JPH1149847A - Photosensitive resin composition and insulation film and multilayer circuit board produced by using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of forming an insulation film having high roughening property and adhesivity and a via-hole having high connection reliability by including an epoxy resin and a resin having an N-substituted carbamic acid ester group and a radically polymerizable unsaturated bond on the side chain. SOLUTION: This resin composition contains the 1st resin consisting of an epoxy resin (e.g. a polyfunctional epoxy resin such as bisphenol A-type resin or phenolic novolak-type epoxy resin having an epoxy equivalent of 100-500 g/equivalent and crosslinkable by cationic polymerization) and the 2nd resin (preferably an epoxyacrylate resin crosslinkable by radical polymerization) having an N-substituted carbamic acid ester group and a radically polymerizable unsaturated bond (preferably a vinyl ester group) on the side chain at a weight ratio (1st resin: 2nd resin) of (0.8-5):1, preferably (1-3):1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition suitable for forming photovia holes when forming a multilayer wiring board by a build-up method, an insulating film obtained by curing the composition, The present invention relates to a multilayer wiring board provided with an insulating film and semiconductor mounting.

[0002]

2. Description of the Related Art In recent years, printed wiring boards have made remarkable progress in order to reduce the size and weight of electronic devices. In particular, bare chips, CSP (Chip Size Package), BGA (B
In order to support high-density mounting such as allGrid Array), a multi-layer wiring board manufacturing method using a build-up method using photolithography, which performs interlayer connection with via holes with a high degree of freedom, is widely used, and is used for this method There is a need for a high-performance photosensitive resin composition.

In high-density surface mounting, especially in BGA and bare chip mounting, which have recently attracted attention, a multilayer wiring board, which is a mounting base, is also exposed to high temperatures in a reflow step, a gold wire bonding step, and the like during mounting. Therefore, it is necessary to use a photosensitive resin having a high glass transition point (Tg) for the insulating layer so that various characteristics such as an adhesive force and an elastic modulus at a high temperature at the time of mounting and repair of a mounted component are not reduced. As such a photosensitive resin having a high glass transition point, a resin mainly composed of an epoxy resin which is cured by cationic polymerization using a photoacid generator is known.
For example, JP-B-49-17040 discloses a widely known technique of a photosensitive resin composition mainly composed of epoxy, and JP-A-54-48881 and JP-A-56-55420. ,
Japanese Patent Application Laid-Open No. Hei 5-273753 discloses a technique mainly using an epoxy resin and a vinyl compound.

In a build-up type multilayer printed wiring board manufacturing process using photolithography, a core substrate 3 having an inner conductor 1 on its surface is usually used as shown in FIG.
A photosensitive material (photosensitive resin composition) is formed on the surface (see FIG. 1).
(A)), the photosensitive film 2 is exposed through a predetermined mask,
After developing, a via-hole forming through-hole is formed which penetrates the photosensitive film 2 and reaches the lower inner wiring (FIG. 1).
(B)) The surface of the insulating layer (including the inner wall of the through hole for forming a via hole) is roughened with an oxidizing agent in order to secure adhesion to a wiring conductor (such as plated copper) to be formed next (FIG. 1).
(C-1)) The plating resist 6 having a predetermined shape on the roughened surface.
Then, outer layer wirings 7 (planar wiring and via hole wiring) are formed by plating on the exposed portion of the roughened surface (FIG. 1).
(d-1)).

[0005]

However, in general, since the amount of ultraviolet light reached by its own absorption of ultraviolet light varies, the degree of curing of the photosensitive resin composition varies depending on the depth from the surface at the time of exposure, and the film surface There is a large difference between the bottom and the bottom. Since the amount of ultraviolet light absorbed by the photosensitive resin composition varies depending on the site, there is a great difference in the degree of curing between the top and bottom of the photosensitive film during exposure. Therefore, when the surface roughening treatment is performed after the exposure and development, the progress of the roughening at the bottom of the via hole forming through hole is larger than that at the top, and therefore, in actuality, the insulating film is peeled off or FIG. As shown in (2) and (d-2), there arises a problem that the inner diameter of the through hole 4 for forming a via hole expands at the bottom (that is, it becomes a reverse tapered shape). The reverse tapered portion 5 of the via hole forming through hole is not preferable because it causes disconnection of the via hole wiring and cracks of the insulating layer.

In order to prevent this and uniformly roughen the inner wall of the via hole for forming a via hole, a sensitizer is added to the photosensitive resin composition, the exposure amount is increased, or a heat treatment is performed after development. Thus, it is conceivable to advance the curing of the insulating layer before the roughening treatment. However, in this case, the hardening of the surface portion of the insulating film proceeds excessively, so that the surface is not satisfactorily roughened in the roughening step, and sufficient adhesion to the planar wiring conductor cannot be obtained.

[0007] Therefore, in the conventional technique, it is impossible to achieve both the roughening property and the adhesive property of the insulating film. This problem becomes conspicuous when the thickness of the insulating film is set to 40 μm or more, and in particular, it was impossible to form a via hole of 25 μm or more in the insulating film having a thickness of 45 μm or more by the conventional technique.

Accordingly, an object of the present invention is to provide a photosensitive resin composition capable of forming an insulating film having good roughening properties and adhesiveness and a via hole having high connection reliability, and a photosensitive resin composition formed using the same. Another object of the present invention is to provide an insulating film, a multilayer wiring board provided with the insulating film, and a semiconductor package.

[0009]

In order to achieve the above object, the present invention provides a first resin which is an epoxy resin, an N-substituted carbamate atomic group and a radical polymerizable unsaturated bond in a main component side chain. And a second resin having the following formula:

The photosensitive resin composition of the present invention comprises an epoxy resin which is crosslinked by cationic polymerization and a second resin which is crosslinked by radical polymerization and has an N-substituted carbamic acid ester atomic group and a radically polymerizable unsaturated bond in a side chain. By using in combination with the resin of the present invention, even if the amount of ultraviolet light is reduced according to the depth, the inner wall of the via hole forming through hole can be uniformly cured, and further, it is possible to prevent the surface from being excessively cured. it can. Therefore, the photosensitive resin composition of the present invention can provide an insulating film having excellent roughening properties and adhesiveness, and can form a through hole that is not reverse-tapered in the insulating film. Particularly suitable as a photosensitive material for film formation.

[0011] The present invention relates to a substrate in which a fiber cloth is impregnated with a thermosetting resin, wiring formed on the surface of the substrate, an interlayer insulating film formed on the substrate and the wiring, and In a multilayer wiring board having a formed wiring and a conductive material filled in a via hole penetrating the film, the interlayer insulating film is made of the above-described photosensitive resin composition.

Further, the present invention resides in a semiconductor package in which a semiconductor element is mounted on the wiring formed on the interlayer insulating film.

Further, in the present invention, an insulating film having the photosensitive resin composition, an insulating film obtained by curing,
A multilayer wiring board including the insulating film as an interlayer insulating film is provided. Further, by using the photosensitive resin composition of the present invention, even when a thick insulating film is formed, a via hole with high connection reliability can be formed in the insulating film. Therefore,
In the present invention, the thickness is 30 μm or more, furthermore, 45 μm or more,
Preferably 50-100 μm, more preferably 50-60
μm, an interconnect formed on the surface of the interlayer insulating film, and a wire having a diameter of 25 μm or more, preferably 40 to 100 μm, which penetrates the interlayer insulating film, and more preferably about the thickness of the interlayer insulating layer. A multilayer wiring board having a 1: 1 diameter via hole for interlayer connection is provided.

