KR101057929B1 - Photosensitive resin composition and its hardened | cured material - Google Patents

Abstract

INDUSTRIAL APPLICATION This invention can suppress the generation | occurrence | production of the curvature by the heating in a process of manufacturing a flexible board | substrate, a subsequent process, and a component mounting process, Furthermore, even if a small amount of photoinitiators are added, it is highly sensitive, and also the photosensitive resin which can also laser direct exposure Provided are a printed wiring board on which a cured film such as a solder resist is formed by the composition, the cured product thereof, and the cured product.

The photosensitive resin composition of this invention is thin which contains (A) carboxyl group-containing resin, (B) the oxime ester type photoinitiator which has group represented by following formula (I), and (C) the compound which has 2 or more ethylenically unsaturated groups in a molecule | numerator. As a composition which can be developed by aqueous alkali solution, the said oxime ester system photoinitiator (B) is contained in the ratio of 0.1-1.5 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (A).

<Formula I>

(Wherein R ¹ is a hydrogen atom, a phenyl group (may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (may be substituted with one or more hydroxyl groups, the middle of the alkyl chain) May have one or more oxygen atoms), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl or phenyl group having 1 to 6 carbon atoms). , R ² is a phenyl group (may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (may be substituted with one or more hydroxyl groups, at least one oxygen atom in the middle of the alkyl chain ), A cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group)

Carboxyl group-containing resin, oxime ester system photoinitiator, ethylenically unsaturated group, dilute alkali aqueous solution, photosensitive resin composition, photosensitive dry film, laser oscillation light source, printed wiring board

Description

Photosensitive resin composition and its hardened | cured material {PHOTOSENSITIVE RESIN COMPOSITION AND CURED PRODUCTS THEREOF}

TECHNICAL FIELD The present invention relates to a thin printed wiring board requiring low warpage, particularly a photosensitive resin composition suitable for forming a flexible cured film such as a solder resist or a resin insulating layer of a flexible wiring board, a cured product thereof, and a printed wiring board having the cured film. .

Conventionally, the flexible wiring board uses an insulating film obtained by applying an adhesive to a polyimide film called a coverlay, which is punched, laminated, and thermally cured under pressure under a press condition, thereby providing a cover layer on the surface of the flexible substrate. Was doing. Since this coverlay is composed of a polyimide film as a base and a low-shrinkable thermosetting resin as an adhesive layer, the warpage after lamination and after press hardening is very small, and furthermore, after the adhesion of the reinforcing plate and the thermal cure, and the ripple of the component mounting thereafter. Curvature during low soldering can also be very small, and is used in large quantities for flexible substrate applications.

However, since the punching process is performed with a press, fine processing is difficult, and there is a disadvantage that the alignment accuracy is not good at the time of lamination with the circuit board formed thereon.

On the other hand, alkali developable photosensitive resin composition and its dry film are proposed as a photosensitive coverlay, For example, following patent document 1 (Unexamined-Japanese-Patent No. 2000-131836) (a) two or more hydroxides Urethane acrylate which has a carboxyl group obtained by making the compound which has a functional group and 1 or more carboxyl groups, (b) the bifunctional or more polyisocyanate which has a 6-membered ring structure, and (c) the (meth) acrylate which has a hydroxyl group react, and a photoinitiator A photosensitive resin composition containing a diluent and a bifunctional or higher epoxy resin is proposed.

However, since it is a photocurable and thermosetting composition, there exists a problem of hardening shrinkage by crosslinking, and causing curvature after photocuring and after thermosetting.

In addition, as a low-curing composition, Patent Document 2 (Japanese Patent Laid-Open No. 2005-10318) discloses an active energy ray-curable resin containing a carboxyl group-containing urethane-modified epoxy (meth) acrylate, and one to two in one molecule. A photosensitive resin composition for use in solder resist of a circuit board containing an active energy ray-curable unsaturated compound having two ethylenically unsaturated bonds, a photopolymerization initiator, a diluent and a thermosetting epoxy compound is proposed, and Patent Document 3 (WO 2004/079452) ), A photosensitive resin composition containing alkali aqueous solution-soluble urethane resin, a photoinitiator, and a reactive crosslinking agent is proposed. Further, Patent Document 4 (Japanese Patent Laid-Open No. 2002-229201) discloses a photocurable component comprising a urethane (meth) acrylate compound having a carboxyl group and a compound having an ethylenically unsaturated group other than this, a thermosetting resin, The photosensitive composition containing the photoinitiator and a thermal polymerization catalyst is proposed.

Although the curvature after hardening is a value small enough, actually, when it is applied to a flexible wiring board, it has a drawback that curvature generate | occur | produces by post-heating by the reinforcement board bonding process, and heating at the time of component mounting.

Moreover, although laser direct exposure is attracting attention recently for the purpose of the improvement of alignment accuracy, when using the conventional photosensitive resin composition as mentioned above, there exists a problem that exposure amount requires a lot and exposure takes time.

[Patent Document 1] Japanese Patent Application Laid-Open No. 2000-131836 (claims)

[Patent Document 2] Japanese Unexamined Patent Publication No. 2005-10318 (Patent Claims)

[Patent Document 3] WO 2004/079452 Publication (claim)

[Patent Document 4] Japanese Unexamined Patent Publication No. 2002-229201 (Patent Claims)

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art as described above, and its main object is to suppress the occurrence of warping due to heating in a step of manufacturing a flexible substrate, a subsequent step, and a part mounting step. Furthermore, even if a small amount of photopolymerization initiator is added, it is highly sensitive, and laser direct exposure is also possible. Furthermore, it is excellent in various properties such as adhesion to various substrates, solder heat resistance, moisture resistance, chemical resistance, electrical insulation, and the like, which are the same as conventional solder resist compositions. It is providing the photosensitive resin composition which can form the pattern of a cured film.

Moreover, the objective of this invention is providing the hardened | cured material excellent in the various characteristics as mentioned above obtained by using such a photosensitive resin composition, and the printed wiring board in which the hardened film, such as a soldering resist, is formed by the said hardened | cured material, especially a flexible printed wiring board. There is.

In order to achieve the above object, according to the present invention, (A) a carboxyl group-containing resin, (B) an oxime ester photopolymerization initiator having a group represented by the following formula (I), and (C) having two or more ethylenically unsaturated groups in the molecule It is a composition which can be developed by the diluted alkali aqueous solution containing a compound, Comprising: The said oxime ester system photoinitiator (B) is contained in the ratio of 0.1-1.5 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (A). A photosensitive resin composition is provided.

<Formula I>

(Wherein R ¹ is a hydrogen atom, a phenyl group (may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (may be substituted with one or more hydroxyl groups, the middle of the alkyl chain) May have one or more oxygen atoms), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (which may be substituted with an alkyl or phenyl group having 1 to 6 carbon atoms), R ² may be substituted with a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups, and at least one oxygen atom in the middle of the alkyl chain; Or a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group)

In a preferred embodiment, the carboxyl group-containing resin (A) is a resin having a structure which is bisphenol A, bisphenol F, biphenyl, bixylenol skeleton, or a hydrogenated skeleton thereof in view of low smoothness, or a resin having a urethane structure. Moreover, it is preferable that the said carboxyl group-containing resin (A) is photosensitive resin which has a 2 or more radically polymerizable unsaturated double bond from a photocurable viewpoint. Moreover, it is preferable that the said photosensitive resin composition has the absorbance at 355 nm of the dry coating film in the range of 0.3-1.2 at 25 micrometers of dry film thickness. Moreover, it is preferable that the photosensitive resin composition of this invention contains a thermosetting component (D) from a viewpoint of the characteristics improvement, such as heat resistance of a cured film.

The said photosensitive resin composition may be any of a liquid form and a form of a dry film.

Moreover, according to this invention, the hardened | cured material obtained by photocuring the said photosensitive resin composition or its dry film on copper, especially the hardened | cured material obtained by photocuring with a laser oscillation light source, and the laser beam whose maximum wavelength is 350-410 nm After hardening, the printed wiring board which has a hardened film obtained by thermosetting is provided.

