JPH10268582A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method by which an image can be formed in a simplified stage without requiring an exposure stage. SOLUTION: In this method, at least one resin layer 1 is provided on a conductive supporting layer 10 and substance to change the electric resistance of the resin layer 1 is supplied to the resin layer 1, then a surface is electrified so as to form an electrostatic latent image. After forming the electrostatic latent image, the formed electrostatic latent image is developed with toner and fixed, whereby a toner image is formed. Furthermore, when the resin layer 1 is a layer including processing solution soluble resin, the image is formed on the conductive supporting layer 10 by eluting and removing a non-image part other than a toner developing part by the processing solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a printing plate, for example,
The present invention relates to an image forming method capable of forming a resist layer when an electronic circuit such as a printed wiring board is manufactured.

[0002]

2. Description of the Related Art At present, a printing plate is manufactured by providing a lipophilic ink-receiving layer on a base material such as an aluminum plate, a zinc plate, or paper having a hydrophilized surface. Is most common.

[0003] Further, in an electronic circuit used inside an electric component such as a printed wiring board, wiring is formed of a conductive material such as copper on an insulating substrate. In the process of manufacturing such an electronic circuit, a substrate for providing a corrosion-resistant etching resist layer on a conductive layer of a laminate in which a conductive layer is laminated on an insulating substrate in advance and etching away the exposed conductive layer is provided. There are a lactive method and an additive method in which a corrosion-resistant plating resist layer is provided on an insulating substrate and then a conductive layer is formed on the exposed insulating substrate by metal plating or the like. At present, even in a method for manufacturing a printed wiring board, a method using a photopolymer is generally used as a method for forming an etching resist layer or a plating resist layer.

The formation of the ink receiving layer, the etching resist layer, and the plating resist layer using the photopolymer utilizes the chemical change of the photopolymer caused by light irradiation to improve the solubility of the photopolymer applied on the base material in a developing solution. By changing. However, in this method,
In order to obtain high resolution, contact exposure using ultraviolet light and white light was necessary.

[0005] Further, as electronic circuits and printing plates are required to have higher densities, finer designs, and shorter manufacturing times, a shift to a method of directly exposing a photopolymer using a laser has been made. However, the optical sensitivity of photopolymers is generally low due to photochemical reactions, and therefore, there is a problem that the laser output device must be high in output, resulting in an increase in size and cost of the device.

[0006] Furthermore, the photochemical reaction of the photopolymer proceeds even under room light or sunlight. In addition, it lacks chemical stability such that the reactivity changes depending on the temperature and that oxygen serves as a reaction inhibitor. Therefore, it is necessary to pay sufficient attention to the environment and working conditions such as the storage of the photopolymer solution, the step of coating the substrate, and the step of exposure.

On the other hand, a method of forming an image by utilizing a surface charge has been known for a long time, for example, Japanese Patent Publication No. 37-17 / 1987.
Japanese Patent Publication No. 162 and Japanese Patent Publication No. 38-6961 describe a printing plate using an electrophotographic method. In these methods, an image is formed by subjecting a photosensitive layer to a process of surface charging, exposure, development, fixing, and elution. This image can be used as a printing plate by subjecting it to a hydrophilic treatment on an aluminum substrate, and can be used for wiring on a printed circuit board as described in JP-A-54-145538 on a copper substrate. .

However, in such an image forming method based on the electrophotographic method, it is possible to use a low-output laser beam because of its high sensitivity. However, after the surface is charged, it is sensitive to light so that it can be used in a dark room or safelight. In addition, it is necessary to perform the following operations, furthermore, the materials related to charge generation and charge transport constituting the electrophotographic photoreceptor are expensive, which raises the cost of the photosensitive layer. About 10% by weight or more was necessary, and it could not be used positively as sludge components after elution of the photosensitive layer caused problems such as disposal and maintenance.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming method capable of forming an image by a simplified process which does not require an exposure process.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have solved the above problem by the following method. That is, an image in which at least one resin layer is provided on a conductive support layer, a material that changes the electrical resistance of the resin layer is supplied on the resin layer, and then the surface is charged to form an electrostatic latent image It is a forming method.

Further, after supplying a material that changes the electric resistance of the resin layer to the surface of at least one resin layer provided on the conductive support layer, the surface is charged to form an electrostatic latent image. This is an image forming method in which the toner is developed with toner.

Further, if the resin layer is a layer containing a processing solution-soluble resin which becomes soluble in the processing solution, a material that changes the electrical resistance of the resin layer is supplied to the surface of the resin layer. An image forming method for developing an image on a conductive support layer by developing an electrostatic image portion formed by charging the surface with toner, and further eluting a non-image portion other than the toner developing portion with a processing liquid. is there.