The weight ratio between the first resin and the second resin is as follows:
0.8: 1 to 5: 1, preferably 1: 1 to 1: 1.
More preferably, the ratio is 3: 1. If the amount of the second resin is small, it may not be possible to sufficiently prevent the via from becoming reversely tapered. If the amount is too large, the cationic polymerization may be inhibited and the resolution may be reduced.

As the first resin in the present invention, it is preferable to use an epoxy resin having an epoxy equivalent of 100 to 500 g / equivalent. The epoxy resin used as the first resin is not particularly limited, but has an epoxy equivalent of 100 to 300.
g / equivalent bifunctional epoxy resin, epoxy equivalent 160 ~
500 g / equivalent of a trifunctional or higher polyfunctional epoxy resin or a mixture thereof can be used. Further, an epoxy resin which is halogenated (preferably brominated) for flame retardation may be used in combination.

The bifunctional epoxy resin reduces the varnish viscosity of the photosensitive resin composition, contributes to flattening when applying the photosensitive resin varnish to the inner layer wiring, and increases the flexibility of the photosensitive film after drying. To prevent the occurrence of cracks,
The resin composition film (insulating film) after curing the photosensitive film is provided with an adhesive force with the inner wiring.

The bifunctional epoxy resin which can be used as the first resin in the present invention includes, for example, various bisphenol A epoxy resins, bisphenol F epoxy resins, aliphatic epoxy resins, alicyclic epoxy resins and the like. For example, Epicoat 801, 802, 807, 815, 819, 825, manufactured by Yuka Shell Epoxy Co., Ltd.
827, 828, 834; Nadecor EX-201, 212, 821 manufactured by Nagase Kasei Kogyo Co., Ltd .; Asahi Denka Kogyo Co., Ltd.
Alicyclic epoxy resins such as KRM2110 and 2410 are commercially available. Further, a bifunctional epoxy resin having an epoxy equivalent of 300 g / equivalent or more, such as Epicoat 1001, 1004, 1009 manufactured by Yuka Shell Epoxy Co., Ltd., can be used. Since the glass transition point may be too low when is used, it is preferable to adjust the epoxy equivalent of the entire first resin to 100 to 300 g / equivalent by adding the above-mentioned bifunctional epoxy resin having a low epoxy equivalent.

The trifunctional or higher epoxy resin has the effect of increasing the crosslink density of the cured resin composition film to increase the glass transition temperature. Examples of the trifunctional epoxy resin that can be used as the first resin in the present invention include a phenol novolak epoxy resin and an ortho-cresol novolak epoxy resin. Commercially available trifunctional epoxy resins include Eicoat 180S65 and 1031S manufactured by Yuka Shell Epoxy Co., Ltd., and E-coat manufactured by Sumitomo Chemical Co., Ltd.
SCN-195,220, BREN- manufactured by Nippon Kayaku Co., Ltd.
104, 105, E00CN-104S, EPPN-2
01, 501 and KRM-2650 manufactured by Asahi Denka Kogyo KK.

As the second resin, a resin having an N-substituted carbamic acid ester atomic group in a side chain and a radical polymerizable unsaturated bond is used. As the radical polymerizable unsaturated bond, a vinyl ester atomic group is preferable.
The resin having a vinyl ester atom group in the side chain is described in Journal of the Adhesion Society of Japan, vol. 31, No. 8, P334
(1995) (by Shibata).

The main chain skeleton of the second resin is not particularly limited, as long as it can form an N-substituted carbamic acid ester atomic group on the side chain (preferably has a hydroxyl group). It can be appropriately selected according to the required film properties. From the glass transition point (Tg), various types of bisphenol A type epoxy resin, bisphenol F type epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, It is preferable to use a polyfunctional epoxy resin such as a phenol novolak type epoxy resin and an ortho-cresol novolak type epoxy resin, or a halide such as a bromide thereof. In particular, a resin obtained by adding acrylic acid or methacrylic acid to a polyfunctional epoxy resin is preferable because a radically polymerizable vinyl group is introduced into a side chain. Therefore, an epoxy acrylate resin or an epoxy methacrylate resin in which a part of the hydroxyl group is substituted with an N-substituted carbamate atom group,
Particularly suitable as a resin.

In order to introduce an N-substituted carbamate atom group into the side chain of these main chain compounds, for example, as shown in FIG.
As shown in the above, a compound having a hydroxyl group may be used as the main chain compound A, and a compound B having an isocyanate group may be added to a part of the hydroxyl group.

As the compound having an isocyanate group, a radically polymerizable vinyl group can be introduced.
In particular, it is preferable to use acryl isocyanate or methacryl isocyanate. Therefore, it is particularly preferable to use an isocyanate-added epoxy acrylate resin or an isocyanate-added epoxy methacrylate resin as the second resin.

Specifically, an oligomer represented by the following general formula (Chemical Formula 1) or a halide of the oligomer, or an oligomer represented by the following general formula (Chemical Formula 3) or a halide of the oligomer is converted into a second compound. It is preferable to use it as a resin.

[0024]

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(Where X is hydrogen or methyl, Y is hydrogen or alkyl having 1 to 4 carbons, n is 0 or 1)
It is. )

[0026]

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(Where X is hydrogen or a methyl group, Y is hydrogen or an alkyl group having 1 to 4 carbon atoms. Two Xs bonded to one carbon atom may be the same or different. In each of the formulas (1) and (3), a part of R ¹ contained in one molecule is an N-substituted carbamine represented by the following general formula (2). An acid ester group, and the remaining R ¹ is a hydroxyl group.

[0028]

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(Here, R ² is an alkylene group having 1 to 4 carbon atoms, and Z is hydrogen or an alkyl group having 1 to 4 carbon atoms.) The total number of R ¹ contained in one molecule is The proportion of the occupied N-substituted carbamate atomic group is desirably 0.5 mol% or more in order to obtain a sufficient effect, and is preferably 20 mol% or less in order to maintain a sufficient resolution. preferable. As the halide, for example, those in which at least one of hydrogens of an aromatic nucleus is substituted by a halogen atom can be used.

The resin composition of the present invention preferably further contains a substance that generates an acid and / or a radical upon irradiation with light, that is, a photoacid generator and / or a photoradical polymerization initiator.

The photoacid generator is a component that generates an acid upon exposure and contributes to the curing of the epoxy resin that undergoes cationic polymerization. The content of the photoacid generator is 1% of the total of the first resin and the second resin.
Preferably, the amount is 1 to 10 parts by weight based on 00 parts by weight. If it is 1 part by weight or more, sufficient resolution can be obtained.
If the amount is 10 parts by weight or less, sufficient roughening properties can be secured.

The photo-radical polymerization initiator is a component that generates a radical species upon exposure to light and radically polymerizes and contributes to the curing of a radical-polymerizable resin having a vinyl group. The amount is preferably 0.1 to 5 parts by weight based on 100 parts by weight in total with the second resin.
When the amount is 0.1 part by weight or more, the effect of suppressing the inversed taper of the via shape is sufficiently obtained, and when the amount is 5 parts by weight or less, sufficient resolution is obtained.

