Alkaline development type photosensitive resin composition, dry film, cured product, and printed wiring board

Abstract

An alkali developing photosensitive resin composition, which is an alkali developing photosensitive resin composition containing a carboxyl group-containing resin, an epoxy-based thermosetting component, a (meth)acrylic monomer, and a photopolymerization initiator, the equivalent ratio of carboxyl group to epoxy group (carboxyl equivalent / epoxy equivalent) being 5.0 to 8.0, the epoxy-based thermosetting component containing a novolak-type epoxy resin and a difunctional crystalline epoxy resin having a softening point of 70°C to 120°C.

Description

Technical Field

[0001] This invention relates to alkali-developable photosensitive resin compositions, dry films, cured products, and printed wiring boards. Background Technology

[0002] Printed wiring boards (PCBs) used in electronic devices are made by printing circuit patterns of electronic circuits onto a substrate using copper wires, and various components are mounted on these PCBs. When components are mounted on PCBs with exposed copper wires, there is a possibility of copper wire breakage due to external force, or short circuits caused by solder adhering to areas outside the circuit pattern. Therefore, a solder resist layer is formed to protect the circuit pattern and prevent short circuits.

[0003] The solder resist layer is formed, for example, using a photosensitive resin composition via an alkaline development method. The alkaline development method involves coating the entire surface of a substrate with the photosensitive resin composition and drying it to form a coating film. This dried coating film is then exposed to light to partially cure it. Finally, an alkaline solution is used to develop the uncured photosensitive resin composition, thereby forming a pattern.

[0004] In recent years, with the miniaturization and increasing density of electronic devices, there is a demand for finer patterns in addition to traditional sizes. Therefore, in addition to the methods mentioned above, it is possible to form fine holes by laser irradiation of the solder resist layer, thereby forming patterns of various sizes (for example, see Patent Document 1).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: International Publication No. 2013 / 094606. Summary of the Invention

[0008] The problem the invention aims to solve

[0009] On the other hand, forming holes using laser irradiation involves removing a portion of the solder resist film using the laser. During this removal, a component of the solder resist film called "smear" is produced. If installation is performed with smear remaining on the solder resist layer surface, poor bonding may occur. Therefore, a "smear removal" process is required after laser-formed holes. Smear removal typically involves swelling with a concentrated alkaline solution followed by decomposition with a permanganate solution. However, performing smear removal on the solder resist layer can sometimes lead to solder resist peeling.

[0010] On the other hand, to make the solder resist layer resistant to descaling, there are methods to increase the proportion of epoxy resin in the photosensitive resin composition. However, increasing the proportion of epoxy resin in the photosensitive resin composition sometimes leads to a decrease in thermal stability and other properties. In addition, the resolution required by the photosensitive resin composition for forming the solder resist layer, which is an indicator of pattern formation ease, may also deteriorate.

[0011] The present invention is made based on the following circumstances, and its object is to provide an alkali-developable photosensitive resin composition, dry film, cured product, and printed wiring board capable of forming a cured product with good resolution, thermal stability, and resistance to descaling.

[0012] means for solving problems

[0013] The inventors conducted in-depth research and discovered that two main factors are required for the formation of alkali-developable photosensitive resin compositions that produce cured products with good resolution, thermal stability, and resistance to descaling. One is the equivalent ratio of carboxyl groups to epoxy groups (carboxyl equivalent / epoxy equivalent), which is the ratio of carboxyl-containing resin to epoxy thermosetting component. When this equivalent ratio is less than 5.0, the proportion of epoxy thermosetting component decreases, resulting in insufficient resistance to descaling; when this equivalent ratio is greater than 8.0, the proportion of epoxy thermosetting component increases, leading to poorer thermal stability and a decrease in the proportion of carboxyl-containing resin that improves the resolution of the alkali-developable resin composition, thus deteriorating the resolution. The other main factor is the use of a combination of phenolic varnish-type epoxy resin and difunctional crystalline epoxy resin in the epoxy thermosetting component. Since phenolic varnish-type epoxy resin has excellent resistance to descaling and difunctional crystalline epoxy resin has excellent thermal stability, combining these improves resolution, thermal stability, and resistance to descaling.

[0014] That is, the alkaline-developable photosensitive resin composition according to the present invention is characterized by containing a carboxyl-containing resin, an epoxy thermosetting component, a (meth)acrylic acid monomer, and a photopolymerization initiator. The equivalence ratio of carboxyl groups to epoxy groups (carboxyl equivalent / epoxy equivalent) is 5.0–8.0. The epoxy thermosetting components contain phenolic varnish-type epoxy resin and difunctional crystalline epoxy resin with a softening point of 70℃~120℃.

[0015] Furthermore, in the present invention, the weight ratio of phenolic varnish-type epoxy resin to difunctional crystalline epoxy resin (phenolic varnish-type epoxy resin / difunctional crystalline epoxy resin) is preferably 1.0 to 2.0.

[0016] Furthermore, the dry film according to another aspect of the present invention is characterized by having a resin layer obtained from the above-described alkali-developable photosensitive resin composition.

[0017] Furthermore, the cured product according to another aspect of the present invention is characterized in that it is obtained by curing the above-mentioned alkali-developable photosensitive resin composition or the above-mentioned resin layer.

[0018] Furthermore, a printed wiring board according to another aspect of the present invention is characterized by having the aforementioned cured material.

[0019] The effects of the invention

[0020] According to the present invention, it is possible to provide an alkali-developable photosensitive resin composition, a dry film, a cured product, and a printed wiring board that can form a cured product with good resolution, thermal stability, and resistance to descaling. Detailed Implementation

[0021] The following describes the alkaline-developable photosensitive resin composition, dry film, cured product, and printed wiring board involved in this embodiment.

