Curable resin composition, dry film, cured product, and printed wiring board

Abstract

To provide a curable resin composition which has good film-forming property on a PET substrate, is excellent in developability and chemical resistance, and has little development residue.SOLUTION: A curable resin composition contains an alkali-soluble resin, a cellulose resin, and a polyfunctional ethylene oxide-modified monomer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition. The present invention also relates to a dry film, a cured product, and a printed wiring board using the curable resin composition. [Background technology]

[0002] Dry films have traditionally been used as one means for forming protective films and insulating layers, such as solder resists and interlayer insulating layers, on printed wiring boards used in electronic devices, etc. With the recent trend toward thinner substrates and finer circuits, there has been an increasing demand for dry films for forming protective films and insulating layers, such as solder resists. A dry film has a resin layer obtained by applying a resin composition having desired properties to a film and then undergoing a drying process. The resin layer of the dry film can be attached to a substrate (hereinafter also referred to as "lamination"), followed by patterning and curing treatments to form such protective films and insulating layers on a printed wiring board. The process of applying this resin layer to a film can sometimes cause problems with film formability.

[0003] Patent Document 1 proposes a dry film having a resin layer that contains a photocurable resin, a photopolymerization initiator, an inorganic filler, and a non-silicone release agent, and the surface of the second film that contacts the resin layer has an arithmetic mean surface roughness Ra of 0.1 μm or more, and the surface of the resin layer that contacts the second film is the surface that is laminated to the substrate, thereby eliminating coating unevenness and repelling, and having a resin layer that has an excellent balance of adhesion to the film and release properties, lamination properties, and adhesion to the substrate.

[0004] Furthermore, for interlayer insulating materials used in wafer-level packaging, in which packaging is performed on a wafer and then the chips are cut out, there is a growing demand for alkaline-developable photosensitive interlayer insulating materials that can be patterned by photolithography in order to form fine patterns in one go from the perspective of production efficiency. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2017-198745 Summary of the Invention [Problem to be solved by the invention]

[0006] In the electronic components mentioned above, there is a demand for higher density wiring, and there are issues with improving the resolution of photosensitive insulating materials and developing residues at the bottom of small vias when opening them. In addition, chemical resistance is required when processing with acetone due to process changes. However, the resin layer of the dry film described in Patent Document 1 leaves room for improvement in terms of resolution, chemical resistance, and development residue at the bottom of the via, and it was difficult to achieve both of these with film-forming properties on a PET substrate.

[0007] The present invention has been made in view of the above problems, and aims to provide a curable resin composition that has good film-forming properties on a PET substrate, excellent resolution and chemical resistance, and little development residue. Another aim of the present invention is to provide a dry film having a resin layer formed from a dried coating film of the resin composition, a cured product of the resin composition or the resin layer of the dry film, and a printed wiring board having the cured product. [Means for solving the problem]

[0008] As a result of intensive research conducted by the inventors in order to achieve the above-mentioned object, they found that the above-mentioned problem can be solved by using an alkali-soluble resin, a cellulose resin, and a polyfunctional ethylene oxide-modified monomer to improve the strength of a dried coating film of a resin composition.

[0009] That is, according to the present invention, the following inventions are provided. [1] A curable resin composition comprising an alkali-soluble resin, a cellulose resin, and a polyfunctional ethylene oxide-modified monomer. [2] The curable resin composition according to [1], wherein the alkali-soluble resin has a structure derived from an imide skeleton. [3] The curable resin composition according to [1] or [2], wherein the weight average molecular weight of the alkali-soluble resin is 1,000 or more and 20,000 or less. [4] The curable resin composition according to any one of [1] to [3], wherein the content of the alkali-soluble resin is 5% by mass or more and 50% by mass or less in terms of solid content, based on the total amount of the curable resin composition. [5] The curable resin composition according to any one of [1] to [4], wherein the cellulose resin has a number average molecular weight of 5,000 or more and 500,000 or less. [6] The curable resin composition according to any one of [1] to [5], wherein the content of the cellulose resin is 0.1 mass % or more and 5.0 mass % or less in terms of solid content, relative to the total amount of the curable resin composition. [7] The curable resin composition according to any one of [1] to [6], wherein the content of the cellulose resin is 5 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the polyfunctional ethylene oxide-modified monomer. [8] The curable resin composition according to any one of [1] to [7], wherein the polyfunctional ethylene oxide-modified monomer is an ethylene oxide-modified monomer having five or more functionalities. [9] The curable resin composition according to any one of [1] to [8], wherein the content of the polyfunctional ethylene oxide-modified monomer is 1.0 mass% or more and 20.0 mass% or less in terms of solid content, relative to the total amount of the curable resin composition.

[10] A dry film comprising a first film and a resin layer formed on the first film and comprising a dried coating film of the curable resin composition according to any one of [1] to [9].

[11] A cured product obtained by curing the curable resin composition according to any one of [1] to [9].

[12] A cured product obtained by curing the resin layer of the dry film described in

[10] .

[13] A printed wiring board comprising the cured product according to

[11] .

[14] A printed wiring board comprising the cured product according to

[12] . [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a curable resin composition that has good film-forming properties on a PET substrate, excellent resolution and chemical resistance, and little development residue. Furthermore, according to the present invention, it is possible to provide a dry film having a resin layer formed from a dried coating film of the resin composition, a cured product of the resin composition or the resin layer of the dry film, and a printed wiring board having the cured product. DETAILED DESCRIPTION OF THE INVENTION

[0011] [Curable resin composition] The curable resin composition of the present invention contains an alkali-soluble resin, a cellulose resin, and a polyfunctional ethylene oxide-modified monomer. The curable resin composition of the present invention may further contain an epoxy resin, an inorganic filler, a curing agent, a colorant, etc.

[0012] The curable resin composition of the present invention contains a cellulose resin in addition to the conventionally used alkali-soluble resin and polyfunctional ethylene oxide-modified monomer, thereby improving film-forming properties on PET substrates. This is because, whereas the curable resin composition contains a large amount of low-molecular-weight components, which makes the film easily break, the addition of a polymeric resin as a binder improves film-forming properties and improves the strength of the dried coating film of the resin composition.

[0013] Hereinafter, each component constituting the curable resin composition of the present invention will be described. In this specification, (meth)acrylic acid is a general term referring to acrylic acid, the corresponding methacrylic acid, and mixtures thereof, and (meth)acrylate is a general term referring to acrylate, the corresponding methacrylate, and mixtures thereof. Similarly, (meth)acryloyl group is a general term referring to acryloyl group and the corresponding methacryloyl group, and (meth)acryloxy group is a general term referring to acryloxy group and the corresponding methacryloxy group.

[0014] (alkali-soluble resin) The alkali-soluble resin may be any resin that is alkali-soluble, and known resins may be used. The alkali-soluble resin may be used alone or in combination of two or more. Examples of alkali-soluble resins include water-soluble resins such as carboxyl group-containing resins and phenolic hydroxyl group-containing resins. Among these, carboxyl group-containing resins and phenolic hydroxyl group-containing resins are preferred due to their excellent developability. Furthermore, the alkali-soluble resin can be made photosensitive by having an ethylenically unsaturated double bond in the molecule in addition to the carboxyl group. The ethylenically unsaturated double bond is preferably derived from acrylic acid, methacrylic acid, or a derivative thereof. In the present invention, the alkali-soluble resin preferably has photosensitivity.

[0015] Specific examples of the carboxyl group-containing resin include the following compounds (which may be either oligomers or polymers):

[0016] (1) Carboxyl group-containing resins obtained by copolymerizing unsaturated carboxylic acids such as (meth)acrylic acid with unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth)acrylates, and isobutylene.

