WO1999010186A1

WO1999010186A1 - Image forming material, image forming method, lithographic printing plate manufacturing method and apparatus, lithographic printing plate making method, and printed wiring board manufacturing method

Info

Publication number: WO1999010186A1
Application number: PCT/JP1997/003819
Authority: WO
Inventors: Kenji Hyodo; Wakana Aizawa; Yuji Takagami; Kenji Tsuda
Original assignee: Mitsubishi Paper Mills Limited
Priority date: 1997-08-22
Filing date: 1997-10-22
Publication date: 1999-03-04
Also published as: DE19781578C2; DE19781578T1

Abstract

An image forming material and an image forming method which are capable of accommodating a direct laser drawing method, producing an image of a high resolution easily and performing an image forming operation easily in a bright room, lithographic printing plate manufacturing method and apparatus, a lithographic printing plate making method, and a printed wiring board manufacturing method are provided. Concretely speaking, an image forming material having a layer of thermally meltable fine particles on a base material, and a method of forming an image on a base material by melt-fixing the portion of a layer of the thermally meltable fine particles of the image forming material which corresponds to an image portion, and then removing the portion of the layer of thermally meltable fine paticles which corresponds to a non-image portion are provided. The layer of thermally meltable fine particles can be melt-fixed by a laser. The removing of the non-image portion of the layer of thermally meltable fine particles can be done more easily by providing a layer of an alkali-soluble resin between the base material and the layer of thermally meltable fine particles, and applying an alkali solution to this layer of an alkali-soluble resin.

Description

Description Image forming material, image forming method, lithographic printing plate manufacturing method and manufacturing apparatus, lithographic printing plate making method, and printed wiring board manufacturing method

The present invention relates to an image forming material and an image forming method capable of easily and inexpensively obtaining an image having high resolution. Further, the present invention relates to a method and an apparatus for manufacturing a lithographic printing plate, a method for manufacturing a lithographic printing plate, and a method for manufacturing a printed wiring board using the image forming material and the image forming method.

Background art

Currently, lithographic printing plates are manufactured by providing a lipophilic ink-receiving layer on a substrate such as an aluminum plate, zinc plate, or paper whose surface has been hydrophilized. A lithographic printing plate using a photosensitive material such as polymer is most common.

In a printed wiring board used inside an electric appliance, a circuit is formed of a conductive material such as copper on an insulating substrate. A method for manufacturing such a printed wiring board is to provide 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 to etch away the exposed conductive layer by etching. Active 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 an applied resist layer.

In the method of forming an ink receiving layer, an etching resist layer, or a plating resist layer (hereinafter referred to as an image layer) using a azo compound or a photopolymer, first, a substrate such as a metal plate, paper, a laminated plate, or an insulating substrate is formed on a substrate. Apply a photosensitive material such as a diazo compound or photopolymer. Then, the photosensitive material is irradiated with light to cause a chemical change, thereby changing the solubility in a developing solution. Photosensitive materials are divided into two types depending on the type of chemical change. being classified. A negative type in which the light-irradiated part is polymerized and cured to become insoluble in the developer, and conversely, the functional group in the light-irradiated part changes to have solubility in the developer. It is a positive type. In either case, the photosensitive material remaining on the substrate after processing with the developer and insoluble in the developer becomes the image layer.

When an image layer is formed using the above-described photosensitive material, the exposure method is one of the important factors that determine the resolution. Conventionally, the mainstream has been to produce a film for exposure and then to perform a contact exposure method using ultraviolet light or white light. However, with the advancement of computers, laser direct writing methods that transmit digital signals from computer information to an exposure device (computer 'edge' plate) and directly expose the photosensitive material using a laser are used. It is like that. This laser direct writing method has advantages such as low cost, high speed, and high productivity with many kinds and small lots.

In order to perform this laser direct writing method, the optical sensitivity of the photosensitive material must be increased. In Jiazo compound or follower Toporima, to accompany the photochemical reaction, optical science sensitivity is low, a few to several hundred m J / cm ^2. Therefore, the laser output device must have a high output, and there have been problems such as an increase in the size of the device and an increase in cost.

Photochemical reactions of diazo compounds and photopolymers also proceed under room light or sunlight. Also, reactivity changes even at high temperatures. In addition, the presence of oxygen is an inhibitor of the reaction. Therefore, the photosensitive material has a drawback that the preservation before the exposure step, the application step to the substrate, and the like must be performed in the dark or under a safety light or under a low oxygen concentration.

