JPH07224149A - Resin composition and production of multilayered wiring board using the same - Google Patents

Abstract

PURPOSE:To obtain an insulating resin composition capable of stably processing fine viewer holes having 100-200mum diameter by using a developer safe in aspects of a working environment and provide a method for efficiently producing a multilayered wiring board by using the resin composition. CONSTITUTION:This photosensitive insulating resin composition comprises (A) an epoxy resin having <=1500 number-average molecular weight (Mn), (B) an acrylated or a methacrylated epoxy resin in which 25-75% epoxy groups in the epoxy resin are substituted with photopolymerizable unsaturated groups, (C) a methacrylic acid adduct acrylonitrile-butadiene rubber, (D) an alkylphenol resin, (E) a photopolymerization initiator for reacting acryloyl groups in the component (B) with ultraviolet rays and (F) a curing agent reactive with epoxy groups in the component (A) and (B) by heating. Furthermore, a wiring board is produced by using this resin composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a multilayer wiring board, and more particularly to an insulating resin for a multilayer wiring board in which an interlayer insulating layer is formed by a build-up method.

[0002]

2. Description of the Related Art In general, a multilayer wiring board is constructed by stacking a semi-hardened material, which is made by impregnating a glass cloth called prepreg with epoxy resin, on a insulating substrate on which an inner layer circuit is formed, and layering it by hot pressing. After that, a hole called a through hole for interlayer connection is opened with a drill, electroless plating is performed on the inner wall of the through hole and the surface of the copper foil, and if necessary, electrolytic plating is performed to obtain the thickness required for the circuit conductor. After that, unnecessary copper is removed to manufacture a multilayer wiring board.

By the way, in recent years, electronic devices have become smaller, lighter, and more multifunctional, and along with this, high integration of LSIs and chip parts has progressed, and their forms have rapidly become multi-pin and miniaturized. Has changed to. For this reason, the multilayer wiring board is under development for fine wiring in order to improve the mounting density of electronic components.

However, there is a technical limit to the reduction of the wiring width, and the wiring width that can be mass-produced at present is around 100 μm. For this reason, it is difficult to achieve not only a reduction in wiring width but also a significant improvement in wiring density.

Further, a bottleneck for improving the wiring density is a through hole occupying an area of about 400 μm in diameter. Since this through hole is generally formed by a mechanical drill, it has a relatively large size, which reduces the degree of freedom in wiring design.

As a solution to these problems, there is a method in which a photosensitive insulating resin is applied onto an insulating base material on which a circuit is formed, and a minute via hole is formed in the insulating resin by a photo process to perform interlayer connection. 4-5555
No. 5 and JP-A-4-148590.

Further, a method of using oxygen gas plasma for the insulating resin layer in order to improve the adhesion between the photosensitive resin layer and the plated copper conductor is disclosed in JP-A-58-2091.
Japanese Laid-Open Patent Publication No. 58-119695 discloses a liquid honing treatment for roughening the surface of the photosensitive insulating resin layer.

[0008]

The above-mentioned conventional method is a multilayer wiring board in which interlayer connection is made by minute via holes formed by a photo process. Regarding the problem of improving the wiring density of the conventional multilayer wiring board, It is a great contribution.

However, in Japanese Patent Publication No. 4-55555, a particulate resin having an average particle diameter of 10 μm or less is used as a photosensitive resin in order to improve the adhesiveness with a plated copper conductor (in order to obtain unevenness on a roughened surface). Although the one contained therein is used, it is usually difficult to obtain a stable roughened shape under the wiring conductor in the case of the wiring width of 75 μm or 50 μm required today. In addition, since the plating is followed and deposited in the recesses in which the particulate matter having an average particle size of 10 μm or less has been removed, there are slight irregularities on the copper surface, which deteriorates the etching accuracy and causes a problem in circuit formability. Remains.

Further, in JP-A-4-148590, a photosensitive solder resist is used for the insulating layer.
Since it is not formulated as a resin for depositing copper plating, there is a problem that the adhesive strength with copper plating is considerably lower than that of a wiring board using a normal glass epoxy prepreg as an insulating material.

Further, in Japanese Patent Publication No. 4-55555 and Japanese Patent Laid-Open No. 4-148590, a chlorine-based solvent or 1 is used as a developer for forming a via hole in a photosensitive insulating resin layer.
A developer solution of 00% solvent is used. There is a problem that chlorine-based solvents cannot be used in the future, and a 100% solvent developer is not dangerous even if a high flash point solvent is used. Explosion proof is also a problem.

Further, in JP-A-58-209195 and JP-A-58-119695, a phenoxy resin having a methacryloyl group as a side chain is used as a photosensitive resin, and the surface of the resin is treated with oxygen gas plasma. And liquid honing. In this oxygen gas plasma treatment, polar groups appear on the resin surface, and in liquid honing treatment, a slight roughened surface can be generated. By this method, the adhesiveness with the plated conductor can be improved, but it is usually difficult to obtain the adhesive force with the plated conductor close to a wiring board using a normal glass epoxy prepreg as an insulating material.

As described above, in the multilayer wiring board using the photosensitive insulating layer, the adhesiveness with the plated conductor is excellent,
A photosensitive insulating resin capable of forming a via hole with a developing solution other than a 100% solvent and a multilayer wiring board using the same are technically difficult to achieve.