The present invention can be practiced without using a photo-radical polymerization initiator when the photo-acid generator generates radicals at the time of light exposure. It is preferable to add a radical polymerization initiator.

The photoacid generator suitable for the present invention includes BF
₄ , onium salts such as sulfonium salts and iodonium salts having ₄ , anion of PF ₆ , AsF ₆ and SbF ₆ as counter anions. Examples of the sulfonium salt include triphenylsulfonium salt, dimethylphenylsulfonium salt, diphenylbenzylsulfonium salt, tolyl sulfonium salt, 4-butoxyphenyldiphenylsulfonium salt, tris (4-phenoxyphenyl) sulfonium salt, and 4-acetoxy-phenyl. Examples include diphenylsulfonium salt, tris (4-thiomethoxyphenyl) sulfonium salt, di (methoxynaphthyl) methylsulfonium salt, dimethylnaphthylsulfonium salt, and phenylmethylbenxylsulfonium salt. Examples of iodonium salts include diphenyliodonium salt, phenyl-2-thienyliodonium salt, di (2,4-methoxyphenyl) iodonium salt, di (3-methoxycarbonylphenyl) iodonium salt, and di (4-acetamidophenyl). ) Iodonium salts and (4-octyloxyphenyl) phenyliodonium salts.

As the photoradical polymerization initiator suitable for the present invention, benzoin, methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1
-Carbonyl compounds represented by polynuclear quinolines such as -chloroanthraquinone, 2-amylanthraquinone, azo compounds represented by azobisisobutyronitrile, diazonium compounds, mercaptans, organic sulfur compounds represented by alkyldisulfide, alkyl There are many compounds such as metals and metal carbonyls, and carbonyl compounds are particularly preferable.

The radical polymerization initiator, which is a carbonyl compound, includes a hydrogen abstraction type and a self-cleavage type. Hydrogen abstraction types include thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone,
There are thioxanthones such as 4-diisopropylthioxanthone and benzophenones such as benzophenone and 4,4-bismethylaminobenzophenone. These are also applicable to the present invention, but the present invention is particularly applicable to the self-cleavage type radical polymerization initiation. Agents are suitable.

The self-cleaving radical polymerization initiator includes benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and benzyl methyl ketal and their alkyl ethers, acetophenone, 2,2- Dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, diethoxyacetophenone, 2,2-
Examples include acetophenones such as diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone and 1-hydroxycyclohexylphenyl ketone, and ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal.

In order to increase the curing speed, polymerization of tertiary amines such as ethanolamine and N-methyldiethanolamine, and benzoic acid derivatives such as 2-dimethylaminoethylbenzoic acid and ethyl 4-dimethylaminobenzoate are accelerated. An agent may be used. The amount of these amine polymerization accelerators to be used should be adjusted so as not to inhibit cationic polymerization.

It is preferable that the photosensitive resin composition of the present invention further contains a third resin having a phenolic hydroxyl group. By adding this third resin, the solubility in an aqueous developer (particularly an aqueous alkaline solution) is improved during development, and the epoxy resin reacts with the epoxy resin during curing to increase the crosslink density. Glass transition point (T
g) can be increased.

Examples of the phenolic hydroxyl group-containing resin that can be used as the third resin in the present invention include novolak resin, resol resin, polyhydroxystyrene as hydroxystyrene polymer, and polyhydroxystyrene as hydroxyphenylmaleimide polymer. Phenylmaleimide and the like. In particular, various resol resins having a phenolic hydroxyl group and a methylol group in the same molecule are preferable. A resin having a phenolic hydroxyl group of a self-condensation type such as a resole resin causes a self-condensation reaction by an acid catalyst, so that the crosslink density at the time of curing is high, and a cured film having a higher glass transition point is provided. Since the amount of phenolic hydroxyl groups remaining in the cured film is reduced, there is an advantage that the plating solution resistance is improved.

As the third resin, a novolak resin which is a condensation product of a compound having a phenolic hydroxyl group and formaldehyde is also suitable. In the present invention, phenol, o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,5-xylenol,
A phenolic hydroxyl group-containing compound such as 3,4-xylenol or 3,5-xylenol or a mixture thereof and a condensation product with formaldehyde are suitable, and m, p-cresol novolac phenol is particularly preferable.

When the third resin is used, it is effective if the content is at least 5 parts by weight and not more than 30 parts by weight based on 100 parts by weight of the total of the first resin and the second resin. If so, good solubility in the developer can be maintained.

Further, the photosensitive resin composition of the present invention preferably contains a rubber component. By adding the rubber component, flexibility can be imparted to the cured resin composition film, cracks can be suppressed, and the adhesive force with the conductor wiring can be increased.

Examples of the rubber component that can be used in the present invention include polybutadiene or an epoxidized product thereof, a copolymer of acrylonitrile butadiene having a vinyl group, an amino group or a carboxyl group at a terminal, or an epoxy resin thereof. And the like. Particularly, a rubber modified with an epoxy resin is preferable. They are,
They may be used alone or in combination of two or more.

When this rubber component is used, its content is preferably 5 to 40 parts by weight based on 100 parts by weight of the total of the first resin and the second resin. When the amount is 5 parts by weight or more, good flexibility is imparted to the cured resin composition film, and adhesion to the plating wiring is also good. Also, 4
If the amount is more than 0 parts by weight, the resolution may be deteriorated, or the glass transition point of the cured resin composition film may be lowered.

The photosensitive resin composition of the present invention preferably contains rubber fine particles. By dispersing the rubber fine particles in the film, it is possible to suppress a decrease in the glass transition point of the cured film. It is desirable that the particle diameter of the rubber fine particles is smaller than the thickness of the insulating film to be formed and the diameter of the via hole. For example, XER91P manufactured by Nippon Synthetic Rubber Co., Ltd. or Y manufactured by Toto Kasei Co., Ltd. in which rubber particles are dispersed in epoxy resin.
R-528, YR-516 and the like are suitable for the present invention. The rubber fine particles are preferably 5 to 40 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the total of the first to third resins. Further, the photosensitive resin of the present invention may include a radical-curable fourth resin. This radical-curable resin is a radical-curable resin having an unsaturated double bond, and may be, for example, a reactive monomer such as styrene, acrylic acid, or methacrylic acid, or a polyfunctional oligomer or the above-described one. The raw material of the second resin, that is, a resin having a vinyl ester atom group in the side chain before the introduction of the N-substituted carbamic acid ester atom group in the side chain may be used. In particular, it is preferable to use a resin in which a carboxylic acid anhydride is added to a hydroxyl group in a side chain and has a vinyl ester atom group in a side chain because solubility in a developing solution is improved.

When the fourth resin is used, its content is preferably 5 to 30 parts by weight based on 100 parts by weight of the total of the above-mentioned first to third resins. This resin can be polymerized by the above-mentioned photo-radical polymerization initiator.

The photosensitive resin composition of the present invention may further comprise, for example, a thermosetting agent,
A release agent, a flame retardant, a sensitizer, inorganic compound particles, a leveling agent and the like may be appropriately contained. By using these, heat resistance, roughening property, plating resistance, developability, tack-free property, crack resistance, and the like can be improved.