In view of the above, an image forming method in which the defects caused by such a diazo compound / photopolymer are improved, and a method using fine particles is disclosed in Japanese Patent Publication No. Hei 4-171889, Japanese Patent Application Laid-open No. Hei 9-1717249. No. 6,086,045. In Japanese Patent Publication No. 4-617889, an aqueous dispersion paint containing a coloring agent and a particulate resin having a hydrophilic surface and a hydrophobic inside is applied to a supporting substrate, The coating is formed by drying while maintaining the particle morphology of the particle layer, and then the fine particle layer corresponding to the image is heated to lose the particle morphology, and is fixed together with the colorant on the supporting substrate, and the image is formed. Is not formed An image forming method of separating with an alkaline aqueous solution is disclosed.

Japanese Patent Application Laid-Open No. 9-117129 / 49 discloses an image forming layer on a hydrophilic surface of a lithographic base, the image forming layer comprising hydrophobic thermoplastic polymer particles dispersed in a hydrophilic binder. A method for making a lithographic printing plate is disclosed in which imagewise exposure is performed, followed by development using fresh water or an aqueous liquid, and further heating the imaged image forming layer.

In the image forming method described in Japanese Patent Publication No. Hei 41-18989, heating is performed because a hydrophilic particulate resin whose surface is dissolved in an alkaline aqueous solution and a hydrophobic resin is used inside. Even in the part where the particle morphology of the fine particle layer has disappeared, the internal hydrophobic part may not completely appear on the surface, and it may be peeled off and pinholes may be generated by the aqueous solution In some cases, highly reliable images could not be obtained.

In the image forming method described in Japanese Patent Application Laid-Open No. Hei 9-171714, the hydrophobic thermoplastic polymer particles in the hydrophilic binder are melted by exposure and become insoluble in fresh water or aqueous liquid. However, in order to exhibit insolubility, it must contain many hydrophobic thermoplastic polymer fine particles. If the amount of the hydrophobic thermoplastic polymer particles is too large, there is a problem that the amount of the hydrophilic binder is too small to completely remove the unnecessary image forming layer in the non-image area. In addition, similar to the image forming method described in Japanese Patent Publication No. Hei 4 6-1789, the problem that the image area is not completely covered by the hydrophobic part, in which case pinholes and the like are generated. There was also. In particular, such a problem is likely to occur in a solid portion (large-area image portion).

In an image forming method using fine particles, the resolution of an image is determined by the melting of the fine particles. In Japanese Patent Application Laid-Open No. Hei 9-171,429, since the hydrophilic binder is contained in the fine particle layer, the resolution is reduced unlike the case where the image layer is formed only with the fine particle layer. There was a disadvantage.

Further, in Japanese Patent Publication No. 4-61789 and Japanese Patent Application Laid-Open No. Hei 9-171429, a coating liquid for forming an image forming layer is an aqueous dispersion using water as a medium. is there. In order for the medium to evaporate after application, work must be performed at low temperatures so that the particulate layer does not melt. The disadvantage was that it took a long time to remove water at low temperatures. An object of the present invention is to provide an image capable of easily and inexpensively obtaining an image having high resolution and reliability in a lithographic printing plate and printed wiring board manufacturing technology, and capable of responding to a laser direct drawing method. An object of the present invention is to provide a forming material and an image forming method. Further, it is intended to provide a method and an apparatus for manufacturing a lithographic printing plate, a method for making a lithographic printing plate, and a method for manufacturing a printed wiring board using the image forming material and the image forming method.

Disclosure of the invention

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found the following invention.

(1) An image-forming material comprising a heat-fusible fine particle layer provided on a substrate.

(2) An image forming material having an alkali-soluble resin layer and a heat-meltable fine particle layer in this order on a substrate.

(3) An image forming method in which a heat-meltable fine particle layer is provided on a base material, and the heat-meltable fine particle layer in a portion to be imaged is heated and melted and fixed on the base material surface.

(4) On a base material, a portion corresponding to an image portion of the heat-fusible fine particle layer of an image forming material having an alkali-soluble resin layer and a heat-fusible fine particle layer in this order is fused and fixed, and then a non-image portion is formed. An image forming method for forming an image on a substrate by removing a hot-melt fine particle layer and a soluble resin layer corresponding to the above-mentioned method using a concentrated liquid.

(5) The image forming material according to the above (1), wherein the heat-fusible fine particle layer contains a light absorbing agent.

(6) The image forming material according to the above (2), wherein at least one of the resin layer and the heat-meltable fine particle layer contains a light absorber.

(7) The image forming method according to the above (3), wherein the heat-fusible fine particle layer contains a light absorbing agent.

(8) The image forming method according to the above (4), wherein at least one of the resin layer and the thermofusible fine particle layer contains a light absorber.

