WO2021025133A1

WO2021025133A1 - Photosensitive resin composition and photosensitive element

Info

Publication number: WO2021025133A1
Application number: PCT/JP2020/030256
Authority: WO
Inventors: 翔太柳; 義貴加持
Original assignee: 旭化成株式会社
Priority date: 2019-08-06
Filing date: 2020-08-06
Publication date: 2021-02-11
Also published as: TW202111429A; TWI770578B; KR20210146977A; JP7214875B2; CN114174922A; JPWO2021025133A1

Abstract

One of the purposes of the present invention is to provide a photosensitive resin composition which is reduced in a side etch amount, can exhibit excellent uniformity in copper line widths, can be promoted with respect to the development of color of a dye contained therein upon exposure to light, and can have a light-exposed part having excellent visibility. 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 general formula shown below (wherein each of R¹ and R² does not have an amino group and is independently selected from the group consisting of a hydrogen atom and an organic group having 1 to 20 carbon atoms, wherein at least one of R¹ and R² has an acidic group having a pKa value of 5 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 generally manufactured by photolithography. In photolithography, a layer made of a photosensitive resin composition is formed on a substrate, a pattern is exposed and developed on the coating film to form a resist pattern, and then a conductor pattern is formed by etching or plating. This is a method of forming a desired wiring pattern on a substrate by removing a resist pattern on the substrate.

In the manufacture of printed wiring boards, a photosensitive element (dry film resist) in which a photosensitive resin layer is laminated on a support is often used. There are many known examples of a method for forming a wiring pattern using this photosensitive element and a photosensitive resin composition suitable for the method, and examples thereof include the following Patent Documents 1 to 5.

Patent Document 1 provides a photosensitive resin composition that is particularly sensitive to ultraviolet light and visible light, can be cured by laser drawing, and has excellent storage stability after film formation on a substrate and after drawing. The purpose is. As a solution to this problem, 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-, 5amino-1H-tetrazole-, and 5-methyl-1H-tetrazole-, and triazole or a derivative thereof includes 1, 2,4-Triazole or 5-chlorobenzotriazole is mentioned.

It is an object of Patent Document 2 to provide a photosensitive resin composition having excellent adhesion to a copper surface and capable of forming an extremely stable resist film that is not affected by changes over time after painting or laminating. As a solution to this problem, Patent Document 2 describes a photosensitive resin composition containing one or more heterocyclic compounds selected from the group consisting of triazoles, tetrazole-classes and imidazoles.

An object of Patent Document 3 is to provide a photosensitive resin composition having high sensitivity, a good resist pattern shape, strong tent film strength, and high-definition and high aspect ratio pattern. And. As a solution to this problem, Patent Document 3 describes a photosensitive resin composition containing a monocarboxylic acid compound having a molecular weight of 180 to 2,000.

Patent Document 4 provides a photosensitive resin composition capable of subdividing the peeled pieces (reducing the size of the resist piece after peeling), having excellent plating resistance, and having excellent sensitivity, resolution and adhesion. With the goal. As a solution thereof, Patent Document 4 contains a binder polymer containing at least (meth) acrylic acid and hydroxyalkyl (meth) acrylic acid ester as a copolymerization component, and further, as an adhesion imparting agent, benzotriazole and a specific A photosensitive resin composition containing a carboxybenzotriazole derivative represented by a general formula is described.

It is an object of Patent Document 5 to provide a photosensitive resin composition which has sufficiently excellent adhesion to a conductor layer and can form a resist which is unlikely to cause discoloration of the conductor layer. .. As a solution thereof, Patent Document 5 contains a binder polymer, a photopolymerizable compound having an ethylenically unsaturated group, a photopolymerization initiator, and a benzotriazole derivative represented by a specific general formula. Describes the resin composition.

JP-A-2002-317005 Japanese Patent No. 4883537 Japanese Unexamined Patent Publication No. 2011-81391 Japanese Unexamined Patent Publication No. 2010-72535 Japanese Patent No. 4449983

In recent years, along with the miniaturization and weight reduction of electronic devices, the miniaturization and high density of printed wiring boards have been progressing, and in the manufacturing process of photosensitive elements, side etching (hereinafter, also simply referred to as "side etching") There is a demand for high-performance photosensitive elements that can reduce the amount of copper line width and provide a more uniform copper line width. In addition, the photosensitive element generally contains a dye so that the resist pattern formed on the copper foil after development can be visually recognized with good contrast. The dye has a function of changing the color of the exposed portion when the DF is exposed.

One of the objects of the present invention is to provide a photosensitive resin composition in which the amount of side etch is reduced, the uniformity of the copper line width is excellent, the color of the dye is promoted during exposure, and the visibility of the exposed portion is excellent. To do.

As a result of diligent studies to solve the above problems, the inventors of the present application have obtained a specific structure of an alkali-soluble polymer, a compound having an ethylenically unsaturated double bond, a photopolymerization initiator, and a dye. It has been found that the above-mentioned problems can be solved by a photosensitive resin composition containing the compound, and the present invention has been completed. That is, the present invention is as follows.
[1]
(A) Alkali-soluble polymer,
(B) A compound having an ethylenically unsaturated double bond,
(C) Photopolymerization initiator,
(D) Dye and (E) Compound represented by the following general formula (3):

{In the formula, neither R ¹ nor R ² has an amino group and is independently selected from the group consisting of a hydrogen atom or an organic group having 1 to 20 carbon atoms, except that of R ¹ and R ² . At least one has an acidic group of pKa5 or less. }, A photosensitive resin composition.
[2]
In the formula, neither R ¹ nor R ² has an amino group and is independently selected from the group consisting of a hydrogen atom or an organic group having 1 to 3 carbon atoms, except that at least R ¹ and R ² are selected. One is the photosensitive resin composition according to item 1, which has an acidic group of pKa5 or less.
[3]
Wherein, ^{R 1} and ^{R 2} are both having no amino group, one of ^{R 1} and ^{R 2} is an organic group having 1 to 3 carbon atoms having a pKa5 following acidic group and the other represents hydrogen The photosensitive resin composition according to item 2, which is an atom.
[4]
The photosensitive resin composition according to any one of items 1 to 3, wherein the acidic group is any one of a carboxy group, a phosphoric acid group, and a sulfonic acid group.
[5]
The photosensitive resin composition according to item 4, wherein the acidic group is a carboxy 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% by mass based on the total 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 a solid at 25 ° C.
[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.
[10]
A photosensitive element comprising a support and a photosensitive resin composition layer formed on the support according to any one of items 1 to 9.