[0017] (2) Carboxylic acid-containing urethane resins obtained by the polyaddition reaction of diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxyl-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and diol compounds such as polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.

[0018] (3) Carboxylic acid group-containing urethane resins obtained by polyaddition reaction of diisocyanates with bifunctional epoxy resins such as bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bixylenol epoxy resins, and biphenol epoxy resins, and monocarboxylic acid compounds having ethylenically unsaturated double bonds such as (meth)acrylic acid, partially acid anhydride-modified products thereof, and carboxyl group-containing dialcohol compounds and diol compounds.

[0019] (4) A curable urethane resin containing a carboxyl group, which is terminally (meth)acrylated by adding a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as a hydroxyalkyl (meth)acrylate, during the synthesis of the resin (2) or (3).

[0020] (5) A carboxyl group-containing curable urethane resin that is (meth)acrylated at the end by adding a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, during the synthesis of the resin (2) or (3).

[0021] (6) A carboxyl group-containing resin obtained by reacting a difunctional or more polyfunctional (solid) epoxy resin with (meth)acrylic acid and adding a dibasic acid anhydride to the hydroxyl groups present in the side chains.

[0022] (7) A carboxyl group-containing resin obtained by reacting a polyfunctional epoxy resin in which the hydroxyl groups of a bifunctional (solid) epoxy resin are further epoxidized with epichlorohydrin, with (meth)acrylic acid, and then adding a dibasic acid anhydride to the resulting hydroxyl groups.

[0023] (8) Carboxyl group-containing polyester resins obtained by reacting a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid with a bifunctional oxetane resin, and then adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to the resulting primary hydroxyl groups.

[0024] (9) A carboxyl group-containing resin obtained by reacting an epoxy compound having multiple epoxy groups in one molecule with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and an unsaturated group-containing monocarboxylic acid, such as (meth)acrylic acid, and then reacting the alcoholic hydroxyl groups of the resulting reaction product with a polybasic acid anhydride, such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic acid.

[0025] (10) A carboxyl group-containing resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, reacting the resulting reaction product with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.

[0026] (11) A carboxyl group-containing resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, reacting the resulting reaction product with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.

[0027] (12) A carboxyl group-containing resin obtained by adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins (1) to (11) above.

[0028] The phenolic hydroxyl group-containing resin is not particularly limited as long as it has a phenolic hydroxyl group in the main chain or side chain, i.e., a hydroxyl group bonded to a benzene ring. A resin containing two or more phenolic hydroxyl groups per molecule is preferred. Examples of resins containing two or more phenolic hydroxyl groups per molecule include, but are not limited to, catechol, resorcinol, hydroquinone, dihydroxytoluene, naphthalenediol, t-butylcatechol, t-butylhydroquinone, pyrogallol, phloroglucinol, bisphenol A, bisphenol F, bisphenol S, biphenol, bixylenol, novolac-type phenolic resins, novolac-type alkylphenolic resins, bisphenol A novolac resins, dicyclopentadiene-type phenolic resins, Xylok-type phenolic resins, terpene-modified phenolic resins, polyvinylphenols, condensates of phenols with aromatic aldehydes having phenolic hydroxyl groups, and condensates of 1-naphthol or 2-naphthol with aromatic aldehydes.

[0029] The alkali-soluble resin preferably has a structure derived from an imide skeleton. This improves the mechanical properties of the cured product of the present invention. In the present invention, the imide skeleton of the alkali-soluble resin having an imide skeleton preferably contains a structure derived from succinimide.

[0030] An alkali-soluble resin having an imide skeleton derived from succinimide can be synthesized, for example, by copolymerizing a maleimide monomer with an unsaturated carboxylic acid monomer. The constituent units of the copolymer may contain a monomer having a hydroxyl group, if necessary, or may contain a structure obtained by reacting an acid group, such as a carboxyl group, of the polymer with a monomer having a functional group reactive with the acid group.

[0031] Examples of maleimide monomers include N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(2-chlorophenyl)maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmethylmaleimide, and N-(2,4,6-tribromophenyl)maleimide. Examples of N-substituted or unsubstituted maleimides include N-substituted maleimides such as N-(2-methylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-laurylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide. These include N-substituted or unsubstituted maleimides such as N-(2-methylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-laurylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide. The content of the maleimide-based monomer-derived structural units in the resin is preferably 10% by mass or more and 60% by mass or less of the total structural units constituting the resin.

[0032] Examples of unsaturated carboxylic acids (monomers) include (meth)acrylic acid, crotonic acid, cinnamic acid, sorbic acid, fumaric acid, and maleic acid. Among these, (meth)acrylic acid is preferred due to its excellent properties in cured products. In another embodiment, other acid groups may be introduced together with or in place of the carboxyl group. Examples of other acid groups include functional groups that undergo a neutralization reaction with alkaline water, such as phenolic hydroxyl groups, carboxylic anhydride groups, phosphate groups, and sulfonic acid groups. Only one of these groups may be present, or two or more may be present. In the following description, descriptions of carboxyl groups also apply to the other acid groups.

[0033] Examples of the hydroxyl group-containing monomer include (di)hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2,3-dihydroxypropyl (meth)acrylate, as well as hydroxyalkyl (meth)acrylamides such as 2-hydroxymethyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylamide, 2-hydroxypropyl (meth)acrylamide, 3-hydroxypropyl (meth)acrylamide, 4-hydroxybutyl (meth)acrylamide, hydroxypivalyl (meth)acrylamide, 5-hydroxypentyl (meth)acrylamide, and 6-hydroxyhexyl (meth)acrylamide. One or more of these can be used. Among these, from the viewpoint of copolymerizability, hydroxyalkyl (meth)acrylates are preferred, and 2-hydroxyethyl (meth)acrylate is particularly preferred.

[0034] The monomer having a functional group capable of reacting with an acid group such as a carboxyl group preferably has a radically polymerizable carbon-carbon double bond (hereinafter, sometimes simply referred to as a radically polymerizable double bond). The functional group capable of reacting with an acid group such as a carboxyl group is preferably selected from the group consisting of a glycidyl group, an oxazolinyl group, an isocyanate group, and an oxetanyl group. The radically polymerizable carbon-carbon double bond is preferably a (meth)acryloyl group. Specific examples of the monomer include glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate.

[0035] The composition may also contain other copolymerizable monomers as long as they do not adversely affect the properties. Examples of such copolymerizable monomers include aromatic monomers not having an ester bond, such as styrene, α-methylstyrene, α-chlorostyrene, and vinyltoluene; vinyl ester monomers, such as vinyl acetate and vinyl adipate; (meth)acrylic monomers, such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; alkyl vinyl ethers and corresponding alkyl vinyl (thio)ethers, such as n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, n-hexyl vinyl ether, cyclohexyl vinyl ether, and 2-ethylhexyl vinyl ether; acid anhydride group-containing monomers, such as maleic anhydride, or monomers obtained by ring-opening the acid anhydride group with alcohols or the like, and unsaturated basic acids other than those mentioned above; N-vinyl monomers, such as N-vinylpyrrolidone and N-vinyloxazolidone; and cyano group-containing monomers, such as acrylonitrile and methacrylonitrile.

[0036] The weight-average molecular weight of the alkali-soluble resin is preferably 1,000 or more and 20,000 or less, more preferably 1,500 or more and 15,000 or less, and even more preferably 2,000 or more and 10,000 or less. When the weight-average molecular weight of the alkali-soluble resin is within the above range, the resin has excellent developability and is particularly effective in reducing residues during development. The weight-average molecular weight can be determined from a standard polystyrene-equivalent value measured by gel permeation chromatography (GPC). The GPC measurement was performed using tetrahydrofuran as an eluent and an RI detector.

