visibility of the exposed part, and when an inspection machine or the like reads the position alignment mark for exposure, the contrast between the exposed part and the unexposed part is large. Easier to identify and more beneficial. It is considered that the compound (E) having an acidic group having a pKa5 or less reacted upon exposure stabilizes a dye, preferably a cation of leuco crystal violet (DMA), and thus becomes favorable for color development and favorable for exposure contrast.

<(A) Alkali-soluble polymer> (A) The alkali-soluble polymer is preferably obtained by polymerizing at least one of the following first monomers. Moreover, it is more preferable that (A) an alkali-soluble polymer is obtained by copolymerizing at least 1 type of 1st monomer, and at least 1 type of the following 2nd monomer.

The first monomer is a monomer containing a carboxyl group in the molecule. As a 1st monomer, (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester, etc. are mentioned, for example. Among these, (meth)acrylic acid is particularly preferable. In this specification, "(meth)acrylic acid" means acrylic acid and methacrylic acid, and "(meth)acrylate" means "acrylate" and "methacrylate".

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

The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-(meth)acrylate Butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid ring (Meth)acrylates such as hexyl ester, 2-ethylhexyl (meth)acrylate, and benzyl (meth)acrylate; vinyl alcohol esters such as vinyl acetate; and (meth)acrylonitrile, styrene , and polymerizable styrene derivatives (such as methylstyrene, vinyltoluene, tertiary butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.) etc. 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 etching, benzyl (meth)acrylate is particularly preferred.

The copolymerization ratio of the second monomer in the (A) alkali-soluble polymer is preferably 70% by mass to 90% by mass, more preferably 70 mass % - 85 mass %, More preferably, it is 72 mass % - 84 mass %.

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

The (A) alkali-soluble polymer having an aromatic group in a side chain can be prepared by using a compound having an aromatic group as at least one of the above-mentioned first monomer and second monomer. Examples of the monomer having an aromatic group include aralkyl (meth)acrylate such as benzyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, styrene, cinnamic acid, polymerizable styrene derivatives (eg, methylstyrene, vinyltoluene, tert-butoxystyrene, acetyloxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene terpolymer, etc.) etc. From the viewpoint of suppressing side etching, aralkyl (meth)acrylate and styrene are preferred, and benzyl (meth)acrylate is particularly preferred.

The copolymerization ratio of the compound having the 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 with respect to the total mass of all monomers or more, or 80% by mass or more. 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.

In the present embodiment, (A) the alkali-soluble polymer can be obtained by using a known polymerization method, preferably addition polymerization, more preferably radical polymerization, to make one selected from the first monomer and the second monomer described above. It is prepared by polymerizing more than one monomer.

(A) The acid equivalent of the alkali-soluble polymer (in the case of including a plurality of copolymers, the acid equivalent of the entire mixture), the development resistance of the photosensitive resin layer, and the resolution and adhesion of the photoresist pattern From the viewpoint of properties, it is preferably 100 or more, and from the viewpoint of the developability and peelability of the photosensitive resin layer, it is preferably 600 or less. The acid equivalent of (A) the alkali-soluble polymer is more preferably 200 to 500, and still more preferably 250 to 450.

(A) The weight average molecular weight of the alkali-soluble polymer (hereinafter abbreviated as "Mw") (in the case of using a plurality of alkali-soluble polymers in combination, it refers to the Mw of the whole), preferably 5,000 to 500,000, More preferably, it is 5,000-100,000, More preferably, it is 10,000-65,000. The ratio of the weight-average molecular weight to the number-average molecular weight (hereinafter sometimes abbreviated as "Mn"), that is, the degree of dispersion (Mw/Mn) (when a plurality of alkali-soluble polymers are used in combination, it is the degree of dispersion of the whole), compared with Preferably it is 1.0-6.0, More preferably, it is 1.5-5.0, More preferably, it is 2.0-5.0, More preferably, it is 2.5-4.5, Especially preferably, it is 3.0-4.2. (A) It is preferable that the weight average molecular weight and the degree of dispersion of the alkali-soluble polymer are in the above-mentioned ranges in terms of obtaining moderate developability, high coating film strength, and uniformity of photoresist thickness.

As the (A) alkali-soluble polymer, when a plurality of alkali-soluble polymers are used in combination, it is particularly preferable to include: (A-1) Alkali-soluble polymers with Mw less than 50,000, and (A-2) An alkali-soluble polymer having Mw of 50,000 or more.

Mw of the said alkali-soluble polymer (A-1) is more preferably 5,000 or more and less than 50,000, more preferably 10,000 to 45,000, and particularly preferably 10,000 to 35,000. Mw of the alkali-soluble polymer (A-1) is in this range, and it is preferable in that it has both developability and resolution. On the other hand, as for Mw of the said alkali-soluble polymer (A-2), 50,000-100,000 are more preferable, 50,000-75,000 are still more preferable, 50,000-65,000 are especially preferable. When the Mw of the alkali-soluble polymer (A-2) is in this range, the product life when the photosensitive resin composition of this embodiment is applied to a photosensitive element (also referred to as "dry film resist") is further extended It is better in this respect.

The content ratio of the alkali-soluble polymer (A-1) component is preferably 3 mass % or more and 30 mass % or less, more preferably 5 mass % or more and 25 mass % with respect to the total amount of the solid content of the photosensitive resin composition. Below, it is more preferable that it is 10 mass % or more and 20 mass % or less. Setting the usage ratio of the component (A-1) within the above-mentioned range is preferable in terms of both resolution and a small amount of undercut. The content ratio of the alkali-soluble polymer (A-2) component is preferably 5 mass % or more and 50 mass % or less, more preferably 15 mass % or more and 48 mass % with respect to the total amount of the solid content of the photosensitive resin composition. Below, it is more preferable that it is 18 mass % or more and 45 mass % or less. Setting the usage ratio of the component (A-2) within the above-mentioned range further extends the product life when the photosensitive resin composition of this embodiment is applied to a photosensitive element (dry film resist) better.

The usage ratio of (A) the alkali-soluble polymer in the photosensitive resin composition of the present embodiment is preferably 25% by mass to 85% by mass, more preferably 35% by mass relative to the total amount of the solid content of the photosensitive resin composition. mass % to 75 mass %. Setting the usage ratio of the (A) alkali-soluble polymer within the above-mentioned range is preferable from the viewpoints of resolution, developability, developer swellability of exposed parts, peelability of photoresist pattern, and product life of photosensitive element .

