KR20130099219A - Photocurable resin composition, dry film and cured object obtained therefrom, and printed wiring board obtained using these - Google Patents

Abstract

Even if the filler is mixed in a large amount, the photocurable resin composition that can be developed by an alkaline solution is preferably a carboxyl group-containing oligomer in order to maintain good handling as a solder resist and to suppress generation and peeling of cracks in the solder resist generated during a cold heat cycle. And a polymer binder having a higher molecular weight than the carboxyl group-containing oligomer, a photopolymerization initiator, a photopolymerizable monomer and a filler, and the content of the filler is 30 to 60 mass% of the total amount of nonvolatile components of the composition. Suitably, said polymeric binder is a thermoplastic resin, preferably a thermoplastic resin solution having a solid content of 10 to 50% by weight in a state dissolved in a solvent. The said photocurable resin composition or its dry film can be advantageously applied to formation of the cured film, such as a soldering resist of a printed wiring board.

Description

PHOTOCURABLE RESIN COMPOSITION, DRY FILM AND CURED OBJECT OBTAINED THEREFROM, AND PRINTED WIRING BOARD OBTAINED USING THESE}

The present invention relates to a photocurable resin composition used as a solder resist of a printed wiring board, a dry film and a cured product thereof, and a printed wiring board using these.

In recent years, in response to the densification of the printed wiring board accompanying the thin and light reduction of electronic devices, workability and high performance are also required for the solder resist. In recent years, miniaturization and multi-pinning of semiconductor packages due to miniaturization, weight reduction, and high performance of electronic devices have been put into practical use, and mass production has been advanced. In response to such high density, BGA (ball grid) instead of IC package called QFP (Quad Flatpack Package), SOP (Small Out-line Package), etc. IC packages called ball grid arrays, CSPs (chip scale packages), etc. have emerged. As a soldering resist used for such a package substrate and a printed wiring board for vehicle mounting, the various photocurable resin composition is proposed conventionally (for example, refer patent document 1).

High insulation reliability is required for insulating materials such as solder resists, and therefore, resistance to PCT (Pressure Cooker Test), also referred to as moist heat resistance, is particularly required. On the other hand, from the viewpoint of productivity, solder resists are also required to have reactivity to ultraviolet rays or the like used in patterning, that is, high exposure sensitivity.

However, there is still room for improvement in the conventional liquid developing solder resists with regard to the above required characteristics. In addition, the conventional liquid developing solder resist has a problem that moisture is absorbed in the package during reflow due to moisture absorption of the solder resist during package mounting, thereby causing cracks in the solder resist film and the surroundings of the package. have. In the case where the solder resist is applied, heat is applied to the substrate and the solder resist when the IC chip is sealed or the IC is driven, and cracks and peeling are likely to occur due to the difference in the expansion coefficient between the substrate and the solder resist.

With respect to this technical problem, an attempt was made to mix a large amount of filler in the photosensitive resin composition for soldering resists (refer patent document 2). Although the present inventors also confirmed that when a large amount of a filler is mix | blended with the photosensitive resin composition, the heat resistance and water absorption of the coating-film external appearance obtained fall, when it mixes in very large quantities, the filler itself is often grounded with respect to a to-be-adhered body, Besides the problem that the adhesion of the coating film is lowered, the fluidity of the composition is significantly worsened. In particular, when blended with the photopolymerizable monomer, it becomes a dilatancy fluid and becomes a state in which stirring or even coating cannot be performed. In addition, with a negative photosensitive resin composition such as a soldering resist, sufficient resolution of a small diameter opening cannot be obtained under the influence of a filler, and the opening is considerably closed due to halation of light. there was.

Japanese Patent Publication No. 61-243869 Japanese Patent Laid-Open No. 2000-181058

Therefore, the object of the present invention is that soldering occurs at the time of cold-heat cycle by reducing the linear expansion coefficient of the solder resist by applying the substrate easily to the substrate without lowering the adhesiveness and fluidity of the composition even if the filler is blended in a large amount. It is providing the photocurable resin composition which can suppress generation | occurrence | production and peeling of a resist.

In addition, the characteristics such as resolution, electroless gold plating resistance, and PCT resistance due to adhesion, which are required for conventional solder resists of printed wiring boards or interlayer insulating materials of multilayer wiring boards, etc., are improved, and particularly, excellent characteristics required for IC packages are excellent. A cured film is obtained, and it can provide the photocurable resin composition which can cope with the densification of a printed wiring board, and surface mounting, and an opening of a small diameter can be formed by alkali-developing.

Moreover, in providing the dry film and hardened | cured material excellent in the various characteristics as mentioned above obtained by using such a photocurable resin composition, and the printed wiring board in which the hardened film, such as a soldering resist, is formed by the said dry film and hardened | cured material, have.

In order to achieve the above object, according to the present invention, a composition comprising a carboxyl group-containing oligomer, a polymer binder having a higher molecular weight than the carboxyl group-containing oligomer, a photopolymerization initiator, a photopolymerizable monomer and a filler, the content of the filler is It is 30-60 mass% of the non volatile component whole quantity, The photocurable resin composition which can be developed by alkaline solution is provided.

According to a preferred embodiment, the polymer binder is a thermoplastic resin, preferably a thermoplastic resin solution having a solid content of 10 to 50% by weight in a solvent. According to a further preferred embodiment, the filler comprises Ba or Mg and / or Al.

Moreover, according to this invention, the photocurable dry film obtained by apply | coating and drying the said photocurable resin composition on a carrier film, and the hardened | cured material obtained by photocuring the said photocurable resin composition or the dry film by irradiation of an active energy ray. Especially, the hardened | cured material obtained by photocuring on copper and the hardened | cured material obtained by photocuring in a pattern form are also provided. In one aspect, a dry film contains the dry layer of several photocurable resin composition, and at least 1 layer is formed with the said photocurable resin composition of this invention.

According to the present invention, there is also provided a printed wiring board comprising a cured film obtained by photocuring the photocurable resin composition or the dry film in a pattern form by irradiation of active energy rays, and preferably further thermal curing. do.

In the photocurable resin composition of the present invention, the content of the filler is 30 to 60% by mass of the total amount of nonvolatile components of the composition, so that the coefficient of linear expansion of the cured product of interest is 15 to 35 × 10 ⁻⁶ / K (hereinafter ppm). Abbreviation), and the occurrence of cracks in the solder resist can be reduced by matching or approaching the ground and the coefficient of linear expansion. By adding a higher molecular weight binder than a carboxyl group-containing oligomer, problems such as a decrease in adhesion of the composition, a decrease in fluidity, a decrease in film formability, and a handling crack when using a film are solved, which are a problem when a large amount of filler is blended. In the cured product thereof, when used for a printed wiring board or a semiconductor package, for example, PCT resistance due to excellent resolution and adhesion can be obtained, and high reliability can be obtained.

The photocurable resin composition (henceforth a photocurable resin composition) which can be developed by the alkali solution of this invention contains a carboxyl group-containing oligomer, a polymeric binder with a molecular weight larger than the said carboxyl group-containing oligomer, a photoinitiator, a photopolymerizable monomer, and a filler. It is a composition containing, and content of the said filler is 30-60 mass% of the total amount of non volatile components of a composition, It is characterized by the above-mentioned.

Hereinafter, each structural component of the photocurable resin composition of this invention is demonstrated in detail.

The photocurable resin composition of this invention can provide alkali developability by using a carboxyl group-containing oligomer. In addition, it is to be understood that the term "oligomer" is used in this specification in order to make it easy to distinguish a molecular binder and a molecular weight. As a carboxyl group-containing oligomer, the conventionally well-known various carboxyl group-containing resin or prepolymer which has a carboxyl group in a molecule | numerator can be used. In particular, carboxyl group-containing photosensitive resin or carboxyl group-containing photosensitive prepolymer having an ethylenically unsaturated double bond in the molecule is more preferable in view of photocurability and developability. The unsaturated double bond is preferably derived from acrylic acid or methacrylic acid, or derivatives thereof. In addition, when using only carboxyl group-containing resin or prepolymer which does not have an ethylenically unsaturated double bond, in order to make a composition photocurable, the compound which has several ethylenically unsaturated groups, ie, a photopolymerizable monomer, may be used together in the molecule | numerator mentioned later. There is a need.

