JPS629690A - Conductive circuit board and improvement in conductivity thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a new conductive circuit board and a new method for improving its conductivity, and its purpose is to improve printed circuit boards, film connectors, and wiring boards. Alternatively, the aim is to produce substrates with precise conductive circuit patterns, such as those for sheet switches, and to provide them to the market as materials for industrial use, industrial use, daily necessities, and the like.

<Details of the structure of the invention> Conventionally, conductive circuit boards have been produced by printing methods, photoresist etching methods, masking vapor deposition methods, laser etching methods, chemical dissolution methods, etc.
Various difficulties arise in terms of accuracy, productivity, economic efficiency, and technical aspects, and when it comes to particularly complex or minute designs, no matter which known manufacturing method is used, it is difficult to achieve precision and beauty. The disadvantage is that it is difficult to consistently produce high-quality products. The present inventor has continued research for many years on a new method to solve this drawback, and has now finally completed the present invention, which should be eliminated.

That is, the present inventor has developed a process of closely adhering a non-hydrophobic polymer thin plate to the cut surface of a laminate in which conductive foil and polymer foil are superimposed so that the vertical or nearly vertical cut surface of the laminate forms a circuit pattern. , a step of installing an electrode facing the thin plate and filling the space between the thin plate and the electrode with a water-containing electrolyte containing a cyclic nitrogen-containing compound having a conjugated double bond; and a step between the conductive foil and the electrode. A conductive circuit board characterized in that it is prepared through the steps of applying electricity to electrolyze and forming a circuit pattern on the thin plate, and separating the thin plate on which the circuit pattern is formed from a cut surface and a water-containing electrolyte. In addition, the present invention has also invented a method for improving the conductivity of a conductive circuit board, which is characterized by bringing the conductive circuit board into contact with a plating solution and performing electroplating to deposit metal only on the circuit pattern.

Examples of laminates in which conductive foil and polymer foil are stacked so that the vertical or nearly vertical cut surfaces of the laminate form a circuit pattern, and where the conductive material is metal, are as follows: It will be included in 12 species such as.

(a) Metal foil and polymer foil are alternately layered and crimped.

(b) Metal foil and polymer foil are crimped and rolled.

A combination of the overlapping parts of (c) and (a) and the rolled part of (b) or a modified part thereof.

(d) A stack of polymer foils with metal adhered to them by vacuum deposition or sputtering.

(e) A roll of polymer foil with metal adhered to it by vacuum evaporation or sputtering.

A combination of the stacked parts of (f) and (d) with the rolled part of (e) or a modified part of this.

(g) A metal foil and a polymer foil in which metal is vacuum-deposited or sputtered and adhered to each other are laminated and pressure-bonded.

(H) Metal foil and polymer foil are coated with metal by vacuum evaporation or sputtering and then rolled.

A combination of the overlapping parts of (S) and (G) and the rolled part of (H) or a modified part thereof.

(N): Polymer foil and metal foil adhered to the polymer foil by vacuum evaporation or sputtering, which are laminated and crimped together.

(ru), Polymer foil and polymer foil with metal adhered by vacuum evaporation or sputtering and rolled.

A combination of the overlapping parts of (E) and (N) and the rolled part of (R) or a modified part thereof.

(A) to (E) are examples of laminated forms when the conductive foil material is metal, but conductive metal compound foils such as tin oxide films, indium oxide films, etc. may also be used, or metal foils may also be used. A suitable laminated form combining these metal compound foils may also be used.

The main materials for the above-mentioned conductive foil are platinum, gold, copper, silver, iron, nickel, stainless steel, titanium, aluminum, aluminum alloy, Nesa film, ITO film, etc. in film or foil form. In particular, materials that can withstand repeated practical use include platinum, gold, amorphous iron, nickel, titanium, and the like.

Regarding the manufacturing method of conductive foil, vacuum deposition method of conductive metal or metal compound, spuntering method, electrolysis method, rolling method, cutting method, casting method, printing coating method, spraying method, chemical reaction generation method There are other methods such as the machined plate method and the machined plate method.

When the above-mentioned laminate is cut at a vertical or near-vertical angle with surface pressure and the cut surface is viewed, it must be practically laminated so that the desired circuit pattern appears on the cut surface.
This cut surface is usually easy to form a smooth surface, but it is also possible to provide a slight height between the conductive foil and the polymer foil, and in reality, as described later, this may be more effective. many.

The above-mentioned cut surface may be obtained by actually cutting the laminate with a cutting blade, but on the other hand, each end of the foil is aligned and laminated as if it had been cut by a cutting blade, forming the same circuit pattern as the true cut surface. For example, if a slight height can be created between the conductive foil and the polymer foil, the height can be created by etching, heating, swelling, expansion, etc. after cutting with a cutting blade. However, in this case as well, the required height can be achieved by laminating the foils while taking into consideration a slight ingress and egress at the ends of each foil. It should be noted that one of the advantages of the present invention is that the above-mentioned cut surface can be made into various shapes such as a curved surface, an uneven surface, a wave surface, etc. in addition to a flat surface. It is possible to create conductive circuit boards with spherical or curved surfaces, something that would be impossible with other methods.