The photosensitive resin composition of this invention is a photoinitiator mix | blended with a carboxyl group-containing resin (A) and the compound (C) which has 2 or more ethylenically unsaturated groups in a molecule | numerator, An oxime ester system photoinitiator which has a group represented by said Formula (I) Since B) is contained, it is possible to suppress the occurrence of warpage due to heating in the step of producing the flexible substrate, the subsequent step, and the part mounting step, and the amount of 100 parts by mass of the carboxyl group-containing resin (A) Even if the oxime ester photopolymerization initiator (B) is contained in a small amount in a proportion of 0.1 to 1.5 parts by mass, it is highly sensitive and laser direct exposure is also possible. In addition, the photosensitive resin composition of the present invention is a composition which can be developed by a dilute aqueous alkali solution, and in addition, even though it has low warpage, adhesion to various substrates similar to the conventional solder resist composition, solder heat resistance, moisture resistance, chemical resistance, and electrical conduction. It is possible to form a pattern of a cured coating having excellent characteristics such as plating plating resistance and electrical insulation. Therefore, the photosensitive resin composition of this invention can be advantageously applied to formation of the cured film, such as the soldering resist of a printed wiring board, especially a flexible printed wiring board, and a resin insulating layer.

The present inventors have found that the warpage during the post-heating process and the component mounting greatly influences the warpage of the composition due to the volatilization of the photopolymerizable initiator and also the warpage of the composition. The present inventors further studied these phenomena, and as a result, an oxime having a group represented by the formula (I) as a photopolymerization initiator blended together with a carboxyl group-containing resin (A) and a compound (C) having two or more ethylenically unsaturated groups in the molecule When the ester type photoinitiator (B) is used, it discovers that the photosensitive resin composition which has sufficient optical characteristics even if a small amount is added, and also enables laser direct exposure is obtained, and has completed this invention.

Hereinafter, each component of the photosensitive resin composition of this invention is demonstrated.

First, as carboxyl group-containing resin (A), both the carboxyl group-containing resin which does not have an ethylenically unsaturated double bond, and the photosensitive carboxyl group-containing resin which has ethylenically unsaturated double bond can be used, It is not limited to a specific thing, Especially The compounds listed below (which may be any of oligomers and polymers) may be preferably used.

(1) Carboxyl group-containing resin obtained by copolymerizing unsaturated carboxylic acids, such as (meth) acrylic acid, and compounds which have unsaturated double bonds, 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 dimethylolpropionic acid and dimethylolbutanoic acid; and polycarbonate polyols and polyethers Carboxyl group content obtained by polyaddition reaction of diol compounds, such as a polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A alkylene oxide adduct diol, a compound which has phenolic hydroxyl group and alcoholic hydroxyl group, etc. Urethane resin.

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

(4) In the synthesis | combination of resin of said (2) or (3), the compound which has one hydroxyl group and one or more (meth) acryl groups in molecule | numerators, such as hydroxyalkyl (meth) acrylate, is added, and a terminal (meth) Acrylated carboxyl group-containing urethane resin.

(5) A compound having one isocyanate group and one or more (meth) acryl groups in a molecule such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate during synthesis of the resin of the above (2) or (3). The carboxyl group-containing urethane resin which added and terminated (meth) acrylates.

(6) Photosensitive carboxyl group-containing resin obtained by making (meth) acrylic acid react with the polyfunctional (solid) epoxy resin mentioned later, and adding dibasic acid anhydride to the produced hydroxyl group.

(7) Photosensitive property obtained by reacting (meth) acrylic acid to the polyfunctional epoxy resin which epoxidized the hydroxyl group of bifunctional (solid) epoxy resin further with epichlorohydrin, and adding dibasic acid anhydride to the produced hydroxyl group. Carboxyl group-containing resin.

(8) The carboxyl group-containing polyester resin obtained by making dicarboxylic acid react with the bifunctional oxetane resin mentioned later and adding dibasic acid anhydride to the produced | generated primary hydroxyl group.

(9) Photosensitive carboxyl group-containing resin formed by adding the compound which has one epoxy group and one or more (meth) acryl groups in 1 molecule further to said resin (1)-(8).

Among these carboxyl group-containing resins, preferable is the case of the diisocyanate in which the compound (including diisocyanate) which has an isocyanate group used for the synthesis | combination of the resin of said (2)-(5) does not have a benzene ring, and said (6 In the case of the polyfunctional and bifunctional epoxy resins used for the synthesis of the resins of (7) and (7), the compounds having a linear structure having a bisphenol A skeleton, a bisphenol F skeleton, a biphenyl skeleton, a bixylenol skeleton, and hydrogenated compounds thereof It is preferable at the point of flexibility. In addition, in another aspect, the resins of the above (2) to (5) and modified substances such as the above (9) have a urethane bond in the main chain and are preferable against warpage. Moreover, since resin other than said (1), (2), (8) has photosensitive group (radical polymerizable unsaturated double bond) in a molecule | numerator, it is preferable at the point of photocurability.

In addition, in this specification, (meth) acrylate is a term which generically mentions acrylate, methacrylate, and a mixture thereof, and is the same also about other similar expression.

Since the carboxyl group-containing resin (A) mentioned above has many free carboxyl groups in the side chain of a backbone polymer, image development by dilute alkali aqueous solution is attained.

Moreover, it is preferable that the acid value of the said carboxyl group-containing resin (A) exists in the range of 40-200 mgKOH / g, More preferably, it is the range of 45-120 mgKOH / g. When the acid value of the carboxyl group-containing resin (A) 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 developer proceeds, so that the line becomes thinner or more than necessary. Therefore, it is not preferable because it is possible to dissolve and peel off the developer without distinction between the exposed portion and the unexposed portion, which makes it difficult to form a normal resist pattern.

Moreover, although the weight average molecular weight of the said carboxyl group-containing resin (A) changes with resin skeleton, generally the range of 2,000-150,000 is preferable, More preferably, it is the range of 5,000-100,000. If the weight average molecular weight is less than 2,000, the tack free performance of the coating film may be inferior, the moisture resistance of the coating film after exposure is poor, and a film reduction may occur at the time of development, and the resolution may be greatly reduced. On the other hand, when a weight average molecular weight exceeds 150,000, developability may remarkably worsen and storage stability may fall.

It is preferable that the compounding quantity of such carboxyl group-containing resin (A) exists in the range of 20-60 mass% of the whole composition, Preferably it is the range of 30-50 mass%. When it is less than the said range, since coating film strength may fall, it is not preferable. 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.

Next, the oxime ester photoinitiator (B) which has group represented by the said general formula (I) used for this invention has sufficient sensitivity, and it is effective in the prevention of the curvature by the initiator volatilization at the time of post-heating and component mounting. . Usually, 5-20 mass parts of photoinitiators are contained in the photosensitive composition used for the photosensitive coverlay and soldering resist with respect to 100 mass parts of carboxyl group-containing resin. However, the oxime ester photopolymerization initiator (B) having a group represented by the above formula (I) is sufficient to 0.1 to 1.5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A), and further provides a cured product having less warpage after component mounting. do. In the case of a composition containing a large number of photopolymerization initiators, it is presumed that warpage has occurred because the photopolymerization initiator volatilizes and volume shrinkage during post-heating or reflow soldering of component mounting. In other respects, this means that, in the case of the photopolymerization initiator which almost volatilizes upon thermal curing of the composition, there is no problem even if a relatively large amount is added. That is, the manufacturing process of a flexible substrate becomes photocuring → thermosetting → post-heating → component mounting (reflow solder). For example, the temperature history is photocuring (a few seconds at 20-30 degreeC) → thermosetting. (30 to 60 minutes at 140 to 160 ° C) → post-heating (2 hours at 150 to 170 ° C) → component mounting (several seconds to several tens of seconds at 240 to 260 ° C). Here, the photopolymerization initiator which most volatilizes at the time of thermosetting hardly remains the component which volatilizes after this hardening, and it is thought that it does not cause a volume shrinkage at the time of post-heating and component mounting. As such a photoinitiator, the compound reduced by 50% or more by the heating of 150 degreeC is mentioned, (B1a) mentioned later is preferable.

