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

Abstract

A photosensitive resin composition containing: a binder polymer having a structure unit based on benzyl methacrylate; a photopolymerizable compound; a photopolymerization initiator; and a coumarin-based sensitizer.

Description

[Technical Field]

[0001] The present disclosure relates to a photosensitive resin composition, a photosensitive element, a method for producing a wiring board, and a photosensitive element roll. [Background technology]

[0002] In the manufacture of wiring boards, a resist pattern is formed to obtain desired wiring. Photosensitive resin compositions are widely used to form resist patterns. In recent years, MSAP (Modified Semi-Additive Process) has attracted attention as a method capable of forming fine wiring. In this method, to form fine wiring, it is necessary to form the resist pattern with higher accuracy than conventional methods.

[0003] In order to form a resist pattern with high precision, a photosensitizer is generally added to the photosensitive resin composition. Known examples of the photosensitizer include anthracene derivatives such as 9,10-dibutoxyanthracene (DBA) (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2007 / 004619 Summary of the Invention [Problem to be solved by the invention]

[0005] However, photosensitive resin compositions containing DBA still have room for improvement in order to obtain resist patterns with higher accuracy. In addition, photosensitive resin compositions are usually used in the form of a photosensitive element sandwiched between polymer films such as polyethylene. However, according to the studies of the present inventors, when a photosensitive resin composition contains DBA, the DBA permeates the polymer film, which can cause a problem in that the desired pattern shape cannot be formed during resist pattern formation. This problem occurs particularly noticeably when the polymer film is a polyethylene film.

[0006] Furthermore, photosensitive resin compositions containing DBA still have room for improvement in terms of forming resist patterns with excellent adhesion to substrates.

[0007] Therefore, an object of the present disclosure is to provide a photosensitive resin composition and a photosensitive element that have excellent adhesion to a substrate and are capable of forming a resist pattern having a good pattern shape, as well as a method for manufacturing a wiring board and a photosensitive element roll that use the same. [Means for solving the problem]

[0008] In order to achieve the above object, the present disclosure provides a photosensitive resin composition containing a binder polymer having a structural unit based on benzyl (meth)acrylate, a photopolymerizable compound, a photopolymerization initiator, and a coumarin-based sensitizer.

[0009] The photosensitive resin composition described above, using a binder polymer having structural units based on benzyl (meth)acrylate in combination with a coumarin-based sensitizer, allows the formation of a resist pattern with excellent adhesion to the substrate and a favorable pattern shape. This is believed to be because the coumarin-based sensitizer penetrates the polymer film less easily than DBA and achieves higher sensitivity with a small amount added, thereby improving the pattern shape of the resist pattern. Furthermore, the combined use of the coumarin-based sensitizer with a binder polymer having structural units based on benzyl (meth)acrylate significantly improves the adhesion of the resist pattern to the substrate. Furthermore, since the amount of coumarin-based sensitizer added can be reduced, the amount of solvent required to dissolve the sensitizer can also be reduced. Furthermore, since the coumarin-based sensitizer has lower absorbance than DBA, the exposed light can easily penetrate deeper into the photosensitive resin layer during resist pattern formation, enhancing the photocurability of the bottom of the photosensitive resin layer. This results in further improvements in adhesion, resolution, and pattern shape.

[0010] In the photosensitive resin composition, the content of the coumarin sensitizer may be 0.01 to 0.5 parts by mass relative to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound. When the content of the coumarin sensitizer is within the above range, it is possible to achieve both excellent adhesion and a good pattern shape of the resist pattern at a higher level.

[0011] In the photosensitive resin composition, the binder polymer may have a content of structural units based on benzyl (meth)acrylate of 10 to 60 mass % based on the total amount of monomers constituting the binder polymer.

[0012] In the photosensitive resin composition, the binder polymer may have a structural unit based on styrene. By including the structural unit based on styrene in the binder polymer, it is possible to achieve both excellent adhesion of the resist pattern and a good pattern shape at a higher level. Furthermore, the content of the structural unit based on styrene in the binder polymer may be 10 to 50 mass% based on the total amount of the monomers constituting the binder polymer.

[0013] In the photosensitive resin composition, the binder polymer may have a structural unit based on a (meth)acrylic acid alkyl ester, and the content of the structural unit based on a (meth)acrylic acid alkyl ester may be 5 to 40 mass % based on the total amount of monomers constituting the binder polymer.

[0014] In the photosensitive resin composition, the binder polymer may have a structural unit based on (meth)acrylic acid, and the content of the structural unit based on (meth)acrylic acid may be 10 to 40 mass % based on the total amount of monomers constituting the binder polymer.

[0015] The photosensitive resin composition may contain a polymerization inhibitor. The content of the polymerization inhibitor in the photosensitive resin composition may be 0.003 parts by mass or less per 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound. By ensuring that the content of the polymerization inhibitor is within the above range, the pattern shape of the resist pattern can be improved.

[0016] The content of the polymerization inhibitor in the photosensitive resin composition may be 0.001 parts by mass or more relative to 100 parts by mass of the total of the binder polymer and the photopolymerizable compound. When the content of the polymerization inhibitor is within the above range, it is possible to achieve a high level of both excellent adhesion and a good pattern shape of the resist pattern, and to suppress line thickening of the resist pattern.

[0017] The polymerization inhibitor may also contain tert-butylcatechol, which makes it possible to achieve a higher level of both excellent adhesion and a good pattern shape of the resist pattern, and also to suppress line thickening of the resist pattern.

[0018] The photosensitive resin composition may contain 2,6-di-tert-butyl-p-cresol as an antioxidant. The content of 2,6-di-tert-butyl-p-cresol in the photosensitive resin composition may be greater than 0.002 parts by mass per 100 parts by mass of the binder polymer and the photopolymerizable compound combined. When the content of 2,6-di-tert-butyl-p-cresol is within the above range, the adhesion of the resist pattern can be further improved and line thickening of the resist pattern can be suppressed.

[0019] In the photosensitive resin composition, the photopolymerization initiator may contain a 2,4,5-triarylimidazole dimer.

