WO2021166082A1

WO2021166082A1 - Photosensitive resin composition, photosensitive element and method for producing wiring board

Info

Publication number: WO2021166082A1
Application number: PCT/JP2020/006345
Authority: WO
Inventors: 禎明加藤; 健一岩下; 公博吉廻
Original assignee: 昭和電工マテリアルズ株式会社
Priority date: 2020-02-18
Filing date: 2020-02-18
Publication date: 2021-08-26
Also published as: CN113544584A; JPWO2021166082A1; JP7494898B2; KR20210114479A

Abstract

A photosensitive resin composition which contains a binder polymer, a photopolymerizable compound containing a trifunctional monomer, a photopolymerization initiator and a coumarin-based sensitizer.

Description

Method for manufacturing photosensitive resin composition, photosensitive element, and wiring board

The present disclosure relates to a method for manufacturing a photosensitive resin composition, a photosensitive element, and a wiring board.

In the manufacture of wiring boards, a resist pattern is formed to obtain the desired wiring. A photosensitive resin composition is widely used for forming a resist pattern. In recent years, MSAP (Modified Semi Additive Process) has been attracting attention as a method capable of forming fine wiring. In this method, in order to form fine wiring, it is necessary to form a resist pattern with higher accuracy than before.

In general, a photosensitizer is added to the photosensitive resin composition in order to form a resist pattern with high accuracy. As a photosensitizer, an anthracene derivatives such as 9,10-dibutoxyanthracene (DBA) are known (see, for example, Patent Document 1).

International Publication No. 2007/004619

However, there is still room for improvement in the photosensitive resin composition containing DBA in order to obtain a more accurate resist pattern. In addition, the photosensitive resin composition is usually used in the form of a photosensitive element sandwiched between polymer films such as polyethylene, but according to the studies of the present inventors, the photosensitive resin composition is available. When DBA is contained, there may be a problem that the DBA permeates the polymer film and the desired pattern shape cannot be formed at the time of forming the resist pattern. Such a problem occurs particularly prominently when the polymer film is a polyethylene film.

Further, the photosensitive resin composition containing DBA still has room for improvement in forming a resist pattern having excellent adhesion to the substrate.

Therefore, the present disclosure describes a photosensitive resin composition and a photosensitive element capable of forming a resist pattern having excellent adhesion to a substrate and having a good pattern shape, and a method for manufacturing a wiring substrate using them. The purpose is to provide.

In order to achieve the above object, the present disclosure provides a photosensitive resin composition containing a binder polymer, a photopolymerizable compound containing a trifunctional monomer, a photopolymerization initiator, and a coumarin-based sensitizer. do.

According to the above-mentioned photosensitive resin composition, by using a trifunctional monomer as a photopolymerizable compound in combination with a coumarin-based sensitizer, it has excellent adhesion to a substrate and has a good pattern shape. It is possible to form a resist pattern having. This is because the coumarin-based sensitizer is less likely to penetrate the polymer film than DBA, and higher sensitivity can be obtained with a small amount of addition, so that the pattern shape of the resist pattern can be improved and the resist pattern can be made good. It is considered that this is because the adhesion of the resist pattern to the substrate can be significantly improved by using the coumarin-based sensitizer in combination with the trifunctional monomer. Further, since the amount of the coumarin-based sensitizer added can be reduced, the amount of the solvent for dissolving the sensitizer can also be reduced. Further, since the coumarin-based sensitizer has a lower absorbance than DBA, the exposed light easily reaches the deep part of the photosensitive resin layer at the time of forming the resist pattern, and the photocurability of the bottom of the photosensitive resin layer is enhanced. Can be done. Therefore, the adhesion, the resolution, and the pattern shape can be further improved.

In the photosensitive resin composition, the coumarin-based sensitizer may contain a compound represented by the following general formula (1).

[In the formula, Z ¹ and Z ² are independently halogen atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an amino group, and 1 carbon atom. Carbon of up to 10 alkylamino groups, dialkylamino group with 2 to 20 carbon atoms, mercapto group, alkyl mercapto group with 1 to 10 carbon atoms, allyl group, hydroxyalkyl group with 1 to 20 carbon atoms, carboxyl group, alkyl group A carboxyalkyl group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms or a group containing a heterocycle, n is An integer of 0 to 4 and m indicate an integer of 0 to 2, respectively. In addition, ^{at least two of n Z 1} and m Z ² may form a ring. ]

By using the compound represented by the above general formula (1) as the photosensitizer, the adhesion and pattern shape of the resist pattern can be improved.

In the photosensitive resin composition, the content of the coumarin-based sensitizer may be 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound. .. When the content of the coumarin-based sensitizer is within the above range, it is possible to achieve both excellent adhesion of the resist pattern and good pattern shape at a higher level.

In the photosensitive resin composition, the binder polymer may contain a polymer containing a hydroxyalkyl (meth) acrylate unit. When the binder polymer contains a hydroxyalkyl (meth) acrylate unit, it is possible to achieve both excellent adhesion of the resist pattern and good pattern shape at a higher level.

The photosensitive resin composition may further contain a polymerization inhibitor. Further, the content of the polymerization inhibitor in the photosensitive resin composition may be 0.003 parts by mass or less with respect to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound. When the content of the polymerization inhibitor is within the above range, the pattern shape of the resist pattern can be made better.

The present disclosure also provides a photosensitive element comprising a support and a photosensitive resin layer formed on the support using the photosensitive resin composition of the present disclosure.

The present disclosure further describes a step of providing a photosensitive resin layer on a substrate using the above-mentioned photosensitive resin composition of the present disclosure or the above-mentioned photosensitive element of the present disclosure, and a step of photocuring a part of the above-mentioned photosensitive resin layer. A wiring substrate comprising a step of removing the uncured portion of the photosensitive resin layer to form a resist pattern and a step of forming a wiring layer in a portion of the substrate where the resist pattern is not formed. Provide a manufacturing method.

According to the present disclosure, a photosensitive resin composition and a photosensitive element capable of forming a resist pattern having excellent adhesion to a substrate and having a good pattern shape, and a method for manufacturing a wiring substrate using them. Can be provided.

It is a schematic cross-sectional view which shows the photosensitive element which concerns on one Embodiment. It is a schematic diagram which shows the manufacturing method of the wiring board which concerns on one Embodiment. It is an electron micrograph of a resist pattern formed by using the photosensitive resin composition of Example 1. FIG. It is an electron micrograph of a resist pattern formed by using the photosensitive resin composition of Comparative Example 1. FIG.

