JPH08139452A - Manufacturing method of multilayer wiring board - Google Patents

Abstract

PURPOSE: To increase the bonding strength between an insulating layer and a conductive circuit for manufacturing high reliable multilayer wiring board by a method wherein, after the formation step of a conductive circuit, the roughening step of conductor surface is performed using a roughening solution containing a conductor corrosion inhibitor within the title manufacturing method by build up mode. CONSTITUTION: A through hole 103 is formed on a glass epoxy laminated board 101 having both surfaces thereof clad with copper foils 102. Next, the copper foils 102 are etched away to form conductor circuit 104 for roughening the conductor surface so as to form conductor roughened surface 105. Next, insulating layers 106 of sensitive resin composition are formed on the board to be selectively etch-patterned and then roughened using roughening solution containing conductor corrosion inhibitor so as to form the other roughened surface 110. Next, the whole body is immersed in a plating catalyst solution to form a copper plating layers 111. Finally, by repeating the steps, conductor circuit layers 112 are formed and then the conductor circuit surfaces are roughened to form the other roughened surfaces 113 further forming the insulating layers 114 on the upper parts of said surfaces 113.

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 a method for manufacturing a multilayer wiring board suitable for a so-called build-up method in which a plurality of insulating layers and conductor circuits are alternately laminated. .

[0002]

2. Description of the Related Art A method for manufacturing a multilayer wiring board by a build-up method using a photosensitive resin as an interlayer insulating layer is disclosed in, for example, Japanese Patent Application Laid-Open Nos. 58-209195 and 3-3297.
No. 6,086,045. It is important that the insulating layer and the conductor circuit forming the laminate of the multilayer wiring board are firmly bonded to each other. In order to improve the adhesive strength, it is roughly divided into a case of forming an insulating layer on the conductor circuit and a case of forming the conductor circuit on the insulating layer from the manufacturing process.

First, regarding the former, a technique for firmly adhering an insulating layer on a conductor circuit is described in, for example, the following (1).
Various proposals have been made as shown in (3). (1) A method of strongly bonding the conductor and the insulating layer by oxidizing and roughening the surface of the copper forming the conductor with an alkaline sodium chlorite aqueous solution or permanganic acid. (2) The surface of the copper forming the conductor is oxidized by an alkaline sodium chlorite aqueous solution, an alkaline potassium persulfate aqueous solution, an aqueous potassium sulfide / ammonia chloride aqueous solution, etc. to form cupric oxide, and then reduction treatment is performed. To roughen the surface of the conductor layer, thereby firmly bonding the conductor to the insulating layer (for example, Japanese Patent Publication No. 64-8479). (3) A method of firmly adhering a conductor and an insulating layer by forming a composite plating layer containing fine particles of a thermosetting resin which has been cured in advance on the surface of the conductor layer (for example, JP-A-59).
-106918).

On the other hand, also in the case of forming a conductor circuit on the latter insulating layer, there is a technique for firmly adhering the conductor circuit.
For example, various proposals have been made as shown in (4) to (5) below. (4) A method of forming an adhesive layer or a resin layer containing a predetermined filler on a substrate and selectively roughening the surface (for example, Japanese Patent Publication No. 63-49397). (5) A method for producing a multilayer wiring board by roughening an insulating layer with a potassium permanganate solution and forming a conductor layer on the surface thereof (for example, JP-A-4-148590).

Further, as in the above-mentioned Japanese Patent Laid-Open No. 3-3297, there is also proposed a build-up method in which both the former and the latter processes are combined to firmly bond the conductor circuit and the insulating layer to each other. . (6) In this method, the roughening treatment of the conductor pattern surface is performed with two kinds of treatment liquids, that is, an oxidizing solution of an alkaline aqueous solution of sodium chlorite and a reducing solution consisting of an alkaline aqueous solution of formalin and potassium hydroxide, and further the interlayer. The roughening treatment of the surface of the insulating layer is performed with a roughening solution of an aqueous chromic acid solution.

[0006]

However, the above-mentioned conventional build-up method has various technical problems in enhancing the adhesiveness between the conductor circuit and the insulating layer as described below. That is, as a method of firmly adhering the insulating layer formed on the conductor layer, the method (1) described above uses a chemical treatment such as acid cleaning in a later step because the surface of the conductor is covered with copper oxide. The haloing or pinking phenomenon, which occurs when the oxide of copper is reduced and the insulating layer is partially peeled off, is liable to occur, and there is a drawback that the reliability of the printed wiring board such as electric insulation is deteriorated. Further, in the above method (2), the copper oxide on the conductor surface is reduced and removed, and the adhesiveness to the insulating layer is good, but the conductor surface is subjected to the roughening by the oxidation treatment, and then the reduction treatment is performed. However, there is a problem in that it requires two processing solutions for oxidation and reduction, and that the work is complicated. Furthermore, the above method (3) is a method of firmly adhering the conductor and the insulating layer via the composite plating layer on the surface of the conductor. However, the composite plating layer formed on the surface of the conductor layer has a conductive resistance. Because,
When manufacturing a multilayer wiring board using a via hole, there is a drawback that the connection reliability of the via hole is low.

On the other hand, as a method for firmly adhering the conductor layer formed by plating on the insulating layer, the above method (4) newly requires a special adhesive or resin composition containing a predetermined filler. Then, there is a problem of increasing the manufacturing cost of the multilayer board. In the method (5), a commercially available insulating material (epoxy resin) is used as an interlayer insulating film without using a special adhesive or resin composition, and the surface is roughened with a potassium permanganate solution. Although the conductor layer is formed on this by plating, there is a drawback that the adhesive strength is insufficient. The adhesive strength is usually evaluated by the peel strength (g / cm), but when using this kind of potassium permanganate solution, the peel strength was at most about 40 (g / cm).

Further, the method (6) has a problem of using two kinds of roughening liquids for oxidation and reduction similar to the above (2) for roughening the surface of the conductor layer, and roughening the surface of the insulating film. Regarding the treatment, an aqueous chromic acid solution was used instead of the potassium permanganate solution of (5), but there was a similar problem regarding the adhesive strength.

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art, and to further enhance the adhesive strength between the insulating layer and the conductor circuit, and to provide a highly reliable method for manufacturing a multilayer wiring board. Especially. Specifically, even if the roughening treatment of the conductor circuit surface is performed with one kind of roughening liquid, high adhesive strength can be obtained, and the roughening liquid can be easily managed. The purpose is to realize a roughening treatment in which the adhesive strength with the conductor layer is dramatically improved even if the roughening is performed with.

[0010]

Means for Solving the Problems As a result of various experiments conducted by the present inventors in order to increase the adhesive strength, the roughening treatment of the conductor circuit surface was performed by etching with a roughening solution containing a conductor corrosion inhibitor. It was found that it is effective to improve the peel strength dramatically. That is, by this roughening process,
A rough surface having a large surface area and a very complicated shape is formed on the conductor circuit, and the insulating layer formed on the rough surface is firmly adhered. In the conventional oxidation / reduction treatment used as a roughening treatment for the surface of a conductor circuit, the number of treatment liquids is large, and management of each treatment condition is complicated.

The roughening liquid used by the present inventors is a one-liquid type, easy to handle, and economically advantageous. In addition, the haloing or pinking phenomenon, which is likely to occur on a roughened surface that is not subjected to ordinary reduction treatment, is caused by the chemical treatment such as acid cleaning in the subsequent step, which causes the oxide of the conductor to be reduced and the insulating layer to be partially peeled off. It has characteristics that do not occur.

