JP3235248B2 - Stripping method and stripping solution for water-soluble resist - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for stripping a water-soluble resist and a stripping solution in a wiring board manufacturing process.

[0002]

2. Description of the Related Art As one method of manufacturing a wiring board, there is known a method of forming wiring by using solder as an etching resist. Taking a general case of this method as an example, a substrate having copper foil laminated on both sides is subjected to copper plating after drilling, and thereafter, portions other than the portion to be plated are covered with an organic resist film. This is subjected to solder plating, and after removing the organic resist film, unnecessary portions of copper are removed by etching. There is a method in which a water-soluble resist is used for the organic resist film and the organic resist film is peeled off with an alkaline aqueous solution. The stripping solution used for stripping the water-soluble resist is generally a strong alkaline aqueous solution such as sodium hydroxide or potassium hydroxide, and is often used at pH 13 or higher. At this time, the temperature is 40 to 50 ° C., and the time required for peeling is
It is generally about two to three minutes. The actual stripping time is set to approximately three times the resist stripping time (approximately 40 to 50 seconds) because the water-soluble resist is completely stripped without leaving a stripped residue in the high-density pattern portion. Is done. For this reason, during much of the stripping operation, copper (the stripped portion of the water-soluble resist) and the solder plating are simultaneously exposed to the stripping solution. Since the stripping solution is a strongly alkaline solution as described above, the solder which should play a role of an etching resist is dissolved and its thickness becomes insufficient, or one of the constituent metals of the solder (tin) May be dissolved excessively. In particular, in the peripheral portion of the substrate and in a sparse pattern, since the current density of the solder plating is large, the tin ratio in the solder plating is high, and the dissolution of the solder plating at the time of peeling tends to increase. For this reason, in the next step, the alkaline etching step,
In some cases, they could not fulfill the role of a sufficient etching resist, causing defects such as disconnection and chipping in wiring. Further, when the water-soluble resist is peeled off, the local battery action due to the contact between the copper and the solder is also a factor promoting the corrosion and melting of the solder described above.

Therefore, in order to prevent the corrosion and dissolution, a method of adding a reducing substance, further, a sodium arylsulfonate or an organic sulfur compound, a method of adding a borohydride compound, a method of adding an imidazole compound And methods of adding 3,5 dimethylpyrazole are disclosed in JP-A-63-183445 and JP-A-64-2425.
No. 4, JP-A-64-81295 and JP-A-62-151589, respectively. Further, in the stripping of the water-soluble resist, lead ions may precipitate on the copper surface after the stripping of the water-soluble resist and hinder etching, thereby causing a short circuit between wirings. Therefore, a method of adding an oxidizing agent in order to prevent the precipitation of lead is disclosed in JP-A-63-38588.

[0004]

SUMMARY OF THE INVENTION The above-mentioned Japanese Patent Application Laid-Open No. 63-18 / 1988
3445, JP-A-64-24254, JP-A-64-81295, and JP-A-62-1515.
In the method disclosed in JP-A-89-89, if the peeling operation is performed by a spray method, a sufficient effect cannot be obtained. Also,
JP-A-63-38588 discloses a method using an oxidizing agent as a method for preventing the precipitation of lead, and JP-A-63-183445 and JP-A-64-81295 disclose the dissolution of solder. It is incompatible with the method using a reducing substance shown as a method for performing the method. That is, until now, it has been difficult to simultaneously suppress the dissolution of solder and prevent the precipitation of lead.

[0005] The present invention is excellent in dissolution inhibiting the I, at the same time, a peeling method of excellent water solubility resist preventing precipitation of lead
It provides a stripping solution .

[0006]

According to the present invention, a plating resist is formed with a water-soluble resist on a substrate on which a copper foil is laminated.
In a water-soluble resist stripping method for performing solder plating and then stripping the water-soluble resist, piperidine, an alkyl group addition compound of piperidine, an alkyl group addition compound of pyrrolidine, a pyridine, an alkyl group addition compound of pyridine are contained in a stripping solution. Or dipicolylamine. Further, aminoguanidine, hydrazines, sulfurous acid, dithionous acid or a salt thereof, borohydride, carbazate, thiourea dioxide, sulfinic acids, sulfoxy acids, hydrazides, semicarbazide salt, including at least one of. Features.

