JP3517286B2 - Master for electrodeposition transfer and method of manufacturing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrodeposition transfer original plate and a method for manufacturing the same, and more particularly, it is capable of efficiently forming a fine pattern on a workpiece in a fine processing step such as a semiconductor process, and durability. To a high electrodeposition transfer original plate and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, printed wiring and circuit pattern formation,
Alternatively, for forming a fine pattern such as formation of a thin film etching resist, there are a photolithography method, a printing method, a transfer method for transferring a fine pattern formed on an original plate having a masking layer of a predetermined pattern onto a workpiece. .

However, the photolithography method has complicated steps, and as the size of the workpiece increases, a dedicated apparatus including a large exposure apparatus is required, resulting in enormous cost required for the apparatus.

In the printing method, the printing pattern is deformed due to the influence of the fluidity of the ink, the pressure of the plate, and the fact that part of the ink remains on the plate without transferring to the work piece. Easy to perform, inferior in dimensional accuracy and reproducibility, and the image line is 100
There is a problem that it is not suitable for forming a fine pattern of less than μm.

On the other hand, the fine pattern transfer method does not have the problems described above, and it is possible to efficiently form a fine pattern having a fine line width and an appropriate film thickness with high accuracy.

[0006]

However, in the fine pattern transfer method, when the fine pattern is formed many times from the same original plate, when the fine pattern formed on the original plate is transferred to the object to be processed, The contact between the object and the masking layer of the original plate, or the contact between the adhesive layer and the masking layer provided on the work piece destroys the masking layer, and the electrical conductivity is formed on the original plate by the electrically insulating masking layer. The part pattern may be deformed. If a fine pattern is formed by depositing an electrodeposition material on the conductive portion pattern of the original plate using the original plate with the masking layer destroyed, the fine pattern formed on the original plate is the conductive portion pattern due to the masking layer destruction. Faithfully reproduce the deformation of. Therefore, when the fine pattern on the original plate is transferred onto the workpiece, the fine pattern is transferred in a deformed state, which causes a problem that a serious defect occurs in the fine processing such as a semiconductor process. there were.

The present invention has been made in view of the above-mentioned circumstances, and has a high durability, which enables a fine pattern having a fine line width and a proper film thickness to be formed efficiently with high accuracy. An object is to provide an original plate for electrodeposition transfer and a method for producing the same.

[0008]

In order to achieve such an object, the electrodeposition transfer original plate of the present invention has a substrate having at least a conductive surface, and a recess formed in a predetermined pattern on the surface of the substrate. And a masking layer made of an insulating material provided in the recess via a chromate-treated surface, and the surface of the masking layer is substantially flush with the surface of the substrate.

In the electrodeposition transfer original plate of the present invention, at least the surface of the substrate is electrically conductive, the recesses formed in the surface of the substrate in a predetermined pattern, and the insulation provided in the recesses through the chromate-treated surface. A masking layer made of a volatile substance,
The surface of the masking layer was lower than the surface of the substrate.

[0010]

Further, in the method for producing an original plate for electrodeposition transfer of the present invention, at least a concave portion having a predetermined pattern is formed on a conductive substrate, and the concave portion is subjected to chromate treatment to form a chromate treated surface, and thereafter, An insulating material is provided in the recess to form the masking layer so that the surface thereof is substantially flush with or lower than the surface of the substrate.

[0012]

The chromate-treated surface formed in a predetermined pattern on the substrate or the chromate-treated surface formed in the recess formed in the substrate in the predetermined pattern has a chromate film. The masking layer formed on the treated surface has a significantly improved adhesion to the substrate due to the above chromic acid film, and when the masking layer is formed in the above recesses, the contact area between the masking layer and the substrate is increased. Is increased, the adhesion between the masking layer and the substrate is further improved, and the electrodeposited substance deposited on the masking layer non-forming portion (conductive portion pattern) of the substrate is transferred onto the workpiece. The destruction of the masking layer by the provided pressure-sensitive adhesive layer and the destruction of the masking layer by other external force are extremely small.

[0013]

Embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a schematic constitutional view showing an intaglio type original plate which is one embodiment of the original plate for electrodeposition transfer of the present invention. In FIG. 1, an electrodeposition transfer original plate 1 includes a substrate 2 at least the surface of which is conductive, a chromate-treated surface 4 formed in a predetermined pattern on the substrate 2, and a masking layer formed on the chromate-treated surface 4. 5 and 5. As shown in the example,
In this electrodeposition transfer original plate 1, the surface of the masking layer 5 is formed higher than the surface of the substrate 2.

FIG. 2 is a schematic constitutional view showing a relief type original plate which is another embodiment of the electrodeposition transfer original plate of the present invention. In FIG. 2, the electrodeposition transfer original plate 11 is formed with a substrate 12 at least the surface of which is conductive, a concave portion 13 formed in a predetermined pattern on the substrate 12, and a chromate-treated surface 14 in the concave portion 13. And a masking layer 15. As in the illustrated example, in the electrodeposition transfer original plate 11, the surface of the masking layer 15 is formed lower than the surface of the substrate 12.