As an example of a carboxyl group-containing oligomer, oligomers enumerated below can be used preferably.

(1) Carboxyl group-containing oligomer obtained by copolymerization of unsaturated carboxylic acids, such as (meth) acrylic acid, and unsaturated group containing compounds, such as styrene, (alpha) -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.

(2) diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylol propionic acid and dimethylol butanoic acid; and polycarbonate polyols and polyether polyols. Carboxyl group-containing urethane resin by polyaddition reaction of diol compounds, such as a polyester polyol, a polyolefin polyol, an acryl polyol, a bisphenol-A alkylene oxide adduct, a compound which has a phenolic hydroxyl group, and alcoholic hydroxyl group. .

(3) bifunctional epoxy resins such as diisocyanate, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, and biphenol type epoxy resin The carboxyl group-containing photosensitive urethane resin by the polyaddition reaction of the (meth) acrylate or its partial acid anhydride modified substance, the carboxyl group-containing dialcohol compound, and a diol compound.

(4) During the synthesis of the resin of the above (2) or (3), a compound having one hydroxyl group and one or more (meth) acryl groups in a molecule such as hydroxyalkyl (meth) acrylate is added to terminate (meth) acrylated. One carboxyl group-containing photosensitive urethane resin.

(5) Compounds having one isocyanate group and one or more (meth) acryl groups in the molecule, such as equimolar reactants of isophorone diisocyanate and pentaerythritol triacrylate, during synthesis of the resin of the above (2) or (3) The carboxyl group-containing photosensitive urethane resin which was added and terminal (meth) acrylated.

(6) (meth) acrylic acid is reacted with a bifunctional or more than one polyfunctional (solid) epoxy resin as described later, and a dibasic group such as phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride, etc. in the hydroxyl group present in the side chain. Carboxyl group containing photosensitive oligomer which added acid anhydride.

(7) A carboxyl group in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin in which the hydroxyl group of the bifunctional (solid) epoxy resin, which will be described later, is further epoxidized with epichlorohydrin, and the dibasic acid anhydride is added to the generated hydroxyl group. Containing photosensitive oligomers.

(8) A carboxyl group-containing polyester oligomer in which dicarboxylic acids such as adipic acid, phthalic acid and hexahydrophthalic acid are reacted with a bifunctional oxetane resin as described later, and a dibasic acid anhydride is added to a primary hydroxyl group generated. .

(9) An unsaturated group-containing mono carboxylic acid is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with alkylene oxides such as ethylene oxide and propylene oxide, and anhydrous to the reaction product obtained. The carboxyl group-containing photosensitive oligomer obtained by making polybasic acid anhydrides, such as maleic acid, tetrahydro phthalic anhydride, trimellitic anhydride, a pyromellitic dianhydride, react.

(10) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, and a polybasic anhydride is reacted with the reaction product obtained. Carboxyl group containing photosensitive oligomer obtained by making it react.

(11) A carboxyl group-containing photosensitive oligomer obtained by further adding a compound having one epoxy group and one or more (meth) acryl groups in one molecule to the resins of (1) to (10).

In addition, in this specification, a (meth) acrylate is a term used generically for acrylate, methacrylate, and mixtures thereof, and the same also about other similar expressions.

Since the carboxyl group-containing oligomer as mentioned above has many carboxyl groups in the side chain of a backbone polymer, image development by a rare alkali aqueous solution is attained.

Moreover, the range of 40-200 mgKOH / g is suitable for the acid value of the said carboxyl group-containing oligomer, More preferably, it is the range of 45-120 mgKOH / g. When the acid value of the carboxyl group-containing oligomer is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed portion by the developing solution proceeds, so that the line becomes thinner than necessary, or in some cases, the exposed portion. It is not preferable because it dissolves and peels off with a developer without distinction between the unexposed portion and the difficulty of drawing a normal resist pattern.

In addition, although the weight average molecular weight of the said carboxyl group-containing oligomer changes with resin frame | skeleton, it is generally preferable to exist in the range of 2,000-150,000, Furthermore, 5,000-100,000. It is necessary to use a carboxyl group-containing oligomer having a smaller weight average molecular weight than the polymer binder to be used, but a particularly preferable weight average molecular weight is 5000 to 35,000. When the weight average molecular weight is less than 2,000, the tack-free performance of a coating film may be inferior, the moisture resistance of the coating film after exposure is bad, the film | membrane decrease at the time of image development, and the resolution may fall significantly. On the other hand, when a weight average molecular weight exceeds 150,000, developability will become remarkably bad. Moreover, when larger than the polymeric binder mentioned later, the weakness of the target coating film cannot be improved.

The compounding quantity of such a carboxyl group-containing oligomer is 10-60 mass% of the whole composition, Preferably the range of 20-50 mass% is suitable. When the compounding quantity of a carboxyl group-containing oligomer is less than the said range, since film strength may fall, it is unpreferable. On the other hand, when more than the said range, since the viscosity of a composition becomes high, applicability | paintability, etc. fall, it is not preferable.

These carboxyl group-containing oligomers can be used without being limited to the above-mentioned, You can also mix and use one type or multiple types. In particular, the resin having an aromatic ring in the carboxyl group-containing oligomer is preferable because of its high refractive index and excellent resolution, and it is more preferable because it has a biphenyl novolak structure because it has not only resolution but also excellent PCT resistance and crack resistance. Do. In addition, carboxyl group-containing oligomers using phenolic compounds such as carboxyl group-containing photosensitive oligomers (9) and (10) as starting materials are also preferable because of the improved PCT resistance. In general, an increase in the filler component tends to cause absorption at the interface between the filler and the resin, whereas the one having a biphenyl novolak structure, and the carboxyl group-containing oligomers such as (9) and (10), is a filler component. Even with this increase, PCT resistance was very good. This is considered to be because the former has improved hydrophobicity by the biphenyl novolak structure, and the latter has a hydroxyl group in the epoxy acrylate structure of the carboxyl group-containing photosensitive oligomers (6) and (7) capable of forming a similar structure. On the other hand, it is considered that the carboxyl group-containing photosensitive oligomers (9) and (10) do not have a hydroxyl group and remarkably improve hydrophobicity.

The polymer binder is not particularly limited as long as it is a thermoplastic resin, regardless of reactivity or non-reactivity. For example, polyphenylene sulfide, polyarylate, polysulfone, polyether sulfone, polyether ether ketone, polyether ketone A solution of thermoplastic resins such as thermoplastic resins such as thermoplastic resins, thermoplastic polyimides and phenoxy resins, cellulose derivatives such as ethyl cellulose, acetyl cellulose, acetylpropyl cellulose, acetyl butyl cellulose, and vinyl derivatives such as various acrylates, styrene and vinyl acetate And polymers obtained by suspension polymerization can be used. Moreover, the binary copolymer obtained by superposing | polymerizing using the monomer which has 2 or more types of vinyl groups, a ternary copolymer, a block copolymer, etc. can also be used. In particular, among these polymers, a cellulose derivative or a block copolymer is preferable. Although the preferable molecular weight of a polymeric binder is 30,000-1,500,000 by weight average molecular weight, it can be used if it is judged that molecular weight is clearly larger than the carboxyl group-containing oligomer to be used. For example, when melt | dissolving in the same solvent, it is a case where a viscosity is high compared with a carboxyl group-containing oligomer. Moreover, since the solubility with respect to a solvent is so low that a molecular weight is large in general, when the quantity of solid content when melt | dissolving in the same solvent is small, it is judged that molecular weight is larger than the said carboxyl group-containing oligomer especially when it is 10-50 weight%. When there is less solid content than 10 weight%, there exists a problem that solvent content increases and a composition cannot be formed. On the other hand, when more than 50 weight%, it may not correspond to a polymer and it is not valid.