[0020] In the photosensitive resin composition, the photopolymerizable compound may contain a bisphenol A di(meth)acrylate compound. The bisphenol A di(meth)acrylate compound may contain 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane and / or 2,2-bis(4-((meth)acryloxydiethoxy)phenyl)propane.

[0021] The photosensitive resin composition may contain leuco crystal violet.

[0022] 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.

[0023] The present disclosure further provides a method for manufacturing a wiring board, comprising the steps of: providing a photosensitive resin layer on a substrate using the photosensitive resin composition of the present disclosure or the photosensitive element of the present disclosure; photocuring a portion of the photosensitive resin layer; removing an uncured portion of the photosensitive resin layer to form a resist pattern; and forming a wiring layer on a portion of the substrate where the resist pattern is not formed.

[0024] The present disclosure also provides a photosensitive element roll including a winding core and the photosensitive element of the present disclosure wound on the winding core. [Effects of the Invention]

[0025] According to the present disclosure, it is possible to provide a photosensitive resin composition and a photosensitive element that have excellent adhesion to a substrate and are capable of forming a resist pattern with a good pattern shape, as well as a method for manufacturing a wiring board and a photosensitive element roll that use the same. [Brief explanation of the drawings]

[0026] [Figure 1] FIG. 1 is a schematic cross-sectional view illustrating a photosensitive element according to one embodiment. [Figure 2] 1A to 1C are schematic diagrams illustrating a method for manufacturing a wiring substrate according to an embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0027] Hereinafter, embodiments of the present disclosure will be described in detail.

[0028] In this specification, the term "process" refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended effect of that process is achieved. A numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. "(Meth)acrylic acid" means at least one of "acrylic acid" and its corresponding "methacrylic acid." The same applies to other similar expressions such as (meth)acrylate. In this specification, "EO-modified" means a compound having a (poly)oxyethylene group.

[0029] In this specification, when a composition contains multiple substances corresponding to each component, the amount of each component refers to the total amount of those multiple substances present in the composition, unless otherwise specified. In this specification, the term "solid content" refers to the non-volatile content of a photosensitive resin composition excluding volatile substances (water, solvent, etc.). In other words, the term "solid content" refers to components other than the solvent that remain unvolatilized during drying of the photosensitive resin composition, as described below, and includes those that are liquid, syrup-like, or waxy at room temperature (25°C).

[0030] <Photosensitive resin composition> The photosensitive resin composition according to this embodiment contains a binder polymer (component A), a photopolymerizable compound (component B), a photopolymerization initiator (component C), and a coumarin-based sensitizer (component D). The component A has a structural unit based on benzyl (meth)acrylate. The photosensitive resin composition according to this embodiment may further contain a polymerization inhibitor (component E). Each component will be described below.

[0031] Component (A): Binder polymer The photosensitive resin composition contains one or more components (A). The component (A) contains a binder polymer having a structural unit based on benzyl (meth)acrylate. The aromatic ring of the benzyl (meth)acrylate may have a substituent.

[0032] In the binder polymer (A), the content of structural units derived from benzyl (meth)acrylate is preferably 10 to 60 mass %, more preferably 15 to 55 mass %, even more preferably 15 to 35 mass %, particularly preferably 20 to 30 mass %, and extremely preferably 20 to 23 mass %, based on the total amount of monomers constituting component (A). This allows for improved adhesion of the photosensitive resin composition layer containing the photosensitive resin composition to a circuit-forming substrate and improved resist stripping properties. Furthermore, the content of the structural units derived from benzyl (meth)acrylate may be less than 23 mass %, or may be 22 mass % or less, based on the total amount of monomers constituting component (A).

[0033] The binder polymer may contain a structural unit based on styrene from the viewpoint of further improving resolution and adhesion. The styrene may have a substituent such as vinyltoluene or α-methylstyrene.

[0034] The content of structural units based on styrene may be 10% by mass or more, 20% by mass or more, or 30% by mass or more, based on the total amount of monomers constituting component (A), from the viewpoint of further improving resolution, and may be 50% by mass or less, 45% by mass or less, or 40% by mass or less, from the viewpoint of excellent release properties.

[0035] From the viewpoint of improving alkaline developability and release properties, the binder polymer may have a structural unit based on a (meth)acrylic acid alkyl ester, and among the (meth)acrylic acid alkyl esters, the binder polymer may have a structural unit based on methyl (meth)acrylate.

[0036] The content of structural units based on a (meth)acrylic acid alkyl ester may be 5% by mass or more, 10% by mass or more, or 14% by mass or more, based on the total amount of monomers constituting the component (A), from the viewpoint of excellent release properties, and may be 40% by mass or less, 30% by mass or less, or 20% by mass or less, from the viewpoint of further improving resolution and adhesion.

[0037] The binder polymer may have a structural unit based on (meth)acrylic acid. The content of the structural unit based on (meth)acrylic acid may be 10 to 40 mass%, 15 to 30 mass parts, 20 to 30 mass parts, or 20 to 25 mass parts, based on the total amount of monomers constituting the component (A). This can improve both resist stripping properties and developability.

[0038] From the viewpoint of achieving favorable development, the acid value of component (A) may be 60 mgKOH / g or more, 65 mgKOH / g or more, 70 mgKOH / g or more, or 75 mgKOH / g or more, and from the viewpoint of improving the adhesion (developer resistance) of the cured product of the photosensitive resin composition, it may be 250 mgKOH / g or less, 240 mgKOH / g or less, or 230 mgKOH / g or less. The acid value of component (A) can be adjusted by the content of structural units constituting component (A) (for example, structural units derived from (meth)acrylic acid).

[0039] The weight average molecular weight (Mw) of 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 a cured product of the photosensitive resin composition, and from the viewpoint of favorable development, may be 80,000 or less, 50,000 or less, or 40,000 or less. The dispersity (Mw / Mn) of component (A) may be, for example, 1.5 or more or 2.0 or more, and from the viewpoint of further improving adhesion and resolution, may be 3.5 or less or 3.3 or less.

[0040] The weight-average molecular weight and dispersity can be measured, for example, by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene. More specifically, they can be measured under the conditions described in the Examples. For compounds with low molecular weights, if it is difficult to measure the weight-average molecular weight using the above-mentioned method, the molecular weight can be measured by another method and the average can be calculated.