The substrates 2 and 12 used for the electrodeposition transfer original plate 1 or the electrodeposition transfer original plate 11 have conductivity, and in particular, the substrate 12 can be formed with recesses by etching treatment or the like. The substrate is made of a conductive metal such as stainless steel, titanium or nickel. The thickness of such substrates 2 and 12 is preferably about 0.2 to 2 mm.

It should be noted that the surfaces of the substrates 2 and 12 are coated with the plated layers when the plated layers are transferred to a workpiece to be described later.
It is preferable that a certain amount of mirror surface treatment is applied in order to easily peel off from No. 2.

Here, referring to FIGS. 3 and 4, an example of manufacturing the intaglio type electrodeposition transfer original plate 1 shown in FIG. 1, FIG.
An example of manufacturing the letterpress type electrodeposition transfer original plate 11 shown in FIG.

First, an example of manufacturing the intaglio type electrodeposition transfer original plate 1 will be described. As shown in FIG. 3, a photoresist layer 6 is formed on the substrate 2 in a predetermined pattern (see FIG.
(A)). Next, the substrate 2 is subjected to a chromate treatment to form a chromate treated surface 4 on the exposed portion of the substrate 2 (FIG. 3).
(B)). After that, a coating liquid of an insulating material is applied to the entire surface of the substrate 2 to form an insulating film 7 (FIG. 3C), the photoresist layer 6 is removed, and at the same time, the insulating film on the photoresist layer 6 is lifted off. 7 is removed to expose the conductive portion of the substrate 2 (FIG. 2 (d)). As a result, the insulating film 7 remains on the substrate 2 only on the chromate-treated surface 4, and the masking layer 5 is formed by hardening the remaining insulating film 7 as necessary.

Then, after the plating layer 8 is formed on the conductive portion of the electrodeposition transfer original plate 1 (FIG. 3 (e)), the adhesive layer 10 is formed.
The work piece 9 provided with and the plated layer 8 are closely attached (see FIG.
(F)), the plated layer 8 is transferred onto the workpiece 9 to form a fine pattern (FIG. 3 (g)).

As described above, the electrodeposition transfer original plate 1 of the present invention
Since the masking layer 5 is formed on the chromate-treated surface 4 of the substrate 2, it has a strong adhesion to the substrate 2. Therefore, destruction of the masking layer 5 due to various external forces applied to the masking layer 5 in forming the fine pattern as described above is extremely small. In the case of a titanium substrate, the surface of the substrate 2 is roughened by immersing it in an HF-NH ₄ F solution, an HF solution or the like for a few tens of seconds before the chromate treatment. May be. By doing so, the adhesion of the masking layer 5 formed on the chromate-treated surface 4 to the substrate 2 can be further improved.

In the manufacturing example of the electrodeposition transfer original plate 1 shown in FIG. 3, the photoresist layer 6 is removed, and at the same time, the insulating film 7 on the photoresist layer 6 is removed by lift-off to remove the conductive portion of the substrate 2. However, the present invention is not limited to this. For example, chromate treated surface 4
It is also possible to grow an electrodeposition insulating substance on the top by electrodeposition to form the insulating film 7, and then remove the photoresist layer 6 by peeling.

Next, a production example of the relief type original plate 11 for electrodeposition transfer will be described. First, the photoresist layer 16 is formed on the substrate 12 in a predetermined pattern (FIG. 4A). next,
The substrate 12 is etched to form the recess 13 (see FIG.
(B)) After that, the substrate 12 is subjected to a chromate treatment to form a chromate treated surface 14 in the recess 13 (FIG. 4).
(C)). Next, using the photoresist layer 16 as an electrodeposition mask, an electrodeposition film is grown in the recesses 13 to form an insulating film 17 (FIG. 4D). After that, the photoresist layer 16 is removed, and the insulating film 17 in the recess 13 is baked if necessary to form a masking layer 15 made of an insulating material (FIG. 4E).

Then, after the plating layer 18 is formed on the conductive portion of the electrodeposition transfer original plate 11 (FIG. 4 (f)), the workpiece 9 having the adhesive layer 10 and the plating layer 18 are brought into close contact with each other. ,
The plating layer 18 is transferred onto the workpiece 9 to form a fine pattern (FIG. 4 (g)).

As described above, the electrodeposition transfer original plate 1 of the present invention
The masking layer 15 of No. 1 has a large contact area with the substrate 12 because it is formed in the recess 13 of the substrate 12, and has a strong adhesion with the substrate 12 because it is formed on the chromate-treated surface 14. The masking layer 15 does not come into contact with the adhesive layer 10 of the workpiece 9. Therefore,
Masking layer 1 in the above fine pattern formation
The destruction of the masking layer 15 due to various external forces applied to 5 is extremely small. Further, since there is no contact between the film surface of the masking layer 15 and the plating layer 18, the destruction of the masking layer 15 is further reduced, and the plating layer 18 is easily transferred onto the workpiece 9.

