KR102056819B1 - Light-curing/heat-curing resin composition, hardened material, and printed circuit board - Google Patents

Abstract

This invention provides the photocurable thermosetting resin composition which has high sensitivity with respect to light, and is hard to generate | occur | produce a developing residue even if it lengthens the drying time before exposure, the hardened | cured material containing the said composition, and the printed wiring board which has this hardened | cured material. It is a task to do it. In order to solve the said subject, in one Embodiment of this invention, (A) polyfunctional epoxy resin and radically polymerizable unsaturated monocarboxylic acid are made to react, the epoxy carboxylate which has a hydroxyl group in a side chain is produced, and this epoxy A carboxyl group-containing photosensitive resin obtained by making a carboxyl group-containing photosensitive resin (A1) react by making a carboxylate and polybasic acid anhydride react, and reacting this carboxyl group-containing photosensitive resin (A1) with the compound which has an epoxy group and a radically polymerizable unsaturated group, ( B) The photocurable thermosetting resin composition containing the polyfunctional epoxy resin of 60 degrees C or less of softening point, and (C) photoinitiator is provided.

Description

Photocurable thermosetting resin composition, hardened | cured material, and printed wiring board {LIGHT-CURING / HEAT-CURING RESIN COMPOSITION, HARDENED MATERIAL, AND PRINTED CIRCUIT BOARD}

This invention relates to a photocurable thermosetting resin composition, hardened | cured material, and a printed wiring board.

Photocurable resin compositions are known as materials for solder resists in printed wiring boards. As such a composition, the composition containing ultraviolet curable resin, a photoinitiator, a diluent, and a thermosetting resin is disclosed like patent document 1, for example. Moreover, the photocurable resin composition for direct exposure which became highly sensitive by containing an oxime ester system photoinitiator like patent document 2 is also disclosed.

Japanese Patent Laid-Open No. 10-282665 Japanese Patent Laid-Open No. 2011-22328

In photocurable resin composition, when content of an oxime ester system photoinitiator is large, for example, when the drying time before exposure becomes long, hardening reaction may advance also in an unexposed part. Moreover, hardening reaction may advance depending on environment, even after leaving the said drying and before exposure. In this case, since it cannot fully develop, the residue of a photocurable resin composition will generate | occur | produce on a circuit. When a residue has arisen, there exists a problem of being unable to perform gold plating process.

On the other hand, when content of an oxime ester system photoinitiator is made small, since the sensitivity with respect to light becomes low, there exists a problem that it cannot fully harden.

This invention provides the photocurable thermosetting resin composition which has high sensitivity with respect to light, and is hard to generate | occur | produce a developing residue even if it lengthens the drying time before exposure, the hardened | cured material containing the said composition, and the printed wiring board which has this hardened | cured material. It is a task to do it.

In order to solve the said subject, by one aspect of this invention, (A) polyfunctional epoxy resin and radically polymerizable unsaturated monocarboxylic acid are made to react, the epoxy carbonate which has a hydroxyl group in a side chain is produced, and this epoxy carbon A carboxyl group-containing photosensitive resin obtained by making a carbonate group containing photosensitive resin (A1) react by making a carbonate group and polybasic acid anhydride react, and making this carboxyl group-containing photosensitive resin (A1) react with the compound which has an epoxy group and a radically polymerizable unsaturated group, (B The photocurable thermosetting resin composition containing the polyfunctional epoxy resin of the softening point of 60 degrees C or less, and (C) photoinitiator is provided.

In one embodiment of the present invention, the photocurable thermosetting resin composition further contains a carboxyl group-containing acrylic copolymer having (D) an alicyclic skeleton.

Moreover, in another aspect of this invention, the said photocurable thermosetting resin composition contains the polyfunctional epoxy resin (B ') which softening point exceeds 60 degreeC, and the polyfunctional epoxy resin of the softening point 60 degrees C or less mentioned above ( The ratio (B1: B'1) of the epoxy group (B1) of B) and the epoxy group (B'1) of the polyfunctional epoxy resin (B ') more than softening point 60 degreeC is 3: 7-9: 1.

Moreover, in another aspect of this invention, the epoxy group (B ') of the polyfunctional epoxy resin (B) whose said softening point is 60 degrees C or less, and the polyfunctional epoxy resin (B') whose said softening point exceeds 60 degreeC (B '). The sum total of 1) is 0.8 equivalent or more and 2.2 equivalent or less with respect to 1 equivalent of carboxyl groups of the said carboxyl group-containing photosensitive resin (A).

Moreover, the hardened | cured material containing the said photocurable thermosetting resin composition is provided by another aspect of this invention.

Moreover, the printed wiring board provided with the insulating layer containing the said hardened | cured material by another aspect of this invention is provided.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a photocurable thermosetting resin composition, a cured product thereof, and a printed wiring board having the cured product, which have high sensitivity to light and are hard to generate a developing residue even if the drying time before exposure is extended. Was done. Moreover, the dry coating film formed using the photocurable thermosetting resin composition provided by this invention is also excellent in a touch drying property.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

First, the component contained in the photocurable thermosetting resin composition (henceforth a "composition of this invention", etc.) of this invention is demonstrated.

[(A) Carboxyl group-containing photosensitive resin (henceforth "photosensitive resin")]

The photosensitive resin (A) contained in the composition of this invention reacts a polyfunctional epoxy resin and a radically polymerizable unsaturated monocarboxylic acid, produces | generates the epoxy carboxylate which has a hydroxyl group in a side chain, and has the epoxy carb which has this hydroxyl group. It is a photosensitive resin obtained by making a carboxylate-containing photosensitive resin (A1) react by making a carboxylate and polybasic acid anhydride react, and making this carboxyl group-containing photosensitive resin (A1) react with the compound which has an epoxy group and a radically polymerizable unsaturated group.