[0007] Japanese Patent Application Laid-Open No. 63-38588 describes the effect of residual solder plating solution components on the precipitation of lead that inhibits wiring formation. However, according to the study results of the authors, it is considered that the precipitation of lead is caused in the stripping solution. This will be described in detail below.

[0008] Tin and lead, which are constituent metals of the solder used for the copper etching resist, can be dissolved at a pH of 13 or more, as shown in Figs. 17-11 in "Introduction to Corrosion and Protection of Metals", p. "Tin potential-p
H diagram ", FIG. 17-12 in p243," Potential-pH diagram ", and the like. Actually, a high-density solder plating pattern having a wiring width and a space width of about 100 to 150 μm is formed on a copper surface, and 400 pp.
When drops of an aqueous solution of sodium hydroxide of about 40 g / l containing lead ions of m are dropped, it is easily observed that the exposed portion of the copper turns gray after standing at room temperature for several minutes.
The authors are heading. In addition, when the gray part is analyzed, lead is detected. The reason for this is that the re-deposition of the solder plating metal component and the lead ion occurs in the droplet at the same time, or
It is happening sequentially. The details of this mechanism are unknown. Lead and tin of solder plating metal, and
Such a phenomenon seems to occur because there are three kinds of metals, namely, copper (a portion not subjected to solder plating). Thus, the dissolution of the solder and the re-precipitation of lead in the alkaline stripping solution are easily confirmed.

Japanese Unexamined Patent Publication (Kokai) No. 63-6397 discloses a method for suppressing melting of solder.
-183445, JP-A-64-81295, JP-A-62-151589 and JP-A-63-151589.
JP-A-38588 discloses examples of the dissolution rate and the amount of dissolution upon standing at room temperature as Examples and Comparative Examples. As shown in the examples of each of these four publications, dissolution can be suppressed to some extent,
It turns out that dissolution cannot be completely suppressed. For actual work, generally, at a spray pressure of 1-2 kg / cm ² ,
In many cases, a spray method is used in which a stripper having a temperature of 40 to 50 ° C. is brought into contact with a substrate being conveyed using a conveyor to strip a water-soluble resist. In this way, when a new liquid is constantly supplied to the substrate surface, the apparent diffusion coefficient becomes incomparably larger than that at the time of standing, and the dissolution rate of the solder is much higher than the value of the example of the above publication. It is easily presumed that it will grow. Therefore, even if the above-described dissolution suppressing method is employed, the solder dissolves in the stripping solution together with the number of processed substrates, and the amount of metal ions increases.

[0010] Actually, using a spray type water-soluble resist stripping apparatus, an OPC parsoli (a product of Okuno Pharmaceutical Co., Ltd. ) To the stripper,
After peeling off the dry film HF450 (trade name, manufactured by Hitachi Chemical Co., Ltd.) on a 200 m ² substrate (solder area: 25%), the lead ion in the liquid was measured, and the concentration was 300 to 400 ppm. Was. The present inventors have found that when the amount of lead ions in the stripping solution is about 400 ppm, the deposition of lead on the substrate surface starts to be visually observed, and the remaining alkali etching causes residual copper. Accordingly, as a result of intensive studies, it was found that when lead ions increase in the solution, dissolution is accelerated.
JP-A-183445, JP-A-64-24254, JP-A-64-81295, and JP-A-62-162.
As a result of a test conducted by the method disclosed in JP-A-151589, it was found that when lead ions were present in the solution, the dissolution increased (dissolution current value was measured), and a sufficient suppressing effect could not be obtained. It is presumed that the reason why the dissolution is accelerated in the presence of lead ions is that the above-described reprecipitation reaction of lead is a counter electrode reaction of corrosion and dissolution. Further, when the dissolution current was measured, it was found that when the amount of lead ions in the liquid was 50 to 100 ppm, the precipitation of lead was not necessarily confirmed visually, but such a dissolution acceleration phenomenon occurred. That is, in general peeling work, it is considered that the dissolution of the solder is particularly problematic due to such an acceleration phenomenon in addition to a simple dissolution phenomenon in which the solder dissolves in an alkaline solution.