According to the present invention, it is possible to provide a photosensitive resin composition in which the amount of side etch is reduced, the uniformity of the copper line width is excellent, the color development of the dye is promoted at the time of exposure, and the visibility of the exposed portion is excellent. It should be noted that the above description shall not be deemed to disclose all the embodiments of the present invention and all the advantages relating to the present invention. Further embodiments of the present invention and their advantages will become apparent with reference to the following description.

Hereinafter, the embodiment of the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail for the purpose of exemplifying, but the present invention is not limited to the present embodiment. In the specification of the present 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 comprises (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, (C) a photopolymerization initiator, and (D) a dye. (E) Contains a compound having a specific heterocyclic structure. The compound (E) is a compound represented by the general formula (3) described later. By having the above structure, the photosensitive resin composition of the present embodiment has a reduced amount of side etch, excellent uniformity of copper line width, promotes color development of the dye during exposure, and has excellent visibility of the exposed portion. A photosensitive resin composition can be provided.
The reason is not yet clear, and the present invention is not limited to theory, but the inventors speculate as follows.
In order to reduce the amount of side etch, the adhesion and reaction rate between the cured resist and the copper interface are important. Since the etching solution soaks into the resist-copper interface by the etching process, a difference (side etch) between the line width of the dry film and the copper line width after etching occurs. If the interaction between the resist and the copper interface is strong, the etching solution is less likely to permeate and the amount of side etching is reduced. As a compound having a strong interaction with copper, imidazole, triazole, tetrazole, etc. are known, but if these compounds have high hydrophobicity, they remain on the substrate even after development, and there is a problem that an etching residue is generated. There is. Therefore, the inventors have found that the etching residue can be reduced by using the compound (E) having an acidic group of pKa5 or less, which is highly soluble in an alkaline aqueous solution. Further, in order to reduce the amount of side etch, it is advantageous that the amount of swelling is small, so that the reaction rate of the resist after curing is also important. In particular, tetrazol- radically cleaves in a short wavelength region of about 200 nm, so that the reaction rate of the copper interface (resist bottom), where many of them are present, increases, the swelling rate of the resist bottom is suppressed, and contributes to low side etching. It is thought that.
On the other hand, the color development of the dye is preferable from the viewpoint of visibility of the exposed portion, and when the inspection machine or the like reads the alignment marker for exposure, it is advantageous that the contrast between the exposed portion and the unexposed portion is large for easy recognition. is there. It is considered that the compound (E) having an acidic group of pKa5 or less reacted at the time of exposure stabilizes the cation of the dye, preferably leuco crystal violet (DMA), so that the color development becomes good and the exposure contrast becomes good.

<(A) Alkali-soluble polymer>
The alkali-soluble polymer (A) is preferably obtained by polymerizing at least one of the first monomers described later. Further, the alkali-soluble polymer (A) can be obtained by copolymerizing at least one kind of the first monomer and at least one kind of the second monomer described later. preferable.

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, maleic acid semi-ester and the like. Among these, (meth) acrylic acid is particularly preferable. As used herein, "(meth) acrylic" means acrylic and methacrylic, and "(meth) acrylate" means "acrylate" and "methacrylate".

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

The second monomer is a monomer that is non-acidic and has 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-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tart-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate and the like (meth) ) Acrylate esters; esters of vinyl alcohols such as vinyl acetate; and (meth) acrylonitrile, styrene, and polymerizable styrene derivatives (eg, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinyl benzo) Acids, styrene dimers, styrene trimmers, etc.) and the like. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate are preferable. Benzyl (meth) acrylate is particularly preferable from the viewpoint of suppressing side etching.

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

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 has an aromatic group in the side chain of the structure. It is more preferable to have.

The (A) alkali-soluble polymer having an aromatic group in the side chain is a compound having an aromatic group as at least one of the above-mentioned first monomer and second monomer. Can be prepared by using. Examples of the monomer having an aromatic group include (meth) acrylic acid aralkyl ester such as benzyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, styrene, silicic acid, and a polymerizable styrene derivative ( For example, methylstyrene, vinyltoluene, ester-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.) and the like. From the viewpoint of suppressing side etching, (meth) acrylic acid aralkyl ester and styrene are preferable, and benzyl (meth) acrylate is particularly preferable.

The copolymerization ratio of the above-mentioned compound having an aromatic group is 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, and 70% by mass with respect to the total mass of all the monomers. % Or more, or 80% by mass or more is preferable. 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, as the (A) alkali-soluble polymer, one or more monomers selected from the above-mentioned first monomer and second monomer are added by a known polymerization method, preferably. It can be prepared by polymerization, more preferably radical polymerization.

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

(A) The weight average molecular weight of the alkali-soluble polymer (hereinafter, may be abbreviated as "Mw") (when a plurality of types of alkali-soluble polymers are used in combination, it means the entire Mw). It is preferably 5,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 65,000. Dispersity (Mw / Mn), which is the ratio of the weight average molecular weight to the number average molecular weight (hereinafter, may be abbreviated as “Mn”) (when a plurality of types of alkali-soluble polymers are used in combination, the total dispersion thereof. The degree) is preferably 1.0 to 6.0, more preferably 1.5 to 5.0, further preferably 2.0 to 5.0, and 2.5 to 5.0. It is even more preferably 4.5, and particularly preferably 3.0 to 4.2.
It is preferable that the weight average molecular weight and the dispersity of the alkali-soluble polymer (A) are in the above ranges from the viewpoints of obtaining appropriate developability, high coating film strength, and uniformity of resist thickness.

(A) When a plurality of types of alkali-soluble polymers are used in combination as the alkali-soluble polymer,
(A-1) an alkali-soluble polymer having an Mw of less than 50,000, and (A-2) an alkali-soluble polymer having an Mw of 50,000 or more.
Is particularly preferable.

The Mw of the alkali-soluble polymer (A-1) is more preferably 5,000 or more and less than 50,000, further preferably 10,000 to 45,000, and 10,000 to 35,000. Is particularly preferable. It is preferable that the Mw of the alkali-soluble polymer (A-1) is in this range from the viewpoint of achieving both developability and resolvability.
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 50,000 to 65, It is particularly preferably 000. The fact that the Mw of the alkali-soluble polymer (A-2) is in this range indicates the product life when the photosensitive resin composition of the present embodiment is applied to a photosensitive element (also referred to as “dry film resist”). It is preferable from the viewpoint of making it longer.