As described above, in order to form the recess 13 by etching the substrate 12 with the photoresist layer 16 as a mask, well-known conventional methods such as wet etching such as dipping and spraying, dry etching, sand blasting and mechanical cutting are used. Means can be used. For example, when the substrate is a stainless steel plate, it is contacted (immersed, etc.) with a ferric chloride solution, and when the substrate is a titanium plate, it is contacted with a HF-H ₂ O ₂ -H ₂ O solution, etc. Therefore, it is preferably performed. In the case of a titanium substrate, the surface of the recess 13 may be roughened by immersing it in a HF-NH ₄ F solution or an HF solution for several tens of seconds after etching. By doing so, the masking layer 1 formed in the recess 13
It is possible to further improve the adhesion of No. 5 to the substrate 12.

As the insulating material for forming the above-mentioned masking layers 5 and 15, an acrylic insulating material, a fluorine insulating material, a tetrafluoroethylene-dispersed electrodeposition resin, an acrylic main chain or a side chain is used. The fluorine-bonded electrodeposition resin, the polyimide-based insulating material, the epoxy-based insulating material, the thermosetting melamine resin-based insulating material, the polyester-based insulating material, and the like can be mentioned.

As another method of forming the insulating film 17 in the concave portion 13 in the manufacturing example of the electrodeposition transfer original plate 11 shown in FIG. 3, a coating solution of an insulating substance is applied to the entire surface of the substrate 12, and then, The insulating material on the substrate 12 other than the recess 13 may be removed by doctoring. In addition, after forming the recesses 13 and performing chromate treatment, as in the manufacturing example of the electrodeposition transfer original plate 1, an insulating material coating solution is applied to the entire surface of the substrate 12 to remove the photoresist layer 16 at the same time. The insulating film 17 on the photoresist layer 16 is removed by lift-off to expose the conductive portion of the substrate 12, and the insulating film 1 is formed only in the recess 13.
7 may be formed. Alternatively, the insulating film 17 is formed on the entire surface of the substrate 12 as described above, and then the entire surface of the insulating film 17 is etched until the surface of the substrate 12 is exposed. Alternatively, 17 may be removed. Further, after the recesses 13 are formed in the substrate 12 and the chromate treatment is performed, the coating liquid of the insulating material is applied to the entire surface of the substrate 2 in a state where the photoresist layer 16 is completely removed, and then by doctoring. The insulating film on the substrate 12 other than the recess 13 may be removed to expose the conductive portion.

The electrodeposition transfer original plates 1 and 11 shown in FIGS. 1 and 2 use conductive substrates (the substrate 12 is a conductive substrate capable of forming recesses) as the substrates 2 and 12. However, the substrate to be used may have a conductive thin film made of the above-mentioned conductive substance formed on the surface thereof. Figure 5
And FIG. 6 is an example of an electrodeposition transfer original plate using such a substrate. In FIG. 5, the electrodeposition transfer original plate 21 is
Substrate 2 in which conductive thin film 22b is formed on the surface of substrate 22a
I am using 2. That is, the above-mentioned electrodeposition transfer original plate 1
In the same manner as described above, a chromate-treated surface 24 is formed on the thin film 22b of the substrate 22 in a predetermined pattern.
4 has a masking layer 25 formed thereon. In addition, FIG.
In the above, the electrodeposition transfer original plate 31 uses the substrate 32 in which the conductive thin film 32b capable of forming a recess is formed on the surface of the substrate 32a. Then, in the same manner as the electrodeposition transfer original plate 11 described above, a recess 33 is formed in the thin film 32b of the substrate 32, a chromate-treated surface 34 is formed in the recess 33, and a masking layer 35 is formed on the chromate-treated surface 34. Has been formed. In the electrodeposition transfer original plates 21 and 31, the substrates 22a and 32a are preferably conductive substrates, but the thin film 22
b after chromate treatment, or thin film 32b
When it is possible to energize each conductive portion pattern without causing a voltage drop after forming the concave portion 33 on the substrate and performing the chromate treatment, the substrates 22a and 32a are made of a glass plate, a resin film such as polyethylene or acrylic, or the like. It may be an insulating substrate.

FIG. 7 is a schematic constitutional view showing a planographic type original plate which is another embodiment of the original plate for electrodeposition transfer of the present invention. Figure 7
In FIG. 3, the electrodeposition transfer original plate 41 includes a substrate 42, a recess 43 formed in the substrate 42 in a predetermined pattern, and a masking layer 45 formed in the recess 43 via a chromate treatment surface 44. As in the illustrated example, in the electrodeposition transfer original plate 41, the surface of the masking layer 45 is substantially flush with the surface of the substrate 41.

As the substrate 42 used for the electrodeposition transfer original plate 41, those mentioned as the substrates used for the above-mentioned electrodeposition transfer original plates 1, 11, 21, 31 can be used.