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

In the present specification, the term "process" is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. Is done. The numerical range indicated by using "-" indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively. The term "layer" includes a structure having a shape formed on the entire surface and a structure having a shape formed on a part of the structure when observed as a plan view. "(Meta) acrylic acid" means at least one of "acrylic acid" and the corresponding "methacrylic acid". The same applies to other similar expressions such as (meth) acrylate.

In the present specification, the "(poly) oxyethylene group" means an oxyethylene group or a polyoxyethylene group in which two or more ethylene groups are linked by an ether bond. The "(poly) oxypropylene group" means an oxypropylene group or a polyoxypropylene group in which two or more propylene groups are linked by an ether bond. "EO modification" means a compound having a (poly) oxyethylene group. "PO modification" means a compound having a (poly) oxypropylene group. "EO / PO modification" means a compound having a (poly) oxyethylene group and / or a (poly) oxypropylene group.

In the present specification, the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. Means. As used herein, the term "solid content" refers to a non-volatile content excluding volatile substances (water, solvent, etc.) in the photosensitive resin composition. That is, the "solid content" refers to a component other than the solvent that remains without volatilizing when the photosensitive resin composition described later is dried, and includes a liquid, starch syrup-like or wax-like component at room temperature (25 ° C.).

<Photosensitive resin composition>
The photosensitive resin composition according to the present embodiment includes (A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: photopolymerization initiator, and (D) component: coumarin-based. Contains a sensitizer. Here, the component (B) contains a trifunctional monomer. Further, the photosensitive resin composition according to the present embodiment may further contain the component (E): a polymerization inhibitor. Hereinafter, each component will be described.

Component (A): Binder polymer The photosensitive resin composition contains one or more of the components (A). Examples of the component (A) include acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, and phenol resin. The component (A) may contain an acrylic resin from the viewpoint of further improving the alkali developability.

The acrylic resin has, for example, a structural unit derived from (meth) acrylic acid, and may further have a structural unit derived from other monomers other than (meth) acrylic acid. The other monomer may be one kind or two or more kinds.

The other monomer may be, for example, a (meth) acrylic acid ester. Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, and (meth) acrylic acid aryl ester.

The other monomer may be preferably a (meth) acrylic acid alkyl ester from the viewpoint of improving alkali developability and peeling characteristics. The alkyl group of the (meth) acrylic acid alkyl ester is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group or These structural isomers may be used, and an alkyl group having 1 to 4 carbon atoms may be used from the viewpoint of further improving the peeling characteristics.

When the other monomer is a (meth) acrylic acid alkyl ester, the content of the (meth) acrylic acid alkyl ester is based on the total amount of the monomers constituting the component (A), and is excellent in peeling characteristics. Therefore, it may be 1% by mass or more, 2% by mass or more, or 3% by mass or more, and is 80% by mass or less, 60% by mass or less, or 50% by mass or less from the viewpoint of further improving the resolution and adhesion. It's okay.

The other monomer may be styrene or a styrene derivative from the viewpoint of further improving the resolution and adhesion. The styrene derivative may be, for example, vinyltoluene, α-methylstyrene, or the like. When the other monomer is styrene or a styrene derivative, the content of styrene and the styrene derivative is 5% by mass from the viewpoint of further improving the resolution based on the total amount of the monomers constituting the component (A). The above may be 10% by mass or more, or 20% by mass or more, and may be 65% by mass or less, 55% by mass or less, or 50% by mass or less from the viewpoint of excellent peeling characteristics.

The other monomer may be hydroxyalkyl (meth) acrylate from the viewpoint of further improving developability, adhesion, and peelability. The hydroxyalkyl (meth) acrylate may be, for example, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and the like. When the other monomer is hydroxyalkyl (meth) acrylate, the content of hydroxyalkyl (meth) acrylate is further improved in developability and peelability based on the total amount of the monomers constituting the component (A). From the viewpoint of improvement, it may be 2% by mass or more, 4% by mass or more, or 6% by mass or more, and from the viewpoint of maintaining high sensitivity, it is 14% by mass or less, 12% by mass or less, or 10% by mass or less. It's okay.

The acid value of the component (A) may be 100 mgKOH / g or more, 120 mgKOH / g or more, 140 mgKOH / g or more, or 150 mgKOH / g or more from the viewpoint of suitable development, and the cured product of the photosensitive resin composition. From the viewpoint of improving the adhesion (developer resistance), it may be 250 mgKOH / g or less, 240 mgKOH / g or less, or 230 mgKOH / g or less. The acid value of the component (A) can be adjusted by the content of the structural unit constituting the component (A) (for example, the structural unit derived from (meth) acrylic acid).

The weight average molecular weight (Mw) of the component (A) may be 10,000 or more, 20,000 or more, or 25,000 or more from the viewpoint of excellent adhesion (developer resistance) of the cured product of the photosensitive resin composition, which is preferable. It may be 100,000 or less, 80,000 or less, or 60,000 or less from the viewpoint of being able to develop. The dispersity (Mw / Mn) of the component (A) may be, for example, 1.0 or more or 1.5 or more, and is 3.0 or less or 2.5 or less from the viewpoint of further improving adhesion and resolution. It may be there.

The weight average molecular weight and the degree of dispersion can be measured by, for example, gel permeation chromatography (GPC) using a standard polystyrene calibration curve. More specifically, the measurement can be performed under the conditions described in the examples. When it is difficult to measure a compound having a low molecular weight by the above-mentioned method for measuring the weight average molecular weight, the molecular weight can be measured by another method and the average thereof can be calculated.

The content of the component (A) may be 20% by mass or more, 30% by mass or more, or 40% by mass or more from the viewpoint of excellent film moldability, based on the total solid content of the photosensitive resin composition. From the viewpoint of further excellent sensitivity and resolution, it may be 90% by mass or less, 80% by mass or less, or 65% by mass or less.

The content of the component (A) is 30 parts by mass or more, 35 parts by mass or more, or 40 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B) from the viewpoint of excellent moldability of the film. It may be 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less from the viewpoint of further improving sensitivity and resolution.

Component (B): Photopolymerizable Compound The photosensitive resin composition contains one or more of the components (B). The component (B) may be a compound that polymerizes by light, and may be, for example, a compound having an ethylenically unsaturated bond. The component (B) contains a trifunctional monomer from the viewpoint of improving adhesion, pattern shape, and developability.

Examples of the trifunctional monomer include trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, and EO / PO-modified trimethylolpropane tri (meth) acrylate. Examples thereof include tetramethylolmethanetri (meth) acrylate. The trifunctional monomer is preferably EO-modified, PO-modified, or EO-PO-modified from the viewpoint of further improving peelability, adhesion, and flexibility.

