JP2001042525A - Alkali developable photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To attain high productivity and reduction of cost and to ensure satisfactory heat and moisture resistances and superior resistance to the heat of soldering by incorporating a carboxyl-containing photopolymerizable unsaturated compound, an epoxy resin containing a condensed polycyclic aromatic skeleton and a photopolymerization initiator. SOLUTION: The alkali developable photosensitive resin composition contains a carboxyl-containing photopolymerizable unsaturated compound, an epoxy resin containing a condensed polycyclic aromatic skeleton and a photopolymerization initiator as essential components. The carboxyl-containing photopolymerizable unsaturated compound may be obtained by allowing a polyfunctional epoxy acrylate compound to react with an acid anhydride compound. The polyfunctional epoxy acrylate compound may be obtained by allowing a polyfunctional epoxy resin such as bisphenol A type epoxy resin to react with an unsaturated carboxylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkali-developable photosensitive resin composition, and more particularly to an alkali-developable photosensitive resin composition which is suitably used as an interlayer insulating material for a build-up multilayer substrate or a permanent insulating protective film for a printed wiring board. The present invention relates to a developable photosensitive resin composition.

[0002]

2. Description of the Related Art In recent years, electronic devices and computers have been required to be smaller and more sophisticated than ever, and accordingly, components used at higher densities have been required. Have been. For example, in printed wiring boards, circuit miniaturization and multilayering are being promoted in order to increase the wiring density per unit volume, and an ultra-high density board called a build-up multilayer board has been proposed and put into practical use. Is being promoted.

[0003] This build-up multilayer substrate replaces the through hole conventionally used for interlayer conduction of the multilayer substrate,
The method is characterized in that interlayer conduction is provided through the inner via hole. As a method for providing the inner via hole in the insulating layer, for example, a method using a laser is known. In this method, a via hole is formed. The productivity was low due to the low speed, and the cost was high because special equipment was additionally required. Therefore, as a via hole forming method capable of realizing higher productivity and lower cost as compared with a method using a laser, for example, Japanese Patent Publication No. 8-3633 discloses that an epoxy resin such as a novolak type epoxy resin contains α, β-ethylene. A method is disclosed in which, after reacting an unsaturated carboxylic acid having one bond, a photosensitive resin further modified with an acid anhydride is used, and an epoxy resin such as a novolak epoxy resin is used as a curing agent.

[0004]

However, the above-mentioned Tokuhei 8
In the method using a photosensitive resin described in JP-B-3633, the heat resistance and humidity resistance of the resin itself are insufficient,
As a result, it was inferior in solder heat resistance when formed into a printed wiring board. The problem to be solved by the present invention is that in a printed wiring board application, high productivity and low cost can be realized, and sufficient heat resistance and moisture resistance reliability, and alkali development type photosensitive material excellent in solder heat resistance are provided. It is to provide a resin composition.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that an epoxy resin containing a condensed polycyclic aromatic skeleton as a curing agent thereof together with a carboxyl group-containing photopolymerizable unsaturated compound. It has been found that heat resistance and moisture resistance reliability can be drastically improved by using, and the present invention has been completed.

That is, the present invention comprises a carboxyl group-containing photopolymerizable unsaturated compound (a), an epoxy resin (b) containing a condensed polycyclic aromatic skeleton, and a photopolymerization initiator (c) as essential components. The present invention relates to an alkali-developable photosensitive resin composition containing as a component (a).

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the contents of the present invention will be described in detail. Carboxyl group-containing photopolymerizable unsaturated compound (a) used in the alkali-developable photosensitive resin composition of the present invention
Is not particularly limited, but can be reacted, for example, with a polyfunctional epoxy acrylate compound and an acid anhydride compound.