The function of these polymeric binders can be mentioned to some extent. One of them is to change the fluidity of the composition. Specifically, when a large amount of filler is blended with the carboxyl group-containing oligomer and the photopolymerizable monomer, in particular, the familiarity between the photopolymerizable monomer and the filler is poor, and the resulting composition becomes a latency fluid. When the composition becomes a latency, it is difficult to stir, print, or coat the composition, and it cannot be used unless it is a substantial dilution. In particular, in the case of printing performed at a relatively high viscosity such as screen printing or roll coating, the required film thickness is 1 There was a problem that could not be secured by conference printing. Adding a polymeric binder to it, the composition could change to thixotropic fluid. In this way, it became a material which can be printed or coated. As for the 2nd effect, when the composition was coated, dried, and made into the dry film state, it became clear to control a handling crack. This is considered to be because the effect of fixing the filler in which the polymer binder is incorporated in a large amount is considered. The third effect of the addition of the polymer binder is that the toughness of the coating film can be increased in physical properties after curing. It is considered that this is because the polymer binder is present in the photocurable resin matrix in the IPN (island) state. For the above three reasons, it is thought that printing and coating are possible even in a composition in which a photopolymerizable monomer and a large amount of filler coexist with the addition of a polymer binder, a low linear expansion coefficient, and a strong coating film.

Moreover, these polymeric binders may exist in functional groups, such as a carboxyl group, a hydroxyl group, and an epoxy group, in a terminal and / or a side chain. The amount of the preferred carboxyl group is 30 mg KOH / g or less.

Preferable compounding quantity of a polymeric binder is 1 mass part or more with respect to 100 mass parts of said carboxyl group-containing oligomers. As such, the fluidity of the composition can be sufficiently achieved even with the addition of a small amount of the polymeric binder. Moreover, in order to fully improve a physical property, a larger amount of polymeric binder can be added, The upper limit is about 30 mass parts with respect to 100 mass parts of carboxyl group containing oligomers. When the amount of the polymer binder is increased, the developability is remarkably deteriorated, and residues may remain on the circuits or circuits of the circuit-formed substrate. In this case, the application of the photocurable resin composition is divided into two times, and at the time of the first application. If the composition which does not contain a polymeric binder or contains less than 5 mass parts is apply | coated, and then the composition of this invention which mix | blended the polymeric binder and a large amount of filler is apply | coated, the problem of the image development defect will be solved. Similarly, when forming a dry film, it is set as the layer structure of two or more layers, and the layer of the side which directly contacts a base material does not have a polymeric binder, or is formed with the composition layer of the ratio of less than 5 mass parts, and the other layer contains many polymeric binders. It can solve by forming a layer with the composition of this invention containing.

As a photoinitiator used for the photocurable resin composition of this invention, it selects from the group which consists of an oxime ester photoinitiator which has an oxime ester group, the (alpha)-amino acetophenone type photoinitiator, and the acylphosphine oxide type photoinitiator. 1 or more types which are mentioned can be used preferably.

As an oxime ester system photoinitiator, it is a commercial item, CGI-325 by the BASF Japan company, Irgacure (trademark) OXE01, Irgacure OXE02, the product made by Adeka (ADEKA), NCI-831, etc. Can be mentioned. Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used preferably, Specifically, the oxime ester compound which has a carbazole structure represented by the following general formula is mentioned.

(Wherein X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkyl group having 1 to 8 carbon atoms) Substituted with an alkylamino group or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group) And Y and Z each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, and a phenyl group (an alkyl group having 1 to 17 carbon atoms, having 1 to 8 carbon atoms). Substituted by an alkoxy group, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, 1 to 8 carbon atoms) Substituted by an alkylamino or dialkylamino group having an alkoxy group, an amino group, an alkyl group having 1 to 8 carbon atoms), an anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, and Ar represents a bond or carbon number 1-10 alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4'-steel Ben-diyl, 4,2'-styrene-diyl, n is an integer of 0 or 1)

In particular, in the above formula, X and Y are each methyl or ethyl, Z is methyl or phenyl, n is 0, and Ar is a bond or phenylene, naphthylene, thiophene or thienylene.

It is preferable that the compounding quantity of such an oxime ester system photoinitiator shall be 0.01-5 mass parts with respect to 100 mass parts of carboxyl group-containing oligomers. If it is less than 0.01 mass part, the photocurability in copper phase will run out, a coating film will peel, and coating film characteristics, such as chemical-resistance, will fall. On the other hand, when it exceeds 5 mass parts, there exists a tendency for the light absorption in a coating film surface to become severe, and deep-part sclerosis | hardenability falls. More preferably, it is 0.5-3 mass parts.

Specific examples of the α-aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl]- 1-butanone, N, N-dimethylaminoacetophenone, etc. are mentioned. As a commercial item, Irgacure 907, Irgacure 369, Irgacure 379 by BASF Japan, etc. are mentioned.

As an acyl phosphine oxide type photoinitiator, 2,4,6- trimethyl benzoyl diphenyl phosphine oxide, bis (2,4,6- trimethyl benzoyl) -phenylphosphine oxide, bis (2, 6) specifically, -Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, etc. are mentioned. As a commercial item, Lucirin TPO by BASF Corporation, Irgacure 819 by BASF Japan Corporation, etc. are mentioned.

It is preferable that the compounding quantity of these (alpha)-amino acetophenone type photoinitiators and an acylphosphine oxide type photoinitiator is 0.01-15 mass parts with respect to 100 mass parts of carboxyl group-containing oligomers. If it is less than 0.01 mass part, similarly, the photocurability in copper phase will run out, a coating film will peel, and coating film characteristics, such as chemical-resistance, will fall. On the other hand, when it exceeds 15 mass parts, the effect of reducing outgas cannot be acquired, light absorption in the coating film surface will become deep, and there exists a tendency for deep-part sclerosis | hardenability to fall. More preferably, it is 0.5-10 mass parts.

As the photoinitiator to be used, since the addition amount of the oxime ester initiator is small and the outgas is suppressed, it is effective in PCT resistance and crack resistance, which is preferable. Moreover, when an acyl phosphine oxide type photoinitiator is used together in addition to an oxime ester initiator, since the shape with favorable resolution is obtained, it is especially preferable.

In addition, as a photoinitiator, a photoinitiation adjuvant, and a sensitizer which can be used suitably for the photocurable resin composition of this invention, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound And tertiary amine compounds and xanthone compounds.

Specifically as a benzoin compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. are mentioned, for example.

Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like. Can be mentioned.

As an anthraquinone compound, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t- butyl anthraquinone, 1-chloro anthraquinone etc. are mentioned specifically ,.

Specifically as a thioxanthone compound, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, 2, 4- diisopropyl thioxanthone, for example Etc. can be mentioned.

As a ketal compound, acetophenone dimethyl ketal, benzyl dimethyl ketal, etc. are mentioned specifically ,.

Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenylsulfide, 4-benzoyl-4'-methyldiphenylsulfide, 4-benzoyl- 4-benzoyl-4'-propyldiphenyl sulfide, and the like.

Specifically as a tertiary amine compound, For example, an ethanolamine compound and the compound which has a dialkylaminobenzene structure, For example, As a commercial item, 4,4'- dimethylamino benzophenone (Nisso made by Nippon Soda Co., Ltd.) Dialkylaminobenzophenones such as cure MABP) and 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran- Dialkylamino group-containing coumarin compounds, such as 2-one (7- (diethylamino) -4-methylcoumarin), 4-dimethylaminobenzoate ethyl (Kayacure (trademark) EPA by Nippon Kayaku Co., Ltd.), 2-dimethylamino Ethyl benzoate (Quantacure DMB manufactured by International Bio-Synthetics Co., Ltd.), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics Co., Ltd.), p-dimethylaminobenzoic acid isocyanate Mil ethyl ester (Kayacure DMBI by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoic acid Sil (Esolol 507 by Van Dyk), 4,4'- diethylamino benzophenone (EAB by Hodogaya Chemical Co., Ltd.), etc. are mentioned.

