KR101488138B1 - Photosensitive resin composition, dry film, cured product, and printed wiring board - Google Patents

Abstract

The present invention provides an alkali development type photosensitve resin composition having excellent development, dryness and punching resistance; a dry film including the composition; a cured product thereof; and a printed wiring board having the cured product. The alkali development type photosensitive resin composition comprises (A) a carboxyl group containing resin, (B) an inorganic filler, (C) a thermosetting component and (D) a photopolymerization initiator, wherein (A) the carboxyl group containing resin comprises (A1) a carboxyl group containing resin having a phenol-based backbone (however, excludes a carboxyl group containing resin having a cresol novolak based backbone), and (A2) a carboxyl group containing resin having a cresol novolak based backbone, or (A3) a carboxyl group containing resin having a phenol-based backbone (however, excludes a carboxyl group containing resin having a cresol novolak based backbone) and a carboxyl group containing resin having a cresol novolak based backbone, and (B) the inorganic filler includes spherical silica.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a dry film, a cured product, and a printed wiring board,

The present invention relates to a photosensitive resin composition, a dry film, a cured product and a printed wiring board.

In general, in a printed wiring board used in electronic equipment or the like, in order to prevent the solder from adhering to an unnecessary portion and to prevent the conductor of the circuit from being corroded by oxidation or moisture, A solder resist is formed in the region except for the hole.

As a method of forming a solder resist of a desired pattern on a substrate, a forming method using a photolithography technique is used. For example, a photosensitive solder resist containing an alkali developing type photosensitive resin composition is exposed through a pattern mask and then alkali-developed to form a pattern using the difference in solubility in an alkali developing solution generated in the exposed portion and the non- can do.

Conventionally, from the viewpoint of developability and the like, there has been proposed a photosensitive resin composition of an alkali developing type, in which a hydroxyl group formed by reacting an unsaturated monocarboxylic acid such as acrylic acid with an epoxy resin of cresol novolak type is reacted with a saturated or unsaturated group such as hexahydrophthalic anhydride A composition containing a carboxyl group-containing resin obtained by reacting an unsaturated polybasic acid anhydride as a main component of a resin component is mainly used (for example, Patent Document 1). However, the solder resist produced using such a composition has a problem that cracks tend to occur due to punching by punching necessary in a manufacturing process of a printed wiring board.

In addition, as the exposure method, a contact exposure which forms a solder resist layer on a substrate having a circuit formed thereon, followed by drying, and then exposing the photo tool in vacuum contact with it forms mainstream. At this time, if the dry touching property of the dry coating film is poor, there is a problem that the phototool sticks to the coated film, the phototool can not be peeled off, or the dry coating film peels off from the substrate.

Japanese Patent Laid-Open No. 7-50473

Accordingly, an object of the present invention is to provide an alkali-developable photosensitive resin composition excellent in developability, touch dryness and punching resistance, a dry film containing the composition, a cured product thereof, and a printed wiring board having the cured product .

As a result of intensive studies in view of the above, the inventors of the present invention have found that when a carboxyl group-containing resin having a phenol skeleton and a carboxyl group-containing resin having a cresol novolak skeleton are blended or a carboxyl group-containing resin having a phenol skeleton and a cresol novolak skeleton , And further adding spherical silica as an inorganic filler, the above problems can be solved, and the present invention has been accomplished.

That is, the alkali developing photosensitive resin composition of the present invention is an alkali developing photosensitive resin composition containing (A) a carboxyl group-containing resin, (B) an inorganic filler, (C) a thermosetting component and (D) (A1) a carboxyl group-containing resin having a phenol skeleton (provided that a carboxyl group-containing resin having a cresol novolak skeleton is excluded), and (A2) a carboxyl group-containing resin having a cresol novolak skeleton, And (B) an inorganic filler, which contains spherical silica.

The alkali-developable photosensitive resin composition of the present invention is obtained by mixing the carboxyl-containing resin (A1) having a phenolic skeleton and the carboxyl-containing resin (A2) having a cresol novolak skeleton in a solid content of 1: 9 to 9: 1 Ratio.

The alkali-developable photosensitive resin composition of the present invention is characterized in that the phenolic skeleton of the carboxyl group-containing resin (A1) having a phenol skeleton is a phenol novolak type, a bisphenol A type, a biphenyl type, a phenol aralkyl type, and a trisphenyl methane type And a skeleton.

Another alkali-developable photosensitive resin composition of the present invention is an alkali-developable photosensitive resin composition containing (A) a carboxyl group-containing resin, (B) an inorganic filler, (C) a thermosetting component and (D) (A3) a carboxyl group-containing resin having a phenol skeleton (except for a cresol novolak skeleton) and a cresol novolak skeleton, (B) an inorganic filler, which contains a spherical silica .

The other alkali-developable photosensitive resin composition of the present invention is characterized in that the phenolic skeleton of the carboxyl group-containing resin having the phenol skeleton and the cresol novolak skeleton of (A3) is a phenol novolak type, a bisphenol A type, a bisphenol F type, Type, a phenol aralkyl type, and a trisphenyl methane type skeleton.

The dry film of the present invention is obtained by applying the alkali-developable photosensitive resin composition to a film and drying the film.

The cured product of the present invention is obtained by subjecting the above-mentioned alkali-developable photosensitive resin composition or the dry film obtained by applying and drying the alkali-developable photosensitive resin composition to a film to perform at least one of photo-curing and thermosetting .

The printed wiring board of the present invention is characterized by having the cured product.

According to the present invention, it is possible to provide an alkali developing photosensitive resin composition excellent in developability, touch dryness and punching resistance, a dry film containing the composition, a cured product thereof, and a printed wiring board having the cured product.