The present invention provides an insulating resin composition capable of stably processing a minute via hole having a diameter of 100 μm to 200 μm by using a developing solution which is safe in terms of working environment, and a multilayer wiring board efficiently using the same. It is an object of the present invention to provide a method for producing.

[0015]

The photosensitive resin composition of the present invention is characterized by comprising the following components (A) to (F). (A) Epoxy resin having a number average molecular weight (Mn) of 1500 or less (B) Epoxy group in the epoxy resin is substituted with a photopolymerizable unsaturated group by 25% to 75% (meth) acrylated epoxy resin (C) Methacrylate Acid-added acrylonitrile butadiene rubber (D) Alkylphenol resin (E) Photoinitiator for reacting acryloyl group of component (B) with ultraviolet rays (F) Curing that reacts with epoxy group of component (B) by heating Agent

In these compositions, the total amount of component (A), component (B), component (C) and component (D) is 100, and the total amount of component (C) and component (D) is 5 It is preferable that it is in the range of -40% and the mixing ratio of the component (C) and the component (D) is 95/5 to 60/40.

Epoxy resins having a number average molecular weight (Mn) of 1500 or less include bisphenol A type, bisphenol F type, cresol novolac type, phenol novolac type, cycloaliphatic epoxy, glycidyl ester type epoxy resins, and the like. Any of the epoxy resins obtained by adding halogen such as bromine to the above epoxy resin for flame retardancy can be used alone or in combination of two or more as long as the number average molecular weight (Mn) is in the range of 1500 or less.
The number average molecular weight can be measured by gel permeation chromatography (GPC).

Examples of the meth) acrylated epoxy resin in which the epoxy group in the epoxy resin is replaced with a photopolymerizable unsaturated group by 25% to 75% include bisphenol A type, bisphenol F type, cresol novolac type and phenol novolak type. The stoichiometric amount of the photopolymerizable unsaturated monomer is 0.25 to 0.
It is manufactured by reacting 75 equivalents. Specific photopolymerizable unsaturated monomers include (meth) acrylic acid, hydroxylethyl (meth) acrylate, hydroxylpropyl (meth) acrylate, methyl (meth) acrylate,
Butyl (meth) acrylate, glycidyl (meth) acrylate, ethylene glycol di (meth) acrylate,
Typical examples include polypropylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.

The methacrylic acid-added acrylonitrile-butadiene rubber is produced by reacting methacrylic acid and acrylonitrile with the unsaturated double bond portion of butadiene. The amount of methacrylic acid added is 2mo
The range of 1% to 12 mol% is good, and other than this range,
It is not preferable in terms of developability and plating resistance. The amount of acrylonitrile is not particularly limited, but is preferably 20% by weight or more from the viewpoint of compatibility with other resins.

The alkylphenol resin is used for thermosetting the methacrylic acid-added acrylonitrile-butadiene rubber. As the alkylphenol resin, there are various kinds depending on the kind of alkyl group, kind of reactive group and molecular weight distribution, but paratertiary butylphenol, paratertiary amylphenol, para-phenylphenol, para-secondary butylphenol and the like can be used.

In these compositions, the total compounding amount of the methacrylic acid-added acrylonitrile-butadiene rubber and the alkylphenol resin is an epoxy resin having a number average molecular weight (Mn) of 150 or less, and the epoxy group in the epoxy resin is photopolymerizable unsaturated. (Meth) acrylated epoxy resin substituted by 25% to 75% with a base, methacrylic acid-added acrylonitrile butadiene rubber, and alkylphenol resin are preferably in the range of 5 to 40% by weight with respect to 100 in total. . If the total content of the methacrylic acid-added acrylonitrile-butadiene rubber and the alkylphenol resin is less than 5% by weight, the adhesion with the plated copper deposited on the insulating resin will be insufficient. If it exceeds 40% by weight, heat resistance and insulation reliability are deteriorated.

The compounding ratio of the methacrylic acid-added acrylonitrile-butadiene rubber and the alkylphenol resin is preferably in the range of 95/5 to 60/40 weight ratio. The compounding ratio of the methacrylic acid-added acrylonitrile-butadiene rubber and the alkylphenol resin is 95
If it is less than / 5 weight ratio, the curing of the methacrylic acid-added acrylonitrile butadiene rubber is insufficient and heat resistance and insulation reliability are reduced. On the other hand, if the compounding ratio exceeds 60/40 weight ratio, the curing of the methacrylic acid-added acrylonitrile butadiene rubber proceeds in the opposite direction, and it becomes difficult to roughen, resulting in insufficient adhesion to the plated copper.

Used as a photoinitiator for reacting the photopolymerizable unsaturated group of the (meth) acrylated epoxy resin in which the epoxy group in the epoxy resin is substituted with 25% to 75% of the photopolymerizable unsaturated group. It is possible to use one having a wavelength in the ultraviolet light of the exposing machine. Specifically, acetophenone, benzophenone, 4,4-bisdimethylaminobenzophenone, benzoin ethyl ether, benzoin butyl ether, benzoin isobutyl ether, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy. -2-
Dimethoxy-1-phenylpropan-1-one, 1-
(4-Isopropylphenyl) -2-hydroxy-2-
Methylpropane, azobisisobutylnitrile, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 3,3-
Dimethyl-4-methoxybenzophenone, 2,4-dimethylthioxanthone, methylbenzoyl formate,
For example, 3,3,4,4-tetra (t-butylperoxycarbonyl) benzophenone can be used.