The content of the trifunctional monomer may be 5% by mass or more or 10% by mass or more from the viewpoint of further improving the developability, adhesion, and pattern shape based on the total amount of the component (B), and the peelability is improved. From the viewpoint of further improvement, it may be 30% by mass or less or 25% by mass or less.

The component (B) may contain a bisphenol A type (meth) acrylate compound from the viewpoint of further improving alkali developability, resolution, and peeling characteristics after curing.

Bisphenol A type (meth) acrylate compounds include 2,2-bis (4-((meth) acryloxipolyethoxy) phenyl) propane (2,2-bis (4-((meth) acryloxipentaethoxy) phenyl). ) Propane, etc.), 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxipolyethoxypolypropoxy) phenyl) propane and the like can be mentioned. The component (B) is 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane (2,2-bis (4-((meth))) from the viewpoint of further improving the resolution and peeling characteristics. Acryloxipentaethoxy) phenyl) propane and the like) may be included.

The content of the bisphenol A type (meth) acrylate compound may be 20% by mass or more or 40% by mass or more, based on the total amount of the component (B), and is 95% by mass from the viewpoint of further improving the resolution of the resist. Hereinafter, it may be 90% by mass or less or 80% by mass or less.

The component (B) is α, β- obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid other than the above-mentioned trifunctional monomer from the viewpoint of further improving the resolution and flexibility. It may contain an unsaturated ester compound. Examples of the α, β-unsaturated ester compound include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate such as EO-modified polypropylene glycol, and trimethylolpropane di (meth) acrylate. ) Acrylate, tetramethylolmethane tetra (meth) acrylate and the like can be mentioned.

The content of the α, β-unsaturated ester compound may be 20% by mass or more or 30% by mass or more from the viewpoint of improving the flexibility based on the total amount of the component (B), and the resolution is further improved. From the viewpoint of the above, it may be 70% by mass or less or 60% by mass or less.

The component (B) may contain a (meth) acrylate compound having a urethane bond from the viewpoint of further improving peelability and developability. Examples of the (meth) acrylate compound having a urethane bond include a (meth) acrylic acid-based monomer having an OH group at the β-position and isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6-. Reactants with diisocyanate compounds such as hexamethylene diisocyanate, tris ((meth) acryloxitetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, PO-modified urethane di (meth) acrylate, EO and PO-modified urethane diisocyanate. Examples thereof include (meth) acrylate and carboxyl group-containing urethane (meth) acrylate. Further, a urethane oligomer is also preferably used as the (meth) acrylate compound having a urethane bond.

The weight average molecular weight of the (meth) acrylate compound having a urethane bond is preferably from the viewpoints of physical properties such as coatability in a liquid state, handleability, curing shrinkage after curing, surface curability, hardness, and elongation. It is 800 or more, more preferably 2000 or more, still more preferably 4000 or more. From the same viewpoint, the weight average molecular weight of the (meth) acrylate compound having a urethane bond is preferably 10,000 or less, more preferably 9000 or less, and further preferably 7,000 or less. The weight average molecular weight is measured by gel permeation chromatography (GPC), and a value converted to standard polystyrene is used.

The content of the (meth) acrylate compound having a urethane bond may be 2% by mass or more or 4% by mass or more from the viewpoint of further improving the peelability and developability based on the total amount of the component (B). From the viewpoint of further improving the fluidity, it may be 10% by mass or less or 8% by mass or less.

The photosensitive resin composition contains, as the component (B), a trifunctional monomer, a bisphenol A-based (meth) acrylate compound, an α, β-unsaturated ester compound, and other photopolymerization other than the (meth) acrylate compound having a urethane bond. It may contain a sex compound.

Other photopolymerizable compounds include nonylphenoxypolyethyleneoxyacrylate, phthalic acid compounds, (meth) acrylic acid alkyl esters, and photopolymerizable compounds (oxetan compounds) having at least one cationically polymerizable cyclic ether group in the molecule. Etc.) and so on. The other photopolymerizable compound is at least one selected from the group consisting of nonylphenoxypolyethyleneoxyacrylate and a phthalic acid-based compound from the viewpoint of further preferably improving the resolution, adhesion, resist shape and peeling property after curing. It may be there.

Examples of nonylphenoxypolyethyleneoxyacrylate include nonylphenoxytriethyleneoxyacrylate, nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, and nonylphenoxyoctaethyleneoxy. Examples thereof include acrylate, nonylphenoxy nonaethyleneoxyacrylate, nonylphenoxydecaethyleneoxyacrylate, and nonylphenoxyundecaethyleneoxyacrylate.

The phthalic acid compound is, for example, γ-chloro-β-hydroxypropyl-β'-(meth) acryloyloxyethyl-o-phthalate (also known as 3-chloro-2-hydroxypropyl-2- (meth) acryloyloxyethyl). Phtalate), β-hydroxyethyl-β'-(meth) acryloyloxyethyl-o-phthalate, β-hydroxypropyl-β'-(meth) acryloyloxyethyl-o-phthalate, etc., preferably γ- It is chloro-β-hydroxypropyl-β'-(meth) acryloyloxyethyl-o-phthalate.

When the component (B) contains other photopolymerizable compounds, the content of the other photopolymerizable compounds is (B) from the viewpoint of further preferably improving the resolution, adhesion, resist shape and peeling characteristics after curing. ) Based on the total amount of the components, it may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, and may be 30% by mass or less, 25% by mass or less, or 20% by mass or less.

The content of the component (B) is 3% by mass or more, 10% by mass or more, or 25% by mass or more from the viewpoint of further improving the sensitivity and resolution based on the total solid content of the photosensitive resin composition. From the viewpoint of excellent moldability of the film, it may be 70% by mass or less, 60% by mass or less, or 50% by mass or less.

Component (C): Photopolymerization Initiator The photosensitive resin composition contains one or more of the components (C). As the component (C), a hexaarylbiimidazole compound; benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2-[(4-) Methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, 2-methyl-1- [4- (Methylthio) Phenyl] -2-Aromatic ketones such as morpholino-propanone-1, quinone such as alkylanthraquinone; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkylbenzoins; benzyl dimethyl ketal and the like Benzyl derivative of; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; bis (2,6-dimethylbenzoyl) -2,4,4-trimethyl-pentylphosphine oxide; (2,4,6 -Trimethylbenzoyl) ethoxyphenylphosphine oxide and the like can be mentioned.

The component (C) may contain a hexaarylbiimidazole compound from the viewpoint of further suppressing the penetration of the photosensitizer into the polyethylene film. The aryl group in the hexaarylbiimidazole compound may be a phenyl group or the like. The hydrogen atom bonded to the aryl group in the hexaarylbiimidazole compound may be substituted with a halogen atom (chlorine atom or the like).