Next, an example of manufacturing the planographic type electrodeposition transfer original plate 41 shown in FIG. 7 will be described with reference to FIG. Figure 8
As shown in FIG. 8, first, a photoresist layer 46 is formed on the substrate 42 in a predetermined pattern (FIG. 8A). next,
The substrate 42 is etched to form a recess 43, and the recess 43 is subjected to a chromate treatment to obtain a chromate treated surface 44.
Are formed (FIG. 8B). After that, using the photoresist layer 46 as an electrodeposition mask, an electrodeposition film is grown in the recess 43 until it becomes substantially the same as the surface of the substrate 42 to form an insulating film 47 (FIG. 8C). Next, the photoresist layer 46 is removed to expose the conductive portion of the substrate 42 (FIG. 8D).
Then, the masking layer 45 is formed by hardening the insulating film 47 existing in the recess 43 of the substrate 42 as needed.

FIG. 9 is a schematic constitutional view showing an intaglio type original plate which is another embodiment of the original plate for electrodeposition transfer of the present invention. Figure 9
In the above, the electrodeposition transfer original plate 51 includes a substrate 52, a recess 53 formed in a predetermined pattern on the surface of the substrate 52, and a masking layer 55 formed in the recess 53 via a chromate-treated surface 54. As in the illustrated example, in the electrodeposition transfer original plate 51, the surface of the masking layer 55 is higher than the surface of the substrate 52.

As the substrate 52 used for the electrodeposition transfer original plate 51, the substrates mentioned above as the substrates used for the electrodeposition transfer original plates 1, 11, 21, and 31 can be used.

Next, an example of manufacturing the intaglio type electrodeposition transfer original plate 51 shown in FIG. 9 will be described with reference to FIG. As shown in FIG. 10, first, the photoresist layer 56 is formed on the substrate 52 in a predetermined pattern (FIG. 10A).
Next, the substrate 52 is etched to form a recess 53,
Chromate treatment is performed in the recess 53 to form a chromate-treated surface 54 (FIG. 10B). After that, a coating liquid of an insulating substance is applied to the entire surface of the substrate 52 to form the insulating film
7 is formed (FIG. 10C). The insulating film 57 is formed until the surface of the insulating film 57 on the recess 53 becomes higher than the surface of the substrate 52. Then, the photoresist layer 56
And at the same time, the insulating film 57 on the photoresist layer 56 is removed by lift-off to expose the conductive portion of the substrate 52 (FIG. 10D). As a result, the insulating film 57 remains only on the concave portion 53 on the substrate 52, and the masking layer 55 is formed by curing the remaining insulating film 57.

Of course, the production of the electrodeposition transfer original plate 51 is not limited to the above-mentioned lift-off method.

In the electrodeposition transfer original plate of the present invention, the relationship between the height of the masking layer surface and the substrate surface is determined by the etching amount of the substrate and the thickness of the masking layer and is shown in FIGS. 2, 7 and 9. As described above, the plate structure is determined by various combinations.

Next, the present invention will be described in more detail with reference to specific examples. (Example 1) A substrate made of titanium (Ti) (thickness: 0.4 m)
m) on the surface by spin coating (rotation speed 1500 rpm,
Photoresist (Tokyo Ohka Kogyo Co., Ltd.) for 40 seconds
OFPR800) was applied and exposed to light and developed using a mask having a predetermined shape with a line width of 5 μm to form a photoresist layer (film thickness 1.0 μm) having a predetermined pattern.

Next, HF (2.5 wt%)-H ₂ O ₂
The exposed portion of the Ti substrate was etched (immersion for 2 minutes, etching depth 2 μm) in a (15 wt%) liquid to form a recess. After that, the surface of the recess was roughened (immersion for 30 seconds) in an HF-NH ₄ solution for the purpose of further improving the substrate adhesion of the electrodeposition material constituting the masking layer.

Next, the above substrate was used as a cathode, and the concave surface was subjected to chromate treatment under the following chromate treatment conditions.

Chromate condition : Chromate bath: Elecoat connector (manufactured by Shimizu Co., Ltd.) pH: 4.5 Liquid temperature: 25 ° C. Current density: 1 A / dm ² Time: 1 minute Membrane thickness: 0 0.5 μm Next, using a photoresist layer as a mask for electrodeposition, tetrafluoroethylene-dispersed electrodeposition resin (Elecoat Nithron made by Shimizu Co., Ltd.) was electrodeposited at 25 mA / dm ^{2 in the} recesses, and then a constant voltage of 20 V was applied. Electrodeposition was performed for about 90 seconds, and an electrodeposition film (insulating film) was grown in the above-mentioned recess until it became the same as the Ti substrate surface.

Next, this substrate was baked at 110 ° C. for 30 minutes in a circulation oven, and then only the photoresist layer was dissolved and removed by immersion in acetone for 30 seconds. Next, only the electrodeposition resin is baked in an oven (180
(° C, 30 minutes) to form a masking layer to prepare a lithographic plate for electrodeposition transfer.

Copper was plated on the conductive portion of the electrodeposition transfer original plate produced as described above under the following plating conditions to form a copper plating layer (thickness: about 1.5 μm).

