JPH11315107A - Alkali developable photosetting and thermosetting composition and cured film obtained from the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of maintaining or improving characteristics such as heat resistance, adhesion, resolution properties or electrical characteristics required for a solder resist, or the like, of a printed wiring board and providing a cured film excellent in pressure cooker resistance, or the like, required for especially an IC package by compounding a specific photosensitive prepolymer. SOLUTION: This composition contains (A) a photosensitive prepolymer prepared by reacting alcoholic hydroxyl groups of a reactional product of (i) an epoxy compound having >=2 epoxy groups with (ii) a phenol compound represented by formula I [(x) is 0-5; R<1> is a 1-4C saturated alkyl, phenyl or the like] and/or a naphthol compound represented by formula II [(y) is 0-7; R<2> is a 1-4C saturated or a 1-4C unsaturated alkyl] and (iii) an unsaturated group-containing monocarboxylic acid with (iv) a polybasic acid anhydride, (B) a diluent comprising a polyfunctional unsatiurated compound and/or an organic solvent which are liquid at room temperature, (C) a photopolymerization initiator, (D) an epoxy resin and (E) a curing catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkali-developable photocurable / thermosetting composition and a cured film obtained therefrom, and more particularly to a permanent mask for a printed wiring board and an interlayer insulating layer for a multilayer wiring board. Suitable for use as etc.,
After irradiation with ultraviolet rays, an image is formed by developing with a diluted alkaline aqueous solution, and heat treatment after irradiation with active energy rays,
Alternatively, by performing an active energy ray irradiation step after the heat treatment or finish curing by the heat treatment, heat resistance, adhesion, electroless plating resistance, electric characteristics, resolution, moisture absorption resistance, and PCT (pressure cooker) resistance. The present invention relates to a liquid alkali-developable photocurable / thermosetting composition capable of forming a cured film having excellent heat resistance and a cured film forming technique using the same.

[0002]

2. Description of the Related Art At present, solder resists of some commercial printed wiring boards and most of industrial printed wiring boards are formed by irradiating with ultraviolet rays and developing them from the viewpoint of high precision and high density. A liquid development type solder resist that is finally cured (finally cured) by heat and light irradiation is used. In consideration of environmental problems, a liquid solder resist of an alkali developing type using a dilute aqueous alkali solution as a developing solution has become mainstream. For example, JP-A-61-243869 discloses an alkali developing type solder resist using a diluted alkaline aqueous solution, in which an acid anhydride is added to a reaction product of a novolak type epoxy compound and an unsaturated monobasic acid. A solder resist composition comprising a photosensitive resin, a photopolymerization initiator, a diluent and an epoxy compound is disclosed in JP-A-3-253093, in which a reaction product of a novolak-type epoxy compound and an unsaturated monobasic acid is converted into an acid anhydride. JP-A-3-71137 and JP-A-3-250012 disclose a solder resin composition comprising a photosensitive resin, a photopolymerization initiator, a diluent, vinyltriazine or a mixture of vinyltriazine and dicyandiamide and a melamine resin. The official gazette describes the reaction products of salicylaldehyde and monohydric phenol with epichlorohydrin. Some epoxy resin, a photopolymerization initiator, a solder resist composition comprising an organic solvent or the like is disclosed.

[0003]

As described above, several material systems have been proposed as solder resists, and they are currently used in large quantities in actual production of printed wiring boards. However, in response to the increase in the density of printed wiring boards accompanying the recent reduction in the size and weight of electronic devices, solder resists are also required to have higher performance. More recently, QFP (Quad Flat Pack Package) and SOP (Small Outline Package) using lead frame and sealing resin
An IC package using a printed wiring board provided with a solder resist and a sealing resin has appeared in place of an IC package referred to as a so-called IC package. In these new packages, metal such as ball-shaped solder is arranged in an area on one side of a printed wiring board with solder resist, and the IC chip is directly connected to the other side by wire bonding, bumps, etc.
It has a structure sealed with a sealing resin.
It is called by a name such as grid array) or CSP (chip scale package). These packages have more pins and are easier to miniaturize than packages of the same size such as QFP. Also, in mounting, a low defect rate is realized by the self-alignment effect of the ball-shaped solder, and the introduction thereof is being rapidly promoted.

However, conventionally, printed wiring boards on which a commercially available alkali-developing solder resist is applied have been inferior in PCT resistance, which is a long-term reliability test of the package, and peeling of the solder resist film has occurred. In addition, the so-called popcorn phenomenon, which causes cracks in the solder resist film inside the package and its surroundings due to the moisture absorbed inside the package during reflow during package mounting due to the moisture absorption of the solder resist, has been regarded as a problem.
Such problems of moisture absorption resistance and long-term reliability are not limited to the above-described mounting technology, but include solder resists of general printed wiring boards and interlayer insulating layers of multilayer wiring boards such as build-up boards. It is also undesirable in products for other uses.

Accordingly, an object of the present invention is to provide heat resistance, adhesion, resolution, electroless plating resistance, electric resistance required for conventional solder resists of printed wiring boards and interlayer insulating layers of multilayer wiring boards. A cured film that maintains or improves the characteristics such as the characteristics and has excellent characteristics such as moisture absorption resistance and PCT (pressure cooker) resistance required especially for IC packages is obtained. An object of the present invention is to provide a liquid photo-curable / thermo-curable composition which can be alkali-developable, and a cured film obtained therefrom.

[0006]

According to one aspect of the present invention, there is provided a photo-curable / thermo-curable composition which is alkali-developable.
(A) (a) an epoxy compound having two or more epoxy groups in one molecule, and (b) a phenol compound represented by the following formula (1) and / or a naphthol compound represented by the following formula (2): (C) With respect to the alcoholic hydroxyl group of the reaction product (X) with the unsaturated group-containing monocarboxylic acid, (d)
A photosensitive prepolymer obtained by reacting a polybasic acid anhydride, (B) a polyfunctional unsaturated compound and / or an organic solvent which is liquid at room temperature as a diluent, (C) a photopolymerization initiator, (D)
It is characterized by containing an epoxy resin and (E) a curing catalyst.

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[0007] In a second aspect of the present invention,
(A) (a) an epoxy compound having two or more epoxy groups in one molecule, and (b-1) a phenol compound represented by the above formula (1) and / or a naphthol compound represented by the above formula (2) (B-2) a phenolic compound having a hydroxyl group-containing substituent, and (c) an alcoholic hydroxyl group of a reaction product (X) of an unsaturated group-containing monocarboxylic acid, and (d) a polybasic anhydride. (B) a liquid polyfunctional unsaturated compound and / or organic solvent at room temperature as a diluent, (C) a photopolymerization initiator, (D) an epoxy resin, and E) It is characterized by containing a curing catalyst. Preferably, the phenol compound having a hydroxyl group-containing substituent (b-
As 2), a compound represented by the following formula (3) is used.

