Photosensitive resin composition

Abstract

To provide a photosensitive resin composition that has improved resolution, can suppress the occurrence of connection failure in via holes with a reduced diameter, and can form an insulating layer with reduced surface roughness.SOLUTION: A photosensitive resin composition comprises (A) a resin comprising a carboxyl group, (B) an α-amino ketone-based photopolymerization initiator comprising a fluorene skeleton, (C) an epoxy resin, (D) a photosensitizer, and (E) an inorganic filler. The component (D) has a maximum absorption wavelength in a range from 350 nm to 400 nm.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photosensitive resin composition, and further to a supported photosensitive film, a printed wiring board, and a semiconductor device obtained by using the photosensitive resin composition. [Background technology]

[0002] In printed wiring boards, solder resist is sometimes provided as a permanent protective film for preventing solder from adhering to areas where solder is not required and for preventing the circuit board from corroding. As the solder resist, a photosensitive resin composition such as that described in Patent Document 1 is generally used. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2014-115672 A Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, with the further miniaturization and densification of wiring on printed wiring boards, it has become necessary to form smaller diameter via holes and fine wiring patterns with a narrow metal area, which requires high resolution. However, when the resolution is further improved, new problems have been discovered, such as the inorganic filler easily falling off the via hole wall and dropping to the bottom of the via hole in the smaller diameter via hole, resulting in a decrease in connection reliability, and the fact that not only the uncured parts but also the cured parts (parts that will become the insulating layer) are easily treated with chemicals, which increases the surface roughness of the insulating layer and makes it difficult to form fine patterns.

[0005] An object of the present invention is to provide a photosensitive resin composition which has superior resolution, can suppress the occurrence of connection defects in small-diameter via holes, and can form an insulating layer with smaller surface roughness. [Means for solving the problem]

[0006] As a result of intensive research, the present inventors have found that by using a photosensitive resin composition comprising (A) a resin containing a carboxyl group, (B) an α-aminoketone-based photopolymerization initiator having a fluorene skeleton, (C) an epoxy resin, (D) a photosensitizer, and (E) an inorganic filler, wherein the maximum absorption wavelength of the (D) photosensitizer is in the range of 350 nm to 400 nm, it is possible to achieve better resolution, suppress the occurrence of connection failures in reduced-diameter via holes, and form an insulating layer with smaller surface roughness, thereby completing the present invention.

[0007] That is, the present invention includes the following. [1] A photosensitive resin composition comprising: (A) a resin containing a carboxyl group; (B) an α-aminoketone-based photopolymerization initiator having a fluorene skeleton; (C) an epoxy resin; (D) a photosensitizer; and (E) an inorganic filler, A photosensitive resin composition, in which the component (D) has a maximum absorption wavelength of 350 nm to 400 nm. [2] The photosensitive resin composition according to the above [1], wherein the component (A) further contains an ethylenically unsaturated group. [3] The photosensitive resin composition according to the above [1] or [2], wherein the component (A) contains a resin selected from the group consisting of an acid-modified epoxy (meth)acrylate resin and an acid-containing (meth)acrylic (meth)acrylate resin. [4] The photosensitive resin composition according to any one of the above [1] to [3], wherein the acid value of the component (A) is 1 mgKOH / g or more. [5] The photosensitive resin composition according to any one of the above [1] to [4], wherein the weight average molecular weight of the component (A) is 1,000 to 20,000. [6] The component (B) is represented by the formula (1):

[0008] [ka]

[0009] [In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 each independently represents a hydrogen atom, a halogen atom, a nitro group, -R, -OR, -NR2, -SR, -SOR, -SOR, -COR, -OCOR, -COOR, or -CONR2; R each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, or an optionally substituted heterocyclic group; R 8 , and R 9 each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aralkyl group, or R 8 , and R 9 are joined together to form an optionally substituted non-aromatic carbocyclic ring; R a , and R b each independently represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aralkyl group which may have a substituent, or R a , and R b are joined together to form an optionally substituted non-aromatic carbocyclic ring; R c , and R d each independently represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aralkyl group which may have a substituent, or R c , and R dare bonded together to form a nitrogen-containing heterocycle which may have a substituent. The photosensitive resin composition according to any one of the above [1] to [5], comprising a compound represented by the following formula: [7] The photosensitive resin composition according to any one of the above [1] to [6], wherein a mass ratio of the component (B) to the component (A) (component (B) / component (A)) is 1 to 30. [8] The photosensitive resin composition according to any one of the above [1] to [7], wherein the component (C) contains an epoxy resin having a skeleton selected from a naphthalene skeleton and a biphenyl skeleton. [9] The photosensitive resin composition according to any one of the above [1] to [8], wherein the lowest excited triplet energy level of the component (D) is 60 kcal / mol to 65 kcal / mol.

[10] The photosensitive resin composition according to any one of the above [1] to [9], wherein the component (E) contains an inorganic filler that has been surface-treated with an amino-silane coupling agent.

[11] The photosensitive resin composition according to any one of the above [1] to

[10] , wherein the content of the component (E) is 10 mass% or more, based on 100 mass% of the total solid content in the photosensitive resin composition.

[12] The photosensitive resin composition according to any one of the above [1] to

[11] , which is for forming a solder resist.

[13] A photosensitive film with a support, comprising: a support; and a photosensitive resin composition layer formed on the support from the photosensitive resin composition according to any one of [1] to

[12] above.

[14] The photosensitive film according to the above

[13] , wherein the photosensitive resin composition layer has a thickness in the range of 20 μm to 100 μm.

[15] A printed wiring board comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of the above [1] to

[12] .

[16] A semiconductor device comprising the printed wiring board according to

[15] above. Effect of the Invention

[0010] According to the present invention, it is possible to provide a photosensitive resin composition which has superior resolution, can suppress the occurrence of connection failures in small-diameter via holes, and can form an insulating layer with smaller surface roughness. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention will be described in detail below with reference to preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be modified and implemented as desired without departing from the scope of the claims of the present invention and their equivalents.

[0012] <Photosensitive resin composition> The photosensitive resin composition of the present invention contains (A) a resin containing a carboxyl group, (B) an α-aminoketone-based photopolymerization initiator having a fluorene skeleton, (C) an epoxy resin, (D) a photosensitizer, and (E) an inorganic filler, and the maximum absorption wavelength of the photosensitizer (D) is 350 nm to 400 nm. Such a photosensitive resin composition has superior resolution, can suppress the occurrence of connection failures in small-diameter via holes, and can form an insulating layer with smaller surface roughness.

[0013] The photosensitive resin composition of the present invention may further contain optional components in addition to (A) a resin containing a carboxyl group, (B) an α-aminoketone-based photopolymerization initiator having a fluorene skeleton, (C) an epoxy resin, (D) a photosensitizer, and (E) an inorganic filler. Examples of the optional components include (F) a reactive diluent, (G) an organic solvent, and (H) other additives. Each component contained in the resin composition will be described in detail below.

[0014] <(A) Resin containing a carboxyl group> The photosensitive resin composition of the present invention contains (A) a resin containing a carboxyl group. The photosensitive resin composition containing (A) a resin containing a carboxyl group is soluble in an alkaline developer (e.g., a 1% by mass aqueous solution of sodium carbonate). The number of carboxyl groups per molecule of (A) the resin containing a carboxyl group may be one or two or more.

[0015] (A) The resin containing a carboxyl group preferably further contains an ethylenically unsaturated group. The ethylenically unsaturated group has a carbon-carbon double bond, and examples thereof include a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimide group, an acryloyl group, and a methacryloyl group. From the viewpoint of the reactivity of photoradical polymerization, a (meth)acryloyl group is preferable. (A) The resin containing a carboxyl group is capable of photoradical polymerization when it contains an ethylenically unsaturated group. (A) The number of ethylenically unsaturated groups per molecule of the resin containing a carboxyl group may be one or may be two or more. In addition, when the resin containing a carboxyl group (A) contains two or more ethylenically unsaturated groups per molecule, the ethylenically unsaturated groups may be the same or different.

[0016] The (A) carboxyl group-containing resin is preferably a resin that has both an ethylenically unsaturated group and a carboxyl group, and that allows photoradical polymerization and alkali development.

[0017] In one embodiment, the (A) resin containing a carboxyl group preferably includes a resin having a skeleton selected from a naphthalene skeleton and a biphenyl skeleton, more preferably includes a resin having a naphthalene skeleton, and particularly preferably includes a resin having a naphthol aralkyl skeleton.

[0018] The (A) resin containing a carboxyl group preferably contains a resin selected from an acid-modified epoxy (meth)acrylate resin and an acid-containing (meth)acrylic (meth)acrylate resin, and more preferably contains an acid-modified epoxy (meth)acrylate resin.

[0019] (Acid-modified epoxy (meth)acrylate resin) The acid-modified epoxy (meth)acrylate resin can be produced by using an epoxy (meth)acrylate resin, for example, by reacting an epoxy resin with acrylic acid or methacrylic acid.

[0020] The epoxy resin for producing the epoxy (meth)acrylate resin is not particularly limited as long as it is a compound having an epoxy group in the molecule, and examples thereof include bisphenol type epoxy resins such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, bisphenol S type epoxy resin, and modified bisphenol F type epoxy resin obtained by reacting bisphenol F type epoxy resin with epichlorohydrin to modify it to have three or more functionalities; biphenol type epoxy resins such as biphenol type epoxy resin and tetramethylbiphenol type; novolac type epoxy resins such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type novolac type epoxy resin, and alkylphenol novolac type epoxy resin; fluorine-containing epoxy resins such as bisphenol AF type epoxy resin and perfluoroalkyl type epoxy resin; naphthalene type epoxy resin, dihydroxynaphthalene type epoxy resin, polyhydroxybinaphthalene type epoxy resin, naphthol type epoxy resin, naphthol aralkyl type epoxy resin. epoxy resins having a naphthalene skeleton (epoxy resins containing a naphthalene skeleton), such as epoxy resins, binaphthol type epoxy resins, naphthylene ether type epoxy resins, naphthol novolac type epoxy resins, and naphthalene type epoxy resins obtained by the condensation reaction of polyhydroxynaphthalene with aldehydes; bixylenol type epoxy resins; dicyclopentadiene type epoxy resins; trisphenol type epoxy resins; tert-butyl-catechol type epoxy resins; epoxy resins containing a condensed ring skeleton, such as anthracene type epoxy resins; glycidylamine type epoxy resins Examples of epoxy resins that can be used include epoxy resins; glycidyl ester type epoxy resins; biphenyl type epoxy resins; linear aliphatic epoxy resins; epoxy resins having a butadiene structure; alicyclic epoxy resins; heterocyclic epoxy resins; spiro ring-containing epoxy resins; cyclohexanedimethanol type epoxy resins; trimethylol type epoxy resins; tetraphenylethane type epoxy resins; glycidyl group-containing acrylic resins such as polyglycidyl (meth)acrylate and copolymers of glycidyl methacrylate and acrylic esters; fluorene type epoxy resins; and halogenated epoxy resins.

[0021] The epoxy resin for producing the epoxy (meth)acrylate resin is preferably an epoxy resin containing an aromatic skeleton from the viewpoint of decreasing the average linear thermal expansion coefficient. Here, the aromatic skeleton is a concept including polycyclic aromatics and aromatic heterocycles. Among them, any of cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, and naphthol aralkyl type epoxy resin is preferable.

[0022] In one embodiment, the acid-modified epoxy (meth)acrylate resin preferably contains an acid-modified epoxy (meth)acrylate resin having a skeleton selected from a naphthalene skeleton and a biphenyl skeleton, and particularly preferably contains an acid-modified epoxy (meth)acrylate resin having a naphthalene skeleton.