[0037] The content of the alkali-soluble resin, calculated as solid content, relative to the total amount of the curable resin composition is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 45% by mass or less, and even more preferably 20% by mass or more and 40% by mass or less. By setting it to 5% by mass or more, the strength of the cured product can be improved. Furthermore, by setting it to 50% by mass or less, the viscosity of the composition can be appropriate, and the coatability, etc. can be improved.

[0038] In the present invention, among the above alkali-soluble resins, it is more preferable to use an alkali-soluble resin having an imide skeleton in combination with an alkali-soluble resin not having an imide skeleton. The weight-average molecular weight of both the alkali-soluble resin having an imide skeleton and the alkali-soluble resin not having an imide skeleton may be 1,000 to 20,000, or at least one of them may not be 1,000 to 20,000. In a preferred embodiment of the present invention, by using an alkali-soluble resin having an imide skeleton with a weight-average molecular weight of 1,000 to 20,000 in combination with an alkali-soluble resin not having an imide skeleton with a weight-average molecular weight of 1,000 to 20,000, it is possible to further improve, in particular, chemical resistance and developability without reducing resolution.

[0039] The content of the alkali-soluble resin having an imide skeleton is preferably 5% by mass or more and 50% by mass or less, more preferably 7% by mass or more and 45% by mass or less, and even more preferably 10% by mass or more and 40% by mass or less, calculated as solid content, relative to the total amount of the curable resin composition. When the content of the alkali-soluble resin having an imide skeleton is within the above range, the strength of the cured product can be improved, and the viscosity of the composition can be appropriate, thereby improving the coatability, etc.

[0040] The content of the alkali-soluble resin having an imide skeleton is preferably 10% by mass or more and 100% by mass or less, more preferably 20% by mass or more and 100% by mass or less, and even more preferably 40% by mass or more and 100% by mass or less, based on the total content of the alkali-soluble resin having an imide skeleton and the alkali-soluble resin not having an imide skeleton. When the content of the alkali-soluble resin having an imide skeleton is within the above range, the strength of the cured product can be improved, and the viscosity of the composition can be appropriate, thereby improving the coatability, etc.

[0041] (cellulose resin) The curable resin composition of the present invention contains a cellulose derivative as the cellulose resin, which can improve the film-forming properties of the dry film. Examples of the cellulose resin that can be used include cellulose esters, cellulose carbamates, and cellulose ethers. The cellulose resins can be used alone or in combination of two or more. In the present invention, cellulose esters are preferred, which can improve the film-forming properties of the dry film.

[0042] Examples of cellulose esters include aliphatic organic acid esters (cellulose acetates such as cellulose diacetate and cellulose triacetate; C esters such as cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose acetate butyrate). 1-6 Aliphatic carboxylic acid esters, aromatic organic acid esters (cellulose phthalate, cellulose benzoate, etc.) 7-12 Examples of cellulose esters include aromatic carboxylic acid esters, inorganic acid esters (e.g., cellulose phosphate, cellulose sulfate, etc.), and mixed acid esters such as cellulose acetate-nitrate esters. These cellulose esters can be used alone or in combination. Among these, cellulose C such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate are particularly preferred. 2―4 Acylate is preferred, and cellulose acetate C such as cellulose acetate propionate is preferred. 3-4 Acylates are particularly preferred.

[0043] More preferred cellulose esters are those in which the hydroxyl groups of cellulose are esterified with an organic acid, and specifically, those represented by the following general formula (1): [ka] (In formula (1), R 1 , R 2 and R 3 are each independently hydrogen, an acyl group, or a group represented by the following general formula (2): [ka] (In formula (2), R 4 is hydrogen or a methyl group, and R 5 is hydrogen, a methyl group, an ethyl group, or a glycidyl group; 1 , R 2 and R 3 At least one of the groups is hydrogen, and n is an integer of 1 or more, the upper limit of which is determined by the molecular weight described below.

[0044] In the cellulose ester represented by the above formula (1), the content of acyl groups relative to the cellulose resin is preferably more than 0% by mass and not more than 60% by mass, more preferably from 5% by mass to 55% by mass.

[0045] In the cellulose ester represented by formula (1), the hydroxyl group content relative to the cellulose resin is preferably 0% to 8% by mass, more preferably 1% to 7% by mass, and even more preferably 3% to 6% by mass. As an organic acid ester, the acetyl group content is preferably 0% to 40% by mass, more preferably 0.2% to 20% by mass, and even more preferably 0.4% to 2.0% by mass. The propionyl and / or butyryl group content is preferably 0% to 55% by mass, more preferably 40% to 50% by mass, and even more preferably 41% to 44% by mass. When the functional group content is within the above range, the viscosity of a composition containing the cellulose ester is improved, resulting in good handleability. Note that "% by mass" refers to the mass percentage of hydrogen or organic acid ester relative to the mass of cellulose.

[0046] Commercially available products of such cellulose esters include cellulose acetates such as CA-398-3, CA-398-6, CA-398-10, CA-398-30, and CA-394-60S; cellulose acetate butyrates such as CAB-551-0.01, CAB-551-0.2, CAB-553-0.4, CAB-531-1, CAB-500-5, and CAB-381-0.1; Examples of cellulose acetate propionates include CAB-381-0.5, CAB-381-2, CAB-381-20, CAB-381-20BP, CAB-321-0.1, and CAB-171-15, and examples of cellulose acetate propionates include CAP-504-0.2, CAP-482-0.5, and CAP-482-20 (all of the above cellulose esters are trade names manufactured by Eastman Chemical Japan Co., Ltd.). Among these, cellulose acetate butyrate and cellulose acetate propionate are preferred from the viewpoint of solubility in solvents, and cellulose acetate propionate is even more preferred from the viewpoint of odor.

[0047] The number-average molecular weight of the cellulose resin is preferably 5,000 to 500,000, more preferably 7,000 to 100,000, and even more preferably 10,000 to 50,000. When the molecular weight is within the above range, a good balance between film-forming properties and developability is achieved. The number-average molecular weight can be determined from the standard polystyrene equivalent value by gel permeation chromatography (GPC). The GPC measurement was performed using tetrahydrofuran as the eluent and an RI detector.

[0048] The content of the cellulose resin, in terms of solid content, relative to the total amount of the curable resin composition, is preferably 0.1% by mass or more and 5.0% by mass or less, more preferably 0.3% by mass or more and 4.0% by mass or less, and even more preferably 0.5% by mass or more and 3.0% by mass or less. When the content of the cellulose resin is 0.1% by mass or more, film-forming properties are improved. On the other hand, when it is 5.0% by mass or less, a good balance between film-forming properties and developability can be achieved.

[0049] The content of the cellulose resin is preferably 5 parts by mass or more and 100 parts by mass or less, more preferably 10 parts by mass or more and 75 parts by mass or less, and even more preferably 20 parts by mass or more and 50 parts by mass or less, relative to 100 parts by mass of the polyfunctional ethylene oxide-modified monomer. When the content of the cellulose resin is 5 parts by mass or more and 100 parts by mass or less, a good balance between film-forming properties and developability can be achieved.

[0050] The glass transition temperature Tg of the cellulose resin is preferably 70° C. or higher and lower than 200° C., and more preferably 100° C. or higher and lower than 180° C. If the glass transition temperature is lower than 70° C., it is difficult to obtain sufficient tack-free properties, while if it is higher than 200° C., the folding resistance of the cured product may be impaired. The glass transition temperature Tg in this specification refers to a glass transition temperature measured by differential scanning calorimetry (DSC) in accordance with the method described in "5.17.5 DSC method" of JIS C 6481:1996.

[0051] The cellulose resin used in the present invention is preferably derived from a natural product from the viewpoint of preventing fossil fuel depletion. Furthermore, the starting material used for the cellulose resin of the present invention can be produced from recycled materials such as recycled pulp, which can provide a composition that is environmentally preferable from the viewpoint of reducing CO2 emissions.

