JPH04211193A - Conductive circuit member, method for manufacturing conductive circuit member, conductive paste, and electronic equipment - 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]

[00011

[Industrial Application Field] The present invention provides a conductive paste and a conductive circuit suitable for printed circuit boards used in optical equipment such as cameras, office machines, audio products, OA equipment, home appliances, meters, communication equipment, etc. Regarding parts. [0002] Conventionally, as a method for forming a conductive circuit on an insulating substrate, vapor deposition, ion blasting, CVD, sputtering, etc. have been used in the in-phase-vapor phase system, and solid phase For a one-liquid phase system, a plating method, a metal solder method, a metal-oxide solder method, etc. are used, and for a solid phase-solid phase system, a DC voltage application method, a pressure bonding high temperature heating method, etc. are used. [0003] However, the conventional circuit forming method has the following drawbacks. [0004] First, as a method for forming a circuit, in the solid phase-vapor phase system, there are vapor deposition methods, sputtering methods, etc., but all of these methods require a vacuum device, and the device itself is not only expensive, but also expensive. The substrates that can be used are limited, and there are problems in terms of cost and mass production. Furthermore, since the circuit formation temperature is high, it can only be applied to heat-resistant substrates, which has its limitations. [00051] Next, in the solid phase-liquid phase system, a plating method, a metal solder method, or a metal-oxide mixed solder method may be mentioned. [0006] Since the L caulking plating method requires a plating thickness of at least 18 μm for the plating portion that becomes a pattern, it takes a long time to form a film, which poses problems in productivity and has a cost limit. In addition, in the soldering method, silver particles with a particle size of about 10 μm,
It is formed by mixing amorphous carbon, graphite powder, etc. with a binder such as phenol resin, epoxy resin, polyester resin, acrylic resin, etc., and then screen printing through a mask. However, in this printing method, the resolution of the printed pattern is very low.
At most, 150 μm is the limit, and in the current situation where the electronic equipment industry, typified by laptop computers, is rapidly becoming smaller, lighter, thinner, or using cards, this is the limit for responding to finer dimensions. Furthermore, there are many quality problems and reproducibility is lacking. For example, blurring, blurring, or missing print films, clogging of screen mask patterns, etc. are causes of quality deterioration. [0007] Further, due to variations in the conditions of the squeegee printing pressure and squeegee speed, the film thickness becomes non-uniform, lacks sharpness, and also lacks reproducibility, causing major problems in quality. [0008] Furthermore, the positional accuracy of the printed pattern is poor, and the curing of the coating film requires a high temperature of 150°C or more,
The occurrence of warpage, twisting, and dimensional defects in the substrate lowers the yield of surface connection mounting in the next process, which also poses a major cost problem and limits mass production. [0009] Furthermore, since the paste itself contains harmful organic solvents, there is a risk of contaminating the working environment or causing fire.

Next, in the solid phase-solid phase system, there is a high melting point metal method in the shell, but like the solid phase-vapor phase method, since a circuit is formed at high temperature, it also requires high melting point metal. It is limited to heat-resistant substrates, such as ceramic plates, and is still at its limit. [0011]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art.
Furthermore, it is an object of the present invention to provide a conductive circuit member with good conductivity. [00121] Another object of the present invention is to provide a method for manufacturing a conductive circuit member having an extremely fine circuit pattern with good positional accuracy. [0013] Another object of the present invention is to provide a conductive paste that has good conductivity and is used for forming fine pattern circuits. [0014] Another object of the present invention is to provide an electronic device that is small, lightweight, and free from defects in conductive circuits. [0015]

[Means for Solving the Problems] The conductive circuit member of the present invention has a conductive circuit formed in a pattern on an insulating base material, wherein the circuit contains conductive particles and a resin. It is characterized by being composed of an electrodeposited coating film. [0016] Furthermore, the method for manufacturing a conductive circuit member of the present invention includes:
In a method for manufacturing a conductive circuit member having a conductive circuit formed in a pattern on an insulating base material, the insulating base material is coated with a conductive paste containing an electrodepositable resin and conductive particles. It is characterized by performing electrodeposition by dipping a base material, selectively forming an electrodeposited film containing the electrodepositable resin and the conductive particles on the base material, and then performing a heat curing treatment. It is something to do. [0017] Furthermore, the conductive paste of the present invention is characterized in that it contains 3 to 50% by weight of an electrodepositable resin and 4 to 80% by weight of conductive particles. [00181 Furthermore, the electronic device of the present invention uses a conductive circuit member in which a conductive circuit having an electrodeposited coating film containing a resin and conductive particles is formed in a pattern on an insulating base material. It is characterized by: [00191] According to the present invention, since the resin and conductive particles are eutectoided only on the circuit pattern by electrodeposition to form an electrodeposited film, the film thickness is uniform and there is no bleeding or blurring of the circuit.
It is possible to obtain an excellent circuit board with no defects such as missing parts,
Further, since conductive particles are deposited at a high density in the electrodeposited film, electrical properties are further improved, and since a circuit pattern is formed by a photolithography process, a circuit board having extremely fine circuits can be obtained. [00201 Furthermore, since the present invention deposits resin and conductive particles by electrophoresis, it requires less energy than plating and can be formed in a shorter time, so it has a fine pattern and is conductive with excellent physical properties. This allows circuit members to be easily manufactured. [0021] The present invention will be described in detail below. [0022] FIGS. 1(a) to 1(e) are process diagrams showing an example of the method for manufacturing a conductive circuit member of the present invention. In FIG. 1, after performing catalyst treatment on an insulating base material 1 to form a catalyst layer 2, electroless plating is performed thereon to form an electroless plating layer 3.
(see FIG. 1(a)). [0023] Next, a photosensitive resin 4 is coated thereon,
Exposure is performed by irradiating light 7 through a pattern mask 8.
(b)), and a resist pattern corresponding to the circuit pattern is formed (see FIG. 1(C)). [0024] Next, the insulating substrate having this resist pattern is immersed in a conductive paste containing an electrodepositable resin and conductive particles, and an electrodeposited film 5 is formed on the plating layer exposed by electrophoresis. (See FIG. 1(d)) Next, the electrodeposited film 5 is cured by heating the whole substrate, and then the photosensitive resin 4 is peeled off, and the parts other than those on which the electrodeposited film 5 is formed are removed. By etching away the plating layer 3, a circuit 6 mainly consisting of the electrodeposited film 5 is formed.
has. The conductive circuit member 11 of the present invention can be obtained (see FIG. 1(e)). [0025] The circuit of the present invention is formed by the electrodeposited film 5, and since the electrodeposited film 5 is formed by eutectoiding conductive particles at high density together with the electrodepositable resin, even if it is a thin film, it is conductive. Moreover, since the circuit can be formed using a photolithography process, it is possible to form an extremely fine circuit with excellent positional accuracy. Furthermore, unlike conventional plating methods, it uses an electrodeposition process, so it can be formed at low voltage and can form a circuit with uniform thickness. [0026] In the present invention, the conductive particles to be eutectoided to the electrodeposited film are not particularly limited as long as they can impart conductivity to the electrodeposited film, but metal-plated powder on the surface of ceramic powder may be used. (hereinafter referred to as metallized ceramic powder),
Natural mica powder with metal plating on its surface (hereinafter referred to as metallized natural mica) is prepared by depositing an electrodeposited film at low temperatures, i.e. from 90°C to 10°C.
It is particularly suitable for use because it can be completely cured by heat treatment at 0°C. It is not clear why the electrodeposited films containing these powders harden at low temperatures, but metallized ceramic and metallized natural mica powders are hard particles, unlike ordinary metal particles whose surfaces are quickly oxidized. It is thought that this is because the surface is maintained in a stable state while being activated to some extent, so that the active surface becomes a crosslinking point during curing and promotes the curing of the electrodeposited film. [00271 The metallized natural mica or metallized ceramic powder used in the present invention is a powder whose surface is plated with metal such as Ag, Ni, Cu, Au, Sn, etc. . [0028] The average particle size of the ceramic powder and natural mica powder is 0.1 to 7 μm when considering the conductivity of the electrodeposited film and the dispersibility of the powder in the conductive paste.
, preferably 0. A range of 5 to 5 μm is preferred. [0029] The particle sizes of the ceramic powder and natural mica powder are values measured using a centrifugal sedimentation type particle size distribution analyzer. The instrument actually used for this measurement was 5ACP.
3 (manufactured by Shimadzu Corporation).