Preferred roughening liquids include, for example, persulfate / acid / conductor corrosion inhibitor system, sulfuric acid / hydrogen peroxide / conductor corrosion inhibitor system, ferric chloride / conductor corrosion inhibitor system, cupric chloride. / Conductor corrosion inhibitor system, tetraammine copper chloride / conductor corrosion inhibitor system and the like. Each of the roughening liquids has a roughening component that etches the conductor layer and a component that partially adsorbs on the surface of the conductor layer and suppresses corrosion of the conductor (this is called a conductor corrosion inhibitor). Is a feature. In such a roughening solution, the conductor corrosion inhibitor is partially adsorbed on the surface of the circuit formed by the conductor layer, and the conductor layer at the adsorbed portion is prevented from being etched. Is estimated to be obtained.

As the conductor corrosion inhibitor in the roughening solution, a corrosion inhibitor suitable for the metal material forming the conductor layer is used. Hereinafter, the case of copper usually used as the conductor layer will be taken as an example. To explain, preferred copper corrosion inhibitors include, for example, benzotriazole derivatives [1,2,3-benzotriazole, 4-or5-methylbenzotriazole,
A benzotriazole skeleton is effective for adsorbing to a conductor surface such as 4-or5-aminobenzotriazole], a thiazole derivative [benzothiazole, 2-mercaptobenzothiazole, 2-methylbenzothiazole, 2-phenylthiazole, etc. A thiazole skeleton is effective for adsorption], an imidazole derivative [imidazole, benzimidazole, 2-methylbenzimidazole, 2-ethyl-5-methylbenzimidazole, 2-mercaptobenzimidazole, 2- (4-thiazole) benzimidazole, conductor Imidazole skeleton is effective for adsorption on the surface], indazoles [6-aminoindazole],
Melamine derivative (melamine, N, N-diallyl melamine, 2-Nn-butyl melamine, etc., melamine skeleton is effective for adsorption on the conductor surface), triazine derivative [2,4
-Diamino-6-phenyltriazine, 2,4-diamino-6-methyl-s-triazine, 2-vinyl-4,6
-Diamino-s-triazine and the like, the triazine skeleton is effective for adsorption to the conductor surface], 2-mercaptobenzoxyazole, pyrimidine derivative [diaminopyrimidine, triaminopyrimidine, tetraaminopyrimidine, diamino-mercaptopyrimidine, etc. to the conductor surface Pyrimidine skeleton is effective for the adsorption of], 3,5-diamino-1,2,4-
Triazole, alkanethiols [CnH2n + 1S
H], thiourea derivative [thiourea, 1-phenyl-2-
The thiourea skeleton is effective for adsorption on the conductor surface, such as thiourea and ethylene thiourea], ethanol thiol, dodecyl mercaptan, and 2-mercaptoethanol. Preferably, 2-mercaptobenzimidazole, 6-aminoindazole, 2,4-diamino-6-
Phenyltriazine, 2-vinyl-4,6-diamino-
They are s-triazine, 2-methylbenzothiazole, melamine and 2-Nn-butylmelamine. The concentration of the copper corrosion inhibitor in the roughening solution is 0.01 to 10 g /
A range of 1, preferably 0.1 to 2 g / l is good.

Next, the inventors of the present invention also conducted a detailed experimental study on the roughening treatment of the surface of the insulating layer for firmly bonding the conductor circuit onto the insulating layer. As a result, extremely effective knowledge as described below was obtained. That is, the surface of the insulating layer is roughened with an aqueous solution of alkaline permanganate, and then manganese dioxide formed on the surface layer is dissolved and removed with a solution such as a hydroxylamine salt, and then roughened. It has been found that it is extremely effective to remove the deteriorated layer formed on the surface of the insulating layer using an aqueous solution of a surfactant. In particular, it has been found that the removal of this deteriorated layer is extremely important for firmly adhering the conductor circuit onto the insulating layer.

In order to remove the deteriorated layer, a method of mechanically removing with a brush or the like and a method of ultrasonic cleaning are conceivable. However, these methods cause pattern collapse in a wiring board having a fine pattern of this kind. There is a risk of damage such as
In addition, it was found that it is not suitable for removing fine parts of the insulating layer and has poor uniformity. Therefore, the present inventor has found that the deteriorated layer can be removed in an extremely short time only by immersing it in an aqueous solution of a surfactant as described above.

As the surface active agent used in the present invention, an anionic surface active agent or, if necessary, a cationic surface active agent having a solubilizing or thickening effect is used in combination. In particular,
The following surfactants can be exemplified as effective ones. (1) Anionic system: any of metal salts of alkylnaphthalene sulfonic acids and alkylsulfosuccinic acids or a mixture thereof (2) Cationic system: any of a mixture of quaternary ammonium salts having 8 to 50 carbon atoms, or Examples thereof include a mixture thereof. More specific compound names include, for example, anionic surfactants include sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium di-2-ethylhexyl sulfosuccinate, and the like. On the other hand, examples of cationic surfactants include triethanolamine toluene sulfonate, triethanolamine dodecylbenzene sulfonate,
A typical example is cetyltrimethylammonium chloride. The concentration of the surfactant is preferably in the range of 1 to 500 g / l, preferably 5 to 200 g / l.

The roughening treatment of the conductor layer surface and the roughening treatment of the insulating layer surface for improving the adhesive strength between the wiring conductor layer and the interlayer insulating layer in manufacturing the multilayer wiring substrate by the build-up method have been described above. However, in the present invention, either one of these roughening treatments, and more preferably, both roughening treatments are performed.

The means for achieving the object of the present invention will be specifically described below. The object is to manufacture a multilayer wiring board by a build-up method by alternately repeating a conductor circuit forming step and an interlayer insulating film forming step. In the method described above, the roughening treatment of the conductor surface after the conductor circuit forming step is performed by a step of treating with a roughening liquid containing a conductor corrosion inhibitor.

Further, the above-mentioned object is to repeat a conductor circuit forming step and an interlayer insulating film forming step alternately to manufacture a multilayer wiring board by a build-up method, in which the insulating film surface after the interlayer insulating film forming step is formed. After the roughening treatment is performed with an alkaline permanganate aqueous solution, the manganese dioxide formed on the surface is dissolved and removed, and then the degraded layer formed on the insulating layer surface is removed with an aqueous solution containing a surfactant. It is also achieved by the method of manufacturing a multilayer wiring board as described above.

Further, the above object is a method of manufacturing a multilayer wiring board by a build-up method by alternately repeating a conductor circuit forming step and an interlayer insulating film forming step, and roughening the conductor surface after the conductor circuit forming step. Is a step of treating with a roughening solution containing a conductor corrosion inhibitor, the roughening treatment of the insulating film surface after the interlayer insulating film forming step, after roughening with an alkaline permanganate aqueous solution, This is accomplished by a method for producing a multilayer wiring board, which comprises a step of dissolving and removing manganese dioxide formed on the surface, and then removing a deteriorated layer formed on the surface of the insulating layer with an aqueous solution containing a surfactant.

The substrate used when manufacturing the multilayer wiring board and the insulating resin forming the interlayer insulating layer will now be described. First, for example, glass fiber is used as a resin in the same manner as a substrate usually used. A substrate in which a conductor thin film such as a copper foil is formed on both sides or one side of an insulating sheet molded in (which is commonly called a copper-clad laminate, and is typically marketed as a glass epoxy copper-clad laminate) ), Or as an inner layer, a laminated plate obtained by laminating a plurality of sheets on which circuit patterns are already formed and press-molding is used. Depending on the application, a laminated board using a ceramic sheet instead of the resin substrate may be used.