As an oxime ester type photoinitiator (B) which has group represented by the said Formula (I), Preferably, it is 2- (acetyloxyiminomethyl) thioxanthene-9-one represented by following formula (V), and following formula (VI) and (VII) The compound shown is mentioned.

(V)

<Formula VI>

(In formula, R <^10> is a hydrogen atom, a halogen atom, a C1-C12 alkyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, a C2-C12 alkanoyl group, a C2-C12 thing. An alkoxycarbonyl group (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups and may have one or more oxygen atoms in the middle of the alkyl chain) or a phenoxycarbonyl group,

R ¹¹ and R ¹³ each independently represent a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom) and an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups, and 1 in the middle of the alkyl chain). May have one or more oxygen atoms), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),

R ¹² is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups, and at least one in the middle of the alkyl chain) May have an oxygen atom), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl or phenyl group having 1 to 6 carbon atoms)

<Formula VII>

(Wherein, R ¹⁴ and R ¹⁵ each independently represent an alkyl group having 1 to 12 carbon atoms, M represents S, O, or NH, and R ¹⁶ , R ¹⁷ , R ¹⁸ , R ^19, and R ²⁰ each independently Hydrogen atom or an alkyl group having 1 to 6 carbon atoms, m and n represent an integer of 0 to 5)

Among the oxime ester photopolymerization initiators (B), 2- (acetyloxyiminomethyl) thioxanthene-9-one represented by the general formula (V) and the compound represented by the general formula (VI) are more preferable. As a commercial item, CGI-325, Irgacure-OXE01, Irgacure-OXE02, etc. made by Ciba Specialty Chemicals, etc. are mentioned.

The oxime ester type photoinitiator as mentioned above can be used individually or in combination of 2 or more types.

As described above, the optimum amount of the oxime ester photopolymerization initiator (B) is sufficient to be 0.1 to 1.5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A), but the oxime in order to ensure more photoreaction. Photoinitiator (B1) or photoinitiator (B2) other than ester type can be added. It is preferable that the compounding quantity of the other initiator to add is 6 mass parts or less in total amount with respect to 100 mass parts of said carboxyl group-containing resin (A) for the purpose of reducing curvature by post-heating, More preferably, it is 5 mass parts or less. In addition, as an exception, the photopolymerization initiator (B1a) volatilized in the thermosetting step (heating at about 150 ° C.) has no effect of volatilization during the post-heating step even if more than the above range is applied. It became clear that it could. Such a heat-volatile photopolymerization initiator (B1a) can be selected by simple analysis by thermogravimetric analysis, headspace GC-MS, etc., and the amount of photopolymerization initiator which volatilizes before and after 150 ° C. is extremely extreme (50 % Or more) The compound which changes is preferable. As a specific example, 2-methyl-1- [4- (methylthio) phenyl] -2- morpholino propanone- 1, a commercial item, Irgacure-907 by Ciba Specialty Chemicals Corporation, etc. are mentioned.

In addition, as a photoinitiator which does not volatilize at 150 degreeC but can add a small amount, 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. Examples of commercially available products include Irgacure-369 and Irgacure-379 manufactured by Ciba Specialty Chemicals.

Moreover, as an acyl phosphine oxide type initiator, 2,4,6- trimethyl benzoyl diphenyl phosphine oxide, bis (2, 4, 6- trimethyl benzoyl)-phenyl phosphine oxide, bis (2, 6- dimethoxybene And crude) -2,4,4-trimethyl-pentylphosphine oxide. As a commercial item, Lucirin TPO by BASF Corporation, Irgacure-819 by Ciba Specialty Chemicals Corporation, etc. are mentioned.

In addition, as a photoinitiation adjuvant and a sensitizer which can be used for the photosensitive resin composition of this invention, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, a xanthone compound, and a tertiary An amine compound etc. are mentioned.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

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

Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.

Specific examples of the thioxanthone compound include 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, and 2,4-diisopropyl thioxanthone.

Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.

Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4'-methyldiphenyl sulfide, 4-benzoyl-4'-ethyldiphenyl sulfide, 4-benzoyl- 4'-propyldiphenylsulfide.

Specific examples of the tertiary amine compound include ethanolamine compounds and compounds having a dialkylaminobenzene structure, for example, 4,4'-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4,4 ' -Dialkylaminobenzophenones such as diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (di Dialkylamino group-containing coumarin compounds, such as ethylamino) -4-methylcoumarin), 4-dimethylaminobenzoate ethyl (Kayakyue EPA by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure by International Bio-Synthetics Co., Ltd.) (Quantacure) DMB), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA, manufactured by International Bio-Synthetics Co., Ltd.) , 4-dimethylaminobenzoic acid 2-ethylhexyl (Esolol manufactured by Van Dyk) ol) 507) and 4,4'-diethylaminobenzophenone (EAB by Hodogaya Chemical Co., Ltd.).

Among the photoinitiators described above, thioxanthone compounds and tertiary amine compounds are preferred. It is preferable that a thioxanthone compound is contained in the photosensitive resin composition of this invention from the point of deep-curing property, Especially, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone Thioxanthone compounds, such as 2, 4- diisopropyl thioxanthone, are preferable.

As a compounding quantity of such a thioxanthone compound, Preferably it is 2 mass parts or less, More preferably, it is the ratio of 1 mass part or less with respect to 100 mass parts of said carboxyl group-containing resin (A). If the compounding quantity of a thioxanthone compound is too large, it will cause curvature at the time of post-heating, and since it leads to the cost increase of a product, it is unpreferable.

As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable. As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is also low in toxicity and preferable. The dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has little coloration because the maximum absorption wavelength is in the ultraviolet region, and of course, the colorless transparent photosensitive resin composition can be used as a color pigment for the color pigment itself. It becomes possible to provide the coloring soldering resist film which reflected the color. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable since it shows the outstanding sensitizing effect with respect to the laser beam of wavelength 400-410 nm.

As a compounding quantity of such a tertiary amine compound, Preferably it is 0.1-2 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (A), More preferably, it is the ratio of 0.1-1 mass part. When the compounding quantity of a tertiary amine compound is 0.1 mass part or less, there exists a tendency for sufficient sensitization effect not to be acquired. When it exceeds 2 mass parts, since it causes curvature at the time of post-heating, and leads to the cost increase of a product, it is unpreferable.

Photoinitiator, photoinitiation adjuvant, and sensitizer as mentioned above can be used individually or as a mixture of 2 or more types.

The compounding ratio of these photoinitiators and an initiator is prescribed | regulated that the compounding ratio of 0.1-1.5 mass parts of oxime ester system photoinitiators (B) which has group represented by the said Formula (I) with respect to 100 mass parts of said carboxyl group-containing resin (A). In addition, it is preferable to add the absorbance at 355 nm of the dry coating film of the composition which contains the coloring agent and sensitizer mentioned later in the ratio which became the range of 0.3-1.2 at 25 micrometers of dry film thickness. This range of absorbance was found to be effective in reducing warping during reheating of the post-heating and component mounting aimed at the present invention. Although the detail is not clear, it is thought that it is because the photoreaction of a composition is the range which can photocure at the surface layer and deep part relatively uniformly. When the absorbance was higher than 1.2, light did not penetrate to the deep portion, and many unreacted photocurable components remained, and the phenomenon was caused by the rapid heating or reflow soldering of the component mounting, causing the substrate to bend or wrinkle. On the other hand, when the absorbance is lower than 0.3, it is not suitable because light cannot be used effectively and cannot cope with high sensitivity and laser direct exposure, which is one of the objects of the present invention. In addition, it became clear that chemical resistance and electroless gold plating property of a hardened film improve also by adjusting absorbance to the said preferable range. These phenomena have not been clarified in the past, and are the first effects discovered by the present inventors.