[0052] (Other thermoplastic resins) The curable resin composition of the present invention may further contain other thermoplastic resins in order to improve the film-forming properties of the dry film.

[0053] Examples of the other thermoplastic resins include styrene-based resins, (meth)acrylic polymers, organic acid vinyl ester-based polymers, vinyl ether-based polymers, halogen-containing resins, polyolefins (including alicyclic polyolefins), polycarbonates, polyesters, polyamides, thermoplastic polyurethanes, polysulfone-based resins (polyethersulfone, polysulfone, etc.), polyphenylene ether-based resins (2,6-xylenol polymers, etc.), silicone resins (polydimethylsiloxane, polymethylphenylsiloxane, etc.), rubber or elastomers (diene rubbers such as polybutadiene and polyisoprene, styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, acrylic rubbers, urethane rubbers, silicone rubbers, etc.), etc. These thermoplastic resins can be used alone or in combination of two or more.

[0054] Among the other thermoplastic resins, styrene-based resins, (meth)acrylic polymers, vinyl acetate-based polymers, vinyl ether-based polymers, halogen-containing resins, alicyclic polyolefins, polycarbonates, polyesters, polyamides, silicone-based resins, rubbers, elastomers, and the like are commonly used because of their excellent transparency when used in forms such as photosensitive materials and optical applications.

[0055] The content of the other thermoplastic resin is not particularly limited and can be appropriately set depending on the effect of improving film-forming properties and the mechanical properties of the film and cured product of the present invention.

[0056] (Polyfunctional ethylene oxide modified monomer) In the present invention, the polyfunctional ethylene oxide-modified monomer is a photopolymerizable monomer having two or more ethylenically unsaturated double bonds in one molecule, and is a monomer containing an ethylene oxide unit (—CH2CHO—) in its backbone structure. The inclusion of this photopolymerizable monomer increases the crosslink density during photopolymerization of the curable resin composition, thereby improving the heat resistance of the curable resin composition and the chemical resistance of the cured product. Furthermore, the inclusion of an ethylene oxide unit improves hydrophilicity and reduces development residues. Examples of such monomers include M-460 (diglycerin ethylene oxide-modified (meth)acrylate, product name, manufactured by Toagosei Co., Ltd.), A-DPH-6E, and A-DPH-12E (ethoxylated dipentaerythritol polyacrylate, all product names, manufactured by Shin-Nakamura Chemical Co., Ltd.). The above-mentioned monomers may be used alone or in combination of two or more. Hereinafter, "ethylene oxide" may also be referred to as "EO."

[0057] The content of the polyfunctional ethylene oxide-modified monomer is preferably 1.0 mass % or more and 20.0 mass % or less, more preferably 1.5 mass % or more and 15.0 mass % or less, and even more preferably 2.0 mass % or more and 9.0 mass % or less, in terms of solid content, relative to the total amount of the curable resin composition. When the content of the polyfunctional ethylene oxide-modified monomer is within the above numerical range, the hydrophilicity of the resin composition of the present invention is improved, development residues are suppressed, and water absorption due to hydrophilicity is also suppressed.

[0058] The content of the polyfunctional ethylene oxide-modified monomer is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 3 parts by mass or more and 45 parts by mass or less, even more preferably 5 parts by mass or more and 40 parts by mass or less, and even more preferably 7 parts by mass or more and 25 parts by mass or less, relative to 100 parts by mass of the total alkali-soluble resin. When the content of the photopolymerizable monomer is within the above-mentioned range, the photocurability of the resin composition of the present invention is good, and pattern formation is easy in alkaline development after irradiation with active energy rays. Furthermore, halation is unlikely to occur, and good resolution can be obtained.

[0059] In the present invention, the polyfunctional ethylene oxide-modified monomer is preferably a pentafunctional or higher photopolymerizable monomer. By including a pentafunctional or higher photopolymerizable monomer, the crosslink density during photopolymerization of the resin composition can be increased, thereby improving the heat resistance of the cured product of the present invention.

[0060] (Other photopolymerizable monomers) Furthermore, in the present invention, in addition to the polyfunctional ethylene oxide-modified monomer, other photopolymerizable monomers that are not modified with ethylene oxide may be further contained. The other photopolymerizable monomers preferably include a trifunctional or higher photopolymerizable monomer, more preferably a pentafunctional or higher photopolymerizable monomer. Examples of trifunctional or higher photopolymerizable monomers include trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, bis-(2-acryloxyethyl)isocyanurate, tris-(2-acryloxyethyl)isocyanurate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, polyepoxy tetra(meth)acrylate, polyester tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, tripentaerythritol Examples of the poly(meth)acrylate include penta(meth)acrylates such as dipentaerythritol penta(meth)acrylate, hexa(meth)acrylates such as dipentaerythritol hexa(meth)acrylate and tripentaerythritol hexa(meth)acrylate, hepta(meth)acrylates such as tripentaerythritol hepta(meth)acrylate, octa(meth)acrylates such as tripentaerythritol octa(meth)acrylate, penta- or higher functional polyurethane poly(meth)acrylates, penta- or higher functional polyepoxy poly(meth)acrylates, penta- or higher functional polyester poly(meth)acrylates, etc. Furthermore, examples thereof include modified products such as polycaprolactone-modified adducts and polycarbonate-modified adducts of these penta- or higher functional (meth)acrylate monomers, tetra- or higher functional polyurethane poly(meth)acrylates, penta- or higher functional polyepoxy poly(meth)acrylates, and penta- or higher functional polyester poly(meth)acrylates, etc. These pentafunctional or higher functional photopolymerizable monomers may be used singly or in combination of two or more.

[0061] Preferred examples of commercially available photopolymerizable monomers include dipentaerythritol triacrylate (a commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (a commercially available product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (a commercially available product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol hexa(meth)acrylate (a commercially available product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.). In addition, examples of polymerizable compounds that can be used include pentaerythritol tetraacrylate (NK Ester A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (KAYARAD HDDA, manufactured by Nippon Kayaku Co., Ltd.), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), and Light Acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.).

[0062] (epoxy resin) The epoxy resin may be a known compound having one or more epoxy groups, such as bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, dicyclopentadiene epoxy resin, and triphenylmethane epoxy resin.

[0063] Examples of commercially available epoxy resins include jER 828, 806, 807, YX8000, YX8034, and 834 manufactured by Mitsubishi Chemical Corporation; YD-128, YDF-170, ZX-1059, and ST-3000 manufactured by Nippon Steel Chemical & Material Co., Ltd.; EPICLON 830, 835, 840, 850, N-730A, N-695, and HP-7200L manufactured by DIC Corporation; and RE-306 manufactured by Nippon Kayaku Co., Ltd.

[0064] The content of the epoxy resin is preferably 10% by mass or more and 50% by mass or less, more preferably 15% by mass or more and 45% by mass or less, and even more preferably 20% by mass or more and 40% by mass or less, calculated as solid content, relative to the total amount of the curable resin composition. By setting the content of the epoxy resin within the above range, a cured product having excellent developability and excellent flexibility, adhesion, and heat resistance can be obtained.

[0065] (inorganic filler) Conventional inorganic fillers can be used, including silica, talc, mica, aluminum oxide, calcium oxide, magnesium oxide, zinc oxide, calcium carbonate, magnesium carbonate, fly ash, dewatered sludge, kaolin, clay, calcium hydroxide, aluminum hydroxide, magnesium hydroxide, hydrotalcite, aluminum silicate, magnesium silicate, calcium silicate, wollastonite, potassium titanate, magnesium sulfate, calcium sulfate, magnesium phosphate, sepiolite, zonolite, boron nitride, aluminum borate, silica balloons, glass flakes, glass balloons, steelmaking slag, copper, iron, iron oxide, sendust, alnico magnets, various ferrites and other magnetic powders, cement, glass powder, Neuburg silica, diatomaceous earth, antimony trioxide, magnesium oxysulfate, aluminum hydrate, hydrated gypsum, alum, and barium sulfate. Among these, silica is preferred. These inorganic fillers may be used alone or in combination of two or more.

