WO2013162015A1

WO2013162015A1 - Light-curing/heat-curing resin composition, hardened material, and printed circuit board

Info

Publication number: WO2013162015A1
Application number: PCT/JP2013/062448
Authority: WO
Inventors: 千穂植田
Original assignee: 太陽インキ製造株式会社
Priority date: 2012-04-27
Filing date: 2013-04-26
Publication date: 2013-10-31
Also published as: JPWO2013162015A1; JP5690973B2; CN104115066B; KR20150005907A; CN104115066A; KR102056819B1

Abstract

The present invention addresses the problem of providing a light-curing/heat-curing resin composition with high sensitivity to light and minimal generation of development residue even if the drying time is extended before exposure to light, a hardened material comprising the composition, and a printed circuit board having the hardened material. In order to overcome the problem, an embodiment of the present invention provides a light-curing/heat-curing resin composition characterized in containing: (A) a carboxyl-containing photosensitive resin obtained by reacting a multifunctional epoxy resin and a radical-polymerizable unsaturated monocarboxylic acid to generate an epoxy carboxylate having a side-chain hydroxyl, reacting the epoxy carboxylate with a polybasic acid anhydride to generate a carboxyl-containing photosensitive resin (A1), and reacting the carboxyl-containing photosensitive resin (A1) with a compound having an epoxy group and a radical-polymerizable unsaturated group; (B) a multifunctional epoxy resin having a hardening point no higher than 60°C; and (C) a photopolymerization initiator.

Description

Photo-curing thermosetting resin composition, cured product, and printed wiring board

The present invention relates to a photocurable thermosetting resin composition, a cured product, and a printed wiring board.

A photo-curable resin composition is known as a material for a solder resist of a printed wiring board. As such a composition, for example, as disclosed in Patent Document 1, a composition containing an ultraviolet curable resin, a photopolymerization initiator, a diluent, and a thermosetting resin is disclosed. Further, as disclosed in Patent Document 2, a photo-curable resin composition for direct exposure that has been made highly sensitive by containing an oxime ester photopolymerization initiator is also disclosed.

JP-A-10-282665 JP 2011-22328 A

In the photocurable resin composition, for example, when the content of the oxime ester-based photopolymerization initiator is large, the curing reaction may proceed even in an unexposed portion when the drying time before exposure becomes long. In addition, the curing reaction may proceed depending on the environment even during the standing after the drying and before the exposure. In this case, since it cannot develop sufficiently, a residue of the photocurable resin composition is generated on the circuit. When the residue is generated, there is a problem that the gold plating process cannot be performed.

On the other hand, when the content of the oxime ester-based photopolymerization initiator is reduced, there is a problem in that it cannot be cured sufficiently because the sensitivity to light is lowered.

The present invention relates to a photocurable thermosetting resin composition that is highly sensitive to light and hardly generates a development residue even if the drying time before exposure is prolonged, a cured product comprising the composition, and the cured product It is an object to provide a printed wiring board having the following.

In order to solve the above problems, according to one embodiment of the present invention, (A) a polyfunctional epoxy resin and a radically polymerizable unsaturated monocarboxylic acid are reacted to produce an epoxy carbolate having a hydroxyl group in a side chain. An epoxy carboxylate and a polybasic acid anhydride are reacted to produce a carboxyl group-containing photosensitive resin (A1), which has the carboxyl group-containing photosensitive resin (A1), an epoxy group, and a radically polymerizable unsaturated group. A photocurable thermosetting comprising a carboxyl group-containing photosensitive resin obtained by reacting a compound, (B) a polyfunctional epoxy resin having a softening point of 60 ° C. or lower, and (C) a photopolymerization initiator. A functional resin composition is provided.

In one embodiment of the present invention, the photocurable thermosetting resin composition further contains (D) a carboxyl group-containing acrylic copolymer having an alicyclic skeleton.
In another embodiment of the present invention, the photocurable thermosetting resin composition further contains a polyfunctional epoxy resin (B ′) having a softening point exceeding 60 ° C., and has a softening point of 60 ° C. or lower. The ratio (B1: B′1) of the epoxy group (B1) of the polyfunctional epoxy resin (B) to the epoxy group (B′1) of the polyfunctional epoxy resin (B ′) having a softening point higher than 60 ° C. is 3: 7-9: 1.

In another embodiment of the present invention, the epoxy group (B1) of the polyfunctional epoxy resin (B) having a softening point of 60 ° C. or lower and the epoxy of the polyfunctional epoxy resin (B ′) having a softening point exceeding 60 ° C. The sum total of group (B'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 which consists of the said photocurable thermosetting resin composition is provided by the other aspect of this invention.
Moreover, the printed wiring board which comprises the insulating layer which consists of the said hardened | cured material is provided by the other aspect of this invention.

INDUSTRIAL APPLICABILITY According to the present invention, a photocurable thermosetting resin composition that has high sensitivity to light and hardly generates a development residue even if the drying time before exposure is increased, a cured product thereof, and a print having the cured product. Wiring boards can be provided. Moreover, the dry coating film formed using the photocurable thermosetting resin composition provided by this invention is excellent also in finger-drying property.

Hereinafter, the present invention will be described in detail.
First, the components contained in the photocurable thermosetting resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) will be described.