[0041] The content of the component (A), based on the total solid content of the photosensitive resin composition, may be 20% by mass or more, 30% by mass or more, or 40% by mass or more from the viewpoint of excellent film formability, and may be 90% by mass or less, 80% by mass or less, or 65% by mass or less from the viewpoint of even better sensitivity and resolution.

[0042] The content of the (A) component may be 30 parts by mass or more, 35 parts by mass or more, or 40 parts by mass or more, relative to 100 parts by mass of the total of the (A) component and the (B) component, from the viewpoint of excellent film formability, and 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.

[0043] The photosensitive resin composition may or may not contain a binder polymer other than the component (A) (that is, a binder polymer that does not have a structural unit based on benzyl (meth)acrylate).

[0044] (B) Component: Photopolymerizable compound The photosensitive resin composition contains one or more components (B). The component (B) may be any compound that can be polymerized by light, such as a compound having an ethylenically unsaturated bond.

[0045] The component (B) may contain a bisphenol A di(meth)acrylate compound from the viewpoint of further improving the alkali developability, resolution, and release properties after curing.

[0046] Examples of bisphenol A di(meth)acrylate compounds include 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane (2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane, etc.), 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolybutoxy)phenyl)propane, and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane.

[0047] From the viewpoint of further improving resolution and release properties, component (B) may contain 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane or 2,2-bis(4-((meth)acryloxydiethoxy)phenyl)propane, or 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane may be used in combination with 2,2-bis(4-((meth)acryloxydiethoxy)phenyl)propane.

[0048] From the viewpoint of further improving the resolution of the resist, the content of the bisphenol A di(meth)acrylate compound may be 60% by mass or more, or 70% by mass or more, and may be 99% by mass or less, 95% by mass or less, or 90% by mass or less, based on the total amount of component (B).

[0049] From the viewpoint of further improving releasability, adhesion, and flexibility, component (B) may contain trimethylolpropane tri(meth)acrylate or tetramethylolmethane tri(meth)acrylate. Note that the trimethylolpropane tri(meth)acrylate or tetramethylolmethane tri(meth)acrylate may be EO-modified, PO-modified, or EO·PO-modified.

[0050] The content of trimethylolpropane tri(meth)acrylate or tetramethylolmethane tri(meth)acrylate may be 1% by mass or more or 10% by mass or more, based on the total amount of component (B), from the viewpoint of further improving developability, adhesion, and pattern shape, and may be 30% by mass or less or 25% by mass or less, from the viewpoint of further improving releasability.

[0051] The content of the component (B) may be 3% by mass or more, 10% by mass or more, or 25% by mass or more, based on the total solid content of the photosensitive resin composition, from the viewpoint of further improving sensitivity and resolution, and may be 70% by mass or less, 60% by mass or less, or 50% by mass or less, from the viewpoint of excellent film formability.

[0052] Component (C): Photopolymerization initiator The photosensitive resin composition contains one or more components (C), such as 2,4,5-triarylimidazole dimer, aromatic ketone compounds, benzoin compounds, and phosphine oxide compounds.

[0053] From the viewpoint of further suppressing the penetration of the photosensitizer into the polyethylene film, component (C) may contain a 2,4,5-triarylimidazole dimer, in which the hydrogen atoms bonded to the phenyl groups in the 2,4,5-triarylimidazole dimer may be substituted with halogen atoms (such as chlorine atoms).

[0054] Examples of the 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer. From the viewpoint of further suppressing the penetration of the photosensitizer into the polyethylene film, the 2,4,5-triarylimidazole dimer may be 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer or 2,2-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole.

[0055] From the viewpoint of further suppressing penetration of the photosensitizer into the polyethylene film, the content of the 2,4,5-triarylimidazole dimer may be 90% by mass or more, 95% by mass or more, or 99% by mass or more, based on the total amount of component (C).Component (C) may consist solely of 2,4,5-triarylimidazole dimer.

[0056] From the viewpoint of further improving sensitivity and adhesion, the content of the component (C) may be 1 mass % or more, 2 mass % or more, or 3 mass % or more, and may be 10 mass % or less, 8 mass % or less, or 6 mass % or less, based on the total solid content of the photosensitive resin composition.

[0057] (D) Component: Coumarin-based sensitizer The photosensitive resin composition contains one or more types of component (D). Component (D) is used as a photosensitizer. Examples of component (D) include compounds represented by the following general formula (1): [ka] In the formula, Z 1 and Z 2 each independently represents a halogen atom, 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, an alkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a mercapto group, an alkylmercapto group having 1 to 10 carbon atoms, an allyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having an alkyl group with 1 to 10 carbon atoms, an acyl group having an alkyl group with 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 is an integer of 0 to 2. 1 and m Z 2 At least two of these may form a ring.

[0058] 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. From the viewpoint of sensitivity, it is preferable that the 3-position is not substituted.

[0059] In general formula (1), examples of halogen atoms include fluorine, chlorine, bromine, iodine, and astatine. Examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl groups, as well as structural isomers thereof. Examples of cycloalkyl groups having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of aryl groups having 6 to 14 carbon atoms include phenyl, tolyl, xylyl, biphenyl, naphthyl, anthryl, and phenanthryl groups, which may be substituted with a halogen atom, amino, nitro, cyano, mercapto, allyl, or an alkyl group having 1 to 20 carbon atoms. Examples of alkylamino groups having 1 to 10 carbon atoms include methylamino, ethylamino, propylamino, and isopropylamino groups. Examples of dialkylamino groups having 2 to 20 carbon atoms include dimethylamino, diethylamino, dipropylamino, and diisopropylamino groups. Examples of alkylmercapto groups having 1 to 10 carbon atoms include methylmercapto, ethylmercapto, and propylmercapto groups. Furthermore, examples of the hydroxyalkyl group having 1 to 20 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxyisopropyl group, and a hydroxybutyl group, and examples of the carboxyalkyl group having 1 to 10 carbon atoms in the alkyl group include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, and a carboxybutyl group.Examples of acyl groups having 1 to 10 carbon atoms in the alkyl group include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, and pivaloyl. Examples of alkoxy groups having 1 to 20 carbon atoms include methoxy, ethoxy, propoxy, and butoxy. Examples of alkoxycarbonyl groups having 1 to 20 carbon atoms include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, and butoxycarbonyl. Examples of groups containing a heterocycle include furyl, thienyl, pyrrolyl, thiazolyl, indolyl, and quinolyl.