As the insulating resin forming the interlayer insulating layer,
Examples thereof include photosensitive epoxy resins, epoxy acrylate resins, urethane acrylate resins, polyimide resins, polyester resins, bismaleimide / triazine resins, and the like. Preferably, the component is (1) a negative photosensitive resin composition containing acrylic acid ester or methacrylic acid ester as a partial structure and containing as a main component a resin obtained from a novolac type epoxy resin. Alternatively, (2) (a) one or more novolak epoxy resins selected from the group consisting of cresol novolac epoxy resins and phenolvolac epoxy resins and an unsaturated carboxylic acid having an acid equivalent / epoxy equivalent ratio of Isocyanate ethyl methacrylate is added to the secondary hydroxyl group of the unsaturated compound obtained by the addition reaction in the range of 0.1 to 0.98 in an isocyanate equivalent / hydroxyl group equivalent ratio of 0.1 to 0.9.
100 parts by weight of a photopolymerizable unsaturated compound obtained by reacting in the range of 1.2, and (b) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-
A negative photosensitive resin composition containing 0.1 to 20 parts by weight of 1-one. Or (3) at least one selected from the group consisting of (a) a prepolymer of diallyl phthalate having a molecular weight of 3,000 to 30,000 as an essential component, and (b) an acrylate or methacrylate of a polyhydroxy compound and an oligoester methacrylate. The above polyfunctional unsaturated compound, (c) a photopolymerization initiator, (d) an epoxy resin, (e) an epoxy resin curing agent, and (f)
A negative photosensitive resin composition containing melamine or a derivative thereof. Or (4) (a) a polyfunctional compound solid at room temperature which is a reaction product of an epoxy resin having an average of a plurality of epoxy groups per molecule and an unsaturated carboxylic acid, and (b) one molecule A polyfunctional acrylate or polyfunctional methacrylate that has a plurality of ethylene bonds per unit at room temperature, (c) a photopolymerization initiator, (d) an epoxy resin, (e) an epoxy resin curing agent, and (f) ) A negative photosensitive resin composition containing melamine or a derivative thereof, and the like.

As the conductor layer to be laminated, copper is generally used, but other conductor metals such as nickel can be used if necessary. Further, as is well known, a plating layer is used for the conductor layer to be laminated on the second layer or more on the substrate. Further, the plating layer may be formed by electroless plating, but since the plating time becomes long, the underlayer is usually formed thinly by electroless plating and then formed by electroplating to a required thickness.

A specific method for manufacturing a multilayer wiring board, which is the object of the present invention, will be described in detail in the section of Examples. An outline of a typical manufacturing process will be described below.
~ D. By appropriately combining these steps,
A multi-layer wiring board in which various connection configurations between desired conductor circuits can be obtained is manufactured. Step (A): copper-clad laminate → through-hole formation → etching resist → conductor circuit formation → conductor surface roughening → insulating layer formation / patterning or copper-clad laminate → etching resist → conductor circuit formation → through-hole formation → Roughening of conductor surface → Insulation layer formation / patterning (B) step: Roughening of insulation layer → Removal of surface deterioration layer → Applying plating catalyst → Copper plating → Etching resist → Conductor circuit formation →
Conductor surface roughening → insulating layer formation / patterning (C) step: copper-clad laminate → etching resist → conductor circuit formation → conductor surface roughening → insulating layer forming / patterning (D) step: through hole formation → insulating layer roughening → Removal of surface deterioration layer → Addition of plating catalyst → Copper plating → Etching resist → Conductor circuit formation → Conductor surface roughening → Insulation layer formation / patterning As a copper-clad laminate, a double-sided two-layer board or a circuit on its inner layer It is preferable that the laminated plate has three or more layers of the laminated plate pressing method.

[0025]

As a roughening technique of the surface of the insulating layer for firmly adhering the conductor circuit to the insulating layer, in the present invention, the insulating layer is formed on the surface layer after roughening with an aqueous solution of alkaline permanganate. Manganese dioxide is dissolved and removed (for example, dissolved with a hydroxylamine salt), and then the deteriorated layer formed on the surface of the insulating layer is removed using an aqueous solution of a surfactant. In this method, the action of the surfactant is extremely high. It becomes important. To explain the action of the surfactant, first, the degraded layer is loosened by the wetting and permeation action, and the degraded product is separated from the surface.
Then, it is adsorbed by a surfactant, and is dropped from the roughened surface and dispersed or suspended in fine particles, whereby the deteriorated layer can be easily removed from the roughened surface of the insulating layer. Since the roughened surface thus formed has a large surface area and constitutes a complicated structure, the circuit conductor formed thereon is firmly bonded. Removal of the deteriorated layer is extremely important for firmly adhering the conductor circuit onto the insulating layer. Further, in order to firmly bond the conductor circuit to such a roughened surface,
It is important that at least the base of the conductor circuit is formed by electroless plating so that the conductor penetrates into a complicated structure.

Next, in order to improve the adhesiveness between the conductor layer and the resin insulation layer formed on the conductor layer, the conductor layer surface is etched with a roughening liquid containing a conductor corrosion inhibitor in the present invention. To do. This is because the conductor corrosion inhibitor in the roughening solution is partially adsorbed on the conductor surface, the etching rate at this location is reduced, and the conductor surface is unevenly etched, so that the conductor circuit has a large surface area and is extremely complicated. This is probably because a roughened surface having a different shape was obtained.

As described above, according to the conventional method, two kinds of roughening liquids are required to obtain a copper roughening surface having a complicated shape. Copper oxide is once grown on the copper surface by oxidation treatment, and this oxidation is performed. It was obtained by reducing the surface of copper. Although this method can achieve a practical level of adhesive strength, it was necessary to strictly control a new liquid phase reduction treatment step and reduction treatment conditions. However, the roughening liquid of the present invention is a one-liquid type and is easy to process control and handling and economically advantageous. Further, in the present invention, haloing, which tends to occur in the conventional roughening treatment, is caused by partial peeling of the insulating layer formed on the top surface of the insulating layer by reduction of copper oxide by chemical treatment such as acid cleaning in the subsequent step, Alternatively, it has a characteristic that the pink ring phenomenon does not occur. Further, by including the step of improving the adhesion between the conductor circuit and the insulating layer, it becomes possible to manufacture a highly reliable build-up multilayer wiring board.

[0028]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail below with reference to the manufacturing process diagrams shown in FIGS. The multilayer wiring board of the present invention is manufactured by a so-called build-up method in which a conductor circuit (wiring pattern) forming step and an interlayer insulating film forming step are alternately repeated a plurality of times to be laminated. Manufactured a multilayer wiring board in which various connection configurations can be taken between required conductor circuits by arbitrarily combining the representative steps described in steps A to D similar to those described above.

Step (A): Copper-clad laminate → through-hole formation →
Etching resist → Conductor circuit formation → Conductor surface roughening → Insulation layer formation / patterning, or copper clad laminate → Etching resist → Conductor circuit formation → Through hole formation → Conductor surface roughening → Insulation layer formation / patterning. Step (B): Roughening of insulating layer → Removal of surface deterioration layer → Applying plating catalyst → Copper plating → Etching resist → Conductor circuit formation →
Roughening of conductor surface → insulating layer formation and patterning. Step (C): copper-clad laminate → etching resist → conductor circuit formation → conductor surface roughening → insulating layer formation / patterning. Step (D): through-hole formation → insulating layer roughening → surface deterioration layer removal → plating catalyst application → copper plating → etching resist → conductor circuit formation → conductor surface roughening → insulating layer formation / patterning.