[(A) carboxyl group-containing photosensitive resin (hereinafter also referred to as “photosensitive resin”)]
The photosensitive resin (A) contained in the composition of the present invention reacts with a polyfunctional epoxy resin and a radically polymerizable unsaturated monocarboxylic acid to produce an epoxy carboxylate having a hydroxyl group in the side chain. The carboxyl group-containing photosensitive resin (A1) is produced by reacting an epoxycarboxylate having a polybasic acid anhydride with the carboxyl group-containing photosensitive resin (A1), and an epoxy group and a radically polymerizable unsaturated group. It is the photosensitive resin obtained by making the compound which has this react.

[Generation of Epoxy Carboxylate Having Hydroxyl Group in Side Chain (hereinafter, also referred to as “Epoxy Carboxylate”)]
Epoxy carboxylate is produced by reacting an epoxy group of a polyfunctional epoxy resin with a carboxyl group of a radically polymerizable unsaturated monocarboxylic acid by a known method. In this reaction, the epoxy group of the polyfunctional epoxy resin is ring-opened to generate a hydroxyl group and an ester bond.

(Polyfunctional epoxy resin)
The polyfunctional epoxy resin is a resin having two or more epoxy groups in the molecule, and a known resin can be used. The polyfunctional epoxy resin may be a hydrogenated polyfunctional epoxy resin.

Polyfunctional epoxy resins include bisphenol A type epoxy resin, bisphenol A novolak type epoxy resin, brominated epoxy resin, phenol type epoxy resin, phenol novolac type epoxy resin, cresol type epoxy resin, cresol type novolak type epoxy resin, bisphenol F Type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, biphenol novolac type epoxy resin, bisphenol S type epoxy Resin, tetraphenylol ethane type epoxy resin, heterocyclic epoxy resin, diglycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin Naphthalene group-containing epoxy resin, an epoxy resin having a dicyclopentadiene skeleton, glycidyl methacrylate copolymerization system epoxy resins, copolymerized epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, and a CTBN modified epoxy, and the like.

(Radically polymerizable unsaturated monocarboxylic acid)
As the radically polymerizable unsaturated monocarboxylic acid, known compounds can be used, and examples thereof include a compound obtained by adding a polybasic acid anhydride to acrylic acid, methacrylic acid, or a hydroxyl group-containing acrylate.

Hydroxyl group-containing acrylates include 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.

The polybasic acid anhydride is not particularly limited, and either a saturated polybasic acid anhydride or an unsaturated polybasic acid anhydride can be used. Examples of such polybasic acid anhydrides include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, and 3,6-endomethylenetetrahydrophthalic anhydride. , Cycloaliphatic dibasic anhydrides such as methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, Examples include aliphatic or aromatic polybasic acid anhydrides such as trimellitic anhydride. These polybasic acid anhydrides may be used alone or in admixture of two or more.

As the radical polymerizable unsaturated monocarboxylic acid, acrylic acid and methacrylic acid are particularly preferable. The radically polymerizable unsaturated monocarboxylic acid can be used alone or in combination of two or more.

In addition, in this specification, (meth) acrylate is a term that collectively refers to acrylate and methacrylate, and the same applies to other similar expressions.

[Generation of carboxyl group-containing photosensitive resin (A1) (hereinafter also referred to as photosensitive resin (A1))]
The photosensitive resin (A1) is obtained by reacting a hydroxyl group of the epoxy carboxylate with a polybasic acid anhydride by a known method. In this reaction, an ester bond and a free carboxyl group are formed. The hydroxyl group of the epoxy carboxylate is not limited to the hydroxyl group produced by the reaction between the epoxy group of the polyfunctional epoxy resin and the radical polymerizable unsaturated monocarboxylic acid, but the hydroxyl group originally possessed by the polyfunctional epoxy resin. It may be included.

(Polyacid 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, the solubility in an alkaline aqueous solution is deteriorated, and development of the formed coating film is difficult. On the other hand, if it is higher than 150 mgKOH / g, the surface of the exposed area is developed regardless of the exposure conditions, which is not preferable.

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

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

In this reaction, the epoxy group of the compound (A2) is opened to form a hydroxyl group and an ester bond. Thereby, the photosensitive resin (A) has more radical polymerizable unsaturated groups than the photosensitive resin (A1). Note that not all carboxyl groups of the photosensitive resin (A1) react with the epoxy group of the compound (A2), but some of the carboxyl groups react with the epoxy group of the compound (A2).

In the photosensitive resin (A) of the present invention, the introduced radically polymerizable unsaturated group is bonded to the outermost part of the main chain of the photosensitive resin (A1), so that the reactivity in the polymerization reaction of the resin by light is performed. Is stereochemically high and has excellent photocurability.

In the present invention, examples of the compound (A2) include glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 3,4-epoxycyclohexylethyl (meth). Examples thereof include acrylate, 3,4-epoxycyclohexylbutyl (meth) acrylate, 3,4-epoxycyclohexylmethylamino acrylate, and the like. Of these, 3,4-epoxycyclohexylmethyl (meth) acrylate is preferred. Such a compound (A) may be used independently or may be used in mixture of 2 or more types.

The acid curable resin (A) of the present invention preferably has an acid value of 40 to 110 mgKOH / g.

