JP2990188B1 - Pattern for repairing printed wiring board and pattern repair method - Google Patents

Abstract

Abstract: [Object] To easily repair a broken wiring of a printed wiring board. A mixture layer containing an oxidizing agent comprising a photosensitive resin and a polyvalent transition metal salt is formed on a surface of a substrate including a repaired portion of a disconnected pattern on a substrate of a printed wiring board, and a photomask is formed. A part of the mixture layer is selectively converted into a corrosion-resistant image 5 by a photochemical reaction method using a polymer, and the repaired portion is corrected by polymerizing a conductive polymer on the image. Since the conductive polymer can be polymerized only in the portion of the printed wiring board surface where correction is necessary, it is possible to appropriately cope with disconnection of a highly integrated circuit.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pattern for repairing a broken printed wiring board and a method for repairing the pattern.
More specifically, the present invention relates to a pattern for correcting a broken portion of a printed wiring board using a photosensitive resin and a conductive polymer in combination, and a pattern correction method.

[0002]

2. Description of the Related Art With the miniaturization and high performance of electronic equipment, the density of wiring has been increasing in printed wiring boards. With the miniaturization of wiring accompanying the increase in density, disconnection of wiring is increasing, and the demand for a simple and reliable wiring correction method is increasing. The conventional wiring correction method has been to correct the wiring by welding a wire having the same width as the wiring width to the broken portion. However, in this method, it is becoming impossible to cope with a recently miniaturized build-up substrate due to the miniaturization of the wire and the work surface.
In addition, there is also a problem that a stepped portion can be formed at a repaired portion, so that it cannot be used for repairing a build-up substrate having a thin interlayer. In recent years, some pattern correction methods using a conductive paste have been reported, but as a practical problem, these methods have a limit in miniaturization.

On the other hand, conductive polymers such as polypyrrole and polyaniline have been developed as polymers having electrical conductivity themselves, and are used for electrodes of electronic parts.
For example, Japanese Patent Application Laid-Open No. 3-46214 discloses a solid electrolytic capacitor having a conductive polypyrrole electrode formed by mixing a methanol solution of dodecylbenzenesulfonic acid and pyrrole at -30 ° C or lower and heating to -20 ° C or higher to polymerize. A manufacturing method is disclosed. Also, Japanese Patent No. 2601207
Japanese Patent Application Publication No. JP-A-2005-17764 discloses a method for producing a sponge-like conductive polymer molded body in which a solution containing aniline, pyrrole, or the like and an oxidizing agent is cooled to freeze the solvent, and the conductive polymer is polymerized below the melting temperature of the solvent. Have been. Further, Japanese Patent No. 26
No. 57956 discloses a conductive polymer composition comprising polyparaphenylenevinylene, polyaniline, polypyrrole and the like and a precursor which generates a dopant by exposure to energy, and a method of exposing this composition to an energy source to form a dopant precursor. A method of forming a conductive polymer structure that decomposes to generate a dopant and renders the exposed area conductive, and exposing the conductive polymer structure to a solvent,
A method is disclosed for forming a conductive polymer structure that dissolves and removes regions other than those exposed to an energy source. Japanese Patent Application Laid-Open No. 61-209225 discloses that an electrolytic polymerization reaction is carried out at an electric potential of 1 V or less using an electrolytic solution containing a 5-membered heterocyclic compound and a sulfonate having a molecular weight of 300 or less, so that a high electrode surface is obtained. A method for forming a conductive polymer is disclosed.