(9) The image forming method according to (4) or (8), wherein the alkali-soluble resin layer is formed by an electrodeposition method.

(10) The above-mentioned (3), (4), and The image forming method according to any one of (7) and (8).

(11) The image forming method according to the above (4) or (8), wherein the alkali-soluble resin layer is formed by an electrodeposition method, and the heat-fusible fine particle layer is fused and fixed by a laser.

(1 2) The image forming method according to any one of the above (3), (4), (7) and (8), wherein the heat-fusible fine particle layer is formed by an electrodeposition method.

(13) The above (4) or (4) wherein the alkali-soluble resin layer is formed by an electrodeposition method, the heat-meltable fine particle layer is formed by an electrodeposition method, and the heat-meltable fine particle layer is fused and fixed by a laser.

8) The image forming method described in the above.

(14) The image forming material according to any one of the above (1), (2), (5) and (6), wherein the substrate is a support for a printing plate.

(15) The image forming method as described in (3), (4), (7) or (8) above, wherein the substrate is a printing plate support.

(16) The substrate according to the above (4) or (8), wherein the substrate is a printing plate support, wherein the alkali-soluble resin layer is formed by an electrodeposition method, and the heat-meltable fine particle layer is fused and fixed by a laser. Image forming method described above.

(17) The substrate is a printing plate support, the alkali-soluble resin layer is formed by electrodeposition, the heat-meltable fine particle layer is formed by electrodeposition, and the heat-meltable fine particle layer is formed by laser. The image forming method according to the above (4) or (8), wherein the image is fused and fixed.

(18) The image forming material according to any one of the above (1), (2), (5) and (6), wherein the substrate is a support for producing a printed wiring board.

(19) The image forming method according to any one of the above (3), (4), (7) and (8), wherein the substrate is a support for manufacturing a printed wiring board.

(20) The substrate is a support for the manufacture of printed wiring boards, the resin layer is formed by electrodeposition, and the layer of heat-meltable fine particles is fused and fixed by laser. (4) or (8) ).

(21) The base material is a support for manufacturing a printed wiring board, the alkali-soluble resin layer is formed by an electrodeposition method, the heat-meltable fine particle layer is formed by an electrodeposition method, and the heat-meltable fine particles are formed. The image forming method according to the above (4) or (8), wherein the layer is fused and fixed by a laser.

(22) On the photosensitive layer of the photosensitive lithographic printing plate before image exposure, A method for producing a lithographic printing plate, comprising: applying a coating liquid containing fine particles; evaporating the dispersion medium at an ambient temperature equal to or lower than the softening point of the heat-meltable fine particles to form the heat-meltable fine particle layer in a layered form.

(23) The coating liquid is heat-fusible fine particles having a charge dispersed in a dispersion medium having a high electrical resistivity, and the heat-fusible fine particles are applied on a photosensitive lithographic printing plate before image exposure by an electrodeposition method. (22) The method for producing a lithographic printing plate as described in (22) above, wherein fine particles are applied.

(24) A coating liquid containing a dispersion medium and heat-meltable fine particles is applied, and the dispersion medium is evaporated at an ambient temperature equal to or lower than the softening point of the heat-meltable fine particles to form the heat-meltable fine particles in a layer. A heat-fusible material having a charge dispersed in a dispersion medium having a high electrical resistivity in a gap formed between the guide plate and the electrode disposed opposite the guide plate, and the guide plate and the electrode. A lithographic printing plate manufacturing apparatus, comprising: means for supplying a fine particle-containing coating liquid; means for applying a voltage from the electrode to the lithographic printing plate; and means for squeezing excess coating liquid downstream of the electrode.

(25) The means for squeezing the excess coating liquid is a squeezing roll pair, and means for blowing gas toward a gap formed between the squeezing roll pair and an end of the photosensitive lithographic printing plate. The lithographic printing plate manufacturing apparatus according to the above (24), comprising:

(26) The apparatus for producing a lithographic printing plate as described in (24) or (25) above, further comprising means for adsorbing and transporting the back surface of the photosensitive lithographic printing plate downstream of the squeezing roll pair.

(27) The apparatus for producing a lithographic printing plate as described in any of (24) or (25) above, further comprising a dispersion medium evaporation promoting means downstream of the squeezing roll pair.

(28) The above (24) or (25) above, further comprising means for adsorbing and transporting the rear surface of the photosensitive lithographic printing plate downstream of the pair of squeezing rolls, and further comprising means for accelerating dispersion medium evaporation. Lithographic printing plate manufacturing equipment.