The polymer foils shown above are hydrophobic and must not particularly have affinity for the hydrous electrolyte used in the present invention, which will be described later. Typical examples thereof are as follows. be. That is, polyolefin, polystyrene, polybutadiene, polyisoprene, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, vinyl chloride copolymer, vinylidene chloride copolymer, vinylidene fluoride copolymer, selected from the group consisting of fluororesin, silicone resin, polyester, wax-impregnated paper, polyolefin-impregnated paper, synthetic fluororesin-impregnated paper, silicone resin-impregnated paper, polyamide, polyimide, polyether, polyether sulfone, polyether ester, and rubber. A membrane, film, sheet or plate based on at least one acid-resistant polymer or a composite thereof.

Among these, those that are easy to use industrially are polyethylene,
Polypropylene, polytetrafluoroethylene, polychlorotrifluoroethylene, polyethylene terephthalate, silicone rubber, etc. Economically, polyethylene, polypropylene, polyethylene terephthalate, °polytetrafluoroethylene, etc., as well as various water-resistant or solvent-resistant Certain composite resins are recommended.

Note that the cut surface of the laminate shown above contains air, gas,
Since the presence of dust or the like has a negative effect on subsequent processes, it is necessary to apply surface pressure to the laminate as tightly as possible under clean conditions. As the circuit pattern becomes more precise, care must be taken not to compress it firmly and cause failure in forming the fine line circuit pattern due to fluctuations. In this case, it is important to note that in order to make the circuit pattern into the desired shape, a thick metal plate or metal wire is inserted into the part of the cut surface mentioned above.
Also, if a thick polymer plate or spacer is inserted in a certain part, this thick metal plate or spacer may be inconvenient if other compression is too strong or too weak during long-term use. For example, in thick areas, high voltage is applied to thin lines, and low voltage that is thought to be caused by protrusion can cause unnecessary fluctuations in the circuit pattern or deformation of the cut surface. Therefore, it is necessary to carry out preliminary tests regarding compression when subjecting laminates to surface pressure, and how to assemble and form designs, to confirm the presence or absence of distortion at cut surfaces, and to ensure that the laminate is fixed.

Next, the process of bringing a non-hydrophobic polymer thin plate into close contact with the cut surface made based on the above considerations will be described. First, non-hydrophobic polymer thin plates include polyvinyl alcohol, polyvinyl acetal, polyvinyl alcohol ester,
Polyvinyl alcohol ether, copolymer having a vinyl alcohol structural moiety, polyvinylpyrrolidone, vinylpyridone copolymer, polyvinylpyridine, vinylpyridine copolymer, cellulose ester, cellulose ether, starch ester, starch ether, protein coagulate, Polyamide, chitinous coagulate, carbohydrate coagulate (carrageenan, alginic acid, glucomannan, galactomannan, pectin, cellulose or starch chemical products)
, a polyacrylic acid copolymer, a polymethacrylic acid copolymer, a polyacrylamide copolymer, a melamine resin, a urethane resin, a urea resin, and a phenolic resin. A membrane with
Either film, sheet or board.

The easiest way to adhere this non-hydrophobic polymer thin plate is to uniformly apply a solution, ink, or paint containing this non-hydrophobic polymer to the cut surface by printing, spraying, coating, etc., and then apply a solvent. At this time, there must be no air bubbles or foaming due to evaporation of the solvent, and on the other hand, adhesion to the cut surface of a separately made film or sheet must be ensured, if necessary. It should be carried out in a vacuum chamber, with very little solvent or adhesive present, at room temperature or under heat. In this case as well, contamination of air, gas, dust, etc. on the contact surface is related to a decline in the quality of the product, so care must be taken to ensure that these do not remain or enter incorrectly, and that even pressure is applied to the film or sheet. Even in this case, unnecessary internal distortion may be left in the film or sheet, or if the thickness is uneven, the conductive circuit pattern should be There is a strong possibility that the beautiful formation of the substrate will be hindered, so substrates that require uneven thickness should be built up in post-processing.

After the above steps are completed, it is next necessary to install an electrode facing the non-hydrophobic polymer thin plate. If this thin plate is flat, the counter electrode should be flat; if this thin plate is curved, the counter electrode should be a curved surface parallel to this; if the thin plate is semicylindrical, the counter electrode should be semicylindrical, cylindrical, or If the thin plate has a spherical surface, the counter electrode uses the spherical surface.

The thin plate and counter electrode are usually placed in a suitable electrolytic cell,
When the area of the thin plate becomes large, a spacer or the like is used to maintain a constant gap between the thin plate and the counter electrode. In any case, it is necessary to fill the thin plate counter electrode with a sufficient amount of water-containing electrolyte, and when using an electrolytic cell, it is sufficient to immerse it in the water-containing electrolyte. In such cases, it is necessary to completely insert and fill the gap between the two electrodes with a liquid or paste-like aqueous electrolyte, and then seal the sides of the gap using a backing or the like to prevent the aqueous electrolyte from leaking out from the sides of the gap. There is. The hydrous electrolyte used here refers to a liquid or paste-like aqueous electrolyte that also contains a cyclic nitrogen-containing compound having a conjugated double bond, and the use temperature of this aqueous electrolyte is preferably -20°C to +80°C. 11
Cyclic nitrogen-containing compounds having a conjugated double bond at 0°C to +60°C include aniline, substituted aliniline, naphthylamine,
substituted naphthylamine, aminoanthracene, substituted aminoanthracene, pyrrole, substituted pyrrole, pyrazole,
substituted pyrazole, imidazole, substituted imidazole, triazole, substituted triazole, pyridine, substituted pyridine, diazine, substituted diazine, triazine, substituted triazine, oxazine, substituted oxazine, benzopyrrole,
substituted benzopyrrole, benzthiazole, benzpyrazole, substituted benzpyrazole, benzimidazole, substituted benzimidazole, oxadiazole, thiadiazole, aminoazobenzene, substituted aminoazobenzene,
At least one compound selected from the group consisting of carbazole, substituted carbazole, quinoline, substituted quinoline, benzoxazole, and substituted benzoxazole.