[0022] It should be noted that in this specification, when “~” is used to indicate a range of values, it refers to the range that includes these values ​​(i.e., above and below).

[0023] (Alkali-developable photosensitive resin composition)

[0024] The alkali-developable photosensitive resin composition (hereinafter also referred to as "photosensitive resin composition") involved in this embodiment contains a carboxyl-containing resin, an epoxy thermosetting component, a (meth)acrylic acid monomer, and a photopolymerization initiator, and may also contain other components as needed.

[0025] <Carboxyl-containing resin>

[0026] Carboxyl-containing resins are resins that have carboxyl groups in their molecules, and various conventionally known resins can be used. Photosensitive resin compositions, by containing carboxyl-containing resins, can impart resolution. In particular, from the perspective of photocurability and resolution, carboxyl-containing photosensitive resins having olefinic unsaturated double bonds in their molecules are preferred. The olefinic unsaturated double bonds are preferably attributed to acrylic acid or methacrylic acid or derivatives thereof.

[0027] Specific examples of carboxyl-containing resins include the compounds described below (both oligomers and polymers). These substances can be used alone or in combination of two or more.

[0028] (1) A carboxyl-containing resin obtained by copolymerizing unsaturated carboxylic acids such as (meth)acrylic acid with compounds containing unsaturated groups such as styrene, α-methylstyrene, lower alkyl esters of (meth)acrylic acid, and isobutylene.

[0029] (2) A polyurethane resin containing carboxyl groups obtained by addition polymerization of diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxyl-containing dihydroxy compounds such as dimethylolpropionic acid and dimethylolbutyric acid, as well as diol compounds such as polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A epoxy alkane adduct diols, and compounds with phenolic hydroxyl and alcoholic hydroxyl groups.

[0030] (3) A carboxyl-containing photosensitive polyurethane resin obtained by the addition polymerization reaction of difunctional epoxy resins such as diisocyanate with bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, and biphenyl type epoxy resin with monocarboxylic acid compounds such as (meth)acrylic acid having olefinic unsaturated double bonds, partially modified acid anhydride compounds, carboxyl-containing dihydroxy compounds, and diol compounds.

[0031] (4) A carboxyl-containing photosensitive polyurethane resin is obtained by adding a compound such as (meth)acrylic acid hydroxyalkyl ester, which has one hydroxyl group and one or more (meth)acryloyl groups in the molecule, to the resin synthesis of (2) or (3) and performing terminal (meth)acrylation.

[0032] (5) A carboxyl-containing photosensitive polyurethane resin obtained by adding an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, etc., in the resin synthesis of (2) or (3), such that the product has one isocyanate group and one or more (meth)acryloyl groups in the molecule, and then performing terminal (meth)acrylation.

[0033] (6) A carboxyl-containing photosensitive resin obtained by reacting (meth)acrylic acid with a difunctional or higher multifunctional (solid) epoxy resin and adding a dicarboxylic acid anhydride to a hydroxyl group present in the side chain.

[0034] (7) A carboxyl-containing photosensitive resin is obtained by reacting (meth)acrylic acid with a multifunctional epoxy resin obtained by further epoxidizing the hydroxyl groups of a difunctional (solid) epoxy resin with epichlorohydrin and adding the generated hydroxyl groups to a dicarboxylic acid anhydride.

[0035] (8) A carboxyl-containing polyester resin is obtained by reacting dicarboxylic acids such as adipic acid, phthalic acid, and hexahydrophthalic acid with a difunctional oxocyclic butane resin and adding dicarboxylic anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride to the generated primary hydroxyl group.

[0036] (9) An epoxy compound having multiple epoxy groups in one molecule is reacted with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenylethanol, and a monocarboxylic acid containing unsaturated groups, such as (meth)acrylic acid, and the alcoholic hydroxyl group of the resulting reaction product is reacted with maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc., to obtain a carboxyl-containing photosensitive resin.

[0037] (10) A carboxyl-containing photosensitive resin is obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with ethylene oxide, propylene oxide and other epoxides, reacting the resulting reaction product with a monocarboxylic acid containing an unsaturated group, and then reacting the resulting reaction product with a polyacid anhydride.

[0038] (11) A carboxyl-containing photosensitive resin is obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with cyclic carbonates such as ethylene carbonate and propylene carbonate, reacting the resulting reaction product with a monocarboxylic acid containing unsaturated groups, and then reacting the resulting reaction product with a polyacid anhydride.

[0039] (12) A carboxyl-containing photosensitive resin is formed by further adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins of (1) to (11) above.

[0040] It should be noted that in this specification, (meth)acrylate is a general term for acrylates, methacrylates and mixtures thereof, and so on.

[0041] The acid value of the carboxyl-containing photosensitive resin is preferably 40 mg KOH / g to 150 mg KOH / g, more preferably 50 mg KOH / g to 130 mg KOH / g. By setting the acid value of the carboxyl-containing photosensitive resin to 40 mg KOH / g to 150 mg KOH / g, the resolution becomes good.

[0042] While the weight-average molecular weight of carboxyl-containing photosensitive resins varies depending on the resin skeleton, it is generally preferred to be between 2,000 and 150,000, and more preferably between 2,000 and 100,000. Setting the weight-average molecular weight to 2,000 or higher can improve non-stick properties and resolution. Furthermore, setting the weight-average molecular weight to 150,000 or lower can improve resolution and storage stability.

[0043] The carboxyl equivalent of the carboxyl-containing photosensitive resin is preferably 100 g / eq. to 1000 g / eq., more preferably 400 g / eq. to 800 g / eq. Here, "eq." is an abbreviation for "equivalent".