The number of the epoxy group in the epoxy resin having a number average molecular weight (Mn) of 1500 or less and the photopolymerizable unsaturated group is 25
% To 75% substituted (meth) acrylated epoxy resin residual curing groups and the curing agent that reacts by heating,
Catalysts which accelerate the curing reaction and those which are well known and which are directly involved in the reaction can be used. For example, aliphatic amine, aromatic amine, aliphatic acid anhydride, aromatic acid anhydride,
Examples thereof include cycloaliphatic acid anhydrides, polyamides, imidazoles, amine complex compounds, amine derivatives and phenols.

In addition to these compositions, fine powder silica, aluminum hydroxide, silica, zirconium silicate, calcium carbonate, talc, barium sulfate, and other inorganic fillers may be mixed in to form irregularities when chemically roughened. Is preferred in terms of easy formation of the adhesive, and also in view of reinforcing the coating film.

Further, a catalyst which becomes a core of electroless plating can be mixed in the composition. As the plating catalyst, an element of Group 8 and / or Group 1B of the periodic table is chemically or physically adsorbed on an inorganic or organic substance, and then mixed in a reduced state with a metal. The elements of Group 8 and / or Group 1B of the periodic table of the elements are platinum, gold, nickel, palladium, cobalt, iron, rhodium, copper, silver and the like, and platinum palladium is preferable in terms of electrical characteristics and plating depositability. .

The resin composition of the present invention is kneaded and mixed in an organic solvent to form a solution mixture. As the organic solvent used at this time, a ketone type, an ester type, an alcohol type, a cellosolve type or the like can be used alone or in combination of two or more.

Using the photosensitive insulating resin composition described above, a multilayer wiring board is manufactured by the process shown in FIG. Figure 1
A detailed description will be given according to the steps shown in FIG. First, an insulating substrate on which the first circuit is formed is prepared (FIG. 1-a). The insulating substrate is not particularly limited, and an insulating substrate used for a normal wiring board such as glass cloth-epoxy resin, paper-phenol resin, paper-epoxy resin, glass cloth / glass paper-epoxy resin can be used. As a method for forming the first circuit of the present invention, a subtractive method for removing unnecessary portions of the copper foil by etching using a copper-clad laminate obtained by laminating a copper foil and the insulating substrate, and the need for the insulating substrate An ordinary method for manufacturing a wiring board, such as an additive method for forming a circuit by electroless plating at various places, can be used.

Next, the photosensitive insulating resin composition is formed on the surface of the first circuit (FIG. 1-b). This formation method is
A method in which a liquid resin is applied by a method such as roll coating, curtain coating, or dip coating, or a method in which a photosensitive insulating resin is formed into a film and laminated together can be used.

Next, the photosensitive insulating resin layer is exposed through a photomask in order to form a via hole connected to the first circuit (FIG. 1-c), and the unexposed portion is etched with a developing solution. By the method described above, a via hole connected to the first circuit is formed in the photosensitive insulating resin layer (FIG. 1-d). For the exposure, the same method as that for forming a resist on a normal wiring board is used. Further, by using the developing solution of the present invention to selectively etch the unexposed portion, safe and fine via holes can be formed.

The developer of the present invention contains water and a vapor pressure of 133 Pa.
(25 ° C.) or less of a mixed solution of an organic solvent and / or a developer of water and a vapor pressure of 133 Pa (25 ° C.) or less of a mixed solution to which borax and / or an alkanolamine as an alkaline component are added. is there. Vapor pressure 133Pa (2
The mixing ratio of the organic solvent of 5 ° C. or less to water is 40 vol% or less, which is not regulated by the Fire Service Law, and the preferable range is 10 to 30 vol% from the viewpoint of developability.

Preferred organic solvents having a vapor pressure of 133 Pa (25 ° C.) or less are triethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol, 2-butoxyethanol, 2-methoxyethanol and triethylene. Glycol monomethyl ether,
Tetraethylene glycol, polyethylene glycol,
Examples include dipropylene glycol, dipropylene glycol monoethyl ether, dipropylene cresol monomethyl ether, tripropylene glycol monomethyl ether, polypropylene glycol, propylene carbonate and the like.

Borax and alkanolamine are used as the alkaline component. As an alkanolamine,
2-aminoethanol, 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, diethanolamine, N-butyldiethanolamine, triethanolamine, triisopropanolamine can be used. In the case of borax, the amount of borax and alkanolamine added to the mixed solution of the organic solvent and water is 1 to 20.
The range is g / l, preferably 5 to 15 g / l. In the case of alkanolamine, 1 to 10
g / l is the optimum range. Furthermore, the development temperature is 30 ° C.
By setting the temperature in the range of -60 ° C, it is possible to improve the developing property and shorten the developing time.