<(B) Compound having ethylenically unsaturated double bond> (B) The compound which has an ethylenically unsaturated double bond is a compound which has polymerizability by having an ethylenically unsaturated double bond in the structure. As such a compound, a compound obtained by adding (meth)acrylic acid to one terminal of polyalkylene oxide, adding (meth)acrylic acid to one terminal of polyalkylene oxide, and adding an alkyl group to the other terminal can be mentioned. Compounds obtained by etherification or allyl etherification, etc. (compounds of the first group); compounds having (meth)acryloyl groups at both ends of alkylene oxide chains, compounds in ethylene oxide chains and propylene oxide chains Compounds having (meth)acryloyl groups at both ends of an alkylene oxide chain formed by random bonding or block bonding, compounds obtained by modifying bisphenol A, etc. (compounds of the second group); one molecule Compounds and the like having three or more (meth)acryloyl groups (compounds of the third group) and the like.

Specific examples of other compounds of the first group include phenoxyhexaethylene glycol mono(meth)acrylate, which is a (methyl) compound obtained by adding polyethylene glycol to a phenyl group. base) acrylate; 4-n-nonylphenoxy heptaethylene glycol dipropylene glycol (meth)acrylate, which is a polypropylene glycol with an average of 2 mol of propylene oxide added and an average of 7 mol of propylene oxide added. (Meth)acrylate of a compound obtained by adding polyethylene glycol of ethylene oxide to nonylphenol; polypropylene glycol with an average of 1 mol of propylene oxide added and an average of 5 mol of propylene oxide added. 4-N-nonylphenoxy pentaethylene glycol monopropylene glycol (meth)acrylate addition of (meth)acrylate of the compound obtained by adding polyethylene glycol of ethylene oxide to nonylphenol 4-n-Nonylphenoxyoctaethylene glycol (meth)acrylate (eg Toa Gosei (stock) Manufacturing, M-114); etc.

Specific examples of other compounds of the second group include tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, and hexaethylene glycol di(meth)acrylic acid. ester, heptaethylene glycol di(meth)acrylate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, Polyethylene glycol (meth)acrylates such as compounds having (meth)acryloyl groups at both ends of a 12-molar ethylene oxide chain; polypropylene glycol di(meth)acrylates; polybutylene glycol di(meth)acrylates base) acrylate, etc. As a polyalkylene oxide di(meth)acrylate compound containing an ethylene oxide group and a propylene oxide group in the compound, for example, the both ends of polypropylene glycol to which an average of 12 moles of propylene oxide is added can be mentioned. And then add the dimethacrylate of the glycol that the average 3 mol of ethylene oxide is formed respectively; To the two ends of the polypropylene glycol with the average 18 mol of propylene oxide added respectively, then add the average 15 mol respectively. Dimethacrylates of diols made of ethylene oxide, etc.; in addition, can also include: A compound having an ethylenically unsaturated double bond at both ends of a polyalkylene glycol obtained by adding an alkylene oxide to bisphenol A, etc.

As a compound obtained by modifying bisphenol A among the compounds of the second group above, it is used for a polyalkylene glycol obtained by adding an alkylene oxide to bisphenol A and having ethylenically unsaturated double bonds at both ends. The compound is preferable from the viewpoint of resolution and adhesion. The ethylenically unsaturated double bond in the compound is preferably contained in the compound in a form contained in a (meth)acryloyl group. In order to modify bisphenol A by adding alkylene oxide, for example, ethylene oxide modification, propylene oxide modification, butylene oxide modification, pentoxide modification, and hexylene oxide modification are known. Alkane modification, etc. A compound having (meth)acryloyl groups at both ends of a polyalkylene glycol obtained by adding ethylene oxide to bisphenol A is preferable.

Examples of such compounds include 2,2-bis(4-((meth)acryloyloxydiethoxy)phenyl)propane (for example, NK ESTER BPE by Shin-Nakamura Chemical Industry Co., Ltd.) 200), 2,2-bis(4-((meth)acryloyloxytriethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxytetraethoxy) (methyl)phenyl)propane, 2,2-bis(4-((meth)acryloyloxypentaethoxy)phenyl)propane (such as NK ESTER BPE-500 manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) Wait. Further, such as di(meth)acrylate of polyalkylene glycol with an average of 2 moles of propylene oxide and an average of 6 moles of ethylene oxide added to both ends of bisphenol A, or Di(meth)acrylate of polyalkylene glycol with an average of 2 moles of propylene oxide and an average of 15 moles of ethylene oxide added to both ends of bisphenol A, etc. Alkane-modified and propylene oxide-modified compounds are also preferred. The molar numbers of ethylene oxide and propylene oxide in the compound having (meth)acryloyl groups at both ends by modifying bisphenol A with alkylene oxide are improved in resolution, adhesion, and From the viewpoint of flexibility, it is preferably 1 mol or more and 60 mol or less, more preferably 4 mol or more and 40 mol or less, and still more preferably 5 mol or more and 20 mol or less.

The compounds of the third group are obtained by adding an ethoxy group, a propoxy group, a butoxy group, etc. to the central skeleton having a group capable of adding an epoxy alkyl group of 3 mol or more in the molecule. An alkyloxy group is extended to obtain an alcohol, and the obtained alcohol is (meth)acrylated. As a compound which can become a central skeleton, glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, an isocyanurate ring, etc. are mentioned, for example. More specifically, for example, ethylene oxide (EO) (3 mol) modified triacrylate of trimethylolpropane, and EO (6 mol) modified triacrylate of trimethylolpropane can be mentioned. , EO (9 moles) modified triacrylate of trimethylolpropane, EO (12 moles) modified triacrylate of trimethylolpropane, etc. Examples of such compounds include: EO (3 mol) modified triacrylate of glycerol (for example, A-GLY-3E manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), EO (9 mol) modified glycerin Triacrylate (such as A-GLY-9E manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), EO (6 mol) modification of glycerin and propylene oxide (PO) (6 mol) modified triacrylate (A -GLY-0606PE), EO (9 mol) modification of glycerol and PO (9 mol) modified triacrylate (A-GLY-0909PE), etc. Further examples include: 4EO-modified tetraacrylate of pentaerythritol (for example, SR-494 manufactured by Sadolan Japan Co., Ltd.), and 35EO-modified tetraacrylate of pentaerythritol (eg, NK manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). ESTER ATM-35E) and so on.