Therefore, as a result of studying a method of forming a complex with lead ions and suppressing the precipitation of lead, piperidine, an alkyl group addition compound of piperidine, an alkyl group addition compound of pyrrolidine, an alkyl group addition compound of pyridine, and pyridine It has been found that it is effective to add either a group addition compound or dipicolylamine. By adding the above compound to the stripping solution, it is possible to prevent a defect such that the wiring portion is etched by a subsequent alkali etching (a chipping or disconnection defect). In general, the effective range of the amount added differs depending on the ratio of lead of the complex formed with lead ions and the molecular weight of the organic substance. However, practically, it is effective in the addition range of 0.5 g / l or more. Also,
Since adding an unnecessarily large amount is disadvantageous in terms of cost, 100 g / l is a practical maximum addition amount. Practically, the more preferable range of the addition amount is 1.0 to 5
0 g / l.

Furthermore, at least one of aminoguanidine, hydrazines, sulfurous acid, dithionous acid or a salt thereof, borohydride, carbazate, thiourea dioxide, sulfinic acids, sulfoxy acids, hydrazides, and semicarbazide salts. Further effects can be obtained by the addition. For aminoguanidines, aminoguanidine bicarbonate, aminoguanidine sulfate,
Aminoguanidine hydrochloride and the like can be used. For hydrazines, hydrazine hydrate, monomethylhydrazine,
Dimethylhydrazine and the like can be used, and as a salt thereof,
Hydrazine sulfate, hydrazine carbonate and hydrazine hydrochloride can be used. As for the sulfite, sodium sulfite and potassium sulfite can be used. As the dithionite,
Hydrosulfite sodium, hydrosulfite potassium, and hydrosulfite ammonium can be used. As borohydride, dimethylamine borane, sodium borohydride or potassium borohydride can be used. As the carbazate, methyl carbazate (alias: methyl carbazate) and ethyl carbazate (alias: ethyl carbazate) can be used.
As the sulfinic acids, formamidine sulfinic acid is used, and as the sulfoxy acids, sodium formaldehyde sulfoxylate (also called Rongalit) (also known as:
Sodium hydroxymethanesulfonate) can be used. Examples of the hydrazides include carbohydrazide, acetohydrazide and isonicotinic acid hydrazide.
Semicarbazide sulfate or semicarbazide hydrochloride can be used as the semicarbazide salt. Note that thiourea dioxide decomposes in an alkaline solution to form formamidine sulfinic acid, and thus has the same effect as formamidine sulfinic acid. Each of the above-mentioned compounds shown as the second additive has a reducing effect in the stripping solution, and the amount of addition varies depending on the reducing equivalent and the life (duration of the reducing effect) of these compounds. However, from a practical viewpoint such as solubility and cost, a desirable addition amount is 0.01 to 100 g / l. When a plurality of second additives are used, the term “addition amount” is replaced with “total addition amount”. Practically, a more desirable range of the addition amount is 0.05 to 50 g / l.

In general, disodium hydrogen phosphite or sodium phosphinate (also known as sodium hypophosphite), which is known as a reducing agent, does not show sufficient reducing properties in a stripping solution. No dissolution inhibiting effect (dissolution current was measured) was obtained. The reason for this is that the pH of the stripper is
It is considered that under the conditions, the reduction life is extremely short, that is, several minutes or less. As for sodium thiosulfate, the reduction life was obtained to some extent, but the dissolution suppressing effect was not obtained. This may be because sodium thiosulfate has a low reducing ability and is insufficient for suppressing dissolution. In addition, aldehydes such as formaldehyde, terephthalaldehyde acid, o-phthalaldehyde acid, benzaldehyde-osulfonic acid, terephthalaldehyde, and benzaldehyde 2,4-disulfonic acid have a very short life as a reducing agent in a stripping solution. In 30 minutes or less, the amount of the reducing agent (measured by redox titration with iodine) was 1/10 or less of the value calculated from the initial charge, which was not practical. Phenols such as gallic acid, ethyl gallate, n-propyl gallate, methyl gallate, pyrogallol, sodium p-hydroxybenzenesulfonate,
For 2,4 xylenol, the reduction life was short and it was not practical. In addition, about aminoguanidine,
Although a reducing effect was obtained in the stripping solution, guanidines having no amino group, such as 1,1,3,3 tetramethylguanidine and guanidine sulfate, were not effective and were not suitable. As described above, the reducing substances that are effective when added to the stripping solution are only extremely limited as shown in the present patent.