Among these, thioxanthone compounds and tertiary amine compounds are preferable. In particular, it is preferable to contain a thioxanthone compound from the point of deep-hardenability. Especially, it is preferable to contain thioxanthone compounds, such as 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, and 2, 4- diisopropyl thioxanthone. Do.

As a compounding quantity of such a thioxanthone compound, it is preferable that it is 20 mass parts or less with respect to 100 mass parts of carboxyl group-containing oligomers. When the compounding quantity of a thioxanthone compound exceeds 20 mass parts, thick film sclerosis | hardenability will fall and it will lead to a cost increase of a product. More preferably, it is 10 mass parts or less.

Moreover, as a tertiary amine compound, the compound which has a dialkylamino benzene structure is preferable, The dialkylamino benzophenone compound, The dialkylamino group containing coumarin compound and ketocoumarin in which the maximum absorption wavelength is 350-450 nm is especially preferable. Particularly preferred.

As a dialkylamino benzophenone compound, 4,4'- diethylamino benzophenone is preferable because it is low in toxicity. Since the dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm in the ultraviolet region, it is less colored, and provides a colored solder resist film reflecting the color of the colored pigment itself using a color pigment as well as a colorless transparent photosensitive composition. It becomes possible. Particularly, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable in that it exhibits an excellent increase / decrease effect on laser light having a wavelength of 400 to 410 nm.

As a compounding quantity of such a tertiary amine compound, it is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of carboxyl group-containing oligomers. When the compounding amount of the tertiary amine compound is less than 0.1 part by mass, there is a tendency that sufficient increase or decrease effect can not be obtained. When it exceeds 20 mass parts, the light absorption in the surface of the dry solder resist coating film by a tertiary amine compound will become deep, and there exists a tendency for deep-part sclerosis | hardenability to fall. More preferably, it is 0.1-10 mass parts.

These photoinitiators, photoinitiation aids, and sensitizers can be used alone or as a mixture of two or more thereof.

It is preferable that the total amount of such a photoinitiator, a photoinitiator, and a sensitizer is 35 mass parts or less with respect to 100 mass parts of said carboxyl group-containing oligomers. When it exceeds 35 mass parts, there exists a tendency for deep-part sclerosis | hardenability to fall by these light absorption.

Moreover, since these photoinitiators, a photoinitiation adjuvant, and a sensitizer absorb a specific wavelength, in some cases, a sensitivity becomes low and may act as a ultraviolet absorber. However, these are not used only for the purpose of improving the sensitivity of a composition. If necessary, light of a specific wavelength can be absorbed to increase the surface light reactivity, and the line shape and opening of the resist can be changed into vertical, tapered, and inverse tapered shapes, and the processing accuracy of the line width and aperture diameter can be improved. have.

Although the filler is mix | blended with the photocurable resin composition of this invention, when the compounding quantity of a filler was examined in detail, by adding 30-60 mass% of fillers of the total amount of non volatile components of a composition, PCT tolerance and electrical characteristics ( HAST resistance). Moreover, when the refractive index of a filler was in the range of 1.50-1.65, it turned out not only that it is excellent in PCT resistance or HAST resistance (resistance to an advanced accelerated life test), but also favorable resolution is obtained. The reason why high resolution is obtained is that the refractive index of the resin having an aromatic ring used to improve the PCT resistance and the HAST resistance is close to that of the filler.

As a filler which can be used for this invention, well-known conventional inorganic fillers, such as barium sulfate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, boehmite, mica powder, hydrotalcite, are used, for example. Can be. According to a preferred embodiment, the filler comprises Ba or Mg and / or Al. Particularly, the filler containing Ba is barium sulfate (refractive index: 1.65), the filler containing Mg is talc (refractive index: 1.54-59), magnesium carbonate (refractive index: 1.57-1.60), and the filler containing Al is kaolinite Including clay (refractive index: 1.55-1.57), aluminum oxide (refractive index: 1.65), aluminum hydroxide (refractive index: 1.65), boehmite (refractive index: 1.62-1.65), mica powder (refractive index: 1.59), Mg and Al As a filler, hydrotalcite (refractive index: 1.50) is preferable.

As for the total amount of a filler, the range of 30-60 mass% of the non volatile component whole quantity of a photocurable resin composition is suitable. When content of a filler is less than 30 mass%, since the fall of a linear expansion coefficient does not appear in the hardened | cured material of a photocurable resin composition, and crack resistance worsens, it is unpreferable. On the other hand, when it exceeds 60 mass%, since the viscosity of a composition becomes high, application | coating and moldability fall, and water absorption also increases, since PCT tolerance and HAST resistance deteriorate, it is unpreferable. In addition, these fillers can be used individually or in combination of 2 or more types.

It is preferable to add a mercapto compound to the photocurable resin composition of this invention. By adding a mercapto compound, it was recognized that PCT resistance and HAST resistance were improved. It is thought that this crosslinking density improves or adhesiveness improves by adding a mercapto compound.

As for the compounding quantity of a mercapto compound, 0.01 mass part or more and 10.0 mass parts or less are suitable with respect to 100 mass parts of said carboxyl group-containing oligomers, More preferably, they are 0.05 mass part or more and 5 mass parts or less. If it is less than 0.01 mass part, the improvement of adhesiveness as an effect of a mercapto compound addition is not confirmed, On the other hand, when it exceeds 10.0 mass parts, there exists a possibility that it may cause the image development defect of a photocurable resin composition, the fall of a dry management width, etc. Not desirable These mercapto compounds can use together single or 2 types or more.

The thermosetting component can be added to the photocurable resin composition of this invention. It was confirmed that heat resistance improves by adding a thermosetting component. As a thermosetting component used for this invention, amino resins, such as a melamine resin, a benzoguanamine resin, a melamine derivative, a benzoguanamine derivative, a block isocyanate compound, a cyclocarbonate compound, a polyfunctional epoxy compound, a polyfunctional oxetane compound, Known thermosetting resins such as episulfide resin, bismaleimide and carbodiimide resin can be used. Especially preferable are the thermosetting components which have a some cyclic ether group and / or cyclic thioether group (henceforth cyclic (thio) ether group) in a molecule | numerator.

The thermosetting component which has a some cyclic (thio) ether group in such a molecule | numerator is a compound which has two or more types of groups of 3, 4, or 5-membered cyclic (thio) ether group in a molecule | numerator, for example, a molecule | numerator Compound having a plurality of epoxy groups in the compound, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, namely episulfide resin Can be.