[式中，R⁵ 、R⁶ 及R⁷ 分別獨立地表示碳數1〜20之伸烷基，R⁸ 、R⁹ 及R¹⁰ 分別獨立地表示氫原子或甲基，L¹ 、L² 及L³ 分別獨立地表示碳數2～4之伸烷基，r3、r4及r5分別獨立地表示1〜40之整數，s3、s4、s5、t3、t4及t5分別獨立地表示0〜40之整數；其中，於s3、s4、s5、t3、t4及t5為0之情形時，L¹ 表示伸乙基，於r3、r4、r5、s3、s4、s5、t3、t4或t5為2以上之情形時，複數個-L¹ -O-、-L² -O-或-L³ -O-所表示之結構單元可無規存在亦可形成嵌段] 所表示之化合物、(EO)改性異氰尿酸酯衍生三(甲基)丙烯酸酯(環氧乙烷平均27 mol加成物)等。 作為此種化合物可使用市售品，例如可列舉：UA-7100、A-9300-1CL(以上為新中村化學工業公司製造)；ARONIX M-327(東亞合成公司製造)等。As a compound which has an ethylenically unsaturated double bond, an isocyanurate compound can also be mentioned. Specific examples of such compounds include ethoxylated isocyanuric acid tri(meth)acrylate, ε-caprolactone-modified isocyanurate tris(2-(meth)acryloyloxy) ethyl) ester, triallyl isocyanurate, the following formula: [Chemical 2]

[In the formula, R ⁵ , R ⁶ and R ⁷ each independently represent an alkylene group having 1 to 20 carbon atoms, R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a methyl group, L ¹ , L ² and L3 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. Integer; wherein, when s3, s4, s5, t3, t4 and t5 are 0, L ¹ represents ethylidene, and when r3, r4, r5, s3, s4, s5, t3, t4 or t5 is 2 or more In this case, the structural units represented by a plurality of -L ¹ -O-, -L ² -O- or -L ³ -O- may exist randomly or form a block] The represented compound, (EO) modified isocyanurate-derived tri(meth)acrylate (average 27 mol of ethylene oxide adduct), etc. As such a compound, a commercial item can be used, for example, UA-7100 and A-9300-1CL (the above are manufactured by Shin-Nakamura Chemical Industry Co., Ltd.);

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

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

In addition, as a compound having an ethylenically unsaturated double bond (B), tricyclodecane di(meth)acrylate or (2,2-bis{4-(methacryloyloxypentaethoxy) may also be included base) cyclohexyl} propane, etc.

The photosensitive resin composition of this 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% by mass to 45% by mass relative to the total mass of the solid content of the photosensitive resin composition. Preferably it is 17 mass % - 40 mass %, More preferably, it is 20 mass % - 40 mass %. Setting the usage ratio in this range is suitable for obtaining a photosensitive resin composition having an excellent balance of resolution and developability.

(B) It is preferable that the ratio of the compound which has an ethylenically unsaturated double bond with respect to the total solid content mass of the photosensitive resin composition is 5 mass % - 70 mass %. It is preferable to set this ratio to 5 mass % or more from the viewpoint of sensitivity, resolution and adhesiveness, more preferably 15 mass % or more, and still more preferably 20 mass % or more. On the other hand, it is preferable to set this ratio to 70 mass % or less from the viewpoint of suppressing edge melting and peeling retardation of the hardened photoresist, and it is more preferable to set this ratio to 60 mass % or less.

化合物、二烷基胺基苯甲酸酯化合物、肟酯化合物、吖啶化合物、吡唑啉衍生物、N-芳基胺基酸之酯化合物、鹵素化合物等。<(C) Photopolymerization initiator> Examples of the (C) photopolymerization initiator include hexaarylbiimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, and aromatic ketone compounds. , acetophenone compounds, acyl phosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, 9-oxysulfur 𠮿

Compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-arylamino acid ester compounds, halogen compounds, and the like.

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-diphenyl) Methoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'- Bis-(2,4-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5- Difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4 ,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5 ,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetra -(3-Methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methyl) oxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl) - Biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2 ,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2' -Bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, and 2,2'-bis -(2,3,4,5,6-Pentafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, etc. Among them, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferable from the viewpoint of high sensitivity, resolution, and adhesion.

Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine Wait. In particular, N-phenylglycine is preferable because of its high sensitizing effect.

Examples of the quinone compound include 2-ethylanthraquinone, octylethylanthraquinone, 1,2-benzoanthraquinone, 2,3-benzoanthraquinone, 2-phenylanthraquinone, 2,3-diphenylene anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 9 , 10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone, etc.

Examples of the aromatic ketone compound include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino) Benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, etc. Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane- 1 ketone, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1 ketone, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl) ) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4 -(Methylthio)phenyl]-2-morpholinyl-acetone-1 and the like. Examples of commercially available acetophenone compounds include Irgacure-907, Irgacure-369, and Irgacure-379 manufactured by Ciba Specialty Chemicals. From the viewpoint of adhesiveness, 4,4'-bis(diethylamino)benzophenone is preferable.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)-phosphine oxide, bis(2,4,6-trimethylbenzyl)-phosphine oxide, 2,6-dimethoxybenzyl)-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.

化合物，例如可列舉：2,4-二乙基9-氧硫𠮿

、2,4-二異丙基9-氧硫𠮿

、2-氯9-氧硫𠮿

等。 作為二烷基胺基苯甲酸酯化合物，例如可列舉：二甲胺基苯甲酸乙酯、二乙基胺基苯甲酸乙酯、對二甲胺基苯甲酸乙酯、4-(二甲胺基)苯甲酸2-乙基己酯等。As a benzoin compound and a benzoin ether compound, benzoin, benzoin ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin, etc. are mentioned, for example. As a dialkyl ketal compound, a benzyl dimethyl ketal, a benzyl diethyl ketal, etc. are mentioned, for example. as 9-oxysulfur 𠮿

Compounds, for example: 2,4-diethyl 9-oxothiocyanate

, 2,4-diisopropyl 9-oxothio

, 2-chloro-9-oxysulfur

Wait. Examples of the dialkylaminobenzoate compound include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl p-dimethylaminobenzoate, 4-(dimethylaminobenzoate) amino) 2-ethylhexyl benzoate and the like.

As the oxime ester compound, for example, 1-phenyl-1,2-propanedione-2-O-benzyl oxime, 1-phenyl-1,2-propanedione-2-(O- ethoxycarbonyl) oxime, etc. As a commercial item of an oxime ester compound, CGI-325 by Ciba Specialty Chemicals, Irgacure-OXE01, and Irgacure-OXE02 are mentioned, for example.

The acridine compound is preferably 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine in terms of sensitivity, resolution, availability, and the like.

The pyrazoline derivative is preferably 1-phenyl-3-(4-tert-butyl-styryl)-5-(4 from the viewpoint of adhesiveness and rectangularity of the photoresist pattern. - 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.