[0060] In general formula (1), Z 1 and Z 2 are preferably each independently an alkyl group having 1 to 20 carbon atoms, an amino group, an alkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms. 1 and m Z 2 At least two of these may form a ring.

[0061] From the viewpoint of resolution and photosensitivity, the coumarin compound represented by general formula (1) is more preferably a compound represented by the following general formula (2): 1 , Z 2 and m is the above Z 1 , Z 2 and m, and Z 11 and Z 12 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and r represents an integer of 0 to 3. 1 , m Z 2 , Z 11 and Z 12 At least two of these may form a ring. In the compound represented by the following general formula (2), Z 11 and Z 12 are each independently preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. 1and Z 2 is the same as above. [ka]

[0062] A compound represented by general formula (2), wherein m Z 2 , Z 11 and Z 12 Examples of embodiments in which at least two of the above form a ring include compounds represented by the following general formula (3) and compounds represented by the following general formula (4). [ka] In the formula, Z 1 , Z 11 , Z 12 and r is the above Z 1 , Z 11 , Z 12 and r, and Z 21 is the above Z 1 In addition, s represents an integer of 0 to 8. 1 , Z 11 and Z 12 is the same as above.

[0063] [ka] In the formula, Z 1 , Z 2 and m is the above Z 1 , Z 2 and m, and Z 31 and Z 32 are each independently the above Z 1 In addition, t represents an integer of 0 to 1, u represents an integer of 0 to 6, and v represents an integer of 0 to 6. 1 and Z 2 is the same as above.

[0064] Examples of the compound represented by general formula (2) (including compounds represented by general formulas (3) and (4)) include 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin (a compound represented by the following formula (5)), 7-methylamino-4-methylcoumarin, 7-ethylamino-4-methylcoumarin, 4,6-dimethyl-7-ethylaminocoumarin (a 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-dimethyl ... coumarin, 4,6-dimethyl-7-ethylaminocoumarin, 7-dimethylaminocyclopenta[c]coumarin (a compound represented by the following formula (7)), 7-aminocyclopenta[c]coumarin, 7-diethylaminocyclopenta[c]coumarin, 2,3,6,7,10,11-hexanhydro-1H,5H-cyclopenta[3,4][1]benzopyrano[6,7,8-ij]quinolizine 12(9H)-one, 7-diethylamino-5',7'-dimethoxy-3,3'-carbonylbiscoumarin, 3,3'-carbonylbis[7-(diethylamino)coumarin], 7-(diethylamino)-3-(2-thienyl)coumarin, and a compound represented by the following formula (8).

[0065] [ka]

[0066] Particularly preferred coumarin compounds represented by general formula (1) are compounds represented by general formula (4): By using a compound represented by general formula (4) as component (D) in combination with a binder polymer having a structural unit based on benzyl (meth)acrylate as component (A), it is possible to significantly improve sensitivity, adhesion, and resolution, and such effects can be sufficiently obtained even by adding only a small amount of component (D).

[0067]

[0073] From the viewpoint of further improving sensitivity, adhesion, and resolution, the amount of the component (D) relative to 100 parts by mass of the total of the component (A) and the component (B) is, for example, 0.01 parts by mass or more, and preferably 0.02 parts by mass or more, more preferably 0.03 parts by mass or more, and even more preferably 0.04 parts by mass or more; and from the viewpoint of improving the resist pattern shape, the amount of the component (D) is, for example, 0.5 parts by mass or less, preferably 0.4 parts by mass or less, more preferably 0.3 parts by mass or less, even more preferably 0.2 parts by mass or less, particularly preferably 0.15 parts by mass or less, and extremely preferably 0.1 part by mass or less.

[0068] The photosensitive resin composition may further contain other known photosensitizers in addition to the component (D). The content of the other sensitizers may be, for example, 0.01 to 0.50 parts by mass or 0.05 to 0.20 parts by mass per 100 parts by mass of the total of the components (A) and (B).

[0069] Component (E): Polymerization inhibitor The photosensitive resin composition may further contain a polymerization inhibitor (component (E)) to suppress polymerization in unexposed areas during resist pattern formation and further improve resolution. Examples of the polymerization inhibitor include tert-butylcatechol and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl.

[0070] Examples of the polymerization inhibitor include alkyl catechols such as catechol, resorcinol (resorcin), 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, and 3,5-di-tert-butylcatechol; 2-methylresorcinol; and 4-methylresorcinol. alkyl resorcinols such as orcinol, 5-methylresorcinol (orcinol), 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; alkylhydroquinones such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone; pyrogallol, phloroglucinol, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl. These may be used alone or in combination of two or more.

[0071] By containing component (D), the photosensitive resin composition can suppress polymerization in unexposed areas during resist pattern formation, even without containing a polymerization inhibitor, compared to compositions containing conventional photosensitizers (e.g., DBA), thereby enabling the formation of resist patterns with greater precision. Therefore, the content of component (E) may be 0.01 parts by mass or less, 0.005 parts by mass or less, 0.003 parts by mass or less, 0.0025 parts by mass or less, or 0.002 parts by mass or less, per 100 parts by mass of the total amount of components (A) and (B). The photosensitive resin composition may not contain component (E). On the other hand, by containing component (E), the photosensitive resin composition can further improve adhesion and resist pattern shape, and can also suppress line thickening of the resist pattern. Therefore, the content of the (E) component may be 0.001 parts by mass or more, 0.0015 parts by mass or more, or 0.002 parts by mass or more relative to 100 parts by mass of the total amount of the (A) component and the (B) component.