1 is a cross-sectional photograph of a cured coating film of the alkali-developable photosensitive resin composition of Example 1. Fig. And the white scale bar at the lower right side indicates 2 mu m.

Each component of the alkali-developable photosensitive resin composition of the present invention will be described below. In addition, unless otherwise specified, in the present specification, the numerical range expressed by using the symbol " (to) " is not limited to the range including the numerical values of the upper limit and the lower limit Range).

[(A) Resin containing a carboxyl group]

(A1) a carboxyl group-containing resin having a phenol skeleton (except for a carboxyl group-containing resin having a cresol novolak skeleton) and (A2) a carboxyl group-containing resin having a phenolic skeleton, (Hereinafter, simply referred to as " carboxyl group-containing resin of (A1) and (A2) ") or (A3) phenol skeleton (except for cresol novolak skeleton) and Containing resin having a cresol novolak skeleton (hereinafter, simply referred to as " the carboxyl group-containing resin of (A3) "). In the present invention, the combination of the above-mentioned (A1) carboxyl group-containing resin having a phenolic skeleton and the carboxyl group-containing resin having a cresol novolak skeleton (A2) can be used for any of punching resistance, developability, solder heat resistance, It is possible to obtain an effect that it is not expected that the developing property and the touch-drying property become better than those used singly. Further, by containing the carboxyl group-containing resin having the phenol skeleton and the cresol novolak skeleton (A3), it can be expected that the developing property and the touch dryness are better than those using the resin having each skeleton alone The effect can not be obtained. The carboxyl group-containing resin of the above-mentioned (A1) and (A2) and the carboxyl group-containing resin of the above (A3) are not particularly limited, and the known carboxyl group-containing resin used for the solder resist or the photo- Can be adopted. The carboxyl group-containing resin having a phenolic skeleton (A1) is preferably a skeleton of the phenolic skeleton. The carboxyl group-containing resin having a cresol novolak skeleton (A2) is preferably a skeleton of a cresol novolak skeleton. In the carboxyl group-containing resin having a phenol skeleton and a cresol novolak skeleton, the phenolic skeleton and the cresol novolak skeleton are preferably the main skeleton. The carboxyl group-containing resin of (A1) and (A2) and the carboxyl group-containing resin of (A3) each preferably have an ethylenically unsaturated bond in the molecule from the viewpoints of photo-curability and resistance to aging, It may not have a bond. In the case of not having an ethylenically unsaturated bond, a compound having at least one ethylenic unsaturated group (photoreactive monomer) is preferably used in combination in order to render the composition photo-curable. As the ethylenically unsaturated double bond, those derived from acrylic acid or methacrylic acid or a derivative thereof are preferable.

The method for producing the carboxyl group-containing resin of (A1) and (A2) is not particularly limited, but it is preferable that the epoxy group of an epoxy resin having a phenol skeleton such as phenol novolac type or an epoxy resin having a cresol novolak skeleton, Can be obtained by subjecting a carboxyl group of a monocarboxylic acid to an esterification reaction (complete esterification or partial esterification, preferably complete esterification) and then reacting the resulting hydroxyl group with a saturated or unsaturated polybasic acid anhydride again. The method for producing the carboxyl group-containing resin (A3) is not particularly limited, but the carboxyl group of the unsaturated monocarboxylic acid may be added to the epoxy group of the epoxy resin having the phenol skeleton and the cresol novolak skeleton such as phenol novolac type, The esterification reaction (complete esterification or partial esterification, preferably complete esterification), and the resulting hydroxyl group is reacted again with a saturated or unsaturated polybasic acid anhydride. Each reaction can be easily carried out in a solvent using a catalyst as described below. Examples of the phenolic skeleton include skeletons such as phenol novolak type, bisphenol A type, bisphenol F type, bisphenol S type, biphenyl type, phenol aralkyl type, and trisphenyl methane type. In the case of the carboxyl group-containing resin, the bisphenol F type skeleton is excluded from the phenolic skeleton). Of these, the phenol novolac type is preferred because of further improving developability, solder heat resistance, and touch dryness.

Representative examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid,? -Cyanosinic acid,? -Styryl acrylic acid and? -Furfuryl acrylic acid. Among them, at least one of acrylic acid and methacrylic acid is preferable due to the photoreactivity and the physical properties of the cured product, in particular, the heat resistance, the electrical characteristics and the moisture absorption resistance. These unsaturated monocarboxylic acids may be used alone or in admixture of two or more.

An epoxy resin having a phenol skeleton such as the phenol novolac type or an epoxy resin having a cresol novolac skeleton or an epoxy resin having a phenol skeleton and a cresol novolak skeleton such as the phenol novolac type, The amount of the polybasic acid anhydride used in the reaction of adding the saturated or unsaturated polybasic acid anhydride to the reaction product obtained by reacting the monocarboxylic acid is preferably 20 to 200 mgKOH / g , More preferably 50 to 120 mgKOH / g. If it is in the range of 20 to 200 mgKOH / g, the solubility in an aqueous alkaline solution is improved, the development of the formed coating film by an aqueous alkali solution becomes easy, and the surface of the exposed portion becomes difficult to develop.

The esterification reaction with the unsaturated group-containing monocarboxylic acid and the addition reaction with the polybasic acid anhydride are carried out usually in the presence of an inhibitor of polymerization such as hydroquinone or oxygen in the presence of an organic solvent described later, usually at about 50 to 150 ° C. If necessary, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, a phosphorus compound such as triphenylphosphine, etc. May be added as a catalyst.

Examples of the polybasic acid anhydride include methyl tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, anhydrous nadic acid, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, Alicyclic dibasic acid anhydrides such as tetrabromophthalic anhydride; Aliphatic or aromatic dibasic acid anhydrides such as succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, dodecenyl, pentadecenylsuccinic anhydride, phthalic anhydride, and trimellitic anhydride; Or biphenyl tetracarboxylic acid dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, anhydrous pyromellitic acid, benzophenonetetracarboxylic acid dianhydride And aliphatic or aromatic tetrabasic acid dianhydrides such as tetrabromobisphenol and the like, and one or more of these may be used. Among them, an alicyclic dibasic acid anhydride is particularly preferable.

The weight average molecular weights of the carboxyl group-containing resin of (A1) and (A2) and the carboxyl group-containing resin of (A3) differ depending on the resin skeleton, but are preferably 2,000 to 150,000. Within this range, the non-sticking performance is good, the moisture resistance of the coated film after exposure is good, the film is hardly reduced at the time of development, the resolution is improved, the developing property is good, and the storage stability is improved. More preferably from 5,000 to 100,000. The weight average molecular weight can be measured by gel permeation chromatography.

Each of the carboxyl group-containing resins (A1) and (A2) may be used alone or in combination of two or more. The alkali-developable photosensitive resin composition of the present invention preferably contains the carboxyl-containing resin (A1) and (A2) in a ratio of (A1) :( A2) = 1: 9 to 9: 1 in terms of solid content , And more preferably in a ratio of 2.5: 7.5 to 7.5: 2.5.

The carboxyl group-containing resin (A3) may be used singly or in combination of two or more kinds. The carboxyl group-containing resin (A3) preferably contains a phenol skeleton and a cresol novolak skeleton at a ratio of 1: 9 to 9: 1, more preferably at a ratio of 2.5: 7.5 to 7.5: 2.5 desirable.

The alkali-developable photosensitive resin composition of the present invention may contain other carboxyl group-containing resins as long as the effect of the present invention is not impaired.

[(B) Inorganic filler]

The alkali-developable photosensitive resin composition of the present invention (B) contains spherical silica as an inorganic filler. In the present invention, by containing the spherical silica, the punching resistance is improved, and further, other characteristics such as developability, solder heat resistance, and touch dryness are not expected to be excellent. The spherical silica may be any spherical silica usable as a filler for electronic materials. The average particle diameter (D50) of the spherical silica may be 0.01 to 5 占 퐉, preferably 0.1 to 5 占 퐉, more preferably 0.1 占 퐉 to 5 占 퐉, and still more preferably 0.1 占 퐉 to 3 占 퐉. The average particle diameter is measured by laser diffraction. The spherical silica may be a surface treated with a silane coupling agent.

The shape of the spherical silica may be spherical, and is not limited to spherical silica. Suitable spherical silicas include, for example, those having a sphericity of not less than 0.8 as measured below, but are not limited thereto.

The sphericity is measured as follows. A photograph is taken with an SEM and is calculated as a value calculated from the area and the circumference of the observed particle (sphericity) = {4 pi x (area) / (circumferential length) ² }. Specifically, an average value measured for 100 particles is adopted by using an image processing apparatus.

The method for producing spherical silica is not particularly limited, and a method known to those skilled in the art can be applied. For example, it can be produced by burning a silicon powder by VMC (Vaporized Metal Combustion) method. The VMC method is a method in which a chemical salt is formed by a burner in an atmosphere containing oxygen and a metal powder constituting a part of a target oxide particle is charged into the chemical salt to such an extent that dust cloud is formed, To obtain oxide particles.

Examples of the commercially available spherical silica include SO series (Admapain SO-E2, Admapain SO-E5, etc.) manufactured by Admatech, HPS series HPS-0500, HPS-1000 and HPS3500 manufactured by Doago Corporation .

The spherical silica may be used singly or in combination of two or more kinds. The amount of the spherical silica to be blended is preferably 30 to 70 parts by mass relative to 100 parts by mass of the total amount of the carboxyl group-containing resins (A1) and (A2) in terms of solid content or 100 parts by mass of the resin (A3) Preferably 40 to 60 parts by mass. When the amount is in the range of from 30 to 70 parts by mass, when the substrate is laminated as a dry film, the embedding and cooling / heating cycle characteristics of the substrate and circuit are improved. The alkali-developable photosensitive resin composition of the present invention may contain other inorganic fillers as long as the effect of the present invention is not impaired. When the carboxyl group-containing resins (A1) to (A3) are contained in combination, the blending amount is the blending amount based on 100 parts by mass of the total amount of the carboxyl group-containing resins (A1) to (A3) .

[(C) Thermal curing component]

The alkali-developable photosensitive resin composition of the present invention contains (C) a thermosetting component. The thermosetting component (C) is not limited as long as it reacts with the carboxyl group-containing resin, and examples thereof include an epoxy compound, a compound having an amino group, an oxetane compound, and an isocyanate compound. Among them, an epoxy compound is preferable.

Examples of the epoxy compound include epoxidized vegetable oil; Bisphenol A type epoxy resin; Hydroquinone type epoxy resins, bisphenol type epoxy resins, and thioether type epoxy resins; Brominated epoxy resin; Novolak type epoxy resins; Biphenol novolak type epoxy resins; Bisphenol F type epoxy resin; Hydrogenated bisphenol A type epoxy resin; Glycidylamine type epoxy resins; Hidanto dolphin epoxy resin; Alicyclic epoxy resins; Trihydroxyphenylmethane type epoxy resin; Biscylenol type or biphenol type epoxy resins or mixtures thereof; Bisphenol S type epoxy resin; Bisphenol A novolak type epoxy resin; Tetraphenylol ethane type epoxy resin; Heterocyclic epoxy resins; Diglycidyl phthalate resin; Tetraglycidylsilanoy ethane resin; A naphthalene group-containing epoxy resin; An epoxy resin having a dicyclopentadiene skeleton; Glycidyl methacrylate copolymer epoxy resin; A copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives, CTBN-modified epoxy resins, and the like, but are not limited thereto. From the viewpoint of reactivity, an epoxy compound having two or more functional groups is preferable. Among them, tetramethyl bisphenol F type epoxy compounds, bisphenol A novolak type epoxy compounds and biphenol novolak type epoxy compounds are more preferable.

The compounding amount of the epoxy compound is preferably 1 to 100 parts by mass relative to 100 parts by mass of the total amount of the carboxyl group-containing resins (A1) and (A2) or 100 parts by mass of the carboxyl group-containing resin (A3) in terms of solid content. Within this range, the curability is improved and various general characteristics such as solder heat resistance are improved. Further, sufficient toughness is obtained, and storage stability is not lowered. More preferably 2 to 70 parts by mass.

Examples of the compound having an amino group include amino resins such as melamine derivatives and benzoguanamine derivatives. For example, methylolmelamine compounds, methylolbenzoguanamine compounds, methylol glycol uril compounds, and methylol urea compounds. The alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound, and the alkoxymethylated urea compound may be prepared by reacting the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound, and methylol urea compound Is converted into an alkoxymethyl group. The kind of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. Particularly, a melamine derivative having a formalin concentration of 0.2% or less which is friendly to human body and environment is preferable.

Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [ Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) (3-ethyl-3-oxetanyl) methyl methacrylate, (3-methyl-3-oxetanyl) methyl methacrylate, Or polyfunctional oxetanes such as polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, , And the like, and the like. In addition to these, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate may also be used.

As the isocyanate compound, a polyisocyanate compound having a plurality of isocyanate groups in the molecule can be used. As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylene diisocyanate, m -Xylene diisocyanate and 2,4-tolylene diisocyanate dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate, and adducts, burettes and isocyanurates of the isocyanate compounds exemplified above. The isocyanate compound may be a block isocyanate compound in which the isocyanate group is protected by a blocking agent to temporarily inactivate it.

(C) The thermosetting component may be a compound other than the above, and may be a known thermosetting component such as a maleimide compound, a benzoxazine resin, a carbodiimide resin, a cyclocarbonate compound, or an episulfide resin. . The thermosetting component (C) may be used alone or in combination of two or more.

[(D) Photopolymerization initiator]

The alkali-developable photosensitive resin composition of the present invention contains (D) a photopolymerization initiator. The photopolymerization initiator (D) is not particularly limited, and a known photopolymerization initiator can be used. For example, benzoin such as benzoin, benzyl, 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, N, N-dimethylaniline, N, N-diethylamino-1- (4- Acetophenones such as N-dimethylaminoacetophenone; Thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-di Thioxanthones such as isopropylthioxanthone; Anthraquinones such as anthraquinone, chloroanthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, 1-chloro anthraquinone, 2-amylanthraquinone and 2-aminoanthraquinone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate and p-dimethylbenzoic acid ethyl ester; (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-2-yl) Oxime esters such as 3-yl] -, 1- (O-acetyloxime); Bis (η ⁵ -2,4- cyclopentadiene-1-yl) -bis (2,6-difluoro -3- (1H- pyrrol-1-yl) phenyl) titanium, bis (cyclopentadienyl) Titanocenes such as bis [2,6-difluoro-3- (2- (1-phenyl-1-yl) ethyl) phenyl] titanium; Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Phenyl disulfide, 2-nitrofluorene, butyloline, anisooin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, and the like. These photopolymerization initiators may be used singly or in combination of two or more.

It is preferable to use thioacetic acid (hereinafter also referred to as " thioxanthone photopolymerization initiator ") in combination with other photopolymerization initiators since the sensitivity to light during exposure can be improved. As the thioxanthene photopolymerization initiator, 2,4-diethylthioxanthone is more preferably used. The blending amount of the thioxanthene photopolymerization initiator is preferably 0.05 to 2 mass parts per 100 mass parts of the above-mentioned (A3) carboxyl group-containing resin in terms of solid content in a total amount of 100 mass parts of the above-mentioned (A1) More preferably 0.1 to 1 part by mass. When the amount is in the range of 0.05 to 2 parts by mass, the effect of improving the sensitivity is large, and as a result, the undercut can be easily suppressed and out gas is hardly generated.

When the oxime ester-based photopolymerization initiator is used, the blending amount of the total amount of the carboxyl group-containing resins (A1) and (A2) in terms of solid content is preferably from 0.01 to 5 mass parts per 100 mass parts of the resin containing the carboxyl group It is preferable to make the portion. In this range, the photocurability on copper is sufficient, the curability of the coating film is improved, the coating film characteristics such as chemical resistance are improved, and the curability of the bottom portion is also improved. More preferably, the total amount of the carboxyl group-containing resins (A1) and (A2) is 100 parts by mass or 0.5 to 3 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A3).

When a photopolymerization initiator other than the thioxanthone-based photopolymerization initiator and the oxime ester-based photopolymerization initiator is used, the total amount of the above-mentioned (A1) and (A2) carboxyl group-containing resins in terms of solid content or 100% ) Is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. In this range, the photocurability on copper is sufficient, the curability of the coating film is improved, the coating film characteristics such as chemical resistance are improved, and the curability of the bottom portion is also improved. More preferably, the total amount of the carboxyl group-containing resins (A1) and (A2) is from 0.5 to 15 parts by mass based on 100 parts by mass of the resin (A3) or 100 parts by mass of the resin containing the carboxyl group.

(Photoreactive monomer)

The alkali-developable photosensitive resin composition of the present invention may contain a photoreactive monomer for publicly known generations. The photoreactive monomer is a compound having at least one ethylenic unsaturated group in the molecule. The photoreactive monomer is to assist in the photocuring of the carboxyl group-containing resin by irradiation with active energy rays.

As the compound used as the photoreactive monomer, for example, known compounds such as polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) Methacrylate, and the like. Specific examples thereof include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; Acrylamides such as N, N-dimethyl acrylamide, N-methylol acrylamide and N, N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; Polyhydric alcohols such as hexanediol, trimethylol propane, pentaerythritol, dipentaerythritol and tris-hydroxyethylisocyanurate, or ethylene oxide adducts thereof, propylene oxide adducts, or? -Caprolactone adducts Polyhydric acrylates; Polyfunctional acrylates such as phenoxy acrylate, bisphenol A diacrylate and ethylene oxide adducts or propylene oxide adducts of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate; The present invention is not limited thereto. Examples of the polyol such as polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene, and polyester polyol may be directly acrylated or urethane acrylated through diisocyanate and melamine acrylate , And the respective methacrylates corresponding to the acrylate.

In addition, an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as cresol novolak type epoxy resin with acrylic acid, or an epoxy acrylate resin obtained by reacting a hydroxy acrylate such as pentaerythritol triacrylate with an isophorone di An epoxy urethane acrylate compound in which a half urethane compound of a diisocyanate such as isocyanate is further reacted may be used as a photoreactive monomer. Such an epoxy acrylate resin can improve photo-curability without deteriorating the touch-dry composition.

The blending amount of the photoreactive monomer is preferably 5 to 100 parts by mass based on 100 parts by mass of the total amount of the carboxyl group-containing resins (A1) and (A2) or 100 parts by mass of the (A3) carboxyl group-containing resin in terms of solid content. In this range, photo-curability is improved, pattern formation is facilitated by the alkali development after irradiation with active energy rays, and the strength of the coating film is improved. More preferably 5 to 70 parts by mass.

(solvent)

The alkali-developable photosensitive resin composition of the present invention may contain an organic solvent for publicly known purposes to adjust the viscosity of the composition or to adjust viscosity for application to a substrate or a carrier film. Examples of the solvent include toluene, xylene, ethyl acetate, butyl acetate, methanol, ethanol, isopropyl alcohol, isobutyl alcohol, 1-butanol, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, Ether acetate, terpineol, methyl ethyl ketone, carbitol, carbitol acetate, butyl carbitol, butyl carbitol acetate and the like. The solvent may be used alone, or two or more solvents may be used in combination.

(Other optional components)

The alkali-developable photosensitive resin composition of the present invention may contain known additives in the field of electronic materials. Examples of additives include thermosetting catalysts, thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, antioxidants, antibacterial and antifungal agents, antifoaming agents, leveling agents, fillers other than the above, thickeners, A tropic imparting agent, a coloring agent, a photoinitiator, and a sensitizer.

The alkali-developable photosensitive resin composition of the present invention may be in the form of a dry film comprising a carrier film (support) and a layer containing the alkali-developable photosensitive resin composition formed on the carrier film.

In the case of dry film formation, the alkali-developable photosensitive resin composition of the present invention is diluted with the above-mentioned organic solvent, adjusted to an appropriate viscosity, and then applied in a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, A gravure coater, a spray coater or the like to a uniform thickness on a carrier film and dried at a temperature of usually 50 to 130 ° C for 1 to 30 minutes to obtain a film. The thickness of the coating film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 占 퐉, preferably 20 to 60 占 퐉 in the film thickness after drying.

As the carrier film, a plastic film is used, and it is preferable to use a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film. The thickness of the carrier film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 mu m.

It is preferable to further laminate a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film after forming the alkali-developable photosensitive resin composition of the present invention on the carrier film.

As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. When the cover film is peeled off, The adhesive force to the film may be smaller.

The alkali-developable photosensitive resin composition of the present invention can be prepared, for example, by adjusting the viscosity with a suitable viscosity for the coating method with the above-mentioned organic solvent, and applying the coating solution onto the substrate by a dip coating method, a flow coating method, a roll coating method, a bar coater method, Curtain coating method and the like, and then the organic solvent contained in the composition is volatilized and dried (dried) at a temperature of about 60 to 100 DEG C, whereby a non-stick coating film can be formed. Further, in the case of a dry film obtained by applying the above composition onto a carrier film and drying the same, the alkali developing type photosensitive resin composition layer is bonded to the base material by a laminator or the like so as to be in contact with the base material, A resin insulating layer can be formed.

In addition to the printed wiring boards and flexible printed wiring boards previously formed in the circuit, the above substrate may be formed of a resin such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / nonwoven epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluorine, (FR-4, etc.), other polyimide films, PET films, glass substrates, glass substrates, and the like. A ceramic substrate, a wafer plate, and the like.

The volatile drying after application of the alkali-developable photosensitive resin composition of the present invention can be carried out by a hot-air circulating drying furnace, a hot plate, a convection oven or the like (a dryer equipped with a heat source of air- A method in which hot air in the nozzle is countercurrently contacted, and a method in which hot air in the nozzle is jetted onto the support).

The alkali-developable photosensitive resin composition of the present invention can be obtained by heating at a temperature of, for example, about 140 to 180 占 폚 to thermally cure the resin of the carboxyl group-containing resin of (A1) or (A2) The carboxyl group and the thermosetting component (C) react with each other to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, hygroscopicity, adhesion, electrical characteristics and the like.

The exposed portions (portions irradiated with active energy rays) are cured by performing exposure (irradiation with active energy rays) on the coating film obtained by applying the alkali-developable photosensitive resin composition of the present invention and volatilizing and drying the solvent. Alternatively, a pattern exposure may be performed by a contact type (or noncontact type) through a photomask having a pattern formed thereon by an active energy ray directly or by a laser direct exposure apparatus, and the unexposed portion may be exposed in a dilute alkali aqueous solution (for example, 0.3 To 3 wt% aqueous sodium carbonate solution) to form a resist pattern.

As an exposure device used for irradiation with the active energy ray, any device that irradiates ultraviolet rays in a range of 350 to 450 nm with a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, A device (e.g., a laser direct imaging device that draws a laser image directly with CAD data from a computer) can also be used. As a laser light source of a direct shot, either a gas laser or a solid laser may be used if laser light having a maximum wavelength in the range of 350 to 410 nm is used. The exposure dose for image formation varies depending on the film thickness and the like, but may be generally within the range of 20 to 800 mJ / cm 2, preferably 20 to 600 mJ / cm 2.

Examples of the developing method include a dipping method, a shower method, a spraying method, a brushing method and the like. As the developing solution, an alkali aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, Can be used.

The alkali-developable photosensitive resin composition of the present invention is suitable for forming a cured coating film such as a solder resist or an interlayer insulating layer of a printed wiring board or a flexible printed wiring board.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is by no means limited by these examples and comparative examples. Unless otherwise stated, " part " means mass part and "% " means mass%.

(Preparation of carboxyl group-containing resin)

(A1-1: production of carboxyl group-containing resin having phenolic skeleton)

190 parts (1 equivalent) of phenol novolac epoxy resin (P-201, epoxy equivalent 190 g / eq, manufactured by Nippon Kayaku Co., Ltd.), 140.1 parts of carbitol acetate and 60.3 parts of solvent naphtha were placed in a flask, Respectively. The obtained solution was once cooled to 60 占 폚, and 72 parts (1 mole) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine were added and heated to 100 占 폚 for about 12 hours to obtain an acid value of 0.2 mgKOH / g. < / RTI > Thereto was added 80.6 parts (0.53 mol) of tetrahydrophthalic anhydride, heated to 90 DEG C and reacted for about 6 hours to obtain a resin solution having a solid acid value of 60 mgKOH / g and a solid content concentration of 65.8%. Hereinafter, it is referred to as a varnish A1-1.

(A1-2: Production of carboxyl group-containing resin having phenolic skeleton)

Then X is dissolved in 925 parts of dimethyl sulfoxide 462.5 parts gave CH _2, in the average degree of polymerization n is 6.2, a bisphenol F type epoxy resin 380 parts with epichlorohydrin in the general formula (1), 98.5 in the stirring 70 ℃ % NaOH 60.9 parts (1.5 moles) was added over 100 minutes. After the addition, the reaction was further carried out at 70 ° C for 3 hours. After the completion of the reaction, 250 parts of water was added and water was washed. After the water separation, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin were distilled off under reduced pressure, and the reaction product containing the remaining unsubstituted salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone , And 10 parts of 30% NaOH were added, and the mixture was reacted at 70 DEG C for 1 hour. After completion of the reaction, the reaction mixture was washed twice with 200 parts of water. After the water separation, methyl isobutyl ketone was distilled off and recovered from the oil layer to obtain an epoxy resin (a) having an epoxy equivalent of 310 g / eq and a softening point of 69 캜. The epoxy resin (a) obtained was epoxidized with about 5 of the 6.2 alcoholic hydroxyl groups in the starting bisphenol F epoxy resin as calculated from the epoxy equivalent. 310 parts of the epoxy resin (a) and 282 parts of carbitol acetate were put into a flask, and dissolved by heating and stirring at 90 캜. The obtained solution was once cooled to 60 占 폚, and 72 parts (1 mole) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine were added and heated to 100 占 폚 for about 60 hours to obtain an acid value of 0.2 mgKOH / g. < / RTI > Thereto was added 140 parts (0.92 mol) of tetrahydrophthalic anhydride, heated to 90 占 폚, and reacted until the solid acid value became 100 mgKOH / g to obtain a resin solution having a solid content concentration of 65%. Hereinafter, it is referred to as a varnish A1-2.

(A2-1: Preparation of carboxyl group-containing resin having cresol novolak skeleton)

220 parts (1 equivalent) of cresol novolac epoxy resin (EOCN-104S, epoxy equivalent 220 g / eq), 140.1 parts of carbitol acetate and 60.3 parts of solvent naphtha were charged into a flask, And dissolved. The obtained solution was once cooled to 60 占 폚, and 72 parts (1 mole) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine were added and heated to 100 占 폚 for about 12 hours to obtain an acid value of 0.2 mgKOH / g. < / RTI > Thereto was added 80.6 parts (0.53 mol) of tetrahydrophthalic anhydride, heated to 90 DEG C and reacted for about 6 hours to obtain a resin solution having a solid acid value of 85 mgKOH / g and a solid content concentration of 65.8%. Hereinafter, it is referred to as a varnish A2-1.

(A3-1: production of carboxyl group-containing resin having phenol novolak skeleton and cresol novolac skeleton)

71 g of phenol, 81 g of cresol, and 1.4 g of oxalic acid as an acid catalyst (0.9 wt% with respect to the total amount of phenol and cresol) were added dropwise over 2 hours while maintaining the temperature at 90 占 폚 or lower. The condensed water or unreacted phenol monomer, cresol monomer and aldehyde were removed by normal pressure and reduced pressure distillation to obtain 152 g of a pale yellow resin having phenol novolak skeleton and cresol novolak skeleton of about 1: 1.

441 parts by weight of epichlorohydrin and 107 parts by weight of dimethyl sulfoxide were added to 152 parts by weight of the obtained pale yellow resin and dissolved, and the mixture was heated to 40 DEG C, and 52 parts by weight of sodium hydroxide (99% pure) And then reacted again at 50 캜 for 2 hours and at 70 캜 for 1 hour. Subsequently, washing with water was repeated to return to neutral. Excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 761 parts by weight of methyl isobutyl ketone was added to dissolve in the residue. Further, the solution of methyl isobutyl ketone was heated to 70 占 폚, and 7.6 parts by weight of a 30% by weight aqueous solution of sodium hydroxide was added. After reacting for 1 hour, washing was repeated to neutralize the solution. Subsequently, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain 210 parts by weight of an epoxy resin.

210 parts of the obtained epoxy resin (1 equivalent), 140.1 parts of carbitol acetate and 60.3 parts of solvent naphtha were charged into a flask, and the mixture was heated and stirred at 90 DEG C to dissolve. The obtained solution was once cooled to 60 占 폚, and 72 parts (1 mole) of acrylic acid, 0.5 part of methylhydroquinone and 2 parts of triphenylphosphine were added and heated to 100 占 폚 for about 12 hours to obtain an acid value of 0.2 mgKOH / g. < / RTI > 80.6 parts (0.53 mol) of tetrahydrophthalic anhydride phthalic acid was added thereto, and the mixture was heated to 90 占 폚 and reacted for about 6 hours to obtain a resin having a solid content acid value of 60 mgKOH / g, a solid content concentration of 69% Solution.

[Examples 1 to 6, 8 and 9, Reference Example 7, Comparative Examples 1 to 4]

The resin solution (varnish) was mixed with the various components shown in Table 1 in the ratio shown in Table 1 (mass part), preliminarily mixed with a stirrer, and kneaded with a three-roll mill to obtain an alkali developing photosensitive resin A composition was prepared.

≪ Preparation of evaluation substrate &

 Each of the alkali-developable photosensitive resin compositions obtained in the above-mentioned Examples and Comparative Examples was coated on the entire surface in such a manner that the film thickness after drying was 20 mu m after being screen-printed, and dried in a hot-air circulation type drying furnace at 80 DEG C for 30 minutes Then, it is allowed to cool to room temperature. The substrate was exposed at an optimum exposure amount using a high pressure mercury lamp mounted exposure apparatus (mercury short arc lamp, manufactured by TOYOTEC Seisakusho Co., Ltd.) and subjected to exposure under the conditions of a temperature of 30 DEG C, a spraying pressure of 0.2 MPa and a developer solution of 1 wt% For 60 seconds to obtain a pattern. The substrate was irradiated with ultraviolet rays under the conditions of an integrated exposure dose of 1000 mJ / cm 2 in a UV conveyer, and then cured by heating at 160 캜 for 60 minutes. The obtained printed board (evaluation board) was evaluated for its characteristics as follows. The optimum exposure dose was exposed through a step tablet (T4105C, manufactured by Stouffer Co.) at the time of exposure, and when the number of stages of the remaining step tablets after development was 8, the optimum exposure dose was used.

<Punching Resistance>

Each of the evaluation boards on which the cured coating film was formed, which had been obtained in the above-mentioned evaluation board, was mounted on a super high speed bench drill (FBD-6, manufactured by FUJI ELECTRIC MACHIN MFG.) ), And the state of the coated film at the punched portion was observed with an optical microscope, and evaluated according to the following criteria. The results are shown in Table 1 below.

◎: No abnormality in the punched portion.

○: There is some deformation at the punched portion.

X: Deformed at the punched portion, and cracks and warpage occur.

<Developability>

In the preparation of the evaluation substrate, the drying conditions after the formation of the coating film were changed to 80 캜 for 90 minutes, and the coating conditions after the drying were set as conditions (a) 30 탆 and (b) 20 탆, And the state of removal of the coating film on the unexposed portion was visually confirmed. The evaluation criteria are as follows. The results are shown in Table 1 below.

⊚: The film thickness condition after drying is 30 탆 or 20 탆 and no developing residue is present at all.

?: When the film thickness condition after drying is 20 占 퐉, there is no developing residue, but 30 占 퐉 shows a little residual filler on the surface.

?: No residue remained when the film thickness condition after drying was 20 占 퐉, but remained remained at 30 占 퐉.

X: The film thickness condition after drying is 30 占 퐉 and 20 占 퐉.

&Lt; Soldering heat resistance &

The rosin-based flux was applied to each of the evaluation substrates on which the cured coating film was formed, which had been obtained by the fabrication of the evaluation substrate, and immersed in a solder bath set at 260 캜 for 30 seconds. The test substrate was washed with an organic solvent, and then subjected to a peeling test with a cellophane adhesive tape, and evaluated according to the following criteria. The results are shown in Table 1 below.

◎: No appearance change.

○: Discoloration to be slightly yellowing.

△: White papers are confirmed on all sides.

X: Deposition of the hard coat film and solder lock are confirmed.

<Touch-up Drying>

Each of the alkali-developable photosensitive resin compositions obtained in the above-mentioned respective Examples and Comparative Examples was coated on the entire surface by screen printing on the patterned copper-clad substrate and dried in a hot-air circulation type drying furnace at 80 캜 for 30 minutes and then cooled to room temperature . A PET film was pressed on this substrate, and thereafter the adhered state of the film when the negative film was peeled off was evaluated based on the following criteria. The results are shown in Table 1 below.

⊚: No peeling off of the film, no marks left on the coating film.

○: When peeling off the film, there is a little resistance, and marks on the film are slightly formed.

X: When the film was peeled off, there was resistance, and the film was clearly stained.

&Lt; Cross section of cured coating film &

Each of the alkali-developable photosensitive resin compositions of Example 1 was used to form a cured coating film on a substrate on the basis of the evaluation substrate. A cross-sectional photograph of the obtained cured coating film is shown in Fig.

* 1: Photosensitive carboxyl group-containing resin (PN (phenol novolak type epoxy resin) / AA (acrylic acid) / THPA (tetrahydrophthalic anhydride)) having a skeleton of phenol novolac type

* 2: Photosensitive carboxyl group-containing resin (BisF (bisphenol type epoxy resin) / AA (acrylic acid) / THPA (tetrahydrophthalic anhydride)) having a skeleton of bisphenol F type

* 3: Photosensitive carboxyl group-containing resin having cresol novolak skeleton (CN (cresol novolak type epoxy resin) / AA (acrylic acid) / THPA (tetrahydrophthalic anhydride))

* 4: Photosensitive carboxyl group-containing resin (PN + CN (phenol novolak type and cresol novolak type epoxy resin) / AA (acrylic acid) / THPA (tetrahydrophthalic anhydride)) having phenol novolac skeleton and cresol novolak skeleton )

* 5: Irgacure 907 (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one manufactured by BASF Japan)

* 6: DETX-S (2,4-diethylthioxanthone) manufactured by Nippon Kayaku Co.,

* 7: ADMATECH CORPORATION ADMAPINE SO-E2

* 8: Admatheque AdMapain SO-E5

* 9: Nippon Aerosil FS-3DC

* 10: Diethylene glycol monoethyl ether acetate

* 11: Aromatic hydrocarbons (Solvesso 150)

* 12: Epiclon N-870 (bisphenol A novolak type epoxy resin) manufactured by DIC Corporation

* 13: NC-3000 manufactured by Nippon Kayaku Co., Ltd. (biphenyl novolak epoxy resin, epoxy equivalent = 275)

* 14: YSLV-80XY (tetramethyl bisphenol F type epoxy resin, epoxy equivalence = 190 to 200), manufactured by Shinnitetsu Chemical Co.,

* 15: Dipentaerythritol hexaacrylate

From the results shown in Table 1, it was found that the alkali-developable photosensitive resin compositions of Examples 1 to 6, 8 and 9 both had good punching resistance, developability and touch-dryness. On the other hand, Comparative Example 1 containing only a carboxyl group-containing water having a cresol novolak skeleton (A2) as the component (A) had poor punching resistance. Comparative Examples 2 and 3 containing only (A1) a carboxyl group-containing water having a phenolic skeleton as the component (A) had poor developability and poor touch-drying characteristics. In addition, Comparative Example 4 containing fused silica which is not spherical silica as the inorganic filler (B) had poor punching resistance.

Claims (9)

(A) a resin containing a carboxyl group, (B) an inorganic filler, (C) a thermosetting component and (D) a photopolymerization initiator,
(A1) a carboxyl group-containing resin having a phenol skeleton (except for a carboxyl group-containing resin having a bisphenol F skeleton and a carboxyl group-containing resin having a cresol novolac skeleton) and (A2) A carboxyl group-containing resin having a cresol novolak skeleton,
(B) an alkali-soluble photosensitive resin composition comprising an inorganic filler, wherein the inorganic filler contains spherical silica having an average particle diameter (D50) of more than 0.1 m but not more than 5 m. The alkali-developable photosensitive resin composition according to claim 1, wherein the spherical silica has an average particle diameter (D50) of more than 0.1 占 퐉 and not more than 3 占 퐉. The positive resist composition according to Claim 1, which contains the carboxyl group-containing resin (A1) having a phenolic skeleton and the carboxyl group-containing resin (A2) having a cresol novolak skeleton in a ratio of 1: 9 to 9: 1 Wherein the photosensitive resin composition is an alkali developing photosensitive resin composition. The resin composition according to claim 1, wherein the phenolic skeleton of the carboxyl group-containing resin (A1) having a phenolic skeleton is at least one of a skeleton of a phenol novolak type, a bisphenol A type, a biphenyl type, a phenol aralkyl type, and a trisphenyl methane type Wherein the alkali-developing photosensitive resin composition is a photosensitive resin composition. (A) a resin containing a carboxyl group, (B) an inorganic filler, (C) a thermosetting component and (D) a photopolymerization initiator,
(A) a carboxyl group-containing resin, (A3) a carboxyl group-containing resin having a phenol skeleton (excluding a cresol novolak skeleton) and a cresol novolak skeleton,
(B) an alkali-developing photosensitive resin composition characterized by containing spherical silica as an inorganic filler. 6. The resin composition according to claim 5, wherein the phenolic skeleton of the carboxyl group-containing resin having the phenol skeleton and the cresol novolak skeleton of (A3) is at least one selected from the group consisting of phenol novolak type, bisphenol A type, bisphenol F type, biphenyl type, phenol aralkyl type, And a skeleton of a trisphenylmethane type. The alkali-developable photosensitive resin composition according to claim 1, A dry film obtained by applying and drying the alkali-developable photosensitive resin composition according to any one of claims 1 to 6 to a film. An alkali-developable photosensitive resin composition according to any one of claims 1 to 6, or a dry film obtained by applying and drying the alkali-developable photosensitive resin composition according to any one of claims 1 to 6 to a film Is obtained by performing at least one of photo-curing and thermosetting. A printed wiring board having the cured product according to claim 8.

Images