Examples of the ester compound of N-arylamino acid include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, Isopropyl N-phenylglycine, 1-butyl N-phenylglycine, 2-butyl N-phenylglycine, 3-butyl N-phenylglycine , Amyl ester of N-phenylglycine, hexyl N-phenylglycine, amyl N-phenylglycine, octyl N-phenylglycine, etc.

Examples of the halogen compound include bromopentane, bromoisopentane, 1,2-dibromo-2-methylpropane, 1,2-dibromoethane, diphenylbromomethane, benzyl bromide, dibromomethane, Tribromomethylphenyl tetramine, carbon tetrabromide, tris(2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, iodoisobutane, 1,1,1-trichloro -2,2-Bis(p-chlorophenyl)ethane, chlorinated tris(II) compounds, diallyl iodonium compounds, etc., particularly preferably, tribromomethyl phenyl sulfone.

The usage ratio of the (C) photopolymerization initiator in the photosensitive resin composition of the present embodiment is preferably 0.01 mass % to 20 mass % with respect to the total mass of the solid content of the photosensitive resin composition, and more Preferably it is 0.5 mass % - 10 mass %. By setting the use ratio of the (C) photopolymerization initiator to this range, the following photosensitive resin composition can be obtained, which can obtain sufficient sensitivity, can sufficiently transmit light to the bottom of the photoresist, and can obtain a high-resolution photosensitive resin composition. Excellent image quality and excellent balance with the undercut amount in the conductor pattern.

As the (C) photopolymerization initiator, a hexaarylbisimidazole compound is preferably used. In this case, the usage 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 with respect to the total mass of the solid content of the photosensitive resin composition. %.

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

＜(D) Dye＞ The photosensitive resin composition of this embodiment contains a dye (D). Since the photosensitive resin composition contains a dye to develop the color of the exposed part, it is preferable in terms of visibility, and when an inspection machine or the like reads a position alignment mark for exposure, the exposed part is different from the exposure part. The larger the contrast of the unexposed part, the easier it is to identify, which is more advantageous. When combined with the compound (E) of this embodiment, a leuco dye and a fluorine dye are preferable, and a leuco dye is more preferable as a dye with a large contrast between an exposed part and an unexposed part.

The above-mentioned leuco dye can be formulated into the photosensitive resin composition of the present embodiment to impart suitable color development and excellent peeling properties to the photoresist cured film. Specific examples of leuco dyes include leuco crystal violet (tris[4-(dimethylamino)phenyl]methane:DMA), 3,3-bis(p-dimethylaminophenyl)- 6-Dimethylaminophthalide, etc. Among these, leuco crystal violet (DMA) is preferred.

The usage ratio of the dye in the photosensitive resin composition of the present embodiment is preferably from 0.01 mass % to the total amount of the solid content of the photosensitive resin composition from the viewpoint of the contrast between the exposed portion and the unexposed portion. 2 mass %, more preferably 0.1 mass % to 1.5 mass %. By setting the usage ratio of the leuco dye within this range, good color rendering properties and sensitivity can be achieved.

In this embodiment, the dye may contain a base dye. Examples of basic dyes include basic green 1 [CAS number (the same below): 633-03-4] (eg, Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), malachite green oxalate [2437 -29-8] (eg Aizen Malachite Green, trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), Brilliant Green [633-03-4], Magenta [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] (eg Aizen Victoria Pure Blue BOH, trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.), Rose Bengal B [81-88-9], Rose Bengal 6G [989-38-8], Basic Yellow 2 [2465-27-2] et al. Among these, one or more kinds selected from the group consisting of basic green 1, malachite green oxalate, and basic blue 7 are preferred, and from the viewpoint of hue stability and exposure contrast, basic green 1 is particularly preferred .

The usage ratio of the base dye in the photosensitive resin composition of the present embodiment is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 2% by mass with respect to the total amount of the solid content of the photosensitive resin composition. The range of mass % is more preferably the range of 0.01 mass % to 1.2 mass %. Good colorability can be obtained by setting the usage ratio within this range.

<(E) Compounds having a specific heterocyclic structure> In the present embodiment, the compound (E) is a compound having no amine group, an acidic group having pKa 5 or less, and a heterocyclic structure containing 4 nitrogen atoms. The compound (E) is preferably solid at normal temperature (25°C).

The compound (E) is a compound represented by the general formula (3) described below.

[hua 3]

In the general formula (3), R ¹ and R ² do not have an amine group, and are independently selected from the group consisting of hydrogen atoms or organic groups having 1 to 20 carbon atoms, preferably independently selected from hydrogen atoms and carbon atoms The group consisting of organic groups having 1 to 10 numbers is more preferably independently selected from the group consisting of hydrogen atoms and organic groups having 1 to 3 carbon atoms. However, in the general formula (3), at least one of R ¹ and R ² has an acidic group with a pKa of 5 or less. When R ¹ and/or R ² are organic groups having an acidic group of pKa5 or less, the "carbon number" refers to the carbon number of the entire organic group including the carbon number of an acidic group of pKa5 or less.

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

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.

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, an isopropyl group, and the like.

In general formula (3), a carboxyl group, a phosphoric acid group, and a sulfonic acid group are specifically mentioned as an acidic group of pKa5 or less. The acid group is preferably a carboxyl group from the viewpoints of excellent color development and low side etching.

By making the compound (E) a compound represented by the general formula (3), excellent color development and low side etching can be obtained.

From the viewpoints of excellent color rendering properties and low side etching, as the compound represented by the general formula (3), it is more preferable that one of R ¹ and R ² is a carbon number 1 having an acidic group of pKa5 or less. ～3 organic groups, the other one is independently selected from the group consisting of hydrogen atoms and organic groups with 1 to 3 carbon atoms; more preferably, one of R ¹ and R ² is an acidic group with pKa5 or less One is an organic group with 1 to 3 carbon atoms, and the other is a hydrogen atom.