As a compound (C) which has two or more ethylenically unsaturated groups in the said molecule, various conventionally well-known (meth) acrylate monomers can be used, It is not limited to a specific thing. As a specific example, For example, Diacrylates of glycol, such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol, propylene glycol; Polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or polyhydric acrylates such as ethylene oxide adducts, propylene oxide adducts or caprolactone adducts Ryu; Polyhydric acrylates, such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols; Urethane acrylates of the polyalcohols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; Melamine acrylate; And each methacrylate corresponding to the said acrylate etc. are mentioned.

Moreover, hydroxy, such as pentaerythritol triacrylate, in the epoxy acrylate resin which made (meth) acrylic acid react with polyfunctional epoxy resins, such as a cresol novolak-type epoxy resin, and the hydroxyl group of this epoxy acrylate resin ( Epoxyurethane acrylate compounds etc. which made the half-urethane compound of diisocyanate, such as meth) acrylate and isophorone diisocyanate react, are mentioned. Such epoxy acrylate-based resin can improve photocurability without deteriorating the touch dryness.

Among the above ethylenically unsaturated group-containing compounds, preferably (meth) acrylates containing two ethylenically unsaturated groups and those modified by addition of polyolethylene oxide, propylene oxide and caprolactone as polyfunctionals are also preferred. .

Further, from the viewpoint of flame retardancy, a modified product by Michael addition reaction of 9,10-dihydro-9-oxa-10-phosphafaphenanthrene-10-oxide with a conventionally known polyfunctional (meth) acrylate is preferable. .

The compounding quantity of the compound (C) which has two or more ethylenically unsaturated groups in a molecule | numerator as mentioned above is 5-100 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (A), More preferably, it is the ratio of 1-70 mass parts. to be. When the said compounding quantity is less than 5 mass parts, since photocurability falls and pattern formation becomes difficult by alkali image development after active energy ray irradiation, it is unpreferable. On the other hand, when it exceeds 100 mass parts, since solubility to aqueous alkali solution falls and a coating film becomes weak, it is unpreferable.

A thermosetting component (D) can be added to the photosensitive resin composition of this invention in order to provide heat resistance. Particularly preferred thermosetting component (D) is a thermosetting resin having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in the molecule. Among these, a bifunctional epoxy resin is preferable and a diisocyanate and its bifunctional block isocyanate can also be used.

The thermosetting component (D) having two or more cyclic (thio) ether groups in such a molecule has two or more of any one or two of three, four or five member cyclic cyclic ether groups, or cyclic thioether groups in the molecule. Compound, for example, a compound having at least two or more epoxy groups in a molecule, that is, a polyfunctional epoxy compound (D-1), a compound having at least two or more oxetanyl groups in a molecule, that is, a polyfunctional oxetane compound (D- 2) and the compound which has 2 or more thioether group in a molecule | numerator, ie, episulfide resin (D-3), etc. are mentioned.

Examples of the polyfunctional epoxy compound (D-1) include JER828, JER834, JER1001 and JER1004 manufactured by Japan Epoxy Resin Co., Ltd., Epiclone 840, Epiclone 850, Epiclone 1050, manufactured by Dainippon Ink Industries, Ltd. Epiclone 2055, Eto Toto YD-011, YD-013, YD-127, YD-128 manufactured by Toto Kasei Co., Ltd., DER317, DER331, DER661, DER664, manufactured by Dow Chemical Co., Ltd. Of die 6071, Araldide 6804, Araldide GY250, Araldide GY260, Sumitomo Kagaku Kogyo Co., Ltd. Sumiepoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo Co., Ltd. Bisphenol A type epoxy resins such as AER330, AER331, AER661, and AER664 (both trade names); YL903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclone 152, Epiclone 165, manufactured by Dainippon Ink & Chemicals Co., Ltd., Efototo YDB-400, YDB-500, manufactured by Toto Kasei Co., Ltd., DER542, Shiva, manufactured by Dow Chemical Co., Ltd. Brominated epoxy resins such as Araldide 8011 manufactured by Specialty Chemicals, Sumitomo Chemical Co., Ltd., Semiepoxy ESB-400, ESB-700, ASA711 manufactured by Asahi Kasei Kogyo Co., Ltd., and all (trade names); JER152, JER154 made in Japan epoxy resin company, DEN431, DEN438 made by Dow Chemical Co., Ltd., Epiclone N-730, Epiclone N-770, Epiclone N-865, Dotogase Co., Ltd. Efototo YDCN-701, YDCN-704, Araldide ECN1235, Araldide ECN1273, Araldide ECN1299, Araldide XPY307, Nippon Kayaku Co., Ltd. EPPN-201, EOCN -1025, EOCN-1020, EOCN-104S, RE-306, AERECN-235, ECN-299 by Sumiepoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo Co., Ltd., all manufactured by Sumitomo Chemical Industries, Ltd. Novolak type epoxy resins); Of epiclon 830 made by Dainippon ink Kagaku Kogyo Co., Ltd., JER807 manufactured by Japan epoxy resin company, Etoto YDF-170, YDF-175, YDF-2001, YDF-2004, product made by Ciba Specialty Chemicals Co., Ltd. Bisphenol F-type epoxy resins, such as Araldide XPY306 (all are brand names); Hydrogenated bisphenol A type epoxy resins such as Efototo ST-2004, ST-2007, ST-3000 (trade name) manufactured by Toto Kasei Co., Ltd .; Glee of JER604 made in Japan epoxy resin company, Etoto YH-434 made by Toto Kasei Co., Ltd., Araldide MY720 made by Ciba Specialty Chemicals, Sumiepoxy ELM-120 made by Sumitomo Chemical Co., Ltd. (all brand names) Cydylamine type epoxy resins; Hydantoin type epoxy resins, such as Araldide CY-350 (brand name) by the Ciba Specialty Chemicals company; Alicyclic epoxy resins such as Celoxide 2021 manufactured by Daicel Chemical Industries, Ltd., Araldide CY175 manufactured by Ciba Specialty Chemicals, and CY179 (both trade names); Trihydroxyphenylmethane type epoxy resins such as YL-933 manufactured by Japan Epoxy Resin Co., Ltd., T.E.N., EPPN-501, EPPN-502 manufactured by Dow Chemical Co., Ltd. (both trade names); Bixylenol type or biphenol type epoxy resins, such as YL-6056, YX-4000, and YL-6121 (all are brand names) by the Japan epoxy resin company, or mixtures thereof; Bisphenol S type epoxy resins, such as Nippon Kayaku Co., Ltd. EBPS-200, Asahi Denka Kogyo Co., Ltd. EPX-30, and Dai Nippon Ink Chemical Co., Ltd. EXA-1514 (brand name); Bisphenol A novolak-type epoxy resins, such as JER157S (brand name) by the Japan epoxy resin company; Tetraphenylolethane type epoxy resins such as YL-931 manufactured by Japan Epoxy Resin Co., Ltd. and Araldide 163 manufactured by Ciba Specialty Chemicals Co., Ltd. (both trade names); Heterocyclic epoxy resins, such as Araldide PT810 by Ciba Specialty Chemicals Co., Ltd. and TEPIC by Nissan Chemical Industries, Ltd. (all are brand names); Diglycidyl phthalate resins such as Bremmer DGT manufactured by Nippon Yushi Corporation; Tetraglycidyl xylenoylethane resins such as ZX-1063 manufactured by Tohto Kasei Co., Ltd .; Naphthalene group-containing epoxy resins such as ESN-190, ESN-360 manufactured by Shinnitetsu Chemical Industries, Ltd., HP-4032, EXA-4750, and EXA-4700 manufactured by Dainippon Ink & Chemicals Co., Ltd .; Epoxy resin which has dicyclopentadiene frame | skeleton, such as the Dai Nippon Ink Industries Co., Ltd. product HP-7200 and HP-7200H; Glycidyl methacrylate copolymer type epoxy resins such as CP-50S and CP-50M manufactured by Nippon Yushi Corporation; Copolymerized epoxy resins 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 Tohto Kasei Co., Ltd.), and the like. Although it is possible, it is not limited to these. These epoxy resins can be used individually or in combination of 2 or more types. Especially among these, a novolak-type epoxy resin, a heterocyclic epoxy resin, a bisphenol-A epoxy resin, or a mixture thereof is preferable.