Example 1 This example describes an example of manufacturing a multilayer wiring board having a total of four layers on both sides (two layers on one side) by combining the steps A and B described above.
The steps will be sequentially described below with reference to the sectional process drawing of FIG.

FIG. 1 (a) step: Glass epoxy laminated plate 1
A copper-clad laminate in which copper foils 102 are laminated on both sides of 01 is prepared as a substrate 100. Step (b) of FIG. 1: A through hole 103 is drilled in the substrate 100. Step (c) of FIG. 1: A dry film (not shown) for resist formation was laminated on both surfaces of the substrate, exposed to a mask having a predetermined circuit pattern formed thereon, and developed to form a resist removal pattern. Using this as an etching resist, the copper foil 102 is etched to form the conductor circuit 10.
4 was formed. After removing the resist, the conductor surface of the substrate was roughened with a persulfate / acid / copper corrosion inhibitor roughening solution to form a conductor roughened surface 105. The roughening liquid used and the roughening conditions are as follows. Composition of roughening solution: Na ₂ S ₂ O ₈ (200 g / l) as a persulfate, 98% H ₂ SO ₄ (10 ml / l) as an acid, and 2-mercaptobenzimidazole (0.5 g as a copper corrosion inhibitor). / L) composition. Roughening conditions: spray etching at a liquid temperature of 40 ° C. Step (d) of FIG. 1: After the roughening treatment, the substrate was washed with water and dried to form an insulating layer 106 on this substrate. The insulating resin used was a photosensitive resin composition, and the adjustment method was as follows. (1) Cresol novolac type epoxy resin EOCN1
A solution of 02 (manufactured by Nippon Kayaku) (1095 parts by weight) in ethyl cellosolve acetate (800 parts by weight) was mixed with acrylic acid (69 parts by weight), benzyltrimethylammonium chloride chloride (7 parts by weight) and p-methoxyphenol (3 parts by weight). Part)
Was mixed with a solution of ethyl cellosolve acetate (100 parts by weight) at 60 ° C. and reacted at 80 ° C. for 15 hours. The resulting unsaturated compound solution was mixed with a solution of isocyanate ethyl methacrylate (163 parts by weight) and dibutyltin dilaurate (0.5 parts by weight) in ethyl cellosolve acetate (100 parts by weight) and reacted at 60 ° C. Methanol (10 parts by weight) was added to obtain a solution of the photopolymerizable unsaturated compound.

To this solution (175 parts by weight) was added 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (IRGACU manufactured by Ciba Geigy).
RE369) (10 parts by weight), Microace P-4 (manufactured by Nippon Talc, fine particle talc) (7 parts by weight), Crystallite 5V (manufactured by Tatsumori, fine particle silica) (36 parts by weight), Torad 7100 (manufactured by Tohto Kasei) , Amine acrylate)
(5 parts by weight), phthalocyanine green (1 part by weight),
2-Methylimidazole (3 parts by weight) and Modaflow (manufactured by Mitsubishi Monsanto) (0.1 parts by weight) were blended and uniformly mixed using a three-roll mill to prepare a photosensitive resin composition solution.

Step (e) of FIG. 1: The insulating layer 106 made of the coating film of the above resin composition is pre-dried at 80 ° C. for 30 minutes, and then 600 mJ / cm ² using a high pressure mercury lamp.
In preparation for formation of the second-layer conductor circuit, exposure is performed through a predetermined mask (not shown), solvent development is performed, and the insulating resin 106 is selectively etched and patterned to form a base necessary for electrical connection. In order to expose a predetermined area of the conductor circuit 104 and further improve the film quality of the insulating resin, it is performed at 150 ° C.
Heated for minutes. Next, the patterned insulating resin layer 106 was roughened with an aqueous solution of alkaline permanganate to form a roughened surface 110. The roughening liquid used and the roughening conditions are as follows. Composition of roughening solution and roughening conditions: KMnO ₄ (60 g /
l), NaOH (40 g / l): Soaked at a liquid temperature of 80 ° C. for 30 minutes.

Manganese dioxide 1 attached to the surface of this substrate
08 was dissolved in a 3% aqueous solution of hydroxylamine hydrochloride, and then the deteriorated layer 109 formed on the surface of the insulating layer was removed using an aqueous solution of a surfactant. The aqueous solution of the surfactant used and its treatment conditions are as follows. Sodium dodecyl sulfate (50 g / l): Soaked at a liquid temperature of 25 ° C. for 60 seconds.

Step (f) in FIG. 1: Next, in order to activate the roughened surface, it is immersed in a plating catalyst solution to form a conductive film as a base by electroless plating to a thickness of 0.2 μm, and then thick copper electroplating is performed. Two
5 μm was applied to form a copper plating layer 111. In both cases, a commercially available product is used as the treatment liquid, and the treatment is performed by a well-known plating method.

Step (g) of FIG. 1: The same method as the step (c) of FIG. 1 is repeated again. That is, an etching resist is formed on the copper plating layer 111, and exposure, development, etching,
The conductor circuit layer 112 is formed through the resist stripping process. Then, the surface of the conductor circuit is roughened by the same method to form a roughened surface 113.

Step of FIG. 1H: Finally, FIG. 1D is repeated to form an insulating layer 114 (used as a solder resist), and then patterning is performed by the same method as a part of FIG. 1E. The conductor circuit surface required for connection is exposed. In this way, as shown in the drawing, a wiring board having a single-sided two-layer laminated structure was obtained.

The adhesive strength between the conductor layer and the insulating layer of the wiring board thus obtained was measured for the peel strength (g / cm) according to the evaluation method of JIS-C-6481, and on the conductor circuit. The presence or absence of the halo of No. 1 was observed, and the results are shown in Table 1. The results of comparative examples described later are also shown in the table. As is clear from this table, the peel strength of this example is 852, which is a comparative example (the highest one is 38).
It is markedly improved in comparison with. Also, there is no halo,
A highly reliable multilayer wiring board with excellent adhesion and extremely excellent adhesive strength was realized.

[0039]

[Table 1]

Example 2 In this example, a multilayer wiring board having three layers on one side and a total of six layers on both sides was manufactured. That is,
Since one conductor layer and one insulating layer were laminated on both sides of the wiring board obtained in Example 1, the number of repeated pattern formation steps was increased accordingly. First,
After the final process of the first embodiment (process of FIG. 1 (h)),
Similar to the roughening treatment of the insulating layer surface of the step (e), the surface roughening treatment of the insulating layer 114 is performed, and then the plating step of FIG. 1F to the insulating layer patterning step of FIG. Was repeated, and basically the same manufacturing process as in Example 1 was performed.

The points of difference in material and processing method from those of Example 1 will be described below in the order of steps. (1) First, in the surface roughening treatment step of the conductor circuit 104 of FIG. 1C, the copper corrosion inhibitor “2-mercaptobenzimidazole” in the roughening liquid was changed to melamine.

(2) In the insulating layer forming step of FIG. 1D, the composition of the insulating resin 106 was changed as follows. That is, diallyl orthophthalate resin (average molecular weight 1
10,000) (100 parts by weight), pentaerythritol tetraacrylate (20 parts by weight), benzophenone (4 parts by weight), 4,4′-bis (N, N′-dimethylamino) benzophenone (2 parts by weight), bisphenol A
-Type epoxy resin (30 parts by weight), 2-phenylimidazole (1 part by weight), melamine (5 parts by weight), silicone oil (5 parts by weight), phthalocyanine green (2 parts by weight), ethyl cellosolve acetate (30 parts by weight). , Butyl cellosolve acetate (30 parts by weight) were mixed and uniformly mixed using a three-roll mill to prepare a photosensitive resin composition solution. (3) In the step of patterning the insulating resin 106 of FIG. 1E, the exposure amount of the high pressure mercury lamp is 600 mJ.
/ Cm ² to 900 mJ / cm ² .