[0044] By setting the carboxyl equivalent to 100 g / eq. or more, the number of carboxyl groups becomes appropriate, thus improving developability. Furthermore, by setting the carboxyl equivalent to 1000 g / eq. or less, the crosslinking density can be increased, thereby improving the strength of the cured product.

[0045] The content of carboxyl-containing photosensitive resin in the photosensitive resin composition, calculated on a solids basis, is preferably 20% to 60% by mass, more preferably 20% to 50% by mass. Setting the content of carboxyl-containing photosensitive resin to 20% by mass or more improves the strength of the cured product. Furthermore, setting the content of carboxyl-containing photosensitive resin to 60% by mass or less results in an appropriate viscosity of the photosensitive resin composition and improved printability.

[0046] <Epoxy Thermosetting Components>

[0047] Epoxy thermosetting components are compounds containing epoxy groups in their molecules. By including epoxy thermosetting components in the photosensitive resin composition, the cured product of the photosensitive resin composition can be endowed with desmear resistance.

[0048] Epoxy thermosetting components contain phenolic varnish-type epoxy resin and difunctional crystalline epoxy resin.

[0049] Examples of phenolic varnish-type epoxy resins include phenolic varnishes obtained by reacting phenols such as phenol, cresol, halogenated phenols, alkylphenols, and bisphenol A with formaldehyde under an acidic catalyst, and substances obtained by reacting epihalopropyl alcohols such as epichlorohydrin and methyl epichlorohydrin. These substances can be used alone or in combination with two or more.

[0050] For phenolic varnish-type epoxy resins, any of the liquid, semi-solid, or solid forms can be used, with solid form being preferred.

[0051] When the phenolic varnish-type epoxy resin has a softening point, the softening point is 60-140°C, preferably 60-130°C.

[0052] Difunctional crystalline epoxy resins are crystalline epoxy resins that have two epoxy groups. Examples of crystalline epoxy resins include those with biphenyl, sulfide, phenylene, naphthalene, or bisphenol structures.

[0053] The softening point of the difunctional crystalline epoxy resin is 70℃~120℃, preferably 70℃~110℃.

[0054] The weight ratio of phenolic varnish-type epoxy resin to difunctional crystalline epoxy resin (phenolic varnish-type epoxy resin / difunctional crystalline epoxy resin) is preferably 1.0 to 2.0, more preferably 1.4 to 1.8. If the weight ratio (phenolic varnish-type epoxy resin / difunctional crystalline epoxy resin) is 1.0 or higher, the resistance to residue removal of the cured photosensitive resin composition can be improved; if the weight ratio is 2.0 or lower, the thermal stability of the photosensitive resin composition can be improved.

[0055] The epoxy equivalent of the epoxy thermosetting component is preferably 100 g / eq. to 1000 g / eq., more preferably 150 g / eq. to 200 g / eq.

[0056] Here, epoxy equivalent, as defined in JIS K 7236:2001, is the mass of resin containing one equivalent of epoxy groups. It should be noted that "eq." is an abbreviation for "equivalent."

[0057] The equivalence ratio of carboxyl groups to epoxy groups (carboxyl equivalent (g / eq.) / epoxy equivalent (g / eq.)) is 5.0 to 8.0, preferably 6.0 to 7.0. If this equivalence ratio is less than 5.0, the resistance to residue removal of the cured photosensitive resin composition may sometimes deteriorate; if it exceeds 8.0, the resolution may sometimes deteriorate. Here, epoxy equivalent and carboxyl equivalent refer to the epoxy and carboxyl groups of all compounds contained in the alkali-developable photosensitive resin composition.

[0058] <(meth)acrylic acid monomer>

[0059] (Meth)acrylic acid monomers are compounds containing (meth)acryloyl groups in their molecules, which are included to promote the photocuring of carboxyl-containing resins.

[0060] As monomers for (meth)acrylic acid, commonly known (meth)acrylic acid monomers can be used. Examples include: polyfunctional allyl compounds such as triallyl isocyanurate, diallyl phthalate, and diallyl isophthalate; alkylene polyol poly(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; and diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane tri(meth)acrylate. Poly(meth)acrylates such as polyoxyalkylene glycol diols; poly(meth)acrylates such as neopentyl glycol hydroxyacetic acid di(meth)acrylate; isocyanurate-type poly(meth)acrylates such as tri[(meth)acryloyloxyethyl]isocyanurate; acrylamides such as N,N-dimethylacrylamide, N-hydroxymethylacrylamide, and N,N-dimethylaminopropylacrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate; and polyacrylates of glycidyl ethers such as diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate. These substances can be used alone or in combination with two or more.

[0061] Regarding the content of (meth)acrylic acid monomer, in terms of solid content, it is preferably 5 to 100 parts by weight relative to 100 parts by weight of the carboxyl-containing resin, more preferably 5 to 70 parts by weight. By setting the content of (meth)acrylic acid monomer to 5 to 100 parts by weight relative to 100 parts by weight of the carboxyl-containing resin, the photocurability and resolution are improved.

[0062] <Photopolymerization Initiator>

[0063] Photopolymerization initiators are included to cure photosensitive resin compositions. There are no particular restrictions on the photopolymerization initiator, as long as it is a commonly used photopolymerization initiator in photosensitive resin compositions; it can be appropriately selected according to the purpose, and any known substance can be used. A single photopolymerization initiator can be used, or two or more can be used in combination.