Examples of the polyfunctional oxetane compound (D-2) 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- Oxetanyl) methylacrylate, (3-ethyl-3-oxetanyl) methylacrylate, (3-methyl-3-oxetanyl) methylmethacrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl methacrylate and oligomers or copolymers thereof, oxetane alcohols and novolac resins, poly (p-hydroxystyrene), cardo-type bisphenols, calix arenes and calyx rezos The etherified substance with resin which has hydroxyl groups, such as lecinarene or silsesquioxane, etc. are mentioned. In addition, the copolymer of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate etc. are mentioned.

As a compound (D-3) which has two or more cyclic thioether group in the said molecule | numerator, bisphenol-A episulfide resin YL7000 by the Japan epoxy resin company, etc. are mentioned, for example. Moreover, 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.

The amount of the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is preferably 0.6 to 2.5 equivalents, with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A), More preferably, it exists in the range which becomes 0.8-2.0 equivalent. When the compounding quantity of the thermosetting component (D) which has a 2 or more cyclic (thio) ether group in a molecule | numerator is less than 0.6 equivalent, since a carboxyl group remains in a hardened film and heat resistance, alkali resistance, electrical insulation, etc. fall, it is unpreferable. On the other hand, when it exceeds 2.5 equivalent, since low-molecular-weight cyclic (thio) ether group remains in a dry coating film, since the intensity | strength of a coating film, etc. fall, it is unpreferable.

When using the thermosetting component (D) which has a 2 or more cyclic (thio) ether group in the said molecule, 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-phenyl are Imidazole derivatives such as midazole, 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, 4-methyl-N, N-dimethylbenzylamine Hydrazine compounds such as compounds, adipic dihydrazide, and sebacic acid dihydrazide; Phosphorus compounds, such as a triphenylphosphine, etc. are mentioned. Moreover, as what is marketed, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all of brand names of imidazole type compounds) by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N from U. Aprosa, 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. It is not limited to these in particular, 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, and 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-4,6-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid It is also possible to use S-triazine derivatives such as adducts. Preferably, compounds which also function as these adhesion imparting agents are used in combination with the thermosetting catalyst.

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

The photosensitive resin composition of this invention can mix | blend a coloring agent. As the colorant, conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and dyes may be used. However, from the viewpoint of reducing the environmental load and the effect on the human body, it is preferable not to contain halogen.

Blue colorant:

As the blue colorant, there are phthalocyanine-based and anthraquinone-based compounds, and the pigment-based compound is classified as Pigment, specifically, the following color index (CI; The Society of Dices & Colors (The Society of Dyers and Colourists) numbered: 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.

As a 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 and the like can be used. In addition to the above, a metal substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant:

Examples of the green colorant include phthalocyanine series and anthraquinone series, and specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, and Solvent Green 28 Etc. can be used. In addition to the above, a metal substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant:

Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone. 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 series: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.

Condensed tones series: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

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

Monoazo series: 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.

Red colorant:

Examples of the red colorant include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone and quinacridone. It can be mentioned.

Monoazo series: 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 meter: Pigment Red 37, 38, 41.

Monoazo Lake system: Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57: 1, 58: 4, 63: 1, 63: 2, 64: 1, 68.

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

Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.

Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.

Condensed tones series: 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 series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

In addition, for the purpose of adjusting the color tone, a coloring agent such as purple, orange, light blue and black may be added.

Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment CI 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 Brown 23, CI Pigment Brown 25, CI Pigment Black 1, and CI Pigment Black 7.

Although the specific compounding ratio of a coloring agent is influenced also by the kind of coloring agent used, the kind of other additives, etc., it cannot say uniformly, but in the photosensitive resin composition of this invention, the light absorbency in 355 nm is 25 micrometers in dry film thickness. It is preferable to mix | blend in the ratio which becomes 0.3 to 1.2 at. Particularly preferred colorants are phthalocyanine-based, anthraquinone-based, yellow anthraquinone-based, red diketopyrrolopyrrole-based and anthraquinone-based, and no halogen atom. Among these, the red colorant and the yellow colorant are particularly preferable in view of sensitivity and resolution.

The photosensitive resin composition of this invention can mix | blend a filler as needed in order to raise the physical strength of the coating film, etc. As such a filler, well-known conventional inorganic or organic filler can be used, Especially barium sulfate, spherical silica, and talc are used preferably. Moreover, in order to obtain a white appearance and flame retardance, metal hydroxides, such as titanium oxide, a metal oxide, and aluminum hydroxide, can also be used as a extender pigment filler. The compounding quantity of a filler becomes like this. Preferably it is 75 weight% or less of a composition whole quantity, More preferably, it is the ratio of 0.1-60 weight%. When the compounding quantity of a filler exceeds 75 weight% of the total amount of a composition, since the viscosity of an insulating composition becomes high and application | coating and moldability fall, or hardened | cured material becomes weak, it is unpreferable.

The compounding quantity of these fillers becomes like this. Preferably it is 300 mass parts or less, More preferably, it is 0.1-300 mass parts, Especially preferably, it is 0.1-150 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (A). When the compounding quantity of a filler exceeds 300 mass parts, since the viscosity of the photosensitive resin composition becomes high and printability falls or hardened | cured material becomes weak, it is unpreferable.

Moreover, the organic solvent can be used for the photosensitive resin composition of this invention for the synthesis | combination of the said carboxyl group-containing resin (A), manufacture of a composition, or viscosity adjustment for apply | coating to a board | substrate or a carrier film.

Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, Ketones, such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether Glycol ethers such as these; Esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. These organic solvents are used alone or as a mixture of two or more thereof.

As needed, the photosensitive resin composition of this invention further contains well-known conventional thermal polymerization inhibitors, such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, and phenothiazine, fine-grained silica, organic bentonite, and montmorillonite. Known conventional thickeners, silicone-based, fluorine-based, antifoaming agents such as polymers and / or leveling agents, silane coupling agents such as imidazole-based, thiazole-based, triazole-based, known conventional additives such as antioxidants and rust inhibitors can do.

The photosensitive resin composition of this invention can also be set as the form of the dry film provided with the carrier film (support) and the layer containing the said photosensitive resin composition formed on the said carrier film.

In dry film formation, the photosensitive resin composition of this invention is diluted with the said organic solvent, it adjusts to an appropriate viscosity, a coater coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure coater, A film can be obtained by apply | coating in a uniform thickness on a carrier film with a spray coater, etc., and drying for 1 to 30 minutes normally at the temperature of 50-130 degreeC. There is no restriction | limiting in particular regarding a coating film thickness, Generally, it is a film thickness after drying, and is suitably selected in 10-150 micrometers, Preferably it is 20-60 micrometers.

As a carrier film, a plastic film is used and it is preferable to use plastic films, such as polyester films, such as a polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film. Although there is no restriction | limiting in particular about the thickness of a carrier film, Usually, it selects suitably in the range of 10-150 micrometers.

After film-forming on a carrier film, it is preferable to further laminate a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film.

As a cover film which can be peeled off, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, the surface-treated paper, etc. can be used, for example, When peeling a cover film, it is a film and a cover film rather than the adhesive force of a film and a carrier film. The adhesive force of may be smaller.