[(B) Polyfunctional epoxy resin having a softening point of 60 ° C. or lower]
In the composition of the present invention, a photosensitive resin (A), a photopolymerization initiator (C), and a polyfunctional epoxy resin (B) having a softening point of 60 ° C. or lower (hereinafter also referred to as “epoxy resin (B)”). By combining these, the sensitivity of the composition can be increased, and the composition is cured well. Moreover, by containing an epoxy resin (B), there is no residue after image development and developability is improved. Here, the softening point means a value measured according to the method described in JIS K 7234. The polyfunctional epoxy resin (B) having a softening point of 60 ° C. or lower may be a known one, but is preferably liquid at room temperature of 20 to 30 ° C., for example. Examples of such polyfunctional epoxy resins include bisphenol A such as Epicoat 834 and 828 (manufactured by Japan Epoxy Resin), YD-128 (manufactured by Tohto Kasei Co., Ltd.), 840 and 850 (manufactured by DIC). Type epoxy resin, 806, 807 (manufactured by Japan Epoxy Resin Co., Ltd.), YDF-170 (manufactured by Tohto Kasei Co., Ltd.), 830, 835, N-730A (manufactured by DIC Co., Ltd.), ZX-1059 (Toto A mixture of bisphenol A and bisphenol F such as YX-8000, 8034 (manufactured by Japan Epoxy Resin) ST-3000 (manufactured by Toto Kasei), such as Nippon Kayaku Co., Ltd. Novolaks such as RE-306CA90 of DEN431, DEN431 and DEN438 manufactured by Dow Chemical Type epoxy resin.

These polyfunctional epoxy resins can be used alone or in combination of two or more.

The molecular weight of the polyfunctional epoxy resin (B) having a softening point of 60 ° C. or lower is preferably 1000 or lower, more preferably 800 or lower, and even more preferably 600 or lower, from the viewpoint of developability. preferable.

The blending ratio of such a polyfunctional epoxy resin (B) having a softening point of 60 ° C. or lower is preferably 1 to 2.8 equivalents of epoxy groups with respect to 1 equivalent of carboxyl groups contained in the photosensitive resin (A). It is a range. The softening point in the polyfunctional epoxy resin (B) is preferably 0 ° C. or higher and 55 ° C. or lower, and more preferably 0 ° C. or higher and 50 ° C. or lower.

In one embodiment, the composition of the present invention may contain a polyfunctional epoxy resin (B ′) having a softening point exceeding 60 ° C. Since the glass transition point (Tg) is increased by using the polyfunctional epoxy resin (B) having a softening point of 60 ° C. or less and the polyfunctional epoxy resin (B ′) having a softening point exceeding 60 ° C., heat resistance is improved. It can be expected to improve the dryness of the touch and to suppress the heat covering. 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, still more preferably 90 ° C. or more, and particularly preferably 100 ° C. or more. The higher the softening point, the better the touch dryness. The softening point in the polyfunctional epoxy resin (B ′) is, for example, 1000 ° C. or less.

As such a polyfunctional epoxy resin (B ′) having a softening point exceeding 60 ° C., for example, ICTEP-S (softening point: 110 ° C.), TEPIC-H, N870 manufactured by Nissan Chemical Co., Ltd., manufactured by Japan Epoxy Resin Co., Ltd. JER1001 (bisphenol A type epoxy resin (softening point: 64 ° C.)).

As the sum of the polyfunctional epoxy resins when the composition of the present invention contains a polyfunctional epoxy resin (B) having a softening point of 60 ° C. or lower and a polyfunctional epoxy resin (B ′) having a softening point exceeding 60 ° C. The blending ratio of the epoxy group is preferably in the range of 0.3 to 2.8 equivalents, more preferably 0.8 to 2.2, with respect to 1 equivalent of the carboxyl group contained in the photosensitive resin (A). The range is 2 equivalents. In particular, when the blending ratio is in the range of 0.8 to 2.2 equivalents, it is possible to improve touch drying, heat resistance and insulation reliability while maintaining good sensitivity and a long development life. preferable.

Moreover, when the composition of this invention contains the polyfunctional epoxy resin (B) with a softening point of 60 degrees C or less and the polyfunctional epoxy resin (B ') with a softening point of over 60 degrees C, the compounding ratio of both resin is the following. It is preferable that it is as follows. That is, the equivalent ratio (B1) of the epoxy group (B1) of the polyfunctional epoxy resin (B) having a softening point of 60 ° C. or less and the epoxy group (B′1) of the polyfunctional epoxy resin (B ′) having a softening point of more than 60 ° C. : B′1) is preferably from 3: 7 to 9: 1, more preferably from 4: 6 to 6: 4. When the ratio of the epoxy group (B1) is 3 or less, the sensitivity may be lowered, which is not preferable.

[(C) Photopolymerization initiator]
The composition of the present invention contains a photopolymerization initiator (C). As the photopolymerization initiator (C), known and commonly used compounds such as benzophenone, acetophenone, aminoacetophenone, benzoin ether, benzyl ketal, acylphosphine oxide, oxime ether, oxime ester, and titanocene are used. Can be mentioned.