The polyfunctional epoxy acrylate compound usable here can be obtained by reacting a polyfunctional epoxy resin with an unsaturated carboxylic acid. Examples of the polyfunctional epoxy resin used include bisphenol A type Epoxy resin, bisphenol F epoxy resin, resorcinol epoxy resin, bisphenol S epoxy resin, dihydroxynaphthalene epoxy resin, binaphthol epoxy resin, biphenol epoxy resin, tetramethylbiphenol epoxy resin, phenol novolak epoxy resin, cresol Novolak-type epoxy resins, naphthol novolak-type epoxy resins, phenol-dicyclopentadiene-type epoxy resins, alkylphenol novolak-type epoxy resins, and the like.

The unsaturated carboxylic acid to be reacted with the polyfunctional epoxy resin is not particularly limited as long as it contains one or more double bonds and a carboxylic acid in one molecule. And methacrylic acid can be used.

The acid anhydride compound to be reacted with the above polyfunctional epoxy acrylate compound includes, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, Trimellitic acid, pyromellitic anhydride,
Examples include polybasic acid anhydrides such as benzophenonetetracarboxylic dianhydride, ethylene glycol bistrimellitate dianhydride, biphenyltetracarboxylic dianhydride, and biphenylethertetracarboxylic dianhydride.

The ratio of the acid anhydride compound to be reacted is not particularly limited, but the amount of the acid anhydride group is 0.2 to 2.5 with respect to 1 hydroxyl group equivalent of the carboxyl group-containing photopolymerizable unsaturated compound. Preferably it is molar. That is, 0.
When the amount is 2 mol or more, the solubility in an aqueous alkali solution is further improved, and when the amount is 2.5 mol or less, the stability is improved.

The carboxyl group-containing photopolymerizable unsaturated compound (a) thus obtained has an acid value of 30 to 200.
Those in the range of mgKOH / g are preferred. That is, when the acid value is in the range of 200 mgKOH / g or less, the cured film has good properties such as alkali resistance and electric properties.
In the range of 30 mgKOH / g or more, the solubility in an aqueous alkali solution becomes remarkably good.

Next, the epoxy resin (b) containing a condensed polycyclic aromatic skeleton is a compound containing at least one epoxy group in one molecule, and is a compound having a condensed skeleton such as a naphthalene skeleton or an anthracene skeleton. What is necessary is just to contain a polycyclic aromatic skeleton, for example, it can be obtained by reacting a condensed polycyclic aromatic compound containing an aromatic hydroxyl group with epihalohydrin.

As the epoxy resin (b) containing such a condensed polycyclic aromatic skeleton, specifically, 1,2-,
1,3-, 1,4-, 1,5-, 1,6-, 2,3-,
Bifunctional epoxy resin which is a reaction product of 2,6-, 2,7-dihydroxynaphthalene and epihalohydrin; a reaction product of condensate of 1-naphthol or 2-naphthol with aldehydes (namely, naphthol novolak resin) and epihalohydrin 1,2-, 1,3-, 1,4-,
1,5-, 1,6-, 2,3-, 2,6-, 2,7-dihydroxynaphthalene and aldehydes and epihalohydrin reactants; aldehydes of mononaphthol and the above dihydroxynaphthalene Reaction product of epihalohydrin with a condensate of mono- or dihydroxynaphthalene and xylylene glycol; reaction product of epihalohydrin with an adduct of mono- or dihydroxynaphthalene and a diene compound; naphthol Are directly coupled to each other, for example, a reaction product of binaphthol in which the 1-position of 2-naphthol is directly coupled to epihalohydrin, and the like.

Here, examples of the aldehydes include formaldehyde, acetaldehyde, benzaldehyde, and hydroxybenzaldehyde. Of these, formaldehyde is preferred because of its good reactivity during the condensation reaction.

Of the above-mentioned condensates of dihydroxynaphthalenes and aldehydes and epihalohydrin reactants, when 2,7-dihydroxynaphthalene is used as dihydroxynaphthalene, 2,7-dihydroxynaphthalene and aldehyde Since the condensate with the compound is only an alkylene group-bridged dimer, the reaction product of this with epihalohydrin has a small molecular weight, but is very high in spite of its low viscosity due to its high symmetry. It is preferable because a transition temperature can be obtained.