[0013] Further, there is provided an image forming method for supplying a substance which changes electric resistance to the resin layer by an ink jet printer.

As described above, the image forming material according to the image forming method of the present invention does not need to contain a photopolymer or a photoconductive substance. Therefore, the resin layer is chemically stable to light, temperature and oxygen. It is. Therefore, it is excellent in storability, and does not require an exposure step, and can perform all image forming steps in a bright room.

[0015]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a schematic view showing an example of an image forming material according to the image forming method of the present invention. First, a substance that changes the electrical resistance of the resin layer 1 is supplied to the resin layer 1 of the image forming material having at least one resin layer on the conductive support layer 10, and after changing the electrical resistance of that portion, The surface of the resin layer is charged to form an electrostatic latent image (A). Next, the electrostatic latent image portion formed as desired is developed with toner (B). Further, if the resin layer is a layer containing a processing solution-soluble resin which becomes soluble in the processing solution, then the non-image area other than the toner developing section is eluted with the processing liquid, thereby forming a resin on the conductive support layer. An image can be formed (C).

The resin layer relating to the image forming material used in the image forming method of the present invention has such a property that the electric resistance of the adhered portion can be changed by supplying a substance which changes the electric resistance. However, more specifically, it is sufficient if there is a clear difference in the specific resistance between the resin layer and the substance that changes the electric resistance. That is, if the resin layer has a charge-dissipating property or a conductive property, the substance that changes the electric resistance may be a substance having a charge-retaining property. The substance which changes the charge may be a substance having a charge dissipating property or a conductive property.

Specific examples of the resin used in the resin layer according to the present invention include styrene / maleic anhydride copolymer, styrene / maleic acid monoalkyl ester copolymer, styrene / methacrylic acid / methacrylic acid ester copolymer,
Methacrylic acid / methacrylic acid ester copolymer, acrylic acid / methacrylic acid ester copolymer, styrene / acrylic acid / methacrylic acid ester copolymer, vinyl acetate /
Styrene, acrylic acid ester, methacrylic acid ester, vinyl acetate, vinyl benzoate, etc. such as crotonic acid copolymer, vinyl acetate / crotonic acid / methacrylic acid ester copolymer, and acrylic acid, methacrylic acid, itaconic acid, crotonic acid , Maleic acid, maleic anhydride, copolymers with carboxylic acid-containing monomers such as fumaric acid or monomers containing acid anhydride groups, methacrylamide, vinylpyrrolidone, phenolic hydroxyl groups, sulfonic acid groups, sulfonamide groups, sulfones Copolymers containing a monomer having an imide group, phenol resins, partially saponified vinyl acetate resins, xylene resins, and vinyl acetal resins such as polyvinyl butyral can be exemplified. In addition, a copolymer containing a monomer containing a basic group such as dimethylaminoethyl methacrylate, vinylpyridine, and aminostyrene can also be used.

The resin layer according to the present invention may be a layer containing a processing solution-soluble resin which becomes soluble in the processing solution. Examples of the processing solution-soluble resin, which is a resin that becomes soluble in an alkaline processing solution, include a resin containing an acidic group such as a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfonamide group, and a sulfonimide group. Examples of the resin that becomes soluble in an acidic processing solution include:
Resins containing a basic group such as an amino group are exemplified.

When these resins are used in the image forming material according to the image forming method of the present invention, if the resin layer is made to be chargeable, hydrophilic functional groups including acidic functional groups and basic functional groups in the above resins are used. If the resin layer is made to have a charge-dissipating property, the content of the hydrophilic functional group including the acidic functional group and the basic functional group in the resin may be reduced. Should be increased. In general, the higher the content of these functional groups, the more soluble in the processing solution.

The processing solution used when the resin layer according to the present invention is a layer containing an alkali-soluble resin includes the processing solution according to the image forming material and the image forming method of the present invention.
It is possible to use alkali metal silicates such as sodium silicate and potassium silicate, alkali metal hydroxide, phosphoric acid and alkali metal carbonate and ammonium salt, ethanolamine, ethylenediamine, propanediamine, triethylenetetramine, morpholine and the like. it can. Also,
When the resin layer according to the present invention is a layer containing an acid-soluble resin, inorganic acids such as hydrochloric acid, phosphoric acid, nitric acid, and sulfuric acid can be used as the treatment liquid. Further, water can be advantageously used as a solvent for the treatment liquid. In any of the treatment liquids, various surfactants may be appropriately used in combination. If the resin layer according to the present invention is essentially water-soluble, the treatment liquid may simply be water or water containing a surfactant.