The electrolyte salts contained in the aqueous electrolyte include perhalogenated acid, hydrofluoroboric acid, hexafluorophosphoric acid, hexafluoroarsenic acid, hexafluoroantimonic acid, trifluoroacetic acid, perfluorofatty acid, trifluoromethanesulfonic acid, and aromatic acid. an anion of at least one strong acid selected from the group consisting of sulfonic acids and fluorosulfonic acids; and a group consisting of lithium salts, sodium salts, ammonium salts, quaternary ammonium salts, silver salts, quaternary phosphonium salts and sulfonium salts. It is a salt in which at least one cation selected from the following is combined with a cation that constitutes the salt.

A hydrous electrolyte is an aqueous solution containing the salts mentioned above, and a mixture of water and an organic solvent to effectively dissolve the salts and the cyclic nitrogen-containing compound having a conjugated double bond to advance the electrolytic polymerization reaction. , a water-containing mixture to which a small amount of surfactant is added to effectively disperse a cyclic nitrogen-containing compound having a conjugated double bond in the liquid, or the electrical conductivity of these solutions;
This is a mixture in which a small amount of additives are dissolved in order to adjust the viscosity, the solution stability of the nitrogen compound, etc.

Organic solvents used as components of the aqueous electrolyte include halogenated hydrocarbons, nitrated hydrocarbons, oxygen-containing halogenated hydrocarbons, alcohols, glycols, polyols, glycol ethers, cyclic ethers, ketones, organic acids, acid amides, and lactones. , nitriles, carbonic esters, sulfoxides, sulfones, and inorganic oxygen-containing esters.

Among the above, economically used cyclic nitrogen-containing compounds having a conjugated double bond are aniline, pyrrole, methylpyrrole, vinylpyridine, etc., and the electrolyte is represented by the chemical formula 1iBF4, LiPFa, LiAsF.
, % Li5bFhsNaPFh% NaAsF, ,
AgBFa, L i C10a, RaNPF & , R
aNBFa, R4NC10s, L i 5OsFs
RaNAS Fh 5RaNSOsChHaR (where R is an alkyl group of 01 to C4), and the like.

Examples of organic solvents used in the present invention include methylene dichloride, ethylene chlorohydrin, chloral, nitromethane, nitroethane, nitropropane, trifluoroethanol, penzotrifluoride, hexafluoroacetone, pentafluoroacetone, O-dichloro Benzene, methanol, ethanol, propatool, isoproptool, butanol, isobutanol, secondary butanol, tertiary butanol, phenol, cresol, ethylene glycol, propylene glycol, butylene gellicol, hexylene glycol, glycerin, tetrahydrofuran, Butyrolactone, methyldioxolane, acetonitrile, propionitrile, benzonitrile, dimethylformaldehyde, dimethylacetamide, diethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, tetramethylenesulfoxide, tetramethylenesulfone, acetone, methylethylketone, acetyl Examples include azetone, propylene carbonate, butylene carbonate, glycol monomethyl ether, glycol dimethyl ether, dimethyl sulfate, etc. alone or in combination of two or more.

The water content in the hydrous electrolyte is not particularly limited, and is 1 to 10
0%, particularly preferably from 5 to 100%. In other words, the hydrous electrolyte referred to in the present invention is an aqueous solution of an electrolyte salt or an organic solvent added thereto. Alternatively, it may be used by dissolving it in an organic solvent.

For example, l, 1BF4・H, 0% L i B F,・3
H80, L 1PFi, HtOlLiAsFa・R20
, L i As F6・3 H*Os L i CI
Oa3 HtOlN a P F h・Hto, N
a CI Oa・Hlo, A g B F4・HzO2
They are AgBFn・AgHFt・5HtO.

Although the composition of the aqueous electrolyte of the present invention can be arbitrarily selected, there is of course a ratio that is easy to use. That is, cyclic nitrogen compound/electrolyte salt (
The molar ratio (in terms of anhydride) is 0.01 to 1.5010.02
~2.00, particularly preferably 0.05~1.0010.
Preliminary experiments revealed that the value is in the range of 0.03 to 1.5. Note that the lower the viscosity of the hydrous electrolyte, the easier it is to use, but depending on the conditions of use, it may be necessary to use it as a paste. In such cases, it may be necessary to cool it to an appropriate temperature or
It is best to mix an appropriate amount of a filler that is not related to the electrolytic reaction, that is, the polymerization reaction, such as an inert neutral salt or an insoluble compound, such as aerosil silica, aerosil alumina, carbon blank, etc., to a water-containing electrolyte and make it into a paste. - The opposing electrode material used in the present invention may be any metal, metal compound, or carbon, but as a result of testing by the present inventors, platinum, gold, palladium,
White gold, nickel, titanium, molybdenum, stainless steel, graphite, carbon fiber, etc. are excellent, and particularly useful electrodes are electrodes made of platinum, nickel, titanium, or graphite. The step of electrolyzing by applying current between the foil and the above electrode is performed using a DC voltage of 0.1 to 100 V, particularly preferably 1 to 30 V, and a current density of 0.1 to 50 mA/
Cm! , particularly preferably 1 to 20 mA/cm"
The electrolysis operation time is from several minutes to several hours.