[0023] It is particularly preferable that the acid-modified epoxy (meth)acrylate resin contains a resin selected from an acid-modified epoxy (meth)acrylate resin in which a hydroxyl group of an epoxy (meth)acrylate resin has been esterified (hereinafter referred to as an "ester-type acid-modified epoxy (meth)acrylate resin"), and an acid-modified epoxy (meth)acrylate resin in which a hydroxyl group of an epoxy (meth)acrylate resin has been urethanized (hereinafter referred to as a "urethane-type acid-modified epoxy (meth)acrylate resin").

[0024] (Ester-type acid-modified epoxy (meth)acrylate resin) The ester-type acid-modified epoxy (meth)acrylate resin can be produced, for example, by reacting an epoxy (meth)acrylate resin with a polyvalent carboxylic acid anhydride.

[0025] Examples of polyvalent carboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride, and these may be used alone or in combination of two or more. Among these, succinic anhydride and tetrahydrophthalic anhydride are preferred, and tetrahydrophthalic anhydride is more preferred.

[0026] The ester-type acid-modified epoxy (meth)acrylate resin preferably contains a resin selected from a cresol novolac skeleton-containing ester-type acid-modified epoxy (meth)acrylate resin, a bisphenol A skeleton-containing ester-type acid-modified epoxy (meth)acrylate resin, a bisphenol F skeleton-containing ester-type acid-modified epoxy (meth)acrylate resin, a biphenyl skeleton-containing acid ester-type modified epoxy (meth)acrylate resin, and a naphthol aralkyl skeleton-containing ester-type acid-modified epoxy (meth)acrylate resin.

[0027] The ester-type acid-modified epoxy (meth)acrylate resin can be synthesized by a known method, but a commercially available product may also be used. Specific examples of commercially available products include "CCR-1373H" (cresol novolac skeleton-containing acid-modified epoxy acrylate), "ZCR-8001H" (biphenyl skeleton-containing acid-modified epoxy acrylate), "ZCR-1569H" (biphenyl skeleton-containing acid-modified epoxy acrylate), "CCR-1171H" (cresol novolac skeleton-containing acid-modified epoxy acrylate), "ZCR-1797H" (biphenyl skeleton-containing acid-modified epoxy acrylate), "ZAR-2000" (bisphenol A skeleton-containing acid-modified epoxy acrylate resin), "ZFR-1491H", "ZFR-1533H" (bisphenol F skeleton-containing acid-modified epoxy acrylate resin), "PR-300CP" (cresol novolac skeleton-containing acid-modified epoxy acrylate resin), and "CCR-1179" (cresol novolac skeleton-containing epoxy acrylate resin), all manufactured by Nippon Kayaku Co., Ltd. These may be used alone or in combination of two or more.

[0028] (Urethane-type acid-modified epoxy (meth)acrylate resin) The urethane-type acid-modified epoxy (meth)acrylate resin can be produced, for example, by reacting an epoxy (meth)acrylate resin with a diisocyanate compound and a carboxy group-containing diol compound.

[0029] Examples of the diisocyanate compound include aromatic diisocyanate compounds such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenyl diisocyanate, and naphthalene diisocyanate; and aliphatic diisocyanate compounds such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, allylene sulfone ether diisocyanate, allyl cyanide diisocyanate, N-acyl diisocyanate, trimethylhexamethylene diisocyanate, and 1,3-bis(isocyanate methyl)cyclohexane.

[0030] Examples of the carboxy group-containing diol compound include dimethylolpropionic acid, dimethylolbutanoic acid, and dimethylolnonanoic acid.

[0031] The urethane-type acid-modified epoxy (meth)acrylate resin preferably contains a resin selected from a cresol novolac skeleton-containing urethane-type acid-modified epoxy (meth)acrylate resin, a bisphenol A skeleton-containing urethane-type acid-modified epoxy (meth)acrylate resin, a bisphenol F skeleton-containing urethane-type acid-modified epoxy (meth)acrylate resin, a biphenyl skeleton-containing acid urethane-type modified epoxy (meth)acrylate resin, and a naphthol aralkyl skeleton-containing urethane-type acid-modified epoxy (meth)acrylate resin.

[0032] The urethane-type acid-modified epoxy (meth)acrylate resin can be synthesized by a known synthesis method, but a commercially available product may also be used. Examples of known synthesis methods include the method described in JP 2016-199719 A. Specific examples of commercially available products include "UXE-3024", "UXE-3011", "UXE-3012", and "UXE-3024" manufactured by Nippon Kayaku Co., Ltd.

[0033] (Acid-containing (meth)acrylic (meth)acrylate resin) The acid-containing (meth)acrylic (meth)acrylate resin can be produced by reacting a portion of the carboxy groups contained in a polymer of (meth)acrylic acid and a (meth)acrylic acid ester with glycidyl (meth)acrylate.

[0034] Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, Monofunctional (meth)acrylates such as lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, and benzyl (meth)acrylate; ethylene glycol di(meth)acrylate, Polyfunctional (meth)acrylates such as bisphenol A di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and ethoxylated bisphenol A di(meth)acrylate.

[0035] Furthermore, the polymer of (meth)acrylic acid and (meth)acrylic acid ester to be reacted with glycidyl (meth)acrylate may contain other structural units derived from styrene, etc., in addition to structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylic acid ester.

[0036] From the viewpoint of improving the alkaline developability of the photosensitive resin composition, the acid value of the (A) carboxyl group-containing resin is preferably 0.1 mgKOH / g or more, more preferably 0.5 mgKOH / g or more, even more preferably 1 mgKOH / g or more, 10 mgKOH / g or more, even more preferably 20 mgKOH / g or more, 30 mgKOH / g or more, particularly preferably 40 mgKOH / g or more, 50 mgKOH / g or more. From the viewpoint of improving the insulation reliability, the upper limit of the acid value of the (A) carboxyl group-containing resin is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, even more preferably 120 mgKOH / g or less, particularly preferably 100 mgKOH / g or less.

[0037] The weight average molecular weight of the (A) carboxyl group-containing resin is preferably not more than 20000, more preferably not more than 17000, and even more preferably not more than 15000. The lower limit of the weight average molecular weight of the (A) carboxyl group-containing resin is preferably not less than 1000, and more preferably not less than 1500. The weight average molecular weight is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

[0038] The content of the (A) carboxyl group-containing resin is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and particularly preferably 15% by mass or more, from the viewpoint of improving alkali developability, when the non-volatile components of the photosensitive resin composition are taken as 100% by mass. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 40% by mass or less, from the viewpoint of improving heat resistance.

[0039] <(B) α-Aminoketone-based photopolymerization initiator having a fluorene skeleton> The photosensitive resin composition of the present invention contains (B) an α-aminoketone-based photopolymerization initiator having a fluorene skeleton.

[0040] In one embodiment, the α-aminoketone-based photopolymerization initiator having a fluorene skeleton (B) is preferably represented by the formula (1):

[0041] [ka]

[0042] [In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 each independently represents a hydrogen atom, a halogen atom, a nitro group, -R, -OR, -NR2, -SR, -SOR, -SOR, -COR, -OCOR, -COOR, or -CONR2; R each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, or an optionally substituted heterocyclic group; R 8 , and R 9 each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aralkyl group, or R 8 , and R 9 are joined together to form an optionally substituted non-aromatic carbocyclic ring; R a , and R b each independently represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aralkyl group which may have a substituent, or R a , and R b are joined together to form an optionally substituted non-aromatic carbocyclic ring; R c , and R deach independently represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aralkyl group which may have a substituent, or R c , and R d are bonded together to form a nitrogen-containing heterocycle which may have a substituent. The compound includes a compound represented by the formula:

[0043] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 each independently represents a hydrogen atom, a halogen atom, a nitro group, -R, -OR, -NR2, -SR, -SOR, -SOR, -COR, -OCOR, -COOR, or -CONR2; in one embodiment, preferably a hydrogen atom, a halogen atom, a nitro group, -R, -OR, -NR2, -SR, or -COR; more preferably, R 1 , R 3 , R 4 , R 5 , R 6 , and R 7 is a hydrogen atom, and R 2 is a hydrogen atom, a halogen atom, a nitro group, -R, -OR, -NR2, -SR, or -COR; particularly preferably a hydrogen atom.

[0044] Each R independently represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or a heterocyclic group which may have a substituent.

[0045] The alkyl group refers to a linear, branched and / or cyclic monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, the alkyl group is preferably an alkyl group having 1 to 14 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a sec-pentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group, an isooctyl group, a tert-octyl group, a cyclopentyl group, a cyclohexyl group, and a cyclohexylmethyl group.

[0046] The term "alkenyl group" refers to a linear, branched and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. Unless otherwise specified, the alkenyl group is preferably an alkenyl group having 2 to 14 carbon atoms, more preferably an alkenyl group having 2 to 10 carbon atoms, and even more preferably an alkenyl group having 2 to 6 carbon atoms. Examples of alkenyl (groups) include vinyl groups, propenyl groups (allyl groups, 1-propenyl groups, isopropenyl groups), butenyl groups (1-butenyl groups, crotyl groups, methallyl groups, isocrotyl groups, etc.), pentenyl groups (1-pentenyl groups, etc.), hexenyl groups (1-hexenyl groups, etc.), heptenyl groups (1-heptenyl groups, etc.), octenyl groups (1-octenyl groups, etc.), cyclopentenyl groups (2-cyclopentenyl groups, etc.), and cyclohexenyl groups (3-cyclohexenyl groups, etc.).

[0047] The aryl group refers to a monovalent aromatic hydrocarbon group formed by removing one hydrogen atom from an aromatic carbon ring. Unless otherwise specified, the aryl group is preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

[0048] The aralkyl group refers to an alkyl group substituted with one or more (preferably one) aryl groups. Unless otherwise specified, the aralkyl group is preferably an aralkyl group having 7 to 15 carbon atoms, and more preferably an aralkyl group having 7 to 11 carbon atoms. Examples of the aralkyl group include a benzyl group, a phenethyl group, a hydrocinnamyl group, an α-methylbenzyl group, an α-cumyl group, a 1-naphthylmethyl group, and a 2-naphthylmethyl group.

[0049] The heterocyclic group is a monovalent cyclic group obtained by removing one hydrogen atom from a heterocycle having heteroatoms such as oxygen, nitrogen, and sulfur atoms as ring constituent atoms in addition to carbon atoms. The heterocyclic group is preferably a 4- to 15-membered heterocyclic group, and more preferably a 5- to 10-membered heterocyclic group. The heterocyclic group may be an aromatic heterocyclic group according to the Huckel rule in which the number of electrons contained in the π electron system on the ring is 4p+2 (p is a natural number), or a non-aromatic heterocyclic group other than an aromatic heterocyclic group in which the entire ring does not have aromaticity, but in one embodiment, a non-aromatic heterocyclic group is preferred. Examples of the heterocyclic group include a pyrrolidinyl group (such as an N-pyrrolidinyl group), a pyrazolidinyl group (such as an N-pyrazolidinyl group), an imidazolidinyl group (such as an N-imidazolidinyl group), a piperidinyl group (such as an N-piperidinyl group), a morpholinyl group (such as an N-morpholinyl group), and a thiomorpholinyl group (such as an N-thiomorpholinyl group).