Plating conditions / Plating bath composition: Copper pyrophosphate ... 94 g / l Potassium pyrophosphate ... 340 g / l P ratio ... 7.0-pH: 8.8-Liquid temperature: 55 ° C.-Current density: 5 A / dm ² -Time: 1.5 minutes After that, an acrylic adhesive (PE-118 manufactured by Nippon Carbide Industry Co., Ltd.) was spin-coated on the workpiece (chromium thin film formed on the glass plate) by a spin coating method (rotation speed: 3000r).
pm, 30 seconds), the pressure-sensitive adhesive surface of this work piece is brought into close contact with the master plate for electrodeposition transfer, and then a pressure roll is rolled from the back surface of the master plate at a speed of 50 cm / min for pressure bonding and then electrodeposition. The original plate for transfer was peeled off and the copper plating layer was transferred to the object to be processed. The resolution of each fine pattern made of the copper plating layer formed by transferring from the electrodeposition transfer original plate in this manner was 5 μm.
At this time, no breakage of the masking layer of the original plate as observed in the conventional method was observed.

Thereafter, the same fine pattern formation was repeated 100 times using this electrodeposition transfer original plate. As a result, the fine pattern formed at the 100th time showed no pattern deformation, and the resolution was the same as that of the fine pattern at the first time. The original plate for electrodeposition transfer of the present invention had excellent durability. Therefore, it was confirmed that it is possible to form a highly precise fine pattern. (Example 2) In the same manner as in Example 1, a recess was formed in the Ti substrate, the surface of the recess was roughened, and then chromate treatment was performed.

Next, ion-exchanged water was added to a water-dispersible varnish containing 80 parts by weight of a bisphenol type epoxy resin (Epicote 1001 manufactured by Shell Chemical Co., Ltd.), 18 parts by weight of tetrahydrophthalic anhydride, and 2 parts by weight of ethylene glycol. To prepare an electrodeposition solution having a total nonvolatile content of 5%.

Next, electrodeposition was carried out at a constant voltage of 100 V using the above-mentioned electrodeposition solution using the photoresist layer as an electrodeposition mask.
An electrodeposition film (insulating film) made of an epoxy electrodeposition resin was grown in the above-mentioned recess until it became the same as the surface of the Ti substrate. Then, the photoresist layer was peeled off from the substrate to prepare a lithographic plate for electrodeposition transfer.

Using this electrodeposition transfer original plate, a fine pattern composed of a copper plating layer was transferred onto a workpiece in the same manner as in Example 1. As a result, the resolution of the fine pattern was 5 μm. Further, as a result of repeating fine pattern formation 100 times using this electrodeposition transfer original plate as in the example, 10
No deformation of the pattern was observed in the 0th fine pattern, and the resolution was the same as that of the 1st fine pattern. The original plate for electrodeposition transfer of the present invention had excellent durability, It was confirmed that highly precise fine pattern formation was possible. (Example 3) In the same manner as in Example 1, a recess was formed in the Ti substrate, the surface of the recess was roughened, and then chromate treatment was performed.

Next, 3.3 parts by weight of p-phenylenediamine was dissolved in 90 parts by weight of N, N-dimethylformaldehyde, 6.7 parts by weight of pyromellitic dianhydride was added, and the mixture was reacted at room temperature for 10 hours. After making a polyamic acid solution,
1.8 parts by weight of triethylamine was added and reacted at room temperature for 1 hour to obtain a polyamic acid salt solution. This solution 60
40 parts by weight of methanol was added to parts by weight to prepare an electrodeposition liquid.

Next, electrodeposition was carried out at a constant voltage of 50 V using the above-mentioned electrodeposition solution using the photoresist layer as an electrodeposition mask, and an electrodeposition film consisting of a polyamic acid thin film was formed in the above-mentioned recesses until it became the same as the Ti substrate surface. (Insulating film) was grown. After that, the photoresist layer was peeled off from the substrate, and then the substrate was pyridine: acetic anhydride: benzene = 1: 1: 3 (volume ratio).
It was immersed in a solution mixed at a ratio of 12 at room temperature for 12 hours to prepare a lithographic structure electrodeposition transfer original plate having a masking layer made of a polyimide film on the surface.

Using this electrodeposition transfer original plate, a fine pattern composed of a copper plating layer was transferred onto a workpiece in the same manner as in Example 1, and the resolution of the fine pattern was 5 μm. Further, as a result of repeating fine pattern formation 100 times using this electrodeposition transfer original plate as in the example, 10
No deformation of the pattern was observed in the 0th fine pattern, and the resolution was the same as that of the 1st fine pattern. The original plate for electrodeposition transfer of the present invention had excellent durability, It was confirmed that highly precise fine pattern formation was possible. (Example 4) In the same manner as in Example 1, a recess was formed in the Ti substrate, the surface of the recess was roughened, and then chromate treatment was performed.

Next, polyester resin (manufactured by Shinto Paint Co., Ltd.)
Electrodeposition consisting of 60 parts by weight, 15 parts by weight of melamine resin (Nikalac MX-40 manufactured by Sanwa Chemical Co., Ltd.), 45 parts by weight of butyl cellosolve, 5 parts by weight of n-butanol, 4 parts by weight of triethylamine, and 800 parts by weight of deionized water. A liquid was prepared.