The liquid photosensitive resin composition of this invention which has a composition as mentioned above is adjusted to the viscosity suitable for the application | coating method with the said organic solvent as needed, and is immersion coating method, flow coating method, roll coating method, bar coater method, screen on a base material. It is apply | coated by methods, such as a printing method and a curtain coating method, and a tack-free coating film can be formed by volatilizing (temporarily drying) the organic solvent contained in a composition at the temperature of about 60-100 degreeC. In addition, in the case of the form of the said dry film, it bonds on a base material using a hot roll laminator etc. (bonding so that the said photosensitive resin composition layer and a base material may contact). In the case of the dry film provided with the cover film which can be peeled further on the photosensitive resin composition layer of the said film, after peeling a cover film, it bonds using a hot roll laminator etc. so that the said photosensitive resin composition layer and a base material may contact.

Then, exposure (irradiation of an active energy ray) is performed about the obtained coating film (photosensitive resin composition layer) (when using the said dry film, after laminating on a base material, without peeling a carrier film). The exposure may be either a contact type (or a non-contact method), a method of selectively exposing the active energy ray through a photomask on which a pattern is formed, or a method of directly exposing the pattern by a laser direct exposure machine. This exposure hardens the exposure part (portion irradiated with the active energy ray) by this exposure. Subsequently, the unexposed part is developed with a dilute aqueous alkali solution (for example, 0.3-3% aqueous solution of sodium carbonate) to form a resist pattern (when using the dry film, the carrier film is peeled off and developed after exposure). . After that, by further curing only by heat curing or by irradiation of active energy rays and finally curing by heat irradiation or irradiation of active energy rays after heat curing (main curing), electrical insulation, adhesion, solder heat resistance, chemical resistance, electroless gold plating resistance, etc. This excellent cured film (cured product) is formed. In the case of the photosensitive resin composition containing a thermosetting component (D), it heats and heats, for example at the temperature of about 140-180 degreeC, and the carboxyl group of the said carboxyl group-containing resin (A), and 2 or more cyclic ether groups in a molecule | numerator And / or a thermosetting component (D) having a cyclic thioether group reacts to form a cured film excellent in various properties such as heat resistance, chemical resistance, hygroscopicity, adhesiveness, and electrical properties.

As said base material, in addition to the printed wiring board previously formed in circuit, especially the flexible printed wiring board, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / nonwoven fabric-epoxy resin, glass cloth / paper- Laminated plates coated with copper of all grades (FR-4, etc.) using composite materials such as epoxy resins, synthetic fiber-epoxy resins, fluorine resins, polyethylene, PPO, and cyanate esters, polyimide films, PET films, glass substrates, ceramics A substrate, a wafer board, etc. can be used.

Volatilization drying after applying the photosensitive resin composition of this invention is a hot-air circulation type drying furnace, IR, hot-plate, a convection oven, etc. (The thing provided with the heat source of the air heating system by steam uses the hot air in a dryer. Or a method of spraying a support from a nozzle onto the support body).

As an exposure machine used for the said active energy ray irradiation, the apparatus which mounts a high pressure mercury lamp lamp, an ultrahigh pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, etc., may irradiate an ultraviolet-ray in the range of 350-450 nm, and may also draw directly. An apparatus (for example, a laser direct imaging apparatus which draws an image directly with a laser by CAD data from a computer) can also be used. As the laser light source of the weaving machine, any one of a gas laser and a solid laser may be used as long as the laser light having a maximum wavelength in the range of 350 to 410 nm is used. Although the exposure amount for image formation changes with film thickness etc., it can be generally in the range of 20-800 mJ / cm <2>, Preferably it is 20-600 mJ / cm <2>.

The developing method may be a dipping method, a showering method, a spraying method, a brush method, or the like. As the developing solution, alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines may be used. .

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

Synthesis Example 1

(A-1) Synthesis | combination of the photosensitive carboxyl group-containing urethane resin which corresponds to carboxyl group-containing resin (3) mentioned above and which has bisphenol A structure using alicyclic diisocyanate: As a bisphenol-A epoxy compound in a separable flask, Nippon Kaya 368.0 g of RE310S (bifunctional bisphenol-A epoxy resin, epoxy equivalent: 184 g / equivalent) manufactured by KK Co., Ltd., 142.7 g of acrylic acid (molecular weight: 72.06), and 2,6-di-tert- as a thermal polymerization inhibitor 2.94 g of butyl-p-cresol and 1.53 g of triphenylphosphine were added as a reaction catalyst, and reacted at a temperature of 98 ° C. until the acid value of the reaction solution became 0.5 mgKOH / g or less, resulting in an epoxy carboxylate compound ( a) (theoretical molecular weight: 510.7) was obtained. Next, 588.2 g of carbitol acetate and 105.5 g of dimethylol propionic acid (b) (molecular weight: 134.16) were added to this reaction liquid as a solvent for reaction, and it heated up at 45 degreeC. 264.7 g of isophorone diisocyanate (c) (molecular weight: 222.28) was slowly added dropwise to the solution so that the reaction temperature did not exceed 65 ° C. After completion of the addition, the temperature was raised to 80 ℃, by the infrared absorption spectroscopic method, 2250 cm ^- was 6 hours until the absorption of near ¹ disappears, and to 2 hours at a temperature of 98 ℃, alkaline aqueous solution-soluble The resin solution containing 60 weight% of urethane resins was obtained. The acid value was measured, resulting in 28.9 mgKOH / g (solid dispersion value: 48.1 mgKOH / g). Hereinafter, this reaction product is referred to as resin solution (A-1).

Synthesis Example 2

(A-2) Synthesis | combination of the photosensitive carboxyl group-containing urethane resin which corresponds to carboxyl group-containing resin (3) mentioned above and which has bisphenol F structure using alicyclic diisocyanate: Bisphenol F-type epoxy resin (R110, Mitsui Chemical Industries, Ltd.) Preparation, epoxy equivalent 169 g / equivalent) 169 parts (0.5 mol), 36 parts (0.5 mol) of acrylic acid, 74 parts (0.5 mol) of dimethylol butanoic acid, 0.10 parts of methylhydroquinone, 185 parts of carbitol acetate, were put into 100 degreeC. After heating and confirming that the mixture was dissolved uniformly, 3.0 parts of triethylamine was added thereto, heated to 110 ° C, and reacted for about 25 hours. Thereafter, the reaction was cooled to room temperature, 152 parts (1.0 mole) of tetrahydrophthalic anhydride was added, heated to 100 ° C, and reacted for about 5 hours to obtain an acid anhydride-modified epoxy acrylate (d). Next, 832.5 parts (3.75 mol) of isophorone diisocyanate, 747 parts (0.75 mol) of polycarbonate polyols (PMHC-1050, Kuraray Co., Ltd.), 222 parts (1.5 mol) of dimethylol butanoic acid, under a nitrogen stream atmosphere, 1662 parts of carbitol acetate and 6.5 parts of dibutyl tin dilaurylate were added, it heated at 70 degreeC and made it react for about 8 hours. After the nitrogen stream was stopped, the reaction mixture was cooled to room temperature, 2463 parts (2.0 mol) of the acid anhydride-modified epoxy acrylate (d) was added under a dry air stream atmosphere, heated to 80 ° C, and reacted for about 6 hours. . Thereafter, the reaction product was cooled to room temperature, 76 parts (0.5 mol) of tetrahydrophthalic anhydride was added, heated to 110 ° C, and reacted for about 4 hours to contain a photosensitive carboxyl group having a solid dispersion value of 93.5 mgKOH / g and a solid content concentration of 60%. Urethane resin was obtained. Hereinafter, this reaction product is referred to as resin solution (A-2).