The electrolysis operation time is the time it takes for a circuit pattern to be formed on a thin non-hydrophobic polymer plate, and if it takes 1 to 10 hours, a fairly thick and strong circuit pattern will be formed. A relatively short electrolysis operation (for example, 1 to 60 minutes) is sufficient to obtain a fine line pattern.

The process of forming a circuit pattern on a non-hydrophobic polymer thin plate is as follows:
As the electrolysis progresses, it starts from the surface of the thin plate in close contact with the conductive foil and progresses toward the inside of the thin plate as time passes. During this process, curved patterns often become patterns in which adjacent lines are glued together, so in such cases, the cut surface is not smooth as described above, and the conductive foil is cut slightly from the smooth surface. It is better to have a low wave-shaped cut surface. In this case, it is better to use fluororesin, silicone resin, or a composite resin containing these as the polymer foil. It is convenient to use fins made of polyester.

The electrolytic polymerization reaction used in the present invention is a reaction in which polymerization is initiated by a DC voltage of several V, which is the oxidation potential of a monomer. For example, in the case of forming polypyrrole from pyrrole, LiB Fa is used. A polymerization reaction proceeds at 1 to IOV using a water-containing electrolyte. The gap between the anode and cathode is not particularly limited, but is about 0.5 to 50 cm, and it is also desirable to moderately mechanically stir the aqueous electrolyte. Since the polymerization reaction occurs on the anode side, care must be taken with the material of the anode. However, the material of the cathode is not particularly limited. Taking electrolytic polymerization of polypyrrole or substituted polypyrrole as an example, even if the same voltage is applied to the electrode, the polymerization current will vary depending on the type of monomer, electrolyte salt, and solvent. It varies depending on the amount used. However, generally the polymerization efficiency is approximately 40-60%.

Now, in the electrolytic process of the present invention, the non-hydrophobic polymer thin plate side is used as an anode and the opposite electrode is used as a cathode, and a desired circuit pattern is formed on the anode side. In order to form a beautiful circuit pattern, the anode surface area / The ratio to the cathode surface area is 110.5 to 1.
If anything, it is better to increase the cathode area so that it is in the range of 0.0, especially l/1 to 3. In this electrolytic polymerization reaction, the polymer substance constituting the circuit pattern deposited on the anode side Some of the anions resulting from the dissociation of the electrolyte are incorporated as dopants, but the extent varies considerably depending on the conditions of each step shown above. However, the polymeric substances that make up the circuit patterns produced here are all doped, and are non-hydrophobic with zero-order circuit patterns that are guaranteed to have considerable electrical conductivity. After removing the hydrous electrolyte from the surface of the polymer thin plate and, if necessary, washing off the adhering aqueous electrolyte with water or an organic solvent, the thin plate is peeled off from the cut surface without tearing. After such separation operation, the thin plate is soaked in water or an organic solvent and washed to remove unnecessary substances, and then dried or left undried to become the product of the present invention.

The conductivity of the circuit pattern obtained here is σ-10-3
~10"S/am, but to further improve this, a suitable dopant (e.g. HzSOa
, 1g , AI C13, I nc13 , A S
It goes without saying that doping can be done using FB, Sb FS, etc.).

The conductive circuit board of the present invention prepared as described above can be used for various purposes as it is, or by surface coating with a resin liquid or laminating with a resin film.

Furthermore, the present inventor succeeded in improving the conductivity of the conductive circuit board by contacting the conductive circuit board prepared as described above with a plating solution and performing electroplating to deposit metal only on the circuit pattern. be.

In other words, the inventors have researched various methods for stabilizing the circuit pattern of the conductive circuit board so as to withstand long-term use and imparting excellent conductivity, and as a result, the most preferred method has been found. was discovered to be a method of electroplating circuit designs. The metal to be plated is not particularly limited, but the single metal used is AI, Cd 1
Cr s Co 1Au, In%Fe, PbXNi, P
t, Ag.

Among Sn, Zn, etc., the industrially important ones are Cu sA.
u%Ni, Pt, Ags Co and various alloys,
Preferably, it is a metal that is brightly plated. For copper plating, copper cyanide bath (e.g. CuCN26g/j, NaCN35
g/j, NatCOx 30g/Jl.

KNaCaHaOh-4HtO45g/l, pH12
,6), copper sulfate bath (e.g. CuSOa・5HtO
188g/j -HgSO474g/J), copper borofluoride bath [e.g. Cu(BFe) dew 224g/j,
HBFa 15g/j-HIBOs 15g/j! %p
H1,2~1.7), copper pyrophosphate bath (Cu”22
~38g/j, Pt0t---150~250g
/i NO3-5~10g/J, NHsl~3g/! ,
pH 8,2-8.8), etc. are used.

For gold plating, use a cyanide gold bath (e.g. Au4.Og/l, K
CN30g/l, KtHP 0430g/J 1K
zCOs 30 g/l, pH 11-11.5), etc. are used. For nickel plating, a mixed nickel salt bath (e.g. N1
5On・7H*0240~340g/IN i CIg
・6 HtO30~60g/1SHsBOs 30~
40g/j, pH2,4>, nickel borofluoride bath [eg N1(BFn)t 220g/j! , Ni5.
5g/g, HBF44g/i H2BO330g/j
! , pH 2.0 to 3.5], etc. are used. For silver plating, use a silver cyanide bath (e.g. AgCN 45 g/l, KCN
4g/II, KtCOs 15g/1, K
For tin plating, a tin borofluoride bath (e.g. Sn 40g/41SHBF44) is used.
0g/l, gelatin 2g/l, β-naphthol 0.5g
/Jri etc. are used.