Next, electrodeposition was carried out at a constant voltage of 20 V using the above-mentioned electrodeposition solution using the photoresist layer as an electrodeposition mask, and the above-mentioned recess was made of a polyester-based melamine electrodeposition resin until it became the same as the Ti substrate surface. An electrodeposition film (insulating film) was grown. After that, the photoresist layer was peeled from the substrate and baked in an oven at 175 ° C. for 30 minutes to form a masking layer, thereby preparing a lithographic plate for electrodeposition transfer.

Using this electrodeposition transfer original plate, a fine pattern made of a copper plating layer was transferred onto a workpiece in the same manner as in Example 1, and the resolution of the fine pattern was 5 μm. Further, as a result of repeating fine pattern formation 100 times using this electrodeposition transfer original plate as in the example, 10
No deformation of the pattern was observed in the 0th fine pattern, and the resolution was the same as that of the 1st fine pattern. The original plate for electrodeposition transfer of the present invention had excellent durability, It was confirmed that highly precise fine pattern formation was possible. (Example 5) In the same manner as in Example 1, a recess was formed in the Ti substrate, the surface of the recess was roughened, and then chromate treatment was performed.

Next, using the photoresist layer as an electrodeposition mask, acrylic electrodeposition resin (Elecoat AM1 manufactured by Shimizu Co., Ltd.) was electrodeposited on the recesses at a constant voltage of 20 V for about 90 seconds, and the Ti substrate was deposited on the recesses. An electrodeposition film (insulating film) made of an acrylic electrodeposition resin was grown until it became the same as the surface.
Then, 110 ° C. in a circulation oven for this substrate,
After baking for 30 minutes, only the photoresist layer is dissolved and removed by immersion in acetone for 30 seconds, and only the electrodeposition resin is baked in an oven (180 ° C, 30 minutes) to form a masking layer, and the lithographic structure is electrodeposited and transferred. A master plate was prepared.

When a fine pattern composed of a copper plating layer was transferred onto a workpiece using the electrodeposition transfer original plate in the same manner as in Example 1, the resolution of the fine pattern was 5 μm. Further, as a result of repeating fine pattern formation 100 times using this electrodeposition transfer original plate as in the example, 10
No deformation of the pattern was observed in the 0th fine pattern, and the resolution was the same as that of the 1st fine pattern. The original plate for electrodeposition transfer of the present invention had excellent durability, It was confirmed that highly precise fine pattern formation was possible. (Example 6) In the same manner as in Example 1, a recess was formed in the Ti substrate and the surface of the recess was roughened.

Next, the above substrate was dipped in a chromate bath under the following conditions for chromate treatment.

Immersion Chromate Treatment Conditions -Chromate bath: Theft Chromate BR (manufactured by Shimizu Co., Ltd.)-Liquid temperature: 25 ° C-Dip time: 10 seconds Next, using a photoresist layer as an electrodeposition mask, acrylic electrodeposition was performed on the recesses. Resin (Shimizu Co., Ltd. Elecoat AM
1) was electrodeposited at a constant voltage of 20 V for about 60 seconds to grow an electrodeposition film (insulating film) having a thickness of about 1 μm. Then, the substrate was baked at 110 ° C. for 30 minutes in a circulation oven, then only the photoresist layer was dissolved and removed by immersion in acetone for 30 seconds, and only the electrodeposition resin was baked in the oven (180 ° C., For 30 minutes) as a masking layer,
An original plate for electrodeposition transfer having a relief structure was produced.

Using this electrodeposition transfer original plate, a fine pattern composed of a copper plating layer was transferred onto a workpiece in the same manner as in Example 1. As a result, the resolution of the fine pattern was 5 μm. Further, as a result of repeating fine pattern formation 100 times using this electrodeposition transfer original plate as in the example, 10
No deformation of the pattern was observed in the 0th fine pattern, and the resolution was the same as that of the 1st fine pattern. The original plate for electrodeposition transfer of the present invention had excellent durability, It was confirmed that highly precise fine pattern formation was possible. (Example 7) In the same manner as in Example 1, a photoresist layer (thickness 1.0 µm) having a predetermined pattern was formed on a Ti substrate.

Then, the exposed portion of the Ti substrate was subjected to a chromate treatment in the same manner as in Example 1 without forming a recess. Then, using the photoresist layer as an electrodeposition mask, 25 mA of a tetrafluoroethylene-dispersed electrodeposition resin (Shimizu Co., Ltd. Elecoat Nithron) was applied to the chromate treated surface.
After electrodeposition at / dm ² , electrodeposition was performed at a constant voltage of 20 V for about 90 seconds to grow an electrodeposition film (insulating film) having a thickness of 2 μm.

Next, this substrate was baked at 110 ° C. for 30 minutes in a circulation oven, and then only the photoresist layer was dissolved and removed by immersion in acetone for 30 seconds. Next, only the electrodeposition resin is baked in an oven (180
(° C., 30 minutes) as a masking layer to prepare an intaglio structure electrodeposition transfer original plate as shown in FIG.