[Production of Epoxycarboxylate (Hereinafter referred to as "Epoxycarboxylate") Having a hydroxyl group in the side chain]

An epoxy carboxylate is produced by making the epoxy group of a polyfunctional epoxy resin and the carboxyl group of a radically polymerizable unsaturated monocarboxylic acid react by a well-known method. In this reaction, a hydroxyl group and an ester bond are produced | generated by ring-opening the epoxy group of a polyfunctional epoxy resin.

(Polyfunctional epoxy resin)

A polyfunctional epoxy resin is resin which has two or more epoxy groups in a molecule | numerator, well-known resin can be used. In addition, the polyfunctional epoxy resin may be a hydrogenated polyfunctional epoxy resin.

As a polyfunctional epoxy resin, bisphenol A epoxy resin, bisphenol A novolak-type epoxy resin, brominated epoxy resin, phenol type epoxy resin, phenol novolak-type epoxy resin, cresol type epoxy resin, cresol novolak-type epoxy resin, bisphenol F Epoxy resin, glycidylamine epoxy resin, hydantoin epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane epoxy resin, bixylenol epoxy resin, biphenol epoxy resin, biphenol novolac epoxy Resin, bisphenol S type epoxy resin, tetraphenylolethane type epoxy resin, heterocyclic epoxy resin, diglycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin, dicyclopentadiene skeleton Epoxy resin, glycidyl methacrylate copolymer type epoxy resin, cyclohexyl maleimide and glycidyl There may be mentioned a copolymer of an epoxy resin other methacrylate, CTBN modified epoxy resins or the like.

(Radical polymerizable unsaturated monocarboxylic acid)

Although a well-known thing can be used as a radically polymerizable unsaturated monocarboxylic acid, the compound etc. which polybasic acid anhydride was added to acrylic acid, methacrylic acid, and hydroxyl-containing acrylate are mentioned, for example.

As the hydroxyl group-containing acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) Acrylate, dipentaerythritol penta (meth) acrylate, phenylglycidyl (meth) acrylate, (meth) acrylic acid caprolactone adduct and the like.

There is no restriction | limiting in particular as polybasic acid anhydride, Saturated polybasic acid anhydride and unsaturated polybasic acid anhydride can be used. As such polybasic acid anhydride, for example, methyl tetrahydro phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride, methyl hexahydro phthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydro phthalic anhydride, methylendomethylenetetrahydro Aliphatic or aromatic such as alicyclic dibasic acid anhydrides such as phthalic anhydride and tetrabromo phthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride and trimellitic anhydride And polybasic acid anhydrides. This polybasic acid anhydride can also be used individually or in mixture of 2 or more types.

As a radically polymerizable unsaturated monocarboxylic acid, acrylic acid and methacrylic acid are especially preferable. A radically polymerizable unsaturated monocarboxylic acid can be used individually or in combination of 2 or more types.

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

[Production of carboxyl group-containing photosensitive resin (A1) (hereinafter also referred to as photosensitive resin (A1))]

Photosensitive resin (A1) is obtained by making a hydroxyl group and polybasic acid anhydride which an epoxy carboxylate have react by a well-known method. In this reaction, an ester bond and free carboxyl group are produced. In addition, the hydroxyl group which an epoxy carboxylate has may contain the hydroxyl group which the polyfunctional epoxy resin originally had in addition to the hydroxyl group produced by reaction of the epoxy group of a polyfunctional epoxy resin with radically polymerizable unsaturated monocarboxylic acid. .

(Polybasic acid anhydride)

The amount of the polybasic acid anhydride used is adjusted so that the acid value of the photosensitive resin (A1) is in the range of 30 to 150 mgKOH / g, preferably 40 to 120 mgKOH / g. When the acid value of the photosensitive resin (A1) is lower than 30 mgKOH / g, solubility in aqueous alkali solution worsens, and developing of the formed coating film becomes difficult. On the other hand, when it becomes higher than 150 mgKOH / g, it develops to the surface of an exposure part irrespective of the exposure conditions, and it is unpreferable.

There is no restriction | limiting in particular as polybasic acid anhydride, For example, the compound similar to polybasic acid anhydride mentioned above can be used.

[Generation of Photosensitive Resin (A)]

The photosensitive resin (A) is produced by reacting the carboxyl group of the photosensitive resin (A1) with a compound (A2) (hereinafter also referred to as compound (A2)) having an epoxy group and a radical polymerizable unsaturated group by a known method.

In this reaction, a hydroxyl group and an ester bond are produced | generated by ring-opening the epoxy group of a compound (A2). Thereby, a radically polymerizable unsaturated group of the photosensitive resin (A) increases rather than the photosensitive resin (A1). In addition, not all carboxyl groups of the photosensitive resin (A1) react with the epoxy group of the compound (A2), but some carboxyl groups react with the epoxy group of the compound (A2).

Since the radically polymerizable unsaturated group which the photosensitive resin (A) of this invention introduce | transduced couple | bonded with the outermost part of the main chain in photosensitive resin (A1), the reactivity in the polymerization reaction of resin by light is stereochemical. It is high and has excellent photocurability.

In the present invention, as the compound (A2), for example, glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3 , 4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylbutyl (meth) acrylate, 3,4-epoxycyclohexylmethylamino acrylate, and the like. Especially, 3, 4- epoxycyclohexyl methyl (meth) acrylate is preferable. These compounds (A) may be used alone or in combination of two or more thereof.

It is preferable that acid value of the photocurable resin (A) of this invention is 40-110 mgKOH / g.

[(B) Polyfunctional Epoxy Resin of Softening Point of 60 ° C. or Less]

In the composition of this invention, the sensitivity of a composition is combined by combining the photosensitive resin (A), a photoinitiator (C), and a polyfunctional epoxy resin (B) (henceforth "epoxy resin (B)") with a softening point of 60 degrees C or less. , The composition is cured satisfactorily. Moreover, by containing an epoxy resin (B), there is no residue after image development, and developability improves. Here, a softening point means the value measured according to the method of JISK7234. As a polyfunctional epoxy resin (B) whose softening point is 60 degrees C or less, although it is well-known, you may be a liquid at room temperature of 20-30 degreeC, for example. Examples of such polyfunctional epoxy resins include bisphenol A type epoxy resins such as Epikoto 834, 828 (manufactured by Japan Epoxy Resin Corporation), YD-128 (manufactured by Toto Kasei Co., Ltd.), 840, 850 (manufactured by DIC Corporation), 806, etc. Bisphenol F epoxy resins, such as 807 (made by Japan Epoxy Resin Co., Ltd.), YDF-170 (made by Toto Kasei Co., Ltd.), 830, 835, N-730A (made by DIC Corporation), ZX-1059 (made by Toto Kasei Co., Ltd.) Hydrogenated bisphenol A type epoxy resin, such as mixture of A and bisphenol F, YX-8000, 8034 (made by Japan epoxy resin company) ST-3000 (made by Toto Kasei Co., Ltd.), RE-306CA90 by Nippon Kayaku Co., Ltd., Dow Chemical Company Novolak-type epoxy resins, such as DEN431 and DEN438, etc. are mentioned.

These polyfunctional epoxy resins can be used individually or in combination of 2 or more types.

As a molecular weight of a polyfunctional epoxy resin (B) of 60 degrees C or less of softening point, it is preferable that it is 1000 or less from a developable viewpoint, for example, it is more preferable that it is 800 or less, and it is still more preferable that it is 600 or less.

The blending ratio of the polyfunctional epoxy resin (B) having a softening point of 60 ° C. or less is preferably in the range of 1 to 2.8 equivalents relative to 1 equivalent of the carboxyl group contained in the photosensitive resin (A). 0 degreeC or more and 55 degrees C or less are preferable, and, as for the softening point in a polyfunctional epoxy resin (B), 0 degreeC or more and 50 degrees C or less are more preferable.

In one embodiment, the composition of the present invention may contain a polyfunctional epoxy resin (B ') having a softening point exceeding 60 ° C. When the polyfunctional epoxy resin (B) having a softening point of 60 ° C. or less and the polyfunctional epoxy resin (B ′) having a softening point of more than 60 ° C. are used in combination, the glass transition point (Tg) increases, so that the heat resistance is improved and the touch drying property is improved. And the effect of suppressing thermal width can be expected. The softening point in the polyfunctional epoxy resin (B ') having a softening point of more than 60 ° C is preferably 70 ° C or more, more preferably 80 ° C or more, even more preferably 90 ° C or more, particularly preferably 100 ° C or more. to be. The higher the softening point, the better the touch drying property. In addition, the softening point in a polyfunctional epoxy resin (B ') is 1000 degrees C or less, for example.

As a polyfunctional epoxy resin (B ') whose softening point is more than 60 degreeC, for example, ICTEP-S (softening point: 110 degreeC) made by Nissan Chemical Industries, Ltd., TEPIC-H, N870, JER1001 (bisphenol A made by Japan epoxy resin company), for example. Type epoxy resin (softening point: 64 degreeC)) etc. are mentioned.

When the composition of the present invention contains a polyfunctional epoxy resin (B) having a softening point of 60 ° C. or less and a polyfunctional epoxy resin (B ′) having a softening point of more than 60 ° C., the blending ratio as a total of the polyfunctional epoxy resin is photosensitive. The epoxy group is preferably in the range of 0.3 to 2.8 equivalents, and more preferably in the range of 0.8 to 2.2 equivalents, relative to 1 equivalent of the carboxyl groups contained in the resin (A). In particular, when the blending ratio is in the range of 0.8 to 2.2 equivalents, it is preferable because the touch drying property, heat resistance and insulation reliability can be improved while maintaining good sensitivity and long developing life.

Moreover, when the composition of this invention contains the polyfunctional epoxy resin (B) of 60 degreeC or less softening point, and the polyfunctional epoxy resin (B ') of more than 60 degreeC softening point, it is preferable that the compounding ratio of both resin is as follows. That is, the equivalent ratio (B1: B'1) of the epoxy group (B1) of the polyfunctional epoxy resin (B) of softening point 60 degrees C or less and the epoxy group (B'1) of the polyfunctional epoxy resin (B ') of softening point more than 60 degreeC is It is preferable that it is 3: 7-9: 1, More preferably, it is 4: 6-6: 4. When the ratio of an epoxy group (B1) is 3 or less, since a sensitivity may become low, it is not preferable.

[(C) Photopolymerization Initiator]

The composition of this invention contains a photoinitiator (C). As a photoinitiator (C), well-known and common uses, such as a benzophenone series, an acetophenone series, an amino acetophenone series, a benzoin ether system, a benzyl ketal, an acylphosphine oxide type, an oxime ether type, an oxime ester type, a titanocene type, The compound can be mentioned.

As a photoinitiator (C), it is an oxime ester system containing the structural part represented by general formula (I), and the (alpha) -amino acetophenone system containing the structural part represented by general formula (II), and general formula (III). It is preferable to contain 1 type (s) or 2 or more types chosen from the group which consists of an acyl phosphine oxide type | system | group containing the structural part shown and the titanocene type represented by general formula (IV).

R <^1> in general formula (I) represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group, or a benzoyl group. R ² represents a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group.

The phenyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, a halogen atom and the like.

As the alkyl group represented by R ¹ and R ² , an alkyl group having 1 to 20 carbon atoms is preferable, and may contain one or more oxygen atoms in the alkyl chain. Moreover, it may be substituted by one or more hydroxyl groups.

As a cycloalkyl group represented by R <^1> and R <^2> , a C5-C8 cycloalkyl group is preferable.

As an alkanoyl group represented by R <^1> and R <^2> , a C2-C20 alkanoyl group is preferable.

The benzoyl group represented by R <^1> and R <^2> may have a substituent, As this substituent, a C1-C6 alkyl group, a phenyl group, etc. are mentioned, for example.

In general formula (II), R <^3> and R <^4> respectively independently represents a C1-C12 alkyl group or an arylalkyl group, R <^5> and R <^6> respectively independently represents a hydrogen atom or a C1-C6 alkyl group, or Or two may combine to form a cyclic alkyl ether group.

R ⁷ and R ⁸ in General Formula (III) are each independently an aryl group substituted with an alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group or a halogen atom, an alkyl group or an alkoxy group, or 1 to 20 carbonyl group (except the case where both are a C1-C20 carbonyl group) is shown.

In General Formula (IV), R ⁹ and R ¹⁰ each independently represent a halogen atom, an aryl group, a halogenated aryl group, and a heterocyclic-containing halogenated aryl group.

As an oxime ester system photoinitiator containing the structural part represented by general formula (I), 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyl oxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), a compound represented by the following formula (I-1), 2- (Acetyloxyiminomethyl) thioxanthene-9-one and the compound represented by the following general formula (I-2), etc. are mentioned.

In formula (I-2), R <^11> is synonymous with R <^1> in general formula (I), R <^12> and R <^14> is respectively independently the same meaning as R <^2> in general formula (I). . R ¹³ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, and an alkoxycarbonyl group having 2 to 12 carbon atoms (alkoxy). When carbon number of the alkyl group which comprises a real group is 2 or more, an alkyl group may be substituted by 1 or more hydroxyl group, and may have 1 or more oxygen atoms in the middle of an alkyl chain), or a phenoxycarboxyl group.

Among these, the compound represented by said formula (I-1) is preferable.

Such an oxime ester photoinitiator (C) is preferable because it can raise the sensitivity of the composition of this invention with respect to the exposure light for direct imaging, and is excellent in resolution.

In particular, when exposure light is h line | wire (405 nm) of single wavelength, it is preferable that an oxime ester system photoinitiator (C) is a dimer.

As a dimer oxime ester system photoinitiator (C), it is more preferable that it is a compound represented with the following general formula (I-3).

In general formula (I-3),

R ²³ represents a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group or a naphthyl group. R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen group, a phenyl group, a naphthyl group, an anthryl group, a pyridyl group, a benzofuryl group and a benzothienyl group.

Ar is a single bond or an alkylene group having 1 to 10 carbon atoms, vinylene group, phenylene group, biphenylene group, pyridylene group, naphthylene group, anthylene group, thienylene group, furylene group, 2,5-pyrrole-di Diary, 4,4'-Stilbene-diyl group, and 4,2'-styrene-diyl group are shown.

n represents the integer of 0-1.

As an alkyl group represented by R <^23> , a C1-C17 alkyl group is preferable.

As an alkoxy group represented by R <^23> , a C1-C8 alkoxy group is preferable.

The phenyl group represented by R ²³ may have a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms), an alkoxy group (preferably having 1 to 8 carbon atoms), an amino group, and an alkylamino group ( Preferably, a C1-C8 of an alkyl group or a dialkylamino group (preferably C1-C8 of an alkyl group) etc. are mentioned.

As the naphthyl group may have a substituent may have, the substituents represented by R ^23, there may be mentioned a group of the same as those of the substituent in a phenyl group that may have represented by R ^23.

As an alkyl group represented by R <^21> and R <^22> , a C1-C17 alkyl group is preferable.

As the alkoxy group represented by R ²¹ and R ²² , an alkoxy group having 1 to 8 carbon atoms is preferable.

The phenyl group represented by R ²¹ and R ²² may have a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms), an alkoxy group (preferably having 1 to 8 carbon atoms), an amino group, Alkylamino group (preferably C1-C8 of an alkyl group) or a dialkylamino group (preferably C1-C8 of an alkyl group) etc. are mentioned.

R may be have a substituent naphthyl group represented by R ^21, and ^22, may be the substituent, R ²¹ and R ²² to a group of the same as those of the substituent in a phenyl group may have displayed by.

In addition, in general formula (I-3), R <^23> , R <^21> is respectively independently a methyl group or an ethyl group, R <^22> is methyl or phenyl, Ar is a single bond, a phenylene group, a naphthylene group, or a thienylene group And n is preferably 0.

As an alpha-amino acetophenone type photoinitiator containing the structural part represented by general formula (II), 2-methyl-1- [4- (methylthio) phenyl] -2- morpholino propane 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 an acyl phosphine oxide type photoinitiator containing the structural part represented by general formula (III), 2,4,6-trimethylbenzoyl diphenyl phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosph Fin oxide, bis (2, 6- dimethoxy benzoyl) -2, 4, 4- trimethyl- pentyl phosphine oxide, etc. are mentioned.

As the metallocene titanocene photopolymerization initiator represented by the general formula (IV), bis (η ⁵ -2,4- cyclopentadiene-1-yl) -bis (2,6-difluoro -3- (1H- pyrrol -1 -Yl) -phenyl) titanium is mentioned.

The compounding ratio of such a photoinitiator (C) becomes like this. Preferably it is 0.01-30 mass parts with respect to 100 mass parts of photosensitive resins (A), More preferably, it is the ratio of 0.5-15 mass parts. If the compounding ratio of a photoinitiator (C) is less than 0.01 mass part with respect to 100 mass parts of photosensitive resins (A), photocurability on copper may run out, a coating film may peel, or coating film characteristics, such as chemical resistance, may be unpreferable. . On the other hand, when the compounding ratio of a photoinitiator (C) exceeds 30 mass parts with respect to 100 mass parts of photosensitive resins (A), deep part sclerosis | hardenability may fall by light absorption of a photoinitiator (C), and it is unpreferable.

Moreover, when the composition of this invention contains the oxime ester system photoinitiator represented by General formula (I-1), its compounding ratio becomes like this. Preferably it is 0.01-20 mass parts with respect to 100 mass parts of photosensitive resin (A), Preferably it is the ratio of 0.01-5 mass parts. When using such an oxime ester photoinitiator, in order to improve the sensitivity with respect to exposure light, it is preferable to use together with the (alpha)-amino acetophenone system photoinitiator.

When the wavelength of the exposure light is h line (405 nm) or i line (365 nm), in the dry coating film of the composition, the absorbance at 405 nm or 365 nm is 0.4 to 1.5 at a film thickness of 10 to 20 μm, It is preferable from a viewpoint of resolution to adjust content of a photoinitiator (C).

[(D) Carboxyl group-containing acrylic copolymer having alicyclic skeleton]

The composition of this invention may contain the carboxyl group-containing acrylic copolymer (henceforth "carboxyl group-containing acrylic copolymer (D)" etc.) which have (D) alicyclic skeleton. The carboxyl group-containing acrylic copolymer (D) is a resin having at least one alicyclic skeleton in the main chain or side chain. As a carboxyl group-containing acrylic copolymer (D), a well-known thing can be used.

As a carboxyl group-containing acrylic copolymer (D), the following are mentioned, for example.

(1) a copolymer obtained by reacting an cyclic group-containing (meth) acrylic copolymer with an alicyclic compound having an epoxy group and a radical polymerizable unsaturated group in one molecule,

(2) A secondary class of epoxy carboxylate produced by this reaction by reacting an unsaturated monocarboxylic acid with a copolymer of an alicyclic compound having an epoxy group and an unsaturated double bond and a compound having an unsaturated double bond in one molecule. Photosensitive resin obtained by reacting a saturated or unsaturated polybasic anhydride with a hydroxyl group of

(3) After the saturated or unsaturated polybasic acid anhydride is reacted with the hydroxyl group-containing polymer, an alicyclic compound having one epoxy group and a radical polymerizable unsaturated double bond in each molecule is reacted with the carboxylic acid produced by this reaction. Photosensitive resin obtained.

Among these, the photosensitive resin of said (2) is preferable.

A carboxyl group-containing acrylic copolymer (D) is obtained by copolymerizing (meth) acrylic acid ester and radically polymerizable unsaturated monocarboxylic acid.

As (meth) acrylic acid ester, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, etc. (Meth) acrylic acid alkyl esters, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate Hydroxyl group-containing (meth) acrylic acid esters such as methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, and phenoxytriethylene glycol (meth) Glycol-modified (meth) acrylates such as acrylate, methoxytriethylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate; Can. These may be used independently, or may mix and use 2 or more types. In addition, the above-mentioned compound can be used as a radically polymerizable unsaturated monocarboxylic acid. Moreover, as an alicyclic compound which has one epoxy group and a radically polymerizable unsaturated double bond, it is the same as that of the compound mentioned above.

It is preferable that the acid value of a carboxyl group-containing acrylic copolymer (D) exists in the range of 50-200 mgKOH / g. When the acid value is less than 50 mgKOH / g, it is difficult to remove the unexposed portion of the coating film of the photocurable thermosetting composition by the weak alkaline aqueous solution. When the acid value exceeds 200 mgKOH / g, there are problems such as poor water resistance and electrical properties of the cured film. Moreover, it is preferable that the mass mean molecular weight of a carboxyl group-containing acrylic copolymer (D) exists in the range of 5,000-100,000. When the mass average molecular weight is less than 5,000, there is a tendency that the touch-drying property of the coating film of the photocurable thermosetting resin composition is remarkably inferior. Moreover, when a mass mean molecular weight exceeds 100,000, it is unpreferable since it produces the problem that developability and storage stability of a photocurable thermosetting composition remarkably deteriorate.

When the compounding ratio of a carboxyl group-containing acrylic copolymer (D) makes 100 mass parts total with photosensitive resin (A), it is 10-95 mass parts, for example, Preferably it is 10-50 mass parts.

[Photocurable Monomer]

The photocurable thermosetting resin composition of this invention may contain the photocurable monomer. As a photocurable monomer, the compound which has a 2 or more ethylenically unsaturated group in a molecule | numerator is preferable, The said compound is photocured by ultraviolet irradiation and insolubilizes the said carboxylic acid resin (A) in aqueous alkali solution, or is insoluble. It helps to get angry. As such a compound, Diacrylates of glycol, such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol, propylene glycol; Polyhydric acrylates such as polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or ethylene oxide adducts or propylene oxide adducts thereof; Polyhydric acrylates such as phenoxy acrylate, bisphenol A diacrylate and ethylene oxide adducts or propylene oxide adducts of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; And melamine acrylate and / or each methacrylate corresponding to the said acrylate etc. are mentioned.

Moreover, hydroxyacrylates, such as pentaerythritol triacrylate, and isophorone di are bonded to the 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. Epoxyurethane acrylate compounds etc. which further reacted the half urethane compound of diisocyanate, such as an isocyanate, are mentioned. Such epoxy acrylate-based resin can improve photocurability without deteriorating the touch dryness.

The compounding ratio of such a photocurable monomer becomes like this. Preferably it is 5-100 mass parts with respect to 100 mass parts of photosensitive resins (A), More preferably, it is the ratio of 1-70 mass parts. When the said compounding rate is less than 5 mass parts, since photocurability falls and pattern formation becomes difficult by alkali image development after ultraviolet irradiation, it is not preferable. On the other hand, when it exceeds 100 mass parts, since the solubility to aqueous alkali solution falls or a coating film falls, it is not preferable.

Thermosetting Catalyst

The photocurable thermosetting resin composition of this invention may contain the thermosetting catalyst.

As such a thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole Imidazole derivatives such as 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 acid hydrazide and sebacic acid hydrazide; As further commercially available phosphorus compounds such as triphenylphosphine, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ and 2P4MHZ (all brand names of imidazole compounds) and acids manufactured by Shikoku Kasei Co., Ltd. U-CAT3503N, U-CAT3502T (both trade names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compounds and salts thereof) manufactured by Afro Corporation, and the like. In particular, it is not limited to these, What is necessary is just to accelerate reaction of the thermosetting catalyst of an epoxy resin, or an epoxy group and a carboxyl group, and can also be used individually or in mixture of 2 or more types. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine and 2-vinyl-4,6-, which also function as an adhesion imparting agent Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-tri S-triazine derivatives, such as azine and isocyanuric acid adduct, can also be used, Preferably, the compound which functions also as these adhesive imparting agents is used together with the said thermosetting catalyst.

The mixing ratio of the thermosetting catalyst may be any ratio that is usually used. For example, the mixing ratio is 0.1 to 20 parts by mass, preferably 0.5 to 15.0 parts by mass, based on 100 parts by mass of the photosensitive resin (A) or the polyfunctional epoxy resin (B). Can be used.

[Filler]

The filler of the photocurable thermosetting resin composition of this invention can be mix | blended as needed in order to raise the physical strength of a coating film, etc. As such a filler, well-known conventional inorganic or organic filler can be used, but barium sulfate, spherical silica, and talc are especially used preferably. In addition, NANOCRYL manufactured by Hanse-Chemie (trade name) XP 0396, XP 0596, XP 0733, XP 0746, which have dispersed nanosilica in the above-mentioned photocurable monomer or (C) epoxy-based thermosetting resin. I use XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all product grade names) and Hansoku company's NANOPOX (brand name) XP 0516, XP 0525, XP 0314 (all product grade names) Can be. These may be used alone or in combination of two or more thereof.

The blending ratio of these fillers is preferably 300 parts by mass or less, more preferably 0.1 to 300 parts by mass, still more preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the photosensitive resin (A). When the compounding ratio of the said filler exceeds 300 mass parts, since the viscosity of a composition becomes high and printability falls or hardened | cured material recedes, it is unpreferable.

[solvent]

The photocurable thermosetting resin composition of this invention may contain the organic solvent, in order to adjust to the viscosity suitable for a coating method.

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, propylene glycol butyl ether acetate, and carbitol acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Aromatic 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.

[Other Ingredients]

The photocurable thermosetting resin composition of this invention is a well-known and commonly used thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, finely divided silica, organic bentonite, montmorillonite, etc., if necessary. Known thickeners, silicone-based, fluorine-based, anti-foaming agents and / or leveling agents, silane coupling agents such as imidazole-based, thiazole-based, triazole-based, blue, sulfur, red, black, white colorants, etc. Ordinary additives can be further blended.

[Manufacture of Printed Wiring Boards]

A printed wiring board has hardened | cured material containing a photocurable thermosetting composition on the base material which has a circuit pattern. Such a printed wiring board can be manufactured by the following method.

First, the photocurable thermosetting resin composition of this invention is adjusted to the viscosity suitable for the application | coating method, for example with the organic solvent, The dip coating method, the flow coating method, the spin coating method, the roll coating method, It is apply | coated by methods, such as the bar coater method, the screen printing method, the curtain coating method, and a dry coating film is formed by volatilizing (temporarily drying) the organic solvent contained in a composition at the temperature of about 60-100 degreeC. Thereafter, ultraviolet rays are selectively exposed through a photomask, and the unexposed portions are developed with a dilute alkaline aqueous solution (for example, 0.3 to 3% aqueous sodium carbonate solution) to form a cured product having a pattern.

As a base material, the copper clad laminated board for high frequency circuits using paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / nonwoven fabric epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluorine polyethylene PPO cyanate ester, etc. The copper clad laminated board of all grades (FR-4 etc.), another polyimide film, PET film, a glass substrate, a ceramic substrate, a wafer board etc. are mentioned using materials, such as these.

In the present invention, the volatilization drying after the photocurable thermosetting resin composition is applied is hot air circulation drying, using an IR plate, a hot plate, a convection oven, or the like (with a heat source of air heating by steam). And a method of bringing hot air in the dryer into countercurrent contact and a method of spraying from the nozzle to the support. As an exposure machine used for the said ultraviolet irradiation, the exposure apparatus which generate | occur | produces an ultraviolet-ray should just be sufficient.

As a light source, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, etc. are preferable. Examples of the exposure apparatus include HMW-680GW manufactured by Oak Co., Ltd. and ADEX600P manufactured by Adtech Engineering Co., Ltd., and the like can be used in the present invention. In addition, as an exposure apparatus for direct imaging exposing at a single wavelength, such as 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), a (super) high pressure mercury lamp, etc. A direct drawing device using an ultraviolet lamp can be used. As such a direct drawing apparatus, things, such as the Nippon Orbotech company make and oak company make, can be used, for example.

Examples of the developing method include a dipping method, a shower method, a spray method, a brush method, and the like, and the developing solution includes potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and tetramethylammonium hydrooxide. Alkali aqueous solution can be used.

Moreover, the printed wiring board which has hardened | cured material can also be manufactured by affixing the dry film which apply | coated the photocurable thermosetting resin composition of this invention on a carrier film, and drying it on the base material on which the circuit pattern was formed.

Although the photocurable thermosetting resin composition of this invention is suitable as a permanent film material of a printed wiring board, it is suitable as a soldering resist material and an interlayer insulation material among them.

Example

Hereinafter, although an Example and a comparative example are described and this invention is demonstrated concretely, of course, this invention is not limited to the following. In addition, below, "part" and "%" represent a "mass part" and the "mass%" unless there is particular notice.

[Synthesis of Photosensitive Resin]

Synthesis Example 1 Photosensitive Resin (A1-1)

600 g of diethylene glycol monoethyl ether acetate orthocresol novolac-type epoxy resins (manufactured by DIC Corporation, EPICLON N-695, softening point 95 ° C, epoxy equivalent 214, average functional group 7.6) 1070 g (glycidyl Radix (total number of aromatic rings): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were thrown in, and it heated and stirred at 100 degreeC, and melt | dissolved uniformly.

Subsequently, 4.3 g of triphenylphosphines were added, it heated at 110 degreeC, after reaction for 2 hours, it heated up at 120 degreeC and reacted again for 12 hours. 415 g of aromatic hydrocarbon (Solvso 150) and 456.0 g (3.0 mol) of tetrahydro phthalic anhydride were added to the obtained reaction liquid, reaction was performed at 110 degreeC for 4 hours, it cooled, and a carboxyl group-containing photosensitive resin solution (A1) was made into Got it.

Thus, the solid content (quantity except a solvent) of the obtained photosensitive resin solution (A1) was 65%, and the acid value of solid content was 89 mgKOH / g.

Synthesis Example 2: Photosensitive Resin (A-1)

700 g of diethylene glycol monoethyl ether acetate orthocresol novolac-type epoxy resins (manufactured by DIC Corporation, Epiclone N-695, softening point 95 deg. C, epoxy equivalent 214, average functional number 7.6) 1070 g (glycidyl group (direction Ring total number): 5.0 mol), acrylic acid 360g (5.0 mol) and hydroquinone 1.5g were thrown in, and it heated and stirred at 100 degreeC, and melt | dissolved uniformly.

Subsequently, 4.3 g of triphenylphosphines were added, and it heated at 110 degreeC, and after reaction for 2 hours, 1.6 g of triphenylphosphines were further added, it heated up at 120 degreeC, and reacted again for 12 hours. 562 g of aromatic hydrocarbon (Solvso 150) and 684 g (4.5 mol) of tetrahydro phthalic anhydride were added to the obtained reaction liquid, and reaction was performed at 110 degreeC for 4 hours. Furthermore, 142.0 g (1.0 mol) of glycidyl methacrylates were thrown into the obtained reaction liquid, and it reacted at 115 degreeC for 4 hours, and obtained the carboxyl group-containing photosensitive resin solution (A-1).

Thus, the solid content of the obtained photosensitive resin solution (A-1) was 65%, and the acid value of solid content was 87 mgKOH / g.

[Production of Photocurable Thermosetting Resin Composition]

The compounding component and the following common component shown in Table 1 were knead | mixed with the triaxial roll mill, and the photocurable thermosetting resin composition was obtained. In addition, in Table 1, content of each component of (A), (B), and (D) is solid content except a solvent.

<Photosensitive resin (A)>

A-2: SP-3900 (made by Showa Denko Corporation, 65% of solid content, acid value: 70 mgKOH / g) <polyfunctional epoxy resin>

B-1: Bisphenol A type epoxy resin (834: Japan epoxy resin company make, epoxy equivalent 250, normal temperature semisolid, softening point 60 degrees C or less, molecular weight 470)

B-2: Polyglycidyl ether of phenol novolak (RE306CA90: Nippon Kayaku Co., Ltd., epoxy equivalent 196, softening point 50 degreeC, molecular weight 400)

B-3: A phenol novolak-type epoxy resin (DEN431: Dow Chemical company, epoxy equivalent 174, normal temperature semisolid, softening point 60 degrees C or less, molecular weight 400)

B-4: Phenol novolak-type epoxy resin (DEN438: Dow Chemical company make, Epoxy equivalent 199, Softening point 40 degreeC, Molecular weight 600)

B-5: Bisphenol A novolak-type epoxy resin (Epiclon N-870: DIC Corporation make, epoxy equivalent 205, softening point 70 degreeC, molecular weight 1600)

B-6: ICTEP-S (made by Nissan Chemical Industries, Epoxy equivalent 100, Softening point 110 degreeC)

<(C) Photoinitiator>

C-1: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one

C-2:

<(D) Carboxyl group-containing acrylic copolymer>

D-1: Cycloma P (ACA) Z250 (manufactured by Daicel Chemical Industries, Ltd., solid content 45%) (carboxyl group-containing acrylic copolymer having an alicyclic skeleton)

D-2: Cychroma P (ACA) Z320 (manufactured by Daicel Chemical Industries, Ltd., solid content 40%) (carboxyl group-containing acrylic copolymer having an alicyclic skeleton)

D-3: VB-5301, styrene copolymerization (manufactured by Mitsubishi Rayon Co., Ltd., solid content 50%) (copolymer without alicyclic skeleton)

[Common Components (Numeric Values)]

(Filler)

Barium sulfate (B-30 manufactured by Kaga Kagaku Co., Ltd.): 100 parts

Talc: Part 10

Silica: 10 parts

(Photocurable monomer)

Dipentaerythritol hexaacrylate: 30 parts

(Thermal curing catalyst)

Dicyandiamide: 0.3 part

Melamine: part three

(Defoamer, colorant, solvent)

Silicone antifoam: 3 parts

Phthalocyanine Blue: Part 2

Aromatic Petroleum Solvents: 10 parts

[Evaluation Methods of Examples 1 to 18 and Comparative Examples 1 and 2]

<Sensitivity: Curable>

After scrub polishing, the entire surface of the photocurable thermosetting resin composition prepared as described above was printed on a circuit pattern substrate having a thickness of 35 µm washed with water and dried by a screen printing method, followed by 30 minutes in a hot air circulation drying furnace at 80 ° C. Dried. This obtained the dry coating film of a photocurable thermosetting resin composition. This dry coating film was 15 micrometers in thickness, and absorbance was 0.8.

Of the dried coating film, using the exposure apparatus equipped with a metal halide lamp, and exposed through a step tablet (Stuffer 41 stage), the developer (1 wt% Na ₂ CO ₃ aqueous solution, 30 ℃, 0.2MPa) for 60 seconds when the line The remaining step tablet pattern was read. When the sensitivity is 7 or more, it is understood that the photocurable resin composition can be sufficiently cured because the sensitivity is high.

Maximum Developing Life: Ease of Residue

After scrub polishing, the whole surface of the photocurable thermosetting resin composition manufactured as mentioned above by screen printing was apply | coated to the circuit pattern board | substrate of water wash and dried copper thickness 35micrometer. When the board | substrate was put into 80 degreeC hot-air circulation type drying oven and dried, the longest time which the developing defect by a heat width does not produce was investigated. Specifically, it dried at 80 degreeC for 30, 40, 50, and 60 minutes, developed on the above-mentioned developing conditions, and tested the development of each time. At this time, the copper phase was visually observed, and if the component of the photocurable thermosetting resin composition did not remain as a residue, image development was possible and this time was described. This is called drying control width, and the longer the drying time, the better the productivity.