Ceramics used in the present invention include aluminum oxide, titanium nitride, manganese nitride, tungsten nitride, tungsten carbide, lanthanum nitride, aluminum silicate, molybdenum disulfide, titanium oxide,
Examples of natural mica include graphite and silicic acid, and examples of natural mica include phlogovite, sericite, and muscovite.

Next, nickel, copper, etc. can be suitably used for plating the ceramic powder or natural mica surface from the viewpoint of shielding properties, and electroless plating is preferred as the method for forming the ceramic surface. Also, the plating thickness on the powder surface is 0.
．． When the thickness is 0.05 to 3 μm, particularly 0.15 to 2 μm, good shielding properties and good coating film properties can be obtained during low-temperature curing. In other words, if the plating is formed thicker than 3 μm, the surface characteristics will be similar to those of metal particles, and the surface will be extremely active, so it will be oxidized in the air and the number of active sites that contribute to crosslinking will decrease, causing the electrodeposited film to deteriorate during low-temperature baking. Curing tends to be insufficient. [00321] Next, the content of conductive particles in the electrodeposited film that is the circuit of the conductive circuit member of the present invention is usually determined by considering the conductivity and the physical properties of the electrodeposited film, especially the adhesion to the base material. 2
0 to 80% by weight, especially 20 to 50% by weight, is heavy.

[0033] The metallized ceramic powder can be identified using an X-ray microanalyzer, and the content can be analyzed using a thermogravimetric analyzer, such as PerkinElmer's Thermal Analysis System 7 Series (trade name). It can be measured by [0034] In the present invention, both metallized ceramic and metallized natural mica may be contained in the electrodeposited film,
The mixing ratio of the metallized ceramic powder and the metallized mica powder is not particularly limited as long as the total content of both is within the range of the content of conductive particles in the electrodeposited film mentioned above. , a range of 1 to 2.5 (weight ratio) of metallized mica powder to 1 part of metallized ceramic powder is preferable. [0035] Further, in the present invention, in addition to the metallized ceramic powder and/or the metallized mica powder, ultrafine metal powder having an average particle size of 0.01 μm to 5 μm may be added to the electrodeposited film. . In this case, the ultrafine metal powder contained in the electrodepositable resin is not particularly limited, but for example, Ag, C
o, Cu, Fe, Mn, Ni, Pd, Sn, Te, etc. The particle size of ultrafine metal powder is usually an average particle size of 0.
．． The range is preferably 0.01 to 5 μm, preferably 0.02 to 5 μm, and more preferably 0.03 to 0.08 μm. If the diameter is less than 0.01 μm, secondary aggregation occurs;
If it exceeds m, it is not preferable due to sedimentation problems. [0036] Such ultrafine metal powder is also produced by a thermal plasma evaporation method. The mixing ratio of the ultrafine metal powder and the metal ceramic and/or metallized natural mica powder is 0.2 to 3. 0 range, especially 0. 3～
2.5, as shown in FIG. 3, the ultrafine metal powder 32 fills the gaps between the metallized ceramics and/or the metallized natural mica (31), increasing the contact area between each powder. Therefore, conductivity is further improved. However, if the mixing ratio of ultrafine metal powder is increased further, the content of metallized ceramic and/or metallized natural mica in the electrodeposited film will decrease relatively, and the contact area between the powders will decrease. On the contrary, the conductivity decreases, and furthermore, the physical properties of the coating film cannot be obtained during low-temperature curing. Furthermore, in order to achieve the conductivity required for a conductive circuit, such as a specific resistance (Ω cm) value of the order of 10-3, preferably of the order of 10-5, more ultrafine metal powder is required. It is necessary to contain powder, and the weight ratio of the ultrafine metal powder to the electrodepositable resin becomes extremely large, deteriorating the physical properties of the coating film such as adhesion to the substrate. [0037] Next, when adding ultrafine metal powder in the present invention, the surface is activated (
For example, it is preferable to remove the oxide film on the surface of the powder, etc.), or it is also effective to protect the surface of the ultrafine metal powder by treating it with a surfactant or the like. [0038] As the electrodepositable resin in the present invention, resins conventionally used for electrodeposition paints can be used,
For example, in the case of anionic electrodeposition paints, resins or prepolymers that have or have introduced anionic functional groups such as carboxyl groups are preferably used to provide the negative charge and hydrophilicity necessary for resin deposition. In the case of cationic electrodeposition paints, resins or prepolymers having or having introduced cationic functional groups such as amino groups are preferably used to impart positive charge and hydrophilicity. [0039]Specifically, acrylic resins, epoxy resins, polyester resins, polyamide resins, acrylic/melamine resins, alkyd resins, or prepolymers thereof having the above-mentioned anionic functional groups or cationic functional groups, as well as double molecules in molecules. A type of resin that hardens by a bonding reaction, specifically a polybutadiene resin, α, β, ethylenically unsaturated compounds, etc. can be used. [0040] The thickness of the electrodeposition coating is 7 to 20 μm.
A range of is preferred. [00411] Next, the method for manufacturing the circuit member of the present invention shown in FIG. 1 will be explained in detail. [0042] In the present invention, a resin material and an inorganic material are used for the insulating base material 1, and examples of the resin material include a film made of polyester, acrylic, polyamide, phenol, epoxy, or polyimide resin. Or you can use a board. Moreover, a ceramic plate is mentioned as an inorganic material. The resin base material is suitable for flexible printed circuits, multilayer printed circuit boards, etc., and the ceramic plate is suitable for hybrid IC boards, etc. [0043] On such an insulating base material, a catalyst treatment is performed using a known method, and then electroless plating is performed to form the plating layer 3. However, before this catalyst treatment, the adhesion to the insulating base material is In order to improve the surface roughness, it is desirable to roughen the surface appropriately. There are various methods for this, such as treatment with caustic soda, a mixture of chromic acid and sulfuric acid, or an organic solvent.
Alternatively, plastic processing, liquid homing treatment, etc. may be mentioned. Examples of the catalyst treatment include palladium treatment. [00441 Examples of electroless plating include gold, silver, palladium, nickel, copper, tin, zinc, etc., but copper is preferred because it has high conductivity, good adhesion of the electrodeposited film 6, and is low in cost. , and this plating layer 3 functions as an electrode during electrodeposition, and its film thickness is 0.1 μm.
The thickness is preferably 1 μm or more and 1 μm or less. If the thickness exceeds 1 μm, it will take a long time to form the film, and the subsequent peeling process will also take a long time. [0045] Next, this plating layer 3 is coated with a dry film, liquid resist, or the like made of a known photosensitive resin, preferably a negative or positive photosensitive resin having an aspect ratio of 1.5 or more. The thickness of the photosensitive resin 4 is appropriately selected depending on the required circuit density, circuit conductor thickness, and the like. Exposure of the pattern corresponding to the circuit pattern is
This can be carried out using a commonly known glass mask or film mask. Further, exposure is performed using an exposure machine that emits parallel light or scattered light. The amount of light at this time (m
J/cm2) and whether to use parallel light or scattered light is selected depending on the required circuit density. [00461] Next, regarding the phenomenon, it is carried out using a developer applied to a photosensitive resin. As the developer, for example, triethane is used for a solvent-type photosensitive resin, and a soda carbonate solution is used for a water-soluble photosensitive resin. [0047] Next, the base material on which the resist pattern corresponding to the above circuit pattern has been formed is immersed in a conductive paste and electrodeposited, and a conductive electrodeposited film 5 is formed on the exposed plating layer 3 by electrophoresis. form. [0048] This electrodeposition step may be performed by a generally known electrodeposition coating method. For example, in anionic electrodeposition coating, the object to be coated, that is, the substrate side is the anode, and in cationic electrodeposition coating, the substrate side is the anode. Film formation is performed using the side as a cathode and a stainless steel plate as a counter electrode, for example. The electrolysis conditions at this time include the concentration of conductive particles in the conductive paste used, and the characteristics required for the electrodeposited film (
Conductivity, coating film physical properties) Although it varies depending on the film thickness, the liquid temperature is usually 20
~27℃, pH 8.0~9.5, applied voltage 50~
200 cm and a processing time of 1 to 5 minutes. [0049] The reason why the resin and the conductive particles are precipitated together at this time is thought to be as follows. In other words, in a resin that can be electrodeposited, the functional groups bonded to the resin in the paint are ionized, and when a DC voltage is applied between the object to be coated and the counter electrode, the resin is drawn to the object and deposits. do. Since this resin is adsorbed around the conductive particles in the paste, as the resin moves to the object to be coated, the conductive particles also move and are deposited together with the resin on the object to be coated. [00501 Next, after forming an electrodeposited film, it is washed with water and subjected to heat treatment to harden the electrodeposited film. As for the curing temperature at this time, for example, metallized ceramic powder as the conductive particles,
When metallized natural mica or a mixture thereof is used, it can be sufficiently cured by curing in an oven at a low temperature of 90° C. to 100° C. for 20 to 180 minutes. Further, when ordinary metal powder is used, it is desirable to perform heat treatment at 120°C to 170°C. [0051] Thereafter, the photosensitive resin on the plating layer 3 is removed using a stripping liquid that can be applied to the photosensitive resin. In the case of a solvent type photosensitive resin, it is removed using, for example, methylene chloride or a special stripping solution, and in the case of a water-soluble type photosensitive resin, it is removed, for example, with a 1 to 5 wt % solution of caustic soda. Thereafter, the exposed plating layer 3 is removed using, for example, an ammonia alkaline copper solution or a ferric chloride solution in the case of copper, and a conductive circuit 6 is formed by the conductive electrodeposited film. A circuit member 11 can be obtained. [0052] As described above, according to the method for manufacturing a circuit member of the present invention, since the circuit pattern is produced by a photolithography process, the positional accuracy is excellent and the pattern is fine, for example, from 1 μm to several tens of μm.
A circuit board having a pattern with a pitch on the order of m can be easily manufactured. [0053] Next, the conductive paste used for manufacturing the conductive circuit member of the present invention will be explained. [0054] The conductive paste of the present invention is prepared by dispersing conductive particles and an electrodepositable resin in a ball mill for 24 to 35 hours, and then diluting with demineralized water to give a solid content concentration of 60 to 9.
It can be obtained by adjusting it to 0 wt%. [0055] When the content of conductive particles in the conductive paste is in the range of 4 to 80 wt%, preferably 7 to 70 wt%, the conductive particles are sufficient to impart a predetermined conductivity to the electrodeposited film. can be eutectoid, and the conductive particles in the paste will not sediment. [0056] Furthermore, when the content of the electrodepositable resin in the conductive paste is in the range of 3 to 50 wt%, especially in the range of 5 to 40 wt%, an electrodeposited film with good physical properties can be formed. . [0057] The conductive particles to be dispersed in the conductive paste include powders to be eutectoided with the resin on the electrodeposited film, such as the above-mentioned metallized ceramic powder, metallized natural mica powder, and mixtures thereof. is a metallized ceramic powder, a metallized natural mica powder, or a mixture thereof with an average particle size of 0.
．． Powder mixed with ultrafine metal powder of 01 to 5 μm can be used. [00581 FIGS. 2(a) to 2(e) are process diagrams showing another example of the method for manufacturing a conductive circuit member of the present invention. In FIG. 2, a catalyst layer 2 is formed on an insulating base material 1 by performing a catalyst treatment using a known method (see FIG. 2(a)). [00591 Then, photosensitive resin 4 is coated thereon,
Exposure is performed by irradiating light 7 through a pattern mask 8.
(see FIG. 2(b)), and is developed to form a resist pattern corresponding to the circuit pattern (see FIG. 2(c)). [0060] Thereafter, electroless plating is performed on the resist pattern to form an electroless plating layer 3, and a conductive paste film is further formed thereon by electrophoresis using the conductive paste 5 (see FIG. 2). d)). [0061] Next, a conductive circuit member can be obtained by peeling off the photosensitive resin 4 other than the circuit pattern portion (see FIG. 2(e)). [0062] In the method shown in FIG. 2, the conditions for each step shown in FIG. 1 can be applied. [0063] In this way, the present invention makes it possible to form fine circuits even on insulating or thin substrates with low heat resistance by applying the electrodeposition coating method to the production of conductive circuit members, for example as shown in FIG. Electronic components 42 such as ICs are mounted on a circuit board 11 having a circuit 6 made of an electrodeposited film 5 on a base material 1, and this board is further fixed to a housing 41 to produce a thin electronic device 43. can. Note that 44 is an electrode of an electronic component. [0064]