[0064] In addition, examples of photopolymerization initiators 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, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and other diacylphosphine oxides; 2,6-dimethoxybenzoyl diphenylphosphine oxide... Monoacylphosphine oxides include methyl phosphine oxides such as 2,6-dichlorobenzoyl diphenylphosphine oxide, methyl 2,4,6-trimethylbenzoyl phenylphosphine ester, 2-methylbenzoyl diphenylphosphine oxide, isopropyl neopentanoyl phenylphosphine ester, and 2,4,6-trimethylbenzoyl diphenylphosphine oxide; ethyl phenyl(2,4,6-trimethylbenzoyl)phosphine ester, 1-hydroxy-cyclohexylphenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propanoyl)-benzyl]phenyl}-2-methyl-propane-1-one, and 2-hydroxy-2-methyl-1-phenylpropane-1-one. Ethyl ketones; benzoin, benzoyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, etc.; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, michalcone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(diethylamino)benzophenone, etc.; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl 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, N,N-dimethylaminoacetophenone and other acetophenone derivatives; thioxanone, 2-ethylthioxanone, 2-isopropylthioxanone, 2,4-dimethylthioxanone, 2,4-diethylthioxanone, 2-chlorothioxanone, 2,4-diisopropylthioxanone and other thioxanone derivatives; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-pentylanthraquinone, 2-aminoanthraquinone and other anthraquinone derivatives; acetophenone dimethyl ketal, benzoyl dimethyl ketal and other ketals; ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, p-dimethylbenzoate and other benzoate derivatives;Oxime esters such as 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] acetone 1-(O-acetyl oxime); diacene titanium compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyrrolo-1-yl)ethyl)phenyl]titanium; phenyl disulfide 2-nitrofluorene, butylin, anisolein ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc.

[0065] The content of photopolymerization initiators other than oxime ester-based photopolymerization initiators, calculated in solids, is preferably 0.01 to 30 parts by weight relative to 100 parts by weight of carboxyl-containing resin, more preferably 0.1 to 20 parts by weight. By setting the content of photopolymerization initiators other than oxime ester-based photopolymerization initiators to 0.01 parts by weight or more, the photocurability of the photosensitive resin composition becomes better, the coating is less prone to peeling, and coating properties such as chemical resistance also become better. In addition, by setting the content of photopolymerization initiators other than oxime ester-based photopolymerization initiators to 30 parts by weight or less, the light absorption of the solder resist coating surface becomes better, and the depth of curing is less likely to decrease.

[0066] Regarding the content of the oxime ester-based photopolymerization initiator, on a solids basis, it is preferably 0.01 to 5 parts by weight relative to 100 parts by weight of the carboxyl-containing resin, more preferably 0.1 to 3.9 parts by weight. By setting the content of the oxime ester-based photopolymerization initiator to 0.01 parts by weight or more, the photocurability of the photosensitive resin composition becomes good, and the coating properties such as heat resistance and chemical resistance also become good. In addition, by setting the content of the oxime ester-based photopolymerization initiator to 5 parts by weight or less, the light absorption of the solder resist coating surface becomes good, and the depth of curing is less likely to decrease.

[0067] <Other Ingredients>

[0068] Other components are not particularly restricted as long as they are commonly used in photosensitive resin compositions, and can be selected appropriately according to the purpose. Examples include curing catalysts, colorants, and fillers. These substances can be used alone or in combination of two or more.

[0069] <<Civilized Catalyst>>

[0070] Curing catalysts are compounds that cure upon heating. Examples of curing catalysts include: imidazole, 2-methylimidazolium, 2-ethylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 4-phenylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazolium and other imidazole derivatives; dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc. Amine compounds such as methylamine; hydrazine compounds such as adipic dihydrazide and sebacic dihydrazide; phosphorus compounds such as triphenylphosphine; guanidineamine, acetylguanidineamine, benzoguanidineamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-triazine, 2-vinyl-2,4-diamino-triazine, 2-vinyl-4,6-diamino-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-triazine-isocyanuric acid adduct and other triazine derivatives, etc.

[0071] <<Coloring Agent>>

[0072] There are no particular restrictions on the colorant used in common photosensitive resin compositions. It can be selected appropriately according to the purpose. Commonly known colorants such as black, red, blue, green, yellow, and white can be used, and it can be any of the pigments, dyes, and colorants.

[0073] Examples of black colorants include carbon black, zirconium nitride, and pigment black (numbers 1, 6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, 32, etc.).

[0074] As red coloring agents, there are monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone series, etc.

[0075] As blue colorants, there are phthalocyanine and anthraquinone compounds, while as pigments, compounds classified as pigments can be used. In addition to these substances, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

[0076] Phthalocyanine, anthraquinone, and perylene derivatives are also used as green colorants. In addition to these substances, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

[0077] As yellow coloring agents, there are monoazo, diazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone series, etc.

[0078] Examples of white colorants include rutile or anatase titanium dioxide. Additionally, colorants such as purple, orange, and brown can be added to adjust the hue.

[0079] <<Packaging>>

[0080] As fillers, known inorganic or organic fillers can be used, but barium sulfate, spherical silica and talc are particularly preferred.

[0081] The photosensitive resin composition of the present invention may, as needed, contain photoinitiator; cyanate ester compound; elastomer; mercapto compound; urethane esterification catalyst; thixotropic agent; adhesion promoter; block copolymer; chain transfer agent; polymerization inhibitor; copper toxicity inhibitor; antioxidant; rust inhibitor; thickener such as organobentonite and montmorillonite; at least one of defoamers and leveling agents such as organosilicon, fluorine, and polymer; silane coupling agent such as imidazole, thiazole, and triazole; flame retardant such as phosphorus compounds such as phosphonates, phosphate derivatives, and phosphazene compounds.

[0082] There are no particular restrictions on the content of other components as long as they do not hinder the effect of the present invention, and they can be appropriately selected according to the purpose.