(29) heat-fusible fine particles are provided in a layer on the photosensitive layer of the photosensitive lithographic printing plate, and the heat-fusible fine particle layer in a portion to be an image is heated and melted and fixed on the photosensitive lithographic printing plate; Next, a plate making method of a lithographic printing plate for eluting and removing a non-image portion.

(30) The method of making a lithographic printing plate as described in (29) above, wherein the heat-fusible fine particle layer contains a light absorbing agent.

(3 1) The lithographic printing according to the above (30), wherein the light absorber has an absorption maximum in a wavelength region of 600 nm or more, and the absorption is a maximum value of 1Z2 at a wavelength of less than 600 nm. Plate making method.

(32) The method of making a lithographic printing plate as described in any of (29) to (31) above, wherein the photosensitive lithographic printing plate is a negative type, and the plate surface is irradiated with ultraviolet light after removing a non-image portion.

(33) The lithographic plate according to any one of the above (29) to (31), wherein the photosensitive lithographic printing plate is a positive type, and the plate surface is irradiated with ultraviolet light before providing the heat fusible fine particle layer. How to make a printing plate.

(34) The method of making a lithographic printing plate as described in any one of (29) to (31) above, wherein a burning process is performed after a non-image portion of the photosensitive lithographic printing plate is eluted and removed.

(35) The photosensitive lithographic printing plate is of a negative type, and the plate surface is irradiated with ultraviolet light after removing the non-image portion, and the non-image portion of the photosensitive lithographic printing plate is eluted and removed, followed by a burning treatment. The method of making a lithographic printing plate according to any one of the above (29) to (31).

(36) The photosensitive lithographic printing plate is of a positive type, and the plate surface is irradiated with ultraviolet light before the hot-melt fine particle layer is provided, and after the non-image portion of the photosensitive lithographic printing plate is eluted and removed. The method of making a lithographic printing plate according to any one of the above (29) to (31), wherein the burning treatment is performed.

(37) After opening a through hole in the laminated board provided with a conductive layer on at least one side of the insulating substrate, form a plated conductive layer on the surface of the laminated board including the inside of the through hole, and then perform etching corresponding to the wiring section A method for manufacturing a printed wiring board, comprising the steps of: providing a resist layer; etching away the attached conductive layer and the conductive layer that are not covered with the etching resist layer; and removing the remaining etching resist layer as the case may be. Is filled in with a filling pad, and then a layer of soluble resin and a layer of heat-meltable fine particles are formed in this order on the conductive layer of plating, and then the layer of heat-meltable fine particles corresponding to the wiring portion is formed. After fusing and fixing, an etching resist layer is formed by removing the heat-meltable fine particle layer and the resin layer soluble in the area corresponding to the non-wiring area Printed wiring The method of production.

(38) After opening a through hole in the laminated board provided with a conductive layer on at least one side of the insulating substrate, form a plated conductive layer on the surface of the laminated board including the inside of the through hole, and then perform etching corresponding to the wiring section Providing a resist layer, and covering with the etching resist layer. In a method for manufacturing a printed wiring board, the uncovered plated conductive layer and the conductive layer are removed by etching, and the remaining etching resist layer is removed as the case may be, the plated conductive layer is coated with a soluble soluble dry film. Thereafter, a heat-fusible fine particle layer is formed on the alkali soluble dry film, and then the heat-fusible fine particle layer in a portion corresponding to the wiring portion is melt-fixed. A method for manufacturing a printed wiring board, wherein an etching resist layer is formed by removing a fine particle layer and a soluble dry film.

(39) The method for producing a printed wiring board according to the above (37), wherein at least one layer selected from an alkali-soluble resin layer and a heat-meltable fine particle layer contains a light absorbing agent.

(40) The method for producing a printed wiring board according to the above (38), wherein at least one layer selected from an alkali-soluble dry film and a heat-meltable fine particle layer contains a light absorbing agent.

(41) The method for producing a printed wiring board according to the above (37) or (39), wherein the alkali-soluble resin layer is formed by an electrodeposition method.

(42) The method for producing a printed wiring board according to any one of the above (37) to (40), wherein the thermofusible fine particle layer is fused and fixed by a laser.

(43) The method for producing a printed wiring board according to the above (37) or (39), wherein the alkali-soluble resin layer is formed by an electrodeposition method, and the heat-meltable fine particle layer is melted and fixed by a laser.

(44) The method for producing a printed wiring board according to any one of the above (37) to (40), wherein the heat-fusible fine particle layer is formed by an electrodeposition method.

(45) The method for producing a printed wiring board according to the above (37) or (39), wherein the alkali-soluble resin layer is formed by an electrodeposition method, and the heat-fusible fine particle layer is formed by an electrodeposition method.

