WO2001037048A1 - Photosensitive composition and products of curing thereof - Google Patents

Abstract

A photosensitive composition, characterized by comprising a prepolymer (A) bearing at least two polymerizable unsaturated groups and at least one carboxyl group in one molecule, a photopolymerization initiator (B), a reactive diluent (C), and a blocked isocyanate (D). It is preferable that the components (B), (C) and (D) are contained in amounts of 1 to 30, 1 to 100, and 2 to 100 parts by weight respectively per 100 parts by weight of the component (A). The composition can give, via irradiation with actinic radiation, cured films which are excellent not only in developability, curing properties, stability, and resistance of exposed areas to developer, but in properties necessary to solder resists, e.g., close adhesion, insulation properties, resistance to soldering heat, resistances to solvent, acid and alkali, and plating resistance.

Description

 Description Photosensitive composition and cured product

 The present invention relates to a novel photosensitive composition, and more particularly, to a solder resist film for printed wiring boards having excellent properties such as developability, curability, stability, adhesion, heat resistance, and chemical resistance. The present invention relates to a photosensitive composition useful for forming an insulating resin layer of an electronic component. Background art

In printed wiring boards, solder resists are widely used as permanent protective films for circuits. Solder resist is a film that is formed on the entire surface of the circuit conductor except for the parts to be soldered. When wiring electronic components on printed wiring boards, it prevents solder from adhering to unnecessary parts, It is used as a protective coating to prevent the circuit from being directly exposed to air. As a solder resist for printed wiring boards, liquid developable solder-resist ink is used from the viewpoint of high precision, high density, and consideration of environmental issues. As a liquid solder resist, for example, Japanese Patent Application Laid-Open Nos. Sho 60-208337 and Sho 61-54947 disclose a part of a novolak-type epoxy resin with acrylic acid. Solder resist ink compositions based on reactants have been proposed. However, these ink compositions have problems such as insufficient curability after exposure, and the problem of leaving a residue after forming a coating film. Japanese Patent Publication No. 1-534390 discloses an energy linear curing resin obtained by reacting a reaction product of a novolak epoxy resin with an unsaturated monocarboxylic acid with a polybasic anhydride, a photopolymerization initiator. A photosensitive resin composition comprising a diluent and an epoxy compound has been proposed. However, since the reaction between the carboxyl group contained in the energy ray-curable resin and the epoxy compound proceeds even at room temperature, the photosensitive resin composition is left unexposed if the ink is left for a long time or the coating film drying time is extended. There were problems such as uneven development in the area. Also, Japanese Unexamined Patent Publication (Kokai) No. 2-169602 discloses an unsaturated group-containing A photosensitive resin composition comprising a potent rubonic acid compound, an oxazoline compound, a photopolymerization initiator, and a diluent has been proposed, but this photosensitive resin composition also has problems such as insufficient stability.

 As described above, the conventionally proposed photosensitive composition does not satisfy all of the properties such as developability, curability, and stability, and a solder resist composition having good properties is required. Was desired. Disclosure of the invention

 The present invention solves the various problems described above, and is excellent in developability, curability, and stability, and also has an energy-ray-curable photosensitive composition having resistance to a developer in an exposed area. The purpose is to provide. Furthermore, in addition to the above excellent properties, it forms a cured coating film with excellent adhesion, electrical insulation, solder heat resistance, solvent resistance, acid resistance, alkali resistance, and plating resistance required for solder resist. A photosensitive composition suitable for the manufacture of printed wiring boards and the like, a cured product obtained from the composition, and a cured film obtained by curing the composition. Another object is to provide a printed wiring board.

 The present inventors have conducted intensive studies in order to solve these problems, and as a result, by using a specific isocyanate compound instead of the epoxy resin usually used for the photosensitive composition, the developing property and the curing property have been improved. The present inventors have found that a photosensitive composition having excellent properties, stability, adhesion, heat resistance, and chemical resistance can be produced, and have completed the present invention. That is, according to the present invention, a prepolymer (A;) having two or more polymerizable unsaturated groups and one or more carboxyl groups in one molecule, a photopolymerization initiator (B), a reactive diluent ( There is provided a photosensitive composition comprising the components C) and the blocked isocyanate (D) as essential components.

In a preferred embodiment of the photosensitive composition of the present invention, the prepolymer (A) has an epoxy compound (a) and one or more polymerizable unsaturated groups and one carboxyl group in one molecule. A product obtained by reacting a reaction product of the compound (b) with a saturated or unsaturated polybasic anhydride (c), and having a solid content acid value of 45 to 20 0 mgKOH / g, wherein the blocked isocyanate (D) is a polyisocyanate compound having two or more isocyanate groups as an average number of functional groups in one molecule and phenols, alcohols, acid amides, oximes, It is a reaction product with a blocking agent selected from the group consisting of esters, diketones, mercapnones, ureas, imidazoles, acid imides, amines and olebamates, and particularly has an isocyanurate ring And each of the above-mentioned components.

The content of (A) to (D) is, by weight, prepolymer (A): 100 and photopolymerization initiator (B):;! ~ 30, Reactive diluent (C)::! And a blocked isocyanate (D): 2 to 100. Further, according to another aspect of the present invention, a cured product obtained by curing the photosensitive composition, and a cured film obtained by curing the photosensitive composition are used. Is provided. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, each component (A) to (D) of the photosensitive composition of the present invention and uses thereof will be described in detail. In this specification, the notation “(meth) acrylic acid” means acrylic acid or methacrylic acid, and the notation “(meth) acrylate” means acrylate or methacrylic acid.

《Prebolimer (A)>

 The prepolymer (A) constituting the photosensitive composition of the present invention has two or more polymerizable unsaturated groups and one or more carboxyl groups in one molecule, and includes, for example, an epoxy compound (a) A reaction product obtained by reacting one or more polymerizable unsaturated groups and a compound having one carboxyl group (b) in one molecule in the presence of a catalyst, if necessary, further adds a saturated or unsaturated polybase. Prepolymer obtained by reacting the acid anhydride (c).