[0066] The inorganic filler may be surface-treated to enhance dispersibility in the curable resin composition. Use of a surface-treated inorganic filler can suppress aggregation. The surface treatment method is not particularly limited, and any known or commonly used method may be used. However, it is preferable to treat the surface of the inorganic filler with a surface treatment agent having a curable reactive group, such as a coupling agent having a curable reactive group as an organic group.

[0067] Examples of coupling agents that can be used include silane-based, titanate-based, aluminate-based, and zircoaluminate-based coupling agents. Among these, silane-based coupling agents are preferred. Examples of such silane-based coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminomethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. These can be used alone or in combination. It is preferred that these silane-based coupling agents are immobilized on the surface of the inorganic filler in advance by adsorption or reaction. Here, the amount of the coupling agent to be treated with respect to 100 parts by mass of the inorganic filler is preferably 0.5 to 10 parts by mass.

[0068] From the viewpoint of dispersibility, the inorganic filler preferably has an average particle size (D50) of 5 nm or more and 500 nm or less, more preferably 7 nm or more and 180 nm or less, and even more preferably 10 nm or more and 100 nm or less. The average particle size refers to the particle size at 50% cumulative volume obtained using a laser diffraction / scattering particle size distribution measurement method. The average particle size of silica refers to the value measured as described above for the inorganic filler before preparing (stirring and kneading) the curable resin composition.

[0069] The content of the inorganic filler is preferably 3% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less, in terms of solid content, relative to the total amount of the curable resin composition. When the content of the inorganic filler is within the above range, the resolution, thermal expansion coefficient, and dielectric properties of the cured product are more likely to be improved.

[0070] (hardening agent) Examples of the curing agent include imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Commercially available examples include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd., and U-CAT 3513N (trade name of a dimethylamine-based compound), DBU, DBN, and U-CAT SA 102 (all bicyclic amidine compounds and salts thereof) manufactured by San-Apro Co., Ltd. However, the curing agent is not limited to these, and any curing agent that promotes the reaction of at least one of an epoxy group and an oxetanyl group with a carboxyl group may be used, and they may be used alone or in combination of two or more.

[0071] Furthermore, S-triazine derivatives such as guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, and 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct can also be used, and these compounds that also function as adhesion promoters are preferably used in combination with a curing agent. The curing agents may be used alone or in combination of two or more.

[0072] The content of the curing agent is preferably 0.1 to 8 mass %, more preferably 0.3 to 5 mass %, calculated as solid content, based on the total amount of the curable resin composition.

[0073] (Photopolymerization initiator) The photopolymerization initiator is used to react a photosensitive alkali-soluble resin or a photopolymerizable monomer by exposure to light. Any known photopolymerization initiator can be used. One photopolymerization initiator may be used alone, or two or more photopolymerization initiators may be used in combination.

[0074] Specific examples of the photopolymerization initiator include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl Phosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and other bisacylphosphine oxides; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphine Monoacylphosphine oxides such as isopropyl sphinic acid ester and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, 1-hydroxy-cyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2 hydroxyacetophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoins such as benzoin, benzil, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; benzoin alkyl ethers; benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone;Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl)-1-[4-(4-morpholinyl)phenyl]-1-butanone acetophenones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, Anthraquinones such as 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; benzoic acid esters such as ethyl 4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, and p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl Examples of suitable oxime esters include bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and titanocenes such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyr-1-yl)ethyl)phenyl]titanium; phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, and tetramethylthiuram disulfide.

[0075] Commercially available α-aminoacetophenone photopolymerization initiators include Omnirad 907, 369, 369E, and 379 manufactured by IGM Resins. Commercially available acylphosphine oxide photopolymerization initiators include Omnirad 819 manufactured by IGM Resins. Commercially available oxime ester photopolymerization initiators include Irgacure OXE01 and OXE02 manufactured by BASF Japan Ltd., N-1919, ADEKA Arcles NCI-831 and NCI-831E manufactured by ADEKA Corporation, and TR-PBG-304 manufactured by Changzhou New Advanced Electronic Materials Co., Ltd.

[0076] Other examples include carbazole oxime ester compounds described in JP-A Nos. 2004-359639, 2005-097141, 2005-220097, 2006-160634, 2008-094770, JP-T Nos. 2008-509967, 2009-040762, and 2011-80036.

[0077] The content of the photopolymerization initiator is preferably 0.1 to 10 mass %, more preferably 1 to 7 mass %, calculated as solid content, relative to the total amount of the curable resin composition. When the content of the photopolymerization initiator is 0.1 mass % or more, the photocurability of the curable resin composition is good, and the properties of the cured product, such as chemical resistance, are also good. On the other hand, when the content is 10 mass % or less, light absorption at the surface of the resist film (cured product) is good, and deep curing is less likely to decrease.

[0078] A photoinitiator aid, sensitizer, or catalyst may be used in combination with the above-described photopolymerization initiator. Examples of the photoinitiator aid, sensitizer, or catalyst include benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. Thioxanthone compounds, such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone, are particularly preferred. The inclusion of a thioxanthone compound can improve deep curing properties. While these compounds may be used as photopolymerization initiators, they are preferably used in combination with a photopolymerization initiator. The photoinitiator aid, sensitizer, or catalyst may be used alone or in combination of two or more.

[0079] These photopolymerization initiators, photoinitiator assistants, sensitizers, and catalysts absorb light of specific wavelengths, which can reduce sensitivity in some cases and function as ultraviolet absorbers. However, they are not used solely for the purpose of improving the sensitivity of the resin composition. By absorbing light of specific wavelengths as needed, they can increase the photoreactivity of the surface, change the line shape and openings of the resist pattern to vertical, tapered, or reverse tapered, and improve the accuracy of the line width and opening diameter.

[0080] (coloring agent) A colorant can be blended into the curable resin composition of the present invention. The colorant is not particularly limited, and known colorants such as red, blue, green, and yellow can be used, and any of pigments, dyes, and coloring matters can be used. However, from the viewpoint of reducing the environmental load and having little effect on the human body, a colorant that does not contain halogen is preferred.

[0081] Red colorants include monoazos, disazos, azolakes, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azos, anthraquinones, and quinacridones, and specific examples thereof include those having the following Color Index (CI; published by The Society of Dyers and Colourists) numbers:

[0082] Examples of monoazo red colorants include Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, and 269. Examples of disazo red colorants include Pigment Red 37, 38, and 41. Examples of monoazo lake-based red colorants include Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1, and 68. Examples of benzimidazolone-based red colorants include Pigment Red 171, 175, 176, 185, and 208. Examples of perylene-based red colorants include Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, and 224. Examples of diketopyrrolopyrrole red colorants include Pigment Red 254, 255, 264, 270, and 272. Examples of condensed azo red colorants include Pigment Red 220, 144, 166, 214, 220, 221, and 242. Examples of anthraquinone red colorants include Pigment Red 168, 177, and 216, Solvent Red 149, 150, 52, and 207. Examples of quinacridone red colorants include Pigment Red 122, 202, 206, 207, and 209.

[0083] Blue colorants include phthalocyanine and anthraquinone types, and pigment types include compounds classified as pigments, such as Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, and 60. Dye types include Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, and 70. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

[0084] Yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone colorants. For example, anthraquinone yellow colorants include Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, and 202. Isoindolinone yellow colorants include Pigment Yellow 110, 109, 139, 179, and 185. Condensed azo yellow colorants include Pigment Yellow 93, 94, 95, 128, 155, 166, and 180. Benzimidazolone yellow colorants include Pigment Yellow 120, 151, 154, 156, 175, and 181. Examples of monoazo yellow colorants include Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, and 183. Examples of disazo yellow colorants include Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, and 198.

[0085] Other colorants such as purple, orange, brown, and black may also be added. Specific examples include Pigment Black 1, 6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, and 32, Pigment Violet 19, 23, 29, 32, 36, 38, and 42, Solvent Violet 13 and 36, CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, and 73, Pigment Brown 23 and 25, and carbon black.

[0086] (organic solvent) The curable resin composition of the present invention may contain an organic solvent for the purpose of adjusting the viscosity when preparing the composition or when applying it to a substrate or film. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, and tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, diethylene glycol monoethyl ether acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, petroleum naphtha, and solvent naphtha. These organic solvents may be used alone or in combination of two or more.

[0087] The content of the organic solvent is not particularly limited, and can be appropriately set depending on the target viscosity so as to facilitate preparation of the curable resin composition.

[0088] (Other added ingredients) The curable resin composition of the present invention may further contain, as necessary, components such as cyanate compounds, elastomers, mercapto compounds, urethanization catalysts, thixotropic agents, adhesion promoters, block copolymers, chain transfer agents, polymerization inhibitors, copper inhibitors, antioxidants, rust inhibitors, thickeners, at least one of silicone-based, fluorine-based, and polymer-based antifoaming agents and leveling agents, imidazole-based, thiazole-based, and triazole-based silane coupling agents, and flame retardants such as phosphinates, phosphate ester derivatives, and phosphorus compounds such as phosphazene compounds. These may be known in the field of electronic materials.

[0089] [Preparation method] The curable resin composition of the present invention can be prepared by weighing and blending the components, pre-mixing them with a mixer, and then dispersing and kneading the components in a kneader.

[0090] Examples of the kneading machine include a bead mill, a ball mill, a sand mill, a three-roll mill, and a two-roll mill. Among these, it is preferable to use a bead mill in order to improve dispersibility. Dispersion conditions such as the type and particle size of the beads of the bead mill can be appropriately set depending on the target viscosity.

[0091] [Application] The curable resin composition of the present invention is useful for forming a pattern layer as a permanent coating on a printed wiring board, and is also useful for forming a solder resist, a coverlay, an interlayer insulating layer, a rewiring layer, etc. Furthermore, since the curable resin composition of the present invention can form a cured product that has excellent film strength even when it is thin, it can also be suitably used for forming a pattern layer on a printed wiring board that requires thinning, such as a package substrate (a printed wiring board used for a semiconductor package).

[0092] Furthermore, the curable resin composition of the present invention can be used not only for forming a pattern layer but also for applications in which a pattern layer is not formed, such as molding applications (sealing applications).

[0093] [Dry film] The curable resin composition of the present invention can also be in the form of a dry film comprising a first film and a resin layer formed on the first film, the resin layer being a dried coating of the curable resin composition. The term "first film" as used herein refers to a film that is at least adhered to the resin layer when the dry film is laminated onto a substrate or other base material by heating or other means so that the resin layer side of the dry film is in contact with the curable resin layer. The first film may be peeled from the resin layer in a post-lamination step. In particular, in the present invention, peeling from the resin layer in a post-exposure step is preferred. To form a dry film, the curable resin composition of the present invention is diluted with the organic solvent to an appropriate viscosity, and then coated to a uniform thickness on the first film using a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater, or the like. The film is typically dried at a temperature of 50 to 130°C for 1 to 30 minutes to obtain a film. There are no particular restrictions on the thickness of the coating film, but it is generally selected appropriately within the range of 1 to 150 μm, preferably 5 to 60 μm, in terms of thickness after drying.

[0094] The first film can be any known film without particular limitation, and examples of suitable films include polyester films such as polyethylene terephthalate and polyethylene naphthalate, and films made of thermoplastic resins such as polyimide films, polyamideimide films, polypropylene films, and polystyrene films. Among these, polyester films are preferred from the viewpoints of heat resistance, mechanical strength, ease of handling, etc. A laminate of these films can also be used as the first film.

[0095] From the viewpoint of improving mechanical strength, the above-mentioned thermoplastic resin film is preferably a film stretched in a uniaxial or biaxial direction.

[0096] The thickness of the first film is not particularly limited, but can be, for example, 10 μm to 150 μm.

[0097] After forming a resin layer consisting of a dried coating film of the curable resin composition of the present invention on the first film, it is preferable to further laminate a peelable second film on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer. The second film in the present invention refers to a film that is peeled from the resin layer before lamination when the dry film is laminated by heating or the like so that the resin layer side of the dry film is in contact with a base material such as a substrate to form an integral mold. Examples of the peelable second film that can be used include polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc., and any film can be used as long as the adhesive strength between the resin layer and the second film is smaller than the adhesive strength between the resin layer and the first film when the second film is peeled off.

[0098] The thickness of the second film is not particularly limited, but can be, for example, 10 μm to 150 μm.

[0099] [Cured product] The cured product of the present invention is obtained by curing the curable resin composition of the present invention or the resin layer of the dry film of the present invention. The manufacturing conditions such as curing conditions will be described later in [Method for manufacturing printed wiring board]. The cured product of the present invention can be suitably used for printed wiring boards, electronic components, etc.

[0100] [Printed wiring board] The printed wiring board of the present invention comprises a circuit board and a cured product obtained from the curable resin composition or the resin layer of the dry film of the present invention.

[0101] Examples of the substrates include printed wiring boards and flexible printed wiring boards with circuits already formed using copper or the like, as well as copper-clad laminates for high-frequency circuits made from materials such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluororesin / polyethylene / polyphenylene ether, polyphenylene oxide / cyanate, etc., including copper-clad laminates of all grades (FR-4, etc.), as well as metal substrates, polyimide film, polyethylene terephthalate film, polyethylene naphthalate (PEN) film, glass substrates, ceramic substrates, wafer plates, etc.

[0102] [Printed wiring board manufacturing method] In a method for producing a printed wiring board of the present invention, for example, the curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method using the organic solvent, and applied to a substrate by a method such as dip coating, flow coating, roll coating, bar coating, screen printing, or curtain coating, and then the organic solvent contained in the composition is evaporated and dried (pre-dried) at a temperature of 60 to 100°C for 15 to 90 minutes to form a tack-free resin layer. Alternatively, in the case of a dry film, the resin layer is attached to the substrate using a laminator or the like so that the resin layer is in contact with the substrate, forming a resin layer on the substrate.

[0103] The dry film is preferably applied to the substrate under pressure and heat using a vacuum laminator or the like. By using such a vacuum laminator, even if a circuit-formed substrate is used, the dry film adheres tightly to the circuit substrate, preventing the inclusion of air bubbles and improving the filling of recesses in the substrate surface. The pressure is preferably about 0.1 to 2.0 MPa, and the heating temperature is preferably 40 to 120°C.

[0104] The volatilization drying carried out after the curable resin composition of the present invention is applied to a substrate can be carried out using a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, etc. (a method in which hot air in a dryer equipped with a heat source of an air heating type using steam is brought into countercurrent contact with the substrate, or a method in which hot air is blown onto the substrate from a nozzle.) Examples of the apparatus include a hot air circulation drying oven such as DF610 manufactured by Yamato Scientific Co., Ltd.

[0105] After forming a resin layer on a substrate, it is selectively exposed to active energy rays through a photomask with a predetermined pattern formed thereon, and the unexposed areas are developed with a dilute alkaline aqueous solution (e.g., a 0.3 to 3.0 mass % sodium carbonate aqueous solution) to form a patterned cured product. In the case of a dry film, after exposure, the first film is peeled off from the dry film and development is carried out to form a patterned cured product on the substrate. Note that, as long as the properties are not impaired, the first film may be peeled off from the dry film before exposure, and the exposed resin layer may be exposed and developed.

[0106] The exposure device used for the above-mentioned active energy ray irradiation may be a device equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like, and capable of irradiating ultraviolet rays in the range of 350 to 450 nm. Furthermore, a direct imaging device (for example, a laser direct imaging device that directly draws an image with a laser based on CAD data from a computer) may also be used. The lamp or laser light source of the direct imaging device may have a maximum wavelength in the range of 350 to 450 nm. The exposure dose for image formation varies depending on factors such as the film thickness, but is generally 10 to 1,000 mJ / cm. 2 , preferably 20 to 800 mJ / cm 2 The range may be:

[0107] The developing method may be a dipping method, a shower method, a spray method, a brush method, or the like, and the developing solution may be an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, or an amine.

[0108] Furthermore, the cured product is irradiated with active energy rays and then heat-cured (for example, at a temperature of 100 to 220°C for 30 to 90 minutes), or is irradiated with active energy rays (for example, at a temperature of 1,000 to 2,000 mJ / cm 2 By performing final curing (main curing) by heating alone, or by heat curing alone, a cured product with excellent properties such as adhesion and hardness can be formed. Examples of equipment include a UV conveyor using a high-pressure mercury lamp, such as the QRM-2082 manufactured by Oak Manufacturing Co., Ltd. [Example]

[0109] The present invention will be described in more detail below using examples, but the present invention is not limited to the following examples. In the following, "parts" and "%" are all based on mass in terms of solid content unless otherwise specified.

[0110] (Synthesis Example 1: Synthesis of Alkali-Soluble Resin 1) A separable flask equipped with a condenser was charged with 82.4 parts of propylene glycol monomethyl ether acetate and 35.3 parts of isopropanol as a reaction vessel. The atmosphere was replaced with nitrogen and the temperature was raised to 100°C. Meanwhile, a mixture of 40 parts of N-phenylmaleimide, 128 parts of propylene glycol monomethyl ether acetate, and 32 parts of isopropanol was charged into dropping vessel 1. A mixture of 13 parts of styrene, 20 parts of 2-hydroxyethyl methacrylate, 27 parts of methacrylic acid, and 22.2 parts of isopropanol was charged into dropping vessel 2. 10 parts of Perbutyl O (t-butylperoxy-2-ethylhexanoate, product of NOF Corporation) was charged into dropping vessel 3 as a polymerization initiator. While maintaining the reaction temperature at 100°C, dropwise addition was carried out from dropping vessels 1 to 3 over a period of 3 hours. After completion of dropwise addition, the reaction was continued for an additional 30 minutes at 100°C. Thereafter, the reaction temperature was raised to 115°C, and the reaction was continued for 1.5 hours to obtain a polymer solution prior to the reaction for introducing radical polymerizable double bonds. Next, 13.7 parts of Cyclomer M100 (trade name: 3,4-epoxycyclohexylmethyl methacrylate, manufactured by Daicel Corporation), 31.2 parts of propylene glycol monomethyl ether acetate, 0.7 parts of triphenylphosphine as a reaction catalyst, and 0.2 parts of Antage W-400 (trade name: 2,2'-methylenebis(4-methyl-6-tert-butylphenol) manufactured by Kawaguchi Chemical Industry Co., Ltd.) as a polymerization inhibitor were added to this polymer solution, and the mixture was reacted at 115°C while bubbling a mixed gas of nitrogen and oxygen (oxygen concentration 7%) to obtain a solution of an alkali-soluble photosensitive resin. The various physical properties of the obtained alkali-soluble photosensitive resin were measured, and the weight average molecular weight was 7,400, the solid content concentration obtained by heating and drying at 160°C under vacuum was 32.0%, and the acid value per solid content was 124 mgKOH / g.

[0111] (Synthesis Example 2: Synthesis of Alkali-Soluble Resin 2) First, 119.4 parts of novolac cresol resin (Showa Denko K.K.'s Shownol CRG951, OH equivalent: 119.4), 1.19 parts of potassium hydroxide, and 119.4 parts of toluene were charged into an autoclave equipped with a thermometer, a nitrogen introducing device / alkylene oxide introducing device, and a stirrer. The system was purged with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 parts of propylene oxide was gradually added dropwise, and the temperature was maintained at 125-132°C and the pressure at 0-4.8 kg / cm. 2The reaction was carried out at 100°C for 16 hours. The system was then cooled to room temperature, and 1.56 parts of 89% by weight phosphoric acid was added to the resulting reaction solution and mixed to neutralize the potassium hydroxide, yielding a propylene oxide reaction solution of novolac cresol resin with a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / eq. The resulting novolac cresol resin had an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group. 293.0 parts of the resulting alkylene oxide reaction solution of novolac cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone, and 252.9 parts of toluene were charged into a reactor equipped with a stirrer, thermometer, and air inlet tube. Air was blown in at a rate of 10 ml / min, and the mixture was stirred while the reaction was carried out at 110°C for 12 hours. The water produced by the reaction was distilled as an azeotrope with toluene, and 12.6 parts of water were distilled off. The system was then cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 parts of 15% aqueous sodium hydroxide solution and washed with water. The toluene was then distilled off using an evaporator while being replaced with 118.1 parts of diethylene glycol monoethyl ether acetate (carbitol acetate), yielding a novolac acrylate resin solution. Next, 332.5 parts of the resulting novolac acrylate resin solution and 1.22 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, thermometer, and air inlet tube. Air was blown in at a rate of 10 ml / min. While stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added. The reaction was carried out at a temperature of 95 to 101°C for 6 hours, and then cooled to yield an alkali-soluble resin solution with a solid acid value of 88 mgKOH / g, a weight-average molecular weight of 2550, and a solids content of 65.8%. In the examples, the weight average molecular weight values ​​are values ​​measured by gel permeation chromatography (GPC).

[0112] [Examples 1 to 4, Comparative Examples 1 to 5] (Preparation of Curable Resin Composition) For each curable resin composition, the components were blended according to the formulation shown in Table 1 below and mixed with a stirrer.

[0113] [Table 1]

[0114] The blending amounts in Table 1 are in parts by mass (solid content equivalent). Details of each component in Table 1 are as follows: *1: Alkali-soluble resin 1 (weight average molecular weight 7400) from Synthesis Example 1 *2: Alkali-soluble resin 2 (weight average molecular weight 2550) from Synthesis Example 2 *3: CAP-504-0.2, cellulose acetate propionate, manufactured by Eastman Chemical Japan Co., Ltd. (number average molecular weight 15,000) *4: CAP-482-0.5, cellulose acetate propionate, manufactured by Eastman Chemical Japan Co., Ltd. (number average molecular weight 25,000) *5: CAP-482-20, cellulose acetate propionate, manufactured by Eastman Chemical Japan Co., Ltd. (number average molecular weight 75,000) *6: Nanostrength M65N, long-chain copolymer resin, manufactured by Arkema Japan Co., Ltd. *7: YX6954BH30, phenoxy resin, manufactured by Mitsubishi Chemical Corporation *8: 1,2-SBS, styrene butadiene styrene resin, manufactured by Nippon Soda Co., Ltd. *9: A-DPH-12E, ethoxylated dipentaerythritol polyacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. *10: DPHA, dipentaerythritol hexaacrylate *11: EPICLON HP-7200L, dicyclopentadiene epoxy resin, manufactured by DIC Corporation *12: Admanano YA050C-HHL, spherical silica particles, manufactured by Admatechs Co., Ltd. (average particle size 50 nm, vinyl silane treatment) *13: Curesol 1B2PZ, imidazole-based epoxy resin curing agent, manufactured by Shikoku Chemicals Corporation *14: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, acylphosphine oxide photopolymerization initiator *15: Quinopower QS-30, 4-methoxy-1-naphthol, manufactured by Air Water Performance Chemicals Inc.