[0072] The photosensitive resin composition may further contain one or more other components in addition to the components described above. Examples of other components include hydrogen donors (such as bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, leucocrystal violet, and N-phenylglycine), dyes (such as malachite green), tribromophenyl sulfone, photocoloring agents, thermal color-developing inhibitors, plasticizers (such as p-toluenesulfonamide), pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion promoters, leveling agents, release promoters, antioxidants, fragrances, imaging agents, and thermal crosslinking agents. The content of these other components may be 0.005 parts by mass or more, or 0.01 parts by mass or more, or 20 parts by mass or less, per 100 parts by mass of the total amount of components (A) and (B).

[0073] Examples of antioxidants include alkylated phenols such as 2,6-di-tert-butyl-4-methylphenol, alkylated bisphenols such as 2,2-methylenebis(4-methyl-6-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2-4-hydroxy-3,5-di-tert-butylanilino-4,6-bis(n-octylthio)-1,3,5-triazine, dilaurylthiodipropionate benzotriazole, benzotriazole hydrochloride, benzotriazole organic acid salts, and aminobenzothiazole. Furthermore, as the antioxidant, phenols such as 4,4'-butylidene-bis(6-tert-butyl-m-cresol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), 4,4'-thio-bis(6-tert-butyl-m-cresol), 2,6-di-tert-butyl-p-cresol, 2,5-di-tert-amylhydroquinone, 2,5-di-tert-butylhydroquinone, 2-methyl-4,6-bis[(octylthio)methyl]phenol, and 2,4-bis(dodecylthiomethyl)-6-methylphenol may be used. These may be used alone or in combination of two or more.

[0074] The antioxidant preferably contains 2,6-di-tert-butyl-p-cresol (also known as dibutylhydroxytoluene, abbreviated as BHT). When the photosensitive resin composition contains BHT, adhesion and the resist pattern shape can be further improved, and line thickening of the resist pattern can be suppressed.

[0075] The content of the antioxidant in the photosensitive resin composition may be 0.001 parts by mass or more, 0.002 parts by mass or more, more than 0.002 parts by mass, 0.003 parts by mass or more, or 0.005 parts by mass or more, relative to 100 parts by mass of the total amount of components (A) and (B). It may be 0.5 parts by mass or less, 0.3 parts by mass or less, or 0.1 parts by mass or less. By ensuring that the content of the antioxidant is at least the above-mentioned lower limit, adhesion and the resist pattern shape can be further improved, and line thickening of the resist pattern can be suppressed. Furthermore, by ensuring that the content of the antioxidant is at most the above-mentioned upper limit, a significant decrease in sensitivity can be suppressed.

[0076] The photosensitive resin composition may further contain one or more organic solvents from the viewpoint of adjusting the viscosity. Examples of organic solvents include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, and propylene glycol monomethyl ether. 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 is easily obtained even if the proportion of toluene in the mixed solvent is reduced, so the amount of toluene used can be reduced.

[0077] The photosensitive resin composition can be suitably used for forming a resist pattern, and can be particularly suitably used in the method for producing a wiring board described below.

[0078] <Photosensitive element> Fig. 1 is a schematic cross-sectional view of a photosensitive element according to one embodiment. As shown in Fig. 1, the photosensitive element 1 includes a support 2, a photosensitive resin layer 3 provided on the support 2, and a protective layer 4 provided on the side of the photosensitive resin layer 3 opposite the support 2.

[0079] The support 2 and the protective layer 4 may each be a polymer film having heat resistance and solvent resistance, such as a polyester film such as a polyethylene terephthalate film, or a polyolefin film such as a polyethylene film or a polypropylene film. The support 2 and the protective layer 4 may each be a film of a hydrocarbon-based polymer other than polyolefin. A film of a hydrocarbon-based polymer including 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 each be a stretched film obtained by stretching such a low-density hydrocarbon-based polymer film. 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.

[0080] These polymer films are commercially available, for example, as polyethylene terephthalate films such as the PS series (e.g., PS-25) manufactured by Teijin Limited, polyethylene films such as NF-15 manufactured by Tamapoly Co., Ltd., or polypropylene films manufactured by Oji Paper Co., Ltd. (e.g., Alphan MA-410, E-200C) and Shin-Etsu Film Co., Ltd.

[0081] The thickness of the support 2 may be 1 μm or more or 5 μm or more from the viewpoint of preventing damage to the support 2 when peeling the support 2 from the photosensitive resin layer 3, and may be 100 μm or less, 50 μm or less, or 30 μm or less from the viewpoint of enabling suitable exposure even when exposure is performed through the support 2.

[0082] The thickness of the protective layer 4 may be 1 μm or more, 5 μm or more, or 15 μm or more from the viewpoint of suppressing damage to the protective layer 4 when the photosensitive resin layer 3 and the support 2 are laminated onto the substrate while peeling off the protective layer 4, and may be 100 μm or less, 50 μm or less, or 30 μm or less from the viewpoint of improving productivity.

[0083] 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 if the photosensitive resin composition contains an organic solvent) may be 1 μm or more or 5 μm or more from the viewpoints of facilitating coating and improving productivity, and may be 100 μm or less, 50 μm or less, or 40 μm or less from the viewpoints of further improving adhesion and resolution.

[0084] The photosensitive element 1 can be obtained, for example, as follows. First, a photosensitive resin layer 3 is formed on a 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 this coating layer. Next, a protective layer 4 is formed on the surface of the photosensitive resin layer 3 opposite the support 2.

[0085] The coating layer is formed by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, bar coating, etc. The coating layer is dried so that the amount of organic solvent remaining in the photosensitive resin layer 3 is, for example, 2% by mass or less, and specifically, for example, at 70 to 150°C for about 5 to 30 minutes.

[0086] In another embodiment, the photosensitive element may not include a protective layer, and may further include other layers such as a cushion layer, an adhesive layer, a light-absorbing layer, and a gas barrier layer.

[0087] 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 core. In the photosensitive element roll, the photosensitive element 1 is preferably wound with the support 2 facing outward. The core is formed of, for example, polyethylene, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, or the like. An end separator may be provided on the end face of the photosensitive element roll 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 wrapped, for example, in a black sheet with low moisture permeability.