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, and 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-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-tetrazole-5-acetic acid, 1-tridecyl-1H-tetrazole-5-acetic acid, 1-dodecane-1H-tetrazole-5-acetic acid, 1-Undecyl-1H-tetrazole-5-acetic acid, 1-decyl-1H-tetrazole-5-acetic acid, 1-nonyl-1H-tetrazole-5-acetic acid, 1-octyl-1H- Tetrazole-5-acetic acid, 1-hept-1H-tetrazole-5-acetic acid, 1-hexyl-1H-tetrazole-5-acetic acid, 1-pentane-1H-tetrazole-5-acetic acid, 1-butyl -1H-tetrazole-5-acetic acid, 1-octadecyl-1H-tetrazole-5-propionic acid, 1-heptadecyl-1H-tetrazole-5-propionic acid, 1-hexadecyl -1H-tetrazole-5-propionic acid, 1-pentadecyl-1H-tetrazole-5-propionic acid, 1-tetradecyl-1H-tetrazole-5-propionic acid, 1-tridecane yl-1H-tetrazole-5-propionic acid, 1-dodecyl-1H-tetrazole-5-propionic acid, 1-undecyl-1H-tetrazole-5-propionic acid, 1-decyl -1H-tetrazole-5-propionic acid, 1-nonyl-1H-tetrazole-5-propionic acid, 1-octane-1H-tetrazole-5-propionic acid, 1-heptyl-1H-tetrazole-5 -Propionic acid, 1-hexyl-1H-tetrazole-5-propionic acid, 1-pentane-1H-tetrazole-5-propionic acid, 1-butyl-1H-tetrazole-5-propionic acid, etc. Among these, from the viewpoint of excellent color development and low side etching, as the compound represented by the general formula (3), 1H-tetrazole-1-acetic acid and 1H-tetrazole-5- Acetic acid, more preferably 1H-tetrazole-5-acetic acid.

The content of the compound (E) in the photosensitive resin composition may be 0.001% by mass to 5% by mass relative to the total amount of the solid content of the photosensitive resin composition from the viewpoint of excellent color development and low side etching. The range of mass % is preferably 0.001 mass % to 0.5 mass %, more preferably 0.001 mass % to 0.3 mass %, still more preferably 0.001 mass % to 0.2 mass %, still more preferably 0.001 mass % to 0.1 mass % %. The lower limit value of the content of the compound (E) in the photosensitive resin composition may 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 .

＜Other ingredients＞ The photosensitive resin composition of this embodiment may contain only the components (A) to (E) explained above, or may contain other components in addition to these components. As another component which can be used here, a stabilizer is mentioned, for example.

The stabilizer is preferable from the viewpoint of improving the thermal stability, storage stability, or both of the photosensitive resin composition. Examples of the stabilizer include at least one compound selected from the group consisting of a radical polymerization inhibitor, a benzotriazole compound, a carboxybenzotriazole compound, and an alkylene oxide compound having a glycidyl group. These can be used individually by 1 type or in combination of 2 or more types.

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, 3 moles of nitrosophenylhydroxylamine (aluminum salt, etc.), diphenylnitrosoamine, etc. are added. Among these, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] or 3-molar nitrosobenzene added is preferred Aluminum salt of hydroxylamine. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

Examples of the benzotriazole compound include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminoidene Methyl-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyethyl) ) aminomethylene-1,2,3-benzotriazole, 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n- 1:1 mixture of butylaminomethyl)-6-carboxybenzotriazole, etc. Among these, 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxy 1:1 mixture of benzotriazoles. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

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)aminoethylidene carboxybenzotriazole and the like. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the alkylene oxide compound having a glycidyl group include neopentyl glycol diglycidyl ether (for example, Epolight 1500 NP manufactured by Kyōeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (for example, co- Epolight 400 E, manufactured by Rongsha Chemical Co., Ltd., diglycidyl ether of a 2-molar adduct of bisphenol A-propylene oxide (such as Epolight 3002 manufactured by Kyoeisha Chemical Co., Ltd.), 1,6- Hexylene glycol diglycidyl ether (for example, Epolight 1600 manufactured by Kyōeisha Chemical Co., Ltd.) and the like. These can be used individually by 1 type or in combination of 2 or more types.

In this embodiment, the total content of the radical polymerization inhibitor, the benzotriazole compound, the carboxybenzotriazole compound, and the alkylene oxide compound having a glycidyl group in the photosensitive resin composition is preferably 0.001 mass % The range of -3 mass %, more preferably the range of 0.05-1.5 mass %. The total content is preferably 0.001 mass % or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and preferably 3 from the viewpoint of maintaining the sensitivity of the photosensitive resin layer. mass % or less.

[Photosensitive resin composition preparation solution] In this embodiment, a photosensitive resin composition preparation liquid can be prepared by adding a solvent to the above-mentioned photosensitive resin composition. As a solvent suitable for use here, ketones, such as methyl ethyl ketone (MEK); Alcohols, such as methanol, ethanol, and isopropyl alcohol, etc. are mentioned. It is preferable to prepare a preparation liquid by adding a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid becomes 500 mPa·sec to 4,000 mPa·sec at 25°C.

[photosensitive element] The photosensitive element (also referred to as dry film resist) of the present embodiment includes a support and a photosensitive resin composition layer formed on the support from the photosensitive resin composition of the present embodiment described above. The photosensitive element of this embodiment may have a protective layer on the surface of the side opposite to a support of the said photosensitive resin composition layer as needed.

[support body] The support is preferably a transparent substrate (film substrate, hereinafter also referred to as "support film") that transmits light radiated from an exposure light source. As such a support film, for example, 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, cellulose derivative film, etc. As these films, those extended as needed can also be used. The haze of the support is preferably 0.01% to 5.0%, more preferably 0.01% to 3.5%, still more preferably 0.01% to 2.5%, still more preferably 0.01% to 1.0%. A thinner thickness of the support is more advantageous in terms of image formability and economy, but it is necessary to maintain strength. Taking these two aspects into consideration, a support having a thickness of 10 to 30 μm can be preferably used.

[Photosensitive resin composition layer] The photosensitive resin composition layer of the photosensitive element of this embodiment consists of the layer of the photosensitive resin composition of the said this embodiment. When the photosensitive resin composition used for formation of the photosensitive resin composition layer contains a solvent, it is preferable to remove the solvent from the photosensitive resin composition layer, but the solvent may remain. The thickness of the photosensitive resin composition layer in the photosensitive element of the present 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-mentioned range according to the application.

[protective film] An important characteristic of the protective layer of the photosensitive element of the present 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, so that it can be easily peeled off. As a protective layer, a polyethylene film, a polypropylene film, etc. can be used suitably, for example, and the film excellent in the peelability disclosed in Unexamined-Japanese-Patent No. 59-202457 can be used, for example. The thickness of the protective layer is preferably 10-100 μm, more preferably 10-50 μm.

[Manufacturing method of photosensitive element] The photosensitive element of this embodiment can be manufactured by laminating|stacking a support body, a photosensitive resin composition layer, and the protective layer laminated|stacked as needed in this order. As a method of laminating the support, the photosensitive resin composition layer, and the protective layer, a known method can be adopted. For example, to prepare the photosensitive resin composition of the present embodiment as the above-mentioned photosensitive resin composition preparation solution, first, it is coated on a support using a bar coater or a roll coater, and dried, and then A photosensitive resin composition layer containing the photosensitive resin composition is formed on the support. Then, if necessary, a protective layer can be laminated on the formed photosensitive resin composition layer, thereby manufacturing a photosensitive element.