EXAMPLES The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to these Examples. [0065] Example 1-1 A PET (polyethylene terephthalate) film with a thickness of 50 μm was heated at 60° C. with 50 g/l of caustic soda.
Processed for minutes. Then 30 g/l of chromic anhydride;
After treatment with a 100 g/l sulfuric acid mixture at 50°C for 5 minutes, a catalyst solution (trade name H3-101B, manufactured by Hitachi Chemical) was added with
It was immersed for a minute and then catalyzed. Next, electroless copper plating solution (
(manufactured by Okuno Pharmaceutical Co., Ltd.) for 5 minutes at a pH of 13.0 and a bath temperature of 70°C to form a copper plating layer with a thickness of 0.2 μm. [0066] After that, using a 70 μm thick photosensitive dry film (manufactured by Hoechst), it was covered with a laminator (manufactured by Asahi Kasei), and then exposed to light at an exposure dose of 120 mJ/cm 2 using a film mask as a pattern mask, Spray development was performed with sodium carbonate Log/l to form a pattern corresponding to a circuit pattern with a width of 40 μm in the exposed portion of the plating layer and a width of 50 μm in the covered portion of the photosensitive layer. [0067] Next, 25 wt % of demineralized water, 5 wt % of melamine/acrylic resin (trade name Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.), and 0.2 μm nickel plating on the alumina surface with an average particle size of 1.0 μm were added. Powder applied to thickness 7
In a conductive paste in which 0wt% was dispersed, the substrate was used as an anode and a stainless steel plate (0.5t) was used as a counter electrode, and current was applied at 170V for 3 minutes at a bath temperature of 23°C and a pH of 8.5, and then washed with water. and cured in an oven at 95°C±1°C for 90 minutes. [0068] At this time, the film thickness was 25 μm, and the concentration of the metallized ceramic powder was 50 wt%. Next, the photosensitive resin was peeled off by immersing it in 50 g/l of caustic soda at 40° C. for 5 minutes. Next, using an ammonia alkaline copper solution, the exposed copper plating film was removed at 50° C. for 7 minutes to obtain a fine printed circuit board. [0069] In order to confirm the performance of this substrate, initial values and values after the environmental test were measured for specific resistance, surface resistance, and adhesion. The results are shown in Table 1. [00701] Also, as Comparative Example 1, values measured using a printed circuit member using a conventional organic solvent type conductive paste are shown. Further, the pitch between the circuits was 100 μm, and the circuit width was 100 μm. Regarding adhesion, JIS
100 squares were prepared according to the K5400 base mesh test, and the condition of the squares was observed after a peel test was performed using cellophane tape. [0071] Also, the measuring device used to measure specific resistance and surface resistance was a transcendental wire resistance measuring device (product name HP4329A; Yokogawa Co., Ltd.).
(manufactured by Huyuret Paracard Co., Ltd.) was used. The results are shown in Table 1-1. [0072]

[Table 1] Table 1-1 [0073] As a result of evaluating the characteristics of the circuit board of the present invention,
As shown in Table 1-1, it was recognized that there was a significant improvement compared to the conventional circuit board, and that the reproducibility was sufficient. [0074] In addition, the circuit of Comparative Example 1 partially has a printed film,
Bleeding occurs and short circuits occur between circuits at a circuit pitch of 100 μm, and it is difficult to produce patterns with a pitch finer than 100 μm by the printing method. [0075] Example 1-2 Using an alumina ceramic plate having a thickness of 0.4 mm, the surface was subjected to blast processing to the extent that the plate was not damaged. Then 30g
/l chromic anhydride and 100g/l sulfuric acid mixture, 5
After processing at 0°C for 5 minutes, the catalyst solution (product name H8-101
B, manufactured by Hitachi Chemical Co., Ltd.) for 2 minutes to perform catalyst treatment. Next, using an electroless copper plating solution (manufactured by Okuno Pharmaceutical Co., Ltd.), the pH
13.0, plated for 3 minutes at a bath temperature of 70°C, 0.1 μm
Copper plating is applied to the thickness of . [0076] Thereafter, a 3.5 μm thick photosensitive dry film (manufactured by Hoechst) was coated with a laminator (manufactured by Asahi Kasei), and then exposed at an exposure dose of 100 mJ/cm2 using a film mask as a pattern mask. Then, spray development was performed with sodium carbonate Log/L to form a resist pattern corresponding to a circuit pattern with a width of 30 μm in the exposed portion of the plating layer and a width of 40 μm in the covered portion of the photosensitive layer. [0077] Next, 55 wt % of demineralized water, 5 wt % of melamine/acrylic resin (trade name Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.), and 0.5 μm nickel plating on the alumina surface with an average particle size of 1.0 μm were added. Powder applied to thickness 4
In a conductive paste in which 0wt% was dispersed, the substrate was used as an anode and a stainless steel plate (0.5t) was used as a counter electrode, and current was applied at 180V for 3 minutes at a bath temperature of 23°C and a pH of 8.5, and then washed with water. and cured in an oven at 95°C±1°C for 90 minutes. At this time, the film thickness was 30 μm, and the concentration of metallized ceramic powder was 60 wt%. Next, the photosensitive resin was peeled off by immersing it in 50 g/l of caustic soda at 40° C. for 5 minutes. [0078] Next, using an ammonia alkaline copper solution, remove the exposed copper plating film at 50° C. for 7 minutes,
A fine printed circuit board was obtained. [0079] The characteristics of this circuit board were evaluated in the same manner as in Example 1-1. [00801 The results are shown in Table 1-2. [00811 Example 1-3 A polyimide film with a thickness of 18 μm was treated with 50 g/l of caustic soda at 60° C. for 5 minutes. Then 30g
/l chromic anhydride and 100g/l sulfuric acid mixture, 5
After processing at 0°C for 5 minutes, the catalyst solution (product name H8-101
B, manufactured by Hitachi Chemical Co., Ltd.) for 2 minutes to perform catalyst treatment. Next, using an electroless copper plating solution (manufactured by Okuno Pharmaceutical Co., Ltd.), the pH
13.0, plated for 3 minutes at a bath temperature of 70°C, 0.1 μm
Copper plating is applied to the thickness of . [0082] Thereafter, using a 50 μm thick photosensitive dry film (manufactured by Hoechst), it was covered with a laminator (manufactured by Asahi Kasei), and then exposed to light at an exposure dose of 90 mJ/cm 2 using a film mask as a pattern mask,
Spray development was performed with 10 g/l of sodium carbonate to form a pattern with a width of 35 μm in the exposed portion of the plating layer and 50 μm in width in the covered portion of the photosensitive layer. [0083] Next, 15 wt % of demineralized water, 5 wt % of melamine/acrylic resin (trade name Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.), and 0.2 μm nickel plating on the alumina surface with an average particle size of 1.0 μm were added. Powder applied to thickness 8
In a conductive paste in which 0wt% was dispersed, using the substrate as an anode and a stainless steel plate (0.5t) as a counter electrode, electricity was applied for 3 minutes at 170μ at a bath temperature of 23°C and a pH of 8.5, and then It was washed with water and cured in an oven at 95°C±1°C for 90 minutes. At this time, the film thickness was 25 μm, and the concentration of metallized ceramic powder was 50 wt%. Next, the photosensitive resin was peeled off by immersing it in 50 g/l of caustic soda at 40° C. for 5 minutes. Next, using an ammonia alkaline copper solution, the exposed copper plating film was removed at 50°C for 7 minutes,
A fine printed circuit board was obtained. [0084] The characteristics of this circuit board were evaluated in the same manner as in Example 1-1. [0085] Example 1-4 Using a beryllia ceramic plate with a thickness of 0.8 mm, blasting was performed to the extent that the surface was not damaged. Then 30g
/l chromic anhydride and 100g/l sulfuric acid mixture, 5
After processing at 0°C for 5 minutes, the catalyst solution (product name H8-101
B, manufactured by Hitachi Chemical Co., Ltd.) for 2 minutes to perform catalyst treatment. Next, using an electroless copper plating solution (manufactured by Okuno Pharmaceutical Co., Ltd.), the pH
13.0, plated for 5 minutes at a bath temperature of 70°C, 0.2 μm
Copper plating is applied to the thickness of . [0086] After that, negative resist (product name 0MR8
3, manufactured by Tokyo Ohka Co., Ltd.) 450 cp, and was formed to a thickness of 10 μm using a spinner. Next, through a glass chrome mask as a pattern mask, 80
Exposure with an exposure amount of mJ/cm", OMR-8
Developing was carried out for 1 minute using a special developer for 3 to form a pattern with a width of 25 μm in the exposed portion of the plating layer and a width of 30 μm in the covered portion of the photosensitive layer. [00871] Next, 67 wt% of demineralized water, 3 wt% of melamine/acrylic resin (trade name: Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.), and nickel plating with a thickness of 0.2 μm on the alumina surface with an average particle size of 1.0 μm. Powder 3 applied to
In a conductive paste in which 0wt% was dispersed, the substrate was used as an anode and a stainless steel plate (0.5t) was used as a counter electrode, and current was applied at 120V for 3 minutes at a bath temperature of 23°C and a pH of 8.5, and then washed with water. and cured in an oven at 95°C±1°C for 90 minutes. At this time, the film thickness was 18 μm, and the concentration of metallized ceramic powder was 30 wt%. Next, OMR
The photosensitive resin was peeled off by immersion in a special stripping solution at 40° C. for 5 minutes. [0088] Next, using an ammonia alkaline copper solution, remove the copper plating film on the exposed part at 50 ° C. for 7 minutes,
A fine printed circuit board was obtained. [0089] The characteristics of this circuit board were evaluated in the same manner as in Example 1. [00901 Example 1-5 A 50 μm thick PET (polyethylene terephthalate) film was heated at 60°C with 50 g/l of caustic soda.
Processed for minutes. Then 30 g/l of chromic anhydride;
After treatment with a 100 g/l sulfuric acid mixture at 50°C for 5 minutes, 2
It was immersed for a minute and then catalyzed. (00911) After that, a 70 μm thick photosensitive dry film (manufactured by Hoechst) was used to cover the film with a laminator (manufactured by Asahi Kasei), and then exposed to light at an exposure dose of 120 mJ/cm2 using a film mask as a pattern mask. Spray development was performed with 10 g/l of sodium to form a pattern with a width of 40 μm in the exposed part of the plating layer and 50 μm in width in the covered part of the photosensitive layer.
Plating was carried out for 2 minutes at pH 13.0 and bath temperature 70° C. to form copper plating with a thickness of 0.1 μm. [0093] Next, 15 wt% of demineralized water and 5 wt% of melamine/acrylic resin (trade name: Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.), nickel plating with a thickness of 0.2 μm was applied to the alumina surface with an average particle size of 1.0 μm. Powder 80 applied to
In a conductive paste with wt% dispersed, the substrate was used as an anode and a stainless steel plate (0.5t) was used as a counter electrode, and current was applied at 170V for 3 minutes at a bath temperature of 23°C and a pH of 8.5, and then washed with water. and cured in an oven at 95°C±1°C for 90 minutes. At this time, the film thickness was 25 μm, and the concentration of the metallized ceramic powder was 20 wt%. Next, the photosensitive resin was peeled off by immersing it in 50 g/l of caustic soda at 40° C. for 5 minutes. Next, using 10% hydrochloric acid, the palladium coating on the exposed portion of the catalyst was removed at 50° C. for 7 minutes to obtain a fine printed circuit board. [0094] The characteristics of this circuit board were evaluated in the same manner as in Example 1-1. [0095] Example 1-6 Example 1-1 except that a powder obtained by plating copper to a thickness of 2 μm on the surface of titanium oxide with an average particle size of 5 μm was used as the conductive particles in Example 1-1. Similarly, the powder concentration is 50wt.
% of the electrodeposited film was prepared and evaluated. [0096] Example 1-7 In Example 1-1, the average particle size was 0.5μ as the conductive particles.
The powder concentration was 55 wt in the same manner as in Example 1-1, except that powder of titanium oxide with a thickness of 2 μm and copper plating was used.
% of the electrodeposited film was prepared and evaluated. [0097] Example 1-8 Using the conductive paste of Example 1-1, the electrolytic conditions were 7.
A circuit board was fabricated and evaluated in which the metallized ceramic concentration in the electrodeposited film after curing was 25 wt % by mold-deposition at 0.0 mm for 3 minutes. [0098] Example 1-9 Using the conductive paste of Example 1-1, the electrolytic conditions were (
Electrodeposition was performed at 180) V for 4 minutes, and a circuit board was prepared and evaluated in which the concentration of metallized ceramic powder in the cured electrodeposited film was 75 wt %. [0099] Example 1-10 The conductive particles were carried out except that electrodeposition was carried out at 170 μm for 3 minutes using powder in which the surface of alumina with an average particle size of 1 μm was plated with nickel to a thickness of 0.06 μm. A circuit board was produced in the same manner as in Example 1-1, with the powder concentration in the electrodeposited film being 50 wt%.

Example 1-11 The resist patterned base material prepared in Example 1-1 was
Electroless gold plating was applied to the surface of alumina with 20 wt% demineralized water and an average particle size of 1 μm. Powder applied to a thickness of 2 μm, 5
0 wt% and melamine/acrylic resin 30 wt% (trade name: Honey Bright C-IL; manufactured by Honey Kasei Co., Ltd.) in a conductive paste in which powder concentration was 40 wt% in the same manner as in Example 1-1. A fine printed circuit board having an electrodeposited film was obtained. [01011 Reference Example 1 As a reference example, 25 wt% of demineralized water, 5 wt% of melamine/acrylic resin (trade name: Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.), nickel plating on the surface of alumina with an average particle size of 1.0 μm 70w of powder with 0.2μm
A circuit board that was electrodeposited on the base material of Example 1-1 at 50V for 2 minutes using the conductive paste dispersed in t%, so that the concentration of metallized ceramic in the cured electrodeposited film was 15wt%. It was created. [0102] Reference Example 2 25wt% of desalinated water, 5w of melamine-acrylic resin (trade name, Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.)
t%, nickel plating on the alumina surface with an average particle size of 1.0 μm. Using a conductive paste in which 70 wt% of powder applied to 2 μm was dispersed, 200 μm was applied to the base material of Example 1-1.
A circuit board was fabricated by mold-deposition for 2 minutes in (3), and the concentration of metallized ceramic in the cured electrodeposited film was 85 wt%. [0103] Reference Example 3 An electrodeposited film with a powder concentration of 50 wt% was prepared in the same manner as in Example 1-1 except that the copper plating layer on the surface of the alumina powder was 0.02 μm thick. A circuit board with the following was created. [0104] Reference Example 4 Nickel plating was applied to the surface of alumina having an average particle size of 0.07 μm as conductive particles. The powder concentration was 50w in the same manner as in Example 1-1 except that powder applied to a thickness of 2 μm was used.
A circuit board having an electrodeposited film of t% was produced. [0105] Reference Example 5 Powder concentration was 50 wt in the same manner as in Example 1-1, except that powder with an average particle size of 8 μm and alumina surface plated with nickel to a thickness of 0.2 μm was used as the conductive particles. % of the electrodeposited film was produced. [0106] The above Examples 1-2 to 1-11 and Reference Example 1
The circuit boards No. 5 to 5 were evaluated in the same manner as in Example 1-1. The results are shown in Table 1-2. [0107]

[0108] As shown in Table 1-2 above, according to the present invention, the physical properties of the circuit board were significantly improved and the reproducibility was sufficient. [0109] Also, regarding the results after the durability test, Example 1
The same results as in Example 1 were obtained.

Example 2-1 A base material having the resist pattern prepared in Example 1-1 was mixed with 35 wt% of demineralized water and 5 wt% of melamine/acrylic resin (trade name: Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.).
, 30wt% copper powder with an average particle size of 0.03 μm, and 0.0% nickel plating on the surface of alumina with an average particle size of 1.0 μm.
In a conductive paste containing 30 wt% of powder applied to a thickness of 2 μm, the substrate was used as an anode and a stainless steel plate (0.5 t) was used as a counter electrode. Electrify for 3 minutes at ■, then wash with water, 95℃±
Cured in an oven at 1° C. for 90 minutes. At this time, the film thickness was 25 μm, and the concentration of the powder mixture was 50 wt%. Next, the photosensitive resin was peeled off by immersing it in 50 g/l of caustic soda at 40° C. for 5 minutes. Next, using an ammonia alkaline copper solution, the exposed copper plating film was removed at 50° C. for 7 minutes to obtain a fine printed circuit board. [0111] This circuit board was evaluated in the same manner as in Example 1-1. [0112] Example 2-2 A substrate having the resist pattern created in Example 1-2 was mixed with 25 wt% of demineralized water and 5 wt% of melamine/acrylic resin (trade name: Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.).
, 40 wt% nickel powder with an average particle size of 0.03 μm,
In a conductive paste in which 30 wt% of powder made of alumina with an average particle size of 1.0 μm and nickel plated to a thickness of 0.5 μm is dispersed, the substrate was used as an anode and a stainless steel plate (0.5 t) was used as a counter electrode. using a bath temperature of 23°C, pH 8,
Under conditions 5, energize at 180μ for 3 minutes, then wash with water,
It was cured in an oven at 95°C±1°C for 90 minutes. At this time, the film thickness was 30 μm, and the concentration of the powder mixture was 60 wt%. Next, 50 g/l of caustic soda was added at 40°C.
The photosensitive resin was peeled off by dipping for a minute. Next, using an ammonia alkaline copper solution, the exposed copper plating film was removed at 50° C. for 7 minutes to obtain a fine printed circuit board. [0113] Example 2-3 35wt% of demineralized water and 5wt of melamine/acrylic resin (trade name: Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.) were added to the base material with the resist pattern created in Example 1-3.
%, 30 wt% copper powder with an average particle size of 0.03 μm, 0 nickel plating on the alumina surface with an average particle size of 1.0 μm.
．． The powder applied to a thickness of 2 μm was used as an anode in a conductive paste containing 30 wt% dispersed, and a stainless steel plate (
0.5t), energized at 170V for 3 minutes at a bath temperature of 23°C and pH of 8.5, then washed with water and heated to 95°C ± 1°C.
Cured in an oven for 90 minutes. At this time, the film thickness is 2
5 μm, and the concentration of the powder mixture was 50 wt%. Next, the photosensitive resin was peeled off by immersing it in 50 g/l of caustic soda at 40° C. for 5 minutes. Next, using an ammonia alkaline copper solution, the exposed copper plating film was removed at 50° C. for 7 minutes to obtain a fine printed circuit board. [0114] Example 2-4 27 wt % of demineralized water and 3 wt % of melamine/acrylic resin (trade name Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.) were added to the resist patterned base material prepared in Example 1-4.
%, 50 wt% silver powder with an average particle size of 0.07 μm, 0 nickel plating on the alumina surface with an average particle size of 1.0 μm.
．． In a conductive paste containing 20 wt% of powder applied to a thickness of 2 μm, the substrate was used as an anode and a stainless steel plate (0.5 t) was used as a counter electrode, at a bath temperature of 23°C and a pH of 8.5. Electrify at 120V for 3 minutes, then wash with water,
Cured for 90 minutes in an oven at ±1°C. At this time,
The film thickness was 18 μm, and the concentration of the powder mixture was 30 wt%. Next, the photosensitive resin was peeled off by immersing it in a stripping solution exclusively for OMR at 40° C. for 5 minutes. Next, using an ammonia alkaline copper solution, the exposed copper plating film was removed at 50° C. for 7 minutes to obtain a fine printed circuit board. [0115] Example 2-5 The resist patterned base material used in Example 1-5 was mixed with 35 wt% demineralized water, 5 wt% melamine acrylic resin (trade name Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.), average The substrate was immersed in a conductive paste containing 30 wt% of copper powder with a particle size of 0.03 μm and 30 wt% of alumina powder with a 0.2 μm thickness of nickel plating on the surface of alumina with an average particle size of 1°0 μm. Using the material side as the anode and a stainless steel plate (0.5t) as the counter electrode, the bath temperature was 23℃, the pH was 8,
Under conditions 5, energize at 170μ for 3 minutes, then wash with water,
It was cured in an oven at 95°C±1°C for 90 minutes. At this time, the film thickness was 25 μm, and the concentration of the powder mixture was 50 wt%. Next, 50 g/l of caustic soda was added at 40°C.
The photosensitive resin was peeled off by dipping for a minute. Next, using 10% hydrochloric acid, the palladium coating on the exposed portion of the catalyst was removed at 50° C. for 7 minutes to obtain a fine printed circuit board. [0116] The circuit boards obtained in Examples 2-1 to 2-5 above were evaluated in the same manner as in Example 1-1. The results are shown in Table 2. [0117]

[Table 3] [0118] Example 3-1 A base material having the resist pattern created in Example 1-1 was mixed with 65 wt% of demineralized water and a melamine/acrylic resin (trade name: Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.). )5wt%
, 30wt powder of natural mica with an average particle size of 2.0μm and electroless nickel plating applied to a thickness of 0.2μm.
% dispersed in a conductive paste, the substrate was used as an anode, and a stainless steel plate (0.5t) was used as a counter electrode.
C. and pH 8.5, electricity was applied for 3 minutes at 170 .ANG., then washed with water, and cured in an oven at 95.degree. C.±1.degree. C. for 90 minutes. At this time, the film thickness was 25 μm, and the powder concentration was 50 W.
It was t%. Then, add 40 g/l of caustic soda to 50 g/l.
℃ for 5 minutes, and the photosensitive resin was peeled off. Next, using an ammonia alkaline copper solution, the exposed copper plating film was removed at 50° C. for 7 minutes to obtain a fine printed circuit board. [0119] In order to confirm the performance of this substrate, initial values and values after the environmental test were measured for specific resistance, surface resistance, and adhesion in the same manner as in Example 1-1. The results are shown in Table 3.

Example 3-2 As a conductive paste, 45 wt% of demineralized water and melamine
Acrylic resin (trade name: Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.) 5 wt%, powder with an average particle size of 1.0 μm and electroless nickel plating applied to a 0.2 μm thickness on the alumina surface, and an average of 30 wt% The same method as Example 3-1 was used, except that a conductive paste containing 20 wt% of powder, which was electroless nickel plated to a thickness of 0.2 μm on the surface of natural mica with a particle size of 2.0 μm, was used. A fine printed circuit board having an electrodeposited film having a powder mixture concentration of 50 wt % was manufactured using the above method.

Example 3-3 As a conductive paste, 15 wt% of demineralized water and melamine.
Electroless nickel plating was applied to the surface of 5 wt% acrylic resin (trade name Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.), 30 wt% copper powder with an average particle size of 0.03 μm, and natural mica with an average particle size of 2.0 μm. An electrodeposited film having a powder mixture concentration of 50 wt% was prepared in the same manner as in Example 3-1, except that a conductive paste in which 50 wt% of powder was dispersed was applied to a thickness of 0.2 μm. , a fine printed circuit board was fabricated. [0122] Example 3-4 As a conductive paste, 35 wt% of demineralized water, melamine
Electroless nickel plating was applied to the surface of 5 wt% acrylic resin (trade name Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.), 30 wt% copper powder with an average particle size of 0.03 μm, and alumina with an average particle size of 1.0 μm. Except for using a conductive paste in which 10 wt% of powder was dispersed and applied to a thickness of 2 μm.
A fine printed circuit board having an electrodeposited film having a powder mixture concentration of 53 wt % was produced by the same method as in Example 3-1. [0123] Example 3-5 The base material having the resist pattern created in Example 1-2 was mixed with 65 wt% of demineralized water and 5 wt% of melamine/acrylic resin (trade name: Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.).
, 30w powder made of natural mica with an average particle size of 1.5 μm and electroless nickel plating applied to a thickness of 0.05 μm.
The substrate is used as an anode in a conductive paste in which t% is dispersed,
Using a stainless steel plate (0.5t) as a counter electrode, a bath temperature of 2
Electrify at 180V for 3 minutes at 3°C and pH 8.5.
Thereafter, it was washed with water and cured in an oven at 95° C.±1° C. for 90 minutes. At this time, the film thickness was 30 μm and the powder concentration was 60 μm.
It was wt%. The photosensitive resin was peeled off by immersing it in 50 g/l of soda at 40°C for 5 minutes. Next, using an ammonia alkaline copper solution, the exposed copper plating film was removed at 50° C. for 7 minutes to obtain a fine printed circuit board. [0124] Example 3-6 As a conductive paste, 35 wt% of demineralized water, melamine.
Acrylic resin (trade name: Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.) 5 wt%, powder with an average particle size of 1.0 μm and electroless nickel plating applied to a 0.5 μm thickness on the alumina surface, and an average of 20 wt% The same method as Example 3-5 was used, except that a conductive paste containing 40 wt% of powder, which was electroless nickel plated to a thickness of 0.05 μm on the surface of natural mica with a particle size of 1.5 μm, was used. A fine printed circuit board having an electrodeposited film with a powder mixture concentration of 60 wt % was manufactured by this method. [0125] Example 3-7 As a conductive paste, 25 wt% of demineralized water, melamine.
Electroless nickel plating on the surface of 5 wt% acrylic resin (trade name Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.), 30 wt% nickel powder with an average particle size of 0.03 μm, and natural mica with an average particle size of 1.5 μm. 0.05μm
By the same method as in Example 3-5, except for using a conductive paste in which 40 wt% of powder was dispersed and applied to a thickness of
A fine printed circuit board having an electrodeposited film with a powder mixture concentration of 60 wt% was produced. [0126] Example 3-8 As a conductive paste, 25 wt% of demineralized water, melamine.
Electroless nickel plating was applied to the surface of 5 wt% acrylic resin (trade name Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.), 40 wt% nickel powder with an average particle size of 0.03 μm, and alumina with an average particle size of 1.0 μm. A conductive paste was used in which 10 wt% of powder was applied to a thickness of 5 μm and 20 wt% of powder was electroless nickel plated to a thickness of 0.05 μm on the surface of natural mica with an average particle size of 1.5 μm. A fine printed circuit board having an electrodeposited film having a mixed powder content of 60 wt % was produced in the same manner as in Example 3-5, except that the mixed powder content was 60 wt %. [0127] Example 3-9 The base material having the resist pattern created in Example 1-3 was mixed with 35 wt% of demineralized water and 5 wt% of melamine/acrylic resin (trade name: Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.).
In a conductive paste containing 60 wt% of powder, which is made by applying electroless nickel plating to a thickness of 0.2 μm on the surface of natural mica with an average particle size of 2 μm, the substrate was used as an anode, and a stainless steel plate (0, 5t), bath temperature 23℃,
Under the condition of pH 8.5, electricity was applied at 170 μm for 3 minutes, then washed with water, and cured in an oven at 95° C.±1° C. for 90 minutes. At this time, the film thickness was 25 μm, and the powder concentration was 50 wt%.
Met. [0128] Then add 50 g/l of caustic soda at 40°C.
, and the photosensitive resin was peeled off by immersion for 5 minutes. Next, using an ammonia alkaline copper solution, the exposed copper plating film was removed at 50° C. for 7 minutes to obtain a fine printed circuit board. [0129] Example 3-10 As a conductive paste, 35 wt% of demineralized water, melamine
Acrylic resin (trade name Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.) 5 wt%, powder with an average particle size of 1.0 μm and electroless nickel plating applied to the alumina surface to a thickness of 0.2 μm, 30 wt%, and an average of 30 wt%. The same method as in Example 3-9 was used, except that a conductive paste containing 30 wt% of powder, which was electroless nickel plated to a thickness of 0.2 μm on the surface of natural mica with a particle size of 2 μm, was used. A fine printed circuit board having an electrodeposited film with a mixed powder concentration of 50 wt % was produced. [01301 Example 3-11 As a conductive paste, 50 wt% of demineralized water, melamine
Electroless nickel plating was applied to the surface of 5 wt% acrylic resin (trade name Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.), 20 wt% copper powder with an average particle size of 0.03 μm, and natural mica with an average particle size of 2 μm. Except for using a conductive paste in which 25 wt% of powder was dispersed and applied to a thickness of 2 μm.
By the same method as in Example 3-9, the concentration of the mixed powder was 5.
A fine printed circuit board having an electrodeposited film of 1 wt % was produced. [0131] Example 3-12 As a conductive paste, 10 wt% of demineralized water, melamine.
Electroless nickel plating was applied to the surface of 5 wt% acrylic resin (trade name Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.), 20 wt% copper powder with an average particle size of 0.03 μm, and alumina with an average particle size of 1.0 μm. Other than using a conductive paste containing 30 wt% of powder applied to a thickness of 2 μm and 35 wt% of powder applied to a natural mica surface with an average particle size of 2 μm and electroless nickel plating applied to a thickness of 0.2 μm. produced a fine printed circuit board having an electrodeposited film containing 50 wt % of mixed powder by the same method as in Example 3-9. [0132] Example 3-13 The resist patterned substrate prepared in Example 1-4 was mixed with 37 wt% of demineralized water, 3 wt% of melamine/acrylic resin (trade name: Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.), and average particles. In a conductive paste containing 60 wt% of powder, which is made by applying electroless nickel plating to a thickness of 0.05 μm on the surface of natural mica with a diameter of 2 μm, the substrate was used as an anode, and a stainless steel plate (0.5 t) was used as a counter electrode. using a bath temperature of 23°C and a pH of
Under the conditions of No. 8.5, electricity was applied for 3 minutes at 120 μm, then washed with water, and cured in an oven at 95° C.±1° C. for 90 minutes. At this time, the film thickness was 18 μm and the powder concentration was 30 wt%. Next, the photosensitive resin was peeled off by immersing it in a stripping solution exclusively for OMR at 40° C. for 5 minutes. Next, using an ammonia alkaline copper solution, the exposed copper plating film was removed at 50° C. for 7 minutes to obtain a fine printed circuit board. [0133] Example 3-14 As a conductive paste, 27 wt% of demineralized water, melamine.
Acrylic resin (trade name: Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.) 3 wt%, 20 wt% powder with electroless nickel plating applied to the alumina surface with an average particle size of 1.0 μm to a thickness of 0.2 μm, and an average of 20 wt% The same method as Example 3-13 was used, except that a conductive paste containing 50 wt% of powder, which was electroless nickel plated to a thickness of 0.05 μm on the surface of natural mica with a particle size of 2 μm, was used. A fine printed circuit board having an electrodeposited film having a mixed powder concentration of 30 wt % was produced. [0134] Example 3-15 As a conductive paste, 27 wt% of demineralized water, melamine.
Electroless nickel plating was applied to the surface of 3 wt% acrylic resin (trade name Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.), 40 wt% silver powder with an average particle size of 0.07 μm, and natural mica with an average particle size of 2 μm. A fine print having an electrodeposited film with a mixed powder concentration of 30 wt% was produced in the same manner as in Example 3-13, except that a conductive paste in which 30 wt% of powder was dispersed was applied to a thickness of 0.05 μm. Created a circuit board. [0135] Example 3-16 As a conductive paste, 27 wt% of demineralized water, melamine.
Electroless nickel plating was applied to the surface of 3 wt% acrylic resin (trade name Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.), 40 wt% silver powder with an average particle size of 0.07 μm, and alumina with an average particle size of 1.0 μm. Other than using a conductive paste containing 20 wt% of powder applied to a thickness of 2 μm and 10 wt% of powder applied to a natural mica surface with an average particle size of 2 μm and electroless nickel plating applied to a thickness of 0.05 μm. produced a fine printed circuit board having an electrodeposited film with a mixed powder concentration of 30% by the same method as in Example 3-13. [0136] Example 3-17 The resist patterned substrate coated with copper plating prepared in Example 1-5 was treated with 35 wt% of demineralized water and melamine/acrylic resin (trade name: Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.). ) 5wt%, the surface of natural mica with an average particle size of 1.0μm is electroless copper plated to a thickness of 0.1μm in a conductive paste in which 60wt% of powder is dispersed, the substrate is used as an anode, and the substrate is used as a counter electrode. Using a stainless steel plate (0.5t),
Under the conditions of a bath temperature of 23°C and a pH of 8.5, electricity was applied at 170V for 3 minutes, followed by washing with water and curing in an oven at 95°C ± 1°C for 90 minutes. At this time, the film thickness was 25 μm and the powder concentration was 50 wt%. Next, the photosensitive resin was peeled off by immersing it in 50 g/l of caustic soda at 40° C. for 5 minutes. Next, using 10% hydrochloric acid, the palladium coating on the exposed portion of the catalyst was removed at 50° C. for 7 minutes to obtain a fine printed circuit board. [0137] Example 3-18 As a conductive paste, 35 wt% of demineralized water, melamine
Electroless copper plating was applied to the surface of alumina containing 5 wt % of acrylic resin (trade name: Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.) and having an average particle size of 1.0 μm. Electroless copper plating was applied to the surface of natural mica with 20 wt% powder and an average particle size of 1.0 μm applied to a thickness of 2 μm. A fine film having an electrodeposited film with a mixed powder concentration of 50 wt% was prepared in the same manner as in Example 3-17, except that a conductive paste in which 40 wt% of powder was dispersed was applied to a thickness of 1 μm. A printed circuit board was fabricated. [0138] Example 3-19 As a conductive paste, 35 wt% of demineralized water, melamine
Acrylic resin (trade name: Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.) 5 wt%, copper powder with an average particle size of 0.03 μm, 30 wt%, average particle size of 0. Except for using a conductive paste in which 30 wt% of powder was applied to the surface of 1 μm natural mica and electroless copper plating was applied to a thickness of 0.1 μm.
A fine printed circuit board having an electrodeposited film with a mixed powder concentration of 50 wt % was produced by the same method as in Example 3-17. [0139] Example 3-20 As a conductive paste, 35 wt% of demineralized water, melamine
Electroless copper plating was applied to the surface of 5 wt% acrylic resin (trade name Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.), 30 wt% copper powder with an average particle size of 0.03 μm, and alumina with an average particle size of 1.0 μm. Powder Lo applied to a thickness of 2 μm
Powder 20 made by applying electroless copper plating to a thickness of 0.1 μm on the surface of natural mica with wt% and average particle size of 1.0 μm.
The concentration of the mixed powder was 50% by the same method as in Example 3-17, except that a conductive paste in which wt% was dispersed was used.
A fine printed circuit board having an electrodeposited film of w:t% was produced. [01401 The fine printed circuit boards prepared in Examples 3-1 to 3-20 above were evaluated in the same manner as in Example 1-1. The results are shown in Table 3-1.3-2. [0141]

[Table 4] Table 3-1 [0142] [0143]

[Table 5] Table 3-2 [0144] Example 4-1 The resist pattern used in Example 1-1 was prepared by coating the substrate with 35 wt% of demineralized water, melamine/acrylic resin (trade name: Honey Bright C-IL, Honey In a conductive paste in which 60 wt% of copper powder (manufactured by Kasei Co., Ltd.) and average particle size of 0.03 μm was dispersed, the substrate was used as an anode and a stainless steel plate (0.5 t) was used as a counter electrode, and the bath temperature was 23. °, pH8.5
Under these conditions, energize at 170V for 3 minutes, then wash with water,
It was cured in an oven at 50°C±1°C for 90 minutes. At this time, the film thickness was 25 μm, and the metal powder concentration was 50 wt%. Next, the photosensitive resin was peeled off by immersing it in 50 g/l of caustic soda at 40° C. for 5 minutes. Next, the exposed copper plating film was removed using an ammonia alkaline copper solution at 50° C. for 7 minutes to obtain a fine printed circuit board. [0145] Example 4-2 The resist patterned base material used in Example 1-2 was mixed with 25 wt% of demineralized water, 5 wt% of melamine/acrylic resin (trade name: Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.), average In a conductive paste in which 70 wt% of nickel powder with a particle size of 0.03 μm was dispersed, the substrate was used as an anode and a stainless steel plate (0.5 t) was used as a counter electrode, and the bath temperature was 23°C and pH 8.
. , 5, electricity was applied for 3 minutes at 180 μm, and then washed with water and cured in an oven at 145° C.±1° C. for 90 minutes. At this time, the film thickness was 30 μm, and the metal powder concentration was 60 wt%. Next, 50 g/l of caustic soda was added at 40°C.
The photosensitive resin was peeled off by dipping for a minute. Next, using an ammonia alkaline copper solution, the exposed copper plating film was removed at 50° C. for 7 minutes to obtain a fine printed circuit board. [0146] Example 4-3 The resist patterned base material used in Example 1-3 was mixed with 15 wt% of demineralized water, 5 wt% of melamine/acrylic resin (trade name: Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.), average In a conductive paste in which 80 wt% of copper powder with a particle size of 0.03 μm was dispersed, the substrate was used as an anode and a stainless steel plate (0.5 t) was used as a counter electrode, at a bath temperature of 23°C and a pH of 8.5. Electrify at 170V for 3 minutes, then wash with water,
It was cured in an oven at 5°C±1°C for 90 minutes. At this time, the film thickness was 25 μm, and the metal powder concentration was 50 wt%. Next, the photosensitive resin was peeled off by immersing it in 50 g/l of caustic soda at 40° C. for 5 minutes. Next, using an ammonia alkaline copper solution, the exposed copper plating film was removed at 50° C. for 7 minutes to obtain a fine printed circuit board. [0147] Example 4-4 The resist patterned substrate used in Example 1-4 was mixed with 47 wt% of demineralized water, 3 wt% of melamine/acrylic resin (trade name Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.), and average particles. In a conductive paste in which 50 wt% of silver powder with a diameter of 0.07 μm was dispersed, the substrate was used as an anode and a stainless steel plate (0.5 t) was used as a counter electrode, and the temperature was 23°C and the pH was 8.5. energize for 3 minutes, then wash with water,
Cured for 90 minutes in an oven at ±1°C. At this time,
The film thickness was 18 μm, and the metal powder concentration was 30 wt%. Then, the photosensitive resin was peeled off by immersing it in a stripping solution exclusively for OMR at 40° C. for 5 minutes. Then, using an ammonia alkaline copper solution, the exposed copper plating film was removed at 50° C. for 7 minutes to obtain a fine printed circuit board. [0148] Example 4-5 The resist patterned substrate coated with copper plating used in Example 1-5 was treated with 35 wt% of demineralized water and melamine/acrylic resin (trade name: Honey Bright C-IL, manufactured by Honey Kasei Co., Ltd.). ) 5wt%, 60w of copper powder with an average particle size of 0.03μm
The substrate is used as an anode in a conductive paste in which t% is dispersed,
Using a stainless steel plate (0.5t) as a counter electrode, a bath temperature of 2
Electrify at 170V for 3 minutes at 3°C and pH 8.5.
Thereafter, it was washed with water and cured in an oven at 145°C±1°C for 90 minutes. The powder used here was treated with a surfactant. [0149] At this time, the film thickness was 25 μm, and the metal powder concentration was 50 wt%. Next, 50% caustic soda
g/l at 40° C. for 5 minutes to peel off the photosensitive resin. Next, using 10% hydrochloric acid, the palladium coating on the exposed portion of the catalyst was removed at 50° C. for 7 minutes to obtain a fine printed circuit board. [01501 The circuit boards produced in Examples 4-1 to 4-5 above were evaluated in the same manner as in Example 1-1. The results are shown in Table 4. [01511

[Table 6] Table 4 [0152] [0153] [Effects of the Invention] As explained above, the circuit pattern of the present invention has an electrocoated film formed by electrocoating using a conductive paste liquid. The conductive circuit member not only solves problems regarding uniformity of film thickness, bleeding, blurring, and missing parts, but also significantly improves electrical characteristics and allows the formation of a member with reproducibility. [0154] Further, according to the present invention, since a circuit pattern is formed by a photorin process and then electrodeposited, a conductive circuit member having an extremely fine circuit pattern can be easily obtained. Even if it is a film, it is possible to obtain a predetermined conductivity, and it becomes possible to manufacture conductive circuit members such as printed circuit boards that are small and resistant to disasters, and can be effectively applied to electronic devices. [0155] In addition, in the present invention, when metallized ceramic powder or metallized natural mica powder is used as the conductive particles, even when the electrodeposited film is heat-treated at a low temperature of about 90°C to 100°C. It is possible to obtain an electrodeposited film with excellent physical properties, and it is possible to form fine circuits on insulating substrates with low heat resistance or flexible thin substrates, and it can be particularly effectively applied to small and lightweight electronic devices. A conductive circuit member can be obtained. [0156] Further, the simplification of the process can greatly contribute to cost reduction.

[Brief explanation of the drawing]

FIG. 1 is a process diagram showing an embodiment of a method for manufacturing a conductive circuit member according to the present invention.

FIG. 2 is a process diagram showing another embodiment of the method for manufacturing a conductive circuit member according to the present invention.

FIG. 3 is an enlarged view of an electrodeposited film forming a circuit of the conductive circuit member of the present invention.

FIG. 4 is a schematic cross-sectional view of an electronic device using the circuit member of the present invention.

[Explanation of symbols]

1 Insulating base material 2 Catalyst layer 3 Plating layer 4 Photosensitive resin 5 Electrodeposition coating film 6 Circuit 7 lights 8 Pattern mask 11 Conductive circuit member 41 Housing 42 Electronic parts 43 Electronic equipment

[Figure 1]

[Figure 2]

[Figure 3]

[Figure 4]

Claims (31)

[Claims] 1. A conductive circuit member having a conductive circuit formed in a pattern on an insulating substrate, characterized in that the circuit has an electrodeposited coating film containing conductive particles and a resin. Conductive circuit components. 2. The conductive circuit member according to claim 1, wherein the conductive particles include powder obtained by metallizing the surface of ceramic powder. [Claim 3] The ceramic powder has an average particle diameter of 0.1.
The conductive circuit member according to claim 2, wherein the conductive circuit member has a thickness of 7 μm. 4. The conductive circuit member according to claim 1, wherein said electrodeposited coating film contains 20 to 80% by weight of conductive particles. 5. The conductive circuit member according to claim 1, wherein the conductive particles include powder obtained by metallizing the surface of ceramic powder and ultrafine metal powder. [Claim 6] The average particle diameter of the ultrafine metal powder is 0.0.
The conductive circuit member according to claim 5, which has a thickness of 1 to 5 μm. 7. The conductive circuit member according to claim 1, wherein the conductive particles include powder obtained by metallizing the surface of natural mica powder. [Claim 8] The average particle diameter of the natural mica powder is 0.1.
8. The conductive circuit member according to claim 7, wherein the conductive circuit member has a thickness of 7 μm. 9. The conductive circuit member according to claim 1, wherein the conductive particles include a mixture of a ceramic powder whose surface is metallized and a natural mica powder whose surface is metallized. 10. Claim 2, wherein the metal layer formed on the surface of the ceramic powder has a thickness of 0.05 to 3 μm.
conductive circuit components. 11. Claim 7, wherein the metal layer formed on the surface of the natural mica powder has a thickness of 0.05 to 3 μm.
conductive circuit components. 12. The conductive material according to claim 1, wherein the conductive particles contain a mixture of a ceramic powder whose surface is metallized, a natural mica powder whose surface is metalized, and an ultrafine metal powder. circuit components. 13. A method for manufacturing a conductive circuit member having a conductive circuit formed in a pattern on an insulating base material, wherein a conductive circuit member containing an electrodepositable resin and conductive particles is provided on the insulating base material. Electrodeposition is performed by immersing the insulating base material in a synthetic paste,
A method for producing a conductive circuit member, comprising selectively forming an electrodeposited film containing the electrodepositable resin and the conductive particles on a base material, and then subjecting the film to a heat curing treatment. 14. Forming a plating layer on the insulating base material,
14. The method of manufacturing a conductive circuit member according to claim 13, wherein electrodeposition is performed after forming a resist pattern corresponding to the circuit pattern on the plating layer. 15. A resist pattern corresponding to a circuit pattern is formed on the insulating base material, and then a plating layer is formed on the resist pattern, and then electrodeposition is performed.
A method for manufacturing a conductive circuit member. 16. The plating layer has a thickness of 0. 15. The method for manufacturing a conductive circuit member according to claim 14, wherein the diameter is 1 μm or more and 1 μm or less. 17. The plating layer has a thickness of 0. 16. The method for manufacturing a conductive circuit member according to claim 15, wherein the diameter is 1 μm or more and 1 μm or less. 18. The heat treatment is performed at a temperature of 90° C. or higher and 100° C.
14. The method for manufacturing a conductive circuit member according to claim 13, wherein the heating is performed at a temperature below .degree. 19. The method for producing a conductive circuit member according to claim 13, wherein the electrodeposited film after the heat treatment contains 20 to 80% by weight of the conductive particles. 20. The method of manufacturing a conductive circuit member according to claim 13, wherein the conductive particles are at least one of ceramic powder with a metalized surface and natural mica powder with a metalized surface. 21. The ceramic powder has an average particle size of 0.
21. The method for manufacturing a conductive circuit member according to claim 20, wherein the thickness is 1 to 7 μm. 22. The natural mica powder has an average particle size of 0.
21. The method for manufacturing a conductive circuit member according to claim 20, wherein the thickness is 1 to 7 μm. 23. The conductive particles have an average particle size of 0.0.
Claim 2 wherein ultrafine metal powder of 1 to 5 μm is added.
0 manufacturing method of conductive circuit member. 24. A conductive paste comprising 3 to 50% by weight of an electrodepositable resin and 4 to 80% by weight of conductive particles. 25. Electrodepositable resin 3 to 50% heavy electrode average particle size 0. Claim 24 containing 4 to 80% by weight of ceramic powder having a diameter of 1 to 7 μm and whose surface is metal-plated.
conductive paste. 26. The conductive particles have an average particle diameter of 0.
25. The conductive paste according to claim 24, which contains powder obtained by metal plating the surface of natural mica powder having a diameter of 1 to 7 μm. 27. The conductive particles have an average particle diameter of 0.
25. The conductive paste according to claim 24, comprising a mixture of a powder obtained by metal plating the surface of ceramic powder having a diameter of 1 to 7 μm and a powder obtained by plating the surface of natural mica powder having an average particle size of 0.1 to 7 μm. . 28. The conductive particles have an average particle diameter of 0.
Claim 24 containing ultrafine metal powder of ゜01 to 5 μm.
conductive paste. 29. The conductive particles have an average particle diameter of 0.
25. The conductive paste according to claim 24, comprising ultrafine metal powder with a diameter of 01 to 5 μm and at least one of a metallized ceramic powder and a metallized natural mica powder. 30. An electronic device comprising a conductive circuit member in which a conductive circuit having an electrodeposited coating film containing a resin and conductive particles is formed in a pattern on an insulating base material. 31. The electronic device according to claim 30, wherein the conductive particles include at least one of ceramic powder with a metalized surface and natural mica powder with a metalized surface.