All of the plating baths shown above are basic, and additives are actually added to complete bright plating. Further, one of the platings most suitable for the present invention is borofluoride bath plating, for example, solder alloy plating is S n "52
g/j! , PbI″30g/l, HBF4100~
200 g/II, HsBOs 25 g/i Peptone 5
．． ．． A bath containing Og/l was used, and the anode plate was S
It is done using an alloy of n/P b-60/40. Typical solder alloy bath (7-93 bath) regarding this
The percentage is 49.6% 5n (BFa) i liquid 11k
g, 51% Pb (BFJg liquid 121 kg, 49% HBF
a 76kg, HsBOs 7kg, peptone 0.2k
g, water 247 kg, operating conditions are cathode current density 20~30mA/cm'', 10~50℃
Electroplating can be done by gently stirring the bath.

In addition, copper plating is performed in layers to create a base for other plating, and by plating nickel or solder alloy again on top of it, the circuit pattern becomes extremely strong and its conductivity becomes extremely high. It will improve.

Of course, the substrate whose conductivity has been improved in this way may be further subjected to secondary processing or tertiary processing.

The present inventor conducted numerous experiments regarding the present invention described above and confirmed the novelty and superiority of the present invention. A few specific examples are extracted and shown below as Examples; therefore, the present invention should not be construed as being limited to the Examples shown below, without departing from the spirit and spirit of the present invention. It goes without saying that the embodiments may be modified and implemented as desired.

The excellence of the present invention will be made clearer by the following examples.

<Example> Example 1 50 layers of 1 mm thick polypropylene sheets and 0.5 mm thick two-layer plates were alternately laminated, and the top and bottom of this laminate were covered with thick unsaturated polyester resin glass cloth impregnated plates. Using scissors, bolts, and nuts, the cured product is pressed against the surface of the product so that the net thickness of the laminated portion is 68 to 72 mm to form a solid product. This laminated material is then cut at an angle perpendicular (90°) or nearly perpendicular (80°) to the lamination direction. The cut surface is buffed and polished with sandpaper, washed with acetone, and dried to make it completely clean. A paste-like aqueous solution of polyvinyl alcohol with a high degree of polymerization is applied to the cut surface in a clean room, and dry air is sent to remove moisture.
After forming a strong film of polyvinyl alcohol with a thickness of 0.4 mm, it is lightly sealed with a polypropylene net. The nickel plate of this laminate was used as an anode, and the nickel plate having an area slightly larger than the cross-sectional area of the mound was used as a cathode, which was placed facing the anode with a gap of about 3 cm. This is immersed in an electrolytic bath filled with aqueous electrolyte, degassed under reduced pressure, and then energized. The electrolyte is lithium borofluoride monohydrate 1i
0.2 mol of BFa HIO and 0.1 mol of pyrrole dissolved in 11% propylene carbonate at a temperature of -10%
It is kept at ℃. Current is 2■, 0.08mA/cm"
During the 12-hour operation, the polyvinyl alcohol film swells, and a circuit corresponding to the linear pattern of the nickel anode is formed on the side in contact with the cut surface, and this circuit gradually becomes stronger. is observed, so after the energization is finished, the electrodes are pulled up, immersed in acetone, washed and dried, and then the polyvinyl alcohol film is peeled off from the cut surface. On the peeled film substrate, a circuit pattern with a similar thickness was formed when cut perpendicular to the nickel linear surface on the cut surface.
Also, when cut at an angle close to vertical, a slightly thicker circuit pattern is formed. In any case, the circuit pattern made of polypyrrole obtained here exhibits a conductivity of 10 to 13 S/cm.

Example 2 A substrate having a circuit pattern made of polypyrrole with a goo of 10 to 13 S/cm obtained in Example 1 was used as a cathode, and S
An alloy of n/P b =60/40 was used as an anode (anode/
Solder alloy plating was performed as a cathode (2/1).

The borofluoride plating bath is 49.6%S n (BF*)t
60m1,51%P b (B F t)g 23m
l 149%HBF#54ml1. The cathode current density was 30 mA/cm" using a mixture of 240 ml of water and 240 ml of water.
, Electrolyze at 25-30°C. If oxidation of Sn occurs during electrolysis, add about 1 g of resorcinol per 12 parts of the electrolyte. Once the black circuit pattern part of the polypyrrole has been plated with solder alloy, finish the electroplating and add pure water. The substrate is cleaned using a nitrogen gas stream, dried in a nitrogen stream, and manufactured into a product. The circuit on the substrate obtained here is S n /
P b is close to 60/40 and close to the eutectic point mixture composition <14
It was tough at temperatures below 0°C and exhibited ρ-10-4 Ω·cm.

Example 3 The circuit board used in Example 2 was treated in a nickel acid fluoride bath (
100% HF43ml, basic nickel carbonate tetrahydrate 1
20g/j! , phosphoric acid 30g/It, sodium lauryl sulfate 1. When the circuit board is immersed in Ogzl) and electrolyzed at 50-60°C, electric density 50A/cm", and pH 3.0 while gently stirring the solution, a circuit board with a thin and uniform coating of nickel on the circuit pattern is formed. was obtained, and it was confirmed that the nickel-plated part had ρ=10-'Ω·cm.This material can be used for film connectors, etc.