Synthesis Example 3

(A-3) Synthesis of photosensitive carboxyl group-containing urethane resin corresponding to carboxyl group-containing resin (4) described above using alicyclic diisocyanate: 1,5-pentanediol in a reaction vessel equipped with a stirring device, a thermometer, and a capacitor And polycarbonate diols derived from 1,6-hexanediol (manufactured by Asahi Kasei Kakalz Co., Ltd., number average molecular weight 800) 2400 g (3 mol), 603 g (4.5 mol) dimethylolpropionic acid, and monohydroxyl compounds 238 g (2.6 mol) of 2-hydroxyethyl acrylate was added thereto. Subsequently, 1887 g (8.5 mol) of isophorone diisocyanates were added as a polyisocyanate, heated to 60 DEG C while stirring, and stopped, and heated again at the time when the temperature in the reaction vessel began to decrease, followed by stirring at 80 DEG C, It was confirmed that the absorption spectrum of the isocyanate group (2280 cm ^-1 ) was lost in the infrared absorption spectrum, and the reaction was terminated. Carbitol acetate was added so that solid content might be 50 mass%. The acid value of solid content of the obtained photosensitive carboxyl group-containing urethane resin was 50 mgKOH / g. Hereinafter, this reaction product is referred to as resin solution (A-3).

(A-4) Photosensitive carboxyl group-containing resin using biphenyl novolak epoxy resin which corresponds to carboxyl group-containing resin (6) mentioned above and which has a biphenyl skeleton: Nippon Kayaku Co., Ltd. product ZCR-1601H (65% of solid content resin) As an acid value, the resin solution of 98 mgKOH / g) is set to A-4.

(A-5) Photosensitive carboxyl group-containing resin using the polyfunctional epoxy resin of bisphenol F structure corresponding to carboxyl group-containing resin (7) mentioned above: Nippon Kayaku Co., Ltd. product ZFR-1124 (solid content as 63% of solid content resin is The resin solution of 102 mgKOH / g) is set to A-5.

Examples 1 to 7 and Comparative Examples 1 to 3

Using each of the resin solutions (A-1) to (A-5), after mixing with various components shown in Table 1 below in the ratio (mass part) shown in Table 1, premixing with a stirrer, triaxial It knead | mixed with the roll mill and manufactured the photosensitive resin composition for soldering resists. Here, when the dispersion degree of the obtained photosensitive resin composition was evaluated by the particle size measurement by the Eriksen company grinder, all compositions were 15 micrometers or less.

Performance rating:

<Optimal exposure amount / sensitivity>

The photosensitive resin composition of each said Example and each comparative example wash | cleans the circuit pattern board | substrate of 35 micrometers in thickness of copper, washes with water, and after drying, apply | coats to the whole surface by the screen printing method, and hot-air circulation of 80 degreeC It was dried for 60 minutes in a food dryer. After drying, exposure through a step tablet (Kodak No. 2) using a direct drawing device equipped with a semiconductor laser with a maximum wavelength of 355 nm, an exposure device equipped with a mercury short arc lamp, and a looming machine equipped with a high pressure mercury lamp. When the development was performed for 60 seconds at a spray pressure of 0.2 MPa with a 30% 1 wt% sodium carbonate aqueous solution, the optimum exposure dose was defined as the remaining six steps of the pattern of the step tablet.

<Resolution>

After buff roll polishing a circuit pattern substrate having a line / space of 300/300 µm and a copper thickness of 35 µm, washed with water and dried, the photosensitive resin compositions of the above Examples and Comparative Examples were applied by screen printing, It dried for 30 minutes in 80 degreeC hot-air circulation type drying furnace. After drying, it exposed using the direct drawing apparatus in which the semiconductor laser of the maximum wavelength of 355 nm was mounted. The exposure pattern used the data for straight drawing which draws the line of 20/30/40/50/60/70/80/90/100 micrometers in a space part. The exposure amount was irradiated with active energy rays so as to be the optimum exposure amount of the photosensitive resin composition. After exposure, image development was performed by the 30 degreeC 1 weight% sodium carbonate aqueous solution, the pattern was drawn, and the cured coating film was obtained by thermosetting 150 degreeC * 60 minutes.

The minimum residual line of the cured coating film of the obtained photosensitive resin composition for soldering resists was calculated | required using the optical microscope which adjusted 200 times.

<Absorbance>

An ultraviolet visible spectrophotometer (Ubest-V-570 DS manufactured by Nippon Bunker Co., Ltd.) and an integrating apparatus (ISN-470 manufactured by Nippon Bunker Co., Ltd.) were used for the measurement of absorbance. After the photosensitive resin composition of each said Example and each comparative example was apply | coated to the glass plate using an applicator, it dried at 80 degreeC for 30 minutes using the hot air circulation type drying furnace, and the dry coating film of the photosensitive resin composition was produced on the glass plate. Using an ultraviolet visible spectrophotometer and an integrating sphere apparatus, the absorbance baseline at 500 to 300 nm was measured with the same glass plate as the glass plate coated with the photosensitive resin composition. The absorbance of the manufactured dry coating part glass plate was measured, and the absorbance of the dry coating film was computed from the baseline, and the absorbance in the wavelength of 355 nm of the target light was obtained. In order to prevent the deviation of absorbance due to the deviation of the coating film thickness, this operation is carried out by changing the coating thickness by the applicator into four stages, a graph of the coating thickness and the absorbance at 355 nm is prepared, and from the approximation formula, the film thickness 25 The absorbance of the dry coating film of µm was calculated and taken as the respective absorbances.

Characteristic test

Evaluation board | substrate manufacturing method: The photosensitive resin composition of each said Example and each comparative example was apply | coated whole surface by the screen printing on the polyimide board | substrate with a copper circuit, dried at 80 degreeC for 20 minutes, and cooled to room temperature. The substrate was exposed to a solder resist pattern at an optimum exposure dose using an exposure apparatus equipped with a mercury short arc lamp, and developed for 30 seconds under conditions of a spray pressure of 0.2 MPa using a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. to resist A pattern was obtained. This board | substrate was heated and hardened | cured at 150 degreeC for 60 minutes. The characteristic was evaluated as follows with respect to the obtained flexible wiring board (evaluation board | substrate).

<Color of coating>

About the resist pattern of each said Example and each comparative example, the color of hardened | cured material was visually judged.

Solder Heat Resistance

The evaluation board | substrate which apply | coated rosin-type flux was immersed in the solder bath previously set to 260 degreeC, and after wash | cleaning the flux with denatured alcohol, it evaluated about swelling and peeling of the resist layer by visual observation. The criteria are as follows.

(Circle): Even if it immerses for 10 second and performs a peel test with a cellophane adhesive tape, peeling is not seen.

(Triangle | delta): When it immerses for 10 second and performs a peel test with a cellophane adhesive tape, it peels slightly.

X: When immersion for 10 second, there exists swelling and peeling in a resist layer.

Electroless Gold Plating Resistant

The evaluation board | substrate is plated on the conditions of 0.5 micrometer of nickel and 0.03 micrometer of gold using the electroless nickel plating bath and electroless gold plating bath of a commercial item, and the peeling of a resist layer or the immersion of plating by tape peeling After evaluating the presence or absence, the peeling of the resist layer was evaluated by tape peeling. The criteria are as follows.

(Circle): Penetration of plating and peeling of a resist layer are not seen.

(Triangle | delta): A very slight soaking is seen after plating, and peeling of a resist layer is seen after tape filling.

X: There exists peeling of a resist layer after plating.

<Electric corrosion resistance>

The evaluation board | substrate was manufactured on the conditions mentioned above using the comb-shaped electrode B coupon of IPC B-25 instead of the copper foil board | substrate, the bias voltage of DC100V was applied to this comb-shaped electrode, and it was made in the constant temperature and humidity chamber of 85 degreeC, 85% RH. The presence or absence of the migration after 1,000 hours was confirmed. The criteria are as follows.

○: almost no change

△: discolored

×: The migration has occurred

<Acid resistance>

Immersing the evaluation substrate vol% H ₂ SO ₄ aqueous solution of 10 to 30 minutes at room temperature, and the elution of the coating film seumyeodeulm or sulfuric acid solution, and also confirmed that the peeling of the resist layer by a tape peel. Judgment criteria are as follows.

(Circle): There is no infiltration of sulfuric acid aqueous solution, elution of a coating film, and peeling of a resist layer.

(Triangle | delta): The seepage of the sulfuric acid aqueous solution, the elution of a coating film, or peeling of a resist layer is confirmed slightly.