[0014]

The conventional method for suppressing the dissolution of the solder in the stripping solution has been effective under the stationary condition. However, under conditions where the new liquid is always in contact, such as a spray, the dissolution of the solder is larger than expected, and as a result, lead ions in the stripping liquid increase as the substrate is processed.
The present invention has been achieved by obtaining the finding that the effect of the conventional dissolution suppressing method is inhibited even in the presence of 100 ppm of lead ions. In the present invention, by adding a specific substance capable of forming a complex with metal ions to the stripping solution, the lead ions are blocked, or the copper surface is blocked,
It is considered that the effect of suppressing the dissolution of the solder plating was obtained.
Further, in order to obtain a further dissolution suppressing effect, a specific reducing agent was added. In the method of adding only a known reducing agent, a sufficient effect could not be obtained due to the action of lead ions dissolved from the solder plating. However, in the case of the present invention, a substance capable of forming a complex with a metal ion prevents the precipitation of lead ions, and as a result, it was possible to obtain a dissolution suppressing effect by adding a reducing agent. Here, the following is presumed as one of the reasons why the dissolution of the solder is suppressed by the reducing agent. Metal in the solder (lead,
A reaction in which tin) dissolves in ions such as zinc acid, lead acid, stannic acid, and stannic acid is an oxygen demanding reaction. The reducing agent added to the stripping solution reduces dissolved oxygen in the solution and reduces the concentration of dissolved oxygen in the solution. For this reason, the melting reaction of the solder is suppressed. In fact, the dissolved oxygen concentration was measured with several reducing agents. As a result, sodium hydrosulfite,
For sodium sulfite, formamidinesulfinic acid and hydrazine, the dissolved oxygen concentration decreased at room temperature. From the measurement of the dissolution current value, the effect was small at room temperature, but the dissolved oxygen concentration was measured for sodium aldehyde sulfoxylate, aminoguanidine sulfate, sodium borohydride, etc. The decrease was not so large at room temperature, and a large decrease was observed at 50 ° C. Thus, there was a correlation between the reduction of the dissolved oxygen concentration due to the addition of the reducing agent and the effect of suppressing the dissolution of the solder. Further, the heavy metal has an action of accelerating the decomposition of the reducing agent, but in the case of the present invention, the decomposition of the reducing agent is suppressed probably because the heavy metal is blocked. As is apparent from the above, the present invention has solved the problems of lead precipitation and dissolution at the same time.

[0015]

【Example】

(Examples and Comparative Examples of Dissolution Inhibiting Additives) An aqueous solution of NaOH (NaOH concentration: 40 g / l) was added with a lead concentration of 150 m
g / l (150 ppm) with lead sulfate,
The mixture was stirred for about 2 hours to completely dissolve the lead sulfate, and the solution was adjusted. 50 ml of this solution was poured into a beaker having a capacity of 100 ml, and copper and a solder plate coated so that each had an exposed area of 4 cm ² were immersed in the solution to form an electrode for measuring current flowing in the solution. Copper and solder electrodes were connected between the lead wires from the electrodes via a 10 ohm resistor. The dissolution current can be measured by measuring the voltage between both ends of the resistor. The measurement is performed at room temperature (about 20 ° C).
This was performed while stirring the liquid with a magnetic stirrer. Further, 1 g of the additive shown in Table 1 was added to a small amount (2 to 3 ml) of N
A solution dissolved in an aOH aqueous solution (NaOH concentration: 40 g / l) was prepared. Pour these liquids into a stirring beaker,
The change in the dissolution current was measured. As a result, when the current value after the addition of the additive (additive concentration: about 20 g / l) was lower than the current value before the addition by more than 20%, the result was evaluated as ○.
If less than a percentage or increased conversely, it is marked as x, and Table 1
(Examples: Table 1-1, Comparative Examples: Table 1-2). In most cases, the current value was not reduced. In particular, with respect to the organic sulfur compounds contained in Comparative Examples 20 to 23, the nitro compounds of Comparative Examples 32 to 35, and the sodium bromate of Comparative Example 54, these compounds were simply added to a sodium hydroxide solution containing no lead ion. , Resulting in a large increase in the melting current and, rather, promoted the melting of the solder.