The method for producing the epoxy resin (b) is not particularly limited, and as described above, a method of reacting a condensed polycyclic aromatic compound containing an aromatic hydroxyl group with epihalohydrin. Specific examples thereof include reacting a condensed polycyclic aromatic compound containing an aromatic hydroxyl group with epihalohydrin such as epichlorohydrin in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. There is a method to make it.

When the condensed polycyclic aromatic compound is a condensate of mono- or dihydroxynaphthalene and an aldehyde, the mono- or dihydroxynaphthalene is dissolved in an appropriate ketone-based or aromatic organic solvent, and In the presence of an acid catalyst such as oxalic acid, hydrochloric acid or sulfuric acid, or an alkali catalyst such as sodium hydroxide or potassium hydroxide, an intermediate was first obtained by adding and reacting aldehydes such as formaldehyde. It is preferred to react the intermediate with an epihalohydrin such as epichlorohydrin.

Next, the photopolymerization initiator (c) used in the present invention.
Is generally used as a photopolymerization initiator for a photopolymerizable unsaturated compound having an ethylene bond. Examples of such a photopolymerization initiator include acetophenone, 2, 2
Acetophenones such as diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone and p-tert-butylacetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone and p, p-bisdimethylaminobenzophenone , Benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone , A sulfur compound such as 2-isopropylthioxanthone, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, , Anthraquinones, such as 3-diphenyl anthraquinone, benzoyl peroxide,
Organic peroxides such as cumene peroxide; thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole; and azobisisobutylnitrile. These compounds may be used alone or in combination of two or more.

Further, although it does not act as a photopolymerization initiator by itself, a compound capable of increasing the capacity of the photopolymerization initiator can be added by using it in combination with the above compounds. Such compounds include:
For example, a tertiary amine such as triethanolamine which is effective when used in combination with benzophenone can be mentioned.

The alkali-developable photosensitive resin composition of the present invention comprises a carboxyl group-containing photopolymerizable unsaturated compound (a), an epoxy resin (b) containing a condensed polycyclic aromatic skeleton, and a photopolymerizable resin. The initiator (c) is a main component, and the mixing ratio of each component is, for example, 100 parts by weight of a carboxyl group-containing photopolymerizable unsaturated compound (a) and a condensed polycyclic aromatic skeleton is contained. Epoxy resin (b)
Is 5 to 50 parts by weight, and the photopolymerization initiator (c) component is 0.1 to 50 parts by weight.
It is preferably in the range of 30 parts by weight.

That is, based on 100 parts by weight of the compound (a),
By using the epoxy resin (b) component containing a condensed polycyclic aromatic skeleton in an amount of 5 parts by weight or more, particularly the alkali resistance is drastically increased, and in the range of 50 parts by weight or less, the solubility in an alkaline aqueous solution is good. And developability is improved.

When the amount of the photopolymerization initiator (c) is 0.1 part by weight or more, the photopolymerization speed is increased, and the sensitivity is further improved. On the other hand, in the range of 30 parts by weight or less, light easily reaches the bottom of the resin layer, the photopolymerizability becomes good, the development margin increases, and the adhesion to the substrate increases.

From the viewpoint of excellent performance balance, the photopolymerizable unsaturated compound (a) containing a carboxyl group is particularly preferred.
It is preferred that the epoxy resin (b) containing a condensed polycyclic aromatic skeleton and the photopolymerization initiator (c) be used in amounts of 10 to 30 parts by weight and 1 to 20 parts by weight, respectively, based on 100 parts by weight of the components.

The alkali-developable photosensitive resin composition of the present invention comprises an epoxy resin component, in addition to the component (b),
Other epoxy resins may be used in combination as long as the effects of the present invention are not impaired. Other epoxy resins that can be used here include bisphenol A epoxy resin, bisphenol F epoxy resin, resorcinol epoxy resin, bisphenol S epoxy resin, dihydroxynaphthalene epoxy resin, binaphthol epoxy resin, and biphenol epoxy resin. And a tetramethylbiphenol type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a naphthol novolak type epoxy resin, a phenol-dicyclopentadiene type epoxy resin, and an alkylphenol type epoxy resin.