As said polyfunctional epoxy compound, Epoxidized vegetable oils, such as Adeka Corporation O-130P, Adekazer O-180A, Adekazer D-32, and Adekaser D-55; JER (registered trademark) 828, jER 834, jER 1001, jER 1004 manufactured by Mitsubishi Chemical Corporation, EHPE 3150 manufactured by Daicel Chemical Industries, Ltd., Epiclone (registered trademark) 840 manufactured by DIC Corporation, Epiclone 850, Epi Clone 1050, Epiclone 2055, Eponto (registered trademark) YD-011, YD-013, YD-127, YD-128, DER 317, DER 331, DER 661 by Shinnitetsu Chemical Co., Ltd. , DER 664, Araldite 6071 of BASF Japan, Araldite 6084, Araldite GY250, Araldite GY260, Sumitomo Chemical Co., Ltd. Sumiepoxy ESA-011, ESA-014, ELA-115, ELA- Bisphenol A type epoxy resins, such as AER 330, AER 331, AER 661, and AER 664 by 128, Asahi Kasei Kogyo Co., Ltd .; Hydroquinone type epoxy resins, such as YDC-1312 (brand name) by Shin-Nitetsu Chemical Co., Ltd., bisphenol-type epoxy resins, such as YSLV-80XY (brand name) by Shin-Nitetsu Chemical Co., Ltd., and YSLV-120TE by Shin-Nitetsu Chemical Co., Ltd. Thioether type epoxy resins, such as (brand name); JERYL 903 manufactured by Mitsubishi Chemical Corporation, Epiclone 152 manufactured by DIC Corporation, Epiclonic 165, Efototo YDB-400, YDB-500 manufactured by Shinnitetsu Chemical Co., Ltd., DER 542 manufactured by Dow Chemical, BASF Japan Brominated epoxy resins such as Araldite 8011 manufactured by Sumitomo Chemical Industries, Ltd., Sumerepoxy ESB-400, ESB-700, manufactured by Asahi Kasei Kogyo Co., Ltd., and AER 711 and AER 714; JER 152, jER 154 manufactured by Mitsubishi Chemical Corporation, DEN 431, DEN 438 manufactured by Dow Chemical Company, Epiclone N-730, Epiclone N-770, Epiclone N-865, Shinnitetsu Chemical Co., Ltd. Efototo YDCN-701, YDCN-704, Araldite ECN1235, Araldite ECN1273, Araldite ECN1299, Araldite XPY307, Nippon Kayaku Co., Ltd. EPPN (registered trademark) -201 , EOCN (registered trademark) -1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Kagaku Kogyo Co., Ltd. Sumiepoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo AER ECN-235, ECN Novolak-type epoxy resins, such as -299 (all trade names); Non-phenol novolak type epoxy resins such as NC-3000 and NC-3100 manufactured by Nippon Kayaku Co., Ltd.; Epiclon 830 manufactured by DIC Corporation, jER807 manufactured by Mitsubishi Chemical Corporation, Efototo YDF-170, YDF-175, YDF-2004 manufactured by Shinnitetsu Chemical Corporation, Araldite XPY306 manufactured by BASF Japan, etc. (all Bisphenol F type epoxy resin; Hydrogenated bisphenol A epoxy resins, such as EPOTO ST-2004, ST-2007, ST-3000 (brand name) by Shin-Nitetsu Chemical Co., Ltd .; JER 604 manufactured by Mitsubishi Chemical Corporation, Efototo YH-434 manufactured by Shinnitetsu Chemical Corporation, Araldite MY720 manufactured by BASF Japan Corporation, Sumiepoxy ELM-120 manufactured by Sumitomo Chemical Industries, Ltd. (all brand names) Glycidyl amine epoxy resins; Hydantoin-type epoxy resins such as Araldite CY-350 (trade name) manufactured by BASF Japan; Alicyclic epoxy resins such as Celoxide (registered trademark) 2021 manufactured by Daicel Chemical Industries, Ltd., Araldite CY175, manufactured by BASF Japan, and CY179 (both trade names); Trihydroxyphenylmethane type epoxy resins such as YL-933 manufactured by Mitsubishi Chemical Corporation, T.E.N., EPPN-501, EPPN-502 manufactured by Dow Chemical, etc. (all of which are trade names); Biscylenol-type or biphenol-type epoxy resins such as YL-6056, YX-4000 and YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation; Bisphenol S type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Co., EPX-30 manufactured by Adeka Co., and EXA-1514 (trade name) manufactured by DIC Corporation; Bisphenol A novolac-type epoxy resins such as jER 157S (trade name) manufactured by Mitsubishi Chemical Corporation; Tetraphenylolethane type epoxy resins such as jERYL-931 manufactured by Mitsubishi Chemical Corporation and Araldite 163 manufactured by BASF Japan Co., Ltd. (both trade names); Heterocyclic epoxy resins such as Araldite PT810 (trade name) manufactured by BASF Japan and TEPIC (registered trademark) manufactured by Nissan Chemical Industries, Ltd .; Diglycidyl phthalate resins such as Bremmer (registered trademark) DGT manufactured by Nippon Yushi Corporation; Tetraglycidyl xylenoylethane resins such as ZX-1063 manufactured by Shinnitetsu Chemical Co., Ltd .; Naphthalene group-containing epoxy resins such as Shinnitetsu Chemical Co., Ltd. ESN-190, ESN-360, DIC Corporation HP-4032, EXA-4750, EXA-4700; Epoxy resins having a dicyclopentadiene skeleton, such as HP-7200 and HP-7200H manufactured by DIC Corporation; Glycidyl methacrylate copolymer-based epoxy resins such as CP-50S and CP-50M manufactured by Nippon Yushi Co., Ltd.; Furthermore, copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives (e.g., PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (e.g., YR-102, YR-450, manufactured by Shinnitetsu Chemical Co., Ltd.), and the like. Although it is possible, it is not limited to these. These epoxy resins may be used alone or in combination of two or more. Especially among these, a novolak-type epoxy resin, a bixylenol-type epoxy resin, a biphenol-type epoxy resin, a biphenol novolak-type epoxy resin, or a mixture thereof is preferable.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1, 4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-jade Cetanyl) methylacrylate, (3-ethyl-3-oxetanyl) methylacrylate, (3-methyl-3-oxetanyl) methylmethacrylate, (3-ethyl-3-oxetanyl) methyl In addition to polyfunctional oxetanes such as methacrylates and oligomers or copolymers thereof, oxetane alcohols and novolac resins, poly (p-hydroxystyrene), cardo-type bisphenols, calix arenes and calyx resorcines And ethers with a resin having a hydroxyl group such as arene or silsesquioxane. In addition, the copolymer etc. of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate are mentioned.

As a compound which has a some cyclic thioether group in a molecule | numerator, Bisphenol-A episulfide resin YL7000 by Mitsubishi Chemical Corporation, etc. are mentioned, for example. Moreover, the episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom can also be used using the same synthesis method.

As for the compounding quantity of the thermosetting component which has several cyclic (thio) ether group in such a molecule, 0.6-2.5 equivalent is preferable with respect to 1 equivalent of carboxyl group of a carboxyl group-containing oligomer. When the compounding amount is less than 0.6, a carboxyl group remains in the solder resist film, whereby heat resistance, alkali resistance, electrical insulation, and the like decrease. On the other hand, when exceeding 2.5 equivalent, the low molecular weight cyclic (thio) ether group remains in a dry coating film, and the intensity | strength of a coating film, etc. fall. More preferably, it is 0.8-2.0 equivalent.

When using the thermosetting component which has a some cyclic (thio) ether group in a molecule | numerator, it is preferable to contain a thermosetting catalyst. As such a thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4- Imidazole derivatives such as phenylimidazole, 1-cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4- Compounds, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine. Moreover, as what is marketed, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are brand names of an imidazole compound) by Shikoku Kasei Kogyo Co., Ltd., U-CAT (all are registered) Trademark) 3503N, U-CAT3502T (all are brand names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compounds and salts thereof) and the like. In particular, it is not limited to these, What is necessary is just to accelerate the reaction of the thermosetting catalyst of an epoxy resin or an oxetane compound, or an epoxy group and / or an oxetanyl group, and a carboxyl group, You may use individually or in mixture of 2 or more types. . Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid S-triazine derivatives, such as an adduct, can also be used, Preferably, the compound which also functions as these adhesive imparting agents is used together with a thermosetting catalyst.

The compounding quantity of these thermosetting catalysts is sufficient in a normal quantity ratio, For example, Preferably it is 0.1-20 mass parts with respect to 100 mass parts of thermosetting components which have a some cyclic (thio) ether group in a carboxyl group-containing oligomer or molecule | numerator, More preferably, it is 0.5-15.0 mass parts.

Moreover, a coloring agent can be mix | blended with the photocurable resin composition of this invention. As a coloring agent, well-known coloring agents, such as red, blue, green, a yellow, can be used, Any of a pigment, dye, and a pigment may be used. However, it is preferable that it does not contain a halogen from a viewpoint of reducing environmental load and an influence on a human body.

Red colorant:

Examples of the red colorant include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone and quinacridone. And the following color index (CI; issued by The Society of Dyers and Colourists) numbers.

Monoazo system: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147 , 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.