The content ratio of the alkali-soluble polymer (A-1) component to the total solid content of the photosensitive resin composition is preferably 3% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 25% by mass or more. It is less than or equal to, more preferably 10% by mass or more and 20% by mass or less. It is preferable to set the usage ratio of the component (A-1) in the above range from the viewpoint of achieving both resolution and a small amount of side etch.
The content ratio of the alkali-soluble polymer (A-2) component with respect to the total solid content of the photosensitive resin composition is preferably 5% by mass or more and 50% by mass or less, and more preferably 15% by mass or more and 48. It is 1% by mass or less, and more preferably 18% by mass or more and 45% by mass or less. Setting the usage ratio of the component (A-2) within the above range makes the product life longer when the photosensitive resin composition of the present embodiment is applied to a photosensitive element (dry film resist). Preferred from the viewpoint.

The proportion of the alkali-soluble polymer (A) used in the photosensitive resin composition of the present embodiment is preferably 25% by mass to 85% by mass, preferably 35% by mass or more, based on the total solid content of the photosensitive resin composition. 75% by mass is more preferable. It is preferable to set the ratio of the alkali-soluble polymer used in the above range from the viewpoints of resolution, developability, developer swellability of the exposed portion, resist pattern peelability, and product life of the photosensitive element.

<(B) Compound having an ethylenically unsaturated double bond>
(B) The compound having an ethylenically unsaturated double bond is a compound having a polymerizable property by having an ethylenically unsaturated double bond in its structure. Such compounds include a compound in which (meth) acrylic acid is added to one end of polyalkylene oxide, and (meth) acrylic acid is added to one end of polyalkylene oxide, and the other end is alkyl ether or allyl. Ethereated compounds, etc. (Group 1 compounds); compounds having (meth) acryloyl groups at both ends of the alkylene oxide chain, both ends of the alkylene oxide chain in which the ethylene oxide chain and the propylene oxide chain are randomly or blocked. Compounds having (meth) acryloyl groups, compounds modified with bisphenol A, etc. (compounds of the second group); compounds having three or more (meth) acryloyl groups in one molecule, etc. (compounds of the third group) ); Etc. can be mentioned.

As the other compounds in the first group, specifically, for example, phenoxyhexaethylene glycol mono (meth) acrylate, which is a (meth) acrylate of a compound in which polyethylene glycol is added to a phenyl group, and an average of 2 mol of propylene oxide are added. 4-Normalrunonylphenoxyheptaethylene glycol dipropylene glycol (meth) acrylate, an average of 1 mol of propylene oxide, which is a (meth) acrylate of a compound obtained by adding polyethylene glycol having an average of 7 mol of ethylene oxide added to nonylphenol. 4-Normalnonylphenoxypentaethylene glycol monopropylene glycol (meth) acrylate, which is a (meth) acrylate of a compound obtained by adding polyethylene glycol to which an average of 5 mol of ethylene oxide is added to nonylphenol, ethylene having an average of 8 mol of ethylene Examples thereof include 4-normalnonylphenoxyoctaethylene glycol (meth) acrylate (for example, manufactured by Toa Synthetic Co., Ltd., M-114), which is an acrylate of a compound in which polyethylene glycol to which oxide is added is added to nonylphenol.

Specific examples of the other compounds in the second group include tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, and heptaethylene glycol di (meth). Polyethylene glycols such as acrylates, octaethylene glycol di (meth) acrylates, nonaethylene glycol di (meth) acrylates, decaethylene glycol di (meth) acrylates, and compounds having (meth) acryloyl groups at both ends of a 12 mol ethylene oxide chain. -Le (meth) glycol; polypropylene glycol di (meth) acrylic; polybutylene glycol di (meth) acrylic and the like can be mentioned. As the polyalkylene oxide di (meth) acrylate compound containing an ethylene oxide group and a propylene oxide group in the compound, for example, ethylene oxide was further added to both ends by an average of 3 mol to polypropylene glycol to which an average of 12 mol of propylene oxide was added. Examples thereof include dimethacrylate of glycol, and dimethacrylate of glycol in which ethylene oxide is further added to both ends by an average of 15 mol each of polypropylene glycol to which an average of 18 mol of propylene oxide is added.
Examples thereof include compounds having ethylenically unsaturated double bonds at both ends of polyalkylene glycol in which alkylene oxide is added to bisphenol A.

As the compound obtained by modifying bisphenol A among the compounds of the second group, it is possible to use a compound having an ethylenically unsaturated double bond at both ends of a polyalkylene glycol obtained by adding an alkylene oxide to bisphenol A in terms of resolution. And from the viewpoint of adhesion, it is preferable. The ethylenically unsaturated double bond in this compound is preferably contained in the compound in the form of being contained in the (meth) acryloyl group.
For denaturation of bisphenol A by adding alkylene oxide, for example, ethylene oxide denaturation, propylene oxide denaturation, butylene oxide denaturation, pentylene oxide denaturation, hexylene oxide denaturation and the like are known. 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 a compound include 2,2-bis (4-((meth) acryloxidiethoxy) phenyl) propane (for example, NK ester BPE-200 manufactured by Shin Nakamura Chemical Industry Co., Ltd.), 2,2-. Bis (4-((meth) acryloxitriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxitetraethoxy) phenyl) propane, 2,2-bis (4-((meth)) Acryloxipentaethoxy) phenyl) propane (for example, NK ester BPE-500 manufactured by Shin Nakamura Chemical Industry Co., Ltd.) and the like can be mentioned. Further, di (meth) acrylate of polyalkylene glycol having an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide added to both ends of bisphenol A, or an average of 2 mol of propylene oxide at both ends of bisphenol A. Ethylene oxide-modified and propylene oxide-modified compounds are also preferred, such as di (meth) acrylates of polyalkylene glycols to which an average of 15 mol of ethylene oxide has been added. The number of moles of ethylene oxide and propylene oxide in a compound having (meth) acryloyl groups at both ends by alkylene oxide modification of bisphenol A is determined from the viewpoint of improving resolution, adhesion, and 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 further preferably 5 mol or more and 20 mol or less.

In the third group of compounds, an alkyleneoxy group such as an ethyleneoxy group, a propyleneoxy group, or a butyleneoxy group is added to a central skeleton having 3 mol or more of groups to which an alkylene oxide group can be added in the molecule. It is obtained by (meth) acrylate-forming the obtained alcohol. Examples of the compound capable of forming the central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate ring.
More specifically, for example, trimethylolpropane ethylene oxide (EO) 3 molar modified triacrylate, trimethylolpropane EO 6 molar modified triacrylate, trimethylolpropane EO 9 molar modified triacrylate, trimethylolpropane EO 12 molar modified triacrylate. Acrylate and the like can be mentioned. Examples of such a compound include EO3 molar modified triacrylate of glycerin (for example, A-GLY-3E manufactured by Shin Nakamura Chemical Industry Co., Ltd.) and EO9 molar modified triacrylate of glycerin (for example, manufactured by Shin Nakamura Chemical Industry Co., Ltd.). A-GLY-9E), EO6 mol of glycerin and 6 mol of propylene oxide (PO) modified triacrylate (A-GLY-0606PE), EO9 mol of glycerin PO9 mol modified triacrylate (A-GLY-0909PE), etc. Can be done. Further, 4EO-modified tetraacrylate of pentaerythritol (for example, SR-494 manufactured by Sartmer Japan Co., Ltd.), 35EO-modified tetraacrylate of pentaerythritol (for example, NK ester ATM-35E manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and the like are mentioned. be able to.

Isocyanurate compounds can also be mentioned as compounds having an ethylenically unsaturated double bond.
Specific examples of such compounds include tri (meth) acrylate ethoxylated isocyanuric acid, ε-caprolactone-modified tris (2- (meth) acryloxyethyl) isocyanurate, triallyl isocyanurate, and the following formulas:

Examples thereof include a compound represented by (EO), a (EO) -modified isocyanurate-induced tri (meth) acrylate (an adduct of 27 mol of ethylene oxide on average) and the like.
Commercially available products can be used as such compounds, and examples thereof include UA-7100, A-9300-1CL (all manufactured by Shin-Nakamura Chemical Co., Ltd.); Aronix M-327 (manufactured by Toagosei Co., Ltd.) and the like. Can be done.

As a compound having a urethane bond and an ethylenically unsaturated double bond, for example, hexamethylene diisocyanate, tolylene diisocyanate, or a diisocyanate compound (for example, 2,2,4-trimethylhexamethylene diisocyanate) and a hydroxyl group in one molecule. And urethane compounds of compounds having a (meth) acrylic group (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 the compound having a phthalate structure and an ethylenically unsaturated double bond include γ-chloro-β-hydroxypropyl-β'-(meth) acryloyloxyethyl-o-phthalate and β-hydroxyalkyl-β'-. Examples thereof include (meth) acryloyloxyalkyl-o-phthalate.

In addition, (B) a compound having an ethylenically unsaturated double bond may contain tricyclodecandi (meth) acrylate, (2,2-bis {4- (methacryloxypentethoxy) cyclohexyl} propane, or the like. ..

It is desirable that the photosensitive resin composition of the present embodiment contains a compound obtained by modifying bisphenol A. The proportion of the bisphenol A-modified compound used in the photosensitive resin composition of the present embodiment is preferably 12% by mass to 45% by mass, preferably 17% by mass, based on the total mass of the solid content of the photosensitive resin composition. -40% by mass is more preferable, and 20% by mass to 40% by mass is further preferable. It is preferable to set the usage ratio within this range from the viewpoint of obtaining a photosensitive resin composition having an excellent balance between resolution and developability.

(B) The ratio of the compound having an ethylenically unsaturated double bond to the total solid content mass of the photosensitive resin composition is preferably 5% by mass to 70% by mass. It is preferable that this ratio is 5% by mass or more from the viewpoint of sensitivity, resolution and adhesion, and it is more preferable that this ratio is 15% by mass or more, and further preferably 20% by mass or more. On the other hand, setting this ratio to 70% by mass or less is preferable from the viewpoint of suppressing peeling delay of the edge fuse and the cured resist, and it is more preferable to set this ratio to 60% by mass or less.

<(C) Photopolymerization Initiator>
Examples of the photopolymerization initiator (C) include hexaarylbiimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, and benzoin ether compounds. , Dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, aclysine compounds, pyrazoline derivatives, N-aryl amino 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'-diphenylbimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylbimidazole, 2,4,5-tris- (o-) Chlorophenyl) -diphenylbimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -bimidazole, 2,2'-bis- (2-fluorophenyl) -4,4 ', 5,5'-Tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3-difluoromethylphenyl) -4,4', 5,5'-Tetrax- (3) -Methenylphenyl) -biimidazole, 2,2'-bis- (2,4-difluorophenyl) -4,4', 5,5'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2' -Bis- (2,5-difluorophenyl) -4,4', 5,5'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,6-difluorophenyl)- 4,4', 5,5'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4-trifluorophenyl) -4,4', 5,5' -Tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,5-trifluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -Bimidazole, 2,2'-bis- (2,3,6-trifluorophenyl) -4,4', 5,5'-tetrax- (3-methoxyphenyl) -Bimidazole, 2,2'- Bis- (2,4,5-trifluorophenyl) -4,4', 5,5'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,4,6- Trifluorophenyl) -4,4', 5,5'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,5-tetrafluorophenyl) -4, 4', 5,5'-tetrax- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,6-tetrafluorophenyl) -4,4', 5,5' -Tetrakiss- (3-methoxyphenyl) -bi Examples include imidazole and 2,2'-bis- (2,3,4,5,6-pentafluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole. Be done. Of these, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is preferable from the viewpoint of high sensitivity, resolution and adhesion.

Examples of the N-aryl-α-amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. In particular, N-phenylglycine has a high sensitizing effect and is preferable.

Examples of the quinone compound include 2-ethylanthraquinone, octaethyl anthraquinone, 1,2-benz anthraquinone, 2,3-benz anthraquinone, 2-phenylanthraquinone, 2,3-diphenyl anthraquinone, 1-chloroanthraquinone and 2-chloro. Anthraquinone, 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 and the like.

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 and the like. be able to.
Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4). -Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2-benzyl- Examples thereof include 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1. Commercially available products of the acetophenone compound include, for example, Irgacure-907, Irgacure-369, and Irgacure-379 manufactured by Ciba Specialty Chemicals. From the viewpoint of adhesion, 4,4'-bis (diethylamino) benzophenone is preferable.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phosphine oxide, and bis (2,6-dimethoxybenzoyl) -2. , 4,4-trimethyl-Pentylphosphon oxide and the like. Commercially available products of the acylphosphine oxide compound include, for example, Lucillin TPO manufactured by BASF and Irgacure-819 manufactured by Ciba Specialty Chemicals.