Examples of the photopolymerization initiator (C) include an oxime ester type containing a structural part represented by the general formula (I), an α-aminoacetophenone type containing a structural part represented by the general formula (II), and a general formula (III It is preferable to contain 1 type (s) or 2 or more types selected from the group which consists of the acyl phosphine oxide type | system | group containing the structural part represented by this, and the titanocene system represented by general formula (IV).

In general formula (I), R ¹ 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, and a halogen atom.

The alkyl group represented by R ¹ and R ² is preferably an alkyl group having 1 to 20 carbon atoms, and may contain one or more oxygen atoms in the alkyl chain. Further, it may be substituted with one or more hydroxyl groups.
The cycloalkyl group represented by R ¹ and R ² is preferably a cycloalkyl group having 5 to 8 carbon atoms.
The alkanoyl group represented by R ¹ and R ² is preferably an alkanoyl group having 2 to 20 carbon atoms.
The benzoyl 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 and a phenyl group.

In the general formula (II), R ³ and R ⁴ each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group, and R ⁵ and R ⁶ each independently represent a hydrogen atom or a carbon number 1 to 6 alkyl groups may be represented, or two may combine to form a cyclic alkyl ether group.

In general formula (III), R ⁷ and R ⁸ are each independently an alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl substituted with a halogen atom, an alkyl group or an alkoxy group. Group, or a carbonyl group having 1 to 20 carbon atoms (except when both are carbonyl groups having 1 to 20 carbon atoms).

In general formula (IV), R ⁹ and R ¹⁰ each independently represent a halogen atom, an aryl group, a halogenated aryl group, or a heterocycle-containing halogenated aryl group.

Examples of the oxime ester photopolymerization initiator containing a structural moiety represented by the general formula (I) include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone , 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), a compound represented by the following formula (I-1), 2 And-(acetyloxyiminomethyl) thioxanthen-9-one, and compounds represented by the following general formula (I-2).

In formula (I-2), R ¹¹ has the same meaning as R ¹ in general formula (I), and R ¹² and R ¹⁴ each independently have 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, or an alkoxy group having 2 to 12 carbon atoms. A carbonyl 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 has one or more oxygen atoms in the middle of the alkyl chain) Or a phenoxycarboxylic group.

Of these, compounds represented by the above formula (I-1) are preferred.

Such an oxime ester photopolymerization initiator (C) is preferable because it can increase the sensitivity of the composition of the present invention to exposure light for direct imaging and has excellent resolution.

In particular, when the exposure light is a single wavelength h ray (405 nm), the oxime ester photopolymerization initiator (C) is preferably a dimer.

The dimer oxime ester photopolymerization initiator (C) is more preferably a compound represented by 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, or 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, anthrylene group, thienylene group, furylene group, 2,5-pyrrole-diyl group, It represents a 4,4′-stilbene-diyl group or a 4,2′-styrene-diyl group.
n represents an integer of 0 to 1.

The alkyl group represented by R ²³ is preferably an alkyl group having 1 to 17 carbon atoms.

The alkoxy group represented by R ²³ is preferably an alkoxy group having 1 to 8 carbon atoms.
The phenyl group represented by R ²³ may have a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms) and an alkoxy group (preferably having 1 to 8 carbon atoms). ), An amino group, an alkylamino group (preferably an alkyl group having 1 to 8 carbon atoms) or a dialkylamino group (preferably an alkyl group having 1 to 8 carbon atoms).

The naphthyl group represented by R ²³ may have a substituent, and examples of the substituent include the same groups as the above-described substituent that the phenyl group represented by R ²³ may have.

The alkyl group represented by R ²¹ and R ²² is preferably an alkyl group having 1 to 17 carbon atoms.
The alkoxy group represented by R ²¹ and R ²² is preferably an alkoxy group having 1 to 8 carbon atoms.
The phenyl group represented by R ²¹ and R ²² may have a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms) and an alkoxy group (preferably having a carbon number). 1-8), an amino group, an alkylamino group (preferably an alkyl group having 1 to 8 carbon atoms) or a dialkylamino group (preferably an alkyl group having 1 to 8 carbon atoms).

The naphthyl group represented by R ²¹ and R ²² may have a substituent, and the substituent is the same as the above substituent that the phenyl group represented by R ²¹ and R ²² may have. Groups.

Furthermore, in general formula (I-3), R ²³ and R ²¹ are each independently a methyl group or an ethyl group, R ²² is methyl or phenyl, and Ar is a single bond, a phenylene group, or a naphthylene. Group or thienylene group, n is preferably 0.

As the α-aminoacetophenone photopolymerization initiator containing a structural moiety represented by the general formula (II), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone, N, N-dimethylaminoacetophenone and the like.

Examples of the acylphosphine oxide photopolymerization initiator containing a structural moiety represented by the general formula (III) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine. Examples include fin oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide.

The titanocene photopolymerization initiator represented by the general formula (IV) includes bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) 1-yl) -phenyl) titanium.

The blending ratio of such a photopolymerization initiator (C) is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the photosensitive resin (A). It is. When the blending ratio of the photopolymerization initiator (C) is less than 0.01 parts by mass with respect to 100 parts by mass of the photosensitive resin (A), photocurability on copper is insufficient and the coating film peels off. The coating properties such as chemical resistance may deteriorate, which is not preferable. On the other hand, when the blending ratio of the photopolymerization initiator (C) exceeds 30 parts by mass with respect to 100 parts by mass of the photosensitive resin (A), the deep curability decreases due to light absorption of the photopolymerization initiator (C). Since it may be, it is not preferable.