[Method for forming a photoresist pattern] A photoresist pattern can be formed on the substrate using the photosensitive element as described above. The method for forming a photoresist pattern sequentially includes the following steps: a lamination step, which uses the photosensitive element of the present embodiment to form a photosensitive resin composition layer on a substrate; an exposure step, which performs a photosensitive resin composition layer on the photosensitive resin composition layer. exposure; and a developing step, which utilizes a developing solution to remove the unexposed portion of the photosensitive resin composition layer, thereby forming a photoresist pattern.

In the formation method of the photoresist pattern of this embodiment, first, a photosensitive resin composition layer is formed on a board|substrate using a laminator in a lamination process. Specifically, when the photosensitive element has a protective layer, after peeling off the protective layer, the photosensitive resin composition layer is heated and pressure-bonded to the substrate surface using a laminator and laminated. As a material of the used board|substrate, copper, stainless steel (SUS), glass, indium tin oxide (ITO), the flexible base material which laminated|stacked a conductor thin film, etc. are mentioned, for example. As said conductor film, ITO, copper, copper-nickel alloy, silver etc. are mentioned, for example; As a material which comprises the said flexible base material, polyethylene terephthalate (PET) etc. are mentioned, for example. The above-mentioned substrate may also have through holes for coping with multilayer substrates.

The photosensitive element of this embodiment can be suitably used for manufacturing a touch panel sensor by an etching method. In order to form the wiring (conductor pattern) in the touch panel sensor, an etching method is generally used. As described above, in the touch panel sensor, it is required to form wirings having a size much smaller than that of ordinary printed wiring boards. Here, if the etching method of the photosensitive element by the prior art is adopted, since the amount of side etching of the formed conductor pattern is large, the product yield of the touch panel sensor is limited. However, the photosensitive element of this embodiment can manufacture a touch panel sensor with a high yield due to its excellent low undercut amount.

Here, the photosensitive resin composition layer may be laminated on only one side of the substrate surface, or may be laminated on both sides of the substrate as required. The heating temperature at this time is preferably set at 40°C to 160°C. By performing the thermocompression bonding twice or more, the adhesiveness of the obtained photoresist pattern to the substrate is further improved. In the case of performing pressure bonding two or more times, a two-stage laminator equipped with a double roller may be used, or the laminate of the substrate and the photosensitive resin composition layer may be repeatedly passed through the rollers for pressure bonding.

Next, the photosensitive resin composition layer is exposed to light using an exposure machine in the exposure step. The exposure may be performed through the support without peeling off the support, or may be performed after peeling off the support if necessary. By performing this exposure in a pattern, a photoresist film (photoresist pattern) having a desired pattern can be obtained after the following development step. The pattern-like exposure can be performed by either a method of exposing through a mask, or a method of exposure without a mask. In the case of exposure through a light shield, the exposure amount is determined by the illuminance of the light source and the exposure time. Exposure can be measured using a light meter. In maskless exposure, exposure is performed on a substrate by a direct drawing device without using a mask. As the light source, a semiconductor laser with a wavelength of 350 nm to 410 nm, an ultra-high pressure mercury lamp, or the like is used. 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 moving speed of the substrate. The photosensitive element of the present embodiment is preferably applied to a method of exposing through a photomask in terms of maximizing the effect of improving the resolution and reducing the amount of side etching.

Then, in a developing process, the unexposed part of the photosensitive resin composition layer is removed by a developing solution. When a support exists on the photosensitive resin composition layer after exposure, it is preferable to use it for a developing process after removing it. In the developing step, a developing solution containing an alkaline aqueous solution is used to develop and remove the unexposed portion, thereby obtaining a photoresist image. As the alkaline aqueous solution, for example, aqueous solutions such as Na ₂ CO ₃ and K ₂ CO ₃ are preferably used. The alkaline aqueous solution is selected according to the characteristics of the photosensitive resin composition layer, and it is preferable to use a Na ₂ CO ₃ aqueous solution having a concentration of 0.2% by mass to 2% by mass. Surfactant, defoaming agent, a small amount of organic solvent for promoting development, etc. can be mixed into the alkaline aqueous solution. The temperature of the developer in the developing step is preferably maintained at a certain temperature within the range of 18°C to 40°C.

A photoresist pattern can be obtained by the above steps. The heating step of 100°C to 300°C can be further performed according to the situation. By carrying out this heating step, chemical resistance can be further improved. For heating, a heating furnace with suitable methods such as hot air, infrared rays, and far infrared rays can be used.

[Method of forming wiring board] The method for forming a wiring board of this embodiment sequentially includes: a lamination step of forming a photosensitive resin composition layer on a substrate using the photosensitive element of this embodiment; an exposure step of subjecting the photosensitive resin composition layer to exposure; developing step, which utilizes a developer to remove the unexposed portion of the photosensitive resin composition layer, thereby forming a photoresist pattern; conductor pattern forming step, which etches or coats the substrate on which the photoresist pattern is formed; and a stripping step, which strips the photoresist pattern. By the above-mentioned method, the wiring board in which the desired wiring pattern is formed on the board|substrate can be obtained.

The lamination step, the exposure step, and the development step are the same as the above-mentioned [Method of forming a photoresist pattern]. After the photoresist pattern is formed by the above-mentioned photoresist pattern formation method, the wiring board with the conductor pattern formed on the substrate can be obtained by going through the following conductor pattern formation step and peeling step. In the conductor pattern forming step, on the substrate on which the photoresist pattern is formed, the conductor pattern may be formed on the substrate surface (eg, copper surface) exposed by the developing step using a known etching method or plating method.

The undercut amount of the photoresist pattern obtained by using the photosensitive resin composition of this embodiment is preferably 5.5 μm or less. More preferably, it is 5.4 μm or less. More preferably, it is 5.3 μm or less. In addition, the width of the tip of the copper wire pattern is preferably 4.2 μm or more. More preferably, it is 4.5 μm or more. More preferably, it is 4.8 μm or more. Thereby, the advantage of being able to form fine wiring can be obtained, which is preferable.

The photosensitive resin composition, the photosensitive element, and the formation method of the conductor pattern of this embodiment can be suitably applied to, for example, a printed wiring board, a lead frame, a substrate having a concavo-convex pattern, a semiconductor package, and a touch panel sensor. Manufacture of measuring instruments, etc.