Examples of the benzoin compound and the benzoin ether compound include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin and the like.
Examples of the dialkyl ketal compound include benzyl dimethyl ketal and benzyl diethyl ketal.
Examples of the thioxanthone compound include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone and the like.
Examples of the dialkylaminobenzoic acid ester compound include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, 2-ethylhexyl-4- (dimethylamino) benzoate and the like.

Examples of the oxime ester compound include 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime and the like. .. Examples of commercially available products of the oxime ester compound include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 manufactured by Ciba Specialty Chemicals.

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

The pyrazoline derivatives include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazolin and 1-phenyl from the viewpoint of adhesion and rectangularity of the resist pattern. -3- (4-Biphenyl) -5- (4-tert-butyl-phenyl) -pyrazolin and 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazolin are preferred. ..

Examples of the ester compound of 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, and N-phenylglycine. 1-butyl ester, 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, N -Examples include octyl ester of phenylglycine.

Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, and tris (2). , 3-Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compound, diallyl iodonium compound, etc. Of particular, tribromomethylphenyl sulfone is preferable.

The ratio of the (C) photopolymerization initiator used in the photosensitive resin composition of the present embodiment is preferably 0.01% by mass to 20% by mass with respect to the total mass of the solid content of the photosensitive resin composition. More preferably, it is 0.5% by mass to 10% by mass. (C) By setting the ratio of the photopolymerization initiator used in this range, sufficient sensitivity can be obtained, light can be sufficiently transmitted to the bottom of the resist, high resolution can be obtained, and a conductor pattern can be obtained. A photosensitive resin composition having an excellent balance with the amount of side etching can be obtained.

(C) It is preferable to use a hexaarylbisimidazole compound as the photopolymerization initiator. In this case, the proportion of the hexaarylbisimidazole compound used is preferably 0.1% by mass to 10% by mass, preferably 0.5% by mass to 5% by mass, based on the total mass of the solid content of the photosensitive resin composition. Is more preferable.

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

<(D) Dye>
The photosensitive resin composition of the present embodiment contains a dye (D). Since the exposed portion develops color when the photosensitive resin composition contains a dye, it is preferable in terms of visibility, and when an inspection machine or the like reads an alignment marker for exposure, the exposed portion and the unexposed portion are used. The larger the contrast, the easier it is to recognize and the more advantageous it is. When combined with the compound (E) in the present embodiment, the dyes having a large contrast between the exposed portion and the unexposed portion are preferably leuco dye and fluorane dye, and more preferably leuco dye.

The leuco dye can be blended in the photosensitive resin composition of the present embodiment in order to impart suitable color development property and excellent peeling property to the resist cured film.
Specific examples of the leuco dye include leuco crystal violet (tris [4- (dimethylamino) phenyl] methane: DMA), 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, and the like. Can be mentioned. Of these, leuco crystal violet (DMA) is preferred.

The ratio of the dye used in the photosensitive resin composition of the present embodiment is 0.01% by mass to 2 with respect to the total solid content of the photosensitive resin composition from the viewpoint of the contrast between the exposed portion and the unexposed portion. It is preferably by mass%, more preferably 0.1% by mass to 1.5% by mass. By setting the usage ratio of the leuco dye in this range, good color development and sensitivity can be realized.

In this embodiment, the dye may include a base dye. Examples of the base dye include basic green 1 [CAS number (hereinafter the same): 633-03-4] (for example, Aizen Diamond Green GH, trade name, manufactured by Hodogaya Chemical Co., Ltd.), malachite green oxalate [2437. -29-8] (for example, Aizen Malachite Green, trade name, manufactured by Hodogaya Chemical Co., Ltd.), Brilliant Green [633-03-4], Fuxin [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 Co., Ltd.), Rhodamin B [81-88-9], Rhodamin 6G [989-38-8], Basic Yellow 2 [2465-272-2] ] Etc. can be mentioned. Of these, one or more selected from Basic Green 1, Malachite Green Oxalate, and Basic Blue 7 is preferable, and Basic Green 1 is particularly preferable from the viewpoint of hue stability and exposure contrast.

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

<(E) Compound having a specific heterocyclic structure>
In the present embodiment, the compound (E) is a compound having no amino group, an acidic group having a pKa of 5 or less, and a heterocyclic structure having four nitrogen atoms. Compound (E) is preferably solid at room temperature (25 ° C.).

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

In the general formula (3), neither R ¹ nor R ² has an amino group and is independently selected from the group consisting of a hydrogen atom or an organic group having 1 to 20 carbon atoms, preferably a hydrogen atom and carbon. It is independently selected from the group consisting of organic groups of numbers 1 to 10, and more preferably it is 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 of pKa5 or less. When R ¹ and / or R ² are organic groups having an acidic group of pKa5 or less, the “carbon number” means the total carbon number of the organic group including the carbon number of the acidic group having pKa5 or less.

In the general formula (3), as the organic group having 1 to 20 carbon atoms, specifically, an octadecyl group, a heptadecyl group, a hexadecyl group, a pentadecyl group, a tetradecyl group, a tridecyl group, a dodecyl group, an undecyl group, and a decyl group are used. Can be mentioned.

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 iso-propyl group and the like.

In the general formula (3), specific examples of the acidic group having a pKa of 5 or less include a carboxy 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 carboxy group.

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

From the viewpoint of excellent color development and low side etching, as the compound represented by the general formula (3), ^one of R ¹ and R ² is an organic having 1 to 3 carbon atoms having an acidic group of pKa5 or less. It is more preferably selected independently from the group consisting of a group, the other being a hydrogen atom and an organic group having 1 to 3 carbon atoms, and one of R ¹ and R ² is a carbon having an acidic group of pKa5 or less. It is even more preferable that the number 1 to 3 is an organic group 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-tetrazol-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-tetrazol-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-tetrazol-5-acetic acid, 1-pentadecyl-1H-tetrazol-5-acetic acid, 1-tetradecyl- 1H-tetrazole-5-acetic acid, 1-tridecyl-1H-tetrazol-5-acetic acid, 1-dodecyl-1H-tetrazol-5-acetic acid, 1-undecyl-1H-tetrazol-5-acetic acid, 1-decyl-1H- Tetrazol-5-acetic acid, 1-nonyl-1H-tetrazole-5-acetic acid, 1-octa-1H-tetrazol-5-acetic acid, 1-hepta-1H-tetrazol-5-acetic acid, 1-hexa-1H-tetrazole -5-acetic acid, 1-penta-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-propion Acid, 1-tetradecyl-1H-tetrazole-5-propionic acid, 1-tridecyl-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-octa-1H-tetrazole-5-propionic acid, 1-hepta-1H- Examples thereof include tetrazole-5-propionic acid, 1-hexa-1H-tetrazole-5-propionic acid, 1-penta-1H-tetrazole-5-propionic acid, 1-butyl-1H-tetrazole-5-propionic acid and the like. Among these, 1H-tetrazole-1-acetic acid and 1H-tetrazol-5-acetic acid are preferable as the compound represented by the general formula (3) from the viewpoint of excellent color development and low side etching. More preferably, 1H-tetrazol-5-acetic acid.

The content of the compound (E) in the photosensitive resin composition is 0.001% by mass to 5% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of excellent color development and low side etching. It may be in the range of mass%, preferably 0.001% by mass to 0.5% by mass, more preferably 0.001% by mass to 0.3% by mass, and further preferably 0.001% by mass to 0.2. It is by mass%, more 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 may be 0.01% by mass, or 0.02% by mass, based on the total solid content of the photosensitive resin composition. It may be 0.03% by mass.

<Other ingredients>
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 components. Other components that can be used here include, for example, stabilizers.

The stabilizer is preferable from the viewpoint of improving the thermal stability and storage stability of the photosensitive resin composition, or both of them. Stabilizers include, for example, at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazole compounds, carboxybenzotriazole compounds, and alkylene oxide compounds having a glycidyl group. These can be used alone or in combination of two or more.

Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, and 2,2'-methylenebis. (4-Methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), triethyleneglycol-bis [3- (3-t-butyl-5-methyl-4) -Hydroxyphenyl) propionate], nitrosophenylhydroxyamine aluminum salt (for example, an aluminum salt to which 3 mol of nitrosophenyl hydroxylamine is added), diphenylnitrosoamine and the like. Among these, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] and an aluminum salt to which 3 mol of nitrosophenylhydroxylamine is added are preferable. In addition, 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) aminomethylene-1,2,3-benzotriazole, and the like. Bis (N-2-ethylhexyl) aminomethylene-1,2,3-triltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole, 1- (2-di-n-) Examples thereof include a 1: 1 mixture of 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 preferable. .. In addition, 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, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole. These can be used alone or in combination of two or more.

Examples of the alkylene oxide compound having a glycidyl group include neopentyl glycol diglycidyl ether (for example, Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (for example, Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), and the like. Examples thereof include bisphenol A-propylene oxide 2 mol additive diglycidyl ether (for example, Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), 1,6-hexanediol diglycidyl ether (for example, Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.), and the like. .. These can be used alone or in combination of two or more.

In the present 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% by mass to 3%. It is in the range of% by mass, more preferably in the range of 0.05 to 1.5% by mass. The total content is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, while 3% by mass from the viewpoint of maintaining the sensitivity of the photosensitive resin layer. % Or less is preferable.

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

[Photosensitive element]
The photosensitive element (also referred to as a dry film resist) in the present embodiment includes a support and a photosensitive resin composition layer formed on the support from the above-mentioned photosensitive resin composition of the present embodiment. .. If necessary, the photosensitive element of the present embodiment may have a protective layer on the surface opposite to the support of the photosensitive resin composition layer.

[Support]
As the support, a transparent base material (film base material, hereinafter also referred to as “support film”) that transmits light emitted from an exposure light source is preferable. Examples of such a support film include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, and polymethylmethacrylate copolymer film. Examples thereof include polystyrene films, polyacrylonitrile films, styrene copolymer films, polyamide films, and cellulose derivative films. As these films, stretched films can also be used if necessary.
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%, and 0.01% to. 1.0% is even more preferable.
The thinner the support, the more advantageous in terms of image formation and economy, but it is necessary to maintain the strength. Considering both of these, a support having a thickness of 10 to 30 μm can be preferably used.

[Photosensitive resin composition layer]
The photosensitive resin composition layer in the photosensitive element of the present embodiment is a layer made of the above-mentioned photosensitive resin composition of the present embodiment. When the photosensitive resin composition used for forming the photosensitive resin composition layer contains a solvent, the solvent is preferably removed in the photosensitive resin composition layer, but the solvent remains. It doesn't matter.
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 better the resolution, and the thicker the thickness, the better the film strength. Therefore, the thickness of the composition layer can be appropriately selected within the above range depending on the application.

[Protective film]
An important property of the protective layer in the photosensitive element of the present embodiment is that the adhesive force with the photosensitive resin composition layer is sufficiently smaller than the adhesive force between the support and the photosensitive resin composition layer, and the protective layer can be easily peeled off. You can do it. As the protective layer, for example, a polyethylene film, a polypropylene film or the like can be preferably used, and for example, a film having excellent peelability disclosed in JP-A-59-202457 can be used.
The thickness of the protective layer is preferably 10 to 100 μm, more preferably 10 to 50 μm.

[Manufacturing method of photosensitive element]
The photosensitive element of the present embodiment can be manufactured by sequentially laminating a support, a photosensitive resin composition layer, and, if necessary, a protective layer. As a method for laminating the support, the photosensitive resin composition layer, and the protective layer, a known method can be adopted.
For example, the photosensitive resin composition of the present embodiment is prepared as the above-mentioned photosensitive resin composition preparation solution, first applied onto a support using a bar coater or a roll coater, dried, and then the mixture is applied onto the support. A photosensitive resin composition layer composed of a photosensitive resin composition is formed. Then, if necessary, the photosensitive element can be manufactured by laminating a protective layer on the formed photosensitive resin composition layer.

[Method of forming resist pattern]
A resist pattern can be formed on the substrate by using the photosensitive element as described above. The method for forming the resist pattern includes a laminating 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 the photosensitive. A developing step of forming a resist pattern by removing an unexposed portion of the resin composition layer with a developing solution is included in the order described above.