(46) The printed wiring board according to any one of (37) to (40), wherein the heat-meltable fine particle layer is formed by an electrodeposition method, and the heat-meltable fine particle layer is fused and fixed by a laser. Construction method.

(47) The method described in (37) above, wherein the alkali-soluble resin layer is formed by an electrodeposition method, the heat-meltable fine particle layer is formed by an electrodeposition method, and the heat-meltable fine particle layer is fused and fixed by a laser.

(39) The method for producing a printed wiring board as described in (39).

BRIEF DESCRIPTION OF THE FIGURES FIG. 1 is a conceptual diagram illustrating an example of the image forming material of the present invention.

FIG. 2 is a conceptual diagram illustrating an example of the image forming method of the present invention.

3A, 3B and 3C are conceptual diagrams showing an example of the image forming material of the present invention. 4A, 48 and 4 (: are conceptual diagrams illustrating an example of the image forming method of the present invention. FIG. 5 is a conceptual diagram illustrating an example of the image forming method of the present invention.

FIG. 6 is a conceptual diagram illustrating an example of the image forming method of the present invention.

FIG. 7 is a conceptual diagram illustrating an example of the image forming method of the present invention.

8A, 8B, 8 and 80 are conceptual diagrams showing a method of forming an etching resist layer according to the method of manufacturing a printed wiring board of the present invention.

9A, 9B, 9C, and 9D are conceptual diagrams illustrating a method of forming an etching resist layer according to the method of manufacturing a printed wiring board of the present invention.

FIG. 10 is a schematic side sectional view showing an example of the lithographic printing plate manufacturing apparatus of the present invention. 11A, 11B, 11C, 11D, 11E, and 11F are schematic diagrams of a method of manufacturing a printed wiring board having through holes by a subtractive method. In these figures, each symbol indicates the following.

1: Hot-melt fine particle layer

2: Soluble resin layer

3: Fusing layer

4: Alkali soluble dry film

5: Filling the hole

10: Base material

1 1: Photosensitive layer

1: Support

1 3: photosensitive lithographic printing plate

20: Laminated plate

2 1: Insulating substrate

2 2: Conductive layer

2 3: Through Hole

2 4: Plated conductive layer P

Ten

25: 25a, 25b etching resist layer

BEST MODE FOR CARRYING OUT THE INVENTION

The image-forming material (1) of the present invention comprises a heat-fusible fine particle layer provided on a substrate. In the image forming method (3) of the present invention, the portion of the image forming material (1) according to the present invention which is to be an image is heated and melted and fixed on the surface of the substrate.

In the image forming method (3) of the present invention, when the corresponding portion is heated in accordance with a desired image on the heat-meltable fine particle layer, the fine particles of the heat-meltable fine particle layer are melted and bonded to each other to form a film structure. Is formed, and the adhesiveness to the substrate is significantly improved. For this reason, the presence or absence of this heat fixing causes a difference in the adhesive strength to the substrate surface. For example, when a printing plate support is used as a base material and the image forming material of the present invention on which an image is formed by the image forming method of the present invention is mounted on a lithographic printing machine and printing is started, the material is heated and fixed. The melt-fixed part receives the ink and becomes an image area, and in the part that is not heated, the heat-fusible fine particle layer has a weak adhesion to the substrate surface, so it is immediately separated and removed, and the hydrophilic surface of the substrate Is exposed and becomes a non-image area of ink non-reception (water reception), and lithographic printing becomes possible.

According to the image-forming material (1) and the image-forming method (3) of the present invention, a liquid developer and its device are heated and fixed according to a desired image, for example, by thermal printing head-laser exposure. It is possible to easily produce an image layer without using any kind.

The image forming material (2) of the present invention has an alkali-soluble resin layer and a heat-meltable fine particle layer in this order on a substrate. In the image forming method (4) of the present invention, the heat-fusible fine particle layer corresponding to the image portion of the image forming material having such a structure is melt-fixed and bonded to each other and to the alkali-soluble resin layer. Allow the structure to form. Next, an image is formed on the substrate by removing the heat-fusible fine particle layer corresponding to the non-image portion and the layer that has not been melt-fixed and the soluble layer using an alkaline solution.

In the image forming method (4) of the present invention, when the relevant portion is heated in accordance with a desired image on the heat-meltable fine particle layer, the fine particles of the heat-meltable fine particle layer are fused and bonded to each other to form a film structure. Is formed, and the image portion develops resistance to the alkaline solution. In the non-image area where the heat-fusible fine particle layer is not fused and fixed, the heat-fusible fine particle layer In this state, the alkaline liquid easily permeates, dissolves the lower alkali-soluble resin layer, and can be removed together with the heat-meltable fine particles.