[0083] <Method for manufacturing photosensitive resin composition>

[0084] There are no particular limitations on the manufacturing method of the photosensitive resin composition. For example, it can be manufactured by mixing the above-mentioned components in a specified ratio, and then mixing or blending them at room temperature using a mixing mechanism such as a three-roll mill, ball mill, bead mill, sand mill, or a stirring mechanism such as a high-speed mixer or planetary mixer. Alternatively, pre-mixing or blending can be performed as needed before the mixing or blending.

[0085] (dry film)

[0086] The dry film involved in this embodiment has a resin layer and may also have other components as needed.

[0087] <Resin Layer>

[0088] The resin layer is formed on the first film described later and is obtained from the above-described photosensitive resin composition. Here, the resin layer refers to the layer obtained by coating and drying the photosensitive resin composition, and refers to the layer that is not laminated with the first film, other components, or other layers described later.

[0089] There are no particular restrictions on the thickness of the resin layer; it can be selected appropriately according to the purpose.

[0090] <Other Components>

[0091] Other components are not particularly restricted and can be selected appropriately according to the purpose; for example, a first membrane, a second membrane, etc. can be listed.

[0092] <<The First Membrane>>

[0093] The first film refers to a film that serves as a resin layer supporting the dry film, and is a film coated with a photosensitive resin composition during the formation of a resin layer composed of a photosensitive resin composition.

[0094] In this invention, a first film refers to a film that is at least bonded to the resin layer when integrally formed by lamination with the resin layer side of the dry film in contact with a substrate such as a substrate through heating or the like. The first film can be peeled off from the resin layer in a post-lamination process. Particularly in this embodiment, it is preferable to peel it off from the resin layer in a post-exposure process.

[0095] As the first membrane, any known membrane can be used without particular restrictions. For example, polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyimide films, polyamide-imide films, polypropylene films, and polystyrene films, all made of thermoplastic resins, can be appropriately used. Among these, polyester films are preferred from the viewpoints of heat resistance, mechanical strength, and processability. Alternatively, laminates of these films can also be used as the first membrane.

[0096] Furthermore, from the viewpoint of improving mechanical strength, the film made of thermoplastic resin is preferably a film obtained by stretching in a uniaxial or biaxial direction.

[0097] When using a thermoplastic resin film as the first film, a film with a specific surface morphology can be used by adding filler to the resin during film formation (kneading treatment), or by applying a matte coating (coating treatment), or by performing a blasting treatment such as sandblasting on the film surface, or by performing a wire drawing process or chemical etching, etc.

[0098] There is no particular limitation on the thickness of the first membrane; for example, it can be set to 10 μm to 150 μm.

[0099] <<Second Membrane>>

[0100] The second film refers to a film laminated for the purpose of preventing dust from adhering to the surface of the resin layer. Specifically, it is a film that is peeled off from the resin layer before lamination when the resin layer side of the dry film is in contact with a substrate such as a substrate and laminated by heating or other means.

[0101] For example, polyethylene film, polytetrafluoroethylene film, polypropylene film, or surface-treated paper can be used as the second film. It should be noted that the adhesion between the second film and the resin layer only needs to be less than the adhesion between the resin layer and the first film. By ensuring that the adhesion between the second film and the first film is less than the adhesion between the second film and the first film, the second film can be peeled off without moving the first film.

[0102] There are no particular limitations on the thickness of the second membrane; for example, it can be set to 10 μm to 150 μm.

[0103] <Method for manufacturing dry film>

[0104] For dry films, the film can be obtained as follows: the above-mentioned photosensitive resin composition is diluted with the above-mentioned organic solvent to adjust to an appropriate viscosity, and then coated on the first film with a uniform thickness using a corner roller coater, doctor blade coater, lip coater, rod coater, extrusion coater, reverse coater, transfer roller coater, gravure coater, sprayer, or coater, etc., and dried at a temperature of 50°C to 130°C for 1 to 30 minutes. There are no particular limitations on the coating film thickness, but it is generally appropriate to select a range of 1 μm to 150 μm, preferably 5 μm to 60 μm, based on the dried film thickness.

[0105] (cured material)

[0106] The cured product involved in the embodiments is obtained by curing the above-described photosensitive resin composition or the resin layer of the above-described dry film.

[0107] There are no particular restrictions on the size and shape of the cured material; it can be selected appropriately according to the purpose.

[0108] As a method for manufacturing the cured product, for example, the photosensitive resin composition of the present invention is adjusted to a viscosity suitable for a coating method using an organic solvent, and then coated onto a substrate, for example, in a manner that results in a thickness of 10 μm to 100 μm after drying, by methods such as dip coating, flow coating, roller coating, rod coating, screen printing, or curtain coating. The mixture is then dried (pre-dried) at a temperature of 60 to 100°C for 15 to 90 minutes to evaporate the organic solvent contained in the composition, thereby forming a non-sticky resin layer. Alternatively, in the case of a dry film, the resin layer is bonded to the substrate in contact with the substrate using a laminator or the like, and then the first film is peeled off, thereby forming a resin layer on the substrate.

[0109] Examples of substrates include: printed wiring boards with circuits pre-formed using copper or similar materials; flexible printed wiring boards; copper-clad laminates using materials such as paper phenolic resin, paper epoxy resin, glass cloth epoxy resin, glass cloth polyimide, glass cloth / non-woven epoxy resin, glass cloth / paper epoxy resin, synthetic fiber epoxy resin, fluoropolymer-polyethylene-polyphenylene ether, and polyphenylene ether-cyanate ester; metal substrates; polyimide films; polyethylene terephthalate films; polyethylene naphthalate (PEN) films; glass substrates; ceramic substrates; and wafer boards.