The thermosetting agent is a thermosetting catalyst for the epoxy resin, and can cure the epoxy resin remaining by the photocuring reaction by heating. In the case of using this, by performing a heat treatment at the time of exposure curing and / or after the exposure curing, the crosslinking density of the cured resin composition film is increased as compared with the case of curing only with the photoacid generator, The glass transition point can be increased.

Examples of the thermosetting agent suitable for the present invention include various epoxy resin thermosetting catalysts such as triphenylphosphine and imidazole, and a thermosensitive onium salt which generates an acid upon heating is particularly preferable. Examples of such a material include 2-butenyltetramethylenesulfonium hexafluoroantimonate (CP-66) manufactured by Asahi Denka Kogyo KK. When a thermosetting agent is used, the glass transition point required for the cured resin composition film,
The type and content can be adjusted by characteristics such as elastic modulus.

When a triphenylphosphine-based or imidazole-based compound is used as the thermosetting agent, its content is adjusted to the total amount of the above-mentioned first to fourth resins so as not to inhibit the photocuring reaction. For 100 parts by weight,
It is desirable that the content be 1 part by weight or less. When an onium salt is used, it does not inhibit the photocuring reaction,
Although it can be used in an amount of 1 part by weight or more based on 100 parts by weight of the total amount of the fourth resin, the amount is desirably 10 parts by weight or less in order to prevent the cured resin composition film from becoming brittle.

The release agent exudes to the surface of the photosensitive film during drying and curing of the photosensitive film, and covers the surface of the photosensitive film.
As a result, the tack-free property of the photosensitive film can be improved, and the penetration of the developer into the exposed and cured portions can be suppressed, and the developability can be improved. Examples of the release agent suitable for the present invention include polysiloxane, polyether, or
The copolymer is mentioned, and they can be used together. Examples of the polysiloxane include straight silicone oils such as dimethyl silicone oil, methyl phenyl silicone oil and methyl hydrogen silicone oil, methyl styrene, long chain alkyl, polyether, carbinol, epoxy, carboxyl, mercapto, higher fatty acid, Examples include dimethylpolysiloxane modified with methacryl and the like. Commercially available products include Perenol F40 and Perenol S43 manufactured by San Nopco, SC5570 manufactured by Dow Corning Toray Silicone Co., Ltd., and TSA750 manufactured by Toshiba Silicone Co., Ltd. When a release agent is used, its content is desirably 1 to 5 parts by weight based on 100 parts by weight of the total of the above-described first to fourth resins.

The flame retardant is a component that contributes to the flame retardancy of the photosensitive resin composition, and a substance known as a flame retardant or a flame retardant auxiliary can be used. Flame retardants suitable for the present invention include, for example, epoxy, aromatic, aliphatic and alicyclic halides, red phosphorus and yellow phosphorus, non-halogen phosphates, halogen-containing phosphates, polyphosphates, polyphosphates. Examples include phosphorus compounds such as phosphonates, phosphorus-containing polyols and polyphosphoric acids, and antimony-based flame retardants such as antimony trioxide. In addition, two or more arbitrarily selected flame-retardant materials can be used in combination and their synergistic effect can be utilized. When a flame retardant is used, its content is based on 100 parts by weight of the total of the first to fourth resins.
It is preferably from 1 to 10 parts by weight, particularly preferably from 3 to 10 parts by weight. If the amount is too small, a sufficient flame-retardant effect cannot be obtained, and if it is too large, the resolution, adhesive strength, plating solution contamination, etc. are adversely affected.

As the sensitizer, compounds that act as a sensitizer for the photoacid generator can be widely used. For example, derivatives that act as sensitizers for sulfonium salts include derivatives such as perylene, anthracene, and phenothiazine. In addition, dyes such as acridine orange, acridine yellow, benzoflavin, phosphine R, and setoflavin T, which act as sensitizers for iodonium salts, are available. As a commercially available product, there is SP100 manufactured by Asahi Denka Kogyo KK. When this sensitizer is used, its content is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the total of the first to fourth resins.

The inorganic compound particles have the effect of improving the tack-free property of the photosensitive film and improving the surface roughening efficiency of the plated surface of the resin composition film after curing.
A hydroxide, oxide or carbonate of a Group IVa or Group IVa element may be used. One of these compounds may be used, or two or more compounds selected therefrom may be used in combination. Examples of the inorganic compound particles that can be used in the present invention include calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, and silicon oxide. The particle diameter of the inorganic compound is desirably smaller than the thickness of the formed insulating film and the diameter of the via hole. When using these inorganic compound particles, the content is 100% of the total amount of the first to fourth resins.
It is desirable that the amount be 3 to 50 parts by weight with respect to parts by weight. When the amount is 3 parts by weight or more, an effective adhesive property improving effect is obtained, but when the amount is 50 parts by weight or more, developability may be impaired.

The leveling agent is an additive for improving the flatness of the photosensitive film after film formation (such as printing), and an acrylate copolymer can be used. Commercial products of this leveling agent include, for example, Modaflow manufactured by Monsanto. When a leveling agent is used, its content is based on 100 parts by weight of the total of the first to fourth resins.
It is desirable to use 0.5 to 10 parts by weight.

Further, the photosensitive resin composition of the present invention may appropriately contain a solvent. That is, a photosensitive resin varnish obtained by dissolving or dispersing components appropriately selected from the above-described components in these solvents is also suitable as the photosensitive resin composition of the present invention.

The resin composition of the present invention includes aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol and ethanol, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and tetrahydrofuran, and ethers. , Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, glycol derivatives such as methylcellosolve acetate and ethylcellosolve acetate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, and alicyclics such as cyclohexanone and cyclohexanol A hydrocarbon or a petroleum solvent such as petroleum ether or petroleum naphtha can be used.

The solid content concentration of the photosensitive resin composition of the present invention can be appropriately determined according to the film formation method, the film thickness after film formation, and the like.
This is preferable because the film can be formed to a thickness of 20 to 100 μm by one application.

[0060]

BEST MODE FOR CARRYING OUT THE INVENTION

<Examples 1 to 9> Each component shown in Table 1 was dissolved and dispersed in 1-acetoxy-2-ethoxyethane to produce a liquid varnish having a solid content concentration of 60% by weight on a substrate in the form of a film. Then, it is dried and solidified at a temperature described below, and the following (1) to
The performance of the test (7) was evaluated, and as shown in Table 1, good results were obtained. In this embodiment, each resin is dried at a temperature at which the resins do not react with each other. That is, in any of Examples 1 to 9, a resin film having excellent adhesive force and showing good characteristics without peeling around the via hole forming through hole was able to be obtained. Further, these resin films have high resolution and a high glass transition point, and have characteristics suitable for an insulating film of a multilayer wiring board.

[0061]

[Table 1]

The first resin is a polyfunctional epoxy resin, and "Ep-828" is a bisphenol A type epoxy resin (189 g) manufactured by Yuka Shell Epoxy Co., Ltd.
/ Equivalent), and “ESCN-195” is a cresol novolak type epoxy resin (19%) manufactured by Sumitomo Chemical Co., Ltd.
8 g / equivalent), and “BREN-105” is a brominated novolak epoxy resin (270 manufactured by Nippon Kayaku Co., Ltd.).
g / equivalent), and “KRM-2650” is Asahi Denka Kogyo
Cresol novolak type epoxy resin (220
g / equivalent), and “CNA105” is an acrylic isocyanate-added epoxy acrylate (acrylisocyanate-added) manufactured by Nippon Kayaku Co., Ltd. as a second resin having an N-substituted carbamate atomic group and a radical polymerizable unsaturated bond. 2%), and “HP-180R” is a resole resin manufactured by Hitachi Chemical Co., Ltd. as a third resin having a phenolic hydroxyl group.