[Touch Panel Sensor] The photosensitive resin composition of this embodiment, the photosensitive element, and the formation method of a conductor pattern are especially suitable for manufacture of a touch panel sensor. The touch panel sensor is manufactured by the following method: On the flexible base material which has a sputtered copper layer, the lead-out wiring containing the conductor pattern formed by the said method is formed. And a touch panel can be obtained by sequentially laminating a liquid crystal display element, the above-mentioned touch panel sensor, and glass.

Unless otherwise stated, the evaluation values of the above-mentioned parameters are all measured values measured according to the measurement methods of the following examples. [Example]

Hereinafter, the present embodiment will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

<Weight average molecular weight and degree of dispersion> The sample was measured by gel permeation chromatography (GPC), and the calibration curve of polystyrene (Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd.) was used to calculate the weight average molecular weight (Mw) and the number average molecular weight (Mn). ), and the degree of dispersion (Mw/Mn). Specifically, the measurement was performed under the following conditions using a gel permeation chromatograph manufactured by JASCO Corporation. Differential Refractometer: RI-1530 Pump: PU-1580 Degasser: DG-980-50 Column oven: CO-1560 Column: Connect KF-8025, KF-806M×2, and KF-807 in series in sequence Eluent: THF (Tetrahydrofuran, tetrahydrofuran)

＜Acid Equivalent＞ The so-called acid equivalent refers to the mass (g) of the polymer having 1 equivalent of carboxyl groups in the molecule. The acid equivalent was measured by potentiometric titration using a 0.1 mol/L sodium hydroxide aqueous solution using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.

<Glass transition temperature> The glass transition temperature of the alkali-soluble polymer is calculated by the above-mentioned Fox formula (I) using the above-mentioned literature value as the _Tgi of each comonomer.

＜Production of photosensitive element＞ Each component shown in Table 1 was mixed, methyl ethyl ketone (MEK) was further added, and the photosensitive resin composition of 61 mass % of solid content density|concentrations was prepared. In addition, the description of each component shown in Table 1 is shown in Table 2. The obtained photosensitive resin composition was uniformly coated on a polyethylene terephthalate film with a thickness of 16 μm as a support film (manufactured by Toray Industries, Ltd., trade name “FB40”) using a bar coater. ), it was heated and dried in a dryer adjusted to 95° C. for 5 minutes to form a photosensitive resin composition layer with a thickness of 5 μm on the support film. Next, a polyethylene film with a thickness of 33 μm (manufactured by Tamapoly Co., Ltd., trade name “GF-858”) as a protective layer was attached to the surface of the photosensitive resin composition layer on the opposite side to the support film. This obtains a photosensitive element.

<Substrate for evaluation> As a substrate for evaluation, a flexible substrate in which ITO and thin-film copper of 5 μm or less were sequentially vapor-deposited on PET was used.

＜Lamination＞ On the above-mentioned substrate, while peeling off the polyethylene film of the photosensitive element obtained in each Example or Comparative Example, a heated roll laminating machine (AL-70 manufactured by Asahi Kasei Co., Ltd.) was used at a roll temperature of 105° C., Lamination was performed under the conditions of an air pressure of 0.35 MPa and a lamination speed of 1.5 m/min.

＜Exposure＞ Using a chrome glass mask, with a parallel light exposure machine (Oak Co., Ltd., HMW-801), the top width of the photoresist obtained after exposure and development becomes the mask design value ratio of 0 μm～+1 Exposure is performed with an exposure amount of μm.

＜Contrast＞ The polyethylene film was peeled off from the photosensitive element, and after 15 minutes of exposure at the above exposure amount, using a spectrometer (Nippon Denshoku Kogyo Co., Ltd., NF333), from the polyethylene terephthalate side, the exposed part and the unaffected part were measured. Contrast of the exposed part. Contrast = transmittance of exposed part (%) / transmittance of unexposed part (%)

<Development> After peeling the support film from the photosensitive resin composition layer after exposure, using an alkali developer (developer for dry film by Fuji Kiko), spraying at 30° C., 1 mass % for twice the minimum development time The aqueous Na ₂ CO ₃ solution was used to dissolve and remove the unexposed portion of the photosensitive resin composition layer. By performing a water washing process after image development, the board|substrate which has the cured film for evaluation is obtained. The above-mentioned minimum development time refers to the shortest time required for complete dissolution and removal of the unexposed part of the photosensitive resin composition layer.

＜Adhesion＞ The minimum line width of the pattern remaining when measuring an independent thin line with a length of 30 mm under the above development conditions is used as the adhesion force

<Amount of side erosion> The evaluation of the undercut amount was used for the laminated substrate after 15 minutes elapsed after the above-mentioned <lamination>. This laminate substrate was developed by the method described in the above-mentioned <Development> after exposing the pattern of line/space=10 μm/10 μm. First, the width Wb of the photoresist bottom end of the pattern is measured by an optical microscope. Next, the substrate having the line/space pattern was subjected to a dipping method at a concentration of 2 mass % of hydrochloric acid, 2 mass % of ferric chloride, and a temperature of 30° C. for 70 seconds (condition I) or 30 seconds (condition II). ) etching. After the above-mentioned etching, the cured film on the substrate was peeled and removed at a temperature of 50° C. using an aqueous NaOH solution having a concentration of 3 mass % as a stripping solution, and the tip width Wt of the obtained copper wire pattern was measured with an optical microscope. Next, by the following formula: Side etch (μm)=Wb-Wt Calculate the amount of side erosion.

＜Uniformity of copper line width＞ After developing by the method described in the above <Development>, a copper wire having a length of 100 mm was measured, the outermost end and the innermost end of the copper wire were determined, and the evaluation was performed according to the following criteria. ◎: The distance from the outermost end of the line to the innermost end of the line is less than 0.2 μm ○: 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 △: The distance from the outermost end of the line to the innermost end of the line is 0.5 μm or more