The hexaarylbiimidazole compound may be a 2,4,5-triarylimidazole dimer. Examples of the 2,4,5-triarylimidazole dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer and 2- (o-chlorophenyl) -4,5-bis- ( Examples thereof include m-methoxyphenyl) imidazole dimer and 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer. The hexaarylbiimidazole compound is preferably a 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, more preferably 2 from the viewpoint of further suppressing the penetration of the photosensitizer into the polyethylene film. , 2-Bis (o-chlorophenyl) -4,5-4', 5'-tetraphenyl-1,2'biimidazole.

The content of the hexaarylbiimidazole compound is 90% by mass or more, 95% by mass or more, or 99% by mass based on the total amount of the component (C) from the viewpoint of further suppressing the penetration of the photosensitizer into the polyethylene film. It may be% or more. The component (C) may consist only of the hexaarylbiimidazole compound.

The content of the component (C) is 0.1% by mass or more, 0.5% by mass or more, or 1% by mass based on the total solid content of the photosensitive resin composition from the viewpoint of further improving the sensitivity and adhesion. % Or more, 20% by mass or less, 10% by mass or less, or 5% by mass or less.

Component (D): Coumarin-based sensitizer The photosensitive resin composition contains one or more of the components (D). The component (D) is used as a photosensitizer. Examples of the component (D) include compounds represented by the following general formula (1).

In the formula, Z ¹ and Z ² are independently halogen atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an amino group, and 1 to 1 carbon atoms, respectively. 10 alkylamino groups, dialkylamino groups with 2 to 20 carbon atoms, mercapto groups, alkyl mercapto groups with 1 to 10 carbon atoms, allyl groups, hydroxyalkyl groups with 1 to 20 carbon atoms, carboxyl groups, alkyl groups Is a carboxyalkyl group having 1 to 10, an acyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms or a group containing a heterocycle, and n is 0. An integer of ~ 4 and m represent an integer of 0 to 2, respectively. In addition, ^{at least two of n Z 1} and m Z ² may form a ring.

In the general formula (1), at least one Z ¹ is preferably substituted at the 7-position, and at least one Z ² is preferably substituted at the 4-position. Further, from the viewpoint of sensitivity, it is preferable that the 3-position is not substituted.

Examples of the halogen atom in the general formula (1) include fluorine, chlorine, bromine, iodine and astatin, and examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group and an n-propyl group. Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, Examples thereof include a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group, an icosyl group and structural isomers thereof. Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a tolyl group, a xsilyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group and the like, and these include a halogen atom, an amino group, a nitro group and a cyano group. It may be substituted with a group, a mercapto group, an allyl group, an alkyl group having 1 to 20 carbon atoms, or the like. Examples of the alkylamino group having 1 to 10 carbon atoms include a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group and the like, and examples of the dialkylamino group having 2 to 20 carbon atoms include dimethylamino. Examples thereof include a group, a diethylamino group, a dipropylamino group, and a diisopropylamino group. Examples of the alkyl mercapto group having 1 to 10 carbon atoms include a methyl mercapto group, an ethyl mercapto group, and a propyl mercapto group. Further, examples of the hydroxyalkyl group having 1 to 20 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxyisopropyl group, a hydroxybutyl group and the like, and the alkyl group has 1 to 10 carbon atoms. Examples of the carboxyalkyl group include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a carboxybutyl group and the like. Examples of the acyl group having 1 to 10 carbon atoms of the alkyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pivaloyl group and the like, and have 1 carbon number. Examples of the alkoxy group to 20 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like. Examples of the alkoxycarbonyl group having 1 to 20 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, and the like, and examples of the group containing a heterocycle include a frill group and a thienyl group. Examples thereof include a group, a pyrrolyl group, a thiazolyl group, an indrill group, a quinolyl group and the like.

In the general formula (1), Z ¹ and Z ² are independently alkyl groups having 1 to 20 carbon atoms, amino groups, alkyl amino groups having 1 to 10 carbon atoms, or dialkyl amino groups having 2 to 20 carbon atoms, respectively. Is preferable. Also in this case, ^{at least two of n Z 1} and m Z ² may form a ring.

From the viewpoint of resolution and light sensitivity, the coumarin compound represented by the general formula (1) is more preferably a compound represented by the following general formula (2). In the general formula (2), Z ¹ , Z ² and m are ^{synonymous with the above Z 1} , Z ² and m, and Z ¹¹ and Z ¹² are independently hydrogen atoms or alkyl having 1 to 20 carbon atoms, respectively. The group and r represent integers from 0 to 3, respectively. At least two of r Z ¹ , m Z ² , Z ¹¹ and Z ¹² may form a ring. In the compound represented by the following general formula (2), Z ¹¹ and Z ¹² are preferably alkyl groups having 1 to 10 carbon atoms independently, and are alkyl groups having 1 to 6 carbon atoms, respectively. Is more preferable. Further, suitable Z ¹ and Z ² are the same as described above.

A compound represented by the general formula (2) in ^{which at least two of m Z 2} , Z ¹¹ and Z ¹² form a ring is represented by the following general formula (3). Examples thereof include compounds and compounds represented by the following general formula (4).

In the formula, Z ¹ , Z ¹¹ , Z ¹² and r are ^{synonymous with Z 1} , Z ¹¹ , Z ¹² and r, and Z ²¹ represents an atom or group similar to ^{Z 1.} Further, s indicates an integer of 0 to 8. The suitable Z ¹ , Z ¹¹ and Z ¹² are the same as described above.

In the formula, Z ¹ , Z ² and m are ^{synonymous with Z 1} , Z ² and m, and Z ³¹ and Z ³² independently represent the same atom or group as ^{Z 1.} Further, t is an integer of 0 to 1, u is an integer of 0 to 6, and v is an integer of 0 to 6, respectively. The suitable Z ¹ and Z ² are the same as described above.