Next, the photosensitive insulating resin is cured by heating. This curing is performed to form a roughened uneven shape for strengthening the adhesiveness with the photosensitive insulating resin circuit when forming a circuit on the photosensitive insulating resin, and to apply a strong alkaline plating solution. This is an important process to endure. When the photosensitive insulating resin is cured by heating,
If necessary, a step of further irradiating ultraviolet rays and then heating may be performed.

After the insulating layer is thus hardened, the insulating layer is roughened with alkaline permanganate, and copper plating is deposited on the insulating layer to form a second circuit and connect via holes (( Figure 1-e). In this case, as the alkaline permanganate roughening solution, an aqueous solution mixture of a 7-valent manganese compound and potassium hydroxide and / or sodium hydroxide can be used. Further, after the alkaline permanganate roughening, a neutralization step is performed in order to change the 7-valent manganese compound into the 6-valent manganese compound.

Further, as a method for forming the second circuit, a catalyst for electroless plating is applied to the surface of the roughened insulating layer to deposit electroless plated copper on the entire surface, and if necessary, electrolytic plating is performed. Method to form circuit conductors with required thickness and remove unnecessary parts by etching, or to form plating resist by using insulating layer containing plating catalyst and form circuits by electroless plating only on necessary parts And a method of roughening an insulating layer not containing a plating catalyst, applying a plating catalyst, forming a plating resist, and forming a circuit by electroless plating only at a necessary portion.

When the present invention is to be multi-layered, the above method (FIGS. 1-b to e) is repeatedly carried out to form a multi-layer (steps: FIGS. 1-f to h). At this time, preferably, before forming the photosensitive insulating resin layer for indicating the next circuit layer, the surface of the underlying circuit layer conductor is roughened or the circuit layer as used in the conventional multilayer wiring board manufacturing is formed. The conductor can be oxidized to form irregularities, or the irregularities formed by oxidation can be reduced by using an alkaline reducing agent such as sodium borohydride or dimethylamineborane to increase the adhesive force between layers.

[0038]

The present invention makes it possible to form safe and fine via holes by using a specific photosensitive insulating resin and a specific developing solution in a wiring board which is multilayered by using a specific photosensitive insulating resin. By treating the specific photosensitive insulating resin with the specific roughening liquid, it is possible to increase the adhesive force with the circuit conductor without impairing the insulation reliability. From these things, it is possible to provide a multilayer wiring board suitable for a high-density wiring board with a thin substrate.

[0039]

