JPH10209604A - Method for manufacturing printed wiring board, roughening solution used therefor, and method for preparing roughening solution - Google Patents

Abstract

(57) Abstract: A method of manufacturing a printed wiring board capable of improving the adhesion between a conductor layer and a photosensitive film and forming a fine wiring pattern having a conductor width of 60 μm or less, a roughening solution used therefor, A method for preparing a roughened liquid is provided. A conductive layer formed on an insulating substrate is provided.
2, a photosensitive film (dry film resist) is laminated, and the photosensitive film is exposed through a wiring circuit forming mask and developed to form a conductive pattern 106 on the substrate. Before bonding on the surface 102, the surface of the conductor layer is treated with a roughening solution containing a conductor corrosion inhibitor to form a roughened surface 104. If the roughening solution contains persulfate, use an acidic solution of pH 4 or less,
It is desirable to process at a solution temperature of room temperature to 40 ° C. Further, it is preferable to dissolve copper or a copper compound at a copper concentration of 5 to 35 g / liter in the roughening solution because the adhesion is further improved.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the manufacture of printed wiring boards, and more particularly to the improvement of the adhesion between a conductor having a roughened conductor surface and a photosensitive film when forming a wiring pattern, which is suitable for forming a conductor circuit. The present invention relates to a method for manufacturing a printed wiring board, a roughening solution used for the same, and a method for preparing a roughening solution.

[0002]

2. Description of the Related Art In manufacturing printed wiring boards,
It is necessary to form a circuit on the surface of a copper foil using a copper-clad laminate. The circuit is formed by laminating an etching resist made of a photosensitive film, which is generally called a dry film resist, on the surface of a copper foil by thermocompression bonding, exposing through a mask on which a circuit pattern is formed, and developing. After that, the resist pattern is immersed in a copper etching solution using the obtained resist pattern as a mask. Before the step of laminating the etching resist on the surface of the copper foil as described above, the surface of the copper foil is subjected to a surface smoothing process.

[0003] With respect to the prior art, for example, see
It is described in detail in Japanese Patent No. 40483, and the surface smoothing treatment is performed to remove impurities such as oxides and dirt on the surface of the copper foil and to form a fine rough surface on the surface of the copper foil. Yes, this is a process for increasing the adhesion of the etching resist to the surface of the copper foil.

[0004] The copper foil is provided with a surface conditioning treatment of # 300 to # 300.
The surface of the copper-clad laminate is mechanically polished with a rag roll, brush roll, or abrasive grain using a leveling polisher, scrub polisher, or century polisher using a # 100 feather roll or brush roll. This is generally done by doing In addition, as a chemical polishing method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 3-140483 has been proposed.

[0005]

However, when the surface of the copper-clad laminate is subjected to mechanical polishing using a cloth roll or a brush roll as described above, the thickness of the copper-clad laminate is 0.2 mm.
When using a thin plate of less than or equal to the thickness, the thin copper-plated plate is weak and has low strength, so the copper-plated plate bends during polishing and gets caught on the feather roll or brush roll, causing many troubles during the process There was a problem of doing.

Further, when the copper-clad board is thin as described above, there has been a problem that the substrate is deformed or uneven polishing is performed by a polishing pressure applied to the copper-clad board by a feather roll or a brush roll. In addition, in the case of polishing with a feather roll, the non-woven fabric constituting the feather roll and a variation in the size of the abrasive such as Al ₂ O ₃ or SiO ₂ cause deep polishing scratches on the surface of the copper foil, and the like. There is also a problem that a uniform uneven surface is formed and a circuit cannot be formed with a high fine pattern.

On the other hand, in the chemical polishing method described in Japanese Patent Application Laid-Open No. 3-140483, the surface shape of the copper foil is gradual, the adhesion to the dry film resist is insufficient, and the pattern of the resist is developed by development. At the time of formation or at the time of forming a circuit of the copper foil by etching, peeling is likely to occur between the dry film resist and the copper foil, and it has been difficult to produce fine wiring having a width of 60 μm or less with a high yield. That is,
With such fine wiring, for example, there has been a problem that the line width is locally narrowed, or the wire is severely broken.

As a technique for forming a circuit with a high fine pattern, a method of forming a resist pattern by applying a photosensitive resist solution to a pattern forming surface is well known. However, in order to form a large area pattern such as a printed wiring board, it is easier to obtain a resist pattern with a uniform film thickness by laminating a dry film resist than by applying this photosensitive resist solution, and the film It is only economical to perform thermocompression bonding on the pattern forming surface, so that the process can be shortened, and thus it is economically excellent. Therefore,
As long as the adhesion of the resist to the pattern formation surface is improved, the use of a dry film resist is remarkably excellent in manufacturing a printed wiring board.

Accordingly, the present invention has been made in view of the above points, and has no problems as in the case of mechanical polishing and chemical polishing using a conventional cloth roll or brush roll. In addition, the present invention provides a method for manufacturing a printed wiring board capable of forming a fine wiring pattern having a conductor width of 60 μm or less, and a method for preparing a roughening solution and a roughening solution used for the same, which enhances adhesion to a dry film resist. It is intended for that purpose.

[0010]

According to a method of manufacturing a printed wiring board according to the present invention, a photosensitive film (dry film resist) is laminated on a copper foil when a wiring pattern is formed using a copper-clad laminate. As a pre-process, a roughening solution containing a copper corrosion inhibitor is applied to the surface of the copper foil to form a roughened surface with a dense and complex uneven shape on the surface, and the adhesion of dry film resist is significantly improved. It is characterized by the following.

Hereinafter, the present invention will be described in detail. The present inventors have conducted various experimental studies to improve the adhesion between the copper foil and the dry film resist when forming the wiring pattern,
For roughening treatment of the conductor layer surface, it is effective to etch the copper foil surface with a roughening solution containing a conductor corrosion inhibitor,
It has been found that the adhesion is dramatically improved. That is,
By this roughening treatment, a roughened surface having a complex shape with a large surface area is formed on the conductor, and the dry film resist formed thereon is firmly adhered.

Preferred roughening liquids are, for example, persulfate / copper corrosion inhibitor system, persulfate / acid / copper corrosion inhibitor system, sulfuric acid / hydrogen peroxide / copper corrosion inhibitor system, ferric chloride / Copper corrosion inhibitors, cupric chloride / copper corrosion inhibitors, tetraammine copper chloride / copper corrosion inhibitors, and the like.

Each of the roughening liquids contains a roughening component for etching the conductor layer and a component for partially adsorbing on the surface of the conductor layer to partially suppress the corrosion of the conductor (this is called a conductor corrosion inhibitor). The feature is that it has. In such a roughening solution, the conductor corrosion inhibitor partially adsorbs on the conductor surface,
It is presumed that an extremely complicated roughened surface is obtained in order to prevent the conductor in the adsorbed portion from being etched.

The conductor corrosion inhibitor in the roughening solution is to use a corrosion inhibitor suitable for the metal material constituting the conductor layer. Hereinafter, the case of copper which is generally used as a conductor will be described as an example. Then, preferred copper corrosion inhibitors include, for example, benzotriazole derivatives [1,2,3-benzotriazole, 4-or5-methylbenzotriazole,
or 5-aminobenzotriazole, etc.), thiazole derivatives [benzothiazole, 2-mercaptobenzothiazole, 2-methylbenzothiazole, 2-phenylthiazole, etc.], imidazole derivatives [imidazole,
Benzimidazole, 2-methylbenzimidazole,
2-ethyl-5-methylbenzimidazole, 2-mercaptobenzimidazole, etc.), indazoles [6
-Aminoindazole), melamine derivatives (melamine,
N, N'-diallylmelamine, 2-Nn-butylmelamine, etc.), triazine derivatives [2,4-diamino-6
-Phenyltriazine, 2,4-diamino-6-methyl-s-triazine, 2-vinyl-4,6-diamino-s
-Triazine, etc.), pyrimidine derivatives [diaminopyrimidine, triaminopyrimidine, tetraaminopyrimidine, diaminomercaptopyrimidine, etc.], 3,5-diamino-1,2,4-triazole, alkanethiols [C _n H _{2n + 1} SH ], Alkylamines [methylamine, ethylamine, propylamine, butylamine, etc.], thiourea derivatives [thiourea, 1-phenyl-2-
Thiourea, ethylene thiourea, etc.], ethanol thiol, dodecyl mercaptan, 2-mercaptoethanol and the like.

Particularly preferred are 2-mercaptobenzimidazole, 6-aminoindazole, 2,4-diamino-6-phenyltriazine, 2-vinyl-4,6-diamino-s-triazine, 2-methylbenzothiazole, melamine , 2-Nn-butylmelamine.

The concentration of the copper corrosion inhibitor in the roughening solution is 0.01 to 10 g / l, preferably 0.1 to 10 g / l.
A range of 2 g / liter is good.

In the case of preparing a solution containing a persulfate such as a persulfate / copper corrosion inhibitor system or a persulfate / acid / copper corrosion inhibitor system in the above roughening solution, it is necessary to prepare a solution after the construction bath. Heating at 40 to 80 ° C. for about 10 minutes to 5 hours to adjust the hydrogen ion concentration pH of the roughening solution to 4 or less, preferably 0.5 to 4, more preferably 1.0 to 2.5. It is possible to prepare a roughening liquid having a rough surface having a good complicated shape.

Further, copper or a copper compound, for example, copper sulfate or the like is converted into a copper concentration of 5 to 35 g in the persulfate / copper corrosion inhibitor system or the persulfate / acid / copper corrosion inhibitor system roughening solution. When dissolved per liter, a stable roughening solution having a good roughened surface state and little fluctuation in pH when the roughening solution is used can be obtained. By heating after the roughening bath and dissolving the copper, the copper foil as well as the electrolytic copper plating layer formed on the insulating layer can be easily roughened.

In the copper foil surface roughening treatment step, it is desirable to carry out the treatment at a solution temperature of room temperature to 40 ° C.

As described above, by performing a roughening treatment on a copper foil, it becomes possible to manufacture a printed wiring board capable of fine wiring. In order to enhance the adhesion between the conductor layer and the dry film resist, in the present invention, the conductor surface is etched with a roughening solution containing a conductor corrosion inhibitor. This is because the conductor corrosion inhibitor in the roughening solution is partially adsorbed on the conductor surface, the intrinsic etching rate is reduced, and the conductor surface is unevenly etched. This is presumably because a roughened surface having the following characteristics was obtained.

In the above-mentioned conventional method, a rough surface having a complicated surface shape as obtained by the present invention cannot be obtained. Also,
By forming such a complicated conductor surface, the adhesion to the dry film resist is improved, and the resist is prevented from peeling off in the resist development step and the etching step for forming the conductor circuit, thereby minimizing fine wiring. It is possible to form the printed wiring board stably with high wiring density.

[0022]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail with reference to the manufacturing process diagrams shown in FIGS. 1, 2 and 3. FIG. 1 shows a semi-additive method, and FIGS. 2 and 3 show a so-called build-up method in which a conductor circuit (wiring pattern) forming step and an interlayer insulating film forming step are alternately and repeatedly repeated a plurality of times. As described above, the present invention can be applied to the formation of fine conductive circuit patterns in other printed wiring board manufacturing methods.

FIG. 1 shows the semi-additive method, specifically, the steps described in (A) below, and the build-up method, arbitrarily combined with the representative steps described in (BE) below. In addition, it is possible to manufacture a multilayer wiring board that can take various connection configurations between required conductor circuit layers.

Step (A): copper-clad laminate 100 → through hole formation 103 → conductor surface roughening 104 → plating catalyst application 10
5 → Etching resist → Conductor circuit formation 106 → Insulating layer formation (permanent resist) 107 / patterning 108 → Copper plating 109 or copper clad laminate 100 → Conductor surface roughening 104 → Plating catalyst application 105 → Etching resist → Conductor circuit formation 106 → formation of through hole 103 → formation of insulating layer (permanent resist) 107 / patterning 108 → copper plating 109.

Step (B): copper-clad laminate 200 → through-hole formation 203 → conductor surface roughening 204 → etching resist → conductor circuit formation 205 → insulating layer formation 206 / patterning 207, or copper-clad laminate 200 → conductor surface Roughening 204 → etching resist → conductor circuit formation 205 → through hole formation 203 → insulating layer formation 206 / patterning 20
7.

Step (C): roughening of insulating layer 307 → removal of surface deterioration layer 308, 309 → application of plating catalyst 311 → copper plating 312 → roughening of conductor surface 313 → etching resist →
Conductive circuit formation 314 → Insulation layer formation / patterning 31
5.

Step (D): copper-clad laminate 300 → conductor surface roughening 303 → etching resist → conductor circuit formation 30
4 → Insulation layer formation / patterning 315.

Step (E): formation of through hole 310 → roughening of insulating layer 307 → removal of surface deteriorated layer 309 → application of plating catalyst 31
1 → copper plating 312 → conductor surface roughening 313 → etching resist → conductor circuit formation 314 → insulation layer formation / patterning 315.

[0029]

【Example】

<Embodiment 1> This embodiment describes an example in which a double-sided wiring board having two layers (one layer on one side) is manufactured in accordance with the above-mentioned step (A). .

FIG. 1A: glass epoxy laminate 1
A copper-clad laminate in which copper foil 102 (35 μm) is adhered to both surfaces of the substrate 01 is prepared as the substrate 100. FIG. 1B: A through hole 103 is formed in the substrate 100 by a drill.

Step (c) of FIG. 1: The conductor surface of this substrate was treated with a persulfate / copper corrosion inhibitor-based roughening solution to form a roughened conductor surface 104. The roughening solution and roughening conditions used are as follows.

(1) Composition of roughening solution: Na as persulfate
₂ S ₂ O ₈ (200 g / l) and melamine (0.5 g / l) as a copper corrosion inhibitor were dissolved in pure water,
After heating for 2 hours, cool to 25 ° C.
1.8).

(2) Roughening conditions: Spray etching is performed at a liquid temperature of 25 ° C. for 50 seconds.

FIG. 1D: Plating catalyst 1 in through-hole
05 is applied. Step (e) of FIG. 1: A dry film resist was laminated on both surfaces of the substrate by thermocompression bonding, and a negative mask having a predetermined circuit pattern formed thereon was exposed thereon and exposed and developed to form a resist removal pattern. Using this as an etching resist, the copper foil was etched to form a conductor circuit 106, and then the resist was removed.

FIG. 1F: An insulating layer 107 was formed on the substrate by spray coating. The insulating resin used was
It is an epoxy acrylate-based photosensitive resin. Step (g) of FIG. 1: The above-mentioned insulating layer 106 is dried at 80 ° C. for 30 minutes, exposed through a predetermined mask (not shown), and subjected to solvent development to selectively etch and pattern insulating resin 107. . Step (h) of FIG. 1: three copper electrolytic layers 109
A 0 μm formation was formed. Thus, FIG. 1 (i)
Was obtained.

The peel strength (g) of the cellophane tape on the plated copper foil of the printed wiring board prepared by such a manufacturing method.
/ Cm), adhesion to dry film resist (JIS
K5400-1979) and the width (μm) of the obtained minimum conductor circuit was measured, and the results are shown in Table 1.
The table also shows the results of comparative examples described later.

As is clear from this table, the film tightly adheres to the dry film resist, and the peel strength of this example is 420 g / cm.
75 g / cm). Further, the obtained minimum conductor circuit width is 50 μm, which is superior to the comparative example (the minimum one is 75 μm), and a printed wiring board capable of fine wiring is realized.

Example 2 A double-sided wiring board was manufactured by basically the same manufacturing method as in Example 1 described above. However, as the roughening solution, copper sulfate was added to the composition of Example 1 at a copper concentration of 15%.
g / liter. The results are shown in Table 1. The peel strength shows 586, which is further improved as compared with Example 1 (420). Further, the obtained minimum conductor circuit width was 35, which was also superior to Example 1 (50), and the effectiveness of adding copper to the roughening solution was confirmed. The addition of copper is not limited to copper sulfate, and the same result can be obtained by dissolving other copper compounds or copper metal dissolved in the roughening solution.

<Embodiment 3> In this embodiment, the above steps (B) and (C) are combined to make a total of four layers on both sides (2 on one side).
In the following, an example in which a multi-layer wiring board of (layer) is manufactured will be described.

Step (a) of FIG. 2: Glass epoxy laminate 2
A copper-clad laminate in which a copper foil 202 is bonded to both surfaces of the substrate 01 is prepared as a substrate 200. Step (b) of FIG. 2: Drill a through hole 203 in the substrate 200.

Step (c) of FIG. 2: The conductor surface of the substrate was treated with a persulfate / acid / copper corrosion inhibitor-based roughening solution to form a roughened conductor surface 204. The roughening solution and roughening conditions used are as follows.

(1) Composition of roughening solution: Na as persulfate
₂ S ₂ O ₈ (200 g / l) and melamine (1.0 g / l) as a copper corrosion inhibitor were dissolved in water,
And then cooled to 25 ° C. for 1 hour (pH 2.
0). (2) Roughening conditions: spray etching at a liquid temperature of 25 ° C. for 50 seconds.

Step (d) of FIG. 2: Next, a dry film resist (not shown) is laminated on both surfaces of the substrate by thermocompression bonding, and exposed and developed by applying a negative mask on which a predetermined circuit pattern is formed in advance. A resist removal pattern was formed. Using this as an etching resist, the copper foil was etched to form a conductor circuit 205, and then the resist was removed.

FIG. 2E: An insulating layer 206 was formed on the substrate by spray coating. The insulating resin used was
It is an epoxy acrylate-based photosensitive resin.

FIG. 2F: Step 8
After drying at 0 ° C. for 30 minutes, in preparation for the formation of the second conductive circuit,
Exposure is performed through a predetermined mask (not shown), solvent development is performed, the insulating resin 206 is selectively etched and patterned 207, and a predetermined area of the underlying conductor circuit 205 necessary for electrical connection is exposed. Heating was performed at 150 ° C. for 30 minutes to enhance the film quality of the insulating resin.

Next, the surface of the patterned insulating resin layer 207 was roughened with an aqueous solution of an alkaline permanganate to form a roughened surface 208. Manganese dioxide 209 adhering to the substrate surface in the roughening step was dissolved with a 3% aqueous solution of hydroxylamine hydrochloride, and then the deteriorated layer 210 formed on the surface of the insulating layer was removed using an aqueous solution of a surfactant.

Step (g) of FIG. 2: Next, in order to activate the roughened surface, the substrate is immersed in a plating catalyst solution 211 to form an underlying conductive film of 0.2 μm by electroless plating. Was applied to form a copper plating layer 212. In each case, the treatment liquid used was a commercially available product and was subjected to a known plating method.

FIG. 2 (h) step: FIG. 2 (c), FIG.
(D) The same method as the step is repeated. That is, the surface of the copper plating layer 212 is roughened 213 with a roughening solution containing a conductor corrosion inhibitor, an etching resist is formed thereon, and the conductor circuit 214 is formed through the steps of exposure, development, etching, and resist peeling. Form.

FIG. 2 (i) step: Finally, the step of FIG. 2 (e) is repeated again to form an insulating layer (solder resist), and then the patterning 215 is performed in the same manner as in the step of FIG. 2 (f). The conductor circuit 214 necessary for the connection is exposed. Thus, a wiring board having a two-layer laminated structure as shown was obtained.

The peel strength (g / c) of the cellophane tape on the plated copper foil of the printed wiring board manufactured by such a method.
m), the adhesion to the dry film resist, and the width (μm) of the obtained minimum conductor circuit were measured, and the results are shown in Table 1. It adheres firmly to the dry film resist, and the peel strength of this example is 520, which is higher than that of the comparative example (275 at the highest). Further, the obtained minimum conductor circuit width is 45, which is excellent as compared with the comparative example (the minimum one is 75), and a printed wiring board capable of fine wiring is realized.

Embodiment 4 In this embodiment, a multilayer wiring board having three layers on one side and a total of six layers on both sides is manufactured. That is, on the wiring board obtained in Example 3, a conductor layer and an insulating layer were further laminated one by one on both sides. The number of repetition steps of pattern formation increased accordingly. First, Example 3
After the final step (step (i) in FIG. 2), the steps from the roughening treatment of the surface of the insulating layer in step (e) of FIG. 2 to the step (i) in FIG. 2 are repeated. Processed.

The differences between the materials and the processing method from Example 3 in the order of the steps are as follows. FIG.
In (c) and (h), in the surface roughening step of the conductors 204 and 213, the copper corrosion inhibitor “melamine” in the roughening solution was changed to 2-mercaptobenzimidazole. The addition amount of 2-mercaptobenzimidazole is 0.7 g / liter.

The peel strength (g / c) of the cellophane tape on the plated copper foil of the printed wiring board manufactured by such a method.
m), the adhesion to the dry film resist, and the width (μm) of the obtained minimum conductor circuit were measured, and the results are shown in Table 1. It is firmly adhered to the dry film resist, and the peel strength of this example is 537, which is higher than that of the comparative example (275 for the highest one). Further, the obtained minimum conductor circuit width was 40, and the comparative example (the smallest one was 7
As compared with 5), a printed wiring board which can be finely wired is realized.

Example 5 A double-sided wiring board having one layer on one side was manufactured by basically the same steps as in Example 1. This embodiment is different from the first embodiment in the following points. FIG.
In the step (c) of roughening the surface of the conductor layer 104, the copper corrosion inhibitor “melamine” in the roughening solution was changed to 2-Nn-butylmelamine (0.5 g / liter). Measure the peel strength (g / cm) of scotch tape on the plated copper foil of the printed wiring board made in this way, the adhesion with the dry film resist, and the width (μm) of the obtained minimum conductive circuit. The results are shown in Table 1.

Firmly adheres to the dry film resist,
The peel strength of this embodiment is 541, which is higher than that of the comparative example (275 at the highest). Further, the obtained minimum conductor circuit width was 40, which was superior to the comparative example (the minimum one was 75), and a printed wiring board capable of fine wiring was realized.

Example 6 A double-sided wiring board having one layer on one side was manufactured by basically the same steps as in Example 1. This embodiment is different from the first embodiment in the following points. FIG.
In the step (c) of roughening the surface of the conductor layer 104, the copper corrosion inhibitor “melamine” in the roughening solution was changed to 6-aminoindazole (0.5 g / liter). Measure the peel strength (g / cm) of scotch tape on the plated copper foil of the printed wiring board made in this way, the adhesion with the dry film resist, and the width (μm) of the obtained minimum conductive circuit. The results are shown in Table 1.

Firmly adheres to the dry film resist,
The peel strength of the present example is 468, which is higher than that of the comparative example (275 at the highest). Further, the obtained minimum conductor circuit width was 45, which was superior to the comparative example (the minimum one was 75), and a printed wiring board capable of fine wiring was realized.

<Example 7> A double-sided wiring board having one side and one layer was manufactured by basically the same steps as in Example 1. This embodiment is different from the first embodiment in the following points. FIG.
In the step (c) of roughening the surface of the conductor layer 104, the copper corrosion inhibitor “Melamine” in the roughening solution is treated with 6-vinyl-4,
6-diamino-s-triazine (0.2 g / l)
Changed to The peel strength (g / c) of the cellophane tape on the plated copper foil of the printed wiring board manufactured by such a method.
m), the adhesion to the dry film resist, and the width (μm) of the obtained minimum conductor circuit were measured, and the results are shown in Table 1.

Firmly adheres to the dry film resist,
The peel strength of the present example is 420, which is higher than that of the comparative example (275 at the highest). Further, the obtained minimum conductor circuit width was 50, which was superior to the comparative example (the minimum one was 75), and a printed wiring board capable of fine wiring was realized.

<Embodiment 8> A single-sided, single-layer double-sided wiring board was manufactured through basically the same steps as in Embodiment 1. This embodiment is different from the first embodiment in the following points. FIG.
In the step (c) of roughening the surface of the conductor layer 104, the copper corrosion inhibitor “melamine” in the roughening solution was changed to 2-methylbenzothiazole (0.3 g / liter). Measure the peel strength (g / cm) of scotch tape on the plated copper foil of the printed wiring board made in this way, the adhesion with the dry film resist, and the width (μm) of the obtained minimum conductive circuit. The results are shown in Table 1.

Firmly adheres to the dry film resist,
The peel strength of this embodiment is 568, which is higher than that of the comparative example (275 at the highest). Further, the obtained minimum conductor circuit width was 35, which was superior to the comparative example (the minimum one was 75), and a printed wiring board capable of fine wiring was realized.

<Embodiment 9> A single-sided, single-layer double-sided wiring board was manufactured by basically the same steps as in Embodiment 1. This embodiment is different from the first embodiment in the following points. FIG.
In the step (c) of roughening the surface of the conductor layer 104, the copper corrosion inhibitor “melamine” in the roughening solution was changed to 2,4-diamino-6-phenyltriazine (1.2 g / liter). The peel strength (g / c) of the cellophane tape on the plated copper foil of the printed wiring board manufactured by such a method.
m), the adhesion to the dry film resist, and the width (μm) of the obtained minimum conductor circuit were measured, and the results are shown in Table 1.

Strongly adheres to the dry film resist,
The peel strength of this example is 520, which is higher than that of the comparative example (275 at the highest). Further, the obtained minimum conductor circuit width was 40, which was superior to the comparative example (the minimum one was 75), and a printed wiring board capable of fine wiring was realized.

Example 10 A double-sided wiring board having one layer on one side was manufactured by basically the same steps as in Example 1. This embodiment is different from the first embodiment in the following points. FIG.
In the step (c) of roughening the surface of the conductor layer 104, “Na ₂ S ₂ O ₈ ”, which is the main component in the roughening solution, is converted into (NH ₄ ) ₂ S ₂
It was changed to O _8. The peel strength (g) of the cellophane tape on the plated copper foil of the printed wiring board manufactured by such a method.
/ Cm), the adhesion to the dry film resist, and the width (μm) of the obtained minimum conductor circuit were measured, and the results are shown in Table 1.

Firmly adheres to the dry film resist,
The peel strength of this embodiment is 515, which is higher than that of the comparative example (275 at the highest). Further, the obtained minimum conductor circuit width was 40, which was superior to the comparative example (the minimum one was 75), and a printed wiring board capable of fine wiring was realized.

<Embodiment 11> In this embodiment, the process D
And step E in combination, a total of 4 layers on both sides (2 layers on one side, 2
A description will be given of an example in which a multilayer wiring board (laminated) is manufactured.
Note that this example is also basically the same as each step in FIG. 2 shown in the third embodiment. However, the timing of opening the through-hole 203 and a part of the processing method are changed.

Step (a) of FIG. 3: A copper-clad laminate in which copper foil is adhered to both surfaces of a glass epoxy laminated substrate 301 is prepared as a substrate 300 in the same step as that of the step (a) of FIG. Step (b) of FIG. 3: The conductor surface of this substrate was treated with a roughening solution of a persulfate / corrosion inhibitor system to form a roughened conductor surface 303. The roughening solution and roughening conditions used are as follows.

(1) Composition of roughening solution: Na as persulfate
₂ S ₂ O ₈ (200 g / liter) and 2-mercaptobenzothiazole (0.5 g / liter) as a copper corrosion inhibitor were dissolved in pure water, heated at 70 ° C. for 20 minutes, and then heated at 25 ° C.
(Roughening solution pH 2.5). (2) Roughening conditions: spray etching at a liquid temperature of 25 ° C. for 50 seconds.

FIG. 3C: Next, a dry film resist (not shown) is laminated on both sides of the substrate by thermocompression bonding, and a negative mask on which a predetermined circuit pattern (not shown) is formed is exposed thereon. The pattern was developed to form a resist removal pattern. Using this as an etching resist, the copper foil was etched to form a conductor circuit 304, and then the resist was removed.

FIG. 3D: An insulating layer 305 was formed on the substrate by spray coating. The insulating resin used was
It is an epoxy acrylate-based photosensitive resin.

Step (e) of FIG.
After drying at 0 ° C. for 30 minutes, in preparation for the formation of the second conductive circuit,
Exposure is performed through a predetermined mask (not shown), solvent development is performed, the insulating resin 305 is selectively etched and patterned 306, and a predetermined region of the underlying conductive circuit 304 necessary for electrical connection is exposed. Heating was performed at 150 ° C. for 30 minutes to enhance the film quality of the insulating resin.

Next, the surface of the patterned insulating resin layer 306 was roughened with an alkaline aqueous solution of permanganate to form a roughened surface 307. Manganese dioxide 308 adhering to the substrate surface in the roughening step was dissolved with a 3% aqueous solution of hydroxylamine hydrochloride, and then the degraded layer 309 formed on the surface of the insulating layer was removed using an aqueous solution of a surfactant.

Step (f) in FIG. 3: In a step corresponding to FIG. 2 (b) in the third embodiment, a through-hole 310 is drilled in a through-hole forming region of the substrate 300.

Step (g) of FIG. 3: Next, in order to activate the roughened surface, the substrate is immersed in a plating catalyst solution 311 to form an underlying conductive film of 0.2 μm by electroless plating. Was applied to form a copper plating layer 312. In each case, the treatment liquid used was a commercially available product and was subjected to a known plating method.

FIG. 3 (h) step: FIG. 3 (b), FIG.
(C) The same method as in the step is repeated. That is, the surface of the copper plating layer 312 is subjected to a roughening treatment 313 with a roughening solution containing the above-mentioned copper corrosion inhibitor, and an etching resist is formed thereon. A circuit 314 is formed.

Step (i) of FIG. 3: Finally, the step of FIG. 3 (d) is repeated to form an insulating layer (which is referred to as a solder resist), and then patterning 315 is performed to expose conductor circuits necessary for connection. Thus, a wiring board having a two-layer laminated structure as shown was obtained.

The peel strength (g / c) of the scotch tape on the plated copper foil of the printed wiring board manufactured by such a method.
m), the adhesion to the dry film resist, and the width (μm) of the obtained minimum conductor circuit were measured, and the results are shown in Table 1.

Firmly adheres to the dry film resist,
The peel strength of the present example is 535, which is higher than that of the comparative example (275 at the highest). Further, the obtained minimum conductor circuit width was 40, which was superior to the comparative example (the minimum one was 75), and a printed wiring board capable of fine wiring was realized.

<Embodiment 12> This embodiment shows an example of manufacturing a multilayer wiring board composed of a laminate of three layers on one side and a total of six layers on both sides in the same manner as in the fourth embodiment. The timing of the step of forming the through hole is different. Since the process is relatively similar to the process of FIG. 3 shown in the eleventh embodiment, a description will be given below with reference to FIG.

First, the processes in FIGS. 3A to 3D are performed in the same manner as in the eleventh embodiment. Next, a process of forming a through hole by a drill in FIG. 3F and a process of forming a pattern of the insulating resin layer 306 in the process of FIG.
The steps up to 7, 308 and 309 were switched, and FIG.
A through hole is formed by a drill in the step (f), and then the step of FIG. 3E (step corresponding to FIG. 2F) is performed. The subsequent steps are the same as those shown in FIGS.
(I) Same as step.

After the two-layer structure on one side is thus obtained, the surface roughening treatment of the insulating resin layer in the step (e) of FIG. 3 and the steps (g) to (i) of FIG. 3 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.

However, the roughening solution and the processing conditions in the surface roughening process of the conductor layers 304 and 311 were different from those in Example 11 and were as follows. As persulfate (N
H ₄ ) ₂ S ₂ O ₈ (200 g / l), 98% as acid
H ₂ SO ₄ 1 ml / liter), 2-methyl-benzothiazole as a copper corrosion inhibitor (0.5 g / l): was 60 seconds spray etching a liquid temperature 25 ° C..

The peel strength (g / c) of the cellophane tape on the plated copper foil of the printed wiring board manufactured by such a method.
m), the adhesion to the dry film resist, and the width (μm) of the obtained minimum conductor circuit were measured, and the results are shown in Table 1.

Firmly adheres to the dry film resist,
The peel strength of this embodiment is 503, which is higher than that of the comparative example (275 at the highest). Further, the obtained minimum conductor circuit width was 40, which was superior to the comparative example (the minimum one was 75), and a printed wiring board capable of fine wiring was realized.

Example 13 A double-sided wiring board having two layers on one side and a total of four layers on both sides was manufactured by basically the same steps as in Example 11. This embodiment is different from the tenth embodiment in the following points.

The roughening solution and the processing conditions in the surface roughening steps 303 and 313 of the conductor layer in the steps (b) and (h) of FIG. 3 are different from those in Example 10 and are as follows. (1) Roughening solution: 98% H ₂ SO ₄ (120 ml /
_{L), 35% H 2 O 2} (80 ml / l), 2-mercaptobenzimidazole (0.5 g /
L) aqueous solution. (2) Condition: spray etching at a liquid temperature of 30 ° C. for 60 seconds.

The peel strength (g / c) of the cellophane tape on the plated copper foil of the printed wiring board manufactured by such a method.
m), the adhesion to the dry film resist, and the width (μm) of the obtained minimum conductor circuit were measured, and the results are shown in Table 1.

Firmly adheres to the dry film resist,
The peel strength of this embodiment is 546, which is higher than that of the comparative example (275 at the highest). Further, the obtained minimum conductor circuit width was 40, which was superior to the comparative example (the minimum one was 75), and a printed wiring board capable of fine wiring was realized.

Example 14 A double-sided wiring board having two layers on one side and a total of four layers on both sides was manufactured by basically the same steps as in Example 11. This embodiment is different from the eleventh embodiment in the following points.

The roughening solution and processing conditions in the surface roughening treatment steps 303 and 313 of the conductor layer in the steps of FIGS. 3B and 3H are different from those in Example 10 and are as follows. (1) Roughening solution: an aqueous solution of FeCl ₃ (370 g / l) and melamine (0.5 g / l).

(2) Roughening conditions: spray etching at a liquid temperature of 25 ° C. for 50 seconds.

The peel strength (g / c) of the cellophane tape on the plated copper foil of the printed wiring board manufactured by such a method.
m), the adhesion to the dry film resist, and the width (μm) of the obtained minimum conductor circuit were measured, and the results are shown in Table 1.

Firmly adheres to the dry film resist,
The peel strength of this embodiment is 428, which is higher than that of the comparative example (275 at the highest). Further, the obtained minimum conductor circuit width was 50, which was superior to the comparative example (the minimum one was 75), and a printed wiring board capable of fine wiring was realized.

Example 15 A double-sided wiring board having two layers on one side and a total of four layers on both sides was manufactured by basically the same steps as in Example 11. This embodiment is different from the eleventh embodiment in the following points.

The roughening solution and the treatment conditions in the surface roughening treatment steps 303 and 313 of the conductor layer in the steps of FIG. 3B and FIG. 3H are different from those of Example 11 and are as follows. (1) Roughening liquid: CuCl ₂ (250 g / liter), 3
An aqueous solution of 6% HCl (130 ml / l), 6-aminoindazole (0.5 g / l). (2) Roughening conditions: spray etching at a liquid temperature of 25 ° C. for 50 seconds.

The peel strength (g / c) of the scotch tape on the plated copper foil of the printed wiring board manufactured by such a method.
m), the adhesion to the dry film resist, and the width (μm) of the obtained minimum conductor circuit were measured, and the results are shown in Table 1.

Firmly adheres to the dry film resist,
The peel strength of this example is 571, which is higher than that of the comparative example (275 at the highest). Further, the obtained minimum conductor circuit width was 35, which was superior to the comparative example (the minimum one was 75), and a printed wiring board capable of fine wiring was realized.

Example 16 A double-sided wiring board having two layers on one side and a total of four layers on both sides was manufactured by basically the same steps as in Example 11. This embodiment is different from the eleventh embodiment in the following points.

The roughening solution and the treatment conditions in the surface roughening treatment steps 303 and 313 of the conductor layer in the steps of FIG. 3B and FIG. 3H are different from those in Example 11 and are as follows. (1) Roughening liquid: Cu (NH ₄ ) ₄ Cl ₂ (450 g / L), NH ₄ Cl (100 g / L), 28% aqueous ammonia (5 mL / L), 2,4-diamino-6-phenyl An aqueous solution of triazine (0.5 g / l). (2) Roughening conditions: spray etching at a liquid temperature of 25 ° C. for 50 seconds.

The peel strength (g / c) of the scotch tape on the plated copper foil of the printed wiring board manufactured by such a method.
m), the adhesion to the dry film resist, and the width (μm) of the obtained minimum conductor circuit were measured, and the results are shown in Table 1.

Firmly adheres to the dry film resist,
The peel strength of this embodiment is 511, which is higher than that of the comparative example (275 at the highest). Further, the obtained minimum conductor circuit width was 40, which was superior to the comparative example (the minimum one was 75), and a printed wiring board capable of fine wiring was realized.

Example 17 A double-sided wiring board having two layers on one side and a total of four layers on both sides was manufactured by basically the same steps as in Example 11. This embodiment is different from the eleventh embodiment in the following points.

The roughening solution and the processing conditions in the surface roughening treatment steps 303 and 313 of the conductor layer in the steps of FIG. 3B and FIG. 3H are different from those in Example 11 and are as follows. (1) Roughening solution: Na ₂ S ₂ O ₈ (200 g / liter),
98% H ₂ SO ₄ (1 ml / liter), 2, 4
-An aqueous solution of diamino-6-phenyltriazine (2.0 g / l). (2) Roughening conditions: immersion in a roughening bath at a liquid temperature of 40 ° C., etching for 60 seconds by air blow stirring and rocking.

The peel strength (g / c) of the cellophane tape on the plated copper foil of the printed wiring board manufactured by such a method.
m), the adhesion to the dry film resist, and the width (μm) of the obtained minimum conductor circuit were measured, and the results are shown in Table 1.

It adheres firmly to the dry film resist,
The peel strength of this embodiment is 507, which is higher than that of the comparative example (275 at the highest). Further, the obtained minimum conductor circuit width was 40, which was superior to the comparative example (the minimum one was 75), and a printed wiring board capable of fine wiring was realized.

<Comparative Example 1> This example was manufactured by omitting the step of roughening the conductor surface (the step of FIG. 1B) in each step of Example 1, and the results are shown in Table 1. 1 is shown. The adhesion between the copper foil 102 and the dry film resist was poor, the peel strength was inferior to 145, and the minimum conductor width that could be formed without causing line breakage was inferior to 110 μm.

<Comparative Example 2> In this example, the step of roughening the conductor surface (step (FIG. 2B)) in each step of Example 3 was changed to scrub polishing of a mechanical polishing method. And the results are shown in Table 1. The adhesion between the copper foil 202 and the dry film resist is poor, and the peel strength is 237.
In addition, the minimum conductor width that could be formed without causing a line defect or the like was also inferior to 80 μm.

<Comparative Example 3> In this example, a step of roughening the conductor surface in each step of Example 13 [FIG. 3 (b), FIG.
(H)] in which the copper corrosion inhibitor in the roughening solution was removed (no addition), and the results are shown in Table 1. The adhesion between the copper foil 302 and the dry film resist is poor,
The peel strength was inferior to 275, and the minimum conductor width that could be formed without causing line breakage was inferior to 75 μm.

[0109]

[Table 1]

[0110]

As described in detail above, the intended object has been achieved by the present invention. That is, in the production of a wiring board, the adhesion between the copper foil and the dry film resist is excellent, and a fine wiring pattern having a line width of 60 μm or less can be easily produced, and the effect of contributing to industry is extremely large.

[Brief description of the drawings]

FIG. 1 is a sectional process view showing a manufacturing process of a wiring board according to one embodiment of the present invention.

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

FIG. 3 is a sectional process view showing a manufacturing process of a wiring board according to another embodiment of the present invention.

[Explanation of symbols]

 Reference Signs List 100: double-sided copper-clad laminated substrate, 101: substrate (laminate), 102: copper foil, 103: through hole, 104: roughened surface of conductor, 105: plating catalyst, 106: conductor circuit, 107: insulating layer, 108 ... Insulating layer patterning, 200: Double-sided copper-clad laminated substrate, 201: Substrate (laminate), 202: Copper foil, 203: Through hole, 204: Roughened surface of conductor, 205: Conductor circuit, 206: Insulating layer, 207 ... patterning of an insulating layer, 208 ... roughening of an insulating layer, 209 ... manganese dioxide (removed), 210 ... degraded layer (removed), 211 ... plating catalyst, 212 ... copper plating 213 ... roughened surface of conductor, 214 ... conductor circuit 215: insulating layer patterning 300: double-sided copper-clad laminate substrate 301: substrate (laminate) 302: copper foil 303: roughened surface of conductor 304: conductor circuit 305 Insulating layer, 306: patterning of insulating layer, 307: roughening of insulating layer, 308: manganese dioxide (removed) 309: degraded layer (removed), 310: through hole 311: plating catalyst, 312: copper plating 313: coarse of conductor 314: Conductor circuit, 315: Insulating layer patterning.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI H05K 3/46 H05K 3/46 E (72) Inventor Hisashi Susumu Sugiyama 292 Yoshida-cho, Totsuka-ku, Yokohama-shi, Kanagawa Prefecture Production by Hitachi, Ltd. Within the Technology Research Laboratory (72) Inventor Nobuo Hamaoka 216 Totsuka-cho, Totsuka-ku, Yokohama-shi, Kanagawa Prefecture Inside the Information and Communications Division, Hitachi, Ltd. (72) Inventor Yoshinori Muramatsu 216 Totsuka-cho, Totsuka-ku, Yokohama-shi, Kanagawa Prefecture In-house Information and Communications Division of Hitachi, Ltd.

Claims (11)

[Claims] 1. A printed wiring for laminating a photosensitive film on a conductor layer formed on an insulating substrate, exposing the photosensitive film via a wiring pattern forming mask, and developing the same to form a wiring pattern on the substrate. In the manufacturing process of the substrate, as a pre-step of laminating the photosensitive film on the conductor layer, the method includes a surface roughening treatment step of chemically treating the surface of the conductor layer with a roughening solution containing a conductor corrosion inhibitor. A method for manufacturing a printed wiring board. 2. The print according to claim 1, wherein said surface roughening treatment step is a step of treating with a roughening solution obtained by dissolving copper or a copper compound at a copper concentration of 5 to 35 g / l in the roughening solution. Manufacturing method of wiring board. 3. The method according to claim 1, wherein the surface roughening treatment step is performed at room temperature to room temperature.
3. The method for manufacturing a printed wiring board according to claim 1, comprising a step of processing at a solution temperature of 40 ° C. 4. A roughening solution containing said conductor corrosion inhibitor,
Persulfate / copper corrosion inhibitor system, persulfate / acid / copper corrosion inhibitor system, sulfuric acid / hydrogen peroxide / copper corrosion inhibitor system, ferric chloride / copper corrosion inhibitor system, cupric chloride / The method for producing a printed wiring board according to any one of claims 1 to 3, comprising an aqueous solution of any one of a copper corrosion inhibitor system and a copper tetraammine chloride / copper corrosion inhibitor system. 5. The method according to claim 1, wherein when the roughening solution contains a persulfate, the roughening solution is converted into an acidic solution having a pH of 4 or less and treated at a solution temperature of room temperature to 40 ° C. A method for manufacturing a printed wiring board according to any one of the first to third aspects. 6. The method according to claim 1, wherein the concentration of the conductor corrosion inhibitor in the roughening solution is 0.01 to 10 g / liter.
The method for manufacturing a printed wiring board according to any one of the above. 7. The conductor corrosion inhibitor is 2-mercaptobenzimidazole, 6-aminoindazole, 2,4-
Diamino-6-phenyltriazine, 2-vinyl-4,
The printed wiring board according to any one of claims 1 to 6, comprising at least one of 6-diamino-S-triazine, 2-methylbenzothiazole, melamine, and 2-N-n-butylmelamine. Production method. 8. The method according to claim 1, wherein the conductor layer formed on the insulating substrate is made of copper foil. 9. A persulfate / copper corrosion inhibitor system, a persulfate / acid / copper corrosion inhibitor system, a sulfuric acid / hydrogen peroxide / copper corrosion inhibitor system, a ferric chloride / copper corrosion inhibitor system, It is composed of an aqueous solution of any one of a cupric chloride / copper corrosion inhibitor system and a copper tetraammine chloride / copper corrosion inhibitor system, and the aqueous solution contains copper or a copper compound at a copper concentration of 5 to 35 g / liter. A roughening solution for a surface roughening treatment of a conductor layer of a printed wiring board having copper as a conductor layer formed by melting. 10. When the roughening solution contains a persulfate,
The roughening solution for roughening the surface of a conductive layer of a printed wiring board according to claim 9, which is an acidic solution having a pH of 4 or less. 11. A method for preparing a roughening solution for a surface roughening treatment of a conductor layer of a printed wiring board, comprising a persulfate / copper corrosion inhibitor system or a persulfate / acid / copper corrosion inhibitor system. A method for preparing a roughening solution which is heated at 40 to 80 ° C. for 10 minutes to 5 hours after the formation of the roughening solution and the roughening solution is converted to an acidic solution having a pH of 4 or less.