Examples of the compound represented by the general formula (2) (including the compound represented by the general formulas (3) and (4)) include 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, and the like. 7-diethylamino-4-methylcoumarin (compound represented by the following formula (5)), 7-methylamino-4-methylcoumarin, 7-ethylamino-4-methylcoumarin, 4,6-dimethyl-7-ethyl Aminocoumarin (compound represented by the following formula (6)), 4,6-diethyl-7-ethylaminocoumarin, 4,6-dimethyl-7-diethylaminocoumarin, 4,6-dimethyl-7-dimethylaminocoumarin, 4,6-diethyl-7-diethylaminocoumarin, 4,6-diethyl-7-dimethylaminocoumarin, 4,6-dimethyl-7-ethylaminocoumarin, 7-dimethylaminocyclopenta [c] coumarin (formula (7) below. ), 7-Aminocyclopenta [c] coumarin, 7-diethylaminocyclopenta [c] coumarin, 2,3,6,7,10,11-hexaanhydro-1H, 5H-cyclopenta [ 3,4] [1] Bentopyrano [6,7,8-ij] Kinolidine 12 (9H) -one, 7-diethylamino-5', 7'-dimethoxy-3,3'-carbonylbiscoumarin, 3,3' Examples thereof include -carbonylbis [7- (diethylamino) coumarin], 7- (diethylamino) -3- (2-thienyl) coumarin, and compounds represented by the following formula (8).

A particularly preferable coumarin compound represented by the general formula (1) is a compound represented by the general formula (4). By using the compound represented by the general formula (4) as the component (D) in combination with the trifunctional monomer as the component (B), the sensitivity, adhesion and resolution can be significantly improved. , Such an effect can be sufficiently obtained even by adding a small amount of the component (D).

The content of the component (D) is, for example, 0.01 part by mass or more from the viewpoint of further improving sensitivity, adhesion and resolution with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It is preferably 0.02 parts by mass or more, more preferably 0.03 parts by mass or more, still more preferably 0.04 parts by mass or more, and from the viewpoint of improving the resist pattern shape, for example, 0.5 parts by mass or less. Yes, preferably 0.4 parts by mass or less, more preferably 0.3 parts by mass or less, still more preferably 0.2 parts by mass or less, and particularly preferably 0.15 parts by mass or less.

The photosensitive resin composition may further contain a photosensitizer known as another photosensitizer in addition to the component (D). The content of other sensitizers is, for example, 0.01 to 0.50 parts by mass or 0.05 to 0.20 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). It may be a department.

Component (E): Polymerization inhibitor The photosensitive resin composition further contains the component (E): polymerization inhibitor from the viewpoint of suppressing polymerization in the unexposed portion during resist pattern formation and further improving the resolution. May be good. The polymerization inhibitor may be, for example, t-butylcatechol, 4-hydroxy-2,2,6,6-tetramethylpiperidin-N-oxyl or the like.

Since the photosensitive resin composition contains the component (D), even if it does not contain a polymerization inhibitor, it has a resist pattern as compared with the case where it contains a conventional photosensitizer (for example, DBA). It is possible to suppress polymerization in the unexposed portion at the time of formation and to form a resist pattern with higher accuracy. Therefore, the content of the component (E) is 0.01 part by mass or less, 0.005 part by mass or less, 0.003 part by mass or less, based on 100 parts by mass of the total amount of the component (A) and the component (B). It may be 0.0025 parts by mass or less, or 0.002 parts by mass or less, and the photosensitive resin composition may not contain the component (E). The content of the component (E) may be 0.001 part by mass or more with respect to 100 parts by mass of the total amount of the component (A) and the component (B).

The photosensitive resin composition may further contain one or more of other components other than the above-mentioned components. Other components include hydrogen donors (bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane, leucocrystal violet, N-phenylglycine, etc.), dyes (malachite green, etc.). , Tribromophenyl sulfone, photocolorant, thermal color inhibitor, plasticizer (p-toluene sulfone amide, etc.), pigment, filler, defoaming agent, flame retardant, stabilizer, adhesion imparting agent, leveling agent, peeling Examples include accelerators, antioxidants, fragrances, imaging agents, thermal cross-linking agents and the like. The content of the other components may be 0.005 parts by mass or more, 0.01 parts by mass or more, and 20 parts by mass or less with respect to 100 parts by mass of the total amount of the components (A) and (B). You may.

The photosensitive resin composition may further contain one or more organic solvents from the viewpoint of adjusting the viscosity. Examples of the organic solvent include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether and the like. The content of the organic solvent may be 40% by mass or more and 70% by mass or less based on the total amount of the photosensitive resin composition. As the organic solvent, for example, a mixed solvent of toluene and another solvent (methanol, ethanol, methyl cellosolve, ethyl cellosolve, etc.) may be used. When the photosensitive resin composition contains a coumarin-based sensitizer, good solubility can be easily obtained even if the proportion of toluene in the mixed solvent is reduced, so that the amount of toluene used can be reduced.

The photosensitive resin composition can be suitably used for forming a resist pattern, and can be particularly preferably used for a method for manufacturing a wiring board, which will be described later.

<Photosensitive element>
FIG. 1 is a schematic cross-sectional view of the photosensitive element according to the embodiment. As shown in FIG. 1, the photosensitive element 1 has a support 2, a photosensitive resin layer 3 provided on the support 2, and a protection provided on the opposite side of the photosensitive resin layer 3 from the support 2. It has a layer 4.

The support 2 and the protective layer 4 may be polymer films having heat resistance and solvent resistance, respectively, and may be, for example, a polyester film such as a polyethylene terephthalate film, a polyethylene film, a polyolefin film such as a polypropylene film, or the like. .. The support 2 and the protective layer 4 may be films of hydrocarbon-based polymers other than polyolefin, respectively. The film of the hydrocarbon polymer containing polyolefin may have a low density, for example, a density of 1.014 g / cm or less. The support 2 and the protective layer 4 may be stretched films obtained by stretching the low-density hydrocarbon-based polymer film, respectively. The type of polymer film constituting the protective layer 4 may be the same as or different from the type of polymer film constituting the support 2.

These polymer films are, for example, polyethylene terephthalate films such as PS series (for example, PS-25) manufactured by Teijin Co., Ltd., polyethylene films such as NF-15 manufactured by Tamapoli Co., Ltd., or Oji Paper Co., Ltd. ( For example, it can be purchased as a polypropylene film manufactured by Alfan MA-410, E-200C), Shinetsu Film Co., Ltd., etc.

The thickness of the support 2 may be 1 μm or more or 5 μm or more from the viewpoint of suppressing damage to the support 2 when the support 2 is peeled from the photosensitive resin layer 3, and is exposed through the support 2. From the viewpoint of suitable exposure, it may be 100 μm or less, 50 μm or less, or 30 μm or less.

The thickness of the protective layer 4 is 1 μm or more, 5 μm or more, or 15 μm from the viewpoint of suppressing damage to the protective layer 4 when laminating the photosensitive resin layer 3 and the support 2 on the substrate while peeling off the protective layer 4. It may be 100 μm or less, 50 μm or less, or 30 μm or less from the viewpoint of improving productivity.