The resin layer according to the present invention is formed by applying a coating liquid containing the above-mentioned treating solution-soluble resin on the conductive support layer by a coating method such as a roll coating method, a curtain coating method, a dip coating method, and the like, and then drying. Can be formed.

As the substance for changing the electric resistance of the resin layer according to the present invention, when the resin layer is inherently chargeable, anionic dyes having an acidic group such as a sulfonic acid group and a carboxylic acid group; Examples include cationic dyes having a basic group such as a group, ionic compounds such as alkali metals such as sodium and potassium, and organic and inorganic metal salts thereof, and pigments such as phthalocyanine, metal phthalocyanine and carbon black.

When the resin layer according to the present invention has a charge retention property, its inherent electric resistance value is about 10 ^-3 to 10 ^-4.
The range is Siemens / cm. Substance for changing the electrical resistance of such charge retention property of the resin layer is a charge dissipative or conductive electrical resistance of about 10 ² to 1
0 is in the range of ⁶ Siemens / cm.

The above-mentioned substances which change the electric resistance of the resin layer are dissolved or dispersed in an aqueous or oily solvent, and the solution or dispersion is applied by a usual printing means such as an ink jet method. The resin can be supplied to the resin layer by attaching it to the surface of the resin layer. When dissolving or dispersing in a solvent, an additive such as a surfactant may be added.

The charging according to the image forming method of the present invention is
It is to give electric charge to the resin layer surface, corona charging,
There are methods such as roller charging and brush charging.

The electrostatic latent image according to the image forming method of the present invention refers to an electrostatic latent image formed on the surface of a resin layer after the surface of the resin layer is charged by attaching a substance that changes the electrical resistance of the resin layer. In addition, it is a pattern of electrostatic charge.

As the toner developing method according to the image forming method of the present invention, a dry developing method (cascade developing, magnetic brush developing, powder cloud developing) or a liquid toner in which toner particles are dispersed in an appropriate insulating liquid. A development method can be used. Among these, the liquid development method can stably reduce the toner particles to a small particle size as compared with the dry development method, so that a finer toner image can be formed. preferable.

As the toner used in the present invention, a wet toner used for an electrophotographic printing plate can be used.
The resin layer according to the present invention is a layer containing a processing solution-soluble resin which becomes soluble with the processing solution, and after the formed electrostatic latent image portion is developed with toner, non-images other than the toner developing portion are formed with the processing solution. In the case of including a step of eluting a part, the resin layer must have a resist property against elution and removal of the resin layer. For this reason, as the resin component of the toner, for example, acrylic resin composed of methacrylic acid, methacrylic acid ester, etc., vinyl acetate resin, copolymer of vinyl acetate with ethylene or vinyl chloride, vinyl chloride resin, vinylidene chloride resin, polyvinyl butyral Vinyl acetal resin, such as polystyrene, copolymers of styrene with butadiene, methacrylate, etc., polyethylene, polypropylene and its chlorides, polyester resins such as polyethylene terephthalate and polyethylene isophthalate, polycapramid and polyhexamethylene adipamide Such as polyamide resin, phenolic resin, xylene resin,
It is preferable to contain an alkyd resin, a vinyl-modified alkyd resin, gelatin, a cellulose ester derivative such as carboxymethyl cellulose, and other waxes and waxes. The toner may contain a dye, a pigment, and 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 at the time of corona charging.

The conductive support layer according to the image forming method of the present invention comprises a laminate having a conductive layer of copper, aluminum, iron, gold, silver or the like provided on at least one surface of a substrate, or a metal thereof. A metal plate or the like can be used.

As the ink jet printer relating to the image forming method of the present invention, an ordinary commercially available ink jet printer such as a thermal jet system or a piezo system can be used.

[0031]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited to the following Examples unless it exceeds the gist of the invention.

Example 1 Synthetic resin soluble in treating solution 35 parts by weight of styrene, 15 parts by weight of n-butyl methacrylate, 20 parts by weight of n-butyl acrylate, 30 parts by weight of methacrylic acid, 2 parts by weight of azobisisobutyronitrile The mixture was dropped into 200 parts by weight of 1-methoxy-2-propanol maintained at 90 ° C. with nitrogen replacement over 1 hour, and a resin solution was obtained over 5 hours.

Formation of Resin Layer After adding 0.60 g of zinc oxide (Hakusui Chemical No. 1), 6.0 g of 1-methoxy-2-propanol and 14.0 g of dimethylformamide to 4.5 g of the above-mentioned treatment solution-soluble resin solution ( (Solid content: 8%) and glass beads were added and dispersed by a paint conditioner. This dispersion was applied with an applicator to a PET film base on which aluminum was deposited on the surface, and dried at 90 ° C. for 10 minutes to form a resin layer.