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According to another aspect of the present invention, there is also provided a cured film obtained from the alkali-developable photocurable and thermosetting composition. In one preferred embodiment, the composition is screen-printed, roll-coated on a substrate, for example, a circuit-formed printed wiring board.
Apply by curtain coating, spray coating, etc., dry in a far-infrared drying oven or hot air drying oven, etc., and then directly irradiate active energy rays such as laser light according to the pattern, or through a patterned photomask Irradiate active energy rays from a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an electrodeless lamp, etc., selectively expose according to a predetermined exposure pattern, develop an unexposed portion with an alkaline aqueous solution to form a pattern,
After that, it is obtained by heat treatment after irradiation with active energy rays, or active energy irradiation step after heat treatment, or finish curing by heat treatment, heat resistance, adhesion, electroless plating resistance, electrical characteristics, resolution Properties, moisture absorption resistance,
A cured film (solder resist film) having excellent properties such as PCT resistance is provided.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The alkali-developable liquid photo-curable / thermo-curable composition of the present invention comprises, as a photosensitive prepolymer (A), in the first embodiment, (a) 2 per molecule. An epoxy compound having at least two epoxy groups, (b) a phenol compound represented by the formula (1) and / or a naphthol compound represented by the formula (2), and (c) a monocarboxylic acid having an unsaturated group. A photosensitive prepolymer obtained by reacting (d) a polybasic acid anhydride with an alcoholic hydroxyl group of the reaction product (X) of the reaction product (X). In the second embodiment, (b) b-1) Photosensitivity generated using a phenol compound represented by the formula (1) and / or a naphthol compound represented by the formula (2) and (b-2) a phenol compound having a hydroxyl group-containing substituent Prepolymer It is characterized by using.

That is, the photosensitive prepolymer (A)
Means that the phenol compound and / or the naphthol compound (b, b-1, b) are added to the epoxy group of the epoxy compound (a).
-2) reacting the phenolic hydroxyl group with the carboxyl group of the unsaturated group-containing monocarboxylic acid (c) so that the unsaturated group of the unsaturated group-containing monocarboxylic acid is introduced to exhibit photocurability. And an alcoholic hydroxyl group (a secondary hydroxyl group formed by the reaction of an epoxy group with a carboxyl group or a phenolic hydroxyl group or a hydroxyl group having a substituent of the component (b-2)) in the obtained reaction product. When the acid anhydride (d) reacts, a carboxyl group is introduced and becomes soluble in an aqueous alkali solution, and developability is improved. However, free hydrophilic groups (carboxyl group and hydroxyl group) are improved. ), It exhibits hygroscopicity, which is a factor that lowers the properties of the cured film. However, in the photosensitive prepolymer (A) of the present invention, a hydrophobic aromatic ring (benzene ring and / or naphthalene ring) is introduced into the photosensitive prepolymer as described above, so that the cured film has a moisture absorption resistance. And PCT resistance, and can also improve cured film properties such as heat resistance, adhesion, plating resistance such as electroless plating resistance, and dryness to the touch after forming a coating.

Further, the phenol compound and / or the naphthol compound represented by the formulas (1) and (2) (b-
By introducing the phenol compound (b-2) having a hydroxyl group-containing substituent together with 1), the heat resistance, moisture absorption resistance and flexibility of the cured film can be improved in a well-balanced manner. Further, the resolution can be improved. That is, when a phenol compound having a hydroxyl group-containing substituent is introduced into the photosensitive prepolymer, the polybasic anhydride selectively reacts with a hydroxyl group having a substituent of the phenol compound to form an epoxy compound. Higher resolution (photocurability, developability) due to the presence of the carboxyl group in the highly hydrophobic region of the skeleton and in the portion away from the photopolymerizable unsaturated group introduced by the unsaturated group-containing molar carboxylic acid Can be. In addition, in order to form a cured film of fine pattern with high reliability and good reproducibility, the unexposed portion of the coating must be removed promptly during development, but the developability and dryness to touch (tack-free) ) Is a contradictory property, and when trying to improve the developability, the dryness to the touch tends to decrease. However, a phenol compound and / or a naphthol compound (b-) represented by the formulas (1) and (2) are added to the photosensitive prepolymer.
By introducing the phenol compound (b-2) having a hydroxyl group-containing substituent together with 1), the dryness to the touch and the developability of the coating film can be improved in a well-balanced manner.

Due to the above-described effects, the use of the photocurable / thermosetting composition of the present invention makes it possible to improve the BG of printed wiring boards.
Even in an IC package such as A or CSP, the solder resist film is not peeled or cracked, and can be mounted with high reliability. In addition, even when exposed to high temperature or high humidity conditions, the cured film does not crack or peel off from the base material, and has excellent properties as described above. It can be advantageously used for applications such as an interlayer insulating layer of a multilayer wiring board.

Hereinafter, each component of the photocurable and thermosetting composition of the present invention will be described in detail. First, the photosensitive prepolymer (A) used in the present invention is, as described above, (a) an epoxy compound having two or more epoxy groups in one molecule, and (b) a compound represented by the formula (1). (D) polybasic anhydride with respect to the alcoholic hydroxyl group of the reaction product (X) of a phenol compound and / or a naphthol compound represented by the formula (2) and (c) an unsaturated group-containing monocarboxylic acid And (a) an epoxy compound having two or more epoxy groups in one molecule, and (b-1) the formula (1).
And / or a naphthol compound represented by the formula (2), (b-2) a phenol compound having a hydroxyl group-containing substituent, and (c) a monocarboxylic acid having an unsaturated group. It is a carboxyl group-containing photosensitive resin obtained by reacting (d) a polybasic acid anhydride with an alcoholic hydroxyl group of the product (X). Such a carboxyl group-containing photosensitive resin (A) preferably has an acid value in the range of 30 to 200 mgKOH / g. When the acid value is less than 30 mgKOH / g, the solubility in an aqueous alkali solution becomes poor, and development becomes difficult. On the other hand, if it exceeds 200 mgKOH / g, the surface of the exposed portion is developed irrespective of the exposure conditions, which is not preferable.