The photosensitive resin layer 3 is made of the above-mentioned photosensitive resin composition. The thickness of the photosensitive resin layer 3 after drying (after volatilizing the organic solvent when the photosensitive resin composition contains an organic solvent) is from the viewpoint of facilitating coating and improving productivity. It may be 1 μm or more or 5 μm or more, and may be 100 μm or less, 50 μm or less, or 40 μm or less from the viewpoint of further improving adhesion and resolution.

The photosensitive element 1 can be obtained, for example, as follows. First, the photosensitive resin layer 3 is formed on the support 2. The photosensitive resin layer 3 can be formed, for example, by applying a photosensitive resin composition containing an organic solvent to form a coating layer, and drying the coating layer. Next, the protective layer 4 is formed on the surface of the photosensitive resin layer 3 opposite to the support 2.

The coating layer is formed by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, bar coating and the like. The coating layer is dried so that the amount of the organic solvent remaining in the photosensitive resin layer 3 is, for example, 2% by mass or less. Specifically, for example, at 70 to 150 ° C. for 5 to 30 minutes. Degree is done.

In another embodiment, the photosensitive element may not be provided with a protective layer, and may be further provided with other layers such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer.

The photosensitive element 1 may be, for example, in the form of a sheet, or may be in the form of a photosensitive element roll wound around a winding core in a roll shape. In the photosensitive element roll, the photosensitive element 1 is preferably wound so that the support 2 is on the outside. The winding core is made of, for example, polyethylene, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer or the like. The end face of the photosensitive element roll may be provided with an end face separator from the viewpoint of end face protection, and a moisture-proof end face separator may be provided from the viewpoint of edge fusion resistance. The photosensitive element 1 may be packaged in, for example, a black sheet having low moisture permeability.

The photosensitive element 1 can be suitably used for forming a resist pattern, and can be particularly preferably used for a method for manufacturing a wiring board, which will be described later. Since the photosensitive element 1 can suppress the penetration of the photosensitizer into the polyethylene film as compared with the conventional photosensitive element, at least one of the support 2 and the protective layer 4 may be a polyethylene film, as described above. It may be a low-density hydrocarbon-based polymer film or a stretched film thereof.

<Manufacturing method of wiring board>
FIG. 2 is a schematic view showing a method of manufacturing a wiring board (also referred to as a printed wiring board) according to an embodiment. In this manufacturing method, first, as shown in FIG. 2A, a substrate having an insulating layer 11 and a conductor layer 12 formed on the insulating layer 11 (for example, a circuit forming substrate) is prepared. The conductor layer 12 may be, for example, a metallic copper layer.

Next, as shown in FIG. 2B, the photosensitive resin layer 13 is provided on the substrate (conductor layer 12). In this step, the photosensitive resin layer 13 made of the above-mentioned photosensitive resin composition is formed on the substrate (conductor layer 12) by using the above-mentioned photosensitive resin composition or the photosensitive element 1. For example, the photosensitive resin layer 13 is formed by applying a photosensitive resin composition onto a substrate and drying it. Alternatively, the photosensitive resin layer 13 is pressed against the substrate while heating the photosensitive resin layer 3 of the photosensitive element 1 after removing the protective layer 4 from the photosensitive element 1. At the time of crimping, at least one of the photosensitive resin layer 3 and the substrate may be heated at, for example, 70 to 130 ° C. The pressure at the time of crimping may be, for example, 0.1 to 1.0 MPa.

Next, as shown in FIG. 2C, the mask 14 is placed on the photosensitive resin layer 13, and the active light 15 is irradiated to expose a region other than the region where the mask 14 is placed to expose the photosensitive resin. The layer 13 is photocured. The light source of the active light 15 is, for example, an ultraviolet light source such as a carbon arc lamp, a mercury steam arc lamp, a high-pressure mercury lamp, a xenon lamp, a gas laser (argon laser, etc.), a solid-state laser (YAG laser, etc.), a semiconductor laser, or a visible light source. It may be there.

In another embodiment, a part of the photosensitive resin layer 13 is exposed by irradiating the active light 15 with a desired pattern by a direct drawing exposure method such as an LDI exposure method or a DLP exposure method without using the mask 14. You may.

Next, as shown in FIG. 2D, the region (uncured portion) other than the photocured portion formed by exposure is removed from the substrate by development, and the photocured portion (cured product of the photosensitive resin layer). A resist pattern 16 composed of the above is formed. The developing method may be, for example, wet development or dry development, preferably wet development.

Wet development is performed by using a developer corresponding to the photosensitive resin composition, for example, by a dip method, a paddle method, a spray method, brushing, slapping, scrubbing, rocking immersion, or the like. The developing solution is appropriately selected according to the composition of the photosensitive resin composition, and may be an alkaline developing solution or an organic solvent developing solution.

The alkaline developing solution is an alkali hydroxide such as a hydroxide of lithium, sodium or potassium; an alkali carbonate such as a carbonate or bicarbonate of lithium, sodium, potassium or ammonium; an alkali metal such as potassium phosphate or sodium phosphate. Phosphate; Alkali metal pyrophosphate such as sodium pyrophosphate, potassium pyrophosphate, etc .; Boso; Sodium metasilicate; Tetramethylammonium hydroxide; Ethanolamine; Ethylenediamine; Diethylenetriamine; 2-Amino-2-hydroxymethyl-1, It may be an aqueous solution containing a base such as 3-propanediol; 1,3-diamino-2-propanol; morpholin.

The alkaline developer is, for example, 0.1 to 5% by mass sodium carbonate aqueous solution, 0.1 to 5% by mass potassium carbonate aqueous solution, 0.1 to 5% by mass sodium hydroxide aqueous solution, 0.1 to 5% by mass. It may be an aqueous solution of sodium acid or the like. The pH of the alkaline developer may be, for example, 9-11.

The alkaline developer may further contain a surface active agent, an antifoaming agent, an organic solvent and the like. Examples of the organic solvent include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and the like. The content of the organic solvent may be 2 to 90% by mass based on the total amount of the alkaline developer.

The organic solvent developer may contain an organic solvent such as 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone and γ-butyrolactone. The organic solvent developer may further contain 1 to 20% by mass of water.

In this step, after removing the unexposed portion, the resist pattern 16 is further cured by further ^{heating at 60 to 250 ° C. or further exposure at 0.2 to 10 J / cm 2 as necessary.} You may.

Next, as shown in FIG. 2E, the wiring layer 17 is formed by, for example, plating a portion of the conductor layer 12 where the resist pattern 16 is not formed. The wiring layer 17 may be made of the same material as the conductor layer 12, or may be made of a different material. The wiring layer 17 may be, for example, a metallic copper layer. The plating treatment may be one or both of an electrolytic plating treatment and an electroless plating treatment.