The image forming materials (1) and (2) of the present invention are very stable against oxygen, sunlight and room light. Therefore, it can be stored in a bright room or under oxygen. Further, the image forming methods (3) and (4) can be performed in a bright room.

In the image forming methods (3) and (4) of the present invention, the heat-meltable fine particle layer corresponding to the image area can be melt-fixed by laser exposure to obtain an image with extremely high resolution. be able to. Therefore, a laser direct drawing method corresponding to a computer 'head' plate can be performed, and high productivity can be obtained.

In order to carry out the laser direct writing method more advantageously, the image-forming material (1) and the heat-meltable fine particle layer according to the image-forming method (3) of the present invention, and the image-forming material (2) and the image of the present invention By including a light absorber in at least one of the alkali-soluble resin layer and the heat-meltable fine particle layer in the formation method (4), energy can be efficiently used for fusing and fixing heat and light. It becomes possible to absorb. Therefore, for example, when fusing and fixing with a laser, a low output laser can be used, and the equipment cost / operating cost can be reduced.

The image forming materials (1) and (2) and the image forming methods (3) and (4) of the present invention can be used in the field of printing and in the field of manufacturing printed wiring boards.

In the method (22) for producing a lithographic printing plate of the present invention, a lithographic printing plate is produced by forming a layer of heat-meltable fine particles on a photosensitive lithographic printing plate. In the method of making a lithographic printing plate of the present invention using the lithographic printing plate (29), the heat corresponding to the image portion of the heat-meltable fine particle layer provided on the surface of the photosensitive lithographic printing plate before image exposure is provided. The fusible fine particle layer is melt-fixed and bound to each other and the alkali-soluble resin layer to form a film structure. Next, an image is formed on the substrate by eluting and removing the non-fused hot-melt fine particle layer corresponding to the non-image portion and the photosensitive layer of the photosensitive lithographic printing plate therebelow.

According to the method (22) for producing a lithographic printing plate of the present invention, a commercially available photosensitive lithographic printing plate (PS plate) is provided with a heat-fusible fine particle layer containing a light absorbing agent. In the plate making method (30), the heat-fusible fine particle layer can be melt-fixed by a laser, and an image with extremely high resolution can be obtained. Therefore, PT /

1 2

Even a normal PS plate having no plate-making sensitivity to a laser can be used for a computer / plate.

In the method (22) for producing a lithographic printing plate according to the present invention, the dispersion medium is evaporated at an ambient temperature equal to or lower than the softening point of the heat-meltable fine particles, so that the heat-meltable fine particles are not fused and fixed. It can be fixed in layers on the lithographic printing plate surface. For this reason, it is possible to prevent the non-image portion from fusing and fixing to become a capri.

In the method (23) for producing a lithographic printing plate according to the present invention, the coating liquid according to the method (22) for producing a lithographic printing plate according to the present invention comprises a hot melt having a charge dispersed in a dispersion medium having a high electrical resistivity. The heat-fusible fine particles in the coating liquid by selectively applying the heat-fusible fine particles in the coating solution to the photosensitive lithographic printing plate before image exposure by electrodeposition. Therefore, the heat-meltable fine particle layer can be formed more efficiently.

According to the planographic printing plate manufacturing apparatus (24) of the present invention, the heat-fusible fine particle layer can be efficiently and uniformly fixed to the surface of the planographic printing plate in a layered manner. Means for squeezing excess coating liquid include, for example, a roll pair, an air knife that blows air over the entire width of a lithographic printing plate, and a corona discharge. The squeezed liquid by a roll pair consisting of is preferred because it can be squeezed efficiently and stably for a long period of time. More preferably, it is a roll pair having nitrile butadiene rubber (NBR) on the surface in a rubber hardness range of 20 to 70 degrees. In the lithographic printing plate manufacturing apparatus (25) of the present invention, the means for squeezing excess coating liquid is a squeezing roll pair, and a gap formed between the squeezing roll pair and an end of the photosensitive lithographic printing plate. By having the gas blowing means directed to the portion, the coating liquid leaking from the gap is suppressed, the amount of the dispersion medium remaining on the plate surface is reduced, and the time required for evaporation is reduced. The apparatus for manufacturing a lithographic printing plate of the present invention (26) has a means for adsorbing and transporting the back surface of the photosensitive lithographic printing plate downstream of the pair of squeezing rolls, so that the formed fusible fine particle layer is brought into contact with It is possible to carry to the next step without performing. Therefore, it is possible to prevent destruction of the heat-meltable fine particle layer due to transportation.