Using this electrodeposition transfer original plate, a fine pattern composed of a copper plating layer was transferred onto a workpiece in the same manner as in Example 1, and the resolution of the fine pattern was 5 μm. Further, as a result of repeating fine pattern formation 100 times using this electrodeposition transfer original plate as in the example, 10
No deformation of the pattern was observed in the 0th fine pattern, and the resolution was the same as that of the 1st fine pattern. The original plate for electrodeposition transfer of the present invention had excellent durability, It was confirmed that highly precise fine pattern formation was possible. (Example 8) In the same manner as in Example 6, a recess was formed in the Ti substrate, the surface of the recess was roughened, and then chromate treatment was performed.

Next, using the photoresist layer as an electrodeposition mask, an acrylic electrodeposition resin (Elecoat AM1 manufactured by Shimizu Co., Ltd.) was electrodeposited in the concave portion at a constant voltage of 30 V for about 90 seconds to form an electrodeposition having a thickness of about 3 μm. A film (insulating film) was grown. After that, 110 ° C., 3
After baking for 0 minutes, only the photoresist layer was dissolved and removed by immersion in acetone for 30 seconds, and only the electrodeposition resin was baked in an oven (180 ° C., 30 minutes) to form a masking layer, as shown in FIG. An original plate for electrodeposition transfer having a simple intaglio structure was produced.

Using this electrodeposition transfer original plate, a fine pattern made of a copper plating layer was transferred onto a workpiece in the same manner as in Example 1, and the resolution of the fine pattern was 5 μm. Further, as a result of repeating fine pattern formation 100 times using this electrodeposition transfer original plate as in the example, 10
No deformation of the pattern was observed in the 0th fine pattern, and the resolution was the same as that of the 1st fine pattern. The original plate for electrodeposition transfer of the present invention had excellent durability, It was confirmed that highly precise fine pattern formation was possible.

(Comparative Example) An electrodeposition transfer original plate was prepared in the same manner as in Example 1 except that the substrate was not provided with recesses and the masking layer was formed without chromate treatment. Then, when the copper plating layer formation and the transfer to the object to be processed were repeated in the same manner as in Example 1, pattern deformation was recognized in the fine pattern formed 10 times.

[0066]

As described above in detail, according to the present invention, the masking layer formed in a predetermined pattern on the substrate is provided on the chromate-treated surface of the substrate or on the chromate-treated surface of the concave portion provided in the substrate. Since it is formed, the contact area with the substrate is larger than that of the conventional masking layer formed on the surface (flat surface) of the substrate, and the adhesion between the masking layer and the substrate is strong, so that no masking layer is formed on the substrate. When the electrodeposited substance deposited on the portion (conductive portion pattern) is transferred to the object to be processed, the masking layer is destroyed very little. In addition to the adhesion between the masking layer and the substrate, the durability of the original plate is affected by the structure of the original plate.For example, in the case of a relief type or planographic type original plate structure, the masking layer is peeled from the original plate during transfer. Since the external force from the electrodeposited material is not received, the masking layer is less destroyed and the durability is improved. In the case of a relief type original plate structure, the adhesive layer on the work piece contacts the masking layer. Since the transfer is performed without any damage, the masking layer is not destroyed by the adhesive layer, and the durability of the original plate is further improved. This makes it possible to provide an electrodeposition transfer original plate having excellent durability capable of transferring a fine pattern having a uniform film thickness and a constant line width and a high dimensional accuracy to a workpiece many times.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram showing an intaglio type original plate which is one embodiment of the original plate for electrodeposition transfer of the present invention.

FIG. 2 is a schematic configuration diagram showing a letterpress type original plate which is another embodiment of the original plate for electrodeposition transfer of the present invention.

FIG. 3 is a diagram for explaining an example of manufacturing the original plate shown in FIG.

FIG. 4 is a diagram for explaining an example of manufacturing the original plate shown in FIG.

FIG. 5 is a schematic configuration diagram showing another embodiment of an intaglio type of the original plate for electrodeposition transfer of the present invention.

FIG. 6 is a schematic configuration diagram showing another embodiment of a letterpress type original plate for electrodeposition transfer of the present invention.

FIG. 7 is a schematic configuration diagram showing a planographic type original plate which is another embodiment of the original plate for electrodeposition transfer of the present invention.

FIG. 8 is a diagram for explaining an example of manufacturing the original plate shown in FIG. 7.

FIG. 9 is a schematic configuration diagram showing an intaglio type original plate which is another embodiment of the original plate for electrodeposition transfer of the present invention.

FIG. 10 is a view for explaining an example of manufacturing the original plate shown in FIG.