Example 4 A number of films made of vacuum-deposited gold on polyethylene terephthalate are stacked one on top of the other, and then both ends are sandwiched between hard vinyl chloride resin plates and fixed by tightening with bolts and nuts. The vertical cut surface of this laminated film is cut using a lathe cutting tool, the surface is curved and smoothed by puffing, and then washed with methanol and dried. Next, a dimethylformamide solution of high molecular weight hydroxypropyl cellulose is applied to this curved cut surface and dried in a clean room to form a 0.2 mm thick hydroxypropyl cellulose film.

A curved nickel electrode was placed 3 cm away from this curved film, and then immersed in an electrolytic solution to form a gold anode.
2.5V, 0.5A/cm with nickel as cathode
Electrification was carried out at 0°C for 10 hours. The electrolytic solution was a mixture of 0.1 mol of β-methylpyrrole and 0.5 mol of silver borofluoride in a mixture of penzotrifluoride tertiary butanol and water (20:
0.2: 0.1) It has a composition dissolved in 1 g. After electrolysis is complete, the electrodes are lifted from the electrolytic bath, thoroughly washed by immersing them in a tertiary butanol/water temperature solution (1:1), and then the hydroxypropyl cellulose film is carefully cut into a curved surface without drying. Peel it off from the surface, place it on a curved rubber sponge, and dry it under reduced pressure. The curved film obtained here has a circuit pattern of the same type and number as the gold wire embedded in polyethylene terephthalate, which is made of conductive polyβ-methylpyrrole (σ=1O3/c
m) is reproduced. This method is an example of obtaining a curved circuit board.
If a cut surface is made using a laminate in which the film has been changed to a different laminate type, such as a spiral, a fingerprint, or a wavy laminate, and the same operation as above is performed, various types of laminates corresponding to the shape of the laminate and the shape of the cut surface can be made. A conductive circuit board having a circuit pattern is obtained.

Example 5 In Example 4, half of β-methylpyrrole was replaced with Ovirol and the same operation was performed to form a conductive circuit (σ”143/cm) of poly(β-methylpyrrole/pyrrole).
was gotten. Furthermore, by replacing β-methylpyrrole in Example 4 with various monomers and carrying out an electrolytic reaction, a circuit board with a pattern drawn with the corresponding polymer can be obtained. Type of monomer and resulting circuit diagram Example 6 Polytrifluorochloroethylene sheets with a thickness of 1 mm and stainless steel plates with a thickness of 0.5 mm were laminated alternately, and the same procedure as in Example 1 was carried out. Stick it to make a block. This block is cut perpendicular to the laminated surface, and the cross section is polished with sandpaper and a puff.A very small amount of benzonitrile is applied to this cut surface, parchment paper is placed on this, and the cross section is heated at 100℃. Dry with hot air and press with a roller to ensure complete adhesion. A polypropylene net is attached to this adhesive, and a counter cathode platinum plate is installed in the same manner as in Example 1, and deposited in an electrolytic solution. The electrolyte was 0.2 mol of benzimidazole and 0.2 mol of tetraethylammonium hexafluoroarsenate in acetonitrile lj containing 10% water.
5 moles were dissolved. Electricity is passed between the electrodes (2V, 3V
mA/cm”) and kept at room temperature for about 1 hour, a circuit diagram of polybenzimidazole (σ-0, OIS/
am) is formed in the same way as the cut surface electrode pattern. Here, the parchment paper was separated, thoroughly washed with acetonitrile, dried, and then laminated with a soft polyvinyl chloride film to obtain a flexible circuit board. This is useful as a low current film connector.

Example 7 In Example 6, a cellulose acetate film was used instead of parchment paper, and as an electrolyte, 0.1 mole of pyrrol and 0.1 mole of tetrabutylammonium hexafluorophosphate were added to acetonitrile IIl containing 2.5% water.
Electrolytic polymerization is carried out in the same manner using a solution of 2 moles. A substrate having a polypyrrole circuit pattern (0.53/cm) formed in a cellulose acetate film is obtained, which is separated, thoroughly washed with methanol, and then dried.

Example 8 The circuit board obtained in Example 7 was coated with CuCN44g/l,
Na CN 67 g/j! -Losocel salt 74g/1
, KOH11g/j! If the substrate is immersed in a copper cyanide solution and operated in the same manner as in Example 3 using a copper electrode, a substrate whose circuit pattern surface is plated with copper can be obtained. If this is further plated with nickel or alloy using a conventional method, it will become a circuit board with extremely strong chemical resistance and weather resistance.

Example 9 A casein aqueous solution was applied to the cut surface of the laminate used in Example 6, and after drying, an acidic aqueous solution of glyoxal was applied, air-dried at 50°C, and thoroughly washed with methanol to a thickness of about 10 μm.
Form a coagulated protein film of m.

Next, as in Example 6, a platinum counter electrode was set in a water-containing electrolyte. The hydrous electrolyte in this case is LiPFi.Hgo in methylene chloride saturated with water.