In the lithographic printing plate manufacturing apparatus (27) of the present invention, a dispersion medium evaporation promoting means is provided downstream of the squeezing roll pair, so that the dispersion medium is continuously formed with the heat-meltable fine particle layer. Can be evaporated, so that the time required for producing a lithographic printing plate can be reduced.

In the method (32) of making a lithographic printing plate of the present invention, the method of making a lithographic printing plate (29) of the present invention is characterized in that the photosensitive lithographic printing plate is a negative type. When a negative photosensitive lithographic printing plate is used, the image area is polymerized and hardened by irradiating the plate surface with ultraviolet light after removing the non-image area, and the printing durability is further improved. be able to.

In addition, the light absorbing agent contained in the heat-meltable fine particle layer has an absorption maximum near the near-infrared region (600 nm to 1200 nm), and has a maximum absorption at a wavelength less than 600 nm. In the plate making method (31) of the lithographic printing plate of the present invention, which has a value of 1/2, the image portion can more efficiently absorb ultraviolet light, especially when the photosensitive lithographic printing plate is a negative type. And

In the method (33) of making a lithographic printing plate according to the present invention, in the method (29) of making a lithographic printing plate according to the present invention, the photosensitive lithographic printing plate is of a positive type. When using a photosensitive lithographic printing plate of the positive type, irradiating the plate surface with ultraviolet light before providing the heat-meltable fine particle layer improves the solubility, so that the heat-meltable fine particle layer is heated. The non-image area can be easily eluted after fixing.

In the method of making a lithographic printing plate according to the present invention (34) to (36), the method of making a lithographic printing plate according to any of (29) to (31) according to the present invention comprises the steps of: Burning is performed after elution and removal of the image part. The binding process crosslinks the binder resin in the image area of the photosensitive lithographic printing plate, forms a stronger film, and further improves printing performance such as printing durability.

In the method (37) for producing a printed wiring board of the present invention, both the heat-meltable fine particle layer and the alkali-soluble resin layer used for forming the etching resist layer are exposed to oxygen, sunlight, and room light. It is very stable. Therefore, it can be stored in a bright room or in the presence of oxygen. Also, the image forming step can be performed in a bright room. The alkali-soluble dry film and the heat-meltable fine particle layer in the printed wiring board manufacturing method (38) of the present invention also have the same properties.

In the method (37) for producing a printed wiring board according to the present invention, the heat-fusible fine particle layer Alternatively, the alkali-soluble resin layer contains a light absorber. In the method (38) for producing a printed wiring board of the present invention, the heat-meltable fine particle layer or the alkali-soluble dry film contains a light absorber. Therefore, it becomes possible to efficiently absorb energy such as heat and light for fusing and fixing the heat-meltable fine particle layer in a portion corresponding to the wiring portion. Therefore, it is possible to reduce the cost, work cost, and the like of the device that provides this energy.

In the method (42) for producing a printed roto-line board of the present invention, the portion of the heat-meltable fine particle layer corresponding to the roto-roof portion is fused and fixed by a laser to provide an etching resist having a very high resolution. Layers can be obtained. In addition, high productivity can be obtained by using a laser direct writing method compatible with computer boards.

Image forming method (9), (11), (13), (16), (17), (20), (21) of the present invention and a method of manufacturing a printed wiring board (41) , (43), (45) and (47), the electrodeposition method is used as a means for forming the alkali-soluble resin layer. The electrodeposition method is used as a method for applying a photopolymer in the manufacture of some printed wiring boards, such as painting automobiles. The electrodeposition method has good followability to the substrate to be coated, and can uniformly form the thickness of the soluble resin layer regardless of the shape of the substrate to be coated. Also, there are very few defects such as pinholes. In the production methods (41), (43), (45) and (47) of the printed wiring board of the present invention, in particular, depending on the types of the conductive conductive layer and the alkali-soluble resin layer, both methods are required. In some cases, chemical bonding may occur between the layers, and it is possible to obtain an Al-soluble resin layer having extremely excellent adhesion.

The image forming method of the present invention (12), (13), (17), (21), the method of manufacturing a lithographic printing plate of the present invention (23), and the method of manufacturing a printed wiring board (44) In (4) to (47), the heat-meltable fine particle layer is formed by the electrodeposition method, but a uniform thin film with few defects can be obtained in the same manner as described above.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

FIG. 1 is a schematic view showing an example of the image forming material (1) of the present invention. The image forming material (1) of the present invention has a structure in which a heat fusible fine particle layer 1 is provided on a substrate 10. T

1 5

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FIG. 2 is a schematic view showing an example of the image forming material (2) of the present invention. The image forming material (2) of the present invention has a structure in which a resin layer 2 and a thermofusible fine particle layer 1 are sequentially formed on a substrate 10.