【Example】

Example 1 (1) MCL-E-6, which is a copper-clad glass cloth epoxy resin laminated plate in which 35 μm double-sided roughened copper foil is laminated on both sides
7 (manufactured by Hitachi Chemical Co., Ltd., trade name) is used to remove unnecessary portions of the copper foil by etching to form a first circuit (shown in FIG. 1-a). (2) On one surface of this surface, a photosensitive insulating resin having the following composition is applied by roll coating and dried at 80 ° C. for 10 minutes to form a first photosensitive insulating resin layer (shown in FIG. 1-b). . -Epoxy resin having a number average molecular weight (Mn) of 1500 or less 24 parts by weight of Epicoat 828 (Mn: 214, manufactured by Yuka Shell Co., Ltd.)-Phenolic resin in which 50% of the epoxy groups in the epoxy resin are replaced with acrylic acid Volak type acrylated epoxy resin EA-6310 (manufactured by Shin-Nakamura Industry Co., Ltd.) 56 parts by weight Acrylonitrile butadiene rubber PNR-1H (Japan Synthetic Rubber) in which 4 mol% of methacrylic acid is added 15 parts by weight of alkylphenol resin Hitanol 2400 (product name of Hitachi Chemical Co., Ltd.) 5 parts by weight of photoinitiator Irgacure 651 (product of Ciba Geigy Co., Ltd.) , Product name) ... 5 parts by weight Thermosetting agent HP-850N (manufactured by Hitachi Chemical Co., Ltd., product name) ... ··· 30 parts by weight 2E4MZ (manufactured by Shikoku Chemicals Co., Ltd.) ····· 0.1 part by weight · Filler Heidilite H-42M (manufactured by Showa Denko KK, product name) ・ ・ ・ 15 1 part by weight (3) Aerosil # 200 (manufactured by Nippon Aerosil Co., Ltd.) (3) Ultraviolet rays having an exposure dose of 300 mJ / cm ² are passed through a photomask having a shielding part formed in a via hole. After irradiation (shown in FIG. 1-c), the unexposed portion was selectively removed by a developing solution having the following composition and the following developing conditions to form a via hole (shown in FIG. 1-d). [Developer] ・ Water ・ ・ ・ ・ ・ ・ ・ 800ml / l ・ Diethylene glycol monobutyl ether ・ ・ ・ ・ 200ml / L ・ borax ・ ・ ・ ・ ・ ・ ・ ・ ・ 10g / l ・ monoethanolamine ・ ・ ・ ・・ ・ ・ ・ ・ ・ ・ ・ 5g / l [Development condition] ・ Temperature ・ ・ ・ ・ ・ ・ ・ ・ 45 ℃ ・ Spray pressure ・・ ・ ・ ・ ・ ・ 0.7kg / cm ²・ hour ・ ・ ・ ・... 5 minutes (4) The photosensitive insulating resin composition is thermally cured under the conditions of 150 ° C and 30 minutes. (5) In order to chemically roughen the surface of the insulating resin, an aqueous solution of KMnO ₄ : 60 g / l and NaOH: 40 g / l is prepared as a roughening liquid, heated to 50 ° C. and immersed for 5 minutes. After the KMnO ₄ immersion treatment, SnCl ₃ : 30 g / l,
A roughening irregular shape was formed by neutralizing by immersion treatment in an aqueous solution of HCl: 300 ml / l for 5 minutes at room temperature. (6) In order to form the second circuit on the surface of the first photosensitive insulating resin layer, first, HS-202B (manufactured by Hitachi Chemical Co., Ltd., which is a catalyst for electroless plating containing palladium chloride) ) At room temperature for 10 minutes, washed with water, and immersed in L-59 plating solution (Hitachi Chemical Co., Ltd., trade name), which is an electroless copper plating solution, at 70 ° C. for 60 minutes. Further, copper sulfate electrolytic plating is performed to form a conductor layer having a thickness of 20 μm on the entire surface of the photosensitive insulating resin layer.
Next, an etching resist is formed and etched in order to remove unnecessary portions of the plated conductor, and then the etching resist is removed to form a second circuit including a via hole connected to the first circuit. Do (Figure 1-
e). (7) Further, in order to make a multilayer, the second circuit conductor is
Sodium chlorite: 50 g / l, NaOH: 20 g /
1, trisodium phosphate: 85 g in an aqueous solution of 10 g / l
Dip for 2 minutes at 80 ° C., wash with water, and dry for 20 minutes at 80 ° C. to form irregularities of copper oxide on the surface of the second circuit conductor. (8) A second photosensitive insulating resin layer is formed on the surface of the second circuit conductor on which the unevenness of the copper oxide is formed, by using the photosensitive insulating resin having the above composition, and the first photosensitive insulating resin layer. It is formed by the same method (FIG. 1-f). (9) An ultraviolet ray having an exposure amount of 300 mJ / cm ² is irradiated through a photomask having a shield portion so as to form the third circuit shape, and the unexposed portion is further developed with a developing solution having the following composition and the following development. Under the conditions, it was selectively removed to form a via hole. [Developer] ・ Water ・ ・ ・ ・ ・ ・ ・ 800ml / l ・ Diethylene glycol monobutyl ether ・ ・ ・ ・ 200ml / L ・ borax ・ ・ ・ ・ ・ ・ ・ ・ ・ 10g / l ・ monoethanolamine ・ ・ ・ ・・ ・ ・ ・ ・ ・ ・ ・ 5g / l [Development condition] ・ Temperature ・ ・ ・ ・ ・ ・ ・ ・ 45 ℃ ・ Spray pressure ・・ ・ ・ ・ ・ ・ 0.7 kg / cm
² hours 5 minutes (10) Heat of the photosensitive insulating resin layer under the condition of 150 ° C-30 minutes Cure. (11) In order to chemically roughen the surface of the insulating resin layer, KMnO ₄ : 60 g / l, NaOH: 40 g / l as a roughening liquid.
1 l of an aqueous solution is prepared, heated to 50 ° C., and immersed for 5 minutes. After KMnO ₄ immersion treatment, SnCl ₃ : 30 g /
1, HCl: 300 ml / l aqueous solution was immersed in the solution at room temperature for 5 minutes for neutralization to form a roughened irregular shape (Fig. 1-
g). (12) In order to form the third circuit on the surface of the second photosensitive insulating resin layer, first, HS-202B (manufactured by Hitachi Chemical Co., Ltd., which is a catalyst for electroless plating containing palladium chloride) ) At room temperature for 10 minutes,
Washed with water, immersed in an electroless copper plating solution L-59 plating solution (trade name, manufactured by Hitachi Chemical Co., Ltd.) at 70 ° C. for 60 minutes, and further subjected to copper sulfate electrolytic plating to obtain a photosensitive insulating resin layer. A conductor layer having a thickness of 20 μm is formed on the entire surface.
Next, an etching resist is formed and etched in order to remove unnecessary portions of the plated conductor, and then the etching resist is removed to form a third circuit including a via hole connected to the second circuit. Do (Figure 1-
h)). A multilayer wiring board was produced by the method described above.

Example 2 In the photosensitive insulating resin composition shown in Example 1, an epoxy resin having a number average molecular weight (Mn) of 1500 or less was used.
Epicoat 828 (Mn: 214, manufactured by Yuka Shell Co., Ltd., trade name) was changed to Epicoat 834 (Mn: 328, manufactured by Yuka Shell Co., Ltd., trade name). Others
The same method as in Example 1 was used.

Example 3 In the photosensitive insulating resin composition shown in Example 1, an epoxy resin having a number average molecular weight (Mn) of 1500 or less was used.
From Epicoat 828 (Mn: 214, manufactured by Yuka Shell Co., Ltd., trade name) to Epicoat 1001 (Mn: 834,
Yuka Shell Co., Ltd., trade name). Others were the same as in Example 1.

Example 4 In the composition shown in Example 1, the acrylic acid 50% -substituted phenol novolac type acrylated epoxy resin was replaced with acrylic acid 50% -substituted bisphenol A type acrylated epoxy resin EA-1010 (Shin Nakamura). Product name manufactured by Kogyo Co., Ltd.). Otherwise, Example 1
The same method was used.