In the method for forming a resist pattern of the present embodiment, first, in the laminating step, a photosensitive resin composition layer is formed on a substrate using a laminator. Specifically, when the photosensitive element has a protective layer, the protective layer is peeled off, and then the photosensitive resin composition layer is heat-bonded to the substrate surface using a laminator and laminated. Examples of the substrate material used include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and a flexible base material on which a conductor thin film is laminated. Examples of the conductor thin film include ITO, copper, copper-nickel alloy, silver and the like; and examples of the material constituting the flexible substrate include polyethylene terephthalate (PET) and the like;
Each can be listed. The above-mentioned substrate may have through holes for dealing with a multilayer substrate.

The photosensitive element of this embodiment is suitably applicable to the manufacture of a touch panel sensor by an etching method. An etching method is generally used for forming wiring (conductor pattern) in a touch panel sensor. As described above, the touch panel sensor is required to form a wiring having a much finer size than a normal printed wiring board. Here, when the etching method using a photosensitive element in the prior art is adopted, the amount of side etching of the formed conductor pattern is large, so that the product yield of touch panel sensor manufacturing is limited. However, since the photosensitive element of this embodiment is excellent in reducing the amount of side etching, it is possible to manufacture the touch panel sensor with a high yield.

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 if necessary. The heating temperature at this time is preferably 40 ° C. to 160 ° C. By performing the heat crimping twice or more, the adhesion of the obtained resist pattern to the substrate is further improved. When crimping twice or more, a two-stage laminator equipped with two rolls may be used, or the laminate of the substrate and the photosensitive resin composition layer is repeated several times to form a roll. It may be crimped through.

Next, in the exposure step, the photosensitive resin composition layer is exposed using an exposure machine. This exposure may be performed through the support without peeling the support, or may be performed after the support has been peeled off if necessary.
By performing this exposure in a pattern, a resist film (resist pattern) having a desired pattern can be obtained after passing through the development step described later. The patterned exposure may be performed by either a method of exposing through a photomask or a method of maskless exposure. When exposing through a photomask, the amount of exposure is determined by the illuminance of the light source and the exposure time. The amount of exposure may be measured using a photometer.
In maskless exposure, a photomask is not used, and the exposure is performed directly on the substrate by a drawing device. As the light source, a semiconductor laser having a wavelength of 350 nm to 410 nm, an ultrahigh 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.
It is preferable that the photosensitive element of the present embodiment is applied to a method of exposing through a photomask in that the effect of improving the resolution and reducing the amount of side etching is maximized.

Next, in the developing step, the unexposed portion of the photosensitive resin composition layer is removed with a developing solution. If there is a support on the photosensitive resin composition layer after exposure, it is preferable to remove the support before subjecting it to the developing step.
In the developing step, a developing solution composed 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, it is preferable to use an aqueous solution of Na ₂ CO ₃ , K ₂ CO _3, or the like. The alkaline aqueous solution is selected according to the characteristics of the photosensitive resin composition layer, but it is preferable to use a Na ₂ CO ₃ aqueous solution having a concentration of 0.2% by mass to 2% by mass. A surfactant, a defoaming agent, a small amount of an organic solvent for accelerating development, or the like may be mixed in the alkaline aqueous solution.
The temperature of the developer in the developing step is preferably kept constant in the range of 18 ° C. to 40 ° C.

A resist pattern can be obtained by the above process. In some cases, a heating step of 100 ° C. to 300 ° C. may be further performed. By carrying out this heating step, it is possible to further improve the chemical resistance. For heating, an appropriate heating furnace of hot air, infrared rays, far infrared rays or the like can be used.

[Method of forming a wiring board]
The method for forming the wiring board in the present embodiment includes a laminating step of forming a photosensitive resin composition layer on a substrate using the photosensitive element of the present embodiment, and an exposure step of exposing the photosensitive resin composition layer. A developing step of forming a resist pattern by removing an unexposed portion of the photosensitive resin composition layer with a developing solution, a conductor pattern forming step of etching or plating a substrate on which the resist pattern is formed, and the resist pattern. The peeling step for peeling is included in the order described above. By the above method, it is possible to obtain a wiring board in which a desired wire pattern is formed on a substrate.

The laminating step, the exposure step, and the developing step are the same as those in the above [resist pattern forming method]. After forming the resist pattern by the above-mentioned resist pattern forming method, a wiring board in which the conductor pattern is formed on the substrate can be obtained by going through the following conductor pattern forming step and peeling step.
In the conductor pattern forming step, a conductor pattern can be formed on the substrate on which the resist pattern is formed by using a known etching method or plating method on the substrate surface (for example, copper surface) exposed by the developing step.

The side etch amount of the resist pattern obtained by using the photosensitive resin composition of the present embodiment is preferably 5.5 μm or less. More preferably, it is 5.4 μm or less. Even more preferably, it is 5.3 μm or less.
The top width of the copper line pattern is preferably 4.2 μm or more. More preferably, it is 4.5 μm or more. Even more preferably, it is 4.8 μm or more.
This is preferable because it has an advantage that fine wiring can be formed.

The method for forming a photosensitive resin composition, a photosensitive element, and a conductor pattern in the present embodiment is extremely suitable for manufacturing, for example, a printed wiring board, a lead frame, a base material having an uneven pattern, a semiconductor package, a touch panel sensor, and the like. Can be applied to.

[Touch panel sensor]
The method for forming the photosensitive resin composition, the photosensitive element, and the conductor pattern in the present embodiment is particularly suitable for manufacturing a touch panel sensor. The touch panel sensor is manufactured by forming a lead-out wiring composed of a conductor pattern formed by the above method on a flexible base material having a sputtered copper layer. Then, a touch panel can be obtained by laminating the liquid crystal display element, the above-mentioned touch panel sensor, and glass in this order.

Unless otherwise specified, the evaluation values of the various parameters described above are measured values measured according to the measurement method in the examples described later.

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 dispersity>
The sample was measured by gel permeation chromatography (GPC), and the weight average molecular weight (Mw), number average molecular weight (Mn), and number average molecular weight (Mn) were measured using a calibration curve of polystyrene (Showa Denko Corporation Shodex STANDARD SM-105). The degree of dispersion (Mw / Mn) was calculated.
Specifically, it was measured under the following conditions using gel permeation chromatography 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 x 2, and KF-807 in series in order. Eluent: THF

<Acid equivalent>
The acid equivalent means the mass (gram) of a polymer having 1 equivalent of a carboxyl group in the molecule. Using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd., the acid equivalent was measured by a potentiometric titration method using a 0.1 mol / L sodium hydroxide aqueous solution.