[Explanation of symbols]

1,11,21,31,41,51 ... Master plate for electrodeposition transfer 2, 12, 22, 32, 42, 52 ... Substrate 13, 33, 43, 53 ... Recessed portion 4, 14, 24, 34, 44, 54 ... Chromate treated surface 5, 15, 25, 35, 45, 55 ... Masking layer 6, 16, 46, 56 ... Resist layer 7, 17, 47, 57 ... Insulating film 8, 18 ... Plating layer 9 ... Workpiece 10 ... Adhesive layer

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-6-82616 (JP, A) JP-A-4-317003 (JP, A) JP-A-4-165306 (JP, A) JP-A-4- 9902 (JP, A) JP 64-51934 (JP, A) JP 62-176836 (JP, A) JP 64-49629 (JP, A) JP 63-6894 (JP, A) JP 63-311788 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G02B 5/20

Claims (20)

(57) [Claims] 1. A substrate having at least a conductive surface, a concave portion formed in a predetermined pattern on the surface of the substrate, and a masking layer made of an insulating material and provided in the concave portion through a chromate-treated surface, The surface of the masking layer is the substrate
An original plate for electrodeposition transfer , which is substantially the same surface as the surface of . 2. A substrate having at least a conductive surface, a recess formed on the surface of the substrate in a predetermined pattern, and a masking layer made of an insulating material and provided in the recess via a chromate-treated surface, The surface of the masking layer is the substrate
An original plate for electrodeposition transfer characterized by being lower than the surface of the . 3. The original plate for electrodeposition transfer according to claim 1, wherein the chromate-treated surface is a rough surface. 4. The master plate for electrodeposition transfer according to claim 1, wherein the masking layer is made of an acrylic insulating material. 5. The original plate for electrodeposition transfer according to claim 1, wherein the masking layer is made of a fluorine-based insulating material. 6. The masking layer is made of tetrafluoroethylene-dispersed electrodeposition resin or an acrylic main chain or fluorine-bonded electrodeposition resin on a side chain.
The original plate for electrodeposition transfer according to claim 3. 7. The masking layer is made of a polyimide-based insulating material.
The original plate for electrodeposition transfer according to any one of 1. 8. The electrodeposition transfer original plate according to claim 1, wherein the masking layer is made of an epoxy-based insulating material. 9. The master plate for electrodeposition transfer according to claim 1, wherein the masking layer is made of a thermosetting melamine resin-based insulating material. 10. The original plate for electrodeposition transfer according to claim 1, wherein the masking layer is made of a polyester insulating material. 11. A recess having a predetermined pattern is formed on a substrate having at least a conductive surface, and the recess is subjected to a chromate treatment to form a chromate-treated surface. Thereafter, an insulating substance is provided in the recess to form a masking layer. The surface is the surface of the substrate
A method for producing an electrodeposition transfer original plate, which is characterized in that it is formed so as to be substantially on the same plane as or lower than the surface . 12. A resist having a predetermined pattern is formed on the substrate, and then the recess is formed in a resist non-forming portion of the substrate by any one of an etching method, a sandblasting method and a mechanical cutting method. Item 12. A method for producing an original plate for electrodeposition transfer according to Item 11. 13. A resist having a predetermined pattern is formed on the substrate, and then a recess is formed in a resist non-forming portion of the substrate.
The insulating film made of the insulating material is formed on the surface of the chromate treatment by electrodeposition after the formation of the chromate treatment on the concave portion , and then the resist is peeled off. The method for producing an original plate for electrodeposition transfer according to claim 12. 14. An insulating film made of the insulating material is formed on the entire surface of the substrate having a chromate-treated surface in the recess, and then the insulating film on the substrate other than in the recess is removed. The method for producing an original plate for electrodeposition transfer according to claim 11 or 12, wherein the masking layer is formed. 15. The insulating film on the substrate other than inside the recess is removed by etching the entire surface of the insulator until the surface of the substrate is exposed. Item 15. A method for manufacturing an original plate for electrodeposition transfer according to Item 14. 16. An insulating film made of an ionizing radiation-curable insulating material is formed on the substrate, and then the insulating film corresponding to the position of the recess is cured, and the insulating film on the substrate other than in the recess is formed. The method for manufacturing an electrodeposition transfer original plate according to claim 14, wherein the insulating film is removed. 17. A photoresist layer is formed on the insulating film so as to correspond to the position of the concave portion , and the insulating film on the substrate other than inside the concave portion is removed by etching using the photoresist layer as a mask. The method for producing an electrodeposition transfer original plate according to claim 14, wherein the photoresist layer is removed thereafter. 18. The method for manufacturing an original plate for electrodeposition transfer according to claim 14, wherein the insulating film on the substrate other than inside the recess is removed by a doctor ring. 19. A resist having a predetermined pattern is formed on the substrate, and then a recess is formed in a resist non-forming portion of the substrate.
Formed, and after the chromate treatment is applied to the concave portion , an insulating film made of the insulating material is formed on the entire surface of the substrate while leaving the resist, and then the resist is peeled off and the resist is lifted off at the same time. The method for producing an electrodeposition transfer original plate according to claim 11 or 12, wherein the masking layer is formed in the recess by removing the insulating film above. 20. The method for producing an electrodeposition transfer original plate according to claim 11, wherein the chromate treatment is performed after roughening the concave portion.