Disazo system: Pigment Red 37, 38, 41.

48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57: 1, 58: 4, 63: 1, 63: 2, 64: 1, 68.

Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.

Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224, Pigment Red 174, Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, .

Diketopyrrolopyrrole-based pigments: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.

Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242.

Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.

Quinacridone pigments: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant:

Examples of the blue colorant include phthalocyanine-based and anthraquinone-based compounds, and pigments include compounds classified into pigments, specifically the following: pigment blue 15, pigment blue 15: 1, pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60.

In dye system, solvent blue 35, solvent blue 63, solvent blue 68, solvent blue 70, solvent blue 83, solvent blue 87, solvent blue 94, solvent blue 97, solvent blue 122, solvent blue 136, solvent blue 67, solvent blue 70 may be used. In addition to the above, metal substituted or unsubstituted phthalocyanine compounds may also be used.

Green colorant:

Examples of the green colorant include phthalocyanine series, anthraquinone series, and perylene series, and specifically, pigment green 7, pigment green 36, solvent green 3, solvent green 5, solvent green 20, solvent green 28, and the like can be used. Can be. In addition to the above, metal substituted or unsubstituted phthalocyanine compounds may also be used.

Yellow colorant:

Examples of the yellow colorant include mono azo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone and the like. Specific examples include the following.

Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.

Isoindolinone pigments: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.

Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

Benzimidazolone pigments: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.

Mono Azo System: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111 , 116, 167, 168, 169, 182, 183.

Disazo system: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

In addition, you may add coloring agents, such as purple, an orange color, a tea color, and black, for the purpose of adjusting a color tone.

Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment There are 23 Brown, CI Pigment Brown 25, CI Pigment Black 1, and CI Pigment Black 7.

Although the above coloring agent can be mix | blended suitably, It is preferable to set it as 10 mass parts or less with respect to 100 mass parts of carboxyl group-containing oligomers or a thermosetting component. More preferably 0.1 to 5 parts by mass.

The compound which has some ethylenically unsaturated group can be mix | blended with the photocurable resin composition of this invention in a molecule | numerator. The compound which has a some ethylenically unsaturated group in the molecule | numerator used for the photocurable resin composition of this invention is photocured by active energy ray irradiation, and insolubilizes the photosensitive compound of this invention and the said carboxyl group-containing photosensitive oligomer in aqueous alkali solution. Or to help insolubilize. As such a compound, conventionally well-known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acryl The rate etc. can be used, Specifically, 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 such as water; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as 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; In addition, acrylates and melamine acrylates in which polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, and polyester polyols are directly acrylated or urethane acrylated through diisocyanates, and / or the Each methacrylate corresponding to an acrylate etc. are mentioned.

Moreover, hydroxyacrylates, such as pentaerythritol triacrylate, and isophorone di are epoxy acrylate resin which made acrylic acid react with polyfunctional epoxy resins, such as a cresol novolak-type epoxy resin, and the hydroxyl group of this epoxy acrylate resin. Epoxy urethane acrylate compounds etc. which further reacted the half urethane compound of diisocyanate, such as an isocyanate, are mentioned. Such epoxy acrylate resin can improve photocurability, without lowering the touch drying property of a coating film.

The compound which has such a some ethylenically unsaturated group can be used individually by 1 type or in combination of 2 or more types. Especially the compound which has 4-6 ethylenically unsaturated groups in 1 molecule is preferable from a viewpoint of photoreactivity and resolution, and when the compound which has two ethylenically unsaturated groups in 1 molecule is used, the linear expansion coefficient of hardened | cured material falls and cold heat More preferred is that the occurrence of cracks in the cycle test is reduced.

As for the compounding quantity of the compound which has a some ethylenically unsaturated group in such a molecule | numerator, 5-100 mass parts is preferable with respect to 100 mass parts of carboxyl group-containing oligomers. When the compounding quantity is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult due to alkali development after active energy ray irradiation. On the other hand, when it exceeds 100 mass parts, the solubility with respect to a dilute alkali aqueous solution falls and a coating film becomes weak. More preferably 1 to 70 parts by mass.

Moreover, the organic solvent can be used for the photocurable resin composition of this invention for the synthesis | combination of the said carboxyl group-containing oligomer, manufacture of a composition, or viscosity adjustment for apply | coating to a board | substrate or a carrier film. These organic solvents are used alone or as a mixture of two or more kinds.

In the photocurable resin composition of the present invention, in order to prevent oxidation, (1) a radical supplement that invalidates the generated radicals and / or (2) a peroxide decomposing agent which decomposes the generated peroxide into a harmless substance so that no new radicals are generated. Antioxidants may be added.

In addition to antioxidant, a ultraviolet absorber can be further used for the photocurable resin composition of this invention.

Examples of such ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives and dibenzoylmethane derivatives.

The photocurable resin composition of this invention is a well-known thickening agent, such as a well-known thermal polymerization inhibitor, fine-grained silica, organic bentonite, and montmorillonite, an antifoamer, such as a silicone type, a fluorine type, a polymer type, and / or a leveling agent, an imidazole type as needed. Known additives such as silane coupling agents such as, thiazole series, triazole series, antioxidants, and rust inhibitors can be further blended.

An adhesion promoter can be used for the photocurable resin composition of this invention in order to improve adhesiveness of an interlayer adhesiveness or the resin insulating layer formed and a base material. Examples of such adhesion promoters are, for example, benzoimidazole, benzoxazole, benzothiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholino Methyl-thiazole-2-thione, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent and the like.

The photocurable resin composition of this invention comprised in this way is manufactured to predetermined | prescribed composition, for example, it adjusts to the viscosity suitable for the application | coating method with an organic solvent, and it is immersion coating method, flow coating method, roll coating method, Coating is carried out by a method such as a bar coater method, a screen printing method or a curtain coating method.

Then, the organic solvent contained in the composition is volatilized (temporarily dried) at a temperature of about 60 to 100 ° C to form a tack free coating film (resin insulating layer). At this time, the volatilization drying is a hot air circulation drying furnace, IR, hot plate, convection oven, etc. (using a method having a heat source of air heating method by steam) such that the hot air in the dryer is countercurrently contacted and sprayed from the nozzle to the support. Can be used).

Moreover, a resin insulating layer can also be formed by forming a dry film with a photocurable resin composition, and bonding this on a base material.

A dry film has a structure in which carrier films, such as polyethylene terephthalate, a resin insulating layer, such as a soldering resist layer, and the peelable cover film used as needed are laminated | stacked in this order, for example.

A resin insulating layer is a layer obtained by apply | coating and drying a photocurable resin composition to a carrier film or a cover film. Such a resin insulating layer is formed by uniformly applying and drying the photocurable resin composition of the present invention to a carrier film in a thickness of 10 to 150 µm with a blade coater, a lip coater, a coater coater, a film coater and the like. And a dry film is formed by further laminating | stacking a cover film as needed. At this time, it is also possible to apply the photocurable resin composition to a cover film, dry it, and then laminate the carrier film.

As a carrier film, thermoplastic films, such as a polyester film with a thickness of 2-150 micrometers, are used, for example.

As a cover film, although a polyethylene film, a polypropylene film, etc. can be used, it is good that adhesive force with a soldering resist layer is smaller than a carrier film.

When a cover film is used in such a dry film, after peeling this, a resin insulating layer is formed on a base material by laminating | stacking a resin insulating layer and a base material and bonding using a laminator etc. In addition, what is necessary is just to peel a carrier film before or after exposure mentioned later.

At this time, as a base material in which a coating film is formed or a dry film is bonded, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / nonwoven fabric epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluorine polyethylene PPO Copper clad laminates for high-frequency circuits using cyanate esters, etc. are used, and copper clad laminates of all grades (FR-4, etc.), other polyimide films, PET films, glass substrates, ceramic substrates, wafer plates, and the like. have.