[0110] It is preferable to use a vacuum laminator or similar device to laminate the dry film onto the substrate under pressure and heat. By using such a vacuum laminator, even when using a substrate with circuitry, the dry film adheres tightly to the substrate surface, preventing air bubbles from being trapped. Furthermore, the filling effect on the recesses of the substrate surface is improved. The pressure conditions are preferably about 0.1 to about 2.0 MPa, and the heating conditions are preferably 40 to 120°C.

[0111] For the volatile drying performed after coating the photosensitive resin composition of the present invention, a hot air circulating drying oven, IR oven, heating plate, convection oven, etc. (using a device with a heat source that heats the air by means of steam to make the hot air inside the dryer come into countercurrent contact and using a method of blowing from a nozzle onto the support) can be used.

[0112] After forming a resin layer on a substrate, the substrate is selectively exposed using active energy rays through a photomask with a predetermined pattern. The unexposed areas are then developed using a dilute alkaline aqueous solution (e.g., 0.3–3% by mass sodium carbonate aqueous solution), thereby forming a patterned cured product. In the case of a dry film, after exposure, the first film is peeled off from the dry film and developed, thus forming a patterned cured product on the substrate. It should be noted that, if it does not impair the properties, the first film can also be peeled off from the dry film before exposure, exposing and developing the exposed resin layer. Furthermore, curing can be achieved by irradiating the cured product with active energy rays followed by heat curing (e.g., 100–220°C), or by irradiating the cured product with active energy rays after heat curing, or by performing final finishing curing (formal curing) solely through heat curing, thereby forming a cured coating film with excellent adhesion, hardness, and other properties.

[0113] As for the exposure machine used in the aforementioned active energy ray irradiation, any device equipped with a high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, or mercury short-arc lamp that irradiates ultraviolet light in the range of 350–450 nm is acceptable. Direct drawing devices (e.g., laser direct imaging devices that directly draw images using lasers from CAD data from a computer) can also be used. The lamp or laser source for the direct drawing machine only needs to have a maximum wavelength in the range of 350–450 nm. Although the exposure amount used for image formation varies depending on the film thickness, it can generally be set to 10–1000 mJ / cm². 2 The preferred value is 20–800 mJ / cm³. 2 Within the range.

[0114] As for the above-mentioned developing methods, immersion, spraying, spraying, brushing, etc. can be used. As for the developing solution, alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines can be used.

[0115] (Printed wiring board)

[0116] One embodiment of the present invention relates to a printed wiring board having the above-described cured material.

[0117] There are no particular restrictions on the size and type of printed wiring boards; they can be selected appropriately according to the purpose.

[0118] [Example]

[0119] Next, the experiments conducted by the inventors will be described, but the invention is not limited thereto.

[0120] <Synthetic Example 1: Preparation of Carboxyl-Containing Resin (A-1)>

[0121] 220 parts (1 equivalent) of cresol phenolic varnish-type epoxy resin (ECON-104S, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 220 g / eq.) were placed in a four-necked flask equipped with a stirrer and a reflux condenser. 218 parts of carbitol acetate were added, and the mixture was heated to dissolve. Next, 0.46 parts of methylhydroquinone as a polymerization inhibitor and 1.38 parts of triphenylphosphine as a reaction catalyst were added. The mixture was heated to 95°C–105°C, and 50.4 parts (0.7 equivalent) of acrylic acid and 41.5 parts (0.3 equivalent) of p-hydroxyphenylethanol were slowly added dropwise, and the reaction was allowed to proceed for 16 hours. The reaction product (hydroxyl group: 1.3 equivalent) was cooled to 80°C–90°C, and 91.2 parts (0.6 equivalent) of tetrahydrophthalic anhydride were added. The reaction was allowed to proceed for 8 hours, and the product was removed after cooling.

[0122] The carboxyl-containing resin obtained in this manner has a non-volatile content of 65%, an acid value of 83 mg KOH / g for the solid substance, a carboxyl equivalent of 676 g / eq. for the solid component, and a weight-average molecular weight of 12000. Hereinafter, this resin solution will be abbreviated as A-1.

[0123] <Synthetic Example 2: Preparation of Carboxyl-Containing Resin (A-2)>

[0124] 119.4 g of phenolic varnish-type cresol resin (Shonol CRG951, manufactured by Aike Industry Co., Ltd., OH equivalent: 119.4 g), 1.19 g of potassium hydroxide, and 119.4 g of toluene were added to a high-pressure reactor equipped with a thermometer, a nitrogen inlet device that also serves as an epoxy alkane inlet device, and a stirrer. While stirring, the system was purged with nitrogen and heated. Then, 63.8 g of propylene oxide was slowly added dropwise at 125°C–132°C and 0 kg / cm³. 2 ~4.8kg / cm 2 The reaction was carried out under the specified conditions for 16 hours. Afterwards, the solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added and mixed to neutralize potassium hydroxide, resulting in a propylene oxide reaction solution of phenolic varnish-type cresol resin with a non-volatile content of 62.1% and a hydroxyl value of 182.2 g / eq. This represents a substance that, on average, added 1.08 moles of propylene oxide relative to 1 equivalent of phenolic hydroxyl groups.

[0125] Next, 293.0 g of the obtained phenolic varnish-type cresol resin propylene oxide reaction solution, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone, and 252.9 g of toluene were loaded into a reactor equipped with a stirrer, thermometer, and air blow-in pipe. Air was blown in at a rate of 10 mL / min, and the reaction was carried out at 110 °C for 12 hours with stirring. The water generated in the reaction was used as an azeotropic mixture with toluene, and 12.6 g of water was distilled off. The mixture was then cooled to room temperature, neutralized with 35.35 g of 15% sodium hydroxide aqueous solution, and then washed with water. Finally, the toluene was removed by distillation in an evaporator while replacing it with 118.1 g of diethylene glycol monoethyl ether acetate, thus obtaining a phenolic varnish-type acrylate resin solution.