In order to impart flame retardancy, bromine-substituted epoxy resins such as tetrabromobisphenol A and brominated phenol novolak type epoxy resins can also be used. In this case, the bromine content in the resin composition is preferably about 3 to 30% by weight from the viewpoint of the flame retardant effect. That is, if the content is more than 30% by weight, problems such as blistering of the plating film tend to occur.

In the alkali-developable photosensitive resin composition of the present invention, a photopolymerizable unsaturated compound (d) having an ethylene bond, in addition to the above-mentioned components, is blended in accordance with the intended physical properties. Can be. In this case, the amount is preferably 50 parts by weight or less based on 100 parts by weight of the carboxyl group-containing photopolymerizable unsaturated compound (a) component from the viewpoint of tackiness after precuring.

Examples of such a photopolymerizable unsaturated compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Monomers having a hydroxyl group such as -ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate,
Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) ) Such as acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaethritol tetra (meth) acrylate, dipentaethritol hexa (meth) acrylate, glycerol (meth) acrylate ) Acrylic esters and the like.

The alkali-developable photosensitive resin composition of the present invention may optionally contain various additives such as an epoxy group curing accelerator, a thermal polymerization inhibitor, a plasticizer, a leveling agent, an antifoaming agent, and an extender. An agent can be compounded. Examples of the epoxy group curing accelerator include amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary ammonium salts, methylol group-containing compounds, and the like.
By heating the coating film in combination with a small amount thereof, it is possible to improve various properties such as heat resistance, solvent resistance, acid resistance, plating resistance, adhesion, electrical characteristics and hardness of the obtained insulating film. .

Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and phenothiazine, and examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl. Examples thereof include silicon-based, fluorine-based, and acrylic-based compounds. Examples of the extender include silica, alumina, talc, calcium carbonate, clay, and aerosil.

The method for preparing the alkali-developable photosensitive resin composition from the above components is not particularly limited, but the components (a) to (c), and (d) other components described above. The respective components can be mixed and kneaded with a three-roll mill or the like to prepare an alkali-developable photosensitive resin composition.

A method for producing a printed wiring board from the thus prepared alkali-developable photosensitive resin composition of the present invention can be carried out, for example, as follows.

That is, after the alkali-developable photosensitive resin composition of the present invention is applied on a substrate by any method such as screen printing, a solvent is evaporated, and precuring is performed to make the coating film tack-free. Then, a desired mask pattern is placed in a contact (contact) or off-contact (non-contact) state, placed on a substrate on which a coating film of the composition is formed, and selectively irradiated with ultraviolet rays. Here, the components of the composition coating film in the region exposed to the ultraviolet rays are photopolymerized to form a crosslinked structure and become insoluble. Then, the unexposed area is removed using an alkaline aqueous solution to obtain a desired developed pattern.

Examples of the aqueous alkali solution that can be used here include 0.1 to 10% by weight of an aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate or an alkanolamine such as monoethanolamine.

The pattern obtained in this way is
Excellent heat resistance and heat resistance by improving the coating strength by performing heat treatment at 0 to 200 ° C. and UV irradiation, then forming signal wiring by electroless plating and plating the inner surface of via holes. Printed wiring board can be obtained.

[0036]

The present invention will be specifically described below based on Reference Examples, Examples and Comparative Examples.

Reference Example 1 [Synthesis of 1-naphthol novolak resin] 1-naphthol 144 was placed in a 5-liter four-neck flask.
0 g (10 mol), 3000 g of methyl isobutyl ketone
And oxalic acid (100 g) were charged and stirred at 80 ° C. in a nitrogen stream at 80 ° C. at a concentration of 41% formalin (512 g, 7.0 mol).
Was added dropwise over 1 hour. The methyl isobutyl ketone is recovered by distillation, and unreacted 1-naphthol is removed by steam distillation to obtain 1-naphthol novolak resin 138.
0 g was obtained. The hydroxyl equivalent of the obtained resin was 152 g / eq.
Met.