The epoxy compound (a) used in the synthesis of these prepolymers (A) can be appropriately selected from those commonly used in the production of solder resists. For example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, biphenyl epoxy resin, bixylenol epoxy resin, N-glycidyl epoxy resin, triglycidyl isocyanurate, phenol Novolak resin, cresol novolak resin, ethyl phenol novolak resin, isopropylphenol novolak resin, tert-butyl phenol novolak resin, 3,5-xylenol novolak resin, bromphenol novolak resin, bisphenol A novolak resin, naphthalene novolak resin Resin, glycidyl compound of polyvinyl phenol, epoxy compound of condensate of phenols and aromatic aldehyde having phenolic hydroxyl group, alkyl acrylate And at least one monomer selected from alkyl methacrylates and at least one epoxy group-containing monomer selected from epoxy group-containing (meth) acrylates And copolymers. These epoxy compounds can be used alone or in combination of two or more. Above all, novolak epoxy resins such as phenol novolak type, cresol novolak type, and bisphenol A novolak type are particularly preferable, and these epoxy resins can be used alone or in combination of two or more.

 Examples of the compound (b) having one or more polymerizable unsaturated groups and one carboxyl group in one molecule used in the synthesis of the prepolymer (A) include (meth) acrylic acid, crotonic acid, Reaction products of cinnamic acid, penyu erythritol tri (meth) acrylate and succinic anhydride, reaction products of penyu erythritol tri (meth) acrylate and fumaric anhydride, penyu erythritol tri (meth) acrylate and tetrahydroxide Reaction product of fluoric anhydride, reaction product of dipentyl erythritol ester (meth) acrylate and succinic anhydride, reaction product of dipentyl erythritol ester and methacrylic acid Products, such as the reaction product of dipentyl erythritol pentyl (meth) acrylate and tetrahydrofluoric anhydride Door can be.

The compound (b) having one or more polymerizable unsaturated groups and one carboxyl group in one molecule is contained in an amount of from 0.8 to 1.0 equivalent of the epoxy group of the epoxy compound (a). It is preferable to add 1.2 equivalents. When the amount of the compound (b) having one or more polymerizable unsaturated groups and one carboxyl group in one molecule is less than 0.8 equivalent, the stability of the photosensitive composition becomes insufficient, and 1.2 equivalents If the ratio exceeds the above range, the content of low molecular weight substances tends to increase, and the curing properties tend to be insufficient.

 The reaction between the epoxy compound (a) and the compound (b) having one or more polymerizable unsaturated groups and one carboxyl group in one molecule is preferably carried out at 100 to 120 ° C.

 Prepolymer (A) is further saturated with the reaction product of the epoxy resin (a) and a compound (b) having one or more polymerizable unsaturated groups and one carboxyl group in one molecule. Alternatively, it can be obtained by reacting an unsaturated polybasic acid anhydride (c). Here, the saturated or unsaturated polybasic acid anhydride (c) used is, for example, maleic anhydride, succinic anhydride, fumaric anhydride, hexahydrofuranic anhydride, 3-methylhexahydroanhydride. Fluoric acid, 4-Methylhexahydrofluoric anhydride, 3-Ethylhexahydrophthalic anhydride, 4-Ethylhexahydrofluoric anhydride, Tetrahydrofuric anhydride, 3-Methyltetrahiic anhydride Acid anhydrides such as drofuric anhydride, 4-methyltetrahydrofluoric anhydride, 3-ethyltetrahydrofuric anhydride, and 4-ethyltetrahydrofuric anhydride. These acid anhydrides are suitable from the viewpoints of developability and reactivity with thermosetting components. Of these, succinic anhydride and tetrahydrofluoric anhydride are particularly preferred.

 The amount of the saturated or unsaturated acid anhydride (c) used is preferably from 0.3 to 1.0 equivalent to 1.0 equivalent of the epoxy group of the epoxy compound (a). When the amount of the saturated or unsaturated acid anhydride (c) is less than 0.3 equivalent, the developability of the photosensitive composition becomes insufficient, and when it exceeds 1.0 equivalent, the solvent resistance becomes insufficient. Tend. The reaction with the saturated or unsaturated anhydride (c) is preferably carried out at 60-120 ° C.

The Pureborima solids acid value one (A) is usually 45 to 200111 1 ^ 0} 1 /, preferably from 1:60 to 10111 1 <011 / ^/ Dearu. If the acid value is less than 45 mgKOH / g, the developability of the photosensitive composition tends to be insufficient, and if it exceeds 200 mgKOH / g, the solvent resistance tends to be insufficient. In the synthesis of the prepolymer (A), for example, when the obtained prepolymer is liquid at room temperature, the reaction can be carried out without a solvent.However, the viscosity of the reaction system is adjusted, and the mixing is sufficiently performed. The reaction is preferably performed using a solvent for the purpose of improving heat and the like. Examples of the solvent that can be used include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methylcell sorb, methyl carbitol Glycol ethers such as diethylene glycol dimethyl ether; esters such as ethyl acetate and butyl acetate; ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, and diethylene glycol monomethyl. Ether acetate, diethylene glycol monoethyl acetate, diethylene glycol monopropyl ether acetate, ethylene glycol monobutyrate Acetates of glycol ethers such as ether acetate; polyhydric alcohols such as ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and nonane; petroleum-based solvents such as petroleum naphtha and solvent naphtha; water; Is mentioned. These solvents can be used alone or in combination of two or more. The amount of the solvent to be used is preferably 5 to 100 parts by weight, more preferably 20 to 100 parts by weight, based on 100 parts by weight of the prepolymer (A).