"UVI-6974" is a triphenylsulfonium hexafluoroantimonate (photoacid generator) manufactured by Union Carbide, and "XER91
“P” is rubber fine particles manufactured by Nippon Synthetic Rubber Co., Ltd.
"-8208" is an epoxy-modified rubber manufactured by Daito Sangyo Co., Ltd., and "R5259" which is a radical-curable resin is an acid anhydride-added epoxy acrylate (acid value 72 mg KOH / mg) manufactured by Nippon Kayaku Co., Ltd. , "CP-66" is 2-butenyltetramethylenesulfonium hexafluoroantimonate (a thermosetting agent) manufactured by Asahi Denka Kogyo Co., Ltd.
"SP100" is Asahi Denka Kogyo Co., Ltd. UVI-697.
"S43" is a polysiloxane copolymer (release agent) manufactured by Sannobuco "Perenol S4".
3 ", and a powder having an average particle diameter of 1 μm was used for silicon oxide.

(1) Evaluation of resolution (developability) A photosensitive resin varnish was formed on the copper surface of a metal foil having a two-layer structure of aluminum and copper (“UTC foil” manufactured by Mitsui Kinzoku Mining Co., Ltd., thickness 50 μm). Was coated with a bar coater and dried at room temperature for 1 hour and at 120 ° C. for 15 minutes to prepare a sample having a photosensitive layer having a thickness of 50 to 55 μm. This sample has a diameter of 10
UV light was irradiated at 2.5 J / cm ² by an ultra-high pressure mercury lamp through a 160 μm via-hole mask, and then irradiated at 120 ° C.
For 15 minutes to accelerate the curing, and then the developer (2, 2
-Spray development with butoxyethoxyethanol (400 ml / L, aqueous solution containing 10 g / L of sodium hydroxide), and the diameter of the developable via hole (that is, the inner diameter of the thinner through-hole obtained) was taken as the resolution.

(2) Evaluation of tack-free property In the resolution test of the above (1), when the via-hole mask was peeled off from the sample after exposure, the sample in which the photosensitive layer adhered to the via-hole mask was regarded as having poor tack-free property. It was determined that the photosensitive layer did not adhere to the mask was good. In Table 1, "x" indicates that the tack-free property is poor, and "o" indicates that the tack-free property is good.

(3) Measurement of Film Thickness The developed sample obtained in the resolution test (1) above was
It was cured by heating at 80 ° C. for 2 hours. Next, the aluminum layer was etched with an aqueous sodium hydroxide solution (100 g / L), washed, and then sulfuric acid (100 g / L) and 35%
The copper layer was etched with an etching solution composed of a hydrogen peroxide solution (200 g / L), a cured film after curing was collected, and the film thickness was measured.

(4) Measurement of Glass Transition Temperature The cured film after measuring the film thickness was cut into a rectangle of 30 mm × 5 mm to prepare a sample, and “D” manufactured by IT Measurement Control Co., Ltd.
The glass transition temperature (Tg) was determined by measuring dynamic viscoelasticity using "VA-200". The measurement condition is the distance between fulcrums of 20m
m, the measurement frequency was 10 Hz, the heating rate was 5 ° C./min, and the measurement range was from room temperature to 300 ° C.

(5) Measurement of Adhesive Strength with Inner Layer Wiring The surface of a copper foil having a thickness of 20 μm was roughened with an aqueous solution of ammonium persulfate, and an oxide film was formed with an aqueous solution mainly containing sodium perchlorate. It was reduced with an aqueous solution and dried. Next, a photosensitive varnish was applied to the obtained roughened surface in the same manner as in the resolution test (1) above.
After drying and exposing the entire surface, it was cured by heating at 180 ° C. for 2 hours. Subsequently, an epoxy adhesive ("Araldite" manufactured by Chise Nagase Co., Ltd.) was applied to the surface of the resin film, bonded to a glass epoxy substrate, and the peel strength of the copper foil was measured by the method of JISC6481.

(6) Measurement of Adhesive Strength to Plating Wiring A copper-clad laminate having a copper foil having a thickness of 18 μm was prepared, and the surface of the copper foil was treated in the same manner as in the above test (5). After applying a varnish and exposing to form a resin film, 140
The composition was heated at 30 ° C. for 30 minutes to accelerate the curing, and the surface was roughened with an aqueous solution of permanganic acid, neutralized, applied with a plating catalyst, and activated. However, only Comparative Example 2 was further heated at 180 ° C. for 60 minutes to promote curing. Next, after a copper layer was formed on the activated resin film surface by chemical plating, electroplating was performed on the copper layer surface to form a panel-plated copper layer having a thickness of about 20 μm. This was further heated at 180 ° C. for 2 hours, and the peel strength of the plated copper layer was measured by the method of JISC6481.

(7) Confirmation of presence / absence of via-hole peeling after roughening treatment Using a copper-clad laminate having a copper foil having a thickness of 18 μm, the surface of the copper foil was treated in the same manner as in the above test (5), A varnish is applied, exposed through a via-hole mask in the same manner as in the above test (1), and developed to form a through hole that penetrates the resin film and reaches the lower copper foil. In the same manner as in the above, the surface was roughened by heating to accelerate the curing, and the periphery of the through hole was observed. However, under the same roughening conditions, the state of peeling slightly changes depending on the diameter of the via hole.
Observation was made on via holes having a diameter of 50 μm. Table 1 shows that no peeling was observed at the bottom of the resin film through-hole.
In the case where peeling occurred and the bottom of the through hole was whitened,
In Table 1, "x" is described.

Comparative Examples 1 to 3 In Comparative Example 1, the second resin of the present invention, that is, a resin (CNA105) having an N-substituted carbamic acid ester atomic group and a radical polymerizable unsaturated bond in a side chain was used. A resin film was formed in the same manner as in Examples 1 to 9 using a photosensitive resin composition containing no resin, but peeling occurred at the bottom of the resin film through-hole, resulting in an inversely tapered shape.

In Comparative Example 2, a film was formed in the same manner as in Comparative Example 1 except that the film was heated at 180 ° C. for 60 minutes before roughening to further promote curing. In Comparative Example 2, peeling did not occur at the bottom of the resin film through-hole in the roughening treatment due to the effect of the thermosetting agent. However, the surface of the resin film could not be sufficiently roughened, and the adhesion between the resin film and the plated copper layer was low, which was not practical.

In Comparative Example 3, a film was formed in the same manner as in Comparative Example 1, except that a sensitizer was added to the photosensitive varnish. In Comparative Example 3, as in Comparative Example 2, the bottom of the resin film through-hole was not peeled off in the roughening treatment, but the surface of the resin film could not be sufficiently roughened. Adhesion was low and was not practical.