Reference Example 2 [Synthesis of co-condensed naphthol novolak resin of 2-naphthol and 1,6-dihydroxynaphthalene] Instead of 1-naphthol, 576 g of 2-naphthol was used.
(4.0 mol) and 1,6-dihydroxynaphthalene 96
Except that 0 g (6.0 mol) was used, 1290 g of a co-condensed naphthol novolak resin was obtained in the same manner as in Reference Example 1.
The hydroxyl equivalent of the obtained resin was 101 g / eq. Met. Reference Example 3 [Synthesis of 1,6-dihydroxynaphthalene novolak resin] Reference Example 1 except that 1600 g (10 mol) of 1,6-dihydroxynaphthalene was used instead of 1-naphthol.
1,680 g of 1,6-dihydroxynaphthalene novolak resin was obtained in the same manner as described above (however, unreacted 1,6-dihydroxynaphthalene was not removed). The hydroxyl equivalent of the obtained resin was 84 g / eq. Met.

REFERENCE EXAMPLE 4 [Synthesis of methylene group-bridged dimer of 2,7-dihydroxynaphthalene] Instead of 1-naphthol, 1600 g (10 mol) of 2,7-dihydroxynaphthalene was used, and 365 g of 41% formalin was used. (5.0 moles) with oxalic acid at 49% N
In the same manner as in Reference Example 1, except that NaOH was neutralized with an equivalent amount of hydrochloric acid after completion of the reaction instead of 40 g of aOH,
Methylene group-bridged dimer of dihydroxynaphthalene 16
20 g were obtained. The hydroxyl equivalent of the obtained resin was 83 g / eq.
Met.

Reference Example 5 [Synthesis of 1,6-dihydroxynaphthalene type epoxy resin] To 1240 g (1.5 mol) of 1,6-dihydroxynaphthalene was added and dissolved 1387 g (15 mol) of epichlorohydrin, and trimethylammonium chloride 1 .
After adding 0 g, 350 g (3 mol) of a 48% aqueous potassium hydroxide solution was added dropwise at 65 ° C. under a reduced pressure of about 140 mmHg over 4 hours. During this time, the generated water was removed from the system by azeotropic distillation with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the completion of the dropwise addition, the reaction was continued for another 30 minutes. Thereafter, water was added in such an amount that the produced salt had a saturated concentration, and the produced salt was removed by washing with water. Next, unreacted epichlorohydrin was recovered by distillation, and the obtained crude resin was dissolved in 300 g of methyl isobutyl ketone and 30 g of 1-butanol. 80 g of a 10% aqueous sodium hydroxide solution was added to the solution,
Stirred at 0 ° C. for 1 hour. Thereafter, the mixture was neutralized with sodium phosphate, dehydrated, and then inorganic salts were removed by filtration. Then, methyl isobutyl ketone was removed by distillation to obtain 367 g of the desired epoxy resin (A). Its epoxy equivalent is 148 g / eq. Met.

Reference Example 6 [Synthesis of 1-naphthol novolak type epoxy resin] Reference example 1 was used in place of 1,6-dihydroxynaphthalene.
591 g of the target epoxy resin (B) was obtained in the same manner as in Reference Example 5, except that 456 g of the 1-naphthol novolak resin obtained in the above was used. Its epoxy equivalent is 230
g / eq. Met.

Reference Example 7 [Synthesis of co-condensed naphthol novolak epoxy resin of 2-naphthol and 1,6-dihydroxynaphthalene] Reference Example 2 was used instead of 1,6-dihydroxynaphthalene.
433 g of the target epoxy resin (C) was obtained in the same manner as in Reference Example 5, except that 303 g of a co-condensed naphthol novolak resin of 2-naphthol and 1,6-dihydroxynaphthalene obtained in the above was used. Its epoxy equivalent is 172
g / eq.

Reference Example 8 [Synthesis of methylene group-crosslinked dimer type epoxy resin of 2,7-dihydroxynaphthalene] Reference Example 4 was used instead of 1,6-dihydroxynaphthalene.
399 g of the target epoxy resin (D) was obtained in the same manner as in Reference Example 5 except that 249 g of a methylene group-crosslinked dimer of 2,7-dihydroxynaphthalene obtained in (2) was used. Its epoxy equivalent is 161 g / eq. Met.

Reference Example 9 [Production of cresol novolak type polyfunctional epoxy acrylate compound] 430 g of cresol novolak type epoxy resin (EPICLON N-690, manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 215 g / eq, softening point 93 ° C.) Was dissolved in 200 g of butyl cellosolve acetate, and further 144 g (2.0 mol) of acrylic acid, 0.8 g of benzyltriethylammonium chloride and 150 mg of hydroquinone were dissolved.
Was added thereto, and the mixture was reacted at 120 ° C. for 6 hours while blowing air to obtain an epoxy acrylate resin solution of a cresol novolak type epoxy resin. 450 g of butyl cellosolve acetate was further added to the obtained resin solution, 182 g of 1,2,3,6-tetrahydrophthalic anhydride was added thereto, and the mixture was reacted at 110 ° C. for 5 hours to obtain the desired cresol novolak-type carboxyl. A group-containing photopolymerizable unsaturated compound (I) solution was obtained. 0.1N KOH / MeOH
After titration with the solution, the acid value was 60 mg KOH / g.
Met.

Example 1 The solid content of the cresol novolak type carboxyl group-containing photopolymerizable unsaturated compound (I) obtained in Reference Example 9 was 100.
22 parts by weight of the 1,6-dihydroxynaphthalene-type epoxy resin obtained in Reference Example 5, 7 parts by weight of dipentaerythritol hexaacrylate as a photopolymerizable unsaturated compound, and 2,2- 4 parts by weight of dimethoxy-1,2-diphenylethan-1-one and 4 parts by weight of 2-ethyl-4-methylimidazole as an epoxy curing agent were mixed, and the viscosity was adjusted with butyl cellosolve acetate to obtain a photosensitive resin composition. . Next, this composition was applied onto a copper-clad laminate and precured at 60 ° C. for 1 hour to form a 40 μm-thick photosensitive layer having no tack at room temperature. Next, using an ultra-high pressure mercury lamp, the diameter is 30 to 200 μm.
a negative mask on which a via hole pattern of m is drawn, and selectively irradiate ultraviolet rays of 500 mJ / cm ² ,
After spraying with a 1% aqueous solution of sodium carbonate at 30 ° C. for 2 minutes for development, a cured coating film was obtained by after-curing at 150 ° C. for 30 minutes. As a result of SEM observation, the minimum diameter of the via hole that was successfully developed was 50 μm.
In addition, even after absorbing moisture at 40 ° C. × 90% RH for 96 hours, 260 ° C.
× 30 seconds of solder heat resistance.

Example 2 The procedure of Example 1 was repeated, except that 35 parts by weight of the 1-naphthol novolak type epoxy resin obtained in Reference Example 6 was used instead of the 1,6-dihydroxynaphthalene type epoxy resin. A photosensitive resin composition was obtained. Next, a coating film was formed on the copper-clad laminate in the same manner as in Example 1. SE
As a result of observation with M, the minimum diameter of the via hole that was successfully developed was 50 μm. In addition, even after absorbing moisture at 40 ° C. × 90% RH for 96 hours, solder heat resistance at 260 ° C. × 30 seconds was exhibited.

Example 3 Instead of the 1,6-dihydroxynaphthalene type epoxy resin, 26 parts by weight of a co-condensed naphthol novolak type epoxy resin of 2-naphthol and 1,6-dihydroxynaphthalene obtained in Reference Example 7 was used. A photosensitive resin composition was obtained in the same manner as in Example 1 except for the above. Next, a coating film was formed on the copper-clad laminate in the same manner as in Example 1. SE
As a result of observation with M, the minimum diameter of the via hole that was successfully developed was 50 μm. In addition, even after absorbing moisture at 40 ° C. × 90% RH for 96 hours, solder heat resistance at 260 ° C. × 30 seconds was exhibited.

Example 4 In place of the 1,6-dihydroxynaphthalene type epoxy resin, 24 parts by weight of a 2,7-dihydroxynaphthalene methylene group-crosslinked dimer type epoxy resin obtained in Reference Example 8 was used. A photosensitive resin composition was obtained in the same manner as in Example 1. Next, a coating film was formed on the copper-clad laminate in the same manner as in Example 1. As a result of SEM observation, the minimum diameter of the via hole that was successfully developed was 50 μm. After absorbing moisture at 40 ° C. × 90% RH for 96 hours, 260 ° C. ×
The solder heat resistance for 45 seconds was shown.

Comparative Example 1 In place of 1-naphthol novolak type epoxy resin,
The same operation as in Example 1 was performed except that 31% by weight of a cresol novolak type epoxy resin (EPICLON N-680, manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 210 g / eq, softening point 86 ° C.) was used. Was. As a result of the SEM observation, the minimum diameter of the via hole that could be successfully developed was 50μ.
m. Further, the solder heat resistance at 260 ° C. after absorbing moisture at 40 ° C. × 90% RH for 96 hours is 15 seconds.
At 0 seconds, cracks occurred.

[0050]

According to the present invention, high productivity and low cost can be realized in printed wiring board applications.
It is possible to provide an alkali-developable photosensitive resin composition having sufficient heat resistance and moisture resistance reliability and excellent solder heat resistance. Also,
The photosensitive resin composition of the present invention can be developed with an alkaline aqueous solution having little adverse effect on the human body and has excellent resolution. Therefore, the photosensitive resin composition of the present invention is particularly useful as a build-up multilayer wiring board, and is also useful for a permanent protective film such as a solder resist.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA00 AA04 AA10 AB15 AC01 AD01 BC12 BC14 BC31 BC34 BC43 BC51 BC74 BC85 BC86 CC17 FA17 4J002 CD062 CD201 ED086 EE036 EE056 EH077 EK036 EK046 ET006 EV206 EV316 EV326 FD 020 5E314 AA27 AA32 CC01 DD06 FF05 FF19 GG01 GG10 GG24 5E346 CC08 CC32 CC55 CC58 EE39 HH18 HH33

Claims (6)

[Claims] An alkali containing a carboxyl group-containing photopolymerizable unsaturated compound (a), an epoxy resin (b) containing a condensed polycyclic aromatic skeleton, and a photopolymerization initiator (c) as essential components. Developable photosensitive resin composition. 2. A photopolymerization initiator comprising 5 to 50 parts by weight of an epoxy resin (b) having a condensed polycyclic aromatic skeleton based on 100 parts by weight of a carboxyl group-containing photopolymerizable unsaturated compound (a). The composition according to claim 1, wherein (c) is contained in a ratio of 0.1 to 30 parts by weight. 3. The epoxy resin (b) containing a condensed polycyclic aromatic skeleton is a reaction product of dihydroxynaphthalene and epihalohydrin, or a reaction product of a condensate of mono- or dihydroxynaphthalene with aldehydes and epihalohydrin. The composition according to claim 1. 4. An epoxy resin (b) containing a condensed polycyclic aromatic skeleton comprising 1,1-bis (2,7-dihydroxy-
4. The composition according to claim 1, which is a reaction product of 1-naphthyl) methane and epihalohydrin. 5. The composition according to claim 1, further comprising a photopolymerizable unsaturated compound (d) having an ethylene bond in addition to the components (a) to (c). . 6. The amount of the photopolymerizable unsaturated compound (d) having an ethylene bond used is 1 to 50 parts by weight based on 100 parts by weight of the carboxyl group-containing photopolymerizable unsaturated compound (a). The composition of claim 5, wherein