Next, as shown in FIG. 2 (f), the resist pattern 16 is removed, and the conductor layer 12 provided at a position corresponding to the resist pattern 16 is removed. As a result, the wiring board 18 in which the wiring layer 17 is formed on the board is obtained.

The resist pattern 16 can be removed by, for example, developing with a strong alkaline aqueous solution by a dipping method, a spray method, or the like. The strongly alkaline aqueous solution may be, for example, a 1 to 10 mass% sodium hydroxide aqueous solution, a 1 to 10 mass% potassium hydroxide aqueous solution, or the like.

The conductor layer 12 can be removed by an etching process. The etching solution is appropriately selected according to the type of the conductor layer 12, and may be, for example, a cupric chloride solution, a ferric chloride solution, an alkali etching solution, a hydrogen peroxide etching solution, or the like.

Hereinafter, the present disclosure will be described in more detail with reference to Examples, but the present disclosure is not limited to these Examples.

<Synthesis of component (A)>
The monomers shown in Table 1 were mixed with 0.9 parts by mass of azobisisobutyronitrile in the blending amount (unit: parts by mass) shown in the same table to prepare a solution (a). A solution (b) was prepared by dissolving 0.6 parts by mass of azobisisobutyronitrile in 50 parts by mass of a mixed solution (x) of 30 parts by mass of methyl cellosolve and 20 parts by mass of toluene. After putting 500 g of the mixed solution (x) into a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, the mixture is stirred while blowing nitrogen gas into the flask and heated to 80 ° C. I let you. The solution (a) was added dropwise to the mixed solution in the flask over 4 hours at a constant dropping rate, and then the mixture was stirred at 80 ° C. for 2 hours. Next, the solution (b) was added dropwise to the solution in the flask over 10 minutes at a constant dropping rate, and then the solution in the flask was stirred at 80 ° C. for 3 hours. Further, the solution in the flask was heated to 95 ° C. over 30 minutes, kept warm at 95 ° C. for 2 hours, then the stirring was stopped, and the solution was cooled to room temperature (25 ° C.) to cool the binder polymers A-1 to A-. A solution of 3 was obtained. The non-volatile content (solid content) of the solutions of the binder polymers A-1 to A-3 was 49.0% by mass. Table 1 shows the weight average molecular weight (Mw), glass transition temperature (Tg), and acid value of the binder polymers A-1 to A-3.

The weight average molecular weight was measured by gel permeation chromatography (GPC) and derived by conversion using a standard polystyrene calibration curve. The conditions of GPC are as shown below.
(GPC condition)
Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd., product name)
Column: A total of 3 of the following Gelpack GL-R420
Gelpack GL-R430
Gelpack GL-R440 (above, manufactured by Hitachi Kasei Co., Ltd., product name)
Eluent: tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., product name)

The glass transition temperature was measured using a DSC (PerkinElmer, DSC-7 type) under the conditions of a sample amount of 10 mg, a heating rate of 10 ° C./min, and a measurement atmosphere: air.

The acid value was measured by a neutralization titration method based on JIS K0070. First, a solution of the binder polymer was heated at 130 ° C. for 1 hour to remove volatiles to obtain a solid content. Then, after 1 g of the solid binder polymer was precisely weighed, 30 g of acetone was added to the binder polymer, and this was uniformly dissolved to obtain a resin solution. Next, an appropriate amount of phenolphthalein, which is an indicator, was added to the resin solution, and neutralization titration was performed using a 0.1 mol / L potassium hydroxide aqueous solution. Then, the acid value was calculated by the following formula.
Acid value = 0.1 x V x f1 x 56.1 / (Wp x I / 100)
In the formula, V is the titration amount (mL) of the 0.1 mol / L potassium hydroxide aqueous solution used for titration, f1 is the factor (concentration conversion coefficient) of the 0.1 mol / L potassium hydroxide aqueous solution, and Wp is the measured resin solution. The mass (g) and I of the above indicate the ratio (mass%) of the non-volatile content in the measured resin solution.

[Examples 1 to 10 and Comparative Examples 1 to 3]
<Preparation of photosensitive resin composition>
The photosensitive resin compositions were prepared by mixing the components shown in Tables 2 to 3 in the blending amounts (parts by mass) shown in the same table. The blending amount (parts by mass) of the component (A) shown in Tables 2 to 3 is the mass of the non-volatile component (solid content). Details of each component shown in Tables 2 to 3 are as follows.

(B) Component FA-321M (70): Propylene glycol monomethyl ether 70% solution of 2,2-bis (4- (methacryloxyethoxy) phenyl) propane (ethylene oxide average 10 mol adduct) (manufactured by Hitachi Kasei Co., Ltd.)
FA-137M: EO-modified trimethylolpropane trimethacrylate (manufactured by Hitachi Kasei Co., Ltd.)
FA-024M: EO, PO-modified dimethacrylate (manufactured by Hitachi Kasei Co., Ltd., number of EO groups: 6 (average value), number of PO groups: 12 (average value)
UA-13: EO, PO-modified urethane dimethacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd., number of EO groups: 2 (average value), number of PO groups: 18 (average value))
(C) Ingredient BCIM: 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Hampford)

(D) Ingredients Coumarin 102: 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidine-11-one (Tokyo Chemical Industry Co., Ltd.) Made)
(D)'Ingredient DBA: 9,10-dibutoxyanthracene (manufactured by Kawasaki Kasei Chemicals Co., Ltd.)
(E) Ingredient DIC-TBC-20: 4-t-Butylcatechol (manufactured by DIC Corporation)

(Other ingredients)
LCV: Leuco Crystal Violet (manufactured by Yamada Chemical Co., Ltd.)
SF-808H: Mixture of carboxybenzotriazole, 5-amino-1H-tetrazole, methoxypropanol (manufactured by Sanwa Kasei Co., Ltd.)
LA-7RD: 4-TEMPO (manufactured by Asahi Denka Kogyo Co., Ltd.)
MKG: Malachite Green (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

(solvent)
TLS: Toluene MAL: Methanol ACS: Acetone

<Manufacturing of photosensitive element>
A polyethylene terephthalate film having a thickness of 16 μm (manufactured by Teijin Co., Ltd., trade name “HTF-01”) is prepared as a support, and the photosensitive resin composition is applied onto the support so as to have a uniform thickness. , 70 ° C. and 110 ° C. were sequentially dried in a hot air convection dryer to form a photosensitive resin layer having a thickness of 25 μm after drying. A polyethylene film (manufactured by Tamapoli Co., Ltd., trade name "NF-15") is bonded onto this photosensitive resin layer as a protective layer, and a photosensitive element in which a support, a photosensitive resin layer, and a protective layer are laminated in order is formed. Obtained.