(CtHs) eNPF & and N-vinylcarbazole each dissolved to a concentration of 0.15N,
When electrolyzed at room temperature for 3 hours under the conditions of 2.5 V and 2 mA/cm'', a circuit pattern doped with P F &- of poly(N-vinylcarbazole) was formed on the protein film. Although the conductivity was rather poor at σ-10-'S/cm, a beautiful copper-clad circuit board could be obtained by copper plating in the same manner as in Example 8.

Examples 1O to 15 After forming the film material shown in the following table on the cut surface of the laminate used in Example 6 to a thickness of 9 to 13 μm by melt coating and drying, a platinum counter electrode was installed as shown in the table below. Set in an electrolyte aqueous solution containing components.

Next, the amines or amine salts shown in the following table were added to this aqueous solution, stirred thoroughly, and then energized in the same manner as in Example 9.
After electrolytic polymerization for a period of time, replace the electrolytic solution with water and rinse thoroughly with water.In this way, carefully wrap the membrane material on which the circuit pattern is formed using the conductive polymer shown in the following table with IF411M and apply it to the cathode. As, KCN100g/j! , K mushroom COs
55g/j, KNOz 80g/l, Ag 40g
/l (Immersed in a silver plating bath of 310g/l of NHthC,
When a silver plate was used as a counter electrode and silver plating was carried out at 30 to 40° C. by applying a current of 0.1 A/cm, a beautiful silver circuit pattern was formed on the membrane material after 1 to 2 hours.

The circuit pattern obtained here was plated with silver in the same manner as in Example 10, and when dried, a relatively strong glucomannan substrate was obtained.Acrylic paint was applied and impregnated to prevent discoloration of the silver circuit part. After drying with warm air, the film became a film connector with excellent weather resistance and mechanical properties. Instead of this acrylic resin paint, polyvinyl butyral
When a 100% phenolic resin paint was applied, a hot-melt type durable film connector was obtained.

<Effects of the Invention> The present invention relates to a conductive circuit board and a method for improving its conductivity, and clarifies a method for easily and mass producing conductive circuit boards useful as electrical and electronic materials ranging from industrial parts to daily necessities. The conductive circuit board obtained by the present invention may be a printed circuit board,
It can be used as film connectors, wiring boards, sheet switches, phases, sensors, high-density circuit boards, etc., and its industrial applicability is extremely large.

Claims (13)