Example 5 An acrylated epoxy resin in which 50% of acrylic acid had been substituted in the composition shown in Example 1 was added with acrylic acid to 75%.
% Of phenol novolac type acrylated epoxy resin (manufactured by Shin-Nakamura Industry Co., Ltd., prototype). Others were the same as in Example 1.

Example 6 In the composition shown in Example 2, 4 m of methacrylic acid was added.
A photosensitive insulating resin having the following composition was prepared so that the total content of the acrylonitrile butadiene rubber added with ol% and the alkylphenol resin was 10%. Others were the same as in Example 2. -Epoxy resin having a number average molecular weight (Mn) of 1500 or less Epicoat 834 (Mn: 328, manufactured by Yuka Shell Co., Ltd., trade name) 27 parts by weight-Phenolic resin obtained by substituting 50% of the epoxy groups in the epoxy resin with acrylic acid Volac type acrylated epoxy resin EA-6310 (manufactured by Shin-Nakamura Kogyo Co., Ltd.) ... 63 parts by weight-Acrylonitrile butadiene rubber PNR-1H (4% by weight of methacrylic acid added) Rubber Co., Ltd., product name) 9 parts by weight Alkylphenol resin Hitanol 2400 (manufactured by Hitachi Chemical Co., Ltd., product name) 1 part by weight Photoinitiator Irgacure 651 ( Product name: Ciba-Geigy Co., Ltd ... 5 parts by weight Thermosetting agent HP-850N (product name: Hitachi Chemical Co., Ltd., product name) ) ... 30 parts by weight 2E4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.) ... 0.1 part by weight-Filler Heidilite H-42M (manufactured by Showa Denko KK) Name) ... 15 parts by weight EROSIL # 200 (manufactured by Nippon Aerosil Co., Ltd., product name) ... 1 parts by weight

Example 7 In the composition shown in Example 2, 4 m of methacrylic acid was added.
A photosensitive insulating resin having the following composition was prepared so that the total content of the acrylonitrile butadiene rubber added with ol% and the alkylphenol resin was 30%. Others were the same as in Example 2. Epoxy resin having a number average molecular weight (Mn) of 1500 or less 21 parts by weight of Epicoat 834 (Mn: 328, trade name, manufactured by Yuka Shell Co., Ltd.) Phenolic resin in which 50% of epoxy groups in the epoxy resin are replaced with acrylic acid Volac type acrylated epoxy resin EA-6310 (manufactured by Shin-Nakamura Kogyo Co., Ltd.) ... 49 parts by weight-Acrylonitrile butadiene rubber PNR-1H (4% by weight of methacrylic acid added) Rubber Co., Ltd., product name) 21 parts by weight Alkylphenol resin Hitanol 2400 (Hitachi Chemical Co., Ltd., product name) 9 parts by weight Photoinitiator Irgacure 651 (Ciba Geigy) 5 parts by weight of thermosetting agent HP-850N (manufactured by Hitachi Chemical Co., Ltd., trade name) ) ... 30 parts by weight 2E4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.) ... 0.1 part by weight-Filler Heidilite H-42M (manufactured by Showa Denko KK) Name) ... 15 parts by weight EROSIL # 200 (manufactured by Nippon Aerosil Co., Ltd., product name) ... 1 parts by weight

Example 8 In Example 1, the developing solution for selectively forming via holes in the photosensitive insulating resin layer was changed as follows. [Developer] ・ Water ・ ・ ・ 780ml / l ・ Diethylene glycol monobutyl ether ・ ・ ・ 220ml / l ・ Borate ・ ・ ・ ・・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 20g / l

Example 9 In Example 1, the developer for selectively forming via holes in the photosensitive insulating resin layer was changed to the following composition.
Others were the same as in Example 1. [Developer] ········ 780ml / l · Dipropylene glycol monoethyl ether ··· 220ml / l · Borax ···・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 20g / l ・ Monoethanolamine ・ ・ ・ ・ ・ ・ ・ ・ ・ 5g / l

Example 10 In Example 1, the developing solution for selectively forming via holes in the photosensitive insulating resin layer was changed to the following composition.
Others were the same as in Example 1. [Developer] ・ Water ・ ・ ・ 800ml / l ・ Diethylene glycol monoethyl ether ・ ・ ・ 200ml / l ・ Borate ・ ・ ・ ・ ・・ ・ ・ ・ ・ ・ ・ ・ ・ 10g / l ・ Monoethanolamine ・ ・ ・ ・ ・ ・ ・ ・ ・ 5g / l

Example 11 In Example 1, the developer for selectively forming via holes in the photosensitive insulating resin layer was changed to the following composition.
Others were the same as in Example 1. [Developer] ················································ Diethylene glycol monobutyl ether ························・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 10g / l ・ Triethanolamine ・ ・ ・ ・ ・ ・ ・ ・ ・ 5g / l

Example 12 In Example 1, the developer for selectively forming via holes in the photosensitive insulating resin layer was changed to the following composition.
Others were the same as in Example 1. [Developer] ················································ Diethylene glycol monobutyl ether ························・ ・ ・ ・ ・ ・ ・ ・ 10g / l ・ Diethanolamine ・ ・ ・ ・ ・ ・ ・ ・ 5g / l