Furthermore, exposure is performed by an active energy ray selectively or directly by a laser direct exposure machine through the photomask in which the pattern was formed by the contact type (or non-contact system). An exposed part (part irradiated with an active energy ray) hardens | cures a coating film.

As an exposure machine used for active energy ray irradiation, a direct drawing apparatus (for example, a laser direct imaging apparatus which draws an image directly with a laser by CAD data from a computer), an exposure machine equipped with a metal halide lamp, (super) high pressure mercury A direct drawing apparatus using ultraviolet lamps such as an exposure machine equipped with a lamp, an exposure machine equipped with a mercury short arc lamp, or a (ultra) high pressure mercury lamp can be used.

As an active energy ray, it is preferable to use the laser beam whose maximum wavelength is in the range of 350-410 nm. By setting the maximum wavelength within this range, it is possible to efficiently generate radicals from the photopolymerization initiator. As long as the laser beam of this range is used, any of a gas laser and a solid state laser may be sufficient. Moreover, although the exposure amount changes with film thickness etc., it can generally be in the range of 5-500mJ / cm <^2> , Preferably it is 10-300mJ / cm <^2> .

As the direct drawing device, for example, Nippon Orbo Tech Co., Ltd., Pantax Co., Ltd., etc. can be used, and any device may be used as long as the device emits a laser light having a maximum wavelength of 350 to 410 nm.

And by exposing in this way, an exposure part (part irradiated with an active energy ray) is hardened | cured, and an unexposed part is developed with a dilute alkali aqueous solution (for example, 0.3-3 weight% sodium-carbonate aqueous solution), and hardened | cured material ( Pattern).

At this time, as a developing method, it can be based on the dipping method, the shower method, the spray method, the brush method, etc. In addition, as a developing solution, aqueous alkali solution, such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, can be used.

In addition, when the thermosetting component is added, for example, a carboxyl group of a carboxyl group-containing oligomer and, for example, a plurality of cyclic ether groups and / or cyclic thioether groups in a molecule are heated by heating to a temperature of about 140 to 180 ° C. The thermosetting component which it has reacts can form hardened | cured material (pattern) excellent in various characteristics, such as heat resistance, chemical-resistance, hygroscopicity, adhesiveness, and electrical characteristics.

As described above, the photocurable resin composition contains a carboxyl group-containing oligomer and a polymer binder having a higher molecular weight than the carboxyl group-containing oligomer, a photopolymerization initiator, a photopolymerizable monomer, and a filler to be used in the cured product. Reliability, such as cold heat cycle resistance, can be obtained, without impairing the heat resistance and migration resistance required at the time. And by using such hardened | cured material for a printed wiring board etc., it becomes possible to obtain high reliability.

Example

Although an Example and a comparative example are shown to the following and this invention is concretely demonstrated to it, it is a matter of course that this invention is not limited to the following Example. In addition, below "part" and "%" are a mass reference | standard unless there is particular notice.

Synthesis Example 1

119.4 parts of a novolak-type cresol resin (brand name "Shonol CRG951", Showa Kobunshi Co., Ltd. make, OH equivalence: 119.4) in the autoclave provided with the thermometer, the nitrogen introduction apparatus, the alkylene oxide introduction apparatus, and the stirring apparatus. 1.19 parts of potassium and 119.4 parts of toluene were thrown in, the inside of the system was nitrogen-substituted and stirred, and it heated up. Next, 63.8 parts of propylene oxides were dripped gradually, and it was made to react at 125-132 degreeC and 0-4.8 kg / cm <^2> for 16 hours. Thereafter, the mixture was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide, and a propylene oxide reaction of a novolak-type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / eq. A solution was obtained. This was an average of 1.08 mol of alkylene oxide added per equivalent of phenolic hydroxyl group.

293.0 parts of the alkylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone and 252.9 parts of toluene were introduced into a reactor equipped with a stirrer, a thermometer, and an air inlet tube, and air was supplied. It was blown at a rate of 10 ml / min and reacted at 110 ° C for 12 hours while stirring. The water produced by the reaction was an azeotropic mixture with toluene, and 12.6 parts of water were spilled. Thereafter, the mixture was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 parts of 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while replacing toluene with 118.1 parts of diethylene glycol monoethyl ether acetate, to obtain a novolac acrylate resin solution. Next, 332.5 parts of the obtained novolak-type acrylate resin solution and 1.22 parts of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer, and an air inlet tube, and the air was blown at a rate of 10 ml / min, and stirred with tetra 60.8 parts of hydrophthalic anhydride were added gradually, it was made to react at 95-101 degreeC for 6 hours, and it cooled, and was taken out. In this way, a solution (hereinafter abbreviated as A-1) of a carboxyl group-containing photosensitive oligomer (Mw: 2650) having a nonvolatile content of 65% and an acid value of 87.7 mgKOH / g of a solid was obtained.

Synthesis Example 2

330 parts of cresol novolac type epoxy resin (Epiclon N-695, manufactured by DIC Corporation, Epoxy Equivalent 220) were placed in a flask equipped with a gas introduction tube, a stirring device, a cooling tube, and a thermometer, and 340 parts of carbitol acetate were added thereto. It melt | dissolved by heat, and 0.46 part of hydroquinone and 1.38 part of triphenylphosphines were added. This mixture was heated to 95-105 degreeC, 108 parts of acrylic acid were dripped gradually, and it was made to react for 16 hours. This reaction product was cooled to 80-90 degreeC, 68 parts of tetrahydrophthalic anhydrides were added, and it reacted for 8 hours, and cooled. In this way, a solution (hereinafter abbreviated as A-4) of a carboxyl group-containing photosensitive oligomer (Mw: 9500) having an acid value of 50 mgKOH / g of solids and a nonvolatile content of 60% was obtained.

Examples 1 to 16 and Comparative Examples 1 to 3

Using the resin solution of the said synthesis example, it mix | blended in the ratio (mass part) shown in Table 1 with the various components shown in following Table 1, pre-mixed with a stirrer, and knead | mixed with a triaxial roll mill, and the photosensitive resin composition for soldering resists Was prepared.

The meanings of the reference signs in Table 1 are as follows.

* 1 ZFR-1124 (non-volatile content 65.0%, solid acid value 100mgKOH / g, Mw: 11500, manufactured by Nippon Kayaku Co., Ltd.)

* 2 ZCR-1601H (non-volatile content 65.0%, solid content acid value 100mgKOH / g, Mw: 1730, manufactured by Nippon Kayaku Co., Ltd.)

* 3 Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] 1,1- (o-acetyloxime) (manufactured by BASF Japan)

* 4 Lucirin TPO (made by BASF Corporation)

* 5 Nippon Talc Co., Ltd. SG-2000 (refractive index: 1.57)

* 6 Sakai Chemical Co., Ltd. make B-33 (refractive index: 1.64)

* 7 Showa Denko Co., Ltd. Hygrite H-42M (refractive index: 1.65)

* 8 Silytin (natural combination of plate kaolinite and spherical silica, refractive index: 1.57)

* 9 SO-E2 (refractive index: 1.45) manufactured by ADDEXTEX

* 10 DHT-4A Kyogawa Chemical Co., Ltd. (refractive index: 1.50)

* 11 Shinnitetsu Chemical Co., Ltd. make YP-50 (phenoxy resin, Mw: about 70,000)

* 12 Carbitol acetate dissolved product of Shinnitetsu Chemical Co., Ltd. product YP-50 (solid content 30%)

* 13 MAM-M51 (A ternary block copolymer: polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate, Mw: about 56,000) by Arkema Corporation

* 14 MAM-M52 (A ternary block copolymer: polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate, Mw: about 96,000) by Arkema Corporation

* 15 Arkema Co., Ltd. SBM-E41 (a ternary block copolymer: polystyrene-polybutadiene-polymethyl methacrylate, Mw: about 42,000)

* 16 CAP-482 (cellulose acetopropionate, Mw: about 75,000) manufactured by Eastman Chemical

* 17 Toyo Spin Co., Ltd. production Byron 670 (amorphous polyester resin, Mn: about 30,000)

* 18 bixylenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation)

* 19 bisphenol type epoxy resin (manufactured by Shinnitetsu Chemical Co., Ltd.)