[0050] The "substituents" of the alkyl group and the alkenyl group are not particularly limited, and examples thereof include a halogen atom, a nitro group, an amino group, a hydroxy group, an aryl group, an alkyl-aryl group (an aryl group substituted with one or more alkyl groups), an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, an alkyl-carbonyl group, an alkenyl-carbonyl group, an aryl-carbonyl group, an aralkyl-carbonyl group, an alkyl-oxy-carbonyl group, an alkenyl-oxy-carbonyl group, an aryl-oxy-carbonyl group, an aralkyl-oxy-carbonyl group, an alkyl-carbonyl-oxy group, an alkenyl-carbonyl-oxy group, an aryl-carbonyl-oxy group, an aralkyl-carbonyl-oxy group, a mono- or di(alkyl)amino group, a mono- or di(alkenyl)amino group, a heterocyclic group, and the like.

[0051] The "substituents" of the aryl group, aralkyl group, and heterocyclic group are not particularly limited, and examples thereof include a halogen atom, a nitro group, an amino group, a hydroxy group, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-aryl group, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, an alkyl-carbonyl group, an alkenyl-carbonyl group, an aryl-carbonyl group, an aralkyl-carbonyl group, an alkyl-oxy-carbonyl group, an alkenyl-oxy-carbonyl group, an aryl-oxy-carbonyl group, an aralkyl-oxy-carbonyl group, an alkyl-carbonyl-oxy group, an alkenyl-carbonyl-oxy group, an aryl-carbonyl-oxy group, an aralkyl-carbonyl-oxy group, a mono- or di(alkyl)amino group, a mono- or di(alkenyl)amino group, and a heterocyclic group.

[0052] In one embodiment, R is each independently preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent; more preferably, (1) an alkyl group which may be substituted with a group selected from a halogen atom, a nitro group, a hydroxy group, an aryl group, an alkyl-aryl group, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, a mono- or di(alkyl)amino group, and a heterocyclic group; (2) an aryl group which may be substituted with a group selected from a halogen atom, a nitro group, a hydroxy group, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-aryl group, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, a mono- or di(alkyl)amino group, and a heterocyclic group; or ( 3) a heterocyclic group optionally substituted with a group selected from a halogen atom, a nitro group, a hydroxy group, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-aryl group, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, a mono- or di-(alkyl)amino group, and a heterocyclic group; particularly preferred is (1) an alkyl group optionally substituted with a group selected from a nitro group, a hydroxy group, an alkyl-oxy group, a mono- or di-(alkyl)amino group, and a heterocyclic group, (2) an aryl group optionally substituted with a group selected from a nitro group, an alkyl group, an alkyl-oxy group, a mono- or di-(alkyl)amino group, and a heterocyclic group, or (3) a heterocyclic group optionally substituted with a group selected from a nitro group, an alkyl group, an alkyl-oxy group, a mono- or di-(alkyl)amino group, and a heterocyclic group.

[0053] R 8 , and R 9 each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aralkyl group, or R 8 , and R 9 are linked together to form a non-aromatic carbocyclic ring which may be substituted.

[0054] A non-aromatic carbocycle means a carbocycle that does not have aromaticity in the entire ring. A non-aromatic carbocycle has only carbon atoms as ring constituent atoms. A non-aromatic carbocycle may be a saturated carbocycle consisting of only single bonds, or an unsaturated carbocycle having at least one of a double bond and a triple bond. A non-aromatic carbocycle also includes a fused ring having aromaticity in a part formed by condensing a non-aromatic ring with an aromatic ring. A non-aromatic carbocycle is preferably a non-aromatic carbocycle having 4 to 20 carbon atoms, more preferably a non-aromatic carbocycle having 5 to 12 carbon atoms. Specific preferred examples of the non-aromatic carbocyclic ring include monocyclic saturated carbocyclic rings such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, and a cyclododecane ring; bicyclic saturated carbocyclic rings such as a bicyclo[2.2.1]heptane ring (norbornane ring), a bicyclo[4.4.0]decane ring (decalin ring), a bicyclo[5.3.0]decane ring, a bicyclo[4.3.0]nonane ring (hydrindane ring), a bicyclo[3.2.1]octane ring, a bicyclo[5.4.0]undecane ring, a bicyclo[3.3.0]octane ring, and a bicyclo[3.3.1]nonane ring; 2,6 ] Decane ring (tetrahydrodicyclopentadiene ring), tricyclo[3.3.1.1 3,7 ]Decane ring (adamantane ring), tricyclo[6.2.1.0 2,7 ]undecane ring and other tricyclic saturated carbocyclic rings; tetracyclo[6.2.1.1 3,6 .0 2,7 ]dodecane ring and other saturated tetracyclic carbocyclic rings; pentacyclo[9.2.1.1 4,7 .0 2,1 .0 3,8 ]Pentadecane ring, pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 ]Pentadecane ring (tetrahydrotricyclopentadiene ring) and other saturated five-ring carbon rings are also included.

[0055] The "substituents" of the non-aromatic carbocyclic ring include the same as the "substituents" of the aryl group, aralkyl group and heterocyclic group exemplified above.

[0056] R 8 , and R 9 In one embodiment, each independently is preferably a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted alkenyl group; 8 , and R 9 are bonded together to form a monocyclic saturated carbocyclic ring which may have a substituent; more preferably, (1) a hydrogen atom, (2) an alkyl group which may be substituted with a group selected from a halogen atom, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, and a mono- or di(alkyl)amino group, or (3) an alkenyl group which may be substituted with a group selected from a halogen atom, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, and a mono- or di(alkyl)amino group, or R 8 , and R 9 are bonded together to form a cyclopentane ring or a cyclohexane ring; more preferably, they are a hydrogen atom, an alkyl group, or an alkenyl group; even more preferably, they are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and particularly preferably, they are a propyl group, a butyl group, or a pentyl group.

[0057] R a , and R b each independently represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aralkyl group which may have a substituent, or R a , and R b are linked together to form a non-aromatic carbocyclic ring which may be substituted.

[0058] R a , and R b In one embodiment, each independently is preferably an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aralkyl group which may have a substituent; a , and R bare bonded together to form a monocyclic saturated carbocyclic ring which may have a substituent; more preferably, (1) an alkyl group which may be substituted with a group selected from a halogen atom, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, and a mono- or di(alkyl)amino group, (2) an alkenyl group which may be substituted with a group selected from a halogen atom, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, and a mono- or di(alkyl)amino group, or (3) an aralkyl group which may be substituted with a group selected from a halogen atom, an alkyl group, an alkenyl group, an alkyl-oxy group, an alkenyl-oxy group, an aryl-oxy group, an aralkyl-oxy group, and a mono- or di(alkyl)amino group, or R a , and R b are bonded together to form a cyclopentane ring or a cyclohexane ring; more preferably, (1) an alkyl group, (2) an alkenyl group, or (3) an aralkyl group which may be substituted with an alkyl group; even more preferably, an alkyl group having 1 to 6 carbon atoms; and particularly preferably, a methyl group or an ethyl group.

[0059] R c , and R d each independently represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aralkyl group which may have a substituent, or R c , and R d are bonded together to form a nitrogen-containing heterocycle which may have a substituent.

[0060] The nitrogen-containing heterocycle means a heterocycle having at least carbon and nitrogen atoms as ring-constituting atoms, and may further have heteroatoms other than nitrogen atoms, such as oxygen and sulfur atoms, as ring-constituting atoms. The nitrogen-containing heterocycle may be a nitrogen-containing aromatic heterocycle according to Huckel's rule in which the number of electrons contained in the π electron system on the ring is 4p+2 (p is a natural number), or a nitrogen-containing non-aromatic heterocycle in which the entire ring does not have aromaticity, but in one embodiment, a nitrogen-containing non-aromatic heterocycle is preferred. The nitrogen-containing heterocycle may be a monocyclic nitrogen-containing heterocycle, a bicyclic nitrogen-containing heterocycle, or a tricyclic nitrogen-containing heterocycle, but in one embodiment, a monocyclic nitrogen-containing heterocycle is preferred. In one embodiment, the nitrogen-containing heterocycle is preferably 3 to 14 members, more preferably 4 to 10 members, and even more preferably 5 or 6 members. Examples of the nitrogen-containing heterocycle include a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, an oxazolidine ring, a piperidine ring, a morpholine ring, and a thiomorpholine ring.

[0061] The "substituents" of the nitrogen-containing heterocycle include the same as the "substituents" of the aryl group, aralkyl group and heterocyclic group exemplified above.

[0062] R c , and R d In one embodiment, each independently preferably represents an alkyl group which may have a substituent, or R c , and R d are bonded together to form a nitrogen-containing non-aromatic heterocycle which may have a substituent; more preferably, R is an alkyl group having 1 to 6 carbon atoms, or c , and R d are joined together to form a 5- or 6-membered nitrogen-containing non-aromatic heterocycle; more preferably, R c , and R d are joined together to form a 5- or 6-membered nitrogen-containing non-aromatic heterocycle; particularly preferably, R c , and R d are joined together to form a morpholine ring.

[0063] In one embodiment, the α-aminoketone-based photopolymerization initiator having a fluorene skeleton (B) is particularly preferably represented by the formulas (2-1) to (2-7):

[0064] [ka]

[0065] [Each symbol is as defined above.] Among them, it is particularly preferable to contain a compound represented by formula (2-1).

[0066] Specific examples of the α-aminoketone photopolymerization initiator having a fluorene skeleton (B) include, but are not limited to, those of the formulae (3-1) to (3-116):

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] [ka]

[0073] Examples of the compound include compounds represented by the following formula:

[0074] The upper limit of the molecular weight of (B) the α-aminoketone photopolymerization initiator having a fluorene skeleton is not particularly limited, but is preferably 3,000 or less, more preferably 2,000 or less, further preferably 1,000 or less, and particularly preferably 500 or less.

[0075] (B) α-aminoketone-based photopolymerization initiator having a fluorene skeleton can be easily synthesized using a known synthesis method or a method similar thereto, but a commercially available product may also be used. (B) An example of a commercially available α-aminoketone-based photopolymerization initiator having a fluorene skeleton is "TR-NPI-20400" (a compound represented by formula (3-41)) from TRONLY.

[0076] The content of the (B) α-aminoketone-based photopolymerization initiator having a fluorene skeleton is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, based on 100% by mass of the non-volatile components of the photosensitive resin composition. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 7% by mass or less.

[0077] The mass ratio of the resin (A) containing a carboxyl group to the α-aminoketone-based photopolymerization initiator (B) having a fluorene skeleton (component (A) / component (B)) is preferably 0.5 or more, more preferably 1 or more, and even more preferably 3 or more. The upper limit is preferably 50 or less, and more preferably 30 or less.

[0078] <(C) Epoxy resin> The photosensitive resin composition of the present invention contains an epoxy resin (C). The epoxy resin (C) is a curable resin having an epoxy group.

[0079] Examples of the epoxy resin (C) include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, cresol novolac type epoxy resins, phenol aralkyl type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, tetraphenylethane type epoxy resins, isocyanurate type epoxy resins, and phenolphthalimidine type epoxy resins. The epoxy resin (C) may be used alone or in combination of two or more kinds.

[0080] The photosensitive resin composition of the present invention preferably contains, as the epoxy resin (C), an epoxy resin having two or more epoxy groups in one molecule. The proportion of the epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of the epoxy resin (C) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0081] The (C) epoxy resin includes an epoxy resin that is liquid at a temperature of 20° C. (hereinafter sometimes referred to as a "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20° C. (hereinafter sometimes referred to as a "solid epoxy resin"). The photosensitive resin composition of the present invention may contain only a liquid epoxy resin as the epoxy resin, or may contain only a solid epoxy resin, or may contain both a liquid epoxy resin and a solid epoxy resin, but it is particularly preferable that the photosensitive resin composition contains only a solid epoxy resin or both a liquid epoxy resin and a solid epoxy resin.

[0082] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0083] As the liquid epoxy resin, glycirol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane dimethanol type epoxy resin, cyclic aliphatic glycidyl ether, and epoxy resin having a butadiene structure are preferred.