The epoxy compound (a) having two or more epoxy groups in one molecule includes Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004 manufactured by Yuka Shell Epoxy, and Dainippon Ink and Chemicals, Inc. Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, Epototh YD-011, YD-013, YD-12 manufactured by Toto Kasei Co., Ltd.
7, YD-128, manufactured by Dow Chemical Company. E. FIG. R. 3
17, D.I. E. FIG. R. 331; E. FIG. R. 661, D.C.
E. FIG. R. 664, Araldide 60 manufactured by Ciba Geigy
71, Araldide 6084, Araldide GY25
0, Araldide GY260, Sumi-Epoxy ESA-011, ESA-014, ELA- manufactured by Sumitomo Chemical Co., Ltd.
115, ELA-128, A.I. E. FIG.
R. 330, A.I. E. FIG. R. 331, A.I. E. FIG. R. 66
1, A. E. FIG. R. Bisphenol A type epoxy resin such as 664 (all trade names); Epicoat YL903 manufactured by Yuka Shell Epoxy Co., Ltd., Epicron 152 and Epicron 165 manufactured by Dainippon Ink and Chemicals, Inc .; Epototo YDB-400, YDB manufactured by Toto Kasei -500, manufactured by Dow Chemical Company. E. FIG. R. 542, Araldide 8011 manufactured by Ciba-Geigy, Sumi-Epoxy E manufactured by Sumitomo Chemical Co., Ltd.
SB-400, ESB-700, A.C.
E. FIG. R. 711, A.I. E. FIG. R. Brominated epoxy resins such as 714 (all trade names); Epicoat 152 and Epicoat 154 manufactured by Yuka Shell Epoxy, and D.C. E. FIG. N. 431; E. FIG. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, manufactured by Dainippon Ink and Chemicals, Epototo YDCN-701, YDCN-704, manufactured by Toto Kasei Co., Ltd., Araldide ECN1235, Araldide ECN1273, Araldide manufactured by Ciba Geigy ECN1299,
Araldide XPY307, Nippon Kayaku's EPPN-
201, EOCN-1025, EOCN-1020, E
OCN-104S, RE-306, Sumi-Epoxy ESCN-195X, ESCN-22 manufactured by Sumitomo Chemical Co., Ltd.
A.0, manufactured by Asahi Kasei Corporation E. FIG. R. ECN-235, E
Novolak type epoxy resin such as CN-299 (all trade names); Epicron 83 manufactured by Dainippon Ink and Chemicals, Inc.
0, Epicoat 807 made of Yuka Shell Epoxy, Epototo YDF-170, YDF-175, Y made by Toto Kasei
DF-2004, Araldide XP manufactured by Ciba-Geigy
Bisphenol F type epoxy resin such as Y306 (all trade names); Epototo ST-2004 manufactured by Toto Kasei Co., Ltd.
Hydrogenated bisphenol A type epoxy resins such as ST-2007 and ST-3000 (trade name); Epicoat 604 manufactured by Yuka Shell Epoxy, Epototo YH manufactured by Toto Kasei
-434, Araldide MY72 manufactured by Ciba-Geigy
0, Sumitomo Chemical Co., Ltd. Sumi-Epoxy ELM-120
(All trade names); Hydantoin type epoxy resin such as Araldide CY-350 (trade name) manufactured by Ciba Geigy; Celloxide 2021 manufactured by Daicel Chemical Industries, Araldide CY175, CY179 manufactured by Ciba Geigy (All trade names); alicyclic epoxy resin; YL-933 manufactured by Yuka Shell Epoxy Co., Ltd .; E. FIG. N. , EP
Trihydroxyphenylmethane type epoxy resins such as PN-501, EPPN-502, etc. (all are trade names); YL-6056, YX-4000, manufactured by Yuka Shell Epoxy Co., Ltd.
Bixylenol type or biphenyl type epoxy resin such as YL-6121 (all trade names); EB manufactured by Nippon Kayaku Co., Ltd.
Bisphenol S-type epoxy resins such as PS-200, EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., and EXA-1514 (brand name) manufactured by Dainippon Ink and Chemicals, Inc .; Epicoat 157S manufactured by Yuka Shell Epoxy (trade name) Bisphenol A novolak type epoxy resin; Epicoat YL-931 manufactured by Yuka Shell Epoxy Co., Ltd., and tetraphenylolethane type epoxy resin such as Araldide 163 manufactured by Ciba Geigy (all trade names); Araldide PT810 manufactured by Ciba Geigy Heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Co., Ltd. (all trade names); Diglycidyl phthalate resin such as Blenmer DGT manufactured by NOF Corporation; Tetraglycidyloxy such as ZX-1063 manufactured by Toto Kasei Co., Ltd. Lenoylethane resin; ESN-19 manufactured by Nippon Steel Chemical Co., Ltd.
0, ESN-360, HP- manufactured by Dainippon Ink and Chemicals, Inc.
Naphthalene group-containing epoxy resins such as 4032, EXA-4750 and EXA-4700; epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink and Chemicals; CP- manufactured by NOF Corporation Glycidyl methacrylate copolymer epoxy resins such as 50S and CP-50M; and copolymer epoxy resins of cyclohexylmaleimide and glycidyl methacrylate. Particularly preferred are novolak epoxy resins and the like, but are not particularly limited thereto. These epoxy resins may be used alone or in combination of two or more.

The phenol compound represented by the formula (1) and the naphthol compound represented by the formula (2) (b, b
As -1), for example, phenol, o-, m- or p-cresol, 2,5-xylenol, 3,5-xylenol, o-isopropylphenol, p-isopropenylphenol, 2,3,5-trimethyl Phenol, 2,3,6-trimethylphenol, o-sec-
Butylphenol, p-sec-butylphenol, 2
-Methyl-4-t-butylphenol, 2-methyl-6
-T-butylphenol, 3-methyl-6-t-butylphenol, di-sec-butylphenol, 2,4-
Di-isobutylphenol, ot-butylphenol, di-t-butyl-p-ethylphenol, o-cyclohexylphenol, p-cyclohexylphenol, 3-methyl-6-cyclohexylphenol, 4-
Methyl-2-cyclohexylphenol, o-allylphenol, 2,3,4,6-tetramethylphenol,
2,4-di-t-butylphenol, 2,6-di-t-
Butylphenol, o-thymol, p-thymol, o-
Phenylphenol, p-phenylphenol, 2-t
-Butyl-6-phenylphenol, 2,4-di-t-
Butyl-6-phenylphenol, 1-naphthol, 2
-Naphthol and the like, but are not limited thereto. Particularly preferred are p-phenylphenol,
p-cyclohexylphenol, 1-naphthol, 2-
Naphthol and the like. These phenol compounds and / or naphthol compounds can be used alone or in combination of two or more. In the above formula (1), R
¹ , when R ² is a saturated or unsaturated alkyl group having 5 or more carbon atoms, inhibits the photoreactivity of the resulting photosensitive prepolymer;
Alternatively, when the substituent is a saturated or unsaturated alkyl group, it is necessary to limit the number of carbon atoms to 4 or less because the developability deteriorates.

Examples of the phenol compound having a hydroxyl group-containing substituent (b-2) include compounds represented by the above formula (3), for example, (bis) hydroxymethylphenol, (bis) hydroxymethylcresol, hydroxymethyl -Di-t-butylphenol, p
-Hydroxyphenyl-2-methanol, p-hydroxyphenyl-3-propanol, p-hydroxyphenyl-4-butanol, hydroxyethylcresol,
2,6-dimethyl-4-hydroxymethylphenol,
Hydroxyalkylphenol or hydroxyalkylcresol such as 2,4-dihydroxymethyl-2-cyclohexylphenol, trimethylolphenol, 3,5-dimethyl-2,4,6-trihydroxymethylphenol; hydroxybenzoic acid, hydroxyphenylbenzoic acid Or a phenol having a carboxyl group-containing substituent such as hydroxyphenoxybenzoic acid and ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethylene glycol,
Esterified products with dipropylene glycol, tripropylene glycol and the like; bisphenol monoethylene oxide adducts, bisphenol monopropylene oxide adducts, p-hydroxyphenethyl alcohol, and the like, with p-hydroxyphenethyl alcohol being particularly preferred. However, the present invention is not limited to these. These phenol compounds having a hydroxyl group-containing substituent can be used alone or in combination of two or more.

Representative examples of the unsaturated group-containing monocarboxylic acid (c) include acrylic acid, methacrylic acid,
Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropanedi (meth)
Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, phenylglycidyl (meth) acrylate,
Examples thereof include unsaturated dibasic acid anhydride adducts of hydroxyl group-containing acrylates such as (meth) acrylic acid caprolactone adducts. Here, particularly preferred are acrylic acid and methacrylic acid. These unsaturated group-containing monocarboxylic acids can be used alone or in combination of two or more.