[0004]

Since the above-mentioned techniques are methods for forming a conductive molded body made of an organic polymer, they cannot be directly applied to pattern correction of a high-density printed wiring board. That is, in a method in which a solution in which the reaction is suppressed at a low temperature is polymerized by raising the temperature or a method in which the conductive polymer is polymerized at a temperature lower than the melting temperature of the solvent, a conductive polymer is formed on the entire surface of the substrate, and It is not a shape that can handle fine wiring. In addition, a composition containing a conductive polymer and a precursor that generates a dopant by exposure to energy is exposed to an energy source to decompose the dopant precursor to generate a dopant, and to make the exposed region conductive. In the method of forming a functional polymer structure and dissolving and removing the region other than the region exposed to the energy source by exposing to a solvent, the compound that can be used as a dopant is limited to a special molecular structure such as an onium salt, Since the number of conductive polymers that dissolve in the polymer is small, it is difficult to manufacture a polymer in which conductivity is arbitrarily controlled. Furthermore, in the electrolytic polymerization method, it is difficult to suppress the spread in the electrode surface direction and grow a conductive polymer having only a necessary wiring width.

Japanese Patent Application Laid-Open No. 1-123228 discloses a method of forming a pattern made of a conductive polymer by photopolymerization. In this method, a film is formed in a portion other than a portion where the conductive polymer is formed. And insulation problems occur. JP-A-5-67405 describes a method of forming a conductive pattern on a substrate using a photosensitive conductive paste. In this method, conductive metal component particles are contained in the paste. And the formation of a fine circuit of 50 μm or less cannot be achieved. These prior arts are not directed to a printed wiring board on which a large number of elements are integrated, and cannot deal with disconnection of the printed wiring board.

[0006]

SUMMARY OF THE INVENTION One of the main objects of the present invention is to provide a highly conductive modified wiring which can cope with fine wiring used for pattern modification of a high-density printed wiring board and a method of manufacturing the same. Is to do. The pattern for repairing a printed wiring board according to the present invention is composed of a photosensitive resin and / or a mixed composition of a reaction product of the photosensitive resin and a conductive polymer. Forming a mixture layer containing an oxidizing agent comprising a photosensitive resin and a polyvalent transition metal salt on a printed wiring board, and selectively forming a corrosion-resistant image on a part of the mixture layer by a photochemical reaction method. It can be performed by an operation including a step of developing a corrosion-resistant image, and a step of polymerizing a monomer of a conductive polymer to form a mixed composition with the photosensitive resin.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The correction pattern of the printed wiring board of the present invention is characterized in that the modified pattern is composed of a mixed composition of a photosensitive resin and a conductive polymer, or a mixed composition of a reaction product of the photosensitive resin and a conductive polymer. The spatial repair of the defective portion can be performed, and the electrical connection can be restored by the conductive polymer. By adjusting the amount of the conductive polymer, the repair pattern of the printed wiring board of the present invention can be improved. It can be conductive. As described above, the composition of the repaired wire breakage repairing portion contains a photosensitive resin (and / or a reaction product thereof) and a conductive polymer. In addition, an oxidizing agent comprising a polyvalent transition metal salt is used. In other words, the printed wiring board pattern correcting method according to the present invention is a method of forming a mixture layer containing an oxidizing agent composed of a photosensitive resin and a polyvalent transition metal salt at a pattern correcting portion, and patterning a corrosion-resistant image by a photochemical reaction method. Developing a corrosion-resistant image; and polymerizing a monomer of a conductive polymer to form a mixed composition with the photosensitive resin. According to the pattern correction method of the present invention, a lithography method using a photochemical reaction can be applied, so that a pattern with a circuit width of 50 μm or less used for a high-density printed wiring board can be corrected.

As described above, by implementing the present invention, a highly conductive correction pattern can be manufactured with high precision of 50 μm or less, and the pattern correction of a high-density printed wiring board can be reliably performed. In the present invention, the photosensitive resin is a resin capable of forming a corrosion-resistant image by a normal photochemical reaction method, and a resin obtained by a photochemical reaction method, and includes various negative photoresists, positive photoresists and dry film resists. However, a photosensitive resin containing an acrylic compound as a main component is preferable from the viewpoint of ease of production, and an acrylic compound having a urethane bond is particularly preferable. Among them, a linear alkylene group having 4 to 22 carbon atoms and a urethane are preferable. Acrylic compounds having a bond are preferred. The photosensitive resin of the present invention may contain at least a polyfunctional acrylate monomer or oligomer for the purpose of introducing a crosslinked structure into a part of the molecular structure.