[0088] The photosensitive element 1 can be suitably used for forming a resist pattern, and is particularly suitable for use in the method for producing a wiring board described below. Compared to conventional photosensitive elements, the photosensitive element 1 can suppress the penetration of a photosensitizer into a polyethylene film, so at least one of the support 2 and the protective layer 4 may be a polyethylene film, or the above-mentioned low-density hydrocarbon-based polymer film or a stretched film thereof.

[0089] <Method of manufacturing wiring board> 2A and 2B are schematic diagrams illustrating a method for manufacturing a wiring board (also called a printed wiring board) according to one embodiment. In this manufacturing method, first, as shown in FIG. 2A, a substrate (e.g., a circuit-forming substrate) is prepared, which includes an insulating layer 11 and a conductor layer 12 formed on the insulating layer 11. The conductor layer 12 may be, for example, a metallic copper layer.

[0090] Next, as shown in FIG. 2(b), a photosensitive resin layer 13 is provided on the substrate (conductor layer 12). In this step, the photosensitive resin layer 13 made of the photosensitive resin composition described above is formed on the substrate (conductor layer 12) using the photosensitive resin composition or photosensitive element 1 described above. For example, the photosensitive resin layer 13 is formed by applying the photosensitive resin composition to the substrate and drying it. Alternatively, the photosensitive resin layer 13 is formed by removing the protective layer 4 from the photosensitive element 1, and then pressing the photosensitive resin layer 3 of the photosensitive element 1 to the substrate while heating. During the pressing, at least one of the photosensitive resin layer 3 and the substrate may be heated, for example, to 70 to 130°C. The pressure during the pressing may be, for example, 0.1 to 1.0 MPa.

[0091] 2(c), a mask 14 is placed on the photosensitive resin layer 13, and actinic rays 15 are irradiated to expose areas other than the area where the mask 14 is placed, thereby photo-curing the photosensitive resin layer 13. The light source for the actinic rays 15 may be an ultraviolet or visible light source such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, a xenon lamp, a gas laser (such as an argon laser), a solid-state laser (such as a YAG laser), or a semiconductor laser.

[0092] In another embodiment, without using the mask 14, a part of the photosensitive resin layer 13 may be exposed by irradiating with actinic rays 15 in a desired pattern by a direct imaging exposure method such as LDI exposure method or DLP exposure method.

[0093] 2(d), the regions (uncured portions) other than the photocured portions formed by exposure are removed from the substrate by development to form a resist pattern 16 consisting of the photocured portions (cured product of the photosensitive resin layer). The development method may be, for example, wet development or dry development, with wet development being preferred.

[0094] Wet development is carried out using a developer suitable for the photosensitive resin composition by, for example, a dipping method, a puddle method, a spray method, brushing, slapping, scrubbing, swinging immersion, etc. The developer is appropriately selected depending on the constitution of the photosensitive resin composition, and may be an alkaline developer or an organic solvent developer.

[0095] The alkaline developer may be an aqueous solution containing a base such as an alkali hydroxide such as lithium, sodium, or potassium hydroxide; an alkali carbonate such as lithium, sodium, potassium, or ammonium carbonate or bicarbonate; an alkali metal phosphate such as potassium phosphate or sodium phosphate; an alkali metal pyrophosphate such as sodium pyrophosphate or potassium pyrophosphate; borax; sodium metasilicate; tetramethylammonium hydroxide; ethanolamine; ethylenediamine; diethylenetriamine; 2-amino-2-hydroxymethyl-1,3-propanediol; 1,3-diamino-2-propanol; morpholine, etc.

[0096] The alkaline developer may be, for example, a 0.1 to 5 mass % aqueous sodium carbonate solution, a 0.1 to 5 mass % aqueous potassium carbonate solution, a 0.1 to 5 mass % aqueous sodium hydroxide solution, a 0.1 to 5 mass % aqueous sodium tetraborate solution, etc. The pH of the alkaline developer may be, for example, 9 to 11.

[0097] The alkaline developer may further contain a surfactant, an antifoaming agent, an organic solvent, etc. Examples of the organic solvent include acetone, ethyl acetate, an 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, and diethylene glycol monobutyl ether. The content of the organic solvent may be 2 to 90 mass % based on the total amount of the alkaline developer.

[0098] The organic solvent developer may contain an organic solvent such as 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyrolactone, etc. The organic solvent developer may further contain 1 to 20% by mass of water.

[0099] In this step, after removing the unexposed portion, if necessary, heating at 60 to 250°C or applying 0.2 to 10 J / cm 2 The resist pattern 16 may be further hardened by further exposure to light at 1000 K.

[0100] 2(e), a wiring layer 17 is formed on the portion of the conductor layer 12 where the resist pattern 16 is not formed, for example, by plating. The wiring layer 17 may be formed of the same material as the conductor layer 12, or may be formed of a different material. The wiring layer 17 may be, for example, a metallic copper layer. The plating may be one or both of an electrolytic plating process and an electroless plating process.

[0101] 2(f), the resist pattern 16 is removed, and the conductor layer 12 provided in a position corresponding to the resist pattern 16 is also removed, thereby obtaining a wiring substrate 18 in which the wiring layer 17 is formed on the substrate.

[0102] The resist pattern 16 can be removed by, for example, developing using a strong alkaline aqueous solution by immersion, spraying, etc. The strong 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.

[0103] The conductive layer 12 can be removed by etching. The etching solution is appropriately selected depending on the type of conductive layer 12, and may be, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, a hydrogen peroxide etching solution, or the like. [Example]

[0104] The present disclosure will be explained in more detail below using examples, but the present disclosure is not limited to these examples.

[0105] <Synthesis of component (A)> Solution (a) was prepared by mixing the monomers shown in Table 1 with 0.9 parts by mass of azobisisobutyronitrile in the amounts shown in the table (unit: parts by mass). Solution (b) was prepared by dissolving 0.6 parts by mass of azobisisobutyronitrile in 50 parts by mass of a mixture (x) of 30 parts by mass of methyl cellosolve and 20 parts by mass of toluene. 500 g of mixture (x) was placed in a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas inlet tube, and the mixture was stirred while blowing nitrogen gas into the flask and heated to 80°C. Solution (a) was added dropwise to the mixture in the flask at a constant rate over 4 hours, followed by stirring at 80°C for 2 hours. Next, solution (b) was added dropwise to the solution in the flask at a constant rate over 10 minutes, followed by stirring the solution in the flask at 80°C for 3 hours. The solution in the flask was then heated to 95°C over 30 minutes and maintained at 95°C for 2 hours. After this, stirring was stopped and the solution was cooled to room temperature (25°C), yielding solutions of binder polymers A-1 to A-3. The non-volatile content (solid content) of the solutions of binder polymers A-1 to A-3 was 49.0% by mass. The weight-average molecular weight (Mw), glass transition temperature (Tg), and acid value of binder polymers A-1 to A-3 are shown in Table 1.