<Examples 1 to 5 and Comparative Examples 1 to 5> The composition of the photosensitive resin composition used in the Example and the comparative example is shown in Table 1, and the details of each component name described in Table 1 are shown in Table 2. The compounding quantity of each component in Table 1 is the mass part of solid content conversion. Table 1 summarizes the evaluation results of adhesion, undercut amount, uniformity of copper line width, and contrast using each photosensitive resin composition. In Table 1, Examples 1 to 5 all obtained the results that the evaluation items "amount of undercut", "uniformity of copper line width" and "contrast" were well balanced, and the respective evaluation results were also good. Especially in Examples 2 and 4, although the content of the compound (E) in the photosensitive resin composition was small, good results were obtained.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Ingredient A-1 parts by mass 14 14 14 14 14 14 14 14 Ingredient A-2 parts by mass 43 43 43 43 43 43 43 43 Ingredient A-3 parts by mass 30 30 Ingredient A-4 parts by mass 28 28 Ingredient B-1 parts by mass 29 29 29 29 28 29 29 29 29 28 Ingredient B-2 parts by mass 8 8 8 8 3 8 8 8 8 3 Ingredient B-3 parts by mass 6 6 6 6 9 6 6 6 6 9 Ingredient B-4 parts by mass 2 2 Ingredient C-1 parts by mass 3 3 3 3 3 3 3 3 3 3 Ingredient C-2 parts by mass 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 Ingredient D-1 parts by mass 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 Ingredient D-2 parts by mass 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 other ingredients 1 parts by mass 0.006 0.006 0.006 0.006 0.006 0.006 0.006 0.006 0.006 0.006 other ingredients 2 parts by mass 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 other ingredients 3 parts by mass 1 1 Ingredient E-1 parts by mass 0.1 0.1 Ingredient E-2 parts by mass 0.1 0.05 0.1 Ingredient E-3 parts by mass 0.1 0.05 Ingredient E-4 parts by mass 0.1 Ingredient E-5 parts by mass 0.1 Ingredient E-6 parts by mass 0.1 total 104.216 104.266 104.216 104.266 104.216 104.216 104.216 104.216 104.22 104.216 Etching time condition I I I I II I I I I II tightness 6 4 6 4 3.5 4 4 4 5 3 Side erosion amount 1.1 2.0 1.6 2.6 0.6 3.3 3.1 3.7 3.4 2.3 Uniformity of copper line width ◎ ◎ ◎ ◎ ○ ◎ ◎ △ ◎ ◎ Contrast 3.5 2.8 3.9 3.4 3.0 2.1 2.4 2.0 1.8 1.7

[Table 2] Element illustrate Ingredient A-1 A 54% (solid content) MEK solution of a copolymer having a composition of methacrylic acid/benzyl methacrylate (polymerization ratio of 20/80), an acid equivalent of 430, and a weight-average molecular weight of 26,000 Ingredient A-2 A 50% (solid content) MEK solution of a copolymer having a composition of methacrylic acid/benzyl methacrylate (polymerization ratio of 20/80), an acid equivalent of 430, and a weight-average molecular weight of 53,000 Ingredient A-3 A 41% (solid content) MEK solution of a copolymer having a composition of methacrylic acid/methyl methacrylate/styrene (polymerization ratio of 21/39/40), an acid equivalent of 413, and a weight-average molecular weight of 50,000 Ingredient A-4 54% of the copolymer having the composition of methacrylic acid/methyl methacrylate/styrene/butyl acrylate (polymerization ratio of 25/10/60/5), acid equivalent of 344 and weight average molecular weight of 17400 ( Solid content) MEK solution Ingredient B-1 Dimethacrylate of polyethylene glycol obtained by adding an average of 5 mol of ethylene oxide to both ends of bisphenol A (BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd., product name) Ingredient B-2 ε-Caprolactone-modified tris(2-propenyloxyethyl) isocyanurate (manufactured by Toagosei Co., Ltd., ARONIX M-327) Ingredient B-3 Hexamethacrylate of polyethylene glycol obtained by adding 13 moles of ethylene oxide to dipentaerythritol Ingredient B-4 Triacrylate obtained by adding an average of 3 mol of ethylene oxide to trimethylolpropane (A - TMPT-3EO manufactured by Shin-Nakamura Chemical Co., Ltd., product name) Ingredient C-1 2-(o-Chlorophenyl)-4,5-diphenylimidazole dimer Ingredient C-2 4,4'-Bis(diethylamino)benzophenone Ingredient D-1 diamond green Ingredient D-2 leuco crystal violet other ingredients 1 Aluminium salt with 3 moles of nitrosophenylhydroxylamine added other ingredients 2 Condensate obtained by reacting 2 moles of 3-[ ( 3-tert-butyl)-5-methyl-4-hydroxyphenyl]propionic acid with 1 mole of triethylene glycol other ingredients 3 Polyoxypropylene glycerol ether obtained by adding an average of 16 moles of ethylene oxide to glycerol Ingredient E-1 1 of 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole: 1 mixture Ingredient E-2 1H-Tetrazole-5-acetic acid Ingredient E-3 1H-tetrazole-1-acetic acid Ingredient E-4 5-Amino-1H-tetrazole Ingredient E-5 1,2,4-Triazole Ingredient E-6 1,2,4-Triazole-3-carboxylic acid [Industrial Availability]

The photosensitive resin composition of the present embodiment is not limited, and can be used, for example, as a dry film for wiring formation, a color-developing aid for dyes, and a permeation inhibitor for preventing etchant from permeating between photoresist and substrate.

Claims (10)

A photosensitive resin composition comprising: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, (C) a photopolymerization initiator, (D) a dye, and (E) a The compound represented by the general formula (3):

{In the formula, both R ¹ and R ² do not have an amine group, and are independently selected from the group consisting of hydrogen atoms or organic groups with 1 to 20 carbon atoms, wherein at least one of R ¹ and R ² has pKa5 The following acidic groups} wherein the content of the compound (E) is 0.1 mass % or less with respect to the total amount of the solid content of the photosensitive resin composition. The photosensitive resin composition of claim 1, wherein R ¹ and R ² in the formula do not have amine groups, and are independently selected from the group consisting of hydrogen atoms or organic groups with 1 to 3 carbon atoms, wherein R At least one of ¹ and R ² has an acidic group with a pKa of 5 or less. The photosensitive resin composition according to claim 2, wherein both R ¹ and R ² in the formula have no amine group, and one of R ¹ and R ² has an acidic group with pKa5 or less and has 1 to 3 carbon atoms. organic group, and the other is a hydrogen atom. The photosensitive resin composition according to any one of claims 1 to 3, wherein the acidic group is any one of a carboxyl group, a phosphoric acid group, or a sulfonic acid group. The photosensitive resin composition according to claim 4, wherein the acidic group is a carboxyl group. The photosensitive resin composition according to any one of claims 1 to 3, wherein the dye (D) is a leuco dye. The photosensitive resin composition in any one of Claims 1-3 which contains the said compound (E) in 0.001 mass % or more and 0.1 mass % or less with respect to the total amount of solid content of the said photosensitive resin composition. The photosensitive resin composition according to any one of claims 1 to 3, wherein the compound (E) is solid at 25°C. The photosensitive resin composition according to any one of claims 1 to 3, wherein the alkali-soluble polymer (A) contains an aromatic ring in its molecular structure. A photosensitive element comprising a support and the photosensitive resin composition layer according to any one of claims 1 to 9 formed on the support.