Example 13 Similar to Example 1, a via hole was formed in the first photosensitive insulating layer.
Forming a second circuit on the first photosensitive insulating layer.
The surface of the second circuit conductor with copper oxide
It was Next, a photosensitive insulating resin containing a plating catalyst having the following composition
Oil as a second photosensitive insulating layer on the surface of the second circuit conductor
Formed. -Epoxy resin having a number average molecular weight (Mn) of 1500 or less 24 parts by weight of Epicoat 828 (Mn: 214, manufactured by Yuka Shell Co., Ltd.)-Phenolic resin in which 50% of the epoxy groups in the epoxy resin are replaced with acrylic acid Volak type acrylated epoxy resin EA-6310 (manufactured by Shin-Nakamura Kogyo Co., Ltd.) ... 56 parts by weight-Acrylonitrile butadiene rubber PNR-1H (4% by weight of methacrylic acid added) Rubber Co., Ltd., trade name) 15 parts by weight Alkylphenol resin Hitanol 2400 (Hitachi Chemical Co., Ltd., trade name) 5 parts by weight Photoinitiator Irgacure 651 (Ciba Geigy) 5 parts by weight of thermosetting agent HP-850N (manufactured by Hitachi Chemical Co., Ltd., trade name) ) ··· 30 parts by weight 2E4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.) ··· 0.1 parts by weight · Filler Heidilite H-42M (manufactured by Showa Denko KK, trade name) ) ... 15 parts by weight EROSIL # 200 (manufactured by Nippon Aerosil Co., Ltd., product name) ... 1 part by weight-Plating catalyst PEC-8 (manufactured by Hitachi Chemical Co., Ltd., product name) ... ...... 6 parts by weight Next, the flap having the shielding portion formed to have the third circuit shape is formed.
Exposure dose of 300 mJ / cm through a photomask²UV rays
The unexposed area is further irradiated with a developer of the following composition and
Selective removal under the following development conditions to form via holes
It was [Developer] ················································· Diethylene glycol monobutyl ether / ······················ Borax.・ ・ ・ ・ ・ ・ ・ ・ 10 g / l ・ Monoethanolamine ・ ・ ・ ・ ・ ・ ・ ・ ・ 5 g / l [Development conditions] ・ Temperature ・ ・ ・ ・・ ・ ・ 45 ℃ ・ Spray pressure ・ ・ ・ ・ ・ ・ 0.7kg / cm²  ・ Time ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5 minutes and photosensitive insulating resin layer under the condition of 150 ℃ -30 minutes
Of the permanent resist for electroless plating SR-
3000 (Hitachi Chemical Co., Ltd., trade name)
Laminated on the photosensitive insulating resin layer, electroless plating copper deposition
After exposing and developing so that the exposed part becomes the third circuit,
A resist layer is formed. Next, the exposed insulating resin layer surface
KMnO as a roughening liquid for chemically roughening the surface_Four: 60
g / l, NaOH: 40 g / l to prepare an aqueous solution,
Heat to ℃ and soak for 5 minutes. KMnO_FourImmersion treatment
After that, SnCL₂: 30 g / l, HCL: 300 ml
Immerse in aqueous solution for 5 minutes at room temperature to neutralize and roughen uneven surface
Formed. Furthermore, L-5 which is an electroless copper plating solution
9 (manufactured by Hitachi Chemical Co., Ltd., product name) at 70 ° C-12
Immerse for 0 hours, including via holes connected to the second circuit
The third circuit is formed by the full additive method,
A wiring board was produced.

Comparative Example 1 In the photosensitive insulating resin composition shown in Example 1, Epicoat 1004 having a number average molecular weight (Mn) of 214 (Mn:
1750, manufactured by Yuka Shell Co., Ltd., trade name). Others were the same as in Example 1.

Comparative Example 2 In the photosensitive insulating resin composition shown in Example 4, a bisphenol A type acrylated epoxy resin EA-1 in which 50% of the epoxy groups in the epoxy resin were replaced with acrylic acid
010 (manufactured by Shin-Nakamura Kogyo Co., Ltd.) was changed to an acrylated epoxy resin having no epoxy group. Others were the same as in Example 4.

Comparative Example 3 In the composition shown in Example 2, 4 m of methacrylic acid was added.
The following composition was used so that the total amount of the acrylonitrile butadiene rubber added with ol% and the alkylphenol resin was 3% by weight. Others were the same as in Example 2. -Epoxy resin having a number average molecular weight (Mn) of 1500 or less 29 parts by weight of Epicoat 834 (Mn: 328, manufactured by Yuka Shell Co., Ltd.)-Phenolic compound obtained by substituting 50% of the epoxy groups in the epoxy resin with acrylic acid Volac type acrylated epoxy resin EA-6310 (manufactured by Shin-Nakamura Kogyo Co., Ltd.) ... 68 parts by weight Acrylonitrile butadiene rubber PNR-1H (4% by weight of methacrylic acid added) Rubber Co., Ltd., product name) 2.5 parts by weight Alkylphenol resin Hitanol 2400 (Hitachi Chemical Co., Ltd., product name) 0.5 parts by weight Product name: Ciba-Geigy Co., Ltd ... 5 parts by weight Thermosetting agent HP-850N (product name: Hitachi Chemical Co., Ltd., product name) ) ... 30 parts by weight 2E4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.) ... 0.1 part by weight-Filler Heidilite H-42M (manufactured by Showa Denko KK) Name) ... 15 parts by weight EROSIL # 200 (manufactured by Nippon Aerosil Co., Ltd., product name) ... 1 parts by weight