Example 10 An inner wiring board was manufactured by etching a glass epoxy substrate having a copper layer having a thickness of 18 μm. The surface of the inner wiring board was roughened with an aqueous solution of ammonium persulfate, an oxide film was formed with an aqueous solution containing sodium perchlorate as a main component, then reduced with an aqueous solution of dimethylamine borane, and dried. Then, Example 4
Was applied by screen printing and dried to form a photosensitive layer. The thickness of the photosensitive layer is about 50 μm
Met.

Next, a predetermined position was exposed to light (2.5 J / cm ² ) via a via-hole mask, heated at 120 ° C. for 15 minutes, and developed in the same manner as in Examples 1 to 9.
Heating was performed at 30 ° C. for 30 minutes to obtain an insulating film having a through-hole for forming a via hole at a predetermined position, which penetrated the insulating film and reached the underlying wiring.

After mechanically polishing the surface of the obtained insulating film,
The inner wall of the via hole and the insulating film surface were roughened with a permanganic acid aqueous solution. Subsequently, after neutralizing and applying a plating catalyst, an etching resist was laminated to form a pattern. Next, the plating catalyst was activated, a conductor was deposited on the activated surface by chemical plating to form via holes and second-layer fine wiring, and after drying, post-curing was performed at 180 ° C. for 2 hours.

Further, the same steps of forming a photosensitive film, surface treatment, and forming a conductor layer are repeated to form a multi-layer structure.
A multilayer wiring board 9 similar to that shown in (e) was obtained. The obtained multilayer wiring board 9 is placed in a solder reflow bath at 200 ° C. for 10 minutes.
After being kept in the solder bath at 288 ° C. for 1 minute, no peeling of the conductor wiring and no peeling between the photosensitive layers occurred.

As a result of this example, the heat-resistant photosensitive resin composition of this example can be developed with a nonflammable aqueous developing solution, and exhibits high tack-free properties without lowering the resolution. It can be seen that the resin has high adhesiveness to the conductor wiring while suppressing a decrease in the glass transition point. In this example, a high-density multilayer wiring board having excellent heat resistance was obtained by using the photosensitive resin composition having these excellent characteristics.

<Examples 11 to 16> A glass epoxy substrate surface having a copper layer having a thickness of 18 μm was prepared, the copper layer surface was roughened with an aqueous solution of ammonium persulfate, and oxidized with an aqueous solution containing sodium perchlorate as a main component. A film was formed, then reduced with an aqueous solution of dimethylamine borane and dried.
An inner layer substrate was used.

A varnish having a solid content of 70% by weight, obtained by dissolving and dispersing the components shown in Table 2 in diethylene glycol monomethyl ether acetate, was applied on the inner layer substrate by screen printing and dried.

Next, a predetermined position was exposed to light (2.7 J / cm ² ) using an ultra-high pressure mercury lamp through a mask having a predetermined pattern for forming via holes of various sizes. For 15 minutes to accelerate curing, and the thickness of the obtained resin film was measured. Table 2 shows the results.

Subsequently, spray development was performed using a quasi-aqueous developer (aqueous solution containing 400 ml / L of 2,2-butoxyethoxyethanol and 10 g / L of sodium hydroxide).
At this time, the diameter of the via hole that can be developed (that is, the inner diameter of the thin through-hole obtained) was taken as the resolution.

Next, the composition was heated at 150 ° C. for 1 hour to accelerate the curing, and further subjected to surface roughening, neutralization treatment, plating catalyst application and activation treatment with an aqueous solution of permanganic acid. Using chemical plating and electroplating together as in 9,
Apply a panel plating of about 20μm thickness, and then 180 ℃
For 2 hours. Thus, a substrate having an insulating film provided with a through hole for forming a via hole was manufactured.

The through hole of the obtained substrate (100 μm in diameter)
The part was cut using a low-speed cutter, the cross section was polished, observed, and evaluated. Table 2 shows the results. In Table 2, among 100 samples (cross-sections of through-holes), the via-hole shape was changed to "only" when no scouring (reverse taper portion) inside the via was observed and a uniform plating film was formed. ○ ”and slight scouring is observed, but when a uniform plating film is obtained and is practicable, it is marked“ △ ”and scouring occurs.
When the plating was not uniform, it was rated "x".

The adhesive strength to the plating wiring and the soldering heat resistance shown in Table 2 were both measured according to the method of JISC6481. The measurement temperature of solder heat resistance is 2
60 ° C.

[0086]

[Table 2]

From these results, it can be seen that the photosensitive resin compositions used in Examples 11 to 16 and the multilayer wiring boards obtained using the same have good connection reliability. Further, it can be seen that the heat resistance of the resin film indicated by the solder heat resistance is also improved due to the improvement of the internal curability.

In particular, in Examples 12 to 15 using the self-cleaving radical polymerization initiator, it was possible to form a through hole having a very good shape (that is, no reverse tapered concave portion). Also, from Example 11, it can be seen that even with a small amount of the photo-radical polymerization initiator, the via hole shape and the solder heat resistance are improved.

"CNA-117" is an acrylic isocyanurate-added epoxy acrylate (acrylisocyanate addition rate: 2%) manufactured by Nippon Kayaku Co., Ltd., and "HP180R" is a resol produced by Hitachi Chemical Co., Ltd. Resin. "SP-70" is a triphenylsulfonium hexafluoroantimonate (photoacid generator) manufactured by Asahi Denka Kogyo KK, and "I-184" is a product of Ciba Geigy.
-Hydroxycyclohexylphenyl ketone (self-cleaving radical polymerization initiator), "I 651" is benzyldimethyl ketal (self-cleaving radical polymerization initiator) manufactured by Ciba Geigy, and "I-1173" is Ciba Geigy. 2-hydroxy-2-methyl-1-phenylpropan-1-one (a self-cleaving type radical polymerization initiator) manufactured by Nippon Kayaku Co., Ltd. “Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd. Ie, 2,4-diethylthioxanthone (hydrogen abstraction type radical polymerization initiator)
It is. Also in this example, as in Examples 1 to 9, powder having an average particle size of 1 μm was used for silicon oxide.

Example 17 A process for manufacturing a multilayer wiring board using the photosensitive resin composition of the present invention will be described with reference to FIG. The multilayer wiring board of the present invention has the following (1) to
It can be manufactured by the process (4).

(1) Step of Forming Photosensitive Film First, a photosensitive film 2 is formed on the surface of a core substrate 3 having an inner wiring 1 made of copper by using the photosensitive resin composition of the present invention so as to cover the wiring. It is formed (FIG. 2A). The core substrate 3 serving as an inner layer, which is a starting material, may be a copper-clad laminate obtained by etching or a laminate formed with wiring by an additive method. Inner layer wiring 1 to be a conductor
When copper is used for copper, known copper surface roughening, oxide film formation,
By performing oxide film reduction, nickel plating, or the like, it is possible to increase the adhesive force between the inner wiring 1 serving as a conductor and the photosensitive film 2 (and the cured resin composition film (that is, the insulating film)).

As a film forming method, a method such as dip coating, curtain coating, roll coating, knife coating, screen printing, or the like can be used. When these coating methods are used, the composition is coated on the substrate surface. After that, it is desirable that the solvent be dried by heating at a temperature at which the epoxy resin does not cure (usually 80 to 120 ° C.) to make it tack-free. Alternatively, the composition may be formed in advance into a self-supporting film, and the film may be formed by attaching the film.

(2) Exposure / Development Step Next, exposure is performed through a via-hole mask (not shown), and the unexposed portion is removed by dissolving with a developing solution to penetrate the photosensitive film 2 serving as an insulating film. After forming the via hole 4 as a through hole reaching the lower layer wiring, it is heated at a predetermined curing temperature (FIG. 2B).

The photosensitive resin composition of the present invention can be developed using an aqueous developer excellent in safety and environmental health. Examples of the aqueous developer suitable for the present invention include an aqueous solution of a water-soluble high-boiling organic solvent or a solution obtained by adding an alkali component to an aqueous solution of a high-boiling organic solvent. As the aqueous organic solvent, 2-butoxyethanol, 2,2-butoxyethoxyethanol and the like are preferable, and as the alkali component, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, borax and the like are used. The concentration of the aqueous organic solvent is preferably about 10 to 80% by weight, which does not cause flammability, and the concentration of the alkali component is preferably about 1 to 20% by weight.

(3) Surface Treatment Step Next, the surface of the photosensitive film 2 serving as an insulating film (including the inner wall of the via hole 4 as a through hole) is roughened, the roughened residue is removed, the plating catalyst 8 is applied, and the insulating film is formed. Then, the surface of the photosensitive film 2 is activated (FIG. 2C). The roughening treatment can be performed using a mixed solution of chromic acid or an aqueous solution of permanganic acid.

(4) Wiring Forming Step Next, on the surface of the photosensitive film 2 serving as the insulating film (including the inner wall of the via hole 4 of the through hole), the outer layer wiring 7 serving as the conductor of a predetermined pattern and the via hole 4 are formed ( FIG. 2 (d)). That is, the surface of the photosensitive film 2 serving as an insulating film to which the plating catalyst 8 has been applied is covered with a plating resist 6, exposed and developed through a mask (not shown) having a predetermined pattern, and subjected to predetermined heating to perform resist heating. After hardening 6, the outer layer wiring 7 serving as a fine conductor is formed by chemical plating or a combination of chemical plating and electroplating, and the plating resist 6 is peeled off. If the heat curing after development is insufficient, after forming the outer layer wiring 7 serving as a conductor, it is further heated (post-cured) at 160 ° C. or higher to promote the curing of the photosensitive film 2 serving as an insulating film. Is also good.

The outer layer wiring 7 (planar wiring and via hole wiring) serving as a conductor can be formed by two methods, a full additive method using only chemical plating and a semi-additive method using both chemical plating and electroplating. In the present invention,
Both methods are applicable. From the viewpoint of miniaturization of wiring,
The former method is more effective, but the plating solution is highly alkaline and the plating conditions are high temperature, so that many of the conventional photosensitive epoxy resins cannot be applied. However, when the photosensitive resin is used, since the plating solution resistance is excellent, the wiring can be formed even by using the full additive method, which is effective.

As described above, the first insulating layer, the wiring for interlayer connection, and the plane wiring are formed, and the steps (1) to (4) are repeated as necessary to form a multilayer (FIG. e)), the multilayer wiring board 9 of the present invention can be obtained.

In the case where the photosensitive resin composition of the present invention is used for forming the photosensitive film 2 in the step (1), the photosensitive resin composition does not penetrate even after roughening and plating catalyst application (in a state after the step (3)). It is possible to prevent the photosensitive film 2 (and the cured insulating film) in the vicinity of the via hole 4 serving as a hole from peeling off or floating from the inner wiring 1 or forming an inversely tapered portion. Further, since the photosensitive resin composition of the present invention is excellent in internal curability, heat resistance is also greatly improved. Furthermore, this photosensitive resin composition is excellent in developability, plating solution resistance and the like, and is useful as a photosensitive resin composition for an interposer substrate and a multi-chip module substrate.

Further, these multilayer wiring boards using the photosensitive resin composition of the present invention have a high adhesive strength between the conductor wiring and the photosensitive film 2 serving as an insulating film at a high temperature. Therefore, according to the present invention, since the photosensitive film 2 serving as the insulating film fixes the conductor wiring in the multilayer wiring board, the conductor wiring does not peel off due to thermal stress generated in a solder reflow process, a repair process, or the like. A highly reliable high-density multilayer wiring board can be obtained.

In particular, when a photosensitive resin composition containing a rubber component, an inorganic filler, a thermosetting agent, and the like is used, the elasticity is reduced due to the effect of the rubber component, so that a high adhesive strength to the inner wiring is obtained. The effect of the inorganic filler improves the surface roughening efficiency, and also has a high adhesive force with the conductor wiring formed by plating, which is preferable.

Example 18 Using the photosensitive resin compositions of Examples 1 to 17, core substrate 3 having four inner wiring layers 1
FIG. 4 is a schematic cross-sectional view showing an example of a multilayer printed wiring board in which two outer layers 7 are formed on both surfaces by a build-up method.

In the present embodiment, the 4
This is an example of a multilayer wiring board that is multilayered by a method similar to that of Embodiment 17 using a core substrate 3 having inner wiring layers as a starting material. The core substrate 3 in this embodiment is a prepreg resin formed by impregnating a glass cloth with a thermosetting epoxy resin between both surfaces of a copper-clad laminate to form a double-sided printed circuit by processing a copper foil on both surfaces of the two substrates. Three layers are formed via layers. Glass cloth is 20
Preferably 40 vol%, the dielectric constant is preferably 3.0 to 4.0, the thermal expansion coefficient is preferably 5.0~8.0 × 10 ~ ⁵ / ℃. The core substrate preferably has 2 to 4 layers. After forming a conductor on the inner peripheral surface of the through hole by chemical copper plating, the through hole 10 is filled with an insulating resin or a conductor mixed with a metal powder. The thickness of one layer of the core substrate 3 is 300 to
400 μm, and the thickness of the inner layer wiring 1 is 10 to 30 μm.

In the above Examples 1 to 17, the photosensitive layer 2
Was 50 μm in thickness. Its thickness is 25-100μm
And more preferably 25 to 50 μm. Further, the diameter of the via hole 4 is preferably the same size as the thickness of the photosensitive layer 2, and is therefore preferably 25 to 100 μm, more preferably 25 to 100 μm.
~ 50 μm is preferred.

<Embodiment 19> FIG. 5 is a schematic cross-sectional view showing an example of an embodiment in which an LSI is mounted on a multilayer printed wiring board obtained by the embodiment 18 by flip mounting via solder bumps 12 made of solder balls. It is. In this embodiment, the plane shape is 10 cm square.

The multilayer wiring board using the photosensitive resin composition of the present invention can be used for a motherboard of an electronic device such as a personal computer.
It is applicable to all multilayer wiring boards such as CM (Muti Chip Module) board and interposer board.

In addition, as a method of mounting the LSI, in addition to the flip chip mounting shown in this embodiment, a CSP (Chip Siz
e Package), BGA (Ball Grid Array), and QFP
Various LSI implementations such as (QuadFlat Package) are possible.

The multilayer printed circuit board in this embodiment can be used for a memory module board, a disk board, or the like.

[0109]

According to the present invention, it is possible to form an insulating film having good roughening properties and adhesion, and a via hole having high connection reliability.