[0126] Next, 332.5 g of the obtained phenolic varnish-type acrylate resin solution and 1.22 g of triphenylphosphine were loaded into a reactor equipped with a stirrer, thermometer and air blow-in pipe. Air was blown in at a rate of 10 mL / min. While stirring, 60.8 g of tetrahydrophthalic anhydride was slowly added. The reaction was carried out at 95℃~101℃ for 6 hours and then removed after cooling.

[0127] The carboxyl-containing resin obtained in this manner has a non-volatile content of 71%, an acid value of 88 mg KOH / g for the solid substance, a carboxyl equivalent of 638 g / eq. for the solid component, and a weight-average molecular weight of 2000. Hereinafter, this resin solution will be abbreviated as A-2.

[0128] (Examples 1-7, Comparative Examples 1-3)

[0129] <Preparation of Photosensitive Resin Compositions>

[0130] The photosensitive resin composition was prepared by premixing the materials according to the proportions shown in Table 1 using a stirrer, followed by kneading using a three-roll mill. It should be noted that the values ​​in the table represent the content in a solution containing the solvent. Furthermore, the units in the table are parts by mass.

[0131] [Table 1]

[0132] The detailed information of each component in Table 1 is as follows.

[0133] <Carboxyl-containing resin> A-1 (Synthetic Example 1) A-2 (Synthetic Example 2) It should be noted that the values ​​for carboxyl-containing resins in Table 1 are values ​​for resin solutions.

[0134] <Epoxy Thermosetting Components> N-770 (Phenolic varnish-type epoxy resin, epoxy equivalent: 190 g / eq., softening point: 70℃, manufactured by DIC Corporation) YX4000H (Difunctional crystalline epoxy resin, epoxy equivalent: 192 g / eq., softening point: 105℃, manufactured by Mitsubishi Chemical Corporation) jER-828 (Difunctional liquid epoxy resin (bisphenol A type epoxy resin), epoxy equivalent: 189 g / eq., manufactured by Mitsubishi Chemical Corporation) <(meth)acrylic acid monomer> Dipentaerythritol hexaacrylate <Photopolymerization Initiator> Omnirad 907 (2-Methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, manufactured by IGM Resins BV) DETX-S (2,4-Diethylthioxanone, manufactured by Nippon Kayaku Co., Ltd.) <Other Ingredients> <<Civilized Catalyst>> DICY (dicyandiamide, manufactured by Mitsubishi Chemical Corporation) Melamine (manufactured by Nissan Chemical Co., Ltd.) <<Pigment>> Phthalocyanine Blue (manufactured by Tokyo Chemical Industry Co., Ltd.) Gumei Translucent Yellow (manufactured by Tokyo Chemical Industry Co., Ltd.) <<Packaging>> Admafine SO-E2 (spherical silica, manufactured by Admatechs Co., Ltd.) The carboxyl equivalent, epoxy equivalent, and softening point of epoxy resin in Table 1 are determined or calculated as follows.

[0135] <Methods for Calculating Carboxyl Equivalent>

[0136] First, the acid value of each photosensitive resin composition was determined. The acid value was determined according to "7. Potential difference titration (acid value)" in JIS K2501:2003.

[0137] Calculate the carboxyl equivalent based on the measured acid value using the following formula.

[0138] Carboxyl equivalent (g / eq.) = 56.11 / acid value (mgKOH / g) × 1000

[0139] <Method for Determination of Epoxy Equivalent>

[0140] Each photosensitive resin composition was determined using tetraethylammonium bromide according to JIS K7236:2001 for the first equivalent. On the other hand, the second equivalent was determined using the same method as for the first equivalent, except that tetraethylammonium bromide was not used.

[0141] Calculate the epoxy equivalent by subtracting the second equivalent from the first equivalent using the following formula.

[0142] Epoxy equivalent (g / eq.) = 1 / ((1 / first equivalent) - (1 / second equivalent))

[0143] <Method for Determining the Softening Point of Epoxy Thermosetting Components>

[0144] The softening point of the epoxy thermosetting component was determined according to the “4.1 Ring and Ball Method” of JIS K7234:1986.

[0145] <Thermal Stability>

[0146] The obtained photosensitive resin composition was screen-printed onto a copper foil substrate to a thickness of 20 μm after drying. The coating was then dried at 80°C for 50 minutes and 70 minutes, respectively. After natural cooling to room temperature, the coating was developed for 60 seconds at 30°C using a 1% (w / w) Na₂CO₃ aqueous solution under a spray pressure of 0.2 MPa. The dried coating was visually inspected for any residual development and evaluated based on the following criteria.

[0147] -Evaluation Criteria-

[0148] ◎: No development residue of the composition was observed under drying conditions of 50 minutes and 70 minutes.

[0149] 〇: No development residue of the composition was observed after drying for 50 minutes, but a small amount of residue was observed after drying for 70 minutes.

[0150] △: A small amount of development residue of the composition was observed after drying for 50 minutes, and obvious development residue was confirmed after drying for 70 minutes.

[0151] ×: Obvious development residue of the composition was confirmed under both 50-minute and 70-minute drying conditions.