[0055]

[Table 1]

As shown in Table 1, the multilayer wiring board according to the present invention is excellent in via hole formability, adhesive strength with circuit conductors, electrolytic corrosion resistance, heat resistance and the like. Further, since the developing solution is not a chlorine-based solvent or a 100% solvent, it is excellent in working environment, and there is no need to newly make the equipment explosion-proof. further,
In the present invention, a developer obtained by mixing water and an organic solvent is used for forming a via hole, and alkaline permanganate is used for forming a roughened irregular shape on the surface of an insulating layer. Therefore, for the power supply through hole that is mechanically formed by a mechanical drill, the smear processing that is usually performed is performed by the developer and alkaline permanganate, so that a wiring board manufacturing process without waste is possible. is there.

[0057]

As described above, it is possible to provide a low-cost multilayer wiring board excellent in fine wiring and thin multilayer without changing the conventional equipment and the conventional method.

[Brief description of drawings]

1A to 1H are cross-sectional views for explaining an embodiment of the present invention.

[Explanation of symbols]

 1. Insulating substrate 2. First circuit 3. First photosensitive insulating layer 4. Photomask 5. UV rays 6. Via hole 61. Via hole 7. Roughened surface 71. Roughened surface 8. Second circuit 9. Second insulating layer 10. Third circuit

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication location H05K 3/46 T 6921-4E N 6921-4E (72) Inventor ▲ Tsuru ▼ Shimodate City, Ibaraki Prefecture Ogawa 1500 Address Hitachi Chemical Co., Ltd. Shimodate Research Laboratory (72) Inventor Hiroyuki Fukai Shimodate City, Ibaraki Prefecture Ogawa 1500 Address Hitachi Chemical Co., Ltd. Shimodate Factory

Claims (8)

[Claims] 1. A photosensitive resin composition comprising the following components (A) to (F). (A) Epoxy resin having a number average molecular weight (Mn) of 1500 or less (B) Epoxy group in the epoxy resin is substituted with a photopolymerizable unsaturated group by 25% to 75% (meth) acrylated epoxy resin (C) Methacrylate Acid-added acrylonitrile butadiene rubber (D) Alkylphenol resin (E) Photoinitiator for reacting acryloyl group of component (B) with ultraviolet rays (F) Curing that reacts with epoxy group of component (B) by heating Agent 2. The total amount of the components (A), (B), (C) and (D) is 100, and the total amount of the components (C) and (D) is 5 to 40%. And the blending ratio of the component (C) and the component (D) is 95/5 to 6
It is 0/40, The photosensitive insulating resin composition of Claim 1 characterized by the above-mentioned. 3. An insulating layer is formed on a circuit surface of an insulating substrate on which a first circuit is formed, a via hole for connecting to the first circuit is formed in the insulating layer, and the insulating layer is cured by heating. In the method of manufacturing a wiring board in which a second circuit is formed on the surface of the insulating layer by copper plating and interlayer connection of via holes is performed to form a multilayer, the insulating layer has (A) a number average molecular weight (Mn) of 1500 or less. (B) Epoxy resin (B) (meth) acrylated epoxy resin in which the epoxy group in the epoxy resin is substituted with 25% to 75% of a photopolymerizable unsaturated group (C) Acrylonitrile butadiene rubber with methacrylic acid addition (D) Alkylphenol resin (E) ) Photoinitiator for reacting the acryloyl group of the component (B) with ultraviolet rays (F) A photosensitive agent comprising (A) and a curing agent that reacts with the epoxy group of the component (B) by heating A method for producing a multilayer wiring board, which is a conductive insulating resin composition. 4. When the total amount of the components (A), (B), (C) and (D) is 100, the total amount of the components (C) and (D) is 5 to 40%. And the blending ratio of the component (C) and the component (D) is 95/5 to 6
It is 0/40, The manufacturing method of the multilayer wiring board of Claim 3 characterized by the above-mentioned. 5. The method of forming a via hole is a method of exposing a photosensitive insulating resin through a photomask and etching an unexposed portion with a developing solution, wherein an alkali is previously prepared when copper plating is performed on the surface of the insulating layer. The method for producing a multilayer wiring board according to claim 3, wherein the surface of the insulating layer is roughened with permanganate. 6. The developer used for forming a via hole in an insulating layer is a developer prepared by mixing water and an organic solvent having a vapor pressure of 133 Pa (25 ° C.) or less.
5. The method for manufacturing a multilayer wiring board according to any one of 5 above. 7. The developing solution is water, the vapor pressure is 133 Pa (25
7. The method for producing a multilayer wiring board according to claim 6, which is a mixed solution of an organic solvent having a temperature equal to or lower than 0 ° C.) and an alkali component. 8. The method for producing a multilayer wiring board according to claim 7, wherein the alkaline component is borax and / or an alkanolamine.