The photosensitive resin composition of the present invention is particularly suitable for a multilayer printed wiring board since an insulating film having high hardness can be obtained, but the application is not limited to this.
The present invention may be applied to an interlayer insulating film of a thin-film multilayer wiring board, a solder resist, or a surface protective film or an α-ray shielding film of a semiconductor device.

[Brief description of the drawings]

FIG. 1 is an explanatory view schematically showing a process of forming an insulating layer and a wiring layer using a conventional photosensitive resin composition.

FIG. 2 is an explanatory view schematically showing a manufacturing process of the multilayer wiring board of the present invention.

FIG. 3 is a schematic view showing a method for introducing an N-substituted carbamate atom group into a side chain of a resin.

FIG. 4 is a sectional view of a multilayer wiring printed board according to the present invention.

FIG. 5 is a cross-sectional view of a multilayer wiring printed board on which the LSI of the present invention is mounted.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Inner wiring, 2 ... Photosensitive film, 3 ... Core substrate, 4 ... Via hole, 5 ... Reverse taper part, 6 ... Plating resist, 7 ... Outer wiring, 8 ... Plating catalyst, 9 ... Multilayer wiring board, 10 ... Through hole, 11: solder resist, 12: solder bump, 13: LSI.

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C08F 299/00 C08F 299/00 (72) Inventor Tokito Suwa 7-1-1, Omika-cho, Hitachi City, Hitachi City, Ibaraki Prefecture Hitachi, Ltd. Hitachi Research, Ltd. In-house (72) Inventor Masao Suzuki 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture Inside Hitachi, Ltd.Hitachi Research Laboratories (72) Inventor Satoru Ama 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture Co., Ltd. Hitachi, Ltd.Hitachi Research Laboratory (72) Inventor Akio Takahashi 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture Hitachi, Ltd.Hitachi Research Laboratory Co., Ltd. (72) Inventor Hiroyuki Fukai 1500 Ogawa Ogawa, Shimodate City, Ibaraki Prefecture Hitachi Chemical Inside Shimodate Plant Co., Ltd. (72) Inventor Mitsuo Yokota 1500 Oji Ogawa, Shimodate City, Ibaraki Prefecture Inside Shimodate Plant Hitachi Chemical Co., Ltd. Within the business division (72) Inventor Masayoshi Miyazaki Kanagawa Prefecture Hadano Horiyamashita one address, Inc. Date falling Mfg general purpose computer business unit

Claims (25)

[Claims] 1. A photosensitive resin comprising: a first resin which is an epoxy resin; and a second resin having an N-substituted carbamate atomic group and a radical polymerizable unsaturated bond in a side chain. Composition. 2. The method according to claim 1, wherein the weight ratio of the first resin to the second resin is 0.1.
8: 1 to 5: 1. 3. The photosensitive resin composition according to claim 1, wherein the second resin is an epoxy resin further having a vinyl ester atom group in a side chain. 4. The resin according to claim 1, wherein the second resin is an epoxy acrylate resin or an epoxy methacrylate resin in which at least a part of a hydroxyl group is substituted with an N-substituted carbamic acid ester atomic group. A photosensitive resin composition comprising: 5. The photosensitive resin composition according to claim 3, wherein the second resin is an oligomer represented by the following general formula (Formula 1) or a halide of the oligomer. Embedded image (Where X is hydrogen or a methyl group, Y is hydrogen or an alkyl group having 1 to 4 carbon atoms, n is 0 or 1, and a part of R ¹ contained in one molecule is represented by the following general formula ( Chemical formula 2)
Wherein the remaining R ¹ is a hydroxyl group. ) (Where R ² is an alkylene group having 1 to 4 carbon atoms;
Z is hydrogen or an alkyl group having 1 to 4 carbon atoms. ) 6. The photosensitive resin composition according to claim 3, wherein the second resin is an oligomer represented by the following general formula (Formula 3) or a halide of the oligomer. Embedded image (Where X is hydrogen or a methyl group, Y is hydrogen or an alkyl group having 1 to 4 carbon atoms, and a part of R ^{1 in} one molecule is represented by the following general formula (Formula 2). (N-substituted carbamate atomic group, and the remaining R ¹ is a hydroxyl group.) (Where R ² is an alkylene group having 1 to 4 carbon atoms;
Z is hydrogen or an alkyl group having 1 to 4 carbon atoms. ) 7. The method according to claim 5, wherein the number of R ^{1 in} one molecule of the second resin is 100.
A photosensitive resin composition, wherein the number of N-substituted carbamic acid ester atomic groups represented by the general formula (Formula 2) is 0.5 to 20. 8. The photosensitive resin composition according to claim 1, further comprising a photoradical polymerization initiator. 9. The photosensitive resin composition according to claim 8, wherein the photo-radical polymerization initiator is of a self-cleaving type. 10. The content of the photo-radical polymerization initiator according to claim 8 or 9, wherein the content of the photo-radical polymerization initiator is 0.1 part by weight based on 100 parts by weight of the total of the first resin and the second resin.
1 to 5 parts by weight. 11. The photosensitive resin composition according to claim 1, wherein the first resin is a polyfunctional epoxy resin. 12. The method according to claim 11, wherein the first resin has an epoxy equivalent of 100 to 500 g / epoxy.
An equivalent amount of the photosensitive resin composition. 13. The photosensitive resin composition according to claim 1, further comprising a photoacid generator. 14. The photosensitive resin composition according to claim 13, wherein said photoacid generator is an onium salt. 15. The content of the photoacid generator according to claim 13 or 14, wherein the content of the photoacid generator is the same as that of the second resin.
1 to 10 parts by weight based on 100 parts by weight of the total amount of the resin and the photosensitive resin composition. 16. The photosensitive resin composition according to any one of claims 1 to 15, further comprising a third resin having a phenolic hydroxyl group. 17. The photosensitive resin composition according to claim 16, wherein the third resin is of a self-condensing type. 18. The method according to claim 16, wherein the third resin is at least one of a novolak resin, a resole resin, a hydroxystyrene polymer, and a hydroxyphenylmaleimide polymer, or any of these. A photosensitive resin composition, which is any copolymer. 19. The method according to claim 16, wherein the content of the third resin is the same as the content of the first resin and the second resin.
The photosensitive resin composition is 5 to 30 parts by weight based on 100 parts by weight of the total amount of the resin. 20. The photosensitive resin composition according to claim 1, further comprising a rubber component. 21. The method according to claim 20, wherein the content of the rubber component is 5 to 40 parts by weight based on 100 parts by weight of the total of the first resin and the second resin. Photosensitive resin composition. 22. An insulating film comprising the photosensitive resin composition according to claim 1. 23. A substrate in which a fiber cloth is impregnated with a thermosetting resin, wiring formed on the surface of the substrate, an interlayer insulating film formed on the substrate and the wiring, and formed on the interlayer insulating film. 23. A multilayer wiring board comprising a wiring and a conductive material filled in a via hole penetrating the film, wherein the interlayer insulating film is the photosensitive resin composition according to claim 1 or 22. A multilayer wiring board comprising the insulating film as described above. 24. A multilayer comprising an interlayer insulating film having a thickness of 30 μm or more, wiring formed on the surface of the interlayer insulating film, and a via hole having a diameter of 25 μm or more penetrating the interlayer insulating film. Wiring board. 25. A semiconductor package in which a semiconductor element is mounted on the wiring formed on the interlayer insulating film according to claim 23.