With respect to the multilayer wiring board thus manufactured, the adhesive strength between the conductor layer and the insulating layer was the same as in Example 1.
The results of the adhesion evaluation test are shown in Table 1. As is apparent from the table, the peel strength is 935, and the adhesive strength is further improved as compared with Example 1.

Example 3 By the same manufacturing process as that of Example 1, two layers were stacked on one side to manufacture a multilayer wiring board having a total of eight layers on both sides. This embodiment is different from Embodiment 1 in that
It is as follows. (1) First, as the double-sided copper-clad laminate 100 of FIG. 1A, a glass epoxy double-sided copper-clad 4-layer laminate containing an inner layer circuit was used. (2) In the surface roughening treatment step of the conductor circuit 104 of FIG. 1C, the copper corrosion inhibitor “2-mercaptobenzimidazole” in the roughening liquid was changed to 2-Nn-butylmelamine.

(3) In the insulating layer forming step of FIG. 1D, the composition of the insulating resin 106 was changed as follows. (A) Epoxy equivalent: A cresol novolac epoxy resin (175 parts by weight) having an epoxy equivalent of 225 and butyl cellosolve acetate (75 parts by weight) are mixed and heated to 90 ° C. to be dissolved. 2,5-Ditertiarybutylhydroquinone (0.02 parts by weight), N, N'-dimethylaniline (1.75 parts by weight), and acrylic acid (22.4 parts by weight) were added thereto and reacted to obtain epoxy vinyl. (Epoxy equivalent 56
0) was obtained. (B) the obtained epoxy vinyl (100 parts by weight), pentaerythritol tetraacrylate (20 parts by weight),
Benzophenone (4 parts by weight), 4,4'-bis (N,
N'-dimethylamino) benzophenone (2 parts by weight),
Bisphenol A type epoxy resin (40 parts by weight), imidazole (1 ′) ethyl-s-triazine (2 parts by weight), melamine (3 parts by weight), silicone oil (5 parts by weight), phthalocyanine green (2 parts by weight), Ethyl cellosolve acetate (30 parts by weight) and butyl cellosolve acetate (30 parts by weight) were blended and uniformly mixed using a three-roll mill to prepare a photosensitive resin composition solution.

(4) In the step of patterning the insulating resin 106 of FIG. 1 (e), the exposure amount of the high pressure mercury lamp is 600 mJ / cm ² to 900 mJ as in the second embodiment.
Changed to / cm ² .

(5) In the surface roughening treatment step of the insulating resin 106 shown in FIG. 1 (e), the deteriorated layer was removed by shortening the immersion time in the aqueous surfactant solution from 60 seconds to 30 seconds.

With respect to the multilayer wiring board thus manufactured, the adhesive strength between the conductor layer and the insulating layer was the same as in Example 1.
The results of the adhesion evaluation test are shown in Table 1. As is apparent from the table, the peel strength is 628, and it can be seen that the adhesive strength is slightly inferior to that of Example 1, but significantly improved as compared with the conventional comparative example.

Example 4 In this example, a multilayer wiring board having three layers on one side and a total of six layers on both sides was manufactured in the same manner as in Example 2. The difference between this embodiment and Embodiment 2 is as follows. (1) In the surface roughening treatment step of the conductor circuit 104 of FIG. 1C, the copper corrosion inhibitor “melamine” in the roughening liquid is added to the 6-
Changed to Aminoindazole. (2) In the insulating layer forming step of FIG. 1D, the composition of the insulating resin 106 was changed to the same as that of the first embodiment. (3) In the step of patterning the insulating resin 106 of FIG. 1E, the exposure amount with the high pressure mercury lamp was set to 600 mJ / cm ² as in the case of Example 1.

(4) In the surface roughening treatment step of the insulating resin 106 shown in FIG. 1E, the deterioration layer removing treatment using the aqueous solution of the surfactant was changed to the following conditions. 1 as a surfactant
-O-Sodium undecenoate (50 g / l): Liquid temperature 2
Soak for 30 seconds at 5 ° C.

With respect to the multilayer wiring board thus manufactured, the adhesive strength between the conductor layer and the insulating layer was the same as in Example 1.
The results of the adhesion evaluation test are shown in Table 1. As apparent from the table, the peel strength was 960, and the adhesive strength was further improved as compared with Example 2.

<Embodiment 5> This embodiment shows an example of manufacturing a multilayer wiring board in which four layers are stacked on one side and a total of eight layers are formed on both sides. Since one conductor layer and one insulating layer were further laminated on both surfaces of the wiring board obtained in Example 4, the number of repeated pattern formation steps was increased by that amount as compared with Example 4. That is, after the final step of Example 4,
The steps shown in FIGS. 1 (e) to 1 (h) are further repeated so that four layers are stacked on one side. Each basic manufacturing process was performed by the same manufacturing process as in Example 1.

The points of difference in material and processing method from those of Example 1 will be described below in the order of steps. (1) In the surface roughening treatment step of the conductor circuit 104 of FIG. 1C, the copper corrosion inhibitor “2-mercaptobenzimidazole” in the roughening liquid is added to 6-vinyl-4,6-diamino-
Changed to s-triazine. (2) In the surface roughening treatment step of the insulating resin 106 of FIG. 1E, the deterioration layer removal treatment with the aqueous solution of the surfactant was changed to the following conditions. Di-2-ethylhexyl sodium sulfosuccinate as a surfactant (50 g / l):
Immerse for 60 seconds at a liquid temperature of 25 ° C.

With respect to the multilayer wiring board thus manufactured, the adhesive strength between the conductor layer and the insulating layer was the same as in Example 1.
The results of the adhesion evaluation test are shown in Table 1. As is clear from the table, the peel strength was 882, and the adhesive strength was further improved in Example 1.

<Embodiment 6> In this embodiment, step C and step D are combined to form a total of four layers on both sides (two layers on one side).
An example in which the multi-layer wiring board is manufactured will be described below, and will be sequentially described below with reference to the sectional process drawing of FIG. It should be noted that this example is also basically the same as that shown in FIG.
It is the same as each step of. However, the timing of opening the through-hole 103 and some materials and processing methods are changed.

Step (a) of FIG. 2: In the same step as the step (a) of Example 1, a copper-clad laminate in which copper foils 102 are laminated on both surfaces of a glass epoxy laminate 101 is prepared as a substrate 100. Step (b) of FIG. 2 is a step corresponding to FIG. 1 (c) of the first embodiment, and a dry film (not shown) for resist formation is laminated on both surfaces of the substrate to form a mask on which a predetermined circuit pattern is formed in advance. It was exposed to light and developed to form a resist removal pattern. Using this as an etching resist, the copper foil 102 was etched to form the conductor circuit 104. After removing the resist, the conductor surface of the substrate was roughened with a persulfate / acid / copper corrosion inhibitor roughening solution to form a conductor roughened surface 105. The roughening liquid used and the roughening conditions are as follows.