When the composition of the present invention contains an oxime ester photopolymerization initiator represented by general formula (I-1), the blending ratio is preferably based on 100 parts by mass of the photosensitive resin (A). Is a ratio of 0.01 to 20 parts by mass, more preferably 0.01 to 5 parts by mass. When such an oxime ester photopolymerization initiator is used, it is preferably used in combination with an α-aminoacetophenone photopolymerization initiator in order to improve the sensitivity to exposure light.

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

[(D) A carboxyl group-containing acrylic copolymer having an alicyclic skeleton]
The composition of the present invention may contain (D) a carboxyl group-containing acrylic copolymer (hereinafter referred to as “carboxyl group-containing acrylic copolymer (D)”) having an 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. A well-known thing can be used as a carboxyl group-containing acrylic copolymer (D).
Examples of the carboxyl group-containing acrylic copolymer (D) include the following.
(1) a copolymer obtained by reacting a carboxyl group-containing (meth) acrylic copolymer with an alicyclic compound having an epoxy group and a radically polymerizable unsaturated group in one molecule;
(2) An unsaturated monocarboxylic acid was reacted with a copolymer of an alicyclic compound having an epoxy group and an unsaturated double bond in one molecule and a compound having an unsaturated double bond, and produced by this reaction. A photosensitive resin obtained by reacting a secondary hydroxyl group of an epoxy carboxylate with a saturated or unsaturated polybasic acid anhydride,
(3) After reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride, the carboxylic acid produced by this reaction has one epoxy group and one radically polymerizable unsaturated double bond in each molecule. The photosensitive resin obtained by making the alicyclic compound which has this react.

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

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

(Meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, etc. Hydroxyl-containing (meth) acrylic acid esters such as acid alkyl esters, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, Methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol Meth) acrylate, methoxy triethylene glycol (meth) acrylate, glycol-modified (meth) acrylates such as methoxy polyethylene glycol (meth) acrylate. These may be used alone or in combination of two or more. On the other hand, the above-mentioned compounds can be used as the radical polymerizable unsaturated monocarboxylic acid. The alicyclic compound having 1 epoxy group and a radically polymerizable unsaturated double bond is the same as the above-described compound.

The carboxyl group-containing acrylic copolymer (D) preferably has an acid value in the range of 50 to 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 with a weak alkaline aqueous solution. When oxidation exceeds 200 mgKOH / g, there exists a problem that the water resistance of a cured film and an electrical property are inferior. The weight average molecular weight of the carboxyl group-containing acrylic copolymer (D) is preferably in the range of 5,000 to 100,000. When the mass average molecular weight is less than 5,000, the dryness to touch of the coating film of the photocurable thermosetting resin composition tends to be extremely inferior. On the other hand, if the mass average molecular weight exceeds 100,000, it is not preferable because the developability and storage stability of the photocurable thermosetting composition are remarkably deteriorated.

The mixing ratio of the carboxyl group-containing acrylic copolymer (D) is, for example, 10 to 95 parts by mass, preferably 10 to 50 parts by mass, when the total amount with the photosensitive resin (A) is 100 parts by mass. It is.

[Photocurable monomer]
The photocurable thermosetting resin composition of the present invention may contain a photocurable monomer. As the photocurable monomer, a compound having two or more ethylenically unsaturated groups in the molecule is preferable, and the compound is photocured by ultraviolet irradiation to insolubilize the carboxylic acid resin (A) in an alkaline aqueous solution. Or it helps insolubilization. Examples of such compounds include glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, and the like. Polyhydric acrylates such as polyhydric alcohols or their ethylene oxide adducts or propylene oxide adducts; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycy Ethers, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or the like each methacrylates corresponding to the acrylates.

Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further, a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. Examples thereof include an epoxy urethane acrylate compound obtained by reacting a half urethane compound. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

The blending ratio of such a photocurable monomer is preferably 5 to 100 parts by mass, more preferably 1 to 70 parts by mass with respect to 100 parts by mass of the photosensitive resin (A). When the blending ratio is less than 5 parts by mass, the photocurability is lowered, and pattern development becomes difficult by alkali development after ultraviolet irradiation, which is not preferable. On the other hand, when the amount exceeds 100 parts by mass, the solubility in an aqueous alkali solution is reduced and the coating film becomes brittle, which is not preferable.

[Thermosetting catalyst]
The photocurable thermosetting resin composition of the present invention may contain a thermosetting catalyst.
Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic hydrazide and sebacic acid hydrazide; phosphorus compounds such as triphenylphosphine, , For example, four 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole compounds) manufactured by Kasei Kogyo Co., Ltd., U-CAT3503N, U-CAT3502T (all are dimethylamine block isocyanate compounds) Product name), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compounds and salts thereof). In particular, the present invention is not limited to these, and any epoxy resin thermosetting catalyst or any one that promotes the reaction between the epoxy group and the carboxyl group may be used alone or in admixture of two or more. . Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, which also functions as an adhesion-imparting agent, S-triazine derivatives such as -vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used, Preferably, a compound that also functions as an adhesion promoter is used in combination with the thermosetting catalyst.