[0084] Specific examples of liquid epoxy resins include "EX-992L" manufactured by Nagase ChemteX Corporation, "YX7400" manufactured by Mitsubishi Chemical Corporation, "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "828EL", "825", and "Epikote 828EL" manufactured by Mitsubishi Chemical Corporation, "850" (bisphenol A type epoxy resin) manufactured by DIC Corporation; and "jER807" manufactured by Mitsubishi Chemical Corporation. ","1750" (bisphenol F type epoxy resin); "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycirol type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L", "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA Corporation; "EP-4088S" manufactured by ADEKA Corporation (dicyclopentadiene type epoxy resin); "ZX1059" manufactured by Nippon Steel Chemical & Material Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagase ChemteX Co., Ltd. (glycidyl ester type epoxy resin); "EX-991L" manufactured by Nagase ChemteX Co., Ltd. (alkyleneoxy skeleton and butadiene skeleton-containing epoxy resin); "Celloxide 2021P" manufactured by Daicel Co., Ltd. (alicyclic epoxy resin with ester skeleton) epoxy resin); "PB-3600" manufactured by Daicel Corporation, "JP-100" and "JP-200" manufactured by Nippon Soda Co., Ltd. (epoxy resins having a butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resins) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EG-280" (fluorene structure-containing epoxy resin) manufactured by Osaka Gas Chemicals Co., Ltd.; and "EX-201" (cyclic aliphatic glycidyl ether) manufactured by Nagase ChemteX Corporation.

[0085] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

[0086] Preferred solid epoxy resins include bixylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, naphthol novolac type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, phenol aralkyl type epoxy resins, tetraphenylethane type epoxy resins, and phenolphthalimidine type epoxy resins.

[0087] Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC Corporation; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene type epoxy resins) manufactured by DIC Corporation; and "EXA-7311" manufactured by DIC Corporation. , "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN475V", "ESN4 100V" (naphthalene type epoxy resin); "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "Y Examples of epoxy resins include "X7700" (phenol aralkyl type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical; and "WHR991S" (phenolphthalimidine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.These may be used alone or in combination of two or more.

[0088] When a solid epoxy resin and a liquid epoxy resin are used in combination as the (C) epoxy resin, the mass ratio thereof (solid epoxy resin:liquid epoxy resin) is preferably 10:1 to 1:50, more preferably 5:1 to 1:20, and particularly preferably 2:1 to 1:10.

[0089] In one embodiment, the (C) epoxy resin preferably includes an epoxy resin having a skeleton selected from a naphthalene skeleton and a biphenyl skeleton, more preferably includes an epoxy resin having a naphthalene skeleton, and particularly preferably includes an epoxy resin having a naphthol aralkyl skeleton.

[0090] In one embodiment, it is particularly preferable that the (C) epoxy resin has the same backbone as the (A) resin containing a carboxyl group.

[0091] The epoxy equivalent of the (C) epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 2,000 g / eq., even more preferably 70 g / eq. to 1,000 g / eq., and even more preferably 80 g / eq. to 500 g / eq. The epoxy equivalent is the mass of the resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

[0092] The weight average molecular weight (Mw) of the epoxy resin (C) is preferably from 100 to 5,000, more preferably from 250 to 3,000, and further preferably from 400 to 1500. The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0093] The content of the (C) epoxy resin is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 7% by mass or more, from the viewpoint of further improving the mechanical strength and insulation reliability, when the non-volatile components of the photosensitive resin composition are taken as 100% by mass. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less.

[0094] The mass ratio of the resin (A) containing a carboxyl group to the epoxy resin (C) (component (A) / component (C)) is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1 or more. The upper limit is preferably 30 or less, more preferably 10 or less, and even more preferably 3 or less.

[0095] <(D) Photosensitizer> The photosensitive resin composition of the present invention contains a photosensitizer (D). By containing the photosensitizer (D), photocurability can be improved. The maximum absorption wavelength of the photosensitizer (D) in the photosensitive resin composition of the present invention is 350 nm to 400 nm. The lowest excited triplet energy level of the photosensitizer (D) in the photosensitive resin composition of the present invention is preferably 60 kcal / mol to 70 kcal / mol, more preferably 60 kcal / mol to 65 kcal / mol, and particularly preferably 60 kcal / mol to 63 kcal / mol.

[0096] Examples of the (D) photosensitizer include thioxanthones having an absorption wavelength maximum value of 350 nm to 400 nm, benzophenones having an absorption wavelength maximum value of 350 nm to 400 nm, etc. Specific examples of the (D) photosensitizer include 2-isopropylthioxanthone, 1-isopropylthioxanthone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.

[0097] The content of the (D) photosensitizer is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more, from the viewpoint of further improving the photocurability, when the non-volatile components of the photosensitive resin composition are taken as 100% by mass. The upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less.

[0098] <(E) Inorganic filler> The photosensitive resin composition of the present invention contains an inorganic filler (E). The inorganic filler (E) is contained in the resin composition in the form of particles.

[0099] (E) An inorganic compound is used as the material of the inorganic filler. (E) Examples of the material of the inorganic filler include silica, alumina, aluminosilicate, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In addition, spherical silica is preferable as the silica. The (E) inorganic filler may be used alone or in combination of two or more kinds in any ratio.

[0100] (E) Examples of commercially available inorganic fillers include "UFP-30" manufactured by Denka Chemical Industry Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Admatechs Co., Ltd.; "UFP-30" manufactured by Denka Company; "Silfill NSS-3N", "Silfill NSS-4N", and "Silfill NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "SC2300-SVJ", and "SC2050-SXF" manufactured by Admatechs Co., Ltd.; and "DAW-03" and "FB-105FD" manufactured by Denka Company, Ltd.

[0101] The average particle size of the (E) inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 2 μm or less, even more preferably 1 μm or less, and particularly preferably 0.7 μm or less. The lower limit of the average particle size of the (E) inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. The average particle size of the (E) inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction / scattering type particle size distribution measuring device, and the median diameter is taken as the average particle size. The measurement sample can be prepared by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing it by ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction type particle size distribution measuring device with blue and red light source wavelengths, and the particle size distribution of the inorganic filler on a volume basis was measured using a flow cell method, and the average particle size was calculated as the median diameter from the particle size distribution obtained. An example of a laser diffraction type particle size distribution measuring device is the "LA-960" manufactured by Horiba, Ltd.

[0102] The specific surface area of ​​the (E) inorganic filler is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, particularly preferably 3m 2 The upper limit of the specific surface area of ​​the (E) inorganic filler is not particularly limited, but is preferably 100 m 2 / g or less, more preferably 70m 2 / g or less, more preferably 50m 2 / g or less, particularly preferably 40m 2 The specific surface area of ​​the inorganic filler is obtained by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multipoint method.

[0103] The inorganic filler (E) is preferably surface-treated with an appropriate surface treatment agent, which can enhance the moisture resistance and dispersibility of the inorganic filler (E). Examples of the surface treatment agent include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy-based silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; styryl-based silane coupling agents such as p-styryltrimethoxysilane; methacryl-based silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; acrylic-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane; amino-based silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; isocyanurate-based silane coupling agents such as tris-(trimethoxysilylpropyl)isocyanurate; ureido-based silane coupling agents such as 3-ureidopropyltrialkoxysilane; mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatepropyltriethoxysilane; and acid anhydride-based silane coupling agents such as 3-trimethoxysilylpropylsuccinic anhydride.The surface treatment agent may be used alone or in combination of two or more kinds in any ratio.

[0104] It is more preferable that the (E) inorganic filler contains an inorganic filler that has been surface-treated with a surface treatment agent selected from a vinyl-based silane coupling agent and an amino-based silane coupling agent, and it is particularly preferable that the (E) inorganic filler contains an inorganic filler that has been surface-treated with an amino-based silane coupling agent.

[0105] Commercially available surface treatment agents include, for example, "KBM-1003" and "KBE-1003" (vinyl-based silane coupling agents), "KBM-303", "KBM-402", "KBM-403", "KBE-402", and "KBE-403" (epoxy-based silane coupling agents), "KBM-1403" (styryl-based silane coupling agents), "KBM-502", "KBM-503", "KBE-502", and "KBE-503" (methacrylic-based silane coupling agents), "KBM-5103" (acrylic-based silane coupling agents), "KBM-602", "KBM-603", "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM5783", and "KBM-575" (amino-based silane coupling agents), all of which are manufactured by Shin-Etsu Chemical Co., Ltd. coupling agents); "KBM-9659" (isocyanurate-based silane coupling agent); "KBE-585" (ureido-based silane coupling agent); "KBM-802", "KBM-803" (mercapto-based silane coupling agent); "KBE-9007N" (isocyanate-based silane coupling agent); "X-12-967C" (acid anhydride-based silane coupling agent); "KBM-13", "KBM-22", "KBM-103", "KBE-13", "KBE-22", "KBE-103", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" (alkylalkoxysilane compound), and the like.

[0106] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably within a predetermined range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% to 5% by mass of the surface treatment agent, more preferably 0.2% to 3% by mass, and even more preferably 0.3% to 2% by mass.

[0107] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler is set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2 On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in the form of a sheet, it is more preferable that the melt viscosity is 1.0 mg / m 2 Less than 0.8 mg / m is preferred. 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0108] (E) The amount of carbon per unit surface area of ​​the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, the "EMIA-320V" manufactured by Horiba, Ltd., or the like can be used.

[0109] The content of the (E) inorganic filler is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, particularly preferably 10% by mass or more, 20% by mass or more, or 30% by mass or more, from the viewpoint of suppressing the average linear thermal expansion coefficient lower, when the nonvolatile components in the photosensitive resin composition are taken as 100% by mass. The upper limit is, for example, preferably 70% by mass or less, more preferably 65% ​​by mass or less, particularly preferably 60% by mass or less, from the viewpoint of further improving the developability.

[0110] <(F) Reactive diluent> The photosensitive resin composition may further contain (F) a reactive diluent as an optional component. However, the components corresponding to (A) a resin containing a carboxyl group, (B) an α-aminoketone-based photopolymerization initiator having a fluorene skeleton, and (C) an epoxy resin are not included in the (F) reactive diluent. By including the (F) reactive diluent in the photosensitive resin composition, the photoreactivity can be improved. As the (F) component, for example, a photosensitive (meth)acrylate compound having one or more (meth)acryloyl groups in one molecule can be used. Room temperature refers to about 25°C. The (F) component may be used alone or in combination of two or more types.

[0111] Representative photosensitive (meth)acrylate compounds include, for example, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; mono- or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; acrylamides such as N,N-dimethylacrylamide and N-methylolacrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate; polyhydric alcohols such as trimethylolpropane, pentaerythritol, and dipentaerythritol, or polyhydric acrylates of their ethylene oxide, propylene oxide, or ε-caprolactone adducts; phenols such as phenoxy acrylate and phenoxyethyl acrylate, or acrylates such as their ethylene oxide or propylene oxide adducts; epoxy acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether, modified epoxy acrylates, melamine acrylates, and / or methacrylates corresponding to the above acrylates.Among these, polyvalent acrylates or polyvalent methacrylates are preferred. For example, trivalent acrylates or methacrylates include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane EO-added tri(meth)acrylate, glycerin PO-added tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetrafurfuryl alcohol oligo(meth)acrylate, ethyl carbitol oligo(meth)acrylate, 1,4-butanediol oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate, trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, Examples of the photosensitive (meth)acrylate compounds include hexa(meth)acrylate and (meth)acrylic acid ester of N,N,N',N'-tetrakis(β-hydroxyethyl)ethyldiamine, and examples of the acrylates or methacrylates having a valence of three or more include phosphoric acid triester (meth)acrylates such as tri(2-(meth)acryloyloxyethyl)phosphate, tri(2-(meth)acryloyloxypropyl)phosphate, tri(3-(meth)acryloyloxypropyl)phosphate, tri(3-(meth)acryloyl-2-hydroxyloxypropyl)phosphate, di(3-(meth)acryloyl-2-hydroxyloxypropyl)(2-(meth)acryloyloxyethyl)phosphate, and (3-(meth)acryloyl-2-hydroxyloxypropyl)di(2-(meth)acryloyloxyethyl)phosphate. These photosensitive (meth)acrylate compounds may be used alone or in combination of two or more. "EO" refers to ethylene oxide.

[0112] (F) The reactive diluent may be a commercially available product, such as "DPHA" manufactured by Nippon Kayaku Co., Ltd. or "EBECRYL3708" manufactured by Daicel Allnex Corporation.

[0113] The content of the (F) reactive diluent, assuming that the non-volatile components in the photosensitive resin composition are 100 mass%, from the viewpoint of promoting photocuring, is preferably 1 mass% or more, more preferably 3 mass% or more, even more preferably 5 mass% or more, particularly preferably 7 mass% or more, and is preferably 40 mass% or less, more preferably 35 mass% or less, even more preferably 30 mass% or less, particularly preferably 25 mass% or less, or 20 mass% or less.

[0114] <(G) Organic solvent> The photosensitive resin composition may further contain an organic solvent (G) as an optional component. The varnish viscosity can be adjusted by including the component (G). Examples of the organic solvent (G) include ketones such as methyl ethyl ketone (MEK) and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, and ethyl diglycol acetate, aliphatic hydrocarbons such as octane and decane, and petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These may be used alone or in combination of two or more. The content of the organic solvent when used may be appropriately adjusted from the viewpoint of the coatability of the photosensitive resin composition.

[0115] The content of the (G) organic solvent is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less, when the total amount of all components in the photosensitive resin composition is 100% by mass. The lower limit of the content may be 1% by mass or more, 10% by mass or more, etc.

[0116] <(H) Other Additives> The photosensitive resin composition may further contain (H) other additives to the extent that the object of the present invention is not hindered. Examples of (H) other additives include other photopolymerization initiators, thermoplastic resins, organic fillers, fine particles such as melamine and organic bentonite, colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black, polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol, thickeners such as bentone and montmorillonite, silicone-based, fluorine-based, and vinyl resin-based defoamers, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus-based compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters, and thermosetting resins such as phenol-based curing agents and cyanate ester-based curing agents.

[0117] <Method for producing photosensitive resin composition> The photosensitive resin composition of the present invention can be produced by appropriately mixing the respective components and, if necessary, kneading or stirring the mixture with a kneading means such as a triple roll mill, a ball mill, a bead mill or a sand mill, or a stirring means such as a super mixer, a planetary mixer or a high-speed rotary mixer.

[0118] <Physical Properties of Photosensitive Resin Composition> The photosensitive resin composition of the present invention has the characteristics of having superior resolution, being able to suppress the occurrence of connection defects in small-diameter via holes, and being able to form an insulating layer with smaller surface roughness.

[0119] The photosensitive resin composition of the present invention has a better resolution, and therefore, in one embodiment, it may have a feature that the minimum opening diameter (minimum via diameter) of the via hole that can be formed when exposed and developed is smaller. Therefore, in one embodiment, the minimum opening diameter when observed as in the following Test Example 2 may be preferably 100 μm or less, more preferably 80 μm or less, even more preferably 60 μm or less, and particularly preferably less than 50 μm. The lower limit is not particularly limited, but may be 1 μm or more, for example.

[0120] The photosensitive resin composition of the present invention may be characterized in that the inorganic filler is less exposed on the wall surface of the via hole after the roughening treatment and is smoother when evaluated in the following Test Example 2. The photosensitive resin composition of the present invention may be characterized in that the inorganic filler is less exposed on the resist surface at the top of the via hole after the roughening treatment and is smoother when evaluated in the following Test Example 2. The photosensitive resin composition of the present invention may be characterized in that the inorganic filler is not dropped off at the bottom of the via hole after the roughening treatment when evaluated in the following Test Example 2.

[0121] In one embodiment, the photosensitive resin composition of the present invention can form a via hole with less undercut, i.e., a via hole with a shape in which the difference between the radius of the top and the radius of the bottom is smaller or no difference, when exposed to light and developed. Therefore, in one embodiment, as in the following Test Example 2, a via hole with an opening diameter of 50 μm is formed, and the radius (μm) of the top of the cross section and the radius (μm) of the bottom are measured by SEM, and the undercut obtained by calculating the difference between the radius of the top and the radius of the bottom (radius of the top - radius of the bottom) is preferably 15 μm or less, more preferably 10 μm or less, even more preferably 6 μm or less, even more preferably less than 3 μm, and particularly preferably no undercut (0 μm). The evaluation of the undercut can be measured according to the method described in the Examples below.

[0122] In one embodiment, the cured product of the photosensitive resin composition of the present invention may have a higher peel strength (peel strength / adhesion) between the cured product and a copper-plated conductor layer. Thus, in one embodiment, the peel strength between the cured product of the photosensitive resin composition of the present invention and a copper-plated conductor layer, as measured in the following Test Example 4, may be preferably 0.3 kgf / cm or more. The upper limit of the peel strength is not particularly limited, but may be, for example, 10 kgf / cm or less.

[0123] In one embodiment, the cured product of the photosensitive resin composition of the present invention may have a characteristic that the arithmetic mean roughness (Ra) after roughening treatment is lower. Therefore, in one embodiment, the arithmetic mean roughness (Ra) of the cured product of the photosensitive resin composition of the present invention, as measured in the following Test Example 3, is preferably 400 nm or less, more preferably 300 nm or less, and even more preferably less than 200 nm. The lower limit is not particularly limited, but may be 1 nm or more, for example.

[0124] In one embodiment, the cured product of the photosensitive resin composition of the present invention may have a characteristic of having a lower average coefficient of linear thermal expansion (CTE). Thus, in one embodiment, the average coefficient of linear thermal expansion (CTE) of the cured product of the photosensitive resin composition of the present invention, as measured in the following Test Example 1, is preferably 100 ppm or less, more preferably 60 ppm or less, even more preferably 50 ppm or less, and particularly preferably less than 40 ppm. The lower limit is not particularly limited, but may be 10 ppm or more, for example.

[0125] <Applications of photosensitive resin composition> The use of the photosensitive resin composition of the present invention is not particularly limited, but it can be used in a wide range of applications requiring a photosensitive resin composition, such as a photosensitive film with a support, an insulating resin sheet such as a prepreg, a circuit board (for laminate boards, for multilayer printed wiring boards, etc.), a solder resist, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, a component embedding resin, etc. Among them, it can be suitably used as a photosensitive resin composition for an insulating layer of a printed wiring board (a printed wiring board in which a cured product of a photosensitive resin composition is used as an insulating layer), a photosensitive resin composition for an interlayer insulating layer (a printed wiring board in which a cured product of a photosensitive resin composition is used as an interlayer insulating layer (interlayer insulating material)), a photosensitive resin composition for plating formation (a printed wiring board in which plating is formed on a cured product of a photosensitive resin composition), and a photosensitive resin composition for forming a solder resist (a printed wiring board in which a cured product of a photosensitive resin composition is used as a solder resist).

[0126] <Photosensitive film with support> The photosensitive resin composition of the present invention can be suitably used in the form of a supported photosensitive film in which a photosensitive resin composition layer is formed on a support. That is, the supported photosensitive film includes a support and a photosensitive resin composition layer formed of the photosensitive resin composition of the present invention provided on the support.

[0127] Examples of the support include a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a polyvinyl alcohol film, a triacetyl acetate film, and the like, with a polyethylene terephthalate film being particularly preferred.

[0128] Examples of commercially available supports include, but are not limited to, polyethylene terephthalate films such as "Alphan MA-410" and "E-200C" manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shin-Etsu Film Co., Ltd., and PS series films such as "PS-25" manufactured by Teijin Co., Ltd. These supports are preferably coated with a release agent such as a silicone coating agent on the surface in order to facilitate removal of the photosensitive resin composition layer. The thickness of the support is preferably in the range of 5 μm to 50 μm, and more preferably in the range of 10 μm to 25 μm. By making the thickness 5 μm or more, it is possible to prevent the support from being torn when peeling off the support before development, and by making the thickness 50 μm or less, it is possible to improve the resolution when exposing from above the support. In addition, a support with low fisheyes is preferable. Here, fisheyes are foreign matter, undissolved matter, oxidized deterioration products, etc. of the material that are taken into the film when the material is thermally melted and then kneaded, extruded, biaxially stretched, cast, etc. to produce a film.

[0129] In addition, in order to reduce scattering of light during exposure to actinic rays such as ultraviolet rays, the support is preferably one having excellent transparency. Specifically, the support is preferably one having a turbidity (haze standardized by JIS-K6714) as an index of transparency of 0.1 to 5. Furthermore, the photosensitive resin composition layer may be protected with a protective film.

[0130] By protecting the photosensitive resin composition layer side of the photosensitive film with a support with a protective film, it is possible to prevent the adhesion of dirt and the like to the surface of the photosensitive resin composition layer and scratches. As the protective film, a film made of the same material as the above-mentioned support can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and even more preferably in the range of 10 μm to 30 μm. By making the thickness 1 μm or more, the handleability of the protective film can be improved, and by making the thickness 40 μm or less, the cost tends to be improved. In addition, it is preferable that the adhesive strength between the photosensitive resin composition layer and the protective film is smaller than the adhesive strength between the photosensitive resin composition layer and the support.

[0131] The photosensitive film with a support can be produced, for example, by applying the photosensitive resin composition of the present invention directly or in a varnish form dissolved in an organic solvent onto a support, and drying the organic solvent by heating or blowing hot air to form a photosensitive resin composition layer. Specifically, first, bubbles in the photosensitive resin composition are completely removed by a vacuum defoaming method or the like, and then the photosensitive resin composition is applied onto a support, the solvent is removed by a hot air oven or a far-infrared oven, the composition is dried, and then a protective film is laminated on the obtained photosensitive resin composition layer as necessary to produce a photosensitive film with a support. Specific drying conditions vary depending on the curability of the photosensitive resin composition and the amount of organic solvent in the resin composition, but in a resin composition containing 30% by mass to 60% by mass of organic solvent, the composition can be dried at 80° C. to 120° C. for 3 minutes to 13 minutes. The amount of the organic solvent remaining in the photosensitive resin composition layer after drying is preferably 5% by mass or less, more preferably 2% by mass or less, based on the total amount of the photosensitive resin composition layer, in order to prevent the diffusion of the organic solvent in a subsequent step. Those skilled in the art can appropriately determine suitable drying conditions through simple experiments.

[0132] From the viewpoints of improving handleability and suppressing a decrease in sensitivity and resolution inside the photosensitive resin composition layer, the thickness of the photosensitive resin composition layer is preferably in the range of 5 μm to 500 μm, more preferably in the range of 10 μm to 200 μm, even more preferably in the range of 15 μm to 150 μm, even more preferably in the range of 20 μm to 100 μm, and especially preferably in the range of 20 μm to 60 μm.

[0133] Examples of the method for applying the photosensitive resin composition include a gravure coating method, a microgravure coating method, a reverse coating method, a kiss reverse coating method, a die coating method, a slot die method, a lip coating method, a comma coating method, a blade coating method, a roll coating method, a knife coating method, a curtain coating method, a chamber gravure coating method, a slot orifice method, a spray coating method, and a dip coating method.

[0134] The photosensitive resin composition may be applied in several portions, may be applied in one portion, or may be applied by combining a plurality of different methods. Among them, the die coating method is preferable because of its excellent uniformity of application. In addition, in order to avoid contamination by foreign matter, it is preferable to carry out the application process in an environment where foreign matter is unlikely to be generated, such as a clean room.

[0135] <Printed wiring board> The printed wiring board of the present invention includes an insulating layer formed from a cured product of the photosensitive resin composition of the present invention. The insulating layer is preferably used as a solder resist.

[0136] In particular, the printed wiring board of the present invention can be produced by using the above-mentioned photosensitive film with a support. Hereinafter, the case where the insulating layer is a solder resist will be described.

[0137] <Lamination and drying process> The photosensitive resin composition layer side of the supported photosensitive film is laminated onto a circuit board and dried to form a photosensitive resin composition layer on the circuit board.

[0138] Examples of the circuit board include a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, and a thermosetting polyphenylene ether board. The circuit board here refers to a board having a patterned conductor layer (circuit) on one or both sides of the board as described above. In addition, in a multilayer printed wiring board formed by alternately laminating a conductor layer and an insulating layer, a board in which one or both sides of the outermost layer of the multilayer printed wiring board are patterned conductor layers (circuits) is also included in the circuit board here. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

[0139] In one embodiment of the lamination process, the photosensitive resin composition layer side is laminated on one or both sides of the circuit board using a vacuum laminator. In the lamination process, if the photosensitive film with a support has a protective film, the protective film is removed, and then the photosensitive film with a support and the circuit board are preheated as necessary, and the photosensitive resin composition layer is pressure-bonded to the circuit board while being pressurized and heated. For the photosensitive film with a support, a method of laminating the film to the circuit board under reduced pressure by a vacuum lamination method is preferably used.

[0140] The conditions for the lamination step are not particularly limited, but for example, the pressure bonding temperature (lamination temperature) is preferably 70° C. to 140° C., and the pressure bonding pressure is preferably 1 kgf / cm. 2 ~11kgf / cm 2 (9.8×10 4 N / m 2 ~107.9×10 4 N / m 2), the pressure bonding time is preferably 5 seconds to 300 seconds, and lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The lamination process may be a batch type or a continuous type using a roll. The vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum applicator manufactured by Nikko Materials Co., Ltd., a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a roll type dry coater manufactured by Hitachi Industries Co., Ltd., and a vacuum laminator manufactured by Hitachi AIC Co., Ltd. In this way, a photosensitive film with a support is formed on the circuit board.

[0141] Instead of laminating a photosensitive film with a support, the photosensitive resin composition may be directly applied to the circuit board, and the organic solvent may be dried to form a photosensitive resin composition layer on the circuit board. As the application method, full-surface printing by screen printing is generally used, but any other application method that can apply uniformly may be used. For example, spray coating, hot melt coating, bar coating, applicator, blade coating, knife coating, air knife coating, curtain flow coating, roll coating, gravure coating, offset printing, dip coating, brush coating, and other normal application methods can all be used. After application, drying is performed in a hot air oven or far infrared oven, etc., as necessary. The drying conditions are preferably 80°C to 120°C for 3 to 13 minutes.

[0142] <Exposure process> After the photosensitive resin composition layer is provided on the circuit board by the above process, an exposure process is then performed in which a predetermined portion of the photosensitive resin composition layer is irradiated with active light through a mask pattern to photocure the photosensitive resin composition layer in the irradiated portion. Examples of active light include ultraviolet light, visible light, electron beams, and X-rays, and ultraviolet light is particularly preferred. The irradiation dose of ultraviolet light is about 10 mJ / cm. 2 ~1000mJ / cm 2The exposure method includes a contact exposure method in which a mask pattern is closely attached to a printed wiring board, and a non-contact exposure method in which exposure is performed using parallel light without closely attaching the mask pattern to the printed wiring board, and either method may be used. In addition, when a support is present on the photosensitive resin composition layer, exposure may be performed from above the support, or after peeling off the support.

[0143] The solder resist is excellent in developability (resolution) because it uses the photosensitive resin composition of the present invention. For this reason, as the exposure pattern in the mask pattern, for example, a pattern in which the ratio (L / S) of the circuit width (line; L) to the width between circuits (space; S) is 100 μm / 100 μm or less (i.e., wiring pitch is 200 μm or less), L / S=80 μm / 80 μm or less (wiring pitch is 160 μm or less), L / S=70 μm / 70 μm or less (wiring pitch is 140 μm or less), or L / S=60 μm / 60 μm or less (wiring pitch is 120 μm or less) can be used. Note that the pitch does not need to be the same over the entire circuit board.

[0144] <Developing process> After the exposure step, if a support is present on the photosensitive resin composition layer, the support is removed, and then the non-photocured portion (unexposed portion) is removed and developed by wet development or dry development, whereby a pattern can be formed.

[0145] In the case of the wet development, a developer that is safe, stable, and easy to operate, such as an alkaline aqueous solution, a water-based developer, or an organic solvent, is used, and among them, a development process using an alkaline aqueous solution is preferred. As a development method, a known method such as spraying, rocking immersion, brushing, or scraping is appropriately adopted.

[0146] Examples of alkaline aqueous solutions used as the developer include aqueous solutions of alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.; alkali metal carbonates or alkali metal bicarbonates such as sodium carbonate and sodium bicarbonate; alkali metal phosphates such as sodium phosphate and potassium phosphate; aqueous solutions of alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; aqueous solutions of organic bases such as tetraalkylammonium hydroxide, etc.; and mixed aqueous solutions of these.

[0147] To improve the development effect, surfactants, antifoaming agents, etc. may be added to these alkaline aqueous solutions. The pH of the alkaline aqueous solution is, for example, preferably in the range of 8 to 12, more preferably in the range of 9 to 11. The base concentration of the alkaline aqueous solution is preferably 0.1% by mass to 10% by mass. The temperature of the alkaline aqueous solution can be appropriately selected according to the developability of the photosensitive resin composition layer, but is preferably 20°C to 50°C.

[0148] Examples of organic solvents used as developers 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, and diethylene glycol monobutyl ether.

[0149] The concentration of such an organic solvent is preferably 2% by mass to 90% by mass based on the total amount of the developer. The temperature of such an organic solvent can be adjusted according to the developability. Furthermore, such an organic solvent can be used alone or in combination of two or more kinds. Examples of organic solvent-based developers used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

[0150] In forming a pattern, two or more of the above-mentioned developing methods may be used in combination as necessary. The developing methods include a dip method, a bath method, a spray method, a high-pressure spray method, brushing, slapping, etc., and the high-pressure spray method is suitable for improving resolution. When adopting a spray method, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

[0151] <Thermal curing (post-bake) process> After the development step, a thermal curing (post-baking) step is performed to form a solder resist. Examples of the post-baking step include an ultraviolet ray irradiation step using a high-pressure mercury lamp and a heating step using a clean oven. When ultraviolet rays are irradiated, the amount of irradiation can be adjusted as necessary, for example, 0.05 J / cm. 2 ~10J / cm 2 The heating conditions may be appropriately selected depending on the type and content of the resin component in the photosensitive resin composition, but are preferably selected within the range of 150°C to 220°C for 20 minutes to 180 minutes, and more preferably 160°C to 200°C for 30 minutes to 120 minutes.

[0152] <Other processes> After the solder resist is formed, the printed wiring board may further include a drilling step and a desmearing step, which may be carried out according to various methods used in the manufacture of printed wiring boards and known to those skilled in the art.

[0153] After the solder resist is formed, via holes and through holes are formed in the solder resist formed on the circuit board by a drilling process, if desired. The drilling process can be performed by a known method such as a drill, a laser, or plasma, or by a combination of these methods if necessary, but a drilling process using a laser such as a carbon dioxide laser or a YAG laser is preferred.

[0154] The desmear process is a process of performing a desmear treatment. Generally, resin residue (smear) adheres to the inside of the opening formed in the hole drilling process. Since the smear can cause poor electrical connection, a process of removing the smear (desmear treatment) is performed in this process.

[0155] The desmear treatment may be performed by a dry desmear treatment, a wet desmear treatment, or a combination thereof.

[0156] The dry desmear treatment may be, for example, a desmear treatment using plasma. The desmear treatment using plasma may be performed using a commercially available plasma desmear treatment device. Among the commercially available plasma desmear treatment devices, examples suitable for use in the manufacture of printed wiring boards include a microwave plasma device manufactured by Nissin Co., Ltd. and an atmospheric pressure plasma etching device manufactured by Sekisui Chemical Co., Ltd.

[0157] The wet desmear treatment may be, for example, a desmear treatment using an oxidizing agent solution. When the desmear treatment is performed using an oxidizing agent solution, it is preferable to perform a swelling treatment using a swelling liquid, an oxidation treatment using an oxidizing agent solution, and a neutralization treatment using a neutralizing liquid in this order. Examples of the swelling liquid include "Swelling Dip Securigance P" and "Swelling Dip Securigance SBU" manufactured by Atotech Japan. The swelling treatment is preferably performed by immersing a substrate on which via holes or the like are formed in a swelling liquid heated to 60°C to 80°C for 5 to 10 minutes. The oxidizing agent solution is preferably an alkaline permanganate solution, and examples of the solution include a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The oxidation treatment using an oxidizing agent solution is preferably performed by immersing a substrate after the swelling treatment in an oxidizing agent solution heated to 60°C to 80°C for 10 to 30 minutes. Commercially available alkaline permanganate aqueous solutions include, for example, "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan. The neutralization treatment using a neutralizing solution is preferably carried out by immersing the substrate after the oxidation treatment in the neutralizing solution at 30°C to 50°C for 3 to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution, and a commercially available product thereof is, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan.

[0158] When the dry desmear treatment and the wet desmear treatment are performed in combination, the dry desmear treatment may be performed first, or the wet desmear treatment may be performed first.

[0159] When the insulating layer is used as an interlayer insulating layer, it can be carried out in the same manner as in the case of a solder resist, and after the thermal curing step, a hole drilling step, a desmearing step, and a plating step may be carried out.

[0160] The plating process is a process of forming a conductor layer on an insulating layer. The conductor layer may be formed by a combination of electroless plating and electrolytic plating, or a plating resist having a reverse pattern to the conductor layer may be formed and the conductor layer may be formed only by electroless plating. Subsequent pattern formation methods may include, for example, subtractive methods and semi-additive methods known to those skilled in the art.

[0161] <Semiconductor device> The semiconductor device of the present invention includes a printed wiring board. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

[0162] Examples of the semiconductor device include various semiconductor devices used in electric appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

[0163] The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conductive portion" refers to a portion of a printed wiring board that transmits an electric signal, and the portion may be either on the surface or embedded. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of semiconductor material.

[0164] The method of mounting the semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specific examples include a wire bonding mounting method, a flip chip mounting method, a mounting method using a bumpless buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), etc. Here, the "mounting method using a bumpless buildup layer (BBUL)" refers to "a mounting method in which a semiconductor chip is directly embedded in a recess in a printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board." EXAMPLES

[0165] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. Unless otherwise specified, the temperature conditions are room temperature (23°C), and unless otherwise specified, the pressure conditions are atmospheric pressure (1 atm). The weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography.

[0166] <Synthesis Example 1: Synthesis of naphthol aralkyl skeleton-containing ester-type acid-modified epoxy (meth)acrylate resin> 325 parts of an epoxy resin having a naphthol aralkyl skeleton ("ESN-475V" manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 325g / eq.) was placed in a flask equipped with a gas inlet tube, a stirrer, a cooling tube and a thermometer, 340 parts of carbitol acetate was added, heated and dissolved, and 0.46 parts of hydroquinone and 1 part of triphenylphosphine were added. This mixture was heated to 95-105°C, 72 parts of acrylic acid were gradually added dropwise, and reacted for 16 hours. This reaction product was cooled to 80-90°C, 80 parts of tetrahydrophthalic anhydride were added, reacted for 8 hours, and cooled. The amount of solvent was adjusted to obtain a resin solution with an acid value of 60mgKOH / g of solid matter (non-volatile content 70%). The weight average molecular weight of the naphthol aralkyl type epoxy acrylate (1000) was 1000.

[0167] <Synthesis Example 2: Synthesis of acid-containing acrylic acrylate resin> A reaction apparatus equipped with a stirrer, a cooling tube, a dropping funnel, and a nitrogen inlet tube was charged with 1000 parts of water, 1 part of polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., "PVA-117"), 200 parts of styrene, 125 parts of methyl methacrylate, 175 parts of methacrylic acid, 5 parts of azobisisobutyronitrile, and 5 parts of dodecyl mercaptan, and a polymerization reaction was carried out by suspension polymerization for 8 hours under a nitrogen gas stream at 80°C. After solid-liquid separation, the mixture was dried under reduced pressure to obtain Synthetic Resin A'. Next, 500 parts of the obtained synthetic resin A' was put into a reaction apparatus equipped with a stirrer, a cooling tube, a dropping funnel, and an air introduction tube, and diluted with 260 parts of carbitol acetate, 2 parts of methoxyhydroquinone as a polymerization inhibitor, and 5 parts of triphenylphosphine, and 100 parts of glycidyl methacrylate was added, and the mixture was heated for 8 hours under air bubbling at 110°C to obtain an acid-containing acrylic acrylate resin solution (70% non-volatile content) with an acid value of 100 mgKOH / g in solid matter. The weight average molecular weight of the acid-containing acrylic acrylate resin was 15,000.

[0168] <Example 1> 25 parts of the naphthol aralkyl skeleton-containing ester-type acid-modified epoxy acrylate resin (non-volatile content 70%) obtained in Synthesis Example 1, 10 parts of a naphthalene-type multifunctional epoxy resin (DIC Corporation's "HP-4710", epoxy equivalent approximately 170 g / eq.), and a fluorene skeleton-containing α-aminoketone-based photopolymerization initiator (TRONLY's "TR-NPI-20400", maximum absorption wavelength 313 nm, triplet energy 61.0 kcal / mol), 0.3 parts of photosensitizer ("DETX-S" manufactured by Nippon Kayaku Co., Ltd., maximum absorption wavelength 385 nm, triplet energy 61.4 kcal / mol), and spherical silica ("SC2050-SXF" manufactured by Admatechs Co., Ltd., specific surface area 5.9 m) surface-treated with aminosilane coupling agent ("KBM5783" manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminooctyltrimethoxysilane). 2A varnish-like photosensitive resin composition was prepared by mixing 20 parts of a diluent (dipentaerythritol hexaacrylate "DPHA" manufactured by Nippon Kayaku Co., Ltd., 1 part of ethyl diglycol acetate, and 10 parts of methyl ethyl ketone using a high-speed rotating mixer.

[0169] <Example 2> A varnish-like photosensitive resin composition was prepared in the same manner as in Example 1, except that the amount of spherical silica ("SC2050-SXF" manufactured by Admatechs Co., Ltd.) surface-treated with an aminosilane coupling agent was changed from 20 parts to 40 parts.

[0170] <Example 3> A varnish-like photosensitive resin composition was prepared in the same manner as in Example 1, except that the amount of spherical silica ("SC2050-SXF" manufactured by Admatechs Co., Ltd.) surface-treated with an aminosilane coupling agent was changed from 20 parts to 60 parts.

[0171] <Example 4> Instead of 20 parts of spherical silica (Admatechs' "SC2050-SXF") surface-treated with an aminosilane coupling agent, spherical silica (Admatechs' "SC2300-SVJ", specific surface area 6 m) surface-treated with a vinylsilane coupling agent (Shin-Etsu Chemical's "KBM-1003", vinyltrimethoxysilane) was used. 2 A varnish-like photosensitive resin composition was prepared in the same manner as in Example 1, except that 20 parts of 1,2-dichlorophenyl ether (1.0 parts by weight / g, average particle size 0.5 μm) was used.

[0172] <Example 5> A varnish-like photosensitive resin composition was prepared in the same manner as in Example 4, except that the amount of spherical silica ("SC2300-SVJ" manufactured by Admatechs Co., Ltd.) surface-treated with a vinylsilane coupling agent was changed from 20 parts to 40 parts.

[0173] <Example 6> A varnish-like photosensitive resin composition was prepared in the same manner as in Example 4, except that the amount of spherical silica ("SC2300-SVJ" manufactured by Admatechs Co., Ltd.) surface-treated with a vinylsilane coupling agent was changed from 20 parts to 60 parts.

[0174] <Example 7> A varnish-like photosensitive resin composition was prepared in the same manner as in Example 2, except that 0.3 parts of a photosensitizer ("EAB" manufactured by Tokyo Chemical Industry Co., Ltd., maximum absorption wavelength 352 nm, triplet energy 62.0 kcal / mol) was used instead of 0.3 parts of the photosensitizer ("DETX-S" manufactured by Nippon Kayaku Co., Ltd.).

[0175] <Example 8> A varnish-like photosensitive resin composition was prepared in the same manner as in Example 2, except that 0.3 parts of a photosensitizer ("EAB" manufactured by Tokyo Chemical Industry Co., Ltd.) was further used.

[0176] <Example 9> A varnish-like photosensitive resin composition was prepared in the same manner as in Example 2, except that 40 parts of a cresol novolac skeleton-containing acid-modified epoxy acrylate resin ("CCR-1171H" manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH / g, non-volatile content 60%, solvent PGMEA) was used instead of 25 parts of the naphthol aralkyl skeleton-containing ester-type acid-modified epoxy (meth)acrylate resin (non-volatile content 70%) obtained in Synthesis Example 1.

[0177] <Example 10> A varnish-like photosensitive resin composition was prepared in the same manner as in Example 2, except that 40 parts of the acid-containing acrylic acrylate resin (non-volatile content 70%, carbitol acetate solvent) obtained in Synthesis Example 2 was used instead of 25 parts of the naphthol aralkyl skeleton-containing ester-type acid-modified epoxy (meth)acrylate resin (non-volatile content 70%) obtained in Synthesis Example 1.

[0178] <Example 11> A varnish-like photosensitive resin composition was prepared in the same manner as in Example 2, except that 30 parts of a urethane-type acid-modified epoxy (meth)acrylate resin ("UXE-3024" manufactured by Nippon Kayaku Co., Ltd., acid value of solid matter 60 mgKOH / g, non-volatile content 60%, solvent PGMEA) was used instead of 25 parts of the naphthol aralkyl skeleton-containing ester-type acid-modified epoxy (meth)acrylate resin (non-volatile content 70%) obtained in Synthesis Example 1.

[0179] <Example 12> A varnish-like photosensitive resin composition was prepared in the same manner as in Example 2, except that 10 parts of a naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent: 330 g / eq.) was used instead of 10 parts of a naphthalene type multifunctional epoxy resin ("HP-4710" manufactured by DIC Corporation, epoxy equivalent: approximately 170 g / eq.).

[0180] <Example 13> A varnish-like photosensitive resin composition was prepared in the same manner as in Example 2, except that 10 parts of a biphenyl-type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq.) was used instead of 10 parts of a naphthalene-type multifunctional epoxy resin ("HP-4710" manufactured by DIC Corporation, epoxy equivalent: approximately 170 g / eq.).

[0181] <Example 14> A varnish-like photosensitive resin composition was prepared in the same manner as in Example 2, except that 10 parts of a bisphenol A type epoxy resin ("850" manufactured by DIC Corporation, epoxy equivalent weight: approximately 188 g / eq.) was used instead of 10 parts of a naphthalene type multifunctional epoxy resin ("HP-4710" manufactured by DIC Corporation, epoxy equivalent weight: approximately 170 g / eq.).

[0182] <Example 15> A varnish-like photosensitive resin composition was prepared in the same manner as in Example 1, except that the amount of spherical silica ("SC2050-SXF" manufactured by Admatechs Co., Ltd.) surface-treated with an aminosilane coupling agent was changed from 20 parts to 5 parts.

[0183] <Comparative Example 1> A varnish-like photosensitive resin composition was prepared in the same manner as in Example 2, except that 3 parts of an α-aminoketone photopolymerization initiator not containing a fluorene skeleton ("Omnirad379EG" manufactured by IGM) was used instead of 3 parts of the α-aminoketone photopolymerization initiator containing a fluorene skeleton ("TR-NPI-20400" manufactured by TRONLY), and no photosensitizer ("DETX-S" manufactured by Nippon Kayaku Co., Ltd.) was used.

[0184] <Comparative Example 2> A varnish-like photosensitive resin composition was prepared in the same manner as in Example 2, except that 3 parts of an α-aminoketone-based photopolymerization initiator not containing a fluorene skeleton ("Omnirad379EG" manufactured by IGM) was used instead of 3 parts of the α-aminoketone-based photopolymerization initiator containing a fluorene skeleton ("TR-NPI-20400" manufactured by TRONLY).

[0185] <Comparative Example 3> A varnish-like photosensitive resin composition was prepared in the same manner as in Example 2, except that 0.3 parts of a photosensitizer ("Omnirad BP" manufactured by IGM Resins BV, maximum absorption wavelength 340 nm, triplet energy 69 kcal / mol) was used instead of 0.3 parts of a photosensitizer ("DETX-S" manufactured by Nippon Kayaku Co., Ltd.).

[0186] <Test Example 1: Evaluation of average linear thermal expansion coefficient> A PET film (manufactured by Toray Industries, Inc., "Lumirror T6AM", thickness 38 μm, softening point 130° C., "release PET") that had been release-treated with an alkyd resin-based release agent (manufactured by Lintec Corporation, "AL-5") was prepared as a support. The varnish-like photosensitive resin compositions obtained in the Examples and Comparative Examples were uniformly applied to the prepared release PET using a die coater so that the thickness of the photosensitive resin composition layer after drying was 25 μm, and the film was dried at 80° C. to 110° C. for 6 minutes to obtain a photosensitive film with a support having a photosensitive resin composition layer on the release PET.

[0187] The photosensitive resin composition layer of the obtained photosensitive film with a support was applied with 2 J / cm 2After that, the support was peeled off to obtain a cured product A for evaluation.

[0188] The cured product A for evaluation was cut into test pieces 5 mm wide and 15 mm long, and thermomechanical analysis was performed by the tensile load method using a thermomechanical analyzer (Rigaku Corporation, Thermo Plus, TMA8310). After mounting the test pieces on the device, measurements were performed twice consecutively under the measurement conditions of a load of 1 g and a heating rate of 5°C / min. The average linear thermal expansion coefficient (ppm) from 25°C to 150°C in the second measurement was calculated and evaluated according to the following criteria.

[0189] Evaluation criteria for average linear thermal expansion coefficient "Good": Average linear thermal expansion coefficient is less than 40 ppm "△": Average linear thermal expansion coefficient is 40 ppm or more and 60 ppm or less "X": Average linear thermal expansion coefficient exceeds 60 ppm

[0190] <Test Example 2: Evaluation of Resolution and Via Holes> The copper layer of a glass epoxy board (copper-clad laminate) on which a circuit patterned with a copper layer having a thickness of 18 μm was formed was roughened by treatment with a surface treatment agent containing an organic acid (CZ8100, manufactured by MEC Co., Ltd.). Next, a photosensitive film with a support similar to that obtained in Test Example 1 was placed so that the photosensitive resin composition layer was in contact with the copper circuit surface, and laminated using a vacuum laminator (manufactured by Nikko Materials Co., Ltd., VP160), and the copper-clad laminate, the photosensitive resin composition layer, and the support were laminated in this order to prepare an evaluation laminate A. The pressure bonding conditions were a vacuum drawing time of 30 seconds, a pressure bonding temperature of 80° C., a pressure bonding pressure of 0.7 MPa, and a pressure application time of 30 seconds. After preparing the evaluation laminate A, it was left to stand at room temperature (25° C.) for 30 minutes or more.

[0191] Using a pattern forming device and a 41-step step tablet and a round hole pattern, ultraviolet exposure was performed from above the support of the evaluation laminate A. The exposure pattern used was a quartz glass mask that drew round holes with openings of 40 μm / 50 μm / 60 μm / 70 μm / 80 μm / 90 μm / 100 μm. After leaving it to stand at room temperature for 30 minutes, the support was peeled off from the evaluation laminate A. A 1% by mass aqueous solution of sodium carbonate at 30° C. was used as a developer for the entire surface of the photosensitive resin composition layer on the evaluation laminate A, and development was performed for 1 minute by spraying at a spray pressure of 0.2 MPa. After spray development, 2 J / cm 2 The photosensitive resin composition layer was then cured by performing a heat treatment at 170° C. for 1 hour.

[0192] The sensitivity of the photosensitive resin composition was determined as the amount of exposure energy at which the number of remaining gloss steps in the 41-step tablet was 8. The round holes patterned on the evaluation laminate A exposed at this sensitivity were observed with an SEM (magnification 1000x) to observe the minimum via hole diameter (minimum opening diameter) without residue or peeling, and evaluated according to the following evaluation criteria.

[0193] (Evaluation criteria for minimum via hole diameter (minimum opening diameter)) "Good": Minimum via hole diameter (minimum opening diameter) is less than 50 μm "△": Minimum via hole diameter (minimum opening diameter) is 50 μm or more and 60 μm or less "X": There is no via hole with a minimum diameter (minimum opening diameter) of 60 μm or less.

[0194] In addition, regarding the observation of undercut, a via hole with a diameter of 50 μm was observed with an SEM (magnification 1000 times). The radius (μm) of the top and bottom of the cross section of a via hole with an opening diameter of 50 μm was measured with an SEM, and the difference between the radius of the bottom and the radius of the top (radius of the bottom - radius of the top) was calculated. The calculated value was regarded as the undercut and evaluated according to the following evaluation criteria.

[0195] (Evaluation criteria for undercuts) "◎": No undercut "Good": Undercut is less than 3μm "△": Undercut is 3μm to 6μm "X": Undercut is larger than 6 μm or via hole with a diameter of 50 μm is not opened

[0196] Moreover, the evaluation laminate A was subjected to the following roughening treatment. The substrate was immersed in a swelling solution, Swelling Dip Securigand P containing diethylene glycol monobutyl ether manufactured by Atotech Japan, for 10 minutes at 60°C, then in a roughening solution, Concentrate Compact P (aqueous solution of KMnO4: 60g / L, NaOH: 40g / L) manufactured by Atotech Japan, for 10 minutes at 80°C, and finally in a neutralizing solution, Reduction Showreusin Securigant P manufactured by Atotech Japan, for 5 minutes at 40°C. Regarding the evaluation of the resolution after desmearing, the via holes were observed (magnification 1000x) with SEM, as well as the observation of the minimum via hole diameter and undercut.

[0197] After desmearing, the state of the wall surface of the via hole, the resist surface at the top of the via hole, and the bottom of the via hole were evaluated according to the following evaluation criteria.

[0198] (Evaluation criteria for via hole walls after desmear) "Good": The inorganic filler is not exposed much on the wall of the via hole, and the wall is smooth. "X": The inorganic filler is exposed to a large extent on the wall of the via hole, resulting in unevenness.

[0199] (Evaluation criteria for the resist surface above the via hole after desmearing) "Good": The inorganic filler is not exposed much on the resist surface above the via hole, and the surface is smooth. "X": The inorganic filler is largely exposed on the resist surface above the via hole, resulting in unevenness.

[0200] (Evaluation criteria for via hole bottom after desmear) "Good": No inorganic filler has fallen off from the bottom of the via hole "X": Inorganic filler has fallen off from the bottom of the via hole

[0201] <Test Example 3: Evaluation of arithmetic mean roughness> Using a pattern forming device, ultraviolet light exposure was performed on the support of evaluation laminate A similar to that produced in Test Example 2, with an exposure energy such that the number of gloss remaining steps of a 41-step tablet was 8. A quartz glass mask without an exposure pattern was used. After leaving it to stand at room temperature for 30 minutes, the support was peeled off from evaluation laminate A. A 1% by mass aqueous solution of sodium carbonate at 30°C was used as a developer for the entire surface of the photosensitive resin composition layer on evaluation laminate A for 1 minute for spray development at a spray pressure of 0.2 MPa. After spray development, 2 J / cm 2 The photosensitive resin composition layer was then cured by performing a heat treatment at 170° C. for 1 hour.

[0202] The evaluation laminate A was immersed in a swelling liquid, Swelling Dip Securigand P containing diethylene glycol monobutyl ether manufactured by Atotech Japan, for 10 minutes at 60°C, then in a roughening liquid, Concentrate Compact P (aqueous solution of KMnO4: 60g / L, NaOH: 40g / L) manufactured by Atotech Japan, for 10 minutes at 80°C, and finally in a neutralizing liquid, Reduction Showreusin Securigant P manufactured by Atotech Japan, for 5 minutes at 40°C. The laminate after this roughening treatment was designated as Sample A.

[0203] For sample A, the arithmetic mean roughness (Ra) was calculated using a non-contact surface roughness meter (WYKO NT3300 manufactured by Beco Instruments) in VSI mode with a 50x lens over a measurement range of 121μm×92μm. The average of 10 points was calculated as the measured value, and the results were evaluated according to the following criteria.

[0204] (Evaluation criteria for arithmetic mean roughness) "Good": Arithmetic mean roughness is less than 200 μm "△": Arithmetic mean roughness is 200μm or more and 400μm or less "X": Arithmetic mean roughness is greater than 400 μm

[0205] <Test Example 4: Evaluation of peel strength of copper-plated conductor layer> Sample A, which is the same as that obtained in Test Example 3, was immersed in an electroless plating solution containing PdCl2 in order to form a circuit on the insulating layer surface, and then immersed in an electroless copper plating solution. After heating at 150°C for 30 minutes to perform an annealing treatment, an etching resist was formed, and after forming a pattern by etching, copper sulfate electroplating was performed to form a conductor layer with a thickness of 25 μm. Next, an annealing treatment was performed at 180°C for 60 minutes. The sample obtained in this manner was designated as Sample B.

[0206] A 10 mm wide and 100 mm long cut was made in the conductive layer of Sample B, and one end of this cut was peeled off and held with a gripper (TSE Corporation, Autocom type testing machine, AC-50C-SL). 35 mm was peeled off vertically at a speed of 50 mm / min at room temperature, and the load (kgf / cm) was measured and evaluated according to the following criteria.

[0207] (Evaluation Criteria for Peel Strength) "Good": Peel strength is 0.3kgf / cm or more "X": Peel strength is less than 0.3kgf / cm

[0208] The amounts of raw materials used in the preparation of the resin compositions of the Examples and Comparative Examples, and the evaluation results of the Test Examples are summarized in Table 1 below.

[0209] [Table 1]

[0210] From the results shown in Table 1 above, it can be seen that by using a photosensitive resin composition containing (A) a carboxyl group-containing resin, (B) an α-aminoketone-based photopolymerization initiator having a fluorene skeleton, (C) an epoxy resin, (D) a photosensitizer, and (E) an inorganic filler, in which the maximum absorption wavelength of the (D) photosensitizer is 350 nm to 400 nm, a better resolution can be achieved. It can also be seen that by using such a photosensitive resin composition, a cured product having a lower arithmetic mean roughness (Ra) after roughening treatment can be obtained. It can also be seen that by using such a photosensitive resin composition, a cured product having a higher peel strength (peel strength / adhesion) from the copper-plated conductor layer can be obtained.

Claims

1. A photosensitive resin composition comprising: (A) a resin containing an ethylenically unsaturated group and a carboxyl group; (B) an α-aminoketone-based photopolymerization initiator having a fluorene skeleton; (C) an epoxy resin; (D) a photosensitizer; and (E) an inorganic filler, A photosensitive resin composition, in which the component (D) has a maximum absorption wavelength in the range of 350 nm to 400 nm.

2. 2. The photosensitive resin composition according to claim 1, wherein the component (A) comprises a resin selected from the group consisting of an acid-modified epoxy (meth)acrylate resin and an acid-containing (meth)acrylic (meth)acrylate resin.

3. 3. The photosensitive resin composition according to claim 1, wherein the acid value of the component (A) is 1 mgKOH / g or more.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the weight average molecular weight of the component (A) is 1,000 to 20,000.

5. The component (B) is represented by the formula (1): 【Chemistry 1】 [In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , and R ７ are each independently a hydrogen atom, a halogen atom, a nitro group, -R, -OR, or -NR ２ , -SR, -SOR, -SO ２ R, -COR, -OCOR, -COOR, or -CONR ２ indicates; R each independently represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or a heterocyclic group which may have a substituent; R ８ , and R ９ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aralkyl group, or R ８ , and R ９ are joined together to form an optionally substituted non-aromatic carbocyclic ring; R ａ , and R ｂ each independently represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aralkyl group which may have a substituent, or R ａ , and R ｂ are joined together to form an optionally substituted non-aromatic carbocyclic ring; R ｃ , and R ｄ each independently represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aralkyl group which may have a substituent, or R ｃ , and R ｄ are bonded together to form a nitrogen-containing heterocycle which may have a substituent. The photosensitive resin composition according to any one of claims 1 to 4, comprising a compound represented by the formula:

6. The photosensitive resin composition according to any one of claims 1 to 5, wherein a mass ratio of the component (A) to the component (B) (component (A) / component (B)) is 1 to 30.

7. The photosensitive resin composition described in any one of claims 1 to 6, wherein the component (C) includes an epoxy resin having a skeleton selected from a naphthalene skeleton, a biphenyl skeleton, and a bisphenol skeleton.

8. 8. The photosensitive resin composition according to claim 1, wherein the component (C) comprises an epoxy resin having a skeleton selected from a naphthalene skeleton and a biphenyl skeleton.

9. 9. The photosensitive resin composition according to claim 1, wherein the lowest excited triplet energy level of the component (D) is 60 kcal / mol to 65 kcal / mol.

10. The photosensitive resin composition according to any one of claims 1 to 9, wherein the component (E) comprises an inorganic filler that has been surface-treated with an amino-silane coupling agent.

11. The photosensitive resin composition according to any one of claims 1 to 10, wherein the content of the component (E) is 10% by mass or more when the total solid content in the photosensitive resin composition is 100% by mass.

12. The photosensitive resin composition according to any one of claims 1 to 11, which is used for forming a solder resist.

13. A photosensitive film with a support, comprising: a support; and a photosensitive resin composition layer formed on the support from the photosensitive resin composition according to any one of claims 1 to 12.

14. The photosensitive film according to claim 13, wherein the photosensitive resin composition layer has a thickness in the range of 20 μm to 100 μm.

15. A printed wiring board comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of claims 1 to 12.

16. A semiconductor device comprising the printed wiring board according to claim 15.

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