[0016]

[Table 1]

(Examples and Comparative Examples of Second Additive) Next, the dissolution inhibiting effect of the second additive (reducing agent) was examined.
The effect was confirmed by measuring the melting current while maintaining the liquid temperature of 50 ° C. and using a solder and a copper electrode while stirring the liquid with a magnetic stirrer. More specifically, 0.2 g of a reducing agent previously dissolved in 10 ml of an aqueous NaOH solution (NaOH concentration: 40 g / l) was added at 50 ° C.
The solution was heated to 50 ° C.
NaOH containing 0 ml of α-picoline (concentration: 4 g / l)
It was carried out by adding to an aqueous solution (NaOH concentration: 40 g / l). The results are shown in Table 2. The evaluation was evaluated as ○ when the current value decreased by 20% or more due to the addition of the second additive, and as X when the addition was not performed.

[0018]

[Table 2]

(Effect of Preventing Precipitation of Lead) A pattern was formed by exposing and developing a copper-clad laminate using a water-soluble dry film HF450 (trade name, manufactured by Hitachi Chemical Co., Ltd.). This was subjected to an electric solder plating having a thickness of about 5 μm. This substrate was cut out to have a size of 2 cm × 5 cm. At this time, half of the substrate (2 cm x 2.5 c
m) was covered with a dry film, and the rest was plated with solder. 400
It was immersed in a NaOH aqueous solution containing ppm of lead ions and additives, and the dry film was peeled off. Peeling is carried out in a beaker at a temperature of 50 ° C. with a magnetic stirrer for about 2 minutes.
Performed with stirring. At this time, the precipitation of lead was visually observed. × indicates that a gray discolored portion was observed on the exposed copper, and ○ indicates that there was no discoloration and the copper was glossy.
And The results are shown in Table 3 (Example: Table 3-1, Comparative Example: Table 3).
-2 and Table 3-3).

[0020]

[Table 3]

[0021]

According to the present invention, when the water-soluble resist is stripped with an alkaline stripping solution, the dissolution of solder plating can be suppressed and the precipitation of lead can be suppressed. Therefore, a favorable wiring without a wiring defect can be formed. As another effect, an organic alkali is used as an additive component in the stripping solution used in the present method, but in order to obtain a necessary alkali strength, inexpensive inorganic alkali such as sodium hydroxide or potassium hydroxide is used. Can be used. Further, since the precipitation of lead is eliminated, the area of the substrate that can be treated with the same amount of the stripping solution increases. Therefore,
The amount of stripper used per unit area of the substrate is reduced, and the amount of waste liquid is reduced. Therefore, the cost for processing is reduced.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-63-183445 (JP, A) JP-A-64-24254 (JP, A) JP-A-59-55438 (JP, A) JP-A-63-543 54991 (JP, A) JP-A-56-32336 (JP, A) JP-A-61-276992 (JP, A) JP-A-2-30770 (JP, A) JP-A-59-25965 (JP, A) JP-B-46-43123 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/42 C23F 1/00 H05K 3/06 H05K 3/24

Claims (5)

(57) [Claims] To 1. A substrate laminated with a copper foil, with water-soluble resist, the plating resist is formed, performs a solder plating, the method of removing the water-soluble resist stripping the water-soluble resist is strongly alkaline aqueous solution, stripping solution the, water to piperidine, alkyl adducts of piperidine, alkyl adducts of pyrrolidine, pyridine, alkyl adducts of pyridine, or characterized by any of dipicolylamine containing 0.5 to 100 g / l Method of stripping resist. 2. As the second additive, aminognidine, hydrazines, sulfurous acid, dithionous acid or a salt thereof,
Borohydrides, carbazates, thiourea dioxide, sulfinic acids, sulfoxy acids, hydrazides,
0.01-100 at least one of the semicarbazide salts
peeling method of the water-soluble resist as claimed in g / l including請 Motomeko 1. 3. A stripping solution is contacted to the substrate by spraying, according to 請 Motomeko 1 or 2 you peel the water-soluble resist
A method for removing a water-soluble resist. (4) Strong alkaline aqueous solution, piperidine, pipet
Lysine alkyl group addition compound, pyrrolidine alkyl
Group addition compound, pyridine, alkylation of pyridine
Compound or dipicolylamine
Stripper. (5) Aminognidine, arsenic as the second additive
Drazines, sulfurous acid, dithionous acid or salts thereof,
Borohydride, carbazate, thiourea dioxide
Hydrogen, sulfinic acids, sulfoxy acids, hydrazides,
5. The method according to claim 4, which comprises at least one of a semicarbazide salt.
Stripping solution.