Examples of such polyfunctional acrylate compounds include bifunctional acrylates such as ethylene glycol diacrylate and methacrylate compounds thereof.
Examples include polyfunctional acrylates such as trimethylolpropane triacrylate and their methacrylate compounds. In the present invention, if necessary, a material obtained by adding a polymerization initiator to a photocurable resin can be used instead of the photosensitive resin. Examples of the polymerization initiator include, for example, acetophenone compounds such as diethoxyacetophenone, benzoin compounds such as benzoin methyl ether and benzoin isobutyl ether, benzophenone compounds, and thioxanthone compounds.

In the present invention, the conductive polymer is a polymer itself which is a conductive polymer, and includes π-electron conjugated polymers such as polyacetylene and polyparaphenylene containing a dopant. From the viewpoints of easy formation of a complex with a resin and stability of a conductive state, those containing at least one of polypyrrole, polyethylenedioxythiophene, and polyaniline are preferable. In the correction method of the present invention, the polyvalent transition metal salt is Fe ²⁺ , C
U ²⁺ , Cr ⁶⁺ , Mn ⁷⁺ and Sn ⁴⁺ are salts having a cation as a cation. A method for forming a mixture layer containing an oxidizing agent composed of a photosensitive resin and a polyvalent transition metal salt includes dip coating. Conventional coating film forming methods such as a coater, a spin coater, a bar coater, and a roll coater can be used.

In the correction method of the present invention, the method of patterning a corrosion-resistant image by a photochemical reaction method on a mixture layer containing an oxidizing agent comprising a photosensitive resin and a polyvalent transition metal salt may be based on a normal photochemical reaction. If there is no particular limitation, visible light,
Irradiation with ultraviolet light, argon laser, Kr-F laser, or the like is performed. Further, in the correction method of the present invention, after irradiation with light, development is performed with various developing solutions corresponding to the photosensitive resin layer to form a predetermined pattern. In the correction method of the present invention, after the development, the conductive polymer is polymerized by contacting with the conductive polymer monomer, or after forming a corrosion-resistant pattern by a photochemical reaction method, the conductive polymer monomer is included. The development of the photosensitive resin and the polymerization of the conductive polymer can be simultaneously performed using an organic solvent. In the latter case, the organic solvent is not particularly limited, but alcohol solvents such as ethyl alcohol, butyl alcohol, and isopropyl alcohol are preferable because of the ease of polymerization reaction.

In the correction method of the present invention, after the conductive polymer is formed, doping is performed to increase the conductivity, and a new function such as heat resistance can be provided. As such a doping method, a molded body containing a conductive polymer is brought into contact with a gas such as iodine, immersed in a solution of various sulfonic acids, carboxylic acids, phosphoric acids, or the like, or oxidized with ferrous chloride or the like. For example, a method of immersing the composition in an agent solution. On this occasion,
The doping temperature, time, and the like are not particularly limited, and are appropriately selected depending on the material used.

In order to clarify the above and other objects, features and advantages of the present invention, the present invention will be described in further detail based on exemplary embodiments of the present invention with reference to the accompanying drawings. FIG. 1 shows the first stage of the correction. FIG. 1 (a) is a longitudinal sectional front view, FIG. 1 (b) is a plan view thereof, and FIG. 2 shows the second stage of the correction. ) Is its longitudinal front view, FIG.
3 (b) is a plan view thereof, FIG. 3 shows a corrected pattern, FIG. 3 (a) is a longitudinal front view thereof, and FIG. 3 (b) is a plan view thereof. The method for correcting a pattern of a printed wiring board according to the present invention is implemented by the method shown in FIGS. That is, a mixed layer containing an oxidizing agent comprising a photosensitive resin and a polyvalent transition metal salt is applied to a printed wiring board including a disconnection pattern 2 requiring pattern correction on a substrate 1 as shown in FIG. A photosensitive resin layer 3 is formed, and as shown in FIG. 2, a pattern is formed by a photochemical reaction method using a photomask 4, for example, irradiation with visible light or ultraviolet light to form a corrosion-resistant image 5. Next, as shown in FIG. 3, the corrosion-resistant image 5 is developed, a monomer of a conductive polymer is polymerized to form a correction pattern 6 formed of a molded product of a mixed composition of a photosensitive resin and a conductive polymer, Correct the pattern of the printed wiring board.