The reaction of the components (a) to (c) is as follows:
A method in which an epoxy compound (a) is reacted simultaneously with a phenol compound and / or a naphthol compound (b, b-1, b-2) and an unsaturated group-containing monocarboxylic acid (c), or first, a phenol compound and / or a naphthol A method of reacting the compounds (b, b-1, b-2) and then reacting the unsaturated group-containing monocarboxylic acid (c), or reacting the unsaturated group-containing monocarboxylic acid (c) and then reacting with the phenol compound And / or a naphthol compound (b, b-1,
There is a method of reacting b-2), and any method can be employed. In such a reaction, a polymerization inhibitor such as hydroquinone or oxygen, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, 2-ethyl The reaction can be easily carried out usually at 80 to 130 ° C. in the presence of a reaction catalyst such as an imidazole compound such as -4-methylimidazole and a phosphorus compound such as triphenylphosphine.

The ratio of each component in the reaction is as follows:
The phenolic hydroxyl group and the unsaturated group-containing monocarboxylic acid (c) of the phenol compound and / or the naphthol compound (b) or (b-1, b-2) are equivalent to 1 equivalent of the epoxy group of the epoxy compound (a). The total number of carboxyl groups is 0.
8 to 1.3 equivalents, and (b): (c) or Δ (b
-1) + (b-2)}: The molar ratio of (c) is 1: 1 to 1:
A ratio of 99 is preferable. The total of the phenolic hydroxyl group of the phenol compound and / or the naphthol compound (b, b-1, b-2) and the carboxyl group of the unsaturated group-containing monocarboxylic acid (c) is the epoxy 1 of the epoxy compound (a).
If the amount is less than 0.8 equivalent to the equivalent, the above-mentioned action and effect of the present invention cannot be sufficiently obtained. Conversely, even if it is used in a large amount exceeding 1.3 equivalent, only one equivalent is theoretically reacted. However, these low molecular weight compounds remaining unreacted are increased, which is a cause of deteriorating the physical properties of the cured film.

On the other hand, the molar ratio of the phenol compound and / or the naphthol compound (b, b-1, b-2) to the unsaturated group-containing monocarboxylic acid (c) is from 1: 1 to 1:99. Preferably it is 4: 6 to 1: 9. When the proportion of the phenol compound and / or the naphthol compound is increased, the moisture absorption resistance and the PCT resistance are improved, and the resolution and the reproducibility of the line width between the surface portion and the bottom portion of the resist line are increased. However, when the proportion of the unsaturated group-containing monocarboxylic acid (c) decreases, the photoreactivity deteriorates, and it becomes impossible to obtain the development resistance of the exposed coating surface. Further, the sensitivity is lowered, which is not preferable in terms of workability. When a phenol compound (b-2) having a hydroxyl group-containing substituent is used together with the phenol compound represented by the formula (1) and / or the naphthol compound (b-1) represented by the formula (2), The ratio (b-1) :( b-2) of these compounds can be any ratio within the range of 1:99 to 99: 1 in molar ratio.

The reaction product (X) produced by the above reaction
The photosensitive prepolymer (A) of the present invention is obtained by reacting a polybasic acid anhydride (d) with the alcoholic hydroxyl group of
In this reaction, the amount of polybasic anhydride (d) used is
The ratio of the anhydride group to the alcoholic hydroxyl group of the reaction product (X) is preferably from 99: 1 to 1:99, and polymerization of hydroquinone, oxygen, or the like in the presence or absence of a diluent described below. The reaction is usually performed at 50 to 130 ° C. in the presence of an inhibitor. At this time, if necessary, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, and a phosphorus compound such as triphenylphosphine are added as catalysts. May be.

The polybasic acid anhydrides include phthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, maleic anhydride,
Dibasic such as itaconic anhydride, nadic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride, etc. Acid anhydride, or biphenyltetracarboxylic dianhydride, diphenylethertetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride And the like. Aliphatic or aromatic tetrabasic dianhydrides and the like can be used, and one or more of these can be used.

As the diluent (B), a polyfunctional unsaturated compound or an organic solvent which is liquid at room temperature can be used. The purpose of using these diluents is to dissolve the photosensitive prepolymer (A) and adjust the composition to a viscosity suitable for various coating methods. Further, the polyfunctional unsaturated compound which is liquid at room temperature has a purpose of increasing the photoreactivity of the composition and a role of assisting solubility in an aqueous alkaline solution. However, when a large amount of a polyfunctional unsaturated compound which is liquid at room temperature is used, the coating film cannot be dried to the touch and the properties of the coating film tend to deteriorate, so that the photosensitive prepolymer (A) It is preferably 50 parts by weight or less based on 100 parts by weight (the same applies hereinafter as solid content). As long as the organic solvent can be dried under predetermined drying conditions, the amount of the organic solvent used is limited only by the coating method without adversely affecting the dried coating film.

Examples of the liquid polyfunctional unsaturated compound include acrylates containing a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate; acrylamide, N-methylol Acrylamide derivatives such as acrylamide; water-soluble acrylates such as polyethylene glycol diacrylate and polypropylene glycol diacrylate; polyfunctional polyester acrylates of polyfunctional alcohols such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate A polyfunctional alcohol such as trimethylolpropane or hydrogenated bisphenol A Acrylates of ethylene oxide adducts and propylene oxide adducts of polyfunctional phenols such as phenol A and biphenol; polyfunctional or monofunctional polyurethane acrylates which are isocyanate-modified hydroxy group-containing acrylates; bisphenol A diglycidyl ether, hydrogenated bisphenol Epoxy acrylates, which are (meth) acrylic acid adducts of A diglycidyl ether or phenol novolak epoxy resin, and methacrylates corresponding to the above acrylates, etc., may be used alone or in combination of two or more. it can.

Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol and butyl. Glycol ethers such as carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carb Tall acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate Acetates such as ethanol; propanol, ethylene glycol and propylene glycol; alcohols such as octane and decane; hydrocarbons such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. And the like,
They can be used alone or as a mixture of two or more.

Examples of the photopolymerization initiator (C) include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, Acetophenones such as 2,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoaminopropanone-1,2-benzyl- Aminoacetophenones such as 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-
Anthraquinones such as butylanthraquinone and 1-chloroanthraquinone; 2,4-dimethylthioxanthone;
Thioxanthones such as 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; organic peroxides such as benzoyl peroxide and cumene peroxide;
Thiol compounds such as 2,4,5-triarylimidazole dimer, riboflavin tetrabutyrate, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole;
Organic halogen compounds such as 6-tris-s-triazine, 2,2,2-tribromoethanol and tribromomethylphenylsulfone; benzophenones such as benzophenone and 4,4'-bisdiethylaminobenzophenone or xanthones; , 6-trimethylbenzoyldiphenylphosphine oxide. These known and commonly used photopolymerization initiators can be used alone or as a mixture of two or more kinds, and further, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-acid Photoinitiating aids such as tertiary amines such as dimethylaminobenzoate, triethylamine and triethanolamine can be added. In addition, a titanocene compound such as CGI-784 (manufactured by Ciba-Geigy) that absorbs in the visible light region can also be added to promote the photoreaction. A particularly preferred photopolymerization initiator is 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoaminopropanone-
1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and the like, but are not particularly limited thereto, and absorb light in the ultraviolet or visible light region. Not limited to photopolymerization initiators and photoinitiating assistants, those that radically polymerize unsaturated groups such as (meth) acryloyl groups and the like can be used alone or in combination. The amount of use is preferably 0.5 to 25 parts by weight based on 100 parts by weight of the photosensitive prepolymer (A).

Specific examples of the epoxy resin (D) include Epicoat 828, Epicoat 834, Epicoat 1001, and Epicoat 10 manufactured by Yuka Shell Epoxy.
04, Epicron 840 manufactured by Dainippon Ink and Chemicals,
Epicron 850, Epicron 1050, Epicron 2
055, Epototo YD-011, YD manufactured by Toto Kasei Co., Ltd.
-013, YD-127, YD-128, D.C. E. FIG. R. 317, D.E. E. FIG. R. 331;
E. FIG. R. 661, D.C. E. FIG. R. 664, Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260 manufactured by Ciba-Geigy, Sumi-Epoxy ESA-011, ESA manufactured by Sumitomo Chemical Co., Ltd.
-014, ELA-115, ELA-128, A.C. E. FIG. R. 330, A.I. E. FIG. R. 331,
A. E. FIG. R. 661, A.I. E. FIG. R. Bisphenol A type epoxy resin such as 664 (all trade names); Epicoat YL903 manufactured by Yuka Shell Epoxy Co., Ltd., Epicron 152 and Epicron 165 manufactured by Dainippon Ink and Chemicals, Inc .; Epototo YDB-400, YDB manufactured by Toto Kasei -50
0, D.C. E. FIG. R. 542, Araldide 8011 manufactured by Ciba-Geigy, Sumi-Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., A.D. E. FIG. R. 711, A.I. E. FIG. R. 714
Epoxy 152, Epicoat 15 manufactured by Yuka Shell Epoxy Co., Ltd.
4, D.C. E. FIG. N. 431; E. FIG.
N. 438, Epicron N manufactured by Dainippon Ink and Chemicals, Inc.
-730, Epicron N-770, Epicron N-86
5. Epotote YDCN-701, YD manufactured by Toto Kasei
CN-704, Araldide ECN manufactured by Ciba-Geigy
1235, Araldide ECN1273, Araldide ECN1299, Araldide XPY307, Nippon Kayaku's EPPN-201, EOCN-1025, EOC
N-1020, EOCN-104S, RE-306, Sumi-Epoxy ESCN-195X manufactured by Sumitomo Chemical Co., Ltd.
ESCN-220, A.C. E. FIG. R. EC
Novolak-type epoxy resins such as N-235 and ECN-299 (all are trade names); Epicron 830 manufactured by Dainippon Ink and Chemicals, Epicoat 80 manufactured by Yuka Shell Epoxy
7. Epototo YDF-170, YDF manufactured by Toto Kasei
-175, YDF-2004, Ciba Geigy's Araldide XPY306, etc. (all trade names) bisphenol F type epoxy resin; Toto Kasei's Epototo ST
Hydrogenated bisphenol A type epoxy resins such as -2004, ST-2007, ST-3000 (trade name); Epicoat 604 manufactured by Yuka Shell Epoxy Co., Ltd., Epotote YH-434 manufactured by Toto Kasei, Araldide MY720 manufactured by Ciba Geigy Sumi-Epoxy E manufactured by Sumitomo Chemical Co., Ltd.
Glycidylamine type epoxy resin such as LM-120 (all trade names); Araldide CY- manufactured by Ciba-Geigy
Hydantoin type epoxy resin such as 350 (trade name); alicyclic epoxy resin such as Celloxide 2021 manufactured by Daicel Chemical Industries, Inc., Araldide CY175, CY179 manufactured by Ciba Geigy (all trade names); YL-933, manufactured by Dow Chemical Company. E. FIG.
N. , EPPN-501, EPPN-502, etc. (all are trade names); trihydroxyphenylmethane type epoxy resin; YL-6056, YX-, manufactured by Yuka Shell Epoxy Co., Ltd.
Bixylenol type or biphenol type epoxy resin such as 4000 or YL-6121 (all trade names) or a mixture thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., Dainippon Bisphenol S type epoxy resin such as EXA-1514 (trade name) manufactured by Ink Chemical Industry; Bisphenol A novolak type epoxy resin such as Epicoat 157S (trade name) manufactured by Yuka Shell Epoxy; Epicoat YL-931, Araldide 163 manufactured by Ciba Geigy
(All trade names) tetraphenylolethane epoxy resin; Araldide PT81 manufactured by Ciba-Geigy
0, a heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Co. (all trade names); Blemmer DG manufactured by NOF Corporation
Diglycidyl phthalate resin such as T; tetraglycidyl xylenoylethane resin such as ZX-1063 manufactured by Toto Kasei; ESN-190, ESN-36 manufactured by Nippon Steel Chemical Co., Ltd.
0, HP-4032 manufactured by Dainippon Ink and Chemicals, EXA
Naphthalene group-containing epoxy resin such as -4750 and EXA-4700; HP-720 manufactured by Dainippon Ink and Chemicals, Inc.
0, an epoxy resin having a dicyclopentadiene skeleton such as HP-7200H; CP-50S manufactured by NOF Corporation,
A glycidyl methacrylate copolymer-based epoxy resin such as CP-50M; and a copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate may be mentioned, but not limited thereto. These epoxy resins can be used alone or in combination of two or more.
These epoxy resins are cured by heat to improve properties such as adhesiveness and heat resistance of the solder resist. The compounding amount is usually 10 to 70 parts by weight, preferably 20 to 60 parts by weight, based on 100 parts by weight of the photosensitive prepolymer (A).

As the curing catalyst (E), for example,
2,4-diamino-6-methacryloyloxyethyl-
S-triazine, 2-vinyl-2,4-diamino-S-
Triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6
Vinyltriazine derivatives such as -methacryloyloxyethyl-S-triazine / isocyanuric acid adduct; 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; guanamines such as guanamine, acetoguanamine and benzoguanamine; dicyandiamide, benzyldimethylamine and 4- ( Dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N,
Amine compounds such as N-dimethylbenzylamine and melamine; hydrazine compounds such as adipic hydrazide and sebacic hydrazide; and phosphorus compounds such as triphenylphosphine. Commercially available products include:
For example, 2MZ-A, 2MZ-OK manufactured by Shikoku Chemicals Co., Ltd.
2PHZ, 2P4BHZ, 2P4MHZ (all are trade names of imidazole compounds), U-C manufactured by San Apro
AT3503X, U-CAT3502X (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-C
AT5002 (both bicyclic amidine compounds and salts thereof). In particular, the present invention is not limited to these, and may be any curing catalyst for an epoxy resin or one that promotes the reaction between an epoxy group and a carboxyl group, and may be used alone or as a mixture of two or more. More preferred are 2,4-diamino-6-methacryloyloxyethyl-S-triazine and 2-vinyl-2,4-diamino-, which also function as an adhesion-imparting agent.
S-triazine, 2-vinyl-4,6-diamino-S-
Triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine
S-triazine derivatives such as isocyanuric acid adducts, melamine, and acetoguanamine are exemplified. The compounding amount of the above-mentioned curing catalyst is sufficient in a usual quantitative ratio, for example, a ratio of 20 parts by weight or less, preferably 0.1 to 15.0 parts by weight based on 100 parts by weight of the photosensitive prepolymer (A). It is.

The photo-curable and thermo-curable compositions of the present invention include:
Further, if necessary, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica,
Known or customary inorganic fillers such as crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica can be used alone or in combination of two or more.
These are used for the purpose of suppressing curing shrinkage of the coating film and improving properties such as adhesion and hardness.

The composition of the present invention may further comprise, if necessary, a known and commonly used coloring agent such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black and naphthalene black; ,
Known and commonly used thermal polymerization inhibitors such as hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, and phenothiazine; known and commonly used thickeners such as finely divided silica, organic bentonite, and montmorillonite; Known and commonly used additives such as a foaming agent and / or a leveling agent, an adhesion-imparting agent such as an imidazole-based, thiazole-based, or triazole-based silane coupling agent can be blended.

The photo-curable / thermo-curable composition of the present invention having the above composition may be diluted as necessary to adjust the viscosity to be suitable for a coating method. It is tack-free by applying to a wiring board by a screen printing method, a curtain coating method, a play coating method, a roll coating method, or the like, and evaporating and drying an organic solvent contained in the composition at a temperature of, for example, 60 to 100 ° C. Can be formed. After that, the resist pattern can be formed by selectively exposing with an active energy ray through a photomask on which a pattern is formed, and developing the unexposed portion with a dilute alkaline aqueous solution to form a resist pattern. Irradiation of active energy rays or final curing (final curing) only by heat curing, adhesion, hardness, solder heat resistance, chemical resistance, solvent resistance, electrical insulation, electrolytic corrosion resistance, resolution , Plating resistance,
A cured film (solder resist film) having excellent PCT resistance and moisture absorption resistance is formed.

As the alkaline aqueous solution, an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used. Further, as an irradiation light source for photocuring, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is appropriate. In addition, a laser beam or the like can be used as the active energy ray.

[0033]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but it is needless to say that the present invention is not limited to the following examples. Note that “parts” and “%” are all based on weight unless otherwise specified.

Synthesis Example 1 Epicron N- of cresol novolak type epoxy resin
695 (manufactured by Dainippon Ink and Chemicals, epoxy equivalent = 2
20) 220 parts (1 equivalent) were placed in a four-necked flask equipped with a stirrer and a reflux condenser, and carbitol acetate 2 was added.
16 parts were added and dissolved by heating. Next, 0.46 parts of methylhydroquinone as a polymerization inhibitor and 1.38 parts of triphenylphosphine as a reaction catalyst were added. The mixture was heated to 95-105 ° C, and 57.6 parts (0.8 equivalents) of acrylic acid and 34 parts of p-phenylphenol (0.
(2 equivalents) was gradually added dropwise and reacted for 16 hours. The reaction product (hydroxyl group: 1 equivalent) was cooled to 80 to 90 ° C., and 87 parts (0.56 equivalent) of tetrahydrophthalic anhydride was added, reacted for 8 hours, and taken out after cooling. The carboxyl group-containing photosensitive resin thus obtained has a nonvolatile content of 65% and an acid value of solid of 80 mgKOH / g.
Met. Hereinafter, this reaction solution is referred to as A-1 varnish.

Synthesis Example 2 EPPN-20, a phenol novolak type epoxy resin
1 (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent = 190) 190 parts was placed in a four-necked flask equipped with a stirrer and a reflux condenser,
206 parts of carbitol acetate was added and dissolved by heating. Next, methylhydroquinone 0.1.
46 parts and triphenylphosphine 1.
38 parts were added. The mixture was heated to 95-105 ° C, and 50.4 parts (0.7 equivalent) of acrylic acid, 35.2 parts (0.2 equivalent) of p-cyclohexylphenol, and 14.4 parts (0.1 equivalent) of 2-naphthol were used. Equivalent) is gradually dropped, and 1
The reaction was performed for 6 hours. This reaction product (hydroxyl group: 1 equivalent)
Was cooled to 80 to 90 ° C., and 91.2 parts (0.6 equivalent) of tetrahydrophthalic anhydride was added, and the mixture was reacted for 8 hours. After cooling, it was taken out. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 65% and an acid value of a solid of 88 mgKOH / g. Hereinafter, this reaction solution is referred to as A-2 varnish.

Synthesis Example 3 EPPN-20, a phenol novolak type epoxy resin
1 (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent = 190) 190 parts was placed in a four-necked flask equipped with a stirrer and a reflux condenser,
196 parts of carbitol acetate were added and dissolved by heating. Next, methylhydroquinone 0.1.
46 parts and triphenylphosphine 1.
38 parts were added. The mixture was heated to 95 to 105 ° C., 64.8 parts (0.9 equivalents) of acrylic acid and 14.4 parts (0.1 equivalents) of 2-naphthol were gradually added dropwise, and reacted for 16 hours. The reaction product (hydroxyl group: 1 equivalent) is
After cooling to 80 to 90 ° C., 92.4 parts (0.6 equivalent) of hexahydrophthalic anhydride was added, reacted for 8 hours, and taken out after cooling. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 65% and an acid value of solid of 93 mgKOH / g. Hereinafter, this reaction solution is referred to as A
-3 varnish.

Synthesis Example 4 ECON-10 of cresol novolak type epoxy resin
220 parts (1 equivalent) of 4S (manufactured by Nippon Kayaku Co., epoxy equivalent = 220) was placed in a four-necked flask equipped with a stirrer and a reflux condenser, and 224 parts of carbitol acetate was added.
Heated and dissolved. Next, 0.46 parts of methylhydroquinone as a polymerization inhibitor and 1.38 parts of triphenylphosphine as a reaction catalyst were added. 95-105 of this mixture
° C, 43.2 parts of acrylic acid (0.6 equivalent), p
-27.6 parts of hydroxyphenethyl alcohol (0.2
Equivalent), 14.4 parts of 2-naphthol (0.1 equivalent), p
17.0 parts (0.1 equivalent) of -phenylphenol was gradually added dropwise, and reacted for 16 hours. The reaction product (hydroxyl group: 1.2 equivalents) was cooled to 80 to 90 ° C, 91.2 parts (0.6 equivalents) of tetrahydrophthalic anhydride was added, reacted for 8 hours, and taken out after cooling. . The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 65% and an acid value of solid of 81 mgKOH / g.
Hereinafter, this reaction solution is referred to as A-4 varnish.

Synthesis Example 5 EPPN-20, a phenol novolak type epoxy resin
1 (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent = 190) 190 parts was placed in a four-necked flask equipped with a stirrer and a reflux condenser,
194 parts of carbitol acetate were added and dissolved by heating. Next, methylhydroquinone 0.1.
46 parts and triphenylphosphine 1.
38 parts were added. The mixture was heated to 95-105 ° C., and 43.2 parts (0.6 equivalent) of acrylic acid, 13.8 parts (0.1 equivalent) of p-hydroxyphenethyl alcohol,
51 parts (0.3 equivalent) of p-phenylphenol was gradually added dropwise, and the mixture was reacted for 16 hours. The reaction product (hydroxyl group: 1.1 equivalents) was cooled to 80 to 90 ° C, 60 parts (0.6 equivalents) of succinic anhydride was added, reacted for 8 hours, and taken out after cooling. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 65% and a solid acid value of 94 mgKOH / g. Hereinafter, this reaction solution is referred to as A-5 varnish.

Synthesis Example 6 Phenol novolak type epoxy resin EPPN-20
1 (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent = 190) 190 parts was placed in a four-necked flask equipped with a stirrer and a reflux condenser,
206 parts of carbitol acetate was added and dissolved by heating. Next, methylhydroquinone 0.1.
46 parts and triphenylphosphine 1.
38 parts were added. The mixture was heated to 95-105 ° C., and 43.2 parts of acrylic acid (0.6 equivalent), 41.4 parts of p-hydroxyphenethyl alcohol (0.3 equivalent),
14.4 parts (0.1 equivalent) of 2-naphthol was gradually added dropwise and reacted for 16 hours. This reaction product (hydroxyl group:
1.3 eq.) To 80-90 ° C., add 92.4 parts (0.6 eq.) Of hexahydrophthalic anhydride and add 8 eq.
The mixture was allowed to react for a period of time, taken out after cooling. The carboxyl group-containing photosensitive resin thus obtained has a nonvolatile content of 65%.
%, The acid value of the solid was 88 mg KOH / g. Less than,
This reaction solution is called A-6 varnish.

Comparative Synthetic Example 1 A cresol novolak type epoxy resin, Epicron N-
695 (manufactured by Dainippon Ink and Chemicals, epoxy equivalent = 2
20) 220 parts were placed in a four-necked flask equipped with a stirrer and a reflux condenser, and 214 parts of carbitol acetate were added and dissolved by heating. Next, 0.46 parts of hydroquinone as a polymerization inhibitor and 1.38 parts of triphenylfuphosphine as a reaction catalyst were added. 95-105 of this mixture
The mixture was heated to 70 ° C., and 72 parts of acrylic acid was gradually dropped, and reacted for 16 hours. The reaction product is cooled to 80 to 90 ° C., 106 parts of tetrahydrophthalic anhydride is added, and
The mixture was allowed to react for a period of time, taken out after cooling. The carboxyl group-containing photosensitive resin thus obtained has a nonvolatile content of 65%.
%, The acid value of the solid was 100 mgKOH / g. Hereinafter, this reaction solution is referred to as B-1 varnish.

Comparative Synthesis Example 2 EPPN-20 of phenol novolak type epoxy resin
1 (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent = 190) 190 parts was placed in a four-necked flask equipped with a stirrer and a reflux condenser,
184 parts of carbitol acetate were added and dissolved by heating. Next, methylhydroquinone 0.1.
46 parts and triphenylphosphine 1.
38 parts were added. The mixture was heated to 95 to 105 ° C., and 72 parts (1 equivalent) of acrylic acid was gradually added dropwise.
Allowed to react for hours. This reaction product (hydroxyl group: 1 equivalent)
Was cooled to 80 to 90 ° C., and 50 parts (0.5 equivalent) of succinic anhydride was added, reacted for 8 hours, and taken out after cooling. The carboxyl group-containing photosensitive resin thus obtained has a nonvolatile content of 65% and an acid value of a solid of 89 mgK.
OH / g. Hereinafter, this reaction solution is referred to as B-2 varnish.

Comparative Synthesis Example 3 EPPN-20, a phenol novolak type epoxy resin
1 (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent = 190) 190 parts was placed in a four-necked flask equipped with a stirrer and a reflux condenser,
215 parts of carbitol acetate were added and dissolved by heating. Next, methylhydroquinone 0.1.
46 parts and triphenylphosphine 1.
38 parts were added. The mixture was heated to 95 to 105 ° C., and 57.6 parts (0.8 equivalent) of acrylic acid and 44.0 parts (0.2 equivalent) of n-nonylphenol were gradually added dropwise.
The reaction was performed for 16 hours. The reaction product (hydroxyl group: 1 equivalent) was cooled to 80 to 90 ° C., and 91.2 parts (0.6 equivalent) of tetrahydrophthalic anhydride was added, reacted for 8 hours, and taken out after cooling. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 65% and a solid acid value of 84 mgKOH / g. Hereinafter, this reaction solution is referred to as B-3 varnish.

Examples 1 to 7, Comparative Examples 1 to 4 The components shown in Table 1 using the varnishes obtained in Synthesis Examples 1 to 6 and Comparative Synthesis Examples 1 to 3 were kneaded with a three-roll mill. Thus, a photosensitive resin composition was obtained. Table 2 shows the characteristic values of each composition. In addition, the method of the performance test in Table 2 is as follows.

(1) Developability The composition of each of the above Examples and Comparative Examples was applied to the entire surface of the patterned copper foil substrate by screen printing, and dried at 80 ° C. for 40, 50, 60, or 70 minutes. After cooling to room temperature, a 1% aqueous Na ₂ CO ₃ solution at 30 ° C. was sprayed at a pressure of 2 k.
Development was performed for 60 seconds under the condition of g / cm ² , and the presence or absence of the development residue of the dried coating film was visually confirmed. ：: Completely developed. Δ: Part of the coating film remains. X: The coating film remains completely.

(2) Drying to the touch The compositions of the above Examples and Comparative Examples were applied to the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C for 20 minutes, and allowed to cool to room temperature. I do. A negative film is applied to this substrate, and a solder resist pattern is exposed at an exposure amount of 500.
The film was exposed under the condition of mJ / cm ^{2 and} the state of sticking of the film when the negative film was peeled was evaluated. ：: peels off without sticking. Δ: peeled off but stuck to the film. X: The coating film is stuck on the film.

Characteristic test: The compositions of the above Examples and Comparative Examples were applied on the entire surface of a copper foil substrate on which patterns were formed by screen printing, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature. A negative film is applied to this substrate, and the solder resist pattern is exposed under the condition of an exposure amount of 500 mJ / cm ² ,
1% Na ₂ CO ₃ aqueous solution at 30 ° C, spray pressure 2kg / c
Development was performed for 60 seconds under the conditions of m ² to obtain a resist pattern. This substrate is exposed to an integrated exposure amount of 10 in a UV conveyor furnace.
After irradiating with ultraviolet light under the condition of 00 mJ / cm ² ,
For 60 minutes to cure.

(3) Solder heat resistance The evaluation substrate coated with the rosin-based flux
After immersion in a solder bath set at ℃ and washing the flux with denatured alcohol, swelling and peeling of the resist layer were evaluated visually. The criteria are as follows. ：: No peeling was observed even when immersion was repeated 6 times or more for 10 seconds. Δ: When immersion is repeated 6 times or more for 10 seconds, the film is slightly peeled off. ×: The resist layer swelled and peeled within 6 times of immersion for 10 seconds.