Composition of roughening solution: Na ₂ S ₂ O as persulfate
₈ (200 g / l), 98% H ₂ SO ₄ as acid (10 m
1 / l), 2-mercaptobenzothiazole (0.5 g / l) as a copper corrosion inhibitor: spray etching at a liquid temperature of 40 ° C. Step (c) of FIG. 2 is a step corresponding to FIG. 1 (d) of Example 1, after the roughening treatment, washed with water and dried to form the insulating layer 1 on the substrate.
06 was formed. The insulating resin used is the same as the photosensitive resin composition used in Example 2. FIG. 2 (d) step: In the step corresponding to FIG. 1 (e) of Example 1, the resin layer was pre-dried at 80 ° C. for 30 minutes, and then two layers were formed at 600 mJ / cm ² using a high pressure mercury lamp. In preparation for the formation of a conductor circuit for the eyes, the insulating resin 106 is exposed through a predetermined mask (not shown) and subjected to solvent development.
Was selectively etched and patterned to expose a predetermined region of the underlying conductor circuit 104 necessary for electrical connection, and further heated at 150 ° C. for 30 minutes to improve the quality of the insulating resin film. Subsequently, the patterned insulating resin layer 106
Was roughened with an alkaline aqueous solution of permanganate to form a roughened surface 110. The roughening liquid used and the roughening conditions are as follows. KMnO ₄ (60 g / l), NaOH (40 g / l):
Immerse for 40 minutes at a liquid temperature of 80 ° C. Manganese dioxide 108 adhering to the surface of the substrate was dissolved in a 3% aqueous solution of hydroxylamine hydrochloride, and then the deteriorated layer 109 formed on the surface of the insulating layer was removed using an aqueous solution of a surfactant. The aqueous solution of the surfactant used and its treatment conditions are as follows. Sodium di-2-ethylhexyl sulphosuccinate (50 g / l): immersed for 60 seconds at a liquid temperature of 25 ° C.

Step (e) of FIG. 2 In the step corresponding to FIG. 1 (b) of the first embodiment, the through hole 103 is drilled in the through hole forming region. 2 (f) step- (h) step: FIG. 1 (f) -of Example 1
These are the same steps as the step (h).

For the multilayer wiring board thus manufactured, the adhesive strength between the conductor layer and the insulating layer was the same as in Example 1.
The results of the adhesion evaluation test are shown in Table 1. As is clear from the table, the peel strength was 953, the adhesive strength was further improved in Example 1, and the characteristics were relatively close to those in Example 2.

<Embodiment 7> This embodiment shows an example of manufacturing a multilayer wiring board composed of a laminated body of 3 layers on one side and 6 layers on both sides as in the case of Example 2. The timing of the process of forming the mouth is different. Although the number of stacked layers is different, the order of the manufacturing process is relatively similar to the process of FIG. 2 shown in the sixth embodiment. Therefore, the description will be given below with reference to FIG.

First, the processes from FIG. 2A to FIG. 2C are performed in the same manner as in the sixth embodiment. However, unlike the case of Example 6, the roughening liquid and the treatment conditions in the surface roughening treatment step of the conductor pattern 104 in the step of FIG. 2B were as follows. (NH ₄ ) ₂ S ₂ O ₈ (200 g / l) as persulfate, 98% H ₂ SO ₄ (10 ml / l) as acid, 2-methylbenzothiazole (0.5 g / l) as copper corrosion inhibitor :
Spray etching at a liquid temperature of 40 ° C. Next, the step of forming a through hole by a drill of FIG. 2E and the step of patterning the insulating resin layer 106 to the surface roughening treatment of FIG. 2D is performed after the through hole forming step by the drill of FIG.
Step corresponding to (e)] is performed. The subsequent steps are the same as those in FIGS. 2F to 2H of the sixth embodiment. However, in the surface roughening treatment step of the insulating resin layer 106 after the pattern formation of FIG. 2D, the step of removing the deteriorated layer 109 using the aqueous solution of the surfactant was performed under the following conditions. Sodium alkyl diphenyl ether disulphonate (50 g / l), alkyl alkanolamide (20
g / l: Aminone L-01, manufactured by Kao): Immersed at a liquid temperature of 25 ° C. for 30 seconds.

After obtaining the laminated structure of two layers on one side in this manner, the surface roughening treatment of the insulating resin layer in FIG. 2D and the steps of FIGS. 2F to 2H are repeated. Thus, a wiring board having a three-layer structure on one side and a total of six layers on both surfaces was obtained.

With respect to the multilayer wiring board thus manufactured, the adhesive strength between the conductor layer and the insulating layer was the same as in Example 1.
The results of the adhesion evaluation test are shown in Table 1. As is clear from the table, the peel strength was 682, and although the adhesive strength was inferior to that of Example 6, the characteristics were relatively close to those of Example 3.

<Embodiment 8> As in Embodiment 5, four layers on one side,
It shows an example of manufacturing a multilayer wiring board composed of a laminated body having a total of eight layers on both sides, but the timing of the step of forming a through hole by a drill is different. Although the number of stacked layers is different, the order of manufacturing steps is basically the same as that of the seventh embodiment. Therefore, redundant description will be omitted here, and only points different from the seventh embodiment will be shown below.

(1) First, the roughening liquid and the treatment conditions in the surface roughening treatment step of the conductor pattern 104 in the step of FIG. 2B are different from those in the case of Example 6 and are as follows. 98% H ₂ SO ₄ (120 ml / l), 35% H ₂ O ₂ (8
0 ml / l), 2-mercaptobenzimidazole (0.5 g / l): spray etching at a liquid temperature of 40 ° C. (2) The insulating resin 106 used in the step of FIG.
The same insulating resin as 6 was used. (3) Insulating resin layer 106 after pattern formation in FIG.
In the surface roughening treatment step of 1., the treatment conditions of the step of removing the deteriorated layer 109 using the aqueous solution of the surfactant are the same as in Example 1 sodium dodecyl sulfate (5 g / l): liquid temperature 25
It was immersed at 30 ° C. for 30 seconds.

After the laminated structure of two layers on one side is obtained in this manner, the surface roughening treatment of the insulating resin layer in FIG. 2D and the steps of FIGS. 2F to 2H are performed twice. By repeating this, a wiring board having a structure of 4 layers on one side and a total of 8 layers on both sides was obtained.

With respect to the multilayer wiring board thus manufactured, the adhesive strength between the conductor layer and the insulating layer was the same as in Example 1.
The results of the adhesion evaluation test are shown in Table 1. As apparent from the table, the peel strength was 980, and the adhesive strength was remarkably improved.

<Embodiment 9> By the same process steps as in Embodiment 7, a multilayer wiring board composed of a laminate of 5 layers on one side and 10 layers on both sides in total was manufactured. Although the number of stacked layers is different, the order of manufacturing steps is basically the same as that of the seventh embodiment. Therefore, redundant description will be omitted here, and only points different from the seventh embodiment will be shown below.

(1) First, the roughening liquid and the treatment conditions in the surface roughening treatment step of the conductor pattern 104 in the step of FIG. 2B are different from those in the case of Example 6 and are as follows. FeCl ₃ (370 g / l), 2-mercaptobenzimidazole (0.05 g / l): Spray etching at a liquid temperature of 40 ° C. (2) As the insulating resin 106 in the step of FIG. 2C, the same insulating resin as in Example 3 was used. (3) Insulating resin layer 106 after pattern formation in FIG.
In the surface roughening treatment step, the treatment conditions for the step of removing the deteriorated layer 109 using the aqueous solution of the surfactant are as follows: 1-o-sodium undecenoate (20 g / l): 3 at a liquid temperature of 25 ° C.
It was immersed for 0 seconds. By thus obtaining a laminated structure of two layers on one side, the surface roughening treatment of the insulating resin layer in FIG. 2D and the steps of FIGS. 2F to 2H are repeated three times. A wiring board having 5 layers on one side and a total of 10 layers on both sides was obtained.