<Manufacturing of laminated body>
A copper-clad laminate (base, manufactured by Hitachi Kasei Co., Ltd., trade name "MCL-E-679"), which is a glass epoxy material in which copper foil (thickness: 35 μm) is laminated on both sides, is applied to the surface roughening treatment liquid “MEC”. Surface treatment was performed using "Epoxy Bond CZ-8100" (manufactured by MEC COMPANY, trade name). Then, after washing with water, pickling and washing with water, it was dried with an air stream. The surface-treated copper-clad laminate was heated to 80 ° C., and the photosensitive elements were laminated so that the photosensitive resin layer was in contact with the copper surface while peeling off the protective layer. As a result, a copper-clad laminate, a photosensitive resin layer, and a laminate in which the support was laminated in this order were obtained. The obtained laminate was used as a test piece in the test shown below. Lamination was performed using a heat roll at 110 ° C. at a crimping pressure of 0.4 MPa and a roll speed of 1.5 m / min.

<Evaluation>
(Measurement of absorbance)
The absorbance of the photosensitive resin layer was measured using a UV spectrophotometer (Spectrophotometer U-3310, manufactured by Hitachi High-Technologies Corporation). The measurement is performed by placing a photosensitive element with the protective layer peeled off on the measurement side, placing a support film on the reference side, continuously measuring wavelengths from 300 to 700 nm in the absorbance mode, and reading the values at wavelengths of 375 nm and 405 nm. rice field. The results are shown in Tables 2 to 3.

(Measurement of minimum development time)
The laminate was cut into 5 cm squares to obtain a test piece for measuring the minimum development time. After peeling the support from the test piece, the unexposed photosensitive resin layer was spray-developed at a pressure of 0.15 MPa using a 1% by mass sodium carbonate aqueous solution at 30 ° C., and the unexposed portion of 1 mm or more was removed. The shortest development time was defined as the shortest time that could be visually confirmed. The nozzle used was a full cone type. The distance between the test piece and the tip of the nozzle was 6 cm, and the test pieces were arranged so that the center of the test piece and the center of the nozzle coincided with each other. The shorter the minimum development time (unit: seconds), the better the developability. The results are shown in Tables 2 to 3.

(Evaluation of adhesion)
Remaining 41-step step tablet using a drawing pattern in which the line width (L) / space width (S) (hereinafter referred to as “L / S”) is 3/400 to 30/400 (unit: μm). The photosensitive resin layer of the laminated body was exposed (drawn) with an energy amount of 14 steps.

After the exposure, the support was peeled off from the laminate to expose the photosensitive resin layer, and the unexposed portion was removed by spraying a 1 mass% sodium carbonate aqueous solution at 30 ° C. for 60 seconds. After development, the space portion (unexposed portion) is removed without residue, and the line portion (exposed portion) is formed by the minimum value of the line width / space width in the resist pattern formed without meandering and chipping. , Adhesion was evaluated. The smaller this value is, the better the adhesion is. The results are shown in Tables 2 to 3.

(Evaluation of resist pattern formation)
The resist pattern having a line width of 10 μm produced in the above evaluation of adhesion was observed with a scanning electron microscope, and the shape of the resist pattern and the presence or absence of line thickening were evaluated. Electron micrographs of the resist patterns of Example 1 and Comparative Example 1 are shown in FIGS. 3 and 4, respectively. The resist pattern shape was evaluated according to the following evaluation criteria based on the ratio of the width of the top of the resist pattern to the width of the bottom (bottom width / top width). The results are shown in Tables 2 to 3.
A: Cross-sectional shape is rectangular (bottom width / top width is 0.9 or more)
B: The cross-sectional shape is a small taper shape (bottom width / top width is 0.8 or more and less than 0.9)
C: Cross-sectional shape is tapered (bottom width / top width is less than 0.8)

The line thickness was evaluated by measuring the difference between the design dimension of the line width in the drawing pattern and the line width (top width) of the formed resist pattern, and evaluating it according to the following evaluation criteria. The results are shown in Tables 2 to 3.
A: Difference is 0.5 μm or less B: Difference is more than 0.5 μm and 1.0 μm or less C: Difference is more than 1.0 μm and 2.0 μm or less D: Difference is more than 2.0 μm

1 ... Photosensitive element, 2 ... Support, 3, 13 ... Photosensitive resin layer, 4 ... Protective layer, 11 ... Insulating layer, 12 ... Conductor layer, 14 ... Mask, 15 ... Active light, 16 ... Resist pattern, 17 ... wiring layer, 18 ... wiring board.

Claims

A photosensitive resin composition containing a binder polymer, a photopolymerizable compound containing a trifunctional monomer, a photopolymerization initiator, and a coumarin-based sensitizer.
The photosensitive resin composition according to claim 1, wherein the coumarin-based sensitizer contains a compound represented by the following general formula (1).

[In the formula, Z 1 and Z 2 are independently halogen atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an amino group, and 1 carbon atom. Carbon of up to 10 alkylamino groups, dialkylamino group with 2 to 20 carbon atoms, mercapto group, alkyl mercapto group with 1 to 10 carbon atoms, allyl group, hydroxyalkyl group with 1 to 20 carbon atoms, carboxyl group, alkyl group A carboxyalkyl group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms or a group containing a heterocycle, n is An integer of 0 to 4 and m indicate an integer of 0 to 2, respectively. In addition, at least two of n Z 1 and m Z 2 may form a ring. ]
The photosensitivity according to claim 1 or 2, wherein the content of the coumarin-based sensitizer is 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound. Sex resin composition.
The photosensitive resin composition according to any one of claims 1 to 3, wherein the binder polymer contains a polymer containing a hydroxyalkyl (meth) acrylate unit.
The photosensitive resin composition according to any one of claims 1 to 4, further containing a polymerization inhibitor.
The photosensitive resin composition according to claim 5, wherein the content of the polymerization inhibitor is 0.003 parts by mass or less with respect to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound.
A photosensitive element comprising a support and a photosensitive resin layer formed on the support using the photosensitive resin composition according to any one of claims 1 to 6.
A step of providing a photosensitive resin layer on a substrate by using the photosensitive resin composition according to any one of claims 1 to 6 or the photosensitive element according to claim 7.
A step of photocuring a part of the photosensitive resin layer and
A step of removing the uncured portion of the photosensitive resin layer to form a resist pattern,
A step of forming a wiring layer on a portion of the substrate on which the resist pattern is not formed, and
A method of manufacturing a wiring board.