* 20 C.I. pigment blue 15: 3

* 21 C.I. pigment yellow 147

* 22 dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)

Characteristic test:

Each composition of the said Example and the comparative example was apply | coated whole surface by screen printing on the patterned copper foil board | substrate, dried at 80 degreeC for 30 minutes, and cooled to room temperature. The soldering resist pattern was exposed by the optimal exposure amount using the exposure apparatus which mounted the high pressure mercury lamp on this board | substrate, and developed the 30-degree-weight 1 weight% sodium carbonate aqueous solution for 90 second on condition of 0.2MPa of spray pressures, and obtained the resist pattern. This board | substrate was irradiated with the ultraviolet-ray on the conditions of the integrated exposure amount 1000mJ / cm <^2> in a UV conveyor, and it heated at 160 degreeC for 60 minutes, and hardened | cured. The properties of the obtained printed board (evaluation board) were evaluated as follows.

<Optimum exposure dose>

After buffing and polishing a circuit pattern substrate having a copper thickness of 35 µm, washing with water and drying, the respective compositions of the above examples and comparative examples were applied to the entire surface by screen printing, and then heated in a hot air circulation drying oven at 80 ° C. It was dried for 30 minutes. Thereafter, the exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp was exposed through a 41-step step tablet of a stopper, and development (30 ° C., 0.2 MPa, 1 wt.% Na ₂ CO ₃ aqueous solution) was performed. When it performed for the second time, when the pattern of the remaining step tablet was seven steps was made into the optimal exposure amount.

<Applicability>

The whole surface was apply | coated by screen printing on the patterned copper foil board | substrate, and the printing state was confirmed. The criteria are as follows.

(Double-circle): The film thickness of a resist ink is maintained without a nonuniformity on a pattern.

(Circle): Although some nonuniformity arises on a pattern, the film thickness of resist ink is maintained.

X: The ink of a pattern becomes thin.

Electroless Gold Plating Resistant

After plating on the conditions of 0.5 micrometer of nickel and 0.03 micrometer of gold using the electroless nickel plating bath and the electroless gold plating bath of a commercial item, the tape peeling evaluated the presence or absence of the peeling of a resist layer, and the plating solution By peeling, the presence or absence of peeling of the resist layer was evaluated. The criteria are as follows.

(Double-circle): No seepage and peeling are seen.

(Circle): Although it penetrates a little after plating, it does not peel after tape peeling.

(Triangle | delta): Slightly seep after plating, and peeling is also seen after tape peeling.

X: There is peeling after plating.

<PCT Resistance>

It put in the high pressure high temperature high humidity tank of 121 degreeC, 2 atmospheres, and humidity 100% for 168 hours, and evaluated the change of the state of a cured coating film with the following evaluation criteria.

(Double-circle): There is no remarkable swelling and discoloration.

(Circle): There is a slight swelling and there is no discoloration.

X: Remarkable swelling and discoloration exist.

<Crack resistance>

The heat history was added by making 30 minutes at -55 degreeC and 30 minutes at 125 degreeC as 1 cycle, and 1000 cycles passed and observed with the optical microscope. The criteria are as follows.

(Double-circle): No crack generation.

○: cracks are present.

X: cracks were remarkable.

<Resolution>

Each photocurable thermosetting resin composition of an Example and a comparative example was apply | coated to the board | substrate with plated copper by screen printing, and it dried for 30 minutes in the 80 degreeC hot-air circulation type drying furnace. After drying, it exposed using the exposure apparatus mounted with the high pressure mercury lamp (short arc lamp). The exposure pattern used the glass dry plate which draws the circle of opening: 50/60/70/80/90/100 micrometers. The exposure amount was irradiated with active energy rays so as to be the optimum exposure amount of the photosensitive resin composition. After exposure, the 1 weight% sodium carbonate aqueous solution of 30 degreeC was developed for 90 second on condition of the spray pressure of 0.2 MPa, and the resist pattern was obtained. This board | substrate was irradiated with the ultraviolet-ray on the conditions of the integrated exposure amount 1000mJ / cm <^2> in a UV conveyor, and it heated at 160 degreeC for 60 minutes, and hardened | cured.

The minimum opening of the cured coating film of the obtained photosensitive resin composition for soldering resists was calculated | required using the optical microscope adjusted to 200 times. The criteria are as follows.

(Double-circle): Less than 60 micrometers.

(Circle): 60 micrometers or more and less than 80 micrometers.

(Triangle | delta): 80 micrometers or more and less than 100 micrometers.

X: 100 micrometers or more.

<Linear expansion coefficient>

The 3 mm x 10 mm sized cured coating film was subjected to the tension test in the temperature range of 0 degreeC-260 degreeC by the constant temperature increase rate, applying 10g load with the Seiko Instruments TMA6100. The linear expansion coefficient was computed from the elongation amount of the cured coating film with respect to temperature.

The result of each said test is put together in Table 2, and is shown.

As shown in the said Table 2, in each Example using the photocurable resin composition of this invention, all of coating property, electroless gold plating tolerance, PCT tolerance, and crack resistance were excellent. On the other hand, in the case of the comparative example 1 which does not mix | blend a polymeric binder, it became remarkably the latencies and it was difficult to apply | coat. Also, the resolution has fallen. On the other hand, in the case of the comparative example 2 which mix | blended the polymeric binder but did not mix | blend filler, there was no problem in applicability | paintability and resolution, but the linear expansion coefficient could not be made low and the crack resistance fell. In addition, by not containing the filler, moisture such as a plating liquid tends to permeate, resulting in poor electroless gold plating resistance and PCT resistance. Moreover, also in the comparative example 3 with little compounding quantity of a filler, a linear expansion coefficient could not be made low enough and there existed a problem in crack tolerance.

By using the photocurable resin composition of this invention, even if it mix | blends a filler in a large amount, since handling is favorable as a soldering resist, since generation | occurrence | production and peeling of the solder resist which generate | occur | produce at the time of a cold-heat cycle can be suppressed, a printed wiring board and a flexible It can be used suitably especially for formation of the soldering resist for semiconductor packages, such as soldering resists, such as a wiring board, and the interlayer insulation material of a multilayer wiring board.

Claims (10)

A composition comprising a carboxyl group-containing oligomer, a polymer binder having a higher molecular weight than the carboxyl group-containing oligomer, a photopolymerization initiator, a photopolymerizable monomer and a filler, wherein the content of the filler is 30 to 60 mass% of the total amount of nonvolatile components of the composition. Photocurable resin composition which can be developed by alkaline solution, It is characterized by the above-mentioned. The photocurable resin composition according to claim 1, wherein the polymer binder is a thermoplastic resin. The photocurable resin composition of Claim 2 which is 10-50 weight% of solid content in the state melt | dissolved in the same solvent. The photocurable resin composition according to claim 1, wherein the filler comprises Ba or Mg and / or Al. The dry film obtained by apply | coating and drying the photocurable resin composition of any one of Claims 1-4 to a carrier film. The dry film contains the dry layer of several photocurable resin composition, and at least 1 layer is formed from the photocurable resin composition in any one of Claims 1-4. Dry film. The curable product obtained by apply | coating the photocurable resin composition in any one of Claims 1-4 to a base material, and photocuring by irradiation of an active energy ray. It has a pattern of the hardened | cured material obtained by apply | coating and drying the photocurable resin composition in any one of Claims 1-4 to a base material, and photocuring by irradiation of an active energy ray. The printed wiring board characterized by the above-mentioned. Hardened | cured material obtained by laminating the dry film of Claim 5 or 6 to a base material, and photocuring by active energy ray irradiation. It has a pattern of the hardened | cured material obtained by laminating the dry film of Claim 5 or 6 to a base material, and photocuring by irradiation of an active energy ray, The printed wiring board characterized by the above-mentioned.