[0106] The weight average molecular weight was determined by measuring by gel permeation chromatography (GPC) and converting the result using a calibration curve of standard polystyrene. The GPC conditions are as follows: (GPC conditions) Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd., product name) Columns: 3 in total Gelpack GL-R420 Gelpack GL-R430 Gelpack GL-R440 (all product names, manufactured by Hitachi Chemical Co., Ltd.) Eluent: tetrahydrofuran Measurement temperature: 40℃ Flow rate: 2.05mL / min Detector: Hitachi L-3300 RI (Hitachi, Ltd., product name)

[0107] The glass transition temperature was measured using a DSC (DSC-7 model, manufactured by PerkinElmer) under the conditions of a sample amount of 10 mg, a temperature rise rate of 10° C. / min, and a measurement atmosphere of air.

[0108] The acid value was measured by the neutralization titration method based on JIS K0070. First, the binder polymer solution was heated at 130°C for 1 hour, and the volatiles were removed to obtain a solid content. Then, 1 g of the solid binder polymer was precisely weighed, and 30 g of acetone was added to this binder polymer and uniformly dissolved to obtain a resin solution. Next, an appropriate amount of phenolphthalein as an indicator was added to the resin solution, and neutralization titration was performed using a 0.1 mol / L potassium hydroxide aqueous solution. The acid value was then calculated using the following formula. Acid value = 0.1 × V × f1 × 56.1 / (Wp × I / 100) In the formula, V is the titration volume (mL) of the 0.1 mol / L potassium hydroxide aqueous solution used in the titration, f1 is the factor (concentration conversion coefficient) of the 0.1 mol / L potassium hydroxide aqueous solution, Wp is the mass (g) of the measured resin solution, and I is the proportion of non-volatile matter (mass%) in the measured resin solution.

[0109] [Table 1]

[0110] [Examples 1 to 9 and Comparative Examples 1 to 3] <Preparation of Photosensitive Resin Composition> Each photosensitive resin composition was prepared by mixing the components shown in Table 2 in the amounts (parts by mass) shown in the table. The amount (parts by mass) of component (A) shown in Table 2 is the mass of the nonvolatile content (solid content). Details of each component shown in Table 2 are as follows.

[0111] (B) Component FA-321M(70): 70% solution of 2,2-bis(4-(methacryloxyethoxy)phenyl)propane (average 10 mol ethylene oxide adduct) in propylene glycol monomethyl ether (Hitachi Chemical Co., Ltd.) FA-137M: EO-modified trimethylolpropane trimethacrylate (Hitachi Chemical Co., Ltd.) (C) Component BCIM: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (Hampford)

[0112] (D) Component Coumarin 102: 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizin-11-one (Tokyo Chemical Industry Co., Ltd.) (D)' component DBA: 9,10-dibutoxyanthracene (Kawasaki Chemical Industries, Ltd.) (E) Component DIC-TBC-20: 4-tert-butylcatechol (DIC Corporation)

[0113] (Other ingredients) BHT: 2,6-di-tert-butyl-p-cresol (antioxidant, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) LCV: Leuco Crystal Violet (Yamada Chemical Industry Co., Ltd.) SF-808H: A mixture of carboxybenzotriazole, 5-amino-1H-tetrazole, and methoxypropanol (manufactured by Sanwa Chemical Co., Ltd.) LA-7RD:4-TEMPO (manufactured by Asahi Denka Kogyo Co., Ltd.) MKG: Malachite Green (Osaka Organic Chemical Industry Co., Ltd.)

[0114] (solvent) TLS: Toluene MAL: Methanol ACS: Acetone

[0115] <Preparation of Photosensitive Element> A 16 μm thick polyethylene terephthalate film (manufactured by Teijin Limited, product name "HTF-01") was prepared as a support, and the photosensitive resin composition was applied to a uniform thickness on the support, followed by drying in a hot air convection dryer at 70°C and 110°C sequentially to form a photosensitive resin layer with a thickness of 25 μm after drying. A polyethylene film (manufactured by Tamapoly Corporation, product name "NF-15") was laminated onto this photosensitive resin layer as a protective layer to obtain a photosensitive element in which the support, photosensitive resin layer, and protective layer were laminated in that order.

[0116] <Preparation of laminate> A copper-clad laminate (substrate, manufactured by Hitachi Chemical Co., Ltd., product name "MCL-E-679"), a glass epoxy material with copper foil (thickness: 35 μm) laminated on both sides, was surface-treated using a surface roughening treatment solution "MEC Etch Bond CZ-8100" (manufactured by MEC Co., Ltd., product name). It was then washed with water, pickled, and washed again with water, and then dried under airflow. The surface-treated copper-clad laminate was heated to 80°C, and while the protective layer was peeled off, the above-mentioned photosensitive element was laminated onto each of the laminates so that the photosensitive resin layer was in contact with the copper surface. This resulted in a laminate in which the copper-clad laminate, photosensitive resin layer, and support were laminated in this order. The resulting laminate was used as a test piece in the tests described below. Lamination was performed using a heat roll at 110°C, with a pressure of 0.4 MPa and a roll speed of 1.5 m / min.

[0117] <Evaluation> (Absorbance measurement) The absorbance of the photosensitive resin layer was measured using a UV spectrophotometer (Hitachi High-Technologies Corporation, Spectrophotometer U-3310). The measurement was performed by placing the photosensitive element with the protective layer peeled off on the measurement side and the support film on the reference side, and continuously measuring wavelengths from 300 to 700 nm in absorbance mode, and reading values ​​at wavelengths of 375 nm and 405 nm. The results are shown in Table 2.