The charging characteristics of the image forming material thus manufactured were evaluated using an electrostatic field measuring device SP-428 manufactured by Kawaguchi Electric. When a corona application voltage of +6.0 kV was applied, the initial potential was +230 V, and the potential retention after 96 seconds was 96%.

The surface of the image forming material was uniformly coated with a black ink in a solid form using an ink jet printer (Epson MJ-510C) and dried at 80 ° C. for 20 minutes. When the charging characteristics were evaluated in the same manner, the electric resistance of the surface was reduced at an initial potential of +80 V and a potential holding ratio of 83% after 10 seconds.

Formation of Toner Image An ink jet printer (Epson M
J-510C), and dried at 80 ° C. for 15 minutes. This was charged to +200 V to form an electrostatic latent image on the ink image portion. This latent image is converted to a positively charged liquid developer toner “ODP-
Using a "TW" (manufactured by Mitsubishi Paper Mills Co., Ltd.), a developing bias of +150 V was applied to the developing electrode to perform reversal development while a part of the resin layer was dissolved and peeled to expose and electrically ground the conductive support layer.
After the toner development, the substrate was dried at 80 ° C. for 5 minutes to fix the toner image.

Removal of Non-Image Area Resin Layer A 1% aqueous solution of sodium carbonate is used to elute and remove the processing solution-soluble resin layer in a portion where no toner adheres, thereby forming a toner layer and an undissolved resin layer thereunder. An image could be formed.

Example 2 Synthesis of Processing Solution-Soluble Resin A mixture consisting of 40 parts by weight of n-butyl methacrylate, 40 parts by weight of n-butyl acrylate, 20 parts by weight of methacrylic acid, and 2 parts by weight of azobisisobutyronitrile was replaced with nitrogen. Then, the solution was added dropwise to 200 parts by weight of 1-methoxy-2-propanol maintained at 90 ° C. over 1 hour, and a resin solution was obtained over 3 hours. Example 1 using this resin solution
An image was formed in the same process as in Example 1.

Example 3 Production of Printed Circuit Board A double-sided copper-clad laminate for printed circuit boards (50 × 100) having a large number of through-holes having a diameter of 0.6 mm and 1.2 mm of a resin layer was formed.
0 × 2.0 mm, copper foil thickness: 5 μm)
Was applied by a curtain coating method, and dried at 90 ° C. for 15 minutes to obtain a resin layer (film thickness: 6.0 μm).

Forming a Toner Image A wiring pattern including a through-hole portion is drawn on both surfaces of a double-sided copper-clad laminate for a printed circuit board on which a soluble resin layer is formed using an ink jet printer (Epson MJ-5000C). It was dried at 80 ° C. for 20 minutes. This was charged to +200 V to form an electrostatic latent image on the ink image portions on both sides. This latent image is reversely developed with a positive biasing liquid developer “LOM-EDIII” for Diafax Master (manufactured by Mitsubishi Paper Mills) at a developing bias of +120 V, and the toner fixing machine “EP-31V” ( The toner image was fixed by Mitsubishi Paper Mills Co., Ltd.). When the cross section was examined separately, it was confirmed that the toner was uniformly developed and fixed in the through holes of both 0.6 mm and 1.2 mm.

Removal of the resin layer of the non-image area by elution Removal of an alkaline developer " Decoating Solution 872" manufactured by Polychrome, USA, diluted 12 times with water, using an aqueous alkaline solution to treat the portion where no toner adheres. By removing the soluble resin layer, a wiring image having a toner image and a resin layer thereunder as an image portion was formed.

[0042]

As described above, according to the image forming method of the present invention, an image can be formed in a simplified process not including an exposure process in a bright room, and a printing plate, a printed wiring board, and the like can be formed. It has become possible to manufacture electronic circuits.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram illustrating an example of an image forming material of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Resin layer 2 Toner layer 10 Conductive support layer

Claims (4)

[Claims] 1. An image recording material comprising at least one resin layer provided on a conductive support layer, a material that changes the electrical resistance of the resin layer is supplied onto the resin layer, and then the surface is charged. An image forming method for forming a latent image. 2. The image forming method according to claim 1, wherein after forming the electrostatic latent image, the image is developed with toner. 3. The method according to claim 1, wherein the resin layer is a layer containing a processing solution-soluble resin which is soluble in the processing solution. 3. The image forming method according to claim 2, wherein the non-image portion is eluted. 4. A substance that changes electric resistance is attached to the resin layer by an inkjet printer.
The image forming method according to claim 1.