<< Photopolymerization initiator (B) >>

The photopolymerization initiator (B) used in the photosensitive composition of the present invention can be appropriately selected from commonly used photopolymerization initiators. Specific examples of the photopolymerization initiator include, for example, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-12 _Phenylacetophenone, 2,2-diethoxy 2 _Phenylacetophenone, 1,1-Dichloroacetophenone, 1-Hydroxycyclohexylphenylketone, 2-Hydroxy1-2-Methyl 1-phenylpropane 1-one, 1- [4- (2-hydroxyethoxy) phenyl] -1-2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1- [ 4- (Methylthio) phenyl]-2-morpholinopropane 1-one, 2-benzyl-12-dimethylamino-11- (41-morpholinophenyl) 1-1-acetophenones such as butenonone; Examples include anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-butyl-butylanthraquinone, 1-monomouth anthraquinone, and 2-amylanthraquinone.

Furthermore, thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; ketals such as acetofphenone dimethyl ketal and benzyl dimethyl ketone; Benzophenones such as benzophenone or xanthone; 2-benzyl-1--2-dimethylamino-1,1- (4-morpholinophenyl) -butanone-one aminoketone; bis (2,6-dimethyl) Tokishibenzoiru) one 2, 4, 4-trimethylpentyl phosphine O wherein, bis (2, 4, 6-tri Mechirubenzoiru) Single-phenylalanine phosphine O wherein, bis (7 ⁵ -? 2, 4-Shi Kuropen evening 1-yl) 1-bis (2,6-difluoro-1 3- (1H-pyrrol-1 1-yl) phenyl Taniumu, ⁵ Shikuropen evening Jeniru one 7 ^fi -? Kume sulfonyl iron (1 +) -. To hexa fluorophosphate Fay preparative (1 I) and the like can also be mentioned These photopolymerization initiators alone or in combination of two or more Can be used.

 The photopolymerization initiator may be used in combination with one or more benzoic acid-based or tertiary amine-based photopolymerization accelerators.

The amount of the photopolymerization initiator (B) used is preferably from 1 to 30 parts by weight, more preferably from 3 to 10 parts by weight, per 100 parts by weight of the prepolymer (A). When the amount of the photopolymerization initiator (B) used is less than 1 part by weight, the curing reaction by the energy beam becomes difficult to proceed. On the other hand, if the amount is more than 3 ° parts by weight, the characteristics as a solder resist tend to decrease. 《Reactive diluent (C)》

 The reactive diluent (C) is used to further sufficiently cure the photosensitive composition by energy rays and obtain a coating film having excellent chemical resistance, heat resistance, and alkali resistance.

 The reactive diluent (C) used in the present invention is a compound having at least two double bonds in one molecule. Examples of such a compound include 1,4-butanediol di (meth) acrylate, 1,6-Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol-di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol adipate (meth) acrylate And di (meth) acrylates of glycols such as neopentyl glycol di (meth) acrylate hydroxypivalate.

 Further examples of the reactive diluent include dicyclopentenyl di (meth) acrylate, di-propentol-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, and ethylene oxide-modified phosphate di (meth) acrylate. (Meth) acrylate, arylated cyclohexyldi (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolpropanetri (meta) acrylate, penyu erythritol tri (meta) Acrylate, pentaerythritol tritetra (meta) acrylate, dipentyl erythritol tri (meta) acrylate, dipentyl erythritol tripentyl (meta) acrylate, propionic acid-modified dipen Erythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, tris (acryloxyshethyl) isocyanurate, probionic acid-modified dipentyl erythritol monotetra (meth) acrylate, propionic acid-modified dipen Erythritol phenol (meta) acrylate, dipentyl erythritol hexa (meth) acrylate, diprothyl erythritol modified hexyl erythritol hexa (meth) acrylate, and the like.

The above polyfunctional reactive diluents can be used alone or in combination of two or more. Wear. The amount of the reactive diluent (C) to be used is preferably from 1 to 100 parts by weight, more preferably from 2 to 50 parts by weight, based on 100 parts by weight of prepolymer (A). If the amount of the reactive diluent (C) is less than 1 part by weight, the curing reaction by the energy beam is difficult to proceed. On the other hand, if it exceeds 100 parts by weight, tackiness tends to be insufficient.

《Blocked isocyanate (D)>

 In the present invention, the blocked isocyanate (D) is added in order to improve the strength of the coated film after curing of the photosensitive composition. Examples of the blocked isocyanate (D) that can be used for this purpose include those obtained by blocking a polyisocyanate compound having two or more isocyanate groups as an average number of functional groups in one molecule with a blocking agent.

 Examples of the polyisocyanate compound having two or more isocyanate groups as an average number of functional groups in one molecule include, for example, a polyisocyanurate compound having an isocyanurate ring introduced by trimerization of a polyisocyanate compound (isocyanuration reaction). (D 1), an isocyanate-terminated polyurethan polyisocyanate compound (D 2), a polyurea polyisocyanate compound, a polymeric isocyanate, or a diisocyanate-terminated polyisocyanate compound obtained by reacting an organic diisocyanate with a polyfunctional active hydrogen compound. Enyl succinate and the like.

Examples of the organic polyisocyanate compound used for producing the polyisocyanurate compound (D 1) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 1,4-xylylene Diisocyanate, 1,3-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4 'diphenylmethane diisocyanate, 4,4' diphenylmethane Terdy succinate, 3,3'-dimethyldiphenylmethane 1,4,4'-diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene 1,4-diisocyanate 1,5-diisocyanate, 3,3'-dimethoxydiphenyl 4,4'-diisocyanate, hi, hi, hi, hi-tetramethylxylylene Diisocyanate, polyphenylenepolymethylene Polyisocyanate, 4,4'-Aromatic diisocyanate such as modified carbodiimide and ureiimine of diphenylmethyldiisocyanate, tetramethylenediisocyanate, hexamethylenediisocyanate, 2-methyl Aliphatic diisocyanates such as pentane 1,5-diisocyanate and lysine diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenyl diisocyanate Aliphatic diisocyanates, such as diisocyanate, and the like.

 Among them, as the organic polyisocyanate compound, those having a cyclic structure such as aromatic diisocyanates and alicyclic diisocyanates are preferable.

 The polyisocyanurate compound (D 1) can be produced by a method known per se. The compound (D 1) is usually produced by a method in which an organic diisocyanate is reacted in the presence of an isocyanuration catalyst. As the isocyanuration catalyst, conventionally known ones can be used. For example, 2,4,6_tris (dimethylaminomethylphenol), triethylamine, N, Ν ', Ν "-trisdimethylaminopropyl Tertiary amines such as hexahydrotriazine, tetraalkylalkylenediamine, diazabicyclooctane and lower alkyl-substituted products thereof; tertiary amine and ethyl alcohol, monosubstituted rubamic acid ester, aldehyde, alkylene oxide, alkyleney Co-catalyst system with min, ethylene carbonate, 2,3-butanedione, etc .; Tertiary alkyl phosphines; Alkyl ammonium, such as tetramethylammonium, tetraethylammonium, tetrabutylammonium Hydroxide of organic acid weak salt; trimethyl Examples of the organic weak acid salts of hydroxyalkyl ammonium such as hydroxypropylammonium, trimethylhydroxypropylammonium, and triethylhydroxypropylammonium.

Other specific examples of the isocyanuration catalyst include alkali metal salts of imids such as potassium imidofluorate; quaternary onium hydroxy compounds of Ν, Ρ, As, Sb, and S or Se. Oxide compounds, such as onium hydroxy compounds; alkyl-substituted ethyleneimines, such as N-methylethyleneimine; Metal salts of carboxylic acids such as thorium, cobalt acetate, lead 2-ethylhexanoate, sodium benzoate, sodium naphthenate and magnesium naphthenate; oxides and hydroxides of metal and alkaline earth metals , Carbonates, phenolic compounds and metal salts of phenols; co-catalysts such as epoxy compounds, epoxy compounds and tertiary amines, metal salts of aromatic secondary amines such as sodium salt of diphenylamine Various organic metals such as titanium tetrabutylate and tributylantimony oxide; Friedel-Crafts catalysts such as aluminum chloride and boron trifluoride; chelate compounds of alkali metal such as sodium salicylaldehyde; Aluminum acetyl acetate, lithium acetyl acetate, etc. Rate compounds and the like.

 Among the above isocyanuration catalysts, tertiary amines such as N, Ν, Ν "—trisdimethylaminopropyl pyrhexahydrotriazine, carboxylic acids such as sodium acetate, cobalt acetate, potassium naphthenate, magnesium naphthenate, etc. Metal salts are preferred.

 The concentration of the isocyanuration catalyst varies depending on the type of the catalyst used, the reaction temperature and the like, but is usually selected from the range of 0.01 to 10% by weight based on the polyisocyanate compound.

 In addition to the above catalysts, co-catalysts include, for example, aliphatic alcohols such as methanol, ethanol and butanol; polyhydric alcohols such as ethylene glycol, 1,3-butanediol, neopentyl glycol and trimethylolpropane; It is preferable that polyethers such as pyrene glycol, phenols, secondary amines, imidazoles and the like are usually used in a proportion of 0.05 to 10% by weight based on the polyisocyanate.

 Alcohols such as aliphatic alcohols, polyhydric alcohols, and phenols as co-catalysts can be added at the same time as the isocyanuration catalyst, or they can be reacted with an organic disocyanate in advance to form urethane bonds, and then the isocyanuration reaction can be performed. You can do it too.

The reaction temperature for the isocyanuration is generally 0 to 200 ° C., preferably 0 to 100 ° C. Is selected from the range.

 A solvent may or may not be used in the isocyanuration reaction. Solvents used are inert solvents commonly used in polyurethane production, for example, aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. Ester solvents such as ethyl acetate, butyl acetate, and isobutyl acetate; ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3 One or more non-protonic polar solvents such as N-methylpyrrolidone can be used; glycol ether ester solvents such as ethoxypropionate; ether solvents such as tetrahydrofuran and dioxane; By selecting the type and amount of the solvent to be used and the resin concentration, the reaction solution can be adjusted to a viscosity according to the use conditions.

 The progress of the reaction can be tracked by measuring the NCO content of the reaction solution, measuring infrared spectroscopy, measuring refractive index, and the like.

When a predetermined NC0 content or isocyanuration rate is reached, the reaction is stopped with a polymerization terminator suitable for the type of catalyst used. Examples of the reaction terminator include inorganic acids such as hydrochloric acid, phosphoric acid, and phosphorous acid; and phosphorous such as monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, dimethyl phosphate, getyl phosphate, and dibutyl phosphate. Acid esters; monophosphites such as monomethyl phosphite, monoethyl phosphite, monobutyl phosphite, dimethyl phosphite, getyl phosphite, dibutyl phosphite; methanesulfonic acid, p-toluene Sulfonic acids such as sulfonic acid, methyl p-toluenesulfonate and ethyl p-toluenesulfonate, and alkyl esters thereof; perfluorinated sulfonic acids such as nonafluorobutanesulfonic acid; and the like. The addition amount of the reaction terminator is preferably in the range of from the same amount to twice the amount of the added catalyst. The polyisocyanurate compound (D 1) can usually be used for the block reaction without removing the unreacted monomer, but it may contain a large amount of unreacted monomer depending on the isocyanurate conversion rate. If the unreacted monomer has an adverse effect, the unreacted monomer may be used for block reaction after removing the unreacted monomer by thin-film distillation or the like. In the production of an isocyanate-terminated polyurethane polyisocyanate compound (D 2) obtained by the reaction of an organic dissionate with a polyfunctional active hydrogen compound, the organic dissocyanate compound may be any one of the organic dissocyanate compounds described above and a bullet-modified product thereof. And modified ureaimine, modified carbodiimide, and the like. These organic isocyanates may be used alone or in combination of two or more.

 Examples of the polyfunctional active hydrogen compound used in the production of the isocyanate group-terminated polyurethane polyisocyanate compound (D 2) include polyfunctional hydroxy compounds. Polyfunctional hydroxy compounds such as glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 2-hydroxyethyl-1,6-hexanediol, 1,2,4-butanetriol Trifunctional or higher polyhydric alcohols such as erythritol, erythritol, sorbitol, pentaerythritol and dipentyl erythritol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 2,2-getyl —1,3-propanediol, 2-methyl- 2 —propyl— 1, 3-propanediol, 2-butyl-2-ethyl 1,3-propanediol, 1,5-pentanedidiol, 3-methyl-1,5-pentanedidiol, 2-methyl-1,4-dienediaminediol, 1,6-hexanediol, 2_ 1,3-hexanediol, neopentyl glycol, 1,3,5-trimethyl-1,3-pentanediol, 2,2,4-trimethyl-1,3-pentendiol, 1,8-ethyl Aliphatic glycols such as butanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, and alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol And monomer glycols such as aromatic glycols such as xylylene glycol and bishydroxyxetoxybenzene.

In addition, polyfunctional hydroxy compounds include high molecular weight polyols such as bis Polyols such as polyether polyols, polyester polyols, polyether ester polyols, polycarbonate polyols, and polyacryl polyols, which are reaction products of phenol A with ethylene oxide or propylene oxide, are also listed. Can be

 Examples of polyether polyols include glycols such as ethylene glycol, propylene glycol, and diethylene glycol; tri- or more functional polyols such as glycerin, trimethylo-leutane, trimethylolpropane, and pen-erythritol; and polyamines such as ethylene diamine and toluene diamine. Examples thereof include hydroxyl-containing polyether polyols obtained by addition-polymerizing an alkylene oxide such as ethylene oxide and propylene oxide, and polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran. Polyester polyols include dicarboxylic acids such as succinic acid, adibic acid, sebacic acid, azelaic acid, and fluoric acid, and carboxylic acids such as trimeric and tetracarboxylic acids such as trimellitic acid and pyromellitic acid; Ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2-getylpropanediol, 2-ethyl-2-butyl Diols such as propanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, triols such as trimethylolpropane, glycerin, or bis Polyhydroxy compounds such as phenol A and bisphenol F And the like obtained by a polycondensation reaction with

 Examples of the polyetherester polyol include, for example, reacting an ether group-containing diol or a mixture thereof with another glycol with the dicarboxylic acid or anhydride thereof, or reacting a polyester glycol with an alkylene oxide. What can be obtained is, for example, poly (polytetramethylene ether) adipate.

Polycarbonate polyols include, for example, polyalcohols and dimethyl carbonate, and de-alcoholization of dialkyl carbonates such as diethyl carbonate. Polycarbonate polyols obtained by condensation reaction, dephenol condensation reaction of polyhydric alcohol and diphenyl carbonate, ethylene glycol condensation reaction of polyhydric alcohol and ethylene carbonate, and the like. Examples of the polyhydric alcohol used in this condensation reaction include 1,6-hexanediol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl Aliphatic diols such as 1,5-pentenediol, 2,2-getylpropanediol, 2-ethyl-2-butylpropanediol, and neopentyl glycol; 1,4-cyclohexanediol, 1 And alicyclic diols such as 4,4-cyclohexanedimethanol.

 As other polyfunctional active hydrogen compounds, for example, diamines, diamino alcohols and the like can be used. Examples of the diamines include hexamethylene diamine, xylene diamine, isophorone diamine, N, N-dimethylethylene diamine, and the like, and examples of the amino alcohol include monoethanolamine and jetanolamine. No.

 The preferred molecular weight of the polyol component as these polyfunctional active hydrogen compounds is from 35 to 500 in number average molecular weight. When a polyol having a molecular weight of more than 500 is used, the crosslinking density tends to decrease, and the strength of the coating film tends to decrease.

 The temperature in the production of the polyisocyanate group polyisocyanate compound (D 2) (urethanization reaction) in the present invention is usually selected from the range of 10 to 90 ° C. A reaction catalyst is not particularly required, but in some cases, an organotin catalyst such as dibutyltin dilaurate or dibutyltin dioctate; an organic lead catalyst such as lead octanoate; triethylamine, dimethyloctylamine, diazabicycloundecene, or the like. It is also effective to use a tertiary amine compound catalyst or the like. The progress of the urethanization reaction can be monitored by measuring the N C◦ content during the reaction. The reaction is stopped when the target NCO content is reached.

These reactions can be carried out without solvent or in a solvent. As the solvent used, one or more of the inert solvents exemplified in the above-mentioned isocyanuration reaction can be used. By selecting the type, amount and resin concentration of the solvent used, The viscosity can be adjusted according to the use conditions.

 As described above, the blocked isocyanate (D) used in the present invention can be obtained by blocking a polyisocyanate compound having two or more isocyanate groups as an average number of functional groups in one molecule with a blocking agent. Can be

 Examples of the blocking agent include oximes such as formamidoxime, methylethylketoxime, acetoxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; phenol, cresol, xylenol, p-ethylphenol, phenols such as o-isopropylphenol, p-tert-butylphenol, thymol, p-naphthol, p-nitrophenol, p-chlorophenol; methanol, ethanol, butanol, tert-butanol, 2 —Ethylhexanol, cyclohexanol, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, butyl cellosolve, methylene carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol Alcohols such as alcohols; £ -caprolactam, acetoanilide, acetoanisidide, acetate amide, benzamide, and acid amides such as (5-valerolactam, abutyrolactam, etc.).

 Further, esters such as dimethyl malonate and getyl malonate; diketones such as methyl acetoacetate, ethyl acetoacetate and acetylacetone; mercapnos such as butyl mercaptan, thiophenol, and tert-dodecyl mercaptan; Ureas such as urea, thiourea and ethylene urea; imidazoles such as imidazole, 2-methylimidazole and 2-ethylimidazole; acid imids such as succinic imid and maleic imid; Amines, such as diphenylamine, phenylnaphthylamine, aniline, and rubazole; imines, such as ethyleneimine, propyleneimine, and polyethyleneimine; levumamates, such as phenylphenylcarbamate and 2-oxazolidine A plot of sulfites such as sodium bisulfite and bisulfite Agents can also be mentioned.

Among these, acid amides, diketones, esters, alcohols and carbamates are preferred as the blocking agent. The blocking reaction of the polyisocyanate compound with the above-mentioned blocking agent is carried out by a conventionally known method. The amount of the blocking agent used in the reaction is generally 1 equivalent or more and 2 equivalents or less, preferably 1.05 to 1.5 equivalents, per 1 equivalent of the active isocyanate group. If it is less than 1 equivalent, active isocyanate groups remain, and if it is more than 2 equivalents, unreacted block agent remains, which may have an adverse effect.

 The blocking reaction temperature is usually selected from the range of 10 to 150 ° C. Although a reaction catalyst is not particularly required, in some cases, an organotin-based catalyst such as dibutyltin dilaurate or dibutyltin dioctate; an organic lead-based catalyst such as lead octanoate; triethylamine, dimethyloctylamine, It is also effective to use a catalyst for urethanizing a tertiary amine compound such as azabicycloundecene.

 Although the molecular weight of the blocked polyisocyanate (D) used in the present invention is not particularly limited, it is usually a number average molecular weight of 300 to 100,000, preferably 500 to 200,0. 0 is 0. If the number average molecular weight exceeds 100,000, the molecular weight between crosslinks becomes longer, and the strength of the coating film decreases, or the viscosity becomes too high, and the workability may decrease.

 In the composition of the present invention, the above blocked isocyanates (D) can be used alone or in combination of two or more.

 The amount of the blocked isocyanate (D) to be used is preferably 2 to 100 parts by weight, more preferably 10 to 50 parts by weight, per 100 parts by weight of the prepolymer (A). If the amount of the blocked isocyanate (D) is less than 2 parts by weight, the hardness of the coating film tends to decrease, and if it exceeds 100 parts by weight, the photocurability tends to decrease.

《Other additives》

The composition of the present invention may be used by adding a solvent in order to adjust viscosity and improve coating properties and handling properties. As such a solvent, the solvent used at the time of synthesizing the prepolymer (A), which is a component of the present invention, may be used as it is, or after removing these once, a solvent suitable for the intended use may be added. You may. The solvent to be used can be appropriately selected from those exemplified as the solvent that can be used for the synthesis of the prepolymer (A). In addition, additives can be added to the composition of the present invention as needed. Specifically, for example, inorganic fillers such as silica, alumina, talc, clay, calcium carbonate, and barium sulfate; organic pigments such as phthalocyanine and azo; Coating additives such as antifoaming agents, force-upling agents, and leveling agents; curing accelerators such as urea derivatives; hydroquinone, hydroquinone monomethyl ether, pyrogallol, Yuichi Shari-butylcatechol, And polymerization inhibitors such as phenothiazine, aluminum salt of N-ditrosophenylhydroxylamine, and N-ditrosophenylhydroxylamineammonium salt.

《Usage ・ Usage》

 As described above, the composition of the present invention is used for a solder-resist film for a printed wiring board and an insulating resin layer of various electronic components.

 Before use, apply it to a metal plate such as aluminum or stainless steel, screen mesh, paper, wood, synthetic resin, semiconductor substrate, or any other base material, and dry and cure it, depending on the application. . For curing, for example, energy beams such as various ionizing radiations and light such as an electron beam, a wire, a? -Ray, an a-ray, an X-ray, a neutron beam or an ultraviolet ray are used.

 When the composition of the present invention is used as a solder resist, for example, the composition is cured as follows to obtain a cured product. First, a composition is applied to a substrate by a screen printing method, a spray method, a roll coating method, an electrostatic coating method, a force coating method, or the like so as to have a thickness of 10 to 100 / m. After the coating film is dried at 60 to 100 ° C., a negative film is brought into contact with the coating film and irradiated with ultraviolet rays. Next, the unexposed portion of the coating film is dissolved and removed with a 0.5 to 5% aqueous sodium carbonate solution or a 0.5 to 2% dilute aqueous solution of sodium hydroxide or the like. A cured film is obtained by heating and hardening at 0 ° C for 30 minutes to 1 hour.

The composition of the present invention described above is excellent in developability, curability, and stability, and is extremely useful for forming a solder resist film for a printed wiring board and an insulating resin layer of various electronic components. It is. Example

 Hereinafter, specific embodiments of the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.

 << Synthesis Example 1: Production of prepolymer (A-1) >>

 In a flask equipped with a thermometer, a stirrer, and a reflux condenser, add epoxy resin "Ebikoto 1002" (bisphenol A type epoxy resin: Yuka Shell Epoxy Co., Ltd .: trade name, epoxy equivalent = 635) After adding and dissolving 635 g and diethylene glycol monoethyl acetate 236 g, 0.35 g of hydroquinone monomethyl ether, 72 g of acrylic acid and triphenylphosphine 3. 5 g was added, and the mixture was reacted at 110 ° C. until the acid value became 2 or less. Thereafter, 200 g of succinic anhydride and 152 g of petroleum-based solvent “Solvesso 150” (trade name, manufactured by Exxon Chemical Co., Ltd.) were added, and the mixture was reacted at 100 ° C. for 4 hours. One (A-1) was generated. The amount of nonvolatile components (solid content) in the obtained resin solution was about 70%, and its acid value was l S O mgKO HZg.

<< Synthesis Example 2: Production of prepolymer (A-2) >>

In the above Synthesis Example 1, the epoxy resin "Evicoat 180 S800" (o-cresol novolak type: Yuka Shell Epoxy Co., Ltd.) is used instead of the epoxy resin "Ebicoat 1002". , Epoxy equivalent = 2 18), the amount used to 2 18 g, and the amount of each of diethylene glycol monoethyl ester teracetate, hydroquinone monomethyl ether and triphenylphosphine to be used. The reaction was carried out in the same manner except that the amount was changed to 5 g, 0.26 and 1.8 g. After the reaction, add 76.1 g of tetrahydrofluoric anhydride and 78.5 g of petroleum-based solvent “Solvesso 150” (trade name, manufactured by Exxon Chemical Co., Ltd.) and add 100 g at 100 ° C. After reacting for 4 hours, prepolymer (A-2) was synthesized. The amount of non-volatile components (solid content) in the obtained resin solution was about 70%, and the acid value thereof was 7411111/11. << Synthesis Example 3: Production of prepolymer (A-3) >>

 In the above Synthesis Example 1, the epoxy resin “Epico 1 57 S70” (bisphenol A novolak type: Yuka Shell Epoxy Co., Ltd.): trade name, epoxy equivalent = 209), the amount used was set to 2009, and the amounts used for diethylene glycol monoethyl acetate, hide-mouth quinone monomethyl ether and triphenylphosphine were set to 94 g and 0.2, respectively. The reaction was carried out in the same manner except that the amount was changed to 1.4 g. After the reaction, add 76.1 g of tetrahydrofluoric anhydride and 59 g of petroleum-based solvent "Sol Besso 150" (trade name, manufactured by Exxon Chemical Co., Ltd.) and react at 100 ° C for 4 hours. Then, Prevolima-1 (A_3) was synthesized. The amount of nonvolatile components (solid content) of the obtained resin solution was about 70%, and the acid value was 7 lmgKOH / g.

<< Synthesis Example 4: Production of prepolymer (A-4) >>

 In a flask equipped with a thermometer, a stirrer and a reflux condenser, add epoxy resin “Epicort 180 S80” (o-cresol novolak type epoxy resin: manufactured by Yuka Shell Epoxy Co., Ltd .: trade name, epoxy equivalent = 21) 8) Add 218 g and 124 g of diethylene glycol monoethyl ether acetate, dissolve, add 0.19 g of hydroquinone monomethyl ether, 59 g of acrylinoleic acid, and erythritol triacrylate of Penyu. Was added to 95.8 g of a reaction product of succinic anhydride and 2.8 g of triphenylphosphine, and reacted at 110 ° C. until the acid value became 2 or less. Then, add 76.1 g of tetrahydrofuronic anhydride and 68 g of a petroleum-based solvent “Solvesso 150” (trade name, manufactured by Exxon Chemical Co., Ltd.) and react at 100 ° C for 4 hours. Prebolimer (A-4) was produced. The amount of nonvolatile components (solid content) of the obtained resin solution was about 70%, and its acid value was 57 mgKOH / g.

<< Synthesis Example 5: Production of polyisocyanurate compound (D_ 1) >>

In a four-necked flask equipped with a thermometer, condenser, stirrer and dropping funnel, add tolylene disocyanate (2, 4--2, 6-tolylene diisocyanate = 80/20 weight Ratio) 38.9.9 g and 368.99 g of butyl acetate were added, the internal temperature was adjusted to 25 ° C, 1.46 g of a 5% methanol solution of sodium acetate was added with stirring, and after stirring for 2 hours, The internal temperature was cooled to 5 ° C.

 Then, 0.45 g of a 5% butyl acetate solution of N, Ν,, Ν "-trisdimethylaminopropylhexahydrotriazine was added and reacted for 2 hours. Thereafter, a 5% solution of potassium acetate in methanol was added. When the isocyanate content reached 8.2%, 0.25 g of phosphoric acid was added as a reaction terminator to stop the isocyanurate reaction, and the polyisocyanurate resin solution (D — 1) was obtained.

<< Synthesis example 6: Production of blocked isocyanate (D-2) >>

 To a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, was added 678.70 g of the polyisocyanurate resin solution (D-1) obtained in Synthesis Example 5, and the internal temperature was raised to 80 °. After the temperature was raised to C, 160.65 g of £ -force prolactam was added and reacted for 8 hours. Then, 160.65 g of butyl acetate was added to synthesize blocked isocyanate (D-2).

<< Synthesis Example 7: Production of blocked isocyanate (D-3) >>

 To a four-necked flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel, was added 57.64 g of the polyisocyanurate resin solution (D-1) obtained in Synthesis Example 5 above, and the internal temperature was reduced to 80%. After raising the temperature to ° C, 17-1.8 g of 2-ethylhexanol was added, and after reacting for 8 hours, 171.18 g of butyl acetate was added, and the blocked isocyanate (D-3) was added. Obtained.

<< Examples 1 to 7 and Comparative Examples 1 to 4 >>

Prepolymers (A-1), (A-2), (A-3) and (A_4) obtained in Synthesis Examples 1 to 4, polyisocyanurate compound (D_l) obtained in Synthesis Example 4, synthesis Using the blocked isocyanates (D-2) and (D-3) obtained in Examples 6 and 7, each was blended to obtain the composition (parts by weight) shown in Table 1 and roll milled. To prepare each resist ink.

 Each of these inks was applied to a copper-clad laminate, and dried in hot air at 80 ° C. for 30 minutes to form a 30-μm-thick coating film. The formed coating film was evaluated for developability, curability, adhesion, solvent resistance, acid resistance, and alkali resistance according to the following procedure. Table 1 shows the results. From the results in Table 2, it can be seen that the composition (resist ink) of the present invention is particularly excellent in stability as compared with the ink of the comparative example.

"Evaluation method"

 (1) Developability

After the ink was applied to the copper-clad laminate, it was dried in hot air at 80 ° C. for 30 minutes to form a coating film having a thickness of 30 m, and the formed coating film was subjected to 1.0% aqueous solution of 1% sodium carbonate. Development was carried out for 60 seconds at a spray pressure of kg / cm ² , and the dissolution state of the coating film was visually determined according to the following criteria.

 〇: Almost no coating film left

 Δ: Some coating film remains

 X: Coating remains

 (2) Curability

The formed Kodak step the coating film on a copper-clad laminate evening breccias DOO N o 2 (2 1 stage) by using a high pressure mercury lamp through an ultraviolet to ² 0 0 m J / cm 2 was irradiated, further 1% carbonated The development was carried out for 60 seconds with a spray pressure of 1.0 kg / cm ² using a sodium aqueous solution, and observation was carried out by observing a portion where the coating film was not removed. The larger the number of steps, the better the photocurability.

 (3) Stability

 The ink was stored in a thermo-hygrostat at 50 ° C for one week, and the viscosity of the ink after storage was checked for any increase in the viscosity of the ink before storage. The viscosity was measured with a B-type viscometer (B8H rotational viscometer, manufactured by Tokimec Co., Ltd.).

 〇: Thickening less than 130%

Δ: Thickening is 130% or more and 200% or less x: Gelation or thickening is 200% or more

 (4) Solvent resistance

The coating on the formed copper-clad laminate, test those high pressure mercury lamp with ultraviolet ² 0 0 m J / cm 2 was irradiated, and further 1 5 0 3 0 minutes boss Tokiyua in an oven at ° C After being immersed in dichloromethane at 25 ° C for 1 hour, the state of the coating film and the adhesion were comprehensively evaluated.

 〇: No change observed

 △: only slight change

 X: markedly changed

 (5) Acid resistance

 Using a test piece prepared in the same manner as in the evaluation of solvent resistance, immersing it in a 10% by volume aqueous solution of hydrochloric acid at 25 ° C for 1 hour, and then examining the state of the coating film and the adhesion Judgment and evaluation were carried out.

 〇: No change observed

 △: only slight change

 X: markedly changed

 (6) Alkali resistance

 Using a test piece prepared in the same manner as in the evaluation of solvent resistance, immersion was carried out at 25 ° C for 1 hour in a 10% by weight aqueous solution of potassium hydroxide. Was comprehensively evaluated.

 〇: No change observed

 △: only slight change

X: markedly changed Table 1

ho

 Prebolimer (Λ—]) (で — 4)

 Photopolymerization initiator (H) “ILGACURE 907” manufactured by Riti Chemicals

Reactive diluent (C)

Thoritol Hexarate

 Thermosetting resin:

 D—2 and D—Synthesis (Blocked isocyanates (D—2) and (D—3) prepared in columns 6 and 7) Epoxy Yuka Shell Epoxy 180 S80

 Oxazoline 2, 2'-bis (2-oxazoline)

Polysocyanate D Polyisocyanurate compound prepared in Synthesis Example 5 (D-1)

Table 1 2

Let's ^: Mebiki 1 King iiD Cho Ϊ 仓: ^ Li 1 King liQT

CJ Youya 1 Tari U 丄 (J

关 也 1 リ d 丄 J U J Re LJ

夹 卡 她 1 tally 4 丄 re

 )

 ^: Kaya 1 Tali ο 丄 U

 C) 10 o Example 7 〇 10 0 〇 〇 〇 O Comparative example 1 〇 8 X Δ Δ Δ Comparative example 2 〇 10 X X Δ Δ Δ Comparative example 3 Δ 1 0 X Δ △ △ Comparative example 4 Δ 1 0 X Δ Δ △

Claims

The scope of the claims

1. Prepolymer having two or more polymerizable unsaturated groups and one or more carboxyl groups in one molecule (A), photopolymerization initiator (B), reactive diluent (C) and blocking A photosensitive composition containing each of the components (D).

2. The reaction product of the prepolymer (A) with the epoxy compound (a) and the compound (b) having one or more polymerizable unsaturated groups and one carboxyl group in one molecule is saturated or saturated. 2. The photosensitive composition according to claim 1, which is a product obtained by reacting an unsaturated polybasic acid anhydride (c), and has an acid value of 45 to 200 mgKOH / g. Composition.

3. The prepolymer (A) is a compound of the formula (b) having at least one polymerizable unsaturated group and one carboxyl group in one molecule per one equivalent of the epoxy group of the epoxy compound (a). A product obtained by reacting 8 to 1.2 equivalents of a saturated or unsaturated polybasic acid anhydride (c) with 0.3 to 1.0 equivalents thereof. Item 3. The photosensitive composition according to Item 2.

4. Blocked isocyanate (D) is a polyisocyanate compound having two or more isocyanate groups as an average number of functional groups in one molecule, and phenols, alcohols, acid amides, oximes, and esters. A reaction product with a blocking agent selected from the group consisting of, diketones, mercaptans, ureas, imidazoles, acid imides, amines and olebamates. Item 4. The photosensitive composition according to any one of Items 1 to 3.

5. The photosensitive composition according to claim 4, wherein the blocking agent is a blocking agent selected from the group consisting of acid amides, diketones, esters, alcohols and olebamates. object.

6. The photosensitive composition according to claim 4 or 5, wherein the polyisocyanate compound is a polyisocyanurate compound obtained by an isocyanuration reaction of a diisocyanate compound.

7. The polyisocyanate compound according to claim 4 or 5, wherein the polyisocyanate compound is an isocyanate group-terminated polyurethane polyisocyanate compound obtained by reacting a diisocyanate compound with a polyfunctional active hydrogen compound. The light-sensitive composition according to the above.

8. The method according to claim 4 or 5, wherein the polyisocyanate compound is a polyurea polyisocyanate compound, a polymeric isocyanate or diphenylmethane diisocyanate. The photosensitive composition as described in the above.

9. The photosensitive composition according to any one of claims 1 to 6, wherein the blocked isocyanate (D) is a compound having an isocyanurate ring.

100. The content of each component (A) to (D) is, by weight ratio, prepolymer (A): 100, photopolymerization initiator (B): 1 to 30, reactive dilution The photosensitive composition according to any one of claims 1 to 9, wherein the composition is (C): 1-100, blocked isocyanate (D): 2 to 100. .

11. A cured product obtained by curing the photosensitive composition according to any one of claims 1 to 10.

12. A printed wiring board comprising a cured film obtained by curing the photosensitive composition according to any one of claims 1 to 10.