In the correction method according to the present invention, since a step of forming a pattern on the photosensitive resin layer by a photochemical reaction method is employed, a correction pattern of an arbitrary shape is formed with a photomask at a high density of about several μm. be able to. Further, in the present invention, since the molecule itself is not a particulate material such as carbon or metal powder but a conductive polymer itself as the conductive material of the correction pattern, the formation precision is substantially the same as the pattern formation of the photosensitive resin. It is possible to reduce to the accuracy. The thickness of the correction pattern is the thickness of the photosensitive resin layer and can be controlled. In the above description, the present invention has been described as a pattern correction method. However, the present invention can change a pattern resistance value by changing the type and concentration of an oxidizing agent. By using this, a substrate with a built-in resistor can be created. As described above, the present invention is not limited to the pattern correction technology of the above-described embodiments, and each embodiment can be appropriately changed within the scope of the technical idea of the present invention.

[0015]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 A urethane acrylate photosensitive resin (Nippon Kayaku) containing 50% by weight of an ethanol solution (concentration 80% by weight) in which ferrous dodecylbenzenesulfonate was dissolved on a printed wiring board requiring pattern correction. KAYARA, manufactured by Co., Ltd.
DUX-3204, hexamethylene diisocyanate) was added dropwise by heating to 60 ° C., a 25 μm resin layer was formed using a bar coater, and dried under reduced pressure at room temperature for 24 hours. Next, a photomask having a wiring width of 50 μm, which is the same as the disconnection shape, and having a 100 μm-long opening covering the disconnection portion is brought into close contact, and ultraviolet light is irradiated at an irradiation intensity of 5 mW / cm2 for 5 seconds to form a corrosion-resistant image. did. Then, the obtained base material was immersed in butyl alcohol to develop a corrosion-resistant image. Next, the obtained base material was immersed in methanol containing 5% by weight of pyrrole and reacted at room temperature for 6 hours to obtain a urethane acrylate-based photosensitive resin molded product on which conductive polypyrrole was formed. This molded product had a width of 50 μm and a length of 100 μm, and had a shape suitable for correcting a broken portion of a printed wiring board.

Example 2 A urethane acrylate photosensitive resin layer containing ferrous dodecylbenzenesulfonate was formed by the method of Example 1 to obtain a substrate on which a corrosion-resistant image was formed. This substrate was immersed in butyl alcohol containing 5% by weight of pyrrole,
The development of the corrosion-resistant image and the polymerization of polypyrrole were simultaneously carried out by holding for a period of one minute to obtain a urethane acrylate-based photosensitive resin molded product on which conductive polypyrrole was formed. This molded body had a width of 50 μm and a length of 100 μm, and had a shape suitable for correction of a broken portion of a printed wiring board.

Example 3 A urethane acrylate photosensitive resin layer was formed in the same manner as in Example 1 except that ferrous paratoluenesulfonate was used in place of ferrous dodecylbenzenesulfonate in the method of Example 1. Thus, a substrate on which a corrosion-resistant image was formed was obtained. This base material is immersed in isopropyl alcohol containing 5% by weight of pyrrole, and kept at room temperature for 15 minutes to simultaneously develop a corrosion-resistant image and polymerize polypyrrole to form a urethane acrylate-based photosensitive resin on which conductive polypyrrole is formed. I got a body. This molded product had a diameter of 50 μm and a length of 100 μm, and had a shape suitable for correcting a broken portion of a printed wiring board.

Example 4 According to the method of Example 1, a urethane acrylate-based photosensitive resin containing 50% by weight of an ethanol solution (concentration: 60% by weight) in which cuprous butyl naphthalenesulfonate was dissolved (manufactured by Nippon Kayaku Co., Ltd.) KAYARAD UX-3204) to 60
The mixture was heated and dropped at a temperature of 0 ° C. to form a 25 μm resin layer using a bar coater. Next, a width of 100 μm and a length of 100 μm
A photomask having an opening of m was adhered and irradiated with ultraviolet light at an irradiation intensity of 5 mW / cm2 for 5 seconds to obtain a substrate on which a corrosion-resistant image was formed. This base material is immersed in butyl alcohol containing 5% by weight of pyrrole, and held at room temperature for 30 minutes to simultaneously develop a corrosion-resistant image and polymerize polypyrrole, thereby forming an acrylate-based photosensitive resin molded article having conductive polypyrrole formed thereon. I got This molded product had a width of 50 μm and a length of 100 μm, and had a shape suitable for a correction pattern of a printed wiring board.

Example 5 A resin layer was prepared in the same manner as in Example 1 except that Alonix M-5700 manufactured by Toagosei Co., Ltd. was used in place of KAYARAD UX-3204 in Example 1 as the urethane acrylate resin. Was formed. Next, width 50
A photomask having an opening of 100 μm in length and having a thickness of 100 μm was adhered thereto, and irradiated with ultraviolet light at an irradiation intensity of 5 mW / cm 2 for 5 seconds to obtain a substrate on which a corrosion-resistant image was formed. This base material is immersed in butyl alcohol containing 5% by weight of pyrrole,
The development of the corrosion-resistant image and the polymerization of polypyrrole were carried out simultaneously at a room temperature for 30 minutes to obtain a urethane acrylate-based photosensitive resin molded product on which conductive polypyrrole was formed. This molded product had a width of 50 μm and a length of 100 μm, and had a shape suitable for a correction pattern of a printed wiring board.

Example 6 A substrate having a corrosion-resistant image formed by forming a urethane acrylate photosensitive resin layer containing ferrous dodecylbenzenesulfonate by the method of Example 1 was obtained. The substrate was immersed in butyl alcohol and kept at room temperature for 30 minutes to develop a corrosion-resistant image. Next, the obtained base material was immersed in methanol containing 5% by weight of aniline, and reacted at room temperature for 6 hours to obtain a urethane acrylate-based photosensitive resin molded product on which conductive polyaniline was formed. This molded product has a width of 50μ.
m, the length was 100 μm, and the shape was suitable for a correction pattern of a printed wiring board.

Example 7 A urethane acrylate photosensitive resin layer was formed in the same manner as in Example 1 except that ferrous paratoluenesulfonate was used in place of ferrous dodecylbenzenesulfonate in the method of Example 1. Thus, a substrate on which a corrosion-resistant image was formed was obtained. This base material is immersed in butyl alcohol containing 5% by weight of ethylenedioxythiophene, and kept at room temperature for 15 minutes to simultaneously develop a corrosion-resistant image and polymerize ethylenedioxythiophene to form conductive polyethylenedioxythiophene. The obtained urethane acrylate-based photosensitive resin molded product was obtained. This molded body is 50 μm in width and 100 μm in length,
The shape was suitable for the correction pattern of the printed wiring board.

[0023]

According to the present invention, the layer of the mixture of the photosensitive resin and / or the reaction product thereof and the conductive polymer is used to repair the defective portion of the disconnection pattern. Spatial repair can be performed by using a conductive polymer to restore electrical connection at a defective portion. On this occasion,
Since the formation of the conductive polymer is a selected part of the surface of the photosensitive resin, there is no problem that unnecessary resin or polymer is coated on the portion other than the broken portion unlike the related art. In particular, if a photomask is used, the required length and width can be repaired, so that the mixture layer can be present only in the defective portion of the disconnection pattern, and the remaining portion does not contain resin or polymer, Therefore, even if a recent high-density printed wiring board is broken, the broken pattern can be repaired without adversely affecting other elements. Further, by adjusting the amount of the conductive polymer, the correction pattern of the printed wiring board of the present invention can be made highly conductive.

[Brief description of the drawings]

1A and 1B show a first stage of correction, and FIG. 1A is a longitudinal sectional front view thereof, and FIG. 1B is a plan view thereof.

2A and 2B show a second stage of the correction, and FIG. 2A is a longitudinal sectional front view thereof, and FIG. 2B is a plan view thereof.

3 (a) is a longitudinal sectional front view of the corrected pattern, and FIG. 3 (b) is a plan view thereof.

[Explanation of symbols]

 Reference Signs List 1 base material 2 pattern 3 photosensitive resin layer 4 photomask 5 corrosion-resistant image 6 correction pattern

Claims (13)

(57) [Claims] 1. A correction pattern for a printed wiring board comprising a photosensitive resin and / or a mixed composition of a reaction product of the photosensitive resin and a conductive polymer. 2. The pattern for repairing a printed wiring board according to claim 1, wherein said photosensitive resin mainly comprises an acrylic compound. 3. The pattern for correcting a printed wiring board according to claim 2, wherein said acrylic compound has a urethane bond. 4. The method according to claim 1, wherein the acrylic compound has 4 or more carbon atoms and 2
3. The pattern for correcting a printed wiring board according to claim 2, wherein the pattern has two or less alkylene groups and a urethane bond. 5. The conductive polymer according to claim 1, wherein the conductive polymer contains at least one selected from the group consisting of polypyrrole, polyethylenedioxythiophene, and polyaniline. The pattern for correcting a printed wiring board described in Crab. 6. A step of forming a mixture layer containing an oxidizing agent comprising a photosensitive resin and a polyvalent transition metal salt on a printed wiring board on which pattern correction is performed, and selecting a part of the mixture layer by a photochemical reaction method. Forming a pattern of a corrosion-resistant image, a step of developing the corrosion-resistant image, and a step of polymerizing a monomer of a conductive polymer to form a mixed composition with the photosensitive resin. How to modify the board pattern. 7. The method according to claim 6, wherein the step of developing the corrosion-resistant image and the step of polymerizing the monomer of the conductive polymer are performed simultaneously using an organic solvent containing a monomer of the conductive polymer. The method for correcting the pattern of the printed wiring board described in the above. 8. The method according to claim 7, wherein the organic solvent mainly comprises an alcohol-based solvent. 9. The method according to claim 6, wherein the photosensitive resin contains an acrylic compound as a main component. 10. The method according to claim 9, wherein the acrylic compound has a urethane bond. 11. The method for correcting a pattern of a printed wiring board according to claim 9, wherein said acrylic compound has an alkylene group having 4 to 22 carbon atoms and a urethane bond. 12. The solution according to claim 6, wherein the solution containing the conductive polymer monomer is an alcohol solution containing at least one of pyrrole, ethylenedioxythiophene, and aniline. The method for correcting the pattern of the printed wiring board described in the above. 13. A mixture layer is formed on substantially the entire surface of a substrate of a printed wiring board, and thereafter the mixture layer is coated using a photomask while leaving a disconnection pattern portion, and a corrosion-resistant image is formed only on the disconnection pattern portion. 7. The print according to claim 6, wherein a pattern is formed and developed, and a monomer of a conductive polymer is polymerized in the corrosion resistant image to form a mixed composition of a photosensitive resin and a conductive polymer. How to correct the wiring board pattern.