X: Infiltration of sulfuric acid aqueous solution, elution of a coating film, or large peeling of a resist layer are confirmed.

<Curve>

The whole surface of the photosensitive resin composition was apply | coated by screen printing on the 50-micrometer-thick polyimide film (Kapton 300H), it dried at 80 degreeC for 20 minutes, and cooled to room temperature. The substrate was exposed to a solder resist pattern at an optimum exposure dose using an exposure apparatus equipped with a mercury short arc lamp, and developed for 30 seconds under conditions of a spray pressure of 0.2 MPa using a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. to resist A pattern was obtained. This board | substrate was heated and hardened | cured at 150 degreeC for 60 minutes. The obtained film was cut out to 10 cm x 10 cm, and the amount of warpage was measured.

Moreover, the curvature amount of the film when the said film was heated again at 170 degreeC for 2 hours in the hot air drying furnace was also measured similarly. (Amount of warpage after post-heating)

The evaluation results are shown in Tables 2 and 3 below.

Example 8

<Dry Film Evaluation>

The composition used in Example 3 was diluted with methyl ethyl ketone, coated on PET film and dried at 80 ° C. for 30 minutes to form a photosensitive resin composition layer having a thickness of 25 μm. Furthermore, the cover film was bonded together on it and the dry film was obtained. Thereafter, the cover film was peeled off, and the film was thermally laminated on a copper foil substrate having a pattern formed at a circuit thickness of 35 μm, and then, on condition of 150 mj / cm 2 using a direct drawing apparatus equipped with a semiconductor laser having a maximum wavelength of 355 nm. It exposed. The carrier film was peeled off after exposure, heat-hardened for 60 minutes with the 150 degreeC hot air dryer, and the test board | substrate was manufactured. About the test board | substrate which has the obtained hardened film, the evaluation test of each characteristic was done by the above-mentioned test method and evaluation method.

As a result, a result almost identical to that of Example 3 shown in Table 3 was obtained.

As shown in Table 2 and Table 3, in Examples 1 to 7 and 8 of the present invention using an oxime ester photopolymerization initiator, it was possible to suppress the occurrence of warpage after heat curing and after post-heating. In contrast, in Comparative Examples 1 to 3 using photopolymerization initiators other than oxime esters, the occurrence of warpage after thermosetting and after heating cannot be suppressed, and in particular, photopolymerization initiators having no volatility other than oxime esters are used. In Comparative Example 2, the absorbance was high and the occurrence of warpage after post-heating was remarkable. Moreover, in Comparative Example 3 using a relatively small amount of photopolymerization initiator other than the oxime ester system, the solder heat resistance was inferior due to insufficient curing.

Claims (13)

(A) (A-1) containing at least one diisocyanate selected from aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate, and at least one carboxyl group selected from dimethylolpropionic acid and dimethylolbutanoic acid Dialcohol compound, and compound having polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A alkylene oxide adduct diol and phenolic hydroxyl group and alcoholic hydroxyl group Carboxyl group-containing urethane resin obtained by polyaddition reaction of 1 or more types of diol compounds chosen from, (A-2) diisocyanate, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, and biphenol Photosensitive carboxyl group-containing urethane resin obtained by the polyaddition reaction of the (meth) acrylate of the 1 or more bifunctional epoxy resin chosen from a type | mold epoxy resin, or its partial acid anhydride modification, a carboxyl group-containing dialcohol compound, and a diol compound, (A-3) During the synthesis of the resin of the above (A-1) or (A-2), a compound having one hydroxyl group and one or more (meth) acryl groups in a molecule which is hydroxyalkyl (meth) acrylate is added Carboxyl group-containing urethane resin which terminalized (meth) acrylication, (A-4) One isocyanate group and one or more (meth) in a molecule which is an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate during the synthesis of the resin of the above (A-1) or (A-2). The carboxyl group-containing urethane resin which added the compound which has an acryl group, and was terminal (meth) acrylated, (A-5) Photosensitive carboxyl group-containing resin obtained by making (meth) acrylic acid react with a polyfunctional (solid) epoxy resin, and adding a dibasic acid anhydride to the produced hydroxyl group, (A-6) The hydroxyl group of a bifunctional (solid) epoxy resin is further obtained by reacting (meth) acrylic acid with the polyfunctional epoxy resin epoxidized with epichlorohydrin, and adding a dibasic acid anhydride to the produced hydroxyl group. Photosensitive carboxyl group-containing resin Carboxyl group-containing resin containing at least 1 type, (B) an oxime ester photoinitiator having a group represented by the following formula (I), and (C) It is a composition which can be developed by the diluted alkali aqueous solution containing the compound which has a 2 or more ethylenically unsaturated group in a molecule | numerator, The compound (including diisocyanate) which has an isocyanate group used for the synthesis | combination of resin of said (A-1)-(A-4) is a diisocyanate which does not have a benzene ring, said (A-5) and (A The polyfunctional and bifunctional epoxy resins used for the synthesis of the resin of -6) are compounds having a linear structure having a bisphenol A skeleton, a bisphenol F skeleton, a biphenyl skeleton, a bixylenol skeleton, and a hydrogenated compound thereof, The said oxime ester type photoinitiator (B) is contained in the ratio of 0.1-1.5 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (A), The photosensitive resin composition characterized by the above-mentioned. <Formula I>

(Wherein R ¹ is a hydrogen atom, a phenyl group (may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (may be substituted with one or more hydroxyl groups, the middle of the alkyl chain) May have one or more oxygen atoms), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (which may be substituted with an alkyl or phenyl group having 1 to 6 carbon atoms), R ² may be substituted with a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups, and at least one oxygen atom in the middle of the alkyl chain; Or a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group) The photosensitive resin composition according to claim 1, wherein the oxime ester photopolymerization initiator (B) is an oxime ester photopolymerization initiator represented by the following general formula (V). (V)

The photosensitive resin composition according to claim 1, wherein the oxime ester photopolymerization initiator (B) is an oxime ester photopolymerization initiator represented by the following general formula (VI). <Formula VI>

(In formula, R <^10> is a hydrogen atom, a halogen atom, a C1-C12 alkyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, a C2-C12 alkanoyl group, a C2-C12 thing. An alkoxycarbonyl group (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups and may have one or more oxygen atoms in the middle of the alkyl chain) or a phenoxycarbonyl group, R ¹¹ and R ¹³ are each independently a phenyl group (may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (may be substituted with one or more hydroxyl groups, and in the middle of the alkyl chain May have one or more oxygen atoms), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (which may be substituted with an alkyl or phenyl group having 1 to 6 carbon atoms), R ¹² is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups, and at least one in the middle of the alkyl chain) May have an oxygen atom), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl or phenyl group having 1 to 6 carbon atoms) The photosensitive resin composition of Claim 1 which contains a photoinitiator (B1a) which volatilizes 50% or more in 150 degreeC other than the said oxime ester system photoinitiator (B) as a photoinitiator. The photosensitive resin composition of Claim 1 which further contains a thermosetting component (D). The photosensitive resin composition according to any one of claims 1 to 5, wherein the absorbance at 355 nm of the dry coating film is within a range of 0.3 to 1.2 at a dry film thickness of 25 µm. The photosensitive dry film obtained by apply | coating and drying the photosensitive resin composition of any one of Claims 1-5 to a carrier film. Hardened | cured material obtained by photocuring the photosensitive dry film obtained by apply | coating and drying the photosensitive resin composition or said composition to a carrier film in any one of Claims 1-5 on copper. Hardened | cured material obtained by photocuring the photosensitive resin composition of any one of Claims 1-5 or the said photosensitive dry film obtained by apply | coating and drying the said composition to a carrier film with a laser oscillation light source. After photocuring the photosensitive resin composition of any one of Claims 1-5 or the photosensitive dry film obtained by apply | coating and drying the said composition to a carrier film with the laser beam whose maximum wavelength is 350-410 nm, The printed wiring board which has a hardened film obtained by thermosetting. delete delete delete