[Claims] (1) A step of bringing a non-hydrophobic polymer thin plate into close contact with a cut surface of a laminate in which a conductive foil and a polymer foil are superimposed so that the vertical or nearly vertical cut surface of the laminate forms a circuit pattern; a step of installing an electrode facing the thin plate and the electrode and filling the space between the thin plate and the electrode with a water-containing electrolyte containing a cyclic nitrogen-containing compound having a conjugated double bond; and supplying current between the conductive foil and the electrode. A conductive circuit board characterized in that it is prepared through the steps of electrolyzing and forming a circuit pattern on the thin plate, and separating the thin plate on which the circuit pattern is formed from a cut surface and a hydrous electrolyte. (2) Conductive foil is a vacuum-deposited film, sputtering film, electrolytic foil, rolled foil, cut foil, cast foil, printed coating film, sprayed foil, chemical reaction product film, and mechanical processing of conductive metal or metal compound. 2. The conductive circuit board according to claim 1, wherein the conductive circuit board is at least one conductor selected from the group consisting of plates. (3) Polymer foil is polyolefin, polystyrene, polybutadiene, polyisoprene, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, vinyl chloride copolymer, vinylidene chloride copolymer, vinylidene fluoride Consisting of copolymers, fluororesins, silicone resins, polyesters, wax-impregnated paper, polyolefin-impregnated papers, fluororesin-impregnated papers, silicone resin-impregnated papers, polyamides, polyimides, polyethers, polyethersulfones, polyetheresters, and rubber. 2. The conductive circuit board according to claim 1, which is a membrane, film, sheet, or board based on at least one water-resistant polymer selected from the group consisting of water-resistant polymers or composites thereof. (4) The non-hydrophobic polymer thin plate is polyvinyl alcohol, polyvinyl acetal, polyvinyl alcohol ester,
Polyvinyl alcohol ether, copolymer having a vinyl alcohol structural moiety, polyvinylpyrrolidone, vinylpyridone copolymer, polyvinylpyridine, vinylpyridine copolymer, cellulose ester, cellulose ether, starch ester, starch ether, protein coagulate, chitinous coagulum, carbohydrate derivatives (carrageenan, alginic acid, glucomannan, galactomannan, pectin,
chemically processed products of cellulose or starch), polyacrylic acid copolymers, polymethacrylic acid copolymers, polyacrylamide copolymers, melamine resins, urea resins,
2. The conductive circuit board according to claim 1, which is a membrane, film, sheet, or board based on at least one polymer selected from the group consisting of urethane resin and phenol resin. (5) The cyclic nitrogen-containing compound having a conjugated double bond is aniline, substituted aliniline, naphthylamine, substituted naphthylamine, aminoanthracene, substituted aminoanthracene,
Pyrrole, substituted pyrrole, pyrazole, substituted pyrazole, imidazole, substituted imidazole, triazole, substituted triazole, pyridine, substituted pyridine, diazine,
substituted diazine, triazine, substituted triazine, oxazine, substituted oxazine, benzopyrrole, substituted benzopyrrole, benzthiazole, benzpyrazole, substituted benzpyrazole, benzimidazole, substituted benzimidazole, oxadiazole, thiadiazole, aminoazobenzene, substituted aminoazobenzene, carbazole,
The conductive circuit board according to claim 1, which is at least one compound selected from the group consisting of substituted carbazole, quinoline, substituted quinoline, benzoxazole, and substituted benzoxazole. (6) The aqueous electrolyte is perhalogenated acid, hydrofluoroboric acid, hexafluorophosphoric acid, hexafluoroarsenic acid, hexafluoroantimonic acid, trifluoroacetic acid, perfluorofatty acid, trifluoromethanesulfonic acid, aromatic sulfonic acid and at least one strong acid anion and lithium salt selected from the group consisting of fluorosulfonic acid;
An aqueous solution of a salt combined with a cation constituting at least one salt selected from the group consisting of sodium salts, ammonium salts, quaternary ammonium salts, silver salts, quaternary phosphonium salts, and sulfonium salts. The conductive circuit board according to claim 1, characterized in that: (7) A step of closely adhering a non-hydrophobic polymer thin plate to the cut surface of a laminate in which conductive foil and polymer foil are superimposed so that the vertical or nearly vertical cut surfaces of the laminate form a circuit pattern; a step of installing an electrode facing the thin plate and the electrode and filling the space between the thin plate and the electrode with a water-containing electrolyte containing a cyclic nitrogen-containing compound having a conjugated double bond; and supplying current between the conductive foil and the electrode. A conductive circuit board prepared through a process of electrolyzing to form a circuit pattern on the thin plate and a process of separating the thin plate with the circuit pattern formed from the cut surface and aqueous electrolyte is brought into contact with a plating solution to electroplating. A method for improving the conductivity of a conductive circuit board, characterized by depositing metal only on the circuit pattern. (8) The conductive foil is a vacuum-deposited film of a conductive metal or metal compound, a sputtered film, an electrolytic foil, a rolled foil, a cut foil, a cast foil, a printed coating film, a sprayed foil, a chemical reaction product film, and a machine. 8. The method for improving the conductivity of a conductive circuit board according to claim 7, wherein the conductor is at least one conductor selected from the group consisting of processed plates. (9) Polymer foil is polyolefin, polystyrene, polybutadiene, polyisoprene, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, vinyl chloride copolymer, vinylidene chloride copolymer, vinylidene fluoride Consisting of copolymers, fluororesins, silicone resins, polyesters, wax-impregnated paper, polyolefin-impregnated papers, fluororesin-impregnated papers, silicone resin-impregnated papers, polyamides, polyimides, polyethers, polyethersulfones, polyetheresters, and rubber. The electrical conductivity of the electrically conductive circuit board according to claim 7, characterized in that the electrically conductive circuit board is a membrane, film, sheet, or board based on at least one water-resistant polymer selected from the group consisting of: Improvement method. (10) The non-hydrophobic polymer thin plate is polyvinyl alcohol,
Polyvinyl acetal, polyvinyl alcohol ester, polyvinyl alcohol ether, copolymer with vinyl alcohol structural moiety, polyvinylpyrrolidone, vinylpyridone copolymer, polyvinylpyridine, vinylpyridine copolymer, cellulose ester, cellulose ether, starch ester, dendritic Powdered ether, protein coagulate,
Chitin coagulates, carbohydrate derivatives (carrageenan, alginic acid, glucomannan, galactomannan, pectin, cellulose or starch chemical products), polyacrylic acid copolymers, polymethacrylic acid copolymers, polyacrylamide copolymers Membranes and films based on at least one polymer selected from the group consisting of copolymers, melamine resins, urea resins, urethane resins, and phenol resins;
8. The method for improving the conductivity of a conductive circuit board according to claim 7, wherein the conductive circuit board is a sheet or a plate. (11) The cyclic nitrogen-containing compound having a conjugated double bond is aniline, substituted aliniline, naphthylamine, substituted naphthylamine, aminoanthracene, substituted aminoanthracene, pyrrole, substituted pyrrole, pyrazole, substituted pyrazole, imidazole, substituted imidazole, triazole,
Substituted triazole, pyridine, substituted pyridine, diazine, substituted diazine, triazine, substituted triazine, oxazine, substituted oxazine, benzopyrrole, substituted benzopyrrole, benzthiazole, benzpyrazole, substituted benzpyrazole, benzimidazole, substituted benzimidazole, oxadiazole , thiadiazole, aminoazobenzene, substituted aminoazobenzene, carbazole, substituted carbazole, quinoline, substituted quinoline, benzoxazole, and substituted benzoxazole. Method for improving the conductivity of a conductive circuit board as described in . (12) The aqueous electrolyte is perhalogenated acid, hydrofluoroboric acid, hexafluorophosphoric acid, hexafluoroarsenic acid,
An anion of at least one strong acid selected from the group consisting of hexafluoroantimonic acid, trifluoroacetic acid, perfluoro fatty acid, trifluoromethanesulfonic acid, aromatic sulfonic acid and fluorosulfonic acid and lithium salt, sodium salt, ammonium salt, A patent characterized in that it is an aqueous solution of a salt combined with a cation constituting at least one salt selected from the group consisting of quaternary ammonium salts, silver salts, quaternary phosphonium salts, and sulfonium salts. A method for improving the conductivity of a conductive circuit board according to claim 7. (13) The plating solution is a solution of a compound capable of electrochemically depositing at least one metal selected from the group consisting of nickel, cobalt, chromium, copper, silver, gold, platinum, tin, solder alloy, and cobalt-nickel alloy. A method for improving conductivity of a conductive circuit board according to claim 8, characterized in that: