JP2000299547A - Manufacture of electrophotographic printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an electrophotographic printed wiring board wherein, even with a fine circuit pattern, the corresponding toner image is formed well on both sides so that multiple printed wiring boards excellent in line thickness homogeneity are efficiently manufactured. SOLUTION: After aligned to one surface, charged, and exposed to provide an electrostatic latent image, toner development is processed to form a toner image, then a substrate is inverted again for alignment and charging on the other side before exposure to provide an electrostatic latent image, and then toner development is processed again to form a toner image on the other side.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an insulating substrate provided with at least a metal conductive layer and a photoconductive layer on both surfaces of the insulating substrate in this order,
A toner image is formed on the photoconductive layer by electrophotography, and then the photoconductive layer other than the toner image portion is dissolved and removed,
Also, the present invention relates to a method for producing an electrophotographic printed wiring board for etching a substrate surface of a photoconductive layer-removed portion. The present invention relates to a method for manufacturing an electrophotographic printed wiring board capable of efficiently manufacturing a large number of printed wiring boards having excellent width uniformity.

[0002]

2. Description of the Related Art As electronic devices become lighter, thinner, shorter and more diverse,
At present, high density and shortened construction period are also required for printed wiring boards, and application of an electrophotographic photosensitive member as a resist material is being studied. Conventionally, in an electrophotographic photoreceptor used for an electrophotographic lithographic printing plate, drawing in an infrared region has already been performed, and image data is directly transmitted from a computer without using a photomask by scanning exposure with a laser beam. Feeding and forming high-density images have been put to practical use.

A printed wiring board (hereinafter, referred to as an electrophotographic printed wiring board) using an electrophotographic method is manufactured as follows. A photoconductive layer is provided on a laminated board provided with a metal conductive layer on an insulating substrate, and after uniformly charging the surface of the photoconductive layer in the dark, exposure is performed according to a wiring pattern. Thus, an electrostatic latent image is formed. The electrostatic latent image is subjected to a toner developing process to form a toner image, and the toner image is used as a resist to dissolve and remove the photoconductive layer other than the toner image portion, and a metal conductive layer including the toner image and the photoconductive layer is formed. Is formed. Dissolution and removal of the unnecessary portion of the metal conductive layer and the subsequent steps of manufacturing the printed wiring board can be performed in the same manner as in the related art.

[0004] Regarding a method of manufacturing an electrophotographic printed wiring board in the case of forming a wiring pattern on both sides of a substrate, as disclosed in JP-A-10-209606, at least a metal conductive layer and a photoconductive layer are formed on both sides of an insulating substrate. Layers are provided in this order, placed on a surface plate of an exposure machine, subjected to alignment and charging, exposed, and provided with an electrostatic latent image on one photoconductive layer surface,
Further reversing and re-positioning and charging, after exposing the photoconductive layer surface on the opposite side to provide an electrostatic latent image, developing the toner, the subsequent processes are performed in the same manner as described above,
A printed wiring board having circuit patterns formed on both sides is manufactured.

However, according to this method, two different operations of an operation of reversing the substrate on the surface plate after the exposure is completed and an operation of transferring the substrate to the entrance of the toner developing section are required alternately. If this is attempted, the size of the apparatus becomes large, and the output data of the exposing machine must be alternately replaced for each surface to be exposed, resulting in poor work efficiency. Also,
In particular, when a high-definition circuit pattern is manufactured, high-resolution exposure is required, and the time required for exposure is correspondingly increased. In this case, the surface potential of the surface on which the charge exposure was first performed is attenuated by time during the exposure of the opposite surface, and becomes lower than an appropriate surface potential during toner development processing. Situation occurs. Since the image quality of the toner image is greatly affected by the distribution of the potential of the electrostatic latent image, if the toner development processing is performed in a state where the surface potential is lower than usual, in the case of reversal development, the line width becomes a direction in which the line width becomes thicker. As a result, there is a problem that the line width of the wiring pattern deviates from a specified value, and in a severe case, a short circuit occurs in the circuit.

In particular, when processing a substrate having a through hole, both sides are charged, and then one side is exposed and a toner developing process is performed by reversal development, as in the method described in Japanese Patent Application No. 10-093311. It is described that a good through-hole substrate can be manufactured by charging both surfaces again, exposing the opposite surface, and similarly performing toner development.

However, when both surfaces are charged, one surface is exposed, and then toner development processing is performed by reversal development, the surface not carrying an electrostatic latent image uniformly holds a certain surface potential, Therefore, in the reversal development using toner particles having the same polarity as the charging polarity, the toner particles do not adhere to the surface that does not carry the electrostatic latent image. During the process, a point defect in which the surface potential is partially reduced may occur, and when the toner development process is performed, the point maintains a certain specified surface potential around the point. Due to the electric field from the non-image portion, toner particles adhere to that point, and a toner image is formed at a point that should be a non-image portion, resulting in a black spot defect. This leaves copper as a final printed circuit board and causes serious defects such as a short circuit.

In the above-described configuration in which double-sided charging is performed and exposure and toner development are repeated one by one, the probability of occurrence of the black spot defect is simply doubled as compared with the case of batch double-sided development. When a large number of printed circuit boards are manufactured, the yield is reduced. Also, even in the case of performing the batch double-sided development described above, when performing exposure on one side with an exposure machine, if there is a contact member on the surface opposite to the exposure surface, it is considered that both surfaces of the substrate are charged. The contact member causes a discharge or a decrease in the surface potential of the contact portion, and when toner development is performed, the portion becomes undesirably defective as in the above case.

[0009]

According to the present invention, at least a metal conductive layer and a photoconductive layer are provided on both sides of an insulating substrate in this order, and a toner image is formed on the photoconductive layer by electrophotography. A method for producing an electrophotographic printed wiring board in which a photoconductive layer other than an image portion is dissolved and removed, and a photoconductive layer removed portion substrate surface is etched. An object of the present invention is to provide a method for manufacturing an electrophotographic printed wiring board, which can form toner images satisfactorily and can efficiently manufacture a large number of printed wiring boards.

[0010]

As a result of investigations to solve the above problems, at least a metal conductive layer and a photoconductive layer are provided in this order on both surfaces of an insulating substrate, and a toner is formed on the photoconductive layer by electrophotography. An image is formed, and then a photoconductive layer other than a toner image portion is dissolved and removed, and a photoconductive layer-removed portion is etched on the substrate surface. After positioning and charging the surface, exposure is performed to form an electrostatic latent image, and then a toner developing process is performed to form a toner image. Then, the substrate is again inverted to perform positioning and charging of the other surface. The above object has been attained by a method for manufacturing a printed wiring board, characterized in that a toner image is formed on the other surface by performing a toner development process again after providing an electrostatic latent image by exposure.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing an electrophotographic printed wiring board of the present invention will be described below in detail.

The toner image formation by electrophotography according to the present invention is performed as follows. A substrate provided with at least a metal conductive layer and a photoconductive layer on both surfaces in this order is placed on a surface plate of a charging exposure machine, and is positioned on the surface plate and a surface opposite to a surface opposite to the surface plate (first surface). Is performed on the photoconductive layer, and then pattern exposure is performed to form an electrostatic latent image. Thereafter, a toner image is formed on the first surface by performing a toner developing process, and then the substrate is turned over and placed again on the surface plate, so that the surface on which the toner image is not formed (the second surface). ) Is performed in the same manner as in the first surface to perform alignment and exposure to form an electrostatic latent image, and thereafter, a toner developing process is performed to form a toner image on the second surface. Thereby, a toner image corresponding to the wiring pattern can be formed on the photoconductive layer on both surfaces of the substrate.

Therefore, the order of the steps of forming a toner image by electrophotography according to the present invention includes a positioning step, a one-side charging step of charging only one side, an exposure step of exposing the charged surface, and a toner developing step ( As described above, the first surface processing step), the substrate reversing step, the opposite surface alignment step, the one-side charging step, the exposure step, and the toner development processing step (above, the second surface processing step) are performed in this order.

Hereinafter, each step will be described in accordance with the above steps.

When the photoconductive layer on one side of the substrate is exposed to a wiring pattern (exposure step) to form a toner image by electrophotography, the wiring pattern on both sides of the substrate according to the present invention is preferably provided through through holes. Are three-dimensionally joined to each other to perform alignment with respect to the exposure position of the substrate.

The alignment step according to the present invention is basically performed by measuring the position of the substrate and changing (aligning) the substrate position so that the exposure position matches the substrate position. .

The alignment is performed by moving the substrate from an initial position where the substrate is mounted on the surface plate, based on the measurement result of the position. A method of rotating or moving in the XY directions with respect to the exposure position can be used. Further, it can be performed by changing the exposure position without moving the substrate according to the measurement result of the substrate position. As a means for measuring the position of the substrate used in the alignment step according to the present invention, CC
D camera.

As a step subsequent to the alignment step, there is a one-side charging step prior to exposure. As the charging method, a non-contact charging method such as a corotron method and a scorotron method, and a contact charging method such as a conductive brush charging and a conductive roll charging have been known.As the charging method used in the charging step according to the present invention, Either of these methods may be employed as long as at least the following photoconductive layer according to the present invention can be uniformly charged and a potential of a certain degree or more can be secured without deterioration of the photoconductive layer.

The charging is performed while moving at least one of the charging means and the substrate, but it is more preferable to perform the charging while moving the substrate in order to simplify the charging mechanism. As a method of moving the substrate, a method using a belt passed in the moving direction, a method of sandwiching between roll pairs, a method using a plurality of rolls passed at right angles to the moving direction, a method of moving while holding on a surface plate, and the like, and the like Is adopted.

Among these methods, the platen holding and moving method in which the gap between the charging means during charging and the charged surface of the substrate and the transfer speed are small are most advantageous. In particular, in the platen holding and moving method, it is desirable to provide a vacuum suction mechanism on the platen and charge the substrate while adsorbing the substrate on the platen.

The substrate on which one surface of the photoconductive layer is charged and the alignment thereof is performed before the charging is performed, in a subsequent exposure step, the charged portion is image-exposed to the charged portion by a known operation. A latent image is formed. Examples of the exposure method include reflection image exposure using a xenon lamp, a tungsten lamp, a fluorescent lamp or the like as a light source, contact exposure through a transparent positive film, and scanning exposure using a laser beam, a light emitting diode, or the like.
The light source in the scanning exposure is He-Ne laser, argon ion laser, krypton ion laser, ruby laser, YAG laser, nitrogen laser, dye laser, excimer laser, GaAs / GaAlAs,
And a laser light source such as a semiconductor laser such as InGaAsP, or a scanning exposure using a light emitting diode and a liquid crystal shutter (including a line printer type light source using a light emitting diode array, a liquid crystal shutter array, etc.)
May be performed.

As an exposure machine applicable to the present invention, a charging device is newly added to a laser drawing apparatus for exposing a substrate using a photopolymer described in JP-A-7-35993 and JP-A-7-35994. The added ones can be mentioned. In particular, when a scanning exposure system is used as the exposure means, at least during the exposure, at least one of the exposure system and the substrate is moved, and the formation of the electrostatic latent image by the exposure is ultimately performed on the printed wiring board. In some cases, the quality of the wiring image may be determined. If any one of them is moved, it is preferable to move the substrate (substrate holding means for holding the substrate).

The substrate on which the electrostatic latent image is formed on one surface after the alignment step, the charging step, and the exposure step are formed in the above order, and a toner image is formed in the toner developing step.
Examples of the developing method in the toner developing process according to the present invention include a reversal developing method in which an exposed portion is developed using a liquid developer containing toner particles having the same polarity as the electrostatic latent image, and an electrostatic latent image. Any of the normal development methods in which a non-exposed portion is developed using a liquid developer containing toner particles having the opposite polarity can be used. In addition to the reversal development method, it is preferable to apply a bias voltage also in the normal development method in order to prevent toner particles from adhering to non-image areas and pinholes in solid areas.

As the liquid developer used in the present invention, those conventionally used in electrophotographic printing plates can be used. It must have resist properties.
Therefore, as the toner particle component in the liquid developer, for example, acryl resin composed of methacrylic acid, methacrylic acid ester, vinyl acetate resin, a copolymer of vinyl acetate and ethylene or vinyl chloride, vinyl chloride resin, vinylidene chloride Resins, vinyl acetal resins such as polyvinyl butyral, polystyrene, copolymers of styrene with butadiene and methacrylate, polyethylene, polypropylene and its chlorides, polyester resins such as polyethylene terephthalate and polyethylene isophthalate, polycapramides and polyhexa Polyamide resin such as methylene adipamide, phenol resin, xylene resin,
Preferred are alkyd resins, vinyl-modified alkyd resins, gelatin, cellulose ester derivatives such as carboxymethyl cellulose, and other waxes and waxes.

The liquid developer may contain a dye or a charge control agent within a range that does not adversely affect development or fixing. Further, it is necessary to use either positive or negative charging depending on the photoconductive compound used and the charging polarity.

On the other hand, as a system in the apparatus for performing the toner developing process according to the present invention, a conventionally used electrostatic latent image forming surface of a substrate is transported substantially horizontally in the vertical direction, and the upper surface or the upper surface thereof is conveyed. One-sided horizontal and horizontal development in which a liquid is supplied from the lower surface to one side, a one-sided vertical and horizontal development in which a substrate as described in JP-A-2-91649 or the like is set up and conveyed substantially horizontally and liquid is supplied to one side thereof, Japanese Laid-Open Patent Application No. 8-254541 discloses a substrate as described in JP-A-224541, which lays down a substrate, transports it substantially horizontally, and supplies liquid to both sides of the substrate from both upper and lower sides.
As described in the specification of Japanese Patent No. 298363, in addition to the two-sided vertical and horizontal development, in addition to the two-sided vertical and horizontal development in which the substrate is set up and conveyed substantially horizontally and the liquid is supplied to both sides thereof,
Although particularly suitable for a flexible plate, there is a development method in which a substrate is transported from above by standing, and liquid is supplied to both surfaces before or after transporting the substrate in a substantially horizontal direction. In the toner developing process according to the present invention, the toner developing process is performed on only one side of the substrate.

Hereinafter, an example of a toner development processing apparatus suitably used in the present invention will be described. The toner development processing apparatus suitably used in the present invention includes a liquid development section, a drying section, and a heat fixing section. By the above charging and exposure processing,
The substrate having the electrostatic latent image formed on one side thereof is carried into the developing electrode unit of the toner developing device by a transporting means such as a pair of transporting rolls, and is subjected to liquid development at the developing electrode unit. The substrate is carried out to the drying section and the heat fixing section by a pair of rolls. After the substrate is developed with toner on one side in the liquid developing section, the dispersion medium in the liquid developer remaining on one or both sides in the drying section is dried. Evaporation is removed, and the toner particles are thermally fixed on the photoconductive layer in the thermal fixing section.

The liquid developing section includes a developing electrode section for supplying a liquid developer to the substrate to substantially perform a toner developing process on the substrate, a transporting means for transporting the substrate to the developing electrode section, and a drying apparatus for nipping the substrate. And a squeeze roll pair for squeezing the liquid developer remaining on the photoconductive layer.
The liquid developer is stored in a liquid developer storage tank, and is supplied to the developing electrode unit through a liquid sending unit.

The developing electrode portion is further provided with a predetermined gap between the developing electrode portion and the surface of the transfer substrate. The developing electrode portion has at least a portion having conductivity, and the liquid stored in the liquid developer storage tank. The liquid developer supply means is configured to temporarily store and rectify the developer, and to supply the rectified and static flow to the gap between the developing electrode and the electrostatic latent image surface of the substrate. Further, a bias voltage applying means is connected to the developing electrode so that a bias voltage can be applied to the electrostatic latent image forming surface of the substrate.

The liquid supply means comprises a liquid supply pump, a liquid amount adjustment valve, and a liquid supply pipe. When the liquid supply pump is operated, the liquid developer is transferred from the liquid developer storage tank through the liquid amount adjustment valve to the liquid developer. The developer is supplied to the developer supply means and supplied to the electrostatic latent image forming surface of the substrate from the liquid developer supply port.

The roll in the transport roll pair comprises a shaft and an elastic body provided on the outer periphery thereof. As the shaft, hard resin can be used in addition to metals such as iron, stainless steel, and aluminum. A hollow shaft may be used for weight reduction or molding, or a combination of a metal and a hard resin may be used.

The elastic body is preferably a rubber made of a component having low solubility in hydrocarbons and solvents.
Acrylonitrile-butadiene copolymer rubber (NBR),
Examples include urethane rubber, isoprene-acrylonitrile copolymer rubber, chloroprene rubber, acrylic rubber, chlorosulfonated polyethylene rubber, polysulfide rubber, silicone rubber, and fluorine rubber. Of these, wear resistance,
NBR having a high acrylonitrile content is excellent in terms of solvent resistance, processability, cost, and the like. These rubbers include reinforcing fillers, fillers for bulking, dispersibility improvers, adhesion improvers, heat-resistant additives, antioxidants, coloring agents, crosslinking agents,
In addition, additives such as a curing catalyst and the like can be contained in a range that does not affect the solvent resistance and the like. The rubber hardness of the transport roll pair is preferably in the range of 30 to 70 degrees, and more preferably in the range of 35 to 60 degrees. Rubber hardness is JI
Spring type hardness tester A specified in SK6301
It can be measured by a mold and may be in the above range regardless of the rubber thickness of the roll.

As the squeeze roll pair, the same roll as the above-mentioned transport roll pair can be used, or a squeeze roll pair using a liquid absorbing member having a capillary action as an elastic body as described in JP-A-8-76603 is also used. it can. In particular, when using the same material as the pair of transport rolls, Japanese Unexamined Patent Application Publication No. 7-24546
The gas blowing means described in Japanese Patent Publication No. 2 may be arranged. On the other hand, examples of the liquid absorbing member include natural rubber, butyl rubber, urethane rubber, and an acrylonitrile-butadiene copolymer rubber having an elastic body having a sponge structure, a woven fabric, a nonwoven fabric, and a resin-impregnated material thereof. . When using a suction roll using a suction member having a capillary action as an elastic body in the squeeze roll pair, a reduced-pressure suction means connected to the suction roll is provided, and the excess liquid developer composition absorbed is provided. Items may be discarded. As a specific example of the liquid absorbing roll pair, a non-woven fabric having a basis weight of 70 g / m ² wound in multiple layers around a shaft made of SUS304 can be used.

In the vicinity of the transport roll pair and the squeeze roll pair, it is desirable to provide a grounding mechanism arranged to be in contact with the metal conductive layer on the side edge or the side surface of the substrate. A power supply is connected to the developing electrode and the grounding mechanism,
When performing reverse development, a bias voltage is applied to the substrate. The bias voltage to be applied depends on the material system factors such as the type of the photoconductive layer and the liquid developer, the surface potential of the charged portion and the non-charged portion of the electrostatic latent image, the distance between the developing electrode and the substrate, and the transport speed of the substrate. Is determined from a plurality of factors such as the factors such as the developing conditions. After a toner image is formed on one surface of the substrate by the above-described toner development processing apparatus, the substrate is reversed in a substrate reversing step to form an electrostatic latent image on the other surface. As a means for reversing the substrate, a method of adsorbing the substrate on a decompression suction pad or a decompression suction disk and reversing the substrate together with these decompression suction means, at least two opposing side surfaces (surfaces in the thickness direction) of the substrate, preferably parallel to the moving direction. A method of rotating and inverting the holding means while pressing and holding at least two side surfaces by the holding means, using two sets of opposed substrate (one-sided) holding means, and holding the substrate by one holding means rather than the other holding means There is a method of inverting by changing the substrate holding surface, and a method of combining them.

The substrate, which has been inverted in the substrate inversion step, undergoes a toner development process through the respective steps of a charging step and an exposure step subsequent to the alignment step, as in the first step described above. An image is formed.

Next, the steps of manufacturing a printed wiring board after the toner developing step according to the present invention will be described. In the present invention, the substrate on which the toner image is provided on the photoconductive layer by electrophotography is used as a resist, and the photoconductive layer in other unnecessary portions (non-image portion) is removed by elution. In the elution treatment, an acidic eluate containing an acidic compound is used when the binder resin of the photoconductive layer is an acid-soluble type, and an alkaline eluate containing an alkaline compound is used when the binder resin of the photoconductive layer is an alkali-soluble type. Acidic compounds include hydrochloric acid, sulfuric acid,
Examples include acidic compounds such as phosphoric acid, formic acid, acetic acid, and metasulfonic acid. In the acidic eluate, these acidic compounds can be used alone or in combination of two or more. Examples of the alkaline compound include inorganic alkali compounds such as alkali metal silicates, alkali metal hydroxides, phosphoric acid and alkali metal carbonates and ammonium salts, ethanolamines, ethylenediamine, propanediamines, triethylenetetramine, and morpholine. Organic alkaline compounds and the like can be used. In the alkaline eluate, these alkaline compounds can be used alone or in combination of two or more. In addition, as the solvent of the eluate, water can be advantageously used whether it is an acidic solution or an alkaline solution.

As the method and apparatus for eluting and removing the non-image portion photoconductive layer of the substrate, conventionally known methods and apparatuses can be applied. As a method and an apparatus for eluting and removing the image forming layer of the body, JP-A-2-52352 and JP-A-2-52353,
2-52354, 2-52355, 2-52
No. 356, No. 2-93474, No. 2-132447
No. 2,275,457, No. 2-275461, No. 3-29953, No. 3-48849, etc., which can also be used advantageously.

In the substrate from which the unnecessary portion of the photoconductive layer is removed by elution, the metal conductive layer exposed by the etching step is removed. The etching method and the etching solution used for the treatment are described in "Printed Circuit Technology Handbook-Second Edition-" (Corporation)
The method described in the Printed Circuit Society of Japan, published in 1993, published by Nikkan Kogyo Shimbun), an etching solution and the like can be used. However, an etching solution having a resistance to the etching resist composed of the toner image and the photoconductive layer is used. Generally, when the binder resin used for the photoconductive layer is an acid-soluble type, an ammoniacal alkaline etching solution can be used. In the case of an alkali-soluble type, a ferric chloride solution, a cupric chloride solution, a hydrogen peroxide-sulfuric acid solution, or the like can be used.

The resist image composed of the photoconductive layer and the toner image remaining after the above etching step is removed when unnecessary when connecting the circuit components. When an acid-soluble binder resin is used, a solution having a higher acidity than the eluate is used, and when an alkali-soluble binder resin is used, a more alkaline solution than the eluate is used. It can be removed by treating with a strong liquid. Further, if necessary, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 2-butanone,
1,4-dioxane, 1,2-dimethoxyethane, methanol, ethanol, 2-propanol, 1-methoxy-2-propanol, 2-methoxyethanol, and 2
-An organic solvent that can dissolve the binder resin of the photoconductive layer, such as butoxyethanol, can also be used. Through the above steps, a printed wiring board having a wiring pattern facing the toner image on both surfaces of the insulating substrate is obtained.

Next, a substrate according to the present invention will be described. The substrate according to the present invention is capable of finally forming a wiring pattern of a metal conductive layer on both surfaces of an insulating substrate as a printed wiring board, and at least one step of forming the wiring pattern uses electrophotography. Is what you do. More specifically, in the metal conductive layer provided substantially uniformly on both surfaces of the insulating substrate, in order to form an important portion of a resist for removing unnecessary portions other than the wiring pattern portion by electrophotography,
An electrophotographic photoconductive layer capable of forming a toner image is provided on at least the metal conductive layer. That is,
The substrate according to the present invention is a substrate having at least a metal conductive layer and a photoconductive layer on both sides of an insulating substrate in this order.
Further, as a substrate used for manufacturing a printed wiring board having a through hole, a through hole is formed in a laminated board having a first metal conductive layer provided on both sides of an insulating substrate, and a metal plating process is performed to perform the through hole. A substrate in which a photoconductive layer is formed on the second metal conductive layer after providing the second metal conductive layer inside and on the surface of the laminate can be used for manufacturing the printed wiring board of the present invention.

The insulating substrate according to the present invention includes a glass-based epoxy resin plate, a paper-based phenolic resin plate, a paper-based epoxy resin plate, a glass-based polyimide resin plate, a polyester film, a polyimide film, a polyamide film, And a polyvinyl fluoride film. The thickness of the insulating substrate is about 80 μm to 3.2 mm, and its material and thickness are selected according to the final use form of the printed wiring board. For a thin substrate, a plurality of thin substrates may be used.

The metal used for the metal conductive layer provided on both sides is copper, silver, aluminum, stainless steel, or the like.
Nichrome, tungsten and the like. The thickness of the metal conductive layer is generally from 5 to 35 μm, but the thickness of the metal conductive layer is preferably thin in order to provide high resolution. These insulated substrates and laminates having a metal conductive layer provided thereon are described in "Printed Circuit Technology Handbook-Second Edition-" (edited by The Printed Circuit Society of Japan, published in 1993, published by Nikkan Kogyo Shimbun). Can be used.

A photoconductive layer is provided on the metal conductive layer of the above-mentioned laminate, and between the laminate and the photoconductive layer, casein, Polyvinyl alcohol, hydroxyethyl cellulose, phenolic resin, styrene / maleic anhydride copolymer, maleic acid / acrylic acid copolymer, acrylic acid / methacrylic acid copolymer, polyacrylic acid, and alkali metal salts of these polymer electrolytes and And / or hydroxycarboxylic acids such as ammonium salts, ethanolamines and their hydrochlorides, oxalates, phosphates, citric acid, and tartaric acid;
And salts thereof, amino acids such as glycine, alanine, and glutamic acid, aliphatic aminosulfonic acids such as sulfamic acid, (poly) aminopolyacetic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and triethylenetetramine hexaacetic acid, and aminotri (methylenephosphonic acid). ) Acids, 1-hydroxyethylidene-1,1-diphosphonic acid, (poly) aminopoly (methylene phosphonic acid) such as ethylenediaminetetra (methylene phosphonic acid) and the like, and at least a part of the acid groups of these compounds is alkali An intermediate layer made of a metal salt, an ammonium salt, or the like may be provided.

The intermediate layer further includes titanium oxide, alumina,
Fine particles such as silica, zirconia, and antimony oxide may be used in combination. There is no particular limitation on the thickness of the intermediate layer,
If the purpose is to achieve the adhesive property of the photoconductive layer, the thickness may be at most about 10 μm, regardless of the laminate used. On the other hand, if the electric conductivity of the intermediate layer is low, the electric charge of the photoconductive layer hardly dissipates, the photosensitivity is lowered, and the resolution of the toner image is lowered. Therefore, the electric conductivity of the intermediate layer is 10 ^-9 S / s. cm or more is preferred.

A photoconductive layer is provided on both sides of the above-mentioned laminated plate to provide a substrate according to the present invention. The photoconductive layer according to the present invention contains at least a photoconductive compound. Examples of the photoconductive compound that can be used in the present invention include organic and inorganic photoconductive compounds. Examples of inorganic photoconductive compounds include selenium and selenium alloys, amorphous silicon,
Cadmium sulfide, zinc oxide, zinc sulfide, titanium oxide and the like can be mentioned. Examples of the organic photoconductive compound include: a) a triazole derivative described in U.S. Pat. No. 3,112,197, etc., and b) an oxalate described in U.S. Pat. No. 3,189,447. Diazole derivatives, c) imidazole derivatives described in JP-B-37-16096, etc., d) U.S. Pat. Nos. 3,542,544 and 3,615,
No. 402, 3,820,989, Japanese Patent Publication No. 45
No.-555, No. 51-10983, JP-A-51-93
No. 224, No. 55-108667, No. 55-1569
Nos. 53 and 56-36656; e) U.S. Pat. Nos. 3,180,729 and 4,278,
746, JP-A-55-88064 and JP-A-55-88064.
No. 88065, No. 49-105537, No. 55-51
Nos. 086, 56-80051, 56-88141
No. 57-45545, No. 54-112637,
Pyrazoline derivatives and pyrazolone derivatives described in JP-A-55-74546; f) U.S. Pat. No. 3,615,404;
Nos. 1-10105, 46-3712, 47-28
No. 336, JP-A-54-83435 and JP-A-54-110.
Phenylenediamine derivatives described in JP-A-836 and JP-A-54-119925; g) U.S. Pat. Nos. 3,567,450 and 3,180,
No. 703, No. 3,240,597, No. 3,658,5
No. 20, 4,232, 103, 4,175,96
1, 4,012,376, and the West German patent (D
AS) 1,110,518, JP-B-49-35702
No. 39-27577, JP-A-55-144250.
Nos. 56-119132 and 56-22437
H) Amino-substituted chalcone derivatives described in U.S. Pat. No. 3,526,501, i) N, N described in U.S. Pat. No. 3,542,546, etc. -Bicarbazyl derivatives; j) oxazole derivatives described in U.S. Pat. No. 3,257,203; k) styryl anthracene derivatives described in JP-A-56-46234; 1) JP-A-54-110837 M) U.S. Pat. No. 3,717,462, JP-A-5
4-59143 (corresponding to U.S. Patent No. 4,150,987), 55-52063 and 55-52064
Hydrazone derivatives described in JP-A-55-46760, JP-A-55-85495, JP-A-57-11350, JP-A-57-148749, and JP-A-57-104144; n) US Patent No. 4,047,948 No. 4,047,
949, 4,265,990, 4,273,8
Nos. 46, 4,299,897 and 4,306,
No. 008, etc., o) JP-A-58-190953 and JP-A-59-95540.
No. 59-97148, No. 59-195658,
And stilbene derivatives described in JP-B-62-36674; p) Polyvinylcarbazole and derivatives thereof described in JP-B-34-10966; q) JP-B-43-18874 and 43-19192.
, Polyvinyl-2-anthracene, poly-2-vinyl-4- (4'-dimethylaminophenyl) -5-phenyloxazole, and poly-3
-Vinyl polymers such as vinyl-N-ethylcarbazole; r) polymers such as polyacenaphthylene, polyindene and acenaphthylene / styrene copolymer described in JP-B-43-19193; Pyrene described in JP 13940 /
Condensed resins such as formaldehyde resin and ethylcarbazole / formaldehyde resin; t) JP-A-56-90883 and 56-161550.
U) U.S. Pat. Nos. 3,397,086 and 4,666.
802, JP-A-51-90827 and 52-655
No. 643, JP-A Nos. 64-2061 and 64-43.
No. 89 and the like include metal-free or metal (oxide) phthalocyanines and naphthalocyanines, and derivatives thereof. The organic photoconductive compound according to the present invention is not limited to the compounds described in a) to u), and other organic photoconductive compounds can be used. These organic photoconductive compounds are:
If desired, two or more kinds may be used in combination.

In the photoconductive layer according to the present invention,
Various pigments, dyes, and the like can be used in combination for the purpose of improving the sensitivity of the photoconductive layer and giving sensitivity to a desired wavelength region. Examples of these include: 1) U.S. Patent Nos. 4,436,800 and 4,439,
506, JP-A-47-37543, 58-
No. 123541, No. 58-192042, No. 58-2
Nos. 19263, 59-78356, 60-179
No. 746, No. 61-148453, No. 61-2380
No. 63, JP-B-60-5941 and JP-B-60-456
No. 64, etc., monoazo, bisazo and trisazo pigments, 2) perylene pigments described in U.S. Pat. No. 3,371,884, etc. 3) British Patent No. 2,237,680, etc. 4) quinacridone pigments described in British Patent No. 2,237,679, etc., 5) British Patent No. 2,237,678, JP-A-5
Nos. 9-184348 and 62-28738; polycyclic quinone pigments; 6) bisbenzimidazole pigments described in JP-A-47-30331; 7) U.S. Pat. No. 4,396 , 610 and 4,64
Squarium salt pigments described in 4,082, etc. 8) JP-A-59-53850 and JP-A-61-21254
And the azurenium salt pigments described in JP-A No. 2 (KOKAI) No. 2 and the like. In addition, sensitizing charges include “electrophotography” 129 (1
973), “Synthetic Organic Chemistry” 24 No. 11 101
0 (1966) and the like can be used. Examples thereof include: 9) U.S. Pat. Nos. 3,141,770 and 4,283,
475 Pat, pyrylium dyes described in JP-B-48-25658, and JP 61-71965 Patent Publication, 10) Applied Optics Supplement 3 50 (196
9) and triarylmethane dyes described in JP-A-50-39548, 11) cyanine dyes described in U.S. Pat. No. 3,597,196, and 12) JP-A-59-164588. No., 60-1630
No. 47, and styryl dyes described in JP-A-60-252517. These sensitizing dyes may be used alone or in combination of two or more.

The photoconductive layer according to the present invention is further provided with compounds such as trinitrofluorenone, chloranil, and tetracyanoethylene, as disclosed in JP-A-58-65439 and JP-A-58-65439.
Nos. 102239, 58-129439, and 60
Compounds described in JP-A-71965 can be used in combination.

The photoconductive layer according to the present invention preferably contains a binder resin in addition to the above photoconductive compound. The binder resin used in the present invention must satisfy electrophotographic properties including chargeability and the like, and have solubility in an eluate. An acidic or alkaline solution is used as the eluate. In the case of an acidic eluate, an acid-soluble binder resin is used as a binder resin, and in the case of an alkaline eluate, an alkali-soluble binder resin is used.

Among the binder resins used in the present invention, examples of the alkali-soluble resin include carboxylic acid groups, methacrylamide, phenolic hydroxyl groups, sulfonic acid groups, sulfonamide groups, sulfonimide groups, and phosphonic acid groups. And a phenol resin and a xylene resin. Among these, a copolymer containing a monomer having a carboxylic acid group and a phenol resin can be advantageously used because of their high charge retention. Examples of the copolymer containing a monomer having a carboxylic acid group include copolymers of styrene and maleic acid monoester, and copolymers of acrylic acid or methacrylic acid and their alkyl esters, aryl esters or aralkyl esters. Polymers are preferred. Further, a copolymer of vinyl acetate or vinyl benzoate and crotonic acid is also good. Particularly preferred phenolic resins include novolak resins obtained by condensing phenol, o-cresol, m-cresol, or p-cresol with formaldehyde or acetaldehyde under acidic conditions.

Specific examples of the binder resin used in the present invention include styrene / maleic acid monoalkyl ester copolymer, methacrylic acid / methacrylic acid ester copolymer,
Styrene / methacrylic acid / methacrylic acid ester copolymer, acrylic acid / methacrylic acid ester copolymer, methacrylic acid / methacrylic acid ester / acrylic acid ester copolymer, styrene / methacrylic acid / acrylic acid ester copolymer, styrene / Acrylic acid / methacrylic acid ester copolymer, vinyl acetate / crotonic acid copolymer, vinyl acetate / crotonic acid / methacrylic acid ester copolymer,
Styrene such as vinyl benzoate / acrylic acid / methacrylic acid ester copolymers, and copolymers of the above carboxylic acid-containing monomers with the above carboxylic acid-containing monomers and the like, such as styrene, acrylic acid esters, methacrylic acid esters, vinyl acetate, and vinyl benzoate. These binder resins may be used alone or in combination of two or more.

As an example of the acid-soluble binder resin, JP-B-1
And triphenylmethane polymer and chitosan described in JP-A-41982.

When the photoconductive layer is thin, a required charging potential cannot be secured and a high-quality toner image cannot be obtained. Conversely, when the photoconductive layer is thick, the photoconductive layer other than the toner image portion in the subsequent process is eluted and removed. Not only promotes the deterioration of the eluate, but also deteriorates the thinning of the photoconductive layer due to the flow of the eluent from the layer direction of the photoconductive layer. Therefore, the thickness of the photoconductive layer according to the present invention is suitably about the minimum thickness at which a desired charging potential can be stably obtained in consideration of development. In the present invention, the thickness of the photoconductive layer is preferably 0.5 to 10 μm,
Further, the thickness is preferably 1 to 7 μm.

In the photoconductive layer according to the present invention, the mixing ratio when a binder resin is used in combination with the photoconductive compound depends on the electrophotographic characteristics of the photoconductive compound. The binder resin is set to the minimum thickness that ensures the property, and then the mixing ratio with the photoconductive compound is determined so that the desired sensitivity and residual potential are obtained. In the photoconductive layer according to the present invention, the content of the photoconductive compound is preferably in the range of about 1 to 100% by weight of the binder resin.
40% by weight is preferred.

The substrate according to the present invention can be obtained by applying and laminating a coating solution for forming a photoconductive layer on both sides of a support in a conventional manner. The coating liquid for forming a photoconductive layer is prepared by dissolving or dispersing components constituting the photoconductive layer in an appropriate solvent. The concentration of the effective components (such as the photoconductive compound and the binder resin) of the coating liquid and the solvent used for the coating liquid are appropriately selected depending on the coating method, drying conditions and the like. In particular, when producing a photoconductive layer by an electrodeposition method, at least water is used in combination as a solvent. Further, in order to make the binder resin water-soluble, the binder resin may be neutralized with a liquid containing a basic compound before use. As the basic compound, for example, an organic base such as triethylamine, diethylamine, and monoethanolamine, and an inorganic base such as sodium hydroxide, potassium hydroxide, and aqueous ammonia can be used.

When a component insoluble in a solvent, such as phthalocyanine, is used as the photoconductive compound, the compound is used after being dispersed to a mean particle size of 0.4 μm or less, more preferably 0.2 μm or less by a dispersing machine. In addition, if necessary,
In addition to the photoconductive compound and the binder resin, a plasticizer, a surfactant, and other additives can be added for the purpose of improving the film physical properties of the photoconductive layer, the viscosity of the coating solution, and the dispersibility. .

The lamination of the photoconductive layer according to the present invention on a support is carried out by a dipping method, a bar coating method, a spray coating method, a roll coating method, a curtain coating method, an electrodeposition method or the like. The photoconductive layer may be formed on one side and the other side by different methods, except when the photoconductive layer can be laminated on both sides of the support at the same time as in the immersion method. Also, the lamination of the photoconductive layer
A method for allowing the components constituting the photoconductive layer to be contained in the same layer,
Alternatively, a method of separately containing two or more layers, for example, disposing an easily dissolving and strongly adhesive binder resin in the lower layer (support side) and disposing a highly-chargeable resin in the upper layer, There is known a method of separating and using different layers, such as increasing the content of an acidic compound, and any method may be used for lamination. In the drying of the coating solution, it is preferable to set a mild drying condition because the electrophotographic characteristics may be deteriorated depending on the drying conditions (temperature and air volume) particularly in the initial drying zone.

[0057]

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

EXAMPLE As a substrate, a double-sided copper-clad laminated board (manufactured by Mitsubishi Gas Chemical, CC
LE170) and a 5m diameter diagonally on a 342mm x 512mm (0.6mm thick) rectangular substrate
m reference hole was drilled. A coating solution for forming an electrophotographic photoconductive layer [methacrylic acid / benzyl methacrylate / n-butyl acrylate copolymer (weight composition ratio 20/30/50, molecular weight) with the long end (512 mm side) sandwiched by a chuck at 10 mm 25,000) 50 parts by weight, χ-type metal-free phthalocyanine (composed of Dainichi Seika Kogyo Co., Ltd., MCP-80) 10 parts by weight, and 1,4-dioxane 690 parts by weight]. Formed a photoconductive layer having a thickness of about 5 μm. In this way, 100 substrates were produced.

The double-sided copper-clad substrate having the photoconductive layer formed on both sides is placed on a surface plate of a laser exposure machine, and two reference holes at diagonally upper corners of the rectangular substrate are monitored by a CCD.
The position in the horizontal plane of the substrate was aligned by slightly rotating the surface plate.

Further, the surface plate is moved by using a corotron charger installed in front of the laser irradiation position of this exposure machine, and immediately after the platen is charged, 488 nm,
A 100 mW Ar laser beam (beam diameter on the surface plate of 30 μm) is scanned by an eight-sided polygon to expose the substrate,
An electrostatic latent image of the wiring pattern was obtained on one surface. As the wiring pattern, a high-definition pattern including a minimum line & space of 50 μm, which is a wiring pattern for a double-sided printed board, was used.

Next, the electrostatic latent image was converted into a toner image on the substrate on which the electrostatic latent image was formed on one side by using a double-sided toner developing machine described in JP-A-6-224541. At that time, the processing was performed with the electrostatic latent image forming surface as the upper surface, and the lower developing electrode was removed so that toner did not adhere to the surface on which the electrostatic latent image was not formed. In this way, 100 substrates were processed, and a toner image corresponding to the wiring pattern was formed on each side. Next, the substrate on which the toner image is formed on one side of 100 sheets is inverted, and the other surface (second surface) is aligned and charged, exposed, and subjected to toner development in the same manner as described above to form a toner image. Then, toner images were formed on both sides of 100 substrates. When exposing the second surface, exposure was performed by exchanging the exposure data of the first surface in the exposure machine with the exposure data of the second surface. The substrate was sprayed with a 1% by weight sodium carbonate solution heated to 30 ° C., washed with tap water to elute and remove the photoconductive layer not covered with the toner, and then heated to 45 ° C. The exposed copper portion was removed by spraying an aqueous solution of diiron. Further, a 3.0% by weight aqueous sodium hydroxide solution heated to 50 ° C. was sprayed to remove the remaining toner and the photoconductive layer to obtain a wiring pattern on both surfaces of the substrate.

The wiring pattern forming surface of the obtained substrate was free of stains on both sides, and the wiring pattern had a uniform and uniform wiring width on both sides. It took about two and a half hours from the preparation of 100 substrates provided with photoconductive layers on both surfaces by the above processing method to the formation of toner images on both surfaces of the 100 substrates.

Comparative Example A substrate 100 provided with a photoconductive layer on both surfaces in the same manner as in the example.
Sheets were produced. An electrostatic latent image was formed on one surface by using the same alignment method, charging method, and exposure method as in the example. Thereafter, the substrate was inverted, placed on a surface plate upside down, and similarly positioned, charged and exposed to form an electrostatic latent image on both surfaces of the substrate. When exposing the second surface,
Exposure was performed by exchanging the exposure data of the first surface. A toner image was formed on both sides of this substrate by using the double-sided toner developing apparatus described in JP-A-6-224541.

The subsequent processing is performed in the same manner as in the embodiment.
Wiring patterns were obtained on both sides of the substrate. Regarding the wiring pattern formation surface of the obtained substrate, 20 out of 100 substrates,
A short circuit of the wiring pattern due to the copper residue is observed, and the state of the copper residue matches the shape of the surface contact portion at the time of adsorption of the surface plate, the potential at the contact position of the electrostatic latent image decreases due to the surface contact, It was found that copper adhered during the toner developing process, resulting in a defect of copper residue.

When the line widths of the wiring patterns on the first surface and the second surface are compared with each other, for all 100 substrates,
It was found that the line width of the surface was 10 μm thicker than the specified value on average, indicating that the line width uniformity was poor. This is because the time between charging the first surface and performing the toner developing process is longer than that of the process of the example and the process of the second surface of the comparative example. This is probably because the image potential decreased due to dark decay.

Further, after preparing 100 substrates having photoconductive layers provided on both sides by the above-described processing method, the toner image was
It took about 3 hours to form on both sides of zero substrate.
Due to the reversal work on the exposure machine surface plate and the time loss due to the exchange of exposure data, it took 20% more time than the processing by the method of the embodiment.

[0067]

As described above, according to the method for manufacturing a printed wiring board of the present invention, at least a metal conductive layer and a photoconductive layer are provided on both sides of an insulating substrate in this order, and an electron is provided on the photoconductive layer. To form an electrophotographic printed wiring board that forms a toner image by a photographic method, then dissolves and removes the photoconductive layer other than the toner image area, and etches the surface of the substrate where the photoconductive layer is removed, using a high-definition circuit pattern Even so, toner images on both sides can be formed satisfactorily, and a large number of printed wiring boards having excellent line width uniformity can be efficiently manufactured.

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Claims (1)

[Claims] At least a metal conductive layer and a photoconductive layer are provided in this order on both surfaces of an insulating substrate, a toner image is formed on the photoconductive layer by electrophotography, and then a photoconductive layer other than the toner image portion is formed. In a method of manufacturing a printed wiring board for dissolving and removing and etching the surface of a substrate where a photoconductive layer has been removed, formation of a toner image by electrophotography is performed by aligning and charging one surface, and then exposing and statically. An electrostatic latent image is provided, and then a toner developing process is performed to form a toner image,
The feature is that the substrate is reversed again, the alignment is performed, the other surface is charged, the exposure is performed, an electrostatic latent image is provided, and then the toner development process is performed again to form a toner image on the other surface. Method for producing an electrophotographic printed wiring board.