[0115] (Evaluation of film-forming properties) <Creating an evaluation board> The curable resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 5 shown in Table 1 above were applied to a first film (PET film) using a bar coater so that the film thickness after drying would be 10 μm, and the film was dried at 80° C. for 20 minutes and allowed to cool to room temperature. The obtained dry film was visually observed from the surface side of the resin layer to check for the presence or absence of repellency and streaks.

[0116] (flick) The surface of the resin layer was visually observed to check for repellency. The film-forming properties were evaluated based on the following criteria, and the evaluation results are shown in Table 2. ◯ or △ was considered to be acceptable. [Evaluation criteria] ○: No repulsion △: Partially occurs ×: Occurs on the entire surface

[0117] (streaks) The surface of the resin layer was visually observed to check for the presence or absence of streaks. The film-forming properties were evaluated based on the following criteria. The evaluation results are shown in Table 2. [Evaluation criteria] ○: No streaks ×: Streaks present

[0118] (Evaluation of developability) <Creating an evaluation board> The curable resin compositions obtained in Examples 1 to 4 and Comparative Example 5 shown in Table 1 above were applied to a first film using an applicator so that the film thickness after drying would be 10 μm, dried at 80°C for 20 minutes, and allowed to cool to room temperature. The film was then laminated onto a copper-clad laminate at 90°C and left to stand for at least 1 hour, after which an opening pattern was exposed to light at an optimal exposure dose using an i-line single beam projection exposure machine. After leaving the film for a certain period of time, the first film on the surface was peeled off, and development was carried out for 90 seconds using a 30°C 1% by mass aqueous solution of sodium carbonate at a spray pressure of 0.2 MPa. The substrate was then exposed to light in a UV conveyor furnace for an integrated exposure dose of 1000 mJ / cm. 2 After exposure to light, the coating was cured by heating at 180°C for 60 minutes. The resulting evaluation substrates were examined using a scanning electron microscope to observe residues at the bottom of vias with an opening diameter of 10 μm. The developability was evaluated based on the following criteria, and the evaluation results are shown in Table 2. A ◎, ○, or △ was considered acceptable. [Evaluation criteria] ⊚: No residue was found on the bottom of the via. ◯: More than 0% and less than 50% of the via bottom was covered with residue. △: 50% or more and less than 90% of the bottom of the via was covered with residue. ×: 90% or more of the bottom of the via was covered with residue. Comparative Examples 1 to 4 were not evaluated due to poor film-forming properties.

[0119] (Evaluation of chemical resistance (acetone crack resistance)) The curable resin compositions obtained in Examples 1 to 4 and Comparative Example 5 shown in Table 1 above were applied to a first film using an applicator so that the film thickness after drying would be 10 μm, dried at 80°C for 20 minutes, and allowed to cool to room temperature. The film was laminated onto a 6-inch wafer at 90°C, left to stand for at least 1 hour, and then subjected to full-surface exposure at an optimum exposure dose using an i-line single-beam projection exposure machine. After being left to stand for a certain period of time, the first film on the surface was peeled off, and development was carried out for 90 seconds using a 30°C 1% by mass aqueous solution of sodium carbonate at a spray pressure of 0.2 MPa. The substrate was then exposed to an integrated exposure dose of 1000 mJ / cm2 in a UV conveyor furnace. 2After exposure to light, the coating was cured by heating at 180°C for 60 minutes. The resulting evaluation substrate was immersed in acetone for 10 minutes, and then the presence or absence of surface cracks was observed using an optical microscope. Acetone crack resistance was evaluated based on the following criteria, and the evaluation results are shown in Table 2. [Evaluation criteria] ○: No cracks were generated after immersion in acetone. ×: Cracks occurred after immersion in acetone. Comparative Examples 1 to 4 were not evaluated due to poor film-forming properties.

[0120] (Evaluation of resolution) A substrate having a cured product was obtained in the same manner as in the above (evaluation of developability) test. The opening diameter of the obtained cured product was observed with a scanning electron microscope, and the resolution was evaluated based on the following criteria to determine whether halation or undercut occurred. The evaluation results are shown in Table 2. [Evaluation criteria] ◯: A good opening diameter was obtained with an opening diameter of 10 μm. ×: A good opening diameter was not obtained with an opening diameter of 10 μm. Comparative Examples 1 to 4 were not evaluated due to poor film-forming properties.

[0121] [Table 2]

[0122] From the evaluation results shown in Table 2, Example 1 was most preferable in terms of film-forming properties and developability, and the other Examples also showed superior film-forming properties to Comparative Examples 1 to 4. This is thought to be because each Example contained a cellulose resin in addition to an alkali-soluble resin and a polyfunctional ethylene oxide-modified monomer, which resulted in good film-forming properties on the PET substrate, excellent resolution and chemical resistance, and reduced development residues. Furthermore, Example 1 exhibited even better developability than the other Examples, which is thought to be due to the fact that Example 1 contains a cellulose resin with a lower molecular weight than the other Examples, or that the cellulose resin content is lower, resulting in increased solubility in the developer. In Comparative Examples 1 to 4, the film-forming properties (repellency and streaks) were lower than in the Examples. This is thought to be because Comparative Examples 1 to 4 did not contain cellulose resin as a binder, which reduced the strength of the dried coating film and made the coating film more likely to break. In Comparative Example 5, the developability was lower than that of each Example. This is thought to be because Comparative Example 5 did not contain an ethylene oxide-modified monomer, which reduced the affinity to the developer and resulted in poor developability.

Claims

1. A curable resin composition comprising an alkali-soluble resin, a cellulose resin, and a polyfunctional ethylene oxide-modified monomer.

2. The curable resin composition according to claim 1 , wherein the alkali-soluble resin has a structure derived from an imide skeleton.

3. The curable resin composition according to claim 1, wherein the alkali-soluble resin has a weight average molecular weight of 1,000 or more and 20,000 or less.

4. The curable resin composition according to claim 1 , wherein the content of the alkali-soluble resin is 5% by mass or more and 50% by mass or less in terms of solid content with respect to the total amount of the curable resin composition.

5. The curable resin composition according to claim 1, wherein the number average molecular weight of the cellulose resin is 5,000 or more and 500,000 or less.

6. The curable resin composition according to claim 1 , wherein the content of the cellulose resin is 0.1 mass % or more and 5.0 mass % or less in terms of solid content with respect to the total amount of the curable resin composition.

7. The curable resin composition according to claim 1, wherein the content of the cellulose resin is 5 parts by mass or more and 100 parts by mass or less relative to 100 parts by mass of the polyfunctional ethylene oxide-modified monomer.

8. The curable resin composition according to claim 1, wherein the polyfunctional ethylene oxide-modified monomer is a pentafunctional or higher ethylene oxide-modified monomer.

9. The curable resin composition according to claim 1, wherein the content of the polyfunctional ethylene oxide-modified monomer is 1.0 mass % or more and 20.0 mass % or less in terms of solid content, based on the total amount of the curable resin composition.

10. A dry film comprising: a first film; and a resin layer formed on the first film, the resin layer being a dried coating film of the curable resin composition according to any one of claims 1 to 9.

11. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 9.

12. A cured product obtained by curing the resin layer of the dry film according to claim 10.

13. A printed wiring board comprising the cured product according to claim 11.

14. A printed wiring board comprising the cured product according to claim 12.

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