The blending ratio of the thermosetting catalyst may be a ratio that is usually used. For example, 0.1 to 20 parts by mass, preferably 0.1 to 0.1 parts by mass with respect to 100 parts by mass of the photosensitive resin (A) or the polyfunctional epoxy resin (B). It can be used at a ratio of 5 to 15.0 parts by mass.

[Filler]
The photocurable thermosetting resin composition of the present invention can contain a filler as necessary in order to increase the physical strength of the coating film. As such a filler, known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica and talc are preferably used. Furthermore, NANOCRYL (trade names) XP 0396, XP 0596, XP 0733, XP 0746, XP 0765, XP manufactured by Hanse-Chemie, in which nano silica is dispersed in the above-mentioned photo-curable monomer or (C) epoxy-based thermosetting resin. 0768, XP 0953, XP 0954, XP 1045 (all product grade names) and NANOOX (trade name) XP 0516, XP 0525, XP 0314 (all product grade names) manufactured by Hanse-Chemie can also be used. These may be used alone or in combination of two or more.

The blending ratio of these fillers is preferably 300 parts by mass or less, more preferably 0.1 to 300 parts by mass, and still more preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the photosensitive resin (A). It is a ratio. When the blending ratio of the filler exceeds 300 parts by mass, it is not preferable because the viscosity of the composition becomes high and the printability is lowered or the cured product becomes brittle.

[solvent]
The photocurable thermosetting resin composition of the present invention may contain an organic solvent in order to adjust to a viscosity suitable for the coating method.
Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. 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 Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate and carbitol acetate Ethanol, propanol, ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether is petroleum naphtha, hydrogenated petroleum naphtha, and aromatic petroleum solvents such as solvent naphtha.
Such organic solvents are used alone or as a mixture of two or more.

[Other ingredients]
The photocurable thermosetting resin composition of the present invention may further comprise a known and commonly used thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, fine silica, organic bentonite, Known and commonly used thickeners such as montmorillonite, defoamers and / or leveling agents such as silicone, fluorine and polymer, silane coupling agents such as imidazole, thiazole and triazole, blue, yellow and red Known additives such as black and white colorants can be blended.

[Manufacture of printed wiring boards]
A printed wiring board has the hardened | cured material which consists of 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 the present invention is adjusted to a viscosity suitable for a coating method with an organic solvent, for example, on a substrate on which a circuit is formed, a dip coating method, a flow coating method, a spin coating method, The coating is applied by a roll coating method, bar coater method, screen printing method, curtain coating method or the like, and the organic solvent contained in the composition is evaporated and dried (temporary drying) at a temperature of about 60 to 100 ° C. Form a coating film. Thereafter, the film is selectively exposed to ultraviolet rays through a photomask, and the unexposed portion is developed with a dilute alkali aqueous solution (for example, 0.3 to 3% sodium carbonate aqueous solution) to form a cured product having a pattern.

For high-frequency circuits using paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluorine / polyethylene / PPO / cyanate ester, etc. A material using a copper clad laminate and the like, and copper graded laminates of all grades (FR-4 etc.), other polyimide films, PET films, glass substrates, ceramic substrates, wafer plates and the like can be mentioned.

In the present invention, the volatile drying performed after the photocurable thermosetting resin composition is applied may be a hot air circulation drying oven, an IR oven, a hot plate, a convection oven or the like (having a heat source of an air heating method using steam). The method can be carried out using a method in which hot air in the dryer is brought into countercurrent contact and a method in which the hot air is blown onto the support from a nozzle. The exposure apparatus used for the ultraviolet irradiation may be an exposure apparatus that generates ultraviolet rays.

As the light source, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp or the like is preferable. Examples of the exposure apparatus include HMW-680GW manufactured by Oak Manufacturing Co., Ltd. and ADEX 600P manufactured by Adtech Engineering Co., Ltd., which can be used in the present invention. In addition, as an exposure apparatus for direct imaging that performs exposure at a single wavelength, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer), an ultraviolet lamp such as a (super) high pressure mercury lamp, and the like. The direct drawing apparatus used can be used. As such a direct drawing apparatus, for example, those made by Nippon Orbotech, Oak, etc. can be used.

Development methods include dipping, showering, spraying, brushing, etc. Developers include potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetra Alkaline aqueous solutions such as methylammonium hydroxide can be used.

In addition, the printed wiring board which has hardened | cured material by apply | coating the photocurable thermosetting resin composition of this invention on a carrier film, and bonding the dried dry film on the base material in which the circuit pattern was formed. May be manufactured.

The photo-curable thermosetting resin composition of the present invention is suitable as a material for a permanent film of a printed wiring board, but is particularly suitable as a material for a solder resist and an interlayer insulating material.

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, it cannot be overemphasized that this invention is not what is limited to the following. In the following, “parts” and “%” indicate “parts by mass” and “% by mass” unless otherwise specified.

[Synthesis of photosensitive resin]
Synthesis Example 1: Photosensitive resin (A1-1)
Orthocresol novolac type epoxy resin (produced by DIC Corporation, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) 1070 g (number of glycidyl groups (total number of aromatic rings)): 600 g of diethylene glycol monoethyl ether acetate 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, heated and stirred at 100 ° C., and uniformly dissolved.

Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C., reacted for 2 hours, heated to 120 ° C., and further reacted for 12 hours. Into the obtained reaction liquid, 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were charged, reacted at 110 ° C. for 4 hours, cooled, and carboxyl group-containing photosensitive. Resin solution (A1) was obtained.

The solid content (amount excluding the solvent) of the photosensitive resin solution (A1) thus obtained was 65%, and the acid value of the solid content was 89 mgKOH / g.

Synthesis Example 2: Photosensitive resin (A-1)
700 g of diethylene glycol monoethyl ether acetate and 1070 g of orthocresol novolac type epoxy resin (manufactured by DIC Corporation, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6): number of glycidyl groups (total number of aromatic rings): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, heated and stirred at 100 ° C., and uniformly dissolved.

Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, and further 1.6 g of triphenylphosphine was added, and the temperature was raised to 120 ° C. and reacted for another 12 hours. To the obtained reaction solution, 562 g of aromatic hydrocarbon (Sorvesso 150) and 684 g (4.5 mol) of tetrahydrophthalic anhydride were charged and reacted at 110 ° C. for 4 hours. Furthermore, 142.0 g (1.0 mol) of glycidyl methacrylate was added to the obtained reaction liquid, and the reaction was performed at 115 ° C. for 4 hours to obtain a carboxyl group-containing photosensitive resin solution (A-1).

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

[Preparation of Photocurable Thermosetting Resin Composition]
The blending components shown in Table 1 and the following common components were kneaded with a three-roll mill to obtain a photocurable thermosetting resin composition. In Table 1, the content of each component (A), (B) and (D) is a solid content excluding the solvent.

<Photosensitive resin (A)>
A-2: SP-3900 (manufactured by Showa Denko KK, solid content 65%, acid value: 70 mg KOH / g) <Polyfunctional epoxy resin>
B-1: Bisphenol A type epoxy resin (834: manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 250, normal temperature semi-solid, softening point 60 ° C. or lower, molecular weight 470)
B-2: Polyglycidyl ether of phenol novolac (RE306CA90: Nippon Kayaku Co., Ltd., epoxy equivalent 196, softening point 50 ° C., molecular weight 400)
B-3: Phenol novolac type epoxy resin (DEN431: manufactured by Dow Chemical Company, epoxy equivalent 174, normal temperature semi-solid, softening point 60 ° C. or lower, molecular weight 400)
B-4: Phenol novolac type epoxy resin (DEN438: manufactured by Dow Chemical Company, epoxy equivalent 199, softening point 40 ° C., molecular weight 600)
B-5: Bisphenol A novolak type epoxy resin (Epiclon N-870: DIC, epoxy equivalent 205, softening point 70 ° C., molecular weight 1600)
B-6: ICTEP-S (Nissan Chemical Co., Ltd., epoxy equivalent 100, softening point 110 ° C.)
<(C) Photopolymerization initiator>
C-1: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one C-2:

<(D) Carboxyl group-containing acrylic copolymer>
D-1: Cyclomer P (ACA) Z250 (manufactured by Daicel Chemical Industries, Ltd., solid content 45%) (carboxyl group-containing acrylic copolymer having an alicyclic skeleton)
D-2: Cyclomer 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 copolymer (manufactured by Mitsubishi Rayon Co., Ltd., solid content 50%) (copolymer having no alicyclic skeleton)
[Common components (numbers are parts by mass)]
(Filler)
Barium sulfate (B-30 manufactured by Sakai Chemical Co., Ltd.): 100 parts Talc: 10 parts Silica: 10 parts (photo-curable monomer)
Dipentaerythritol hexaacrylate: 30 parts (thermosetting catalyst)
Dicyandiamide: 0.3 part Melamine: 3 parts (Antifoaming agent, coloring agent, solvent)
Silicone antifoaming agent: 3 parts Phthalocyanine blue: 2 parts Aromatic petroleum solvent: 10 parts [Evaluation methods of Examples 1 to 18 and Comparative Examples 1 and 2]
<Sensitivity: Curability>
After the scrubbing, the photocurable thermosetting resin composition prepared above is printed on the entire surface of the circuit pattern substrate having a thickness of 35 μm, which is washed with water and dried, by screen printing, and then dried at 80 ° C. with hot air circulation. Dry in an oven for 30 minutes. Thereby, the dry coating film of the photocurable thermosetting resin composition was obtained. This dried coating film had a thickness of 15 μm and an absorbance of 0.8.

This dried coating film is exposed through a step tablet (Stuffer 41 stage) using an exposure apparatus equipped with a metal halide lamp, and development (1 mass% Na ₂ CO ₃ aqueous solution, 30 ° C., 0.2 MPa) is performed in 60 seconds. I read the pattern of the remaining step tablet. It can be seen that when the sensitivity is 7 or more, the photocurable resin composition can be sufficiently cured because the sensitivity is high.

<Maximum development life: Ease of residue generation>
After scrubbing, the photocurable thermosetting resin composition prepared above was applied onto the entire surface of a circuit pattern substrate having a thickness of 35 μm which was washed with water and dried by screen printing. When the substrate was put into an 80 ° C. hot air circulation drying oven and dried, the longest time during which development failure due to heat covering did not occur was examined. Specifically, drying was performed at 80 ° C. for 30, 40, 50, and 60 minutes, development was performed under the above-described development conditions, and whether or not development was possible at each time was tested. At this time, the surface of copper was visually observed, and development was possible if the components of the photocurable thermosetting resin composition did not remain as a residue, and this time was described. This is called the drying control width, and the longer the drying time, the better the productivity.

<Dry touch dryness>
After scrubbing, the photocurable thermosetting resin composition prepared above was applied onto the entire surface of a circuit pattern substrate having a thickness of 35 μm which was washed with water and dried by screen printing. The substrate was placed in a hot air circulation drying oven at 80 ° C. and dried for 40 minutes. After drying, a negative pattern film (negative film) was placed on the dried coating film and exposed using an exposure apparatus equipped with a metal halide lamp. Specifically, a cured film was obtained by irradiating the dry coating film under the negative film so that the integrated exposure amount was 50 mJ / cm ² . When the negative film was peeled off from the cured film, the presence or absence of negative film marks was confirmed. When there is no negative film mark, it means that the dry touch of the dried coating film is good. On the other hand, when there is a negative film mark on the cured film, the dry touch of the dried coating film is poor.

In addition, when the dry touch of the dry coating film is poor, handling becomes difficult during substrate transportation, and suction marks on the exposure machine stage are attached.

◯: No negative film trace Δ: Negative film trace ×: Adhered to the negative film and peeled off with the dry coating film.

<Heat resistance>
After the scrubbing, the photocurable thermosetting resin composition prepared above is printed on the entire surface of the circuit pattern substrate having a thickness of 35 μm, which is washed with water and dried, by screen printing, and then dried at 80 ° C. with hot air circulation. Dry in an oven for 30 minutes. Thereby, the dry coating film of the photocurable thermosetting resin composition was obtained.

This dry coating film was exposed with an exposure amount obtained by 8 steps using a step tablet (Stuffer 41 steps) using an exposure apparatus equipped with a metal halide lamp, and developed (1 mass% Na ₂ CO ₃ aqueous solution, 30 ° C., 0.2 MPa). Was performed in 60 seconds, and further cured at 150 ° C. for 60 minutes to prepare a cured coating film.

The evaluation board | substrate which apply | coated water-soluble flux to the obtained cured coating film is immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning a flux with about 50 degreeC hot water washing, swelling of the cured coating film by visual observation The peeling was evaluated. The judgment criteria are as follows.

○: No peeling is observed after immersion for 10 seconds. Δ: The resist layer is whitened after immersion for 10 seconds. ×: The resist layer swells and peels after immersion for 10 seconds. <Insulation reliability>
After the scrubbing, the photocurable thermosetting resin composition prepared above was screen-printed on a substrate having a comb-type electrode pattern of line / space = 100/100 washed with water and dried and having a copper thickness of 18 μm. Was printed on the entire surface and dried in a hot air circulating drying oven at 80 ° C. for 30 minutes, thereby obtaining a dry coating film of the photocurable thermosetting resin composition.

A bias voltage of DC 30 V was applied to this comb-shaped electrode, and the insulation resistance value and corrosion after 1000 hours were evaluated while humidifying at 80 ° C. and 80%. The judgment criteria are as follows.

○: Insulation resistance value is 1 × 10 ¹² Ω or more. No corrosion is seen.

Δ: The insulation resistance value is 1 × 10 ⁹ Ω or more and less than 1 × 10 ¹² Ω. Corrosion is seen.

×: Insulation resistance value is less than 1 × 10 ⁹ Ω. Corrosion is seen.

[Evaluation method of Examples 19 and 20]
Evaluation was performed in the same manner as in Example 1 except that the exposure apparatus mounted with a metal halide lamp was changed to an exposure apparatus mounted with a single laser of 405 nm using the composition described in Table 2. The results are shown in the same table.

Claims

(A) A polyfunctional epoxy resin and a radically polymerizable unsaturated monocarboxylic acid are reacted to form an epoxy carboxylate having a hydroxyl group in the side chain, and this epoxy carboxylate is reacted with a polybasic acid anhydride to produce a carboxyl. A carboxyl group-containing photosensitive resin obtained by producing a group-containing photosensitive resin (A1) and reacting the carboxyl group-containing photosensitive resin (A1) with a compound having an epoxy group and a radically polymerizable unsaturated group,
(B) a polyfunctional epoxy resin having a softening point of 60 ° C. or lower, and
(C) A photocurable thermosetting resin composition comprising a photopolymerization initiator.
The photocurable thermosetting resin composition according to claim 1, further comprising (D) a carboxyl group-containing acrylic copolymer having an alicyclic skeleton.
Furthermore, it contains a polyfunctional epoxy resin (B ′) having a softening point exceeding 60 ° C., the epoxy group (B1) of the polyfunctional epoxy resin (B) having a softening point of 60 ° C. or less, and a polyfunctional epoxy resin (B ′) having a softening point exceeding 60 ° C. The photocurable thermosetting resin composition according to claim 1, wherein the ratio of the functional epoxy resin (B ') to the epoxy group (B'1) is from 3: 7 to 9: 1.
A cured product comprising the photocurable thermosetting resin composition according to any one of claims 1 to 3.
A printed wiring board comprising the cured product according to claim 3.