(4) Adhesion The above evaluation substrate was cut in a grid pattern in accordance with the test method of JIS D0202, and a peel test was performed with a cellophane tape to evaluate the peeling of the resist layer. The criteria are as follows. ：: no peeling was observed at all △: slight peeling ×: peeling of the resist layer

(5) Electroless Plating Resistance Using a commercially available electroless nickel plating bath and electroless gold plating bath, plating was performed under the conditions of nickel 0.5 μm and gold 0.03 μm, and the resist was removed by tape peeling. After evaluating the presence or absence of peeling of the layer and the presence or absence of plating soaking, the resist layer was peeled off by tape peeling after immersing in a solder bath for 10 seconds under the above-mentioned (3) solder heat resistance test conditions, washing and drying. Was evaluated. The criteria are as follows. A: No change is observed after gold plating and after subsequent soldering. ：: No change was observed after plating, but slight discoloration or peeling was observed after soldering. Δ: Slight peeling and soaking were observed after plating, and peeling after soldering was also observed. ×: Peeling occurs after plating.

(6) Resistance to Electrocorrosion An evaluation substrate was prepared under the above conditions using a comb electrode B coupon of IPC B-25 instead of the copper foil substrate, and a bias voltage of DC 100 V was applied to the comb electrode. , 85
° C, 85% R.C. H. The presence / absence of migration after 1,000 hours in the constant temperature / humidity bath was confirmed. The criteria are as follows. ：: no change observed at all △: slight change ×: migration occurred

(7) Insulation Characteristics An evaluation substrate was prepared under the above conditions using a comb electrode B coupon of IPC B-25 in place of the copper foil substrate, and a bias voltage of 500 V DC was applied to the comb electrode. The insulation resistance was measured.

(8) Line width reproducibility Line / space = 80 for negative film used for exposure
μm / 80μm pattern is formed in advance and solder
-Image on resist 500 mJ / cm ^TwoCondition
Baking in 1% Na at 30 ° C_TwoCO_ThreeSpray aqueous solution
Pressure 2kg / cm^TwoDevelopment for 60 seconds under the conditions of
Curing by heating at 150 ° C. was performed for 60 minutes. After curing, shape
Measure the width of the top and bottom lines of the resulting line, and
Was evaluated as the line width reproducibility.

(9) Water Absorption A cured solder resist film is formed on a ceramic substrate (alumina substrate) whose weight has been measured in advance under the above conditions, and the total weight is measured. Then, add this to 22 ° C. ion-exchanged water for 2 hours.
After immersion for 4 hours, the weight was measured, and the rate of increase in weight was defined as the water absorption.

(10) PCT resistance The printed wiring board on which the solder resist film was formed under the above conditions was used in a PCT apparatus (TABAI ESPEC HAS).
T SYSTEM TPC-412MD)
The treatment was performed at 1 ° C. and 2 atm for 168 hours, and the state of the cured film was evaluated. ：: Peeling, discoloration and no elution. Δ: Any of peeling, discoloration and elution was observed. X: Many peeling, discoloration and elution are observed.

[0055]

[Table 1]

[0056]

[Table 2]

[0057]

As described above, according to the present invention, the heat resistance, adhesion, and resolution required for conventional solder resists for printed wiring boards and interlayer insulating layers for multilayer wiring boards are obtained.
Maintains or improves properties such as electroless plating resistance and electrical properties, and obtains a cured film with excellent properties such as moisture absorption resistance and PCT resistance required for IC packages. Provided is a liquid photocurable / thermosetting composition that can be applied to surface mounting and that can be alkali-developed. By using such a photocurable / thermosetting composition of the present invention, a printed wiring board is provided. BGA, CS
Even in an IC package such as P, peeling and cracking do not occur in the solder resist film, and highly reliable mounting is possible. In addition, even when exposed to high temperature or high humidity conditions, the cured film does not crack or peel off from the base material, and has excellent properties as described above. It can be advantageously used for applications such as an interlayer insulating layer of a multilayer wiring board.

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code FI // H05K 3/28 H05K 3/28 D 3/46 3/46 T (72) Inventor Kyoichi Yoda Arashiyama-cho, Hiki-gun, Saitama 388, Okura, Taiyo Ink Manufacturing Co., Ltd.Arashiyama Plant (72) Inventor, Seio Arima, 388, Oaza, Arashiyama-cho, Hiki-gun, Saitama

Claims (6)

[Claims] (A) (a) an epoxy compound having two or more epoxy groups in one molecule; and (b) an epoxy compound represented by the following formula (1):
(D) polyhydric base with respect to the alcoholic hydroxyl group of the reaction product (X) of the phenol compound represented by the following formula and / or the naphthol compound represented by the following formula (2) and (c) an unsaturated group-containing monocarboxylic acid: A photosensitive prepolymer obtained by reacting an acid anhydride, (B) a polyfunctional unsaturated compound and / or an organic solvent which is liquid at room temperature as a diluent, (C) a photopolymerization initiator, (D) an epoxy resin, And (E) a photocurable alkali-developable resin containing a curing catalyst.
Thermosetting composition. Embedded image 2. The photosensitive prepolymer (A) is composed of a phenolic hydroxyl group and an unsaturated group-containing monocarboxylic acid of a phenol compound and / or a naphthol compound (b) per one equivalent of an epoxy group of the epoxy compound (a). The carboxyl group of the acid (c) is reacted in a ratio of 0.8 to 1.3 equivalents in total and the molar ratio of (b) :( c) is 1: 1 to 1:99, and the reaction is obtained. The anhydride group of polybasic acid anhydride (d) is added to the alcoholic hydroxyl group of product (X) by 9
The composition according to claim 1, which is obtained by reacting at a ratio of 9: 1 to 1:99. 3. (A) (a) an epoxy compound having two or more epoxy groups in one molecule, (b-1) a phenol compound represented by the following formula (1) and / or (2) a phenol compound represented by the following formula (1): A naphthol compound represented by: and (b-2) a phenol compound having a hydroxyl group-containing substituent,
(C) a photosensitive prepolymer obtained by reacting (d) a polybasic acid anhydride with an alcoholic hydroxyl group of a reaction product (X) with an unsaturated group-containing monocarboxylic acid, (B)
Room temperature liquid polyfunctional unsaturated compound as a diluent and / or
Alternatively, an alkali-developable photocurable / thermosetting composition comprising an organic solvent, (C) a photopolymerization initiator, (D) an epoxy resin, and (E) a curing catalyst. Embedded image 4. The photosensitive prepolymer (A) comprises a phenol compound and / or a naphthol compound (b-1) and a phenol having a hydroxyl group-containing substituent per one equivalent of an epoxy group of the epoxy compound (a). Compound (b
-2) The phenolic hydroxyl group and the carboxyl group of the unsaturated group-containing monocarboxylic acid (c) are 0.8 to 1.3 equivalents in total, and {(b-1) + (b-2)} :( The reaction is carried out at a molar ratio of c) of from 1: 1 to 1:99, and the anhydride group of the polybasic anhydride (d) is added to the alcoholic hydroxyl group of the obtained reaction product (X) by 99. The composition according to claim 3, which is obtained by reacting at a ratio of 1: 1 to 1:99. 5. The composition according to claim 3, wherein the phenol compound having a hydroxyl group-containing substituent (b-2) is a compound represented by the following formula (3). Embedded image 6. A photo-curable / thermo-curable composition according to any one of claims 1 to 5, applied to a substrate, dried, exposed to light and developed, heat-treated after irradiation with active energy rays, or A cured film obtained by performing an active energy ray irradiation step after heat treatment or finish curing by heat treatment.