<Glass transition temperature>
The glass transition temperature of the alkali-soluble polymer, using literature values described above as Tg _i for each comonomer, was calculated by the Fox equation (I).

<Manufacturing of photosensitive element>
Each component shown in Table 1 was mixed, and methyl ethyl ketone (MEK) was further added to prepare a photosensitive resin composition having a solid content concentration of 61% by mass. In addition, Table 2 shows a description of each component shown in Table 1.
The obtained photosensitive resin composition was uniformly applied to a support film, a polyethylene terephthalate film having a thickness of 16 μm (manufactured by Toray Industries, Inc., product name “FB40”) using a bar coater, and then adjusted to 95 ° C. It was heated and dried in a warm dryer for 5 minutes to form a photosensitive resin composition layer having a thickness of 5 μm on the support film.
Next, a polyethylene film having a thickness of 33 μm (manufactured by Tamapoli Co., Ltd., product name “GF-858”), which is a protective layer, is attached on the surface of the photosensitive resin composition layer opposite to the support film to make the photosensitive resin composition layer photosensitive. Obtained a sex element.

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

<Laminate>
While peeling off the polyethylene film of the photosensitive element obtained in each Example or Comparative Example on the substrate, a hot roll laminator (AL-70 manufactured by Asahi Kasei Corporation) was used to roll temperature 105 ° C. and air pressure 0.35 MPa. , And the laminating speed was 1.5 m / min.

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

<Contrast>
After peeling off the polyethylene film from the photosensitive element and 15 minutes after exposure at the above exposure amount, using a spectrometer (Nippon Denshoku Kogyo Co., Ltd., NF333), the exposed part and the exposed part are not exposed from the polyether terephthalate side. The contrast of the exposed part was measured.
Contrast = Exposed area transmittance (%) / Unexposed area transmittance (%)

<Development>
After peeling the support film from the photosensitive resin composition layer after exposure, a 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. is used in an alkaline developing machine (manufactured by Fuji Kiko Co., Ltd., a developing machine for dry film) for a minimum developing time. The unexposed portion of the photosensitive resin composition layer was dissolved and removed by spraying for twice as long as. After the development, it was washed with water to obtain a substrate having a cured film for evaluation.
The minimum development time refers to the minimum time required for the unexposed portion of the photosensitive resin composition layer to be completely dissolved and removed.

<Adhesion>
The minimum line width at which the pattern remains when the independent thin wire with a length of 30 mm is measured under the above development conditions is used as the adhesion force.

<Amount of side etch>
For the evaluation of the amount of side etch, a laminated substrate 15 minutes after the above <lamination> was used.
A pattern of line / space = 10 μm / 10 μm was exposed on the laminated substrate, and then developed by the method described in <Development> above.
First, the resist bottom width Wb of the pattern was measured with an optical microscope.
Then, for the substrate having this line / space pattern, using a dip method, the hydrochloric acid concentration was 2% by mass, ferric chloride was 2% by mass, and the temperature was 30 ° C. for 70 seconds (condition I) or 30 seconds (condition II). ) Etched.
After the etching, a NaOH aqueous solution having a concentration of 3% by mass was used as a stripping solution, and the top width Wt of the copper line pattern obtained by stripping and removing the cured film on the substrate at a temperature of 50 ° C. was measured with an optical microscope.
And the following formula:
Side etch (μm) = Wb-Wt
The side etch amount was calculated by

<Copper line width uniformity>
After developing by the method described in <Development> above, the copper line was measured over a length of 100 mm, the outermost end and the innermost end of the copper line were determined, and evaluated according to the following criteria.
⊚: Distance from the outermost end of the line to the innermost end of the line is less than 0.2 μm ○: 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 Δ: From the outermost end of the line to the line Distance to the innermost end 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 Examples and Comparative Examples is shown in Table 1, and the details of each component name shown in Table 1 are shown in Table 2. The blending amount of each component in Table 1 is a mass part in terms of solid content. Table 1 summarizes the evaluation results of adhesion, side etch amount, copper line width uniformity, and contrast performed using each photosensitive resin composition. In Table 1, in each of Examples 1 to 5, the evaluation items "side etch amount", "copper line width uniformity" and "contrast" are well-balanced, and the respective evaluation results are also good. It was. In particular, in Examples 2 and 4, good results were obtained even though the content of the compound (E) in the photosensitive resin composition was small.

The photosensitive resin composition of the present embodiment can be used, for example, as a dry film for wiring formation, a dye coloring aid, and an inhibitor of etching solution from penetrating between the resist and the substrate, without limitation.

Claims

(A) Alkali-soluble polymer,
(B) A compound having an ethylenically unsaturated double bond,
(C) Photopolymerization initiator,
(D) Dye and (E) Compound represented by the following general formula (3):

{In the formula, neither R 1 nor R 2 has an amino group and is independently selected from the group consisting of a hydrogen atom or an organic group having 1 to 20 carbon atoms, except that of R 1 and R 2 . At least one has an acidic group of pKa5 or less. }, A photosensitive resin composition.
In the formula, neither R 1 nor R 2 has an amino group and is independently selected from the group consisting of a hydrogen atom or an organic group having 1 to 3 carbon atoms, except that at least R 1 and R 2 are selected. One is the photosensitive resin composition according to claim 1, which has an acidic group of pKa5 or less.
Wherein, R 1 and R 2 are both having no amino group, one of R 1 and R 2 is an organic group having 1 to 3 carbon atoms having a pKa5 following acidic group and the other represents hydrogen The photosensitive resin composition according to claim 2, which is an atom.
The photosensitive resin composition according to any one of claims 1 to 3, wherein the acidic group is any of a carboxy group, a phosphoric acid group, and a sulfonic acid group.
The photosensitive resin composition according to claim 4, wherein the acidic group is a carboxy group.
The photosensitive resin composition according to any one of claims 1 to 5, wherein the dye (D) is a leuco dye.
The photosensitive resin composition according to any one of claims 1 to 6, wherein the compound (E) is contained in an amount of 0.001 to 0.5% by mass based on the total solid content of the photosensitive resin composition. Stuff.
The photosensitive resin composition according to any one of claims 1 to 7, wherein the compound (E) is solid at 25 ° C.
The photosensitive resin composition according to any one of claims 1 to 8, wherein the alkali-soluble polymer (A) contains an aromatic ring in its molecular structure.
A photosensitive element comprising a support and a photosensitive resin composition layer formed on the support according to any one of claims 1 to 9.