<Touch dryness>

After scrub polishing, the whole surface of the photocurable thermosetting resin composition manufactured as mentioned above by screen printing was apply | coated to the circuit pattern board | substrate of water-washed and dried copper thickness 35 micrometers. The board | substrate was put into 80 degreeC hot air circulation drying furnace, and it dried for 40 minutes. After drying, the negative pattern film (negative film) was mounted on the dry coating film, and it exposed using the exposure apparatus mounted with a metal halide lamp. Specifically, the cured film was obtained by irradiating so that the accumulated exposure amount might be set to 50 mJ / cm <2> with respect to the dry coating film under a negative film. When peeling a negative film from a cured film, the presence or absence of a negative film mark was confirmed. When there is no negative film mark, the touch drying property of a dry coating film becomes good. On the other hand, when there is a negative film mark in a cured film, the touch drying property of a dry coating film becomes bad.

In addition, when the dryness of the dry coating film is poor, handling becomes difficult at the time of conveyance of the substrate or adsorption marks of the exposure stage may occur, and therefore, the dryness characteristic of the touch is required.

○: no negative film marks

△: with negative film marks

X: It adhere | attaches to a negger film and peels off a dry coating film

<Heat resistance>

After scrub polishing, the entire surface of the photocurable thermosetting resin composition prepared as described above was printed on a circuit pattern substrate having a thickness of 35 µm by washing with water and dried by screen printing, It was dried for a minute. This obtained the dry coating film of a photocurable thermosetting resin composition.

Of the dried coating film, using the exposure apparatus of the metal halide lamp with a step tablet (Stuffer 41 column) 8-stage exposure is obtained by exposure and developing (1 wt% Na ₂ CO ₃ aqueous solution, 30 ℃, 0.2MPa) by It carried out for 60 seconds, and also the hardened coating film was produced by thermosetting 150 degreeC and 60 minutes.

The evaluation board | substrate which apply | coated the water-soluble flux to the obtained cured coating film was immersed in the solder tank set previously to 260 degreeC, and after wash | cleaning the flux with the hot water of about 50 degreeC, it evaluated visually about expansion and peeling of a cured coating film. Judgment criteria are as follows.

(Circle): Peeling was not confirmed after immersion for 10 second.

(Triangle | delta): After immersion for 10 second, a resist layer is whitened.

X: After immersion for 10 seconds, a resist layer swells and peels

Insulation Reliability

After scrub polishing, the entire surface of the photocurable thermosetting resin composition prepared as described above was printed on a substrate having a copper thickness of 18 µm by a washed, dried line / space = 100/100 comb electrode pattern by screen printing. Then, it dried in the 80 degreeC hot air circulation type drying furnace for 30 minutes, and obtained the dry coating film of the photocurable thermosetting resin composition by this.

Of the dried coating film, using the exposure apparatus of the metal halide lamp with a step tablet (Stuffer 41 column) 8-stage exposure is obtained by exposure and developing (1 wt% Na ₂ CO ₃ aqueous solution, 30 ℃, 0.2MPa) by It carried out for 60 seconds, and also the hardened coating film was produced by thermosetting 150 degreeC and 60 minutes.

A bias voltage of DC30V was applied to this comb-shaped electrode, and the insulation resistance value and corrosion after 1000 hours were evaluated, humidifying at 80 degreeC and 80%. Judgment criteria are as follows.

○: The insulation resistance value is 1 × 10 ¹² Ω or more. Corrosion is not seen.

(Triangle | delta): Insulation resistance value is 1 * 10 <^9> or more and less than 1 * 10 <^12> . Corrosion is seen.

X: The insulation resistance value is less than 1x10 ⁹ Ω. Corrosion is seen.

[Evaluation Method of Examples 19 and 20]

Using the composition of Table 2, it evaluated similarly to Example 1 except having changed the exposure apparatus with a metal halide lamp into the exposure apparatus with 405 nm single laser mounting. The results are shown in the same table.

Claims (6)

(A) Polyfunctional epoxy resin and radically polymerizable unsaturated monocarboxylic acid are made to react, the epoxy carboxylate which has a hydroxyl group in a side chain is produced, this epoxy carboxylate and polybasic acid anhydride are made to react, and a carboxyl group-containing photosensitive resin ( Carboxyl group-containing photosensitive resin obtained by producing | generating A1) and making this carboxyl group-containing photosensitive resin (A1) react with the compound which has an epoxy group and a radically polymerizable unsaturated group,
(B) a polyfunctional epoxy resin having a softening point of 60 ° C. or less,
(B ') a polyfunctional epoxy resin having a softening point greater than 60 ° C, and
(C) photopolymerization initiator
It is a photocurable thermosetting resin composition containing,
The total blending ratio of the polyfunctional epoxy resin (B) having the softening point of 60 ° C. or less and the polyfunctional epoxy resin (B ′) of the softening point of more than 60 ° C. per 1 equivalent of the carboxyl group contained in the carboxyl group-containing photosensitive resin (A) The epoxy group is a range of 0.8 to 2.2 equivalents. Photocurable thermosetting resin composition characterized by the above-mentioned. The photocurable thermosetting resin composition according to claim 1, further comprising (D) a carboxyl group-containing acrylic copolymer having an alicyclic skeleton. The ratio of the epoxy group (B1) of the polyfunctional epoxy resin (B) having the softening point of 60 ° C. or less and the epoxy group (B ′ 1) of the polyfunctional epoxy resin (B ′) of the softening point of more than 60 ° C. It is 3: 7-9: The photocurable thermosetting resin composition characterized by the above-mentioned. The dry film provided with a carrier film and the dry coating film of the photocurable thermosetting resin composition of any one of Claims 1-3 on this carrier film. Hardened | cured material containing the photocurable thermosetting resin composition of any one of Claims 1-3. It has the hardened | cured material of Claim 5, The printed wiring board characterized by the above-mentioned.