[0152] <Resolution>

[0153] The obtained photosensitive resin composition was screen-printed onto a copper foil substrate to a thickness of 20 μm after drying, and dried at 80°C for 30 minutes. After natural cooling to room temperature, a Kodak Step Tablet No. 2 was placed on the dried coating, and direct imaging exposure was performed using a direct imaging exposure device with an exposure level of 7 and an opening size of 60 μm for the SRO (Solder Resist Opening). Next, the coating on the exposed substrate was developed for 60 seconds using a 1% (w / w) Na₂CO₃ aqueous solution at 30°C, and then washed with water. Finally, it was cured at 150°C for 60 minutes to produce a test piece for resolution evaluation.

[0154] Subsequently, the top and bottom diameters of the SRO test pieces were observed using a 1000x scanning electron microscope (SEM) and evaluated based on the following evaluation criteria.

[0155] -Evaluation Criteria-

[0156] ◎: The ratio of the bottom diameter to the top diameter is between 1.00 and 0.85.

[0157] ○: The ratio of the bottom diameter to the top diameter is less than 0.85 and greater than 0.70.

[0158] ×: The ratio of the bottom diameter to the top diameter is less than 0.70.

[0159] <Resistance to glue residue>

[0160] The evaluation test pieces prepared in the resolution evaluation above were immersed in a swelling solution (a mixture of Swelling Dip Securiganth P (manufactured by Atotech Japan Co., Ltd.) and 48% sodium hydroxide) at 60°C for 5 minutes. Next, they were immersed in a roughening solution (a mixture of Concentrate Compact CP (manufactured by Atotech Japan Co., Ltd.) and 48% sodium hydroxide) at 80°C for 20 minutes, and finally immersed in a neutralization solution (Reduction Securiganth P 500 (manufactured by Atotech Japan Co., Ltd.) and 96% sulfuric acid) at 40°C for 5 minutes to remove adhesive residue. The periphery of the SRO on the surface of the cured coating after the adhesive residue removal treatment was observed using a 1000x scanning electron microscope (SEM), and evaluated based on the following evaluation criteria.

[0161] -Evaluation Criteria-

[0162] ◎: No damage was observed around the SRO even after descaling.

[0163] 〇: After descaling, a small amount of damage was observed around the SRO, but no peeling was observed.

[0164] △: After descaling, partial peeling was observed around the SRO area.

[0165] ×: Delamination was observed throughout the periphery of the SRO after the descaling process.

[0166] [Table 2]

[0167] The thermal stability, resolution, and resistance to descaling of Examples 1-7, with an equivalent ratio (carboxyl equivalent / epoxy equivalent) of 5.0-8.0, were rated as "◎", "〇", or "△". In contrast, Comparative Example 1, with an equivalent ratio (carboxyl equivalent / epoxy equivalent) of 4.1, received a "×" rating for resistance to descaling, and Comparative Example 2, with an equivalent ratio (carboxyl equivalent / epoxy equivalent) of 8.9, received a "×" rating for both thermal stability and resolution. Furthermore, Comparative Example 3, which did not contain a difunctional crystalline epoxy resin as the epoxy thermosetting component, received a "×" rating for thermal stability. In other words, the compositions of Comparative Examples 1-3 all received a "×" rating for thermal stability, resolution, and resistance to descaling. Based on the above, it can be concluded that the alkali-developable photosensitive resin compositions of Examples 1-7 are alkali-developable photosensitive resin compositions capable of forming cured products with good resolution, thermal stability, and resistance to descaling.

[0168] The resistance to degumming in Examples 1-4 and 7, where the equivalent ratio (carboxyl equivalent / epoxy equivalent) is 5.0-8.0 and the weight ratio of the epoxy thermosetting component (phenolic varnish-type epoxy resin / difunctional crystalline epoxy resin) is 1.0-2.0, was rated as "◎" or "〇". In contrast, the resistance to degumming in Example 6, where the weight ratio of the epoxy thermosetting component (phenolic varnish-type epoxy resin / difunctional crystalline epoxy resin) is 0.7, was rated as "△". The thermal stability in Example 5, where the weight ratio of the epoxy thermosetting component (phenolic varnish-type epoxy resin / difunctional crystalline epoxy resin) is 2.3, was rated as "△". Therefore, it can be said that an alkaline-developable photosensitive resin composition with an equivalent ratio (carboxyl equivalent / epoxy equivalent) of 5.0 to 8.0 and a weight ratio of epoxy thermosetting components (phenolic varnish-type epoxy resin / difunctional crystalline epoxy resin) of 1.0 to 2.0 is an alkaline-developable photosensitive resin composition capable of forming cured products with further improved resolution, thermal stability, and resistance to desizing.

[0169] The above describes in detail the methods for implementing the present invention, but the present invention is not limited thereto and various modifications can be made without departing from its spirit.

Claims

1. An alkaline-developable photosensitive resin composition, comprising a carboxyl-containing resin, an epoxy thermosetting component, a (meth)acrylic acid monomer, and a photopolymerization initiator, characterized in that, The equivalence ratio of carboxyl groups to epoxy groups, i.e., carboxyl equivalent / epoxy equivalent, is 5.0–8.

0. The epoxy thermosetting component contains phenolic varnish-type epoxy resin and a difunctional crystalline epoxy resin with a softening point of 70℃~120℃.

2. The alkali-developable photosensitive resin composition according to claim 1, wherein, The weight ratio of the phenolic varnish-type epoxy resin to the difunctional crystalline epoxy resin, i.e., phenolic varnish-type epoxy resin / difunctional crystalline epoxy resin, is 1.0 to 2.

0.

3. A dry film, characterized in that, The dry film has a resin layer obtained from the alkali-developable photosensitive resin composition of claim 1.

4. A cured product, characterized in that, The cured product is obtained by curing the resin layer of the alkali-developable photosensitive resin composition of claim 1 or the dry film of claim 3.

5. A printed wiring board, characterized in that, The printed wiring board has the cured material as described in claim 4.

Images