[0118] (Measurement of minimum development time) The laminate was cut into 5 cm squares to obtain test pieces 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 weight aqueous solution of sodium carbonate at 30°C. The shortest time required for visually confirming that at least 1 mm of unexposed area had been removed was defined as the minimum development time. A full-cone type nozzle was used. The test piece was positioned so that the center of the nozzle coincided with the center of the test piece. The shorter the minimum development time (unit: seconds), the better the developability. The results are shown in Table 2.

[0119] (Evaluation of Adhesion) Using a drawing pattern with a line width (L) / space width (S) (hereinafter referred to as "L / S") ratio of 3 / 400 to 30 / 400 (unit: μm), exposure (drawing) was performed on the photosensitive resin layer of the laminate with an energy amount that resulted in 14 remaining steps on a 41-step tablet.

[0120] After exposure, the support was peeled off from the laminate to expose the photosensitive resin layer, and the unexposed portions were removed by spraying a 1% by weight aqueous solution of sodium carbonate at 30°C for 60 seconds. After development, the space portions (unexposed portions) were removed without residue, and the line portions (exposed portions) were formed without meandering or chipping. Adhesion was evaluated based on the minimum value of the line width / space width ratio in the resist pattern. The smaller this value, the better the adhesion. The results are shown in Table 2.

[0121] (Evaluation of resist pattern forming ability) The resist patterns with a line width of 10 μm prepared for the above adhesion evaluation were observed under a scanning electron microscope to evaluate the shape of the resist pattern and the presence or absence of line thickening. The resist pattern shape was evaluated based on the ratio of the top width to the bottom width of the resist pattern (bottom width / top width) according to the following evaluation criteria. The results are shown in Table 2. A: Cross-sectional shape is rectangular (bottom width / top width is 0.9 or more) B: Cross-sectional shape is slightly tapered (bottom width / top width is 0.8 or more and less than 0.9) C: Cross section is tapered (bottom width / top width is less than 0.8)

[0122] The line thickening was evaluated by measuring the difference between the design dimension of the line width in the written pattern and the line width (top width) of the formed resist pattern, and using the following evaluation criteria. The results are shown in Table 2. A: Difference is 0.5 μm or less B: Difference is more than 0.5 μm and less than 1.0 μm C: Difference is more than 1.0 μm and less than 2.0 μm D: Difference is more than 2.0 μm

[0123] [Table 2] [Explanation of symbols]

[0124] 1...photosensitive element, 2...support, 3, 13...photosensitive resin layer, 4...protective layer, 11...insulating layer, 12...conductor layer, 14...mask, 15...actinic light, 16...resist pattern, 17...wiring layer, 18...wiring board.

Claims

1. The composition contains a binder polymer having a structural unit based on benzyl (meth)acrylate, a photopolymerizable compound, a photopolymerization initiator, a coumarin-based sensitizer, and 2,6-di-tert-butyl-p-cresol as an antioxidant, The coumarin-based sensitizer contains a compound represented by the following general formula (4): The photosensitive resin composition has a content of the coumarin-based sensitizer of 0.01 to 0.15 parts by mass relative to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound. 【Chemistry 1】 [In the formula, Z １ , Z ２ , Z ３１ and Z ３２ each independently represents a halogen atom, 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, an alkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a mercapto group, an alkylmercapto group having 1 to 10 carbon atoms, an allyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having an alkyl group with 1 to 10 carbon atoms, an acyl group having an alkyl group with 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, m is an integer of 0 to 2, 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. ２ Two of them may form a ring.

2. 2. The photosensitive resin composition according to claim 1, wherein the binder polymer contains structural units based on benzyl (meth)acrylate in an amount of 10 to 60 mass % based on the total amount of monomers constituting the binder polymer.

3. The photosensitive resin composition according to claim 1 or 2, wherein the binder polymer has a structural unit based on styrene.

4. 4. The photosensitive resin composition according to claim 3, wherein the binder polymer contains 10 to 50 mass% of structural units based on styrene, based on the total amount of monomers constituting the binder polymer.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the binder polymer has a structural unit based on a (meth)acrylic acid alkyl ester.

6. 6. The photosensitive resin composition according to claim 5, wherein the binder polymer contains structural units based on a (meth)acrylic acid alkyl ester in an amount of 5 to 40 mass% based on the total amount of monomers constituting the binder polymer.

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the binder polymer has a structural unit based on (meth)acrylic acid.

8. 8. The photosensitive resin composition according to claim 7, wherein the binder polymer contains structural units based on (meth)acrylic acid in an amount of 10 to 40 mass% based on the total amount of monomers constituting the binder polymer.

9. The photosensitive resin composition according to any one of claims 1 to 8, further comprising a polymerization inhibitor.

10. The photosensitive resin composition according to claim 9 , wherein the content of the polymerization inhibitor is 0.003 parts by mass or less relative to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound.

11. The photosensitive resin composition according to any one of claims 1 to 10, wherein the content of the 2,6-di-tert-butyl-p-cresol is more than 0.002 parts by mass with respect to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound.

12. The photosensitive resin composition according to any one of claims 1 to 11, wherein the photopolymerization initiator contains a 2,4,5-triarylimidazole dimer.

13. The photosensitive resin composition according to any one of claims 1 to 12, wherein the photopolymerizable compound contains a bisphenol A di(meth)acrylate compound.

14. 14. The photosensitive resin composition according to claim 13, wherein the bisphenol A di(meth)acrylate compound comprises 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane and / or 2,2-bis(4-((meth)acryloxydiethoxy)phenyl)propane.

15. The photosensitive resin composition according to any one of claims 1 to 14, further comprising leuco crystal violet.

16. 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 15.

17. a step of providing a photosensitive resin layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 15 or the photosensitive element according to claim 16; photocuring a portion of the photosensitive resin layer; removing uncured portions of the photosensitive resin layer to form a resist pattern; forming a wiring layer on a portion of the substrate where the resist pattern is not formed; A method for manufacturing a wiring board, comprising:

18. A photosensitive element roll comprising: a winding core; and the photosensitive element of claim 16 wound on the winding core.

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