With respect to the multilayer wiring board thus manufactured, the adhesive strength between the conductor layer and the insulating layer was the same as in Example 1.
The results of the adhesion evaluation test are shown in Table 1. As apparent from the table, the peel strength was 985, and the adhesive strength was remarkably improved.

<Embodiment 10> This embodiment shows an example of manufacturing a multilayer wiring board composed of a laminated body of three layers on one side and a total of six layers on both sides as in the case of the second embodiment. The timing of the process of forming the mouth is different.
Although the number of stacked layers is different, the order of the manufacturing process is relatively similar to the process of FIG. 2 shown in the sixth embodiment. Therefore, the description will be given below with reference to FIG.

First, the same processes as in Example 6 are carried out in the steps of FIGS. 2 (a) to 2 (b). However, unlike the case of Example 6, the roughening liquid and the treatment conditions in the surface roughening treatment step of the conductor pattern 104 in the step of FIG. 2B were as follows. CuCl ₂ (250 g / l), 36% HCl (130 m
1 / l), 6-aminoindazole (0.2 g / l):
Spray etching at a liquid temperature of 40 ° C.

Next, in the step of forming the insulating resin 106 shown in FIG. 2C, the same resin as that used in Examples 3 and 9 was used.

Then, in the surface roughening treatment step of the insulating resin layer 106 after the pattern formation of FIG. 2D, the treatment conditions of the step of removing the deteriorated layer 109 using the aqueous solution of the surfactant are dodecynylbenzene. Sodium sulfonate (20 g / l): Immersed at a liquid temperature of 25 ° C. for 60 seconds.

After that, the step of forming the through hole 103 by the drill of FIG. 2E is shifted after FIG. 2F to FIG. 2G and moved immediately before the step of FIG. Perform each step.

After obtaining the laminated structure of two layers on one side in this manner, the surface roughening treatment of the insulating resin layer in FIG. 2D and the steps of FIGS. 2F to 2H are repeated. Thus, a wiring board having a three-layer structure on one side and a total of six layers on both surfaces was obtained.

With respect to the multilayer wiring board thus manufactured, the adhesive strength between the conductor layer and the insulating layer was the same as in Example 1.
The results of the adhesion evaluation test are shown in Table 1. As apparent from the table, the peel strength was 766, and the adhesive strength was remarkably improved.

<Embodiment 11> This embodiment shows an example of manufacturing a multilayer wiring board composed of a laminate of four layers on one side and a total of eight layers on both sides as in the case of the fifth embodiment. The timing of the process of forming the mouth is different.
Although the number of stacked layers is different, the order of the manufacturing process is relatively similar to the process of FIG. 2 shown in the sixth embodiment. Therefore, the description will be given below with reference to FIG.

First, the same processes as in Example 6 are carried out in the steps of FIGS. 2 (a) to 2 (b). However, unlike the case of Example 6, the roughening liquid and the treatment conditions in the surface roughening treatment step of the conductor pattern 104 in the step of FIG. 2B were as follows. Cu (NH ₃ ) ₄ Cl ₂ (450 g / l), NH ₄ Cl, 2
8% aqueous ammonia (15 ml / l), 2,4-diamino-6-phenyltriazine (0.5 g / l): liquid temperature 40
Spray etching at ℃.

Next, in the step of forming the insulating resin 106 of FIG. 2C, the same resin as that used in Examples 1, 4 and 5 was used.

Next, in the surface roughening treatment step of the insulating resin layer 106 after the pattern formation of FIG. 2D, the treatment condition of the step of removing the deteriorated layer 109 using the aqueous solution of the surfactant is sulfosuccinic acid di- 2-Ethylhexyl sodium (50 g / l): Soaked at a liquid temperature of 25 ° C. for 30 seconds.

Next, the through hole 1 by the drill shown in FIG.
2 (f) to FIG.
By carrying out (h), a single-sided two-layer structure is obtained. After this,
(D) and FIGS. 2 (f) to 2 (h) are repeated again to obtain a single-sided three-layer structure. At this stage, the step of forming the through hole 103 with the drill shown in FIG. 2E is performed. Then, FIG.
(D) and FIGS. 2 (f) to 2 (h) are repeated again,
Finally, a wiring board having a four-layer structure on one side and a total of eight layers on both sides is obtained.

With respect to the multilayer wiring board thus manufactured, the adhesive strength between the conductor layer and the insulating layer was the same as in Example 1.
The results of the adhesion evaluation test are shown in Table 1. As apparent from the table, the peel strength was 768, and the adhesive strength was remarkably improved.

<Embodiment 12> The liquid composition and the treatment conditions used in the roughening treatment step of the conductor surface and the step of removing the deteriorated layer of the insulating layer surface in the respective steps of Embodiment 1 were changed as follows. Then, a wiring board similar to that in Example 1 was manufactured.

(1) The conductor layer roughening liquid and the roughening treatment conditions are as follows:
It is as follows. Na ₂ S ₂ O ₈ (200 g / l) as a persulfate, 98% H ₂ SO ₄ (10 ml / l) as an acid, and 2-mercaptobenzimidazole (0.1 g / l) as a copper corrosion inhibitor.
l): Immersion in a roughening tank with a liquid temperature of 40 ° C., air blow stirring,
Etching by rocking.

(2) The aqueous solution of the surfactant for removing the deteriorated layer generated during the surface roughening treatment of the insulating layer and the treatment conditions thereof are as follows. 1-o-sodium undecenoate (5 g / l): liquid temperature 2
Soak at 5 ° C for 2 minutes.

Regarding the multilayer wiring board thus manufactured, the adhesive strength between the conductor layer and the insulating layer was the same as in Example 1.
The results of the adhesion evaluation test are shown in Table 1. As apparent from the table, the peel strength was 627, and the adhesive strength was similar to that in the case of Example 3.

<Embodiment 13> The liquid composition and treatment conditions used in the conductor surface roughening treatment step and the step of removing the deteriorated layer on the insulating layer surface in the respective steps of Embodiment 1 were changed as follows. Then, a wiring board similar to that in Example 1 was manufactured.

(1) The roughening liquid for the conductor layer and the roughening treatment conditions are as follows:
It is as follows. Na ₂ S ₂ O ₈ (200 g / l) as a persulfate, 98% H ₂ SO ₄ (10 ml / l) as an acid, and 6-vinyl-4,6-diamino-s-triazine (2 as a copper corrosion inhibitor).
g / 1): Etching by immersing in a roughening tank at a liquid temperature of 40 ° C., stirring with air blow and shaking.

(2) The aqueous solution of the surfactant for removing the deteriorated layer generated during the surface roughening treatment of the insulating layer and the treatment conditions thereof are as follows. Sodium dodecyl sulfate (200g / 1): Liquid temperature 25 ° C
Soak for 30 seconds.

For the multilayer wiring board thus manufactured, the adhesive strength between the conductor layer and the insulating layer was the same as in Example 1.
The results of the adhesion evaluation test are shown in Table 1. As apparent from the table, the peel strength was 890, which was significantly superior to the comparative example.

<Comparative Example 1> In this example, a conductor surface roughening treatment step [FIG.
It was manufactured by omitting the step of removing the deteriorated layer during the roughening treatment of the surface of the insulating layer [step of FIG. 1 (e)], and the results are shown in Table 1. The peel strength was inferior to 38, and a halo was observed.

Comparative Example 2 Among the steps of Example 7, a conductor surface roughening treatment step [step (c) in FIG. 2] and a step of removing a deteriorated layer during the insulating layer surface roughening treatment [ Figure 2
The step (e)] was omitted, and the results are shown in Table 1. The peel strength was remarkably inferior at 15, and a halo was also observed.

Comparative Example 3 Among the steps of Example 9, the conductor surface roughening step [step (c) of FIG. 2] and the step of removing the deteriorated layer during the insulating layer surface roughening treatment [ Figure 2
The step (e)] was omitted, and the results are shown in Table 1. The peel strength was remarkably inferior at 28, and halo was also observed.

[0095]

As described above in detail, according to the present invention, the intended purpose can be achieved. That is, it is possible to easily manufacture a build-up multilayer wiring board having excellent adhesion between the conductor circuit and the resin insulating layer, and the effect of contributing to the industry is extremely large.

[Brief description of drawings]

FIG. 1 is a sectional process drawing showing a manufacturing process of a multilayer wiring board according to an embodiment of the present invention.

FIG. 2 is a sectional process drawing showing a manufacturing process of a multilayer wiring board according to another embodiment of the present invention.

[Explanation of symbols]

100 ... Double-sided copper-clad laminated substrate, 101 ... Substrate (laminated plate), 102 ... Copper foil, 103 ... Through hole, 104 ... Conductor circuit, 105 ... Roughened surface of conductor, 106 ... Insulating layer (resin), 108 ... MnO ₂ , 109 ... Degraded layer, 110 ... Roughened surface of insulating layer, 111 ... Plating, 112 ... Conductor circuit, 113 ... Roughened surface of conductor, 114 ... Patterning of insulating layer (resin).

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshihide Yamaguchi 292 Yoshida-cho, Totsuka-ku, Yokohama-shi, Kanagawa Inside the Institute of Industrial Science, Hitachi, Ltd. (72) Inventor Sai Oka 292 Yoshida-cho, Totsuka-ku, Yokohama-shi, Kanagawa Address Company Hitachi, Ltd., Production Technology Research Institute (72) Inventor Satoru Hashimoto, 216 Totsuka-cho, Totsuka-ku, Yokohama-shi, Kanagawa Address Information Company Hitachi, Ltd. (72) Shigeru Fujita Totsuka, Totsuka-ku, Yokohama-shi, Kanagawa 216, Machi, Hitachi Ltd., Information & Communication Division (72) Inventor Terutake Kato, 216, Totsuka-cho, Totsuka-ku, Yokohama, Kanagawa Prefecture Hitachi, Ltd., Information & Communication Division

Claims (12)

[Claims] 1. A method of manufacturing a multilayer wiring board by a build-up method by alternately repeating a conductor circuit forming step and an interlayer insulating film forming step, wherein the conductor surface is roughened after the conductor circuit forming step. A method for manufacturing a multilayer wiring board, which comprises a step of treating with a roughening liquid containing a corrosion inhibitor. 2. A method of manufacturing a multilayer wiring board by a build-up method by alternately repeating a conductor circuit forming step and an interlayer insulating film forming step, wherein roughening treatment of the insulating film surface after the interlayer insulating film forming step is performed. , Multi-layer wiring consisting of a step of dissolving and removing manganese dioxide formed on the surface after roughening with an alkaline aqueous solution of permanganate, and then removing a deteriorated layer formed on the surface of the insulating layer with an aqueous solution containing a surfactant. Substrate manufacturing method. 3. A method of manufacturing a multilayer wiring board by a build-up method by alternately repeating a conductor circuit forming step and an interlayer insulating film forming step, wherein the conductor surface is roughened after the conductor circuit forming step. Along with the step of treating with a roughening solution containing a corrosion inhibitor, the roughening treatment of the insulating film surface after the interlayer insulating film forming step is formed on the surface after roughening with an alkaline permanganate aqueous solution. A method of manufacturing a multilayer wiring board, which comprises a step of dissolving and removing the formed manganese dioxide, and then removing a deteriorated layer formed on the surface of the insulating layer with an aqueous solution containing a surfactant. 4. The negative type photosensitive resin composition containing the acrylic ester or methacrylic ester as a partial structure and containing a resin obtained from a novolac type epoxy resin as a main component in the step of forming the interlayer insulating film. The method for manufacturing a multilayer wiring board according to claim 1, wherein the method is provided as a step. 5. The negative photosensitive resin composition is selected from the group consisting of (a) a cresol novolac type epoxy resin and a phenol volak type epoxy resin, or 2 types thereof.
The secondary hydroxyl group of the unsaturated compound obtained by addition reaction of one or more novolac type epoxy resin and unsaturated carboxylic acid in the acid equivalent / epoxy equivalent ratio of 0.1 to 0.98,
100 parts by weight of a photopolymerizable unsaturated compound obtained by reacting isocyanate ethyl methacrylate in an isocyanate equivalent / hydroxyl group equivalent ratio of 0.1 to 1.2, and (b)
The multilayer wiring board according to claim 4, which is composed of a composition containing 0.1 to 20 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one. Manufacturing method. 6. The negative type photosensitive resin composition, wherein (a) a prepolymer of diallyl phthalate having a molecular weight of 3,000 to 30,000 and (b) an acrylate or a methacrylate of a polyhydroxy compound and an oligo as an essential component. At least one polyfunctional unsaturated compound selected from the group consisting of ester methacrylate, (c) a photopolymerization initiator, (d) an epoxy resin, (e) an epoxy resin curing agent, and (f) The method for producing a multilayer wiring board according to claim 4, which is composed of a composition containing melamine or a derivative thereof. 7. The negative photosensitive resin composition is solidified at room temperature which is a reaction product of (a) an epoxy resin having an average of a plurality of epoxy groups per molecule and an unsaturated carboxylic acid. A polyfunctional compound of (b), a polyfunctional acrylate or a polyfunctional methacrylate having a plurality of ethylene bonds per molecule and being liquid at room temperature, (c) a photopolymerization initiator, and (d) an epoxy resin. The method for producing a multilayer wiring board according to claim 4, comprising a composition containing (e) a curing agent for an epoxy resin and (f) melamine or a derivative thereof. 8. The method for manufacturing a multilayer wiring board according to claim 2, wherein the surfactant is an anionic surfactant. 9. The surface active agent comprises a surface active agent containing an anionic surface active agent as a main component and a soluble cationic surface active agent as an auxiliary component. A method for manufacturing the multilayer wiring board according to. 10. The anionic surfactant is any one of a metal salt of an alkylbenzene sulfonic acid having a hydrophobic alkyl chain carbon number of 8 to 30, an alkylnaphthalene sulfonic acid, or an alkylsulfosuccinic acid, or 10. The method for manufacturing a multilayer wiring board according to claim 8, which is composed of a mixture thereof. 11. The conductor circuit is composed of a copper layer, and
A roughening solution containing a conductor corrosion inhibitor is treated with a persulfate / acid / copper corrosion inhibitor system, sulfuric acid / hydrogen peroxide / copper corrosion inhibitor system, ferric chloride / copper corrosion inhibitor system, second chloride The method for producing a multilayer wiring board according to any one of claims 1 to 3 to 10, which comprises a solution of any one of a copper / copper corrosion inhibitor system and a tetraammine copper chloride / copper corrosion inhibitor system. 12. The copper corrosion inhibitor is added to 2-mercaptobenzimidazole, 6-aminoindazole, 2,4-
Diamino-6-phenyltriazine, 2-vinyl-4,
The method for producing a multilayer wiring board according to claim 11, comprising at least one of 6-diamino-s-triazine, 2-methylbenzothiazole, melamine, and 2-Nn-butylmelamine.