FIG. 3 is a schematic view showing an example of the image forming method (3) of the present invention. In the image forming method (3) of the present invention, first, the heat fusible fine particle layer 1 is provided on the substrate 10 (FIG. 3A). Next, the portion of the heat-meltable fine particle layer 1 corresponding to the image area is melt-fixed to form a melt-fixing layer 3 (FIG. 3B).

FIG. 4 is a schematic diagram illustrating an example of the image forming method (4) of the present invention. In the image forming method of the present invention, first, a portion corresponding to an image portion of an image forming material (FIG. 4A) having an alkali-soluble resin layer 2 and a heat-fusible fine particle layer 1 on a substrate 10 in this order. The heat-fusible fine particle layer 1 is fused and fixed to form a fusion-fixed layer 3 (FIG. 4B). Next, the non-image portion of the heat-meltable fine particle layer 1 and the resin layer 2 are removed with an alkaline solution (FIG. 4C). The heat-fusible fine particle layer 1 in the non-image area, which is not fused and fixed, is in a very sparse state, so that the alkali liquid can easily penetrate and can be removed together with the underlying alkali-soluble resin layer 2 It is. An image is formed with the fusion fixing layer 3 and the alkali-soluble resin layer 2 remaining on the substrate 10 (FIG. 4).

The base material 10 having a surface on which a fusion-fixing layer 3 corresponding to an image area and a heat-fusible fine particle layer 1 corresponding to a non-image area obtained by the image forming method (3) of the present invention, The layer 1 is in a sparse state and has poor adhesion to the substrate 10 as compared with the fusion-fixing layer 3. Therefore, when printing is performed using a printing plate support as the substrate 10 and printing is performed as a printing plate, the thermally fusible fine particle layer 1 having poor adhesion is removed at the initial stage of printing, and the substrate 10 The surface will be exposed (Figure 3C). In this manner, a form in which the fusion fixing layer 3 which is the lipophilic ink receiving layer is formed on the base material having the hydrophilic surface, and printing is possible.

5 to 7 are schematic views showing an example of the method (29) of making a lithographic printing plate according to the present invention. First, the heat-meltable fine particle layer 1 is provided on the photosensitive layer 11 of the photosensitive lithographic printing plate (PS plate) 13 (FIG. 5). Next, the heat-fusible fine particle layer 1 at the portion corresponding to the image area is melted and fixed by heating to form a melt-fixed layer 3 (FIG. 6). continue, The photosensitive layer 11 of the photosensitive lithographic printing plate is removed together with the heat-fusible fine particle layer 1 in the non-image area using a treatment solution capable of eluting and removing (FIG. 7). The heat-fusible fine particle layer 1 in the non-image area, which has not been fused and fixed, is in a very sparse state, so that the processing liquid can easily penetrate, and together with the lower photosensitive layer 11 of the photosensitive lithographic printing plate. It is possible to remove it. An image is formed with the fusion fixing layer 3 and the photosensitive layer 11 remaining on the support 12 (FIG. 7). FIG. 11 is a schematic diagram showing a general method of manufacturing a printed rookie board having through holes by a subtractive method. When manufacturing a printed wiring board having a through-hole, first, a through-hole 23 is formed in a laminated board 20 (FIG. 11A) provided with a conductive layer 22 on at least one surface of an insulating substrate 21 (see FIG. 11B), the conductive layer 24 is formed on the surface of the laminated layer 20 including the inside of the through hole 23 (FIG. 11C). Next, an etching resist layer 25 corresponding to the wiring portion is provided (FIG. 11D), and the plating conductive layer 24 and the conductive layer 22 not covered with the etching resist layer 25 are etched and removed (see FIG. 11D). 11E) and, if necessary, the remaining etching resist layer 25 is removed (FIG. 11F), and the printed wiring board on which the wiring is formed by the conductive layer and the plated conductive layer is formed on the insulating substrate. Manufactured.

FIG. 8 is a conceptual diagram showing a method of forming an etching resist layer in the method (37) of manufacturing a printed wiring board of the present invention. After the inside of the through hole 23 of the laminated board (Fig. 11C) after the formation of the plated conductive layer 24 is filled with the filling ink 5 (Fig. 8A), it is possible to apply a force on the plated conductive layer 24. The molten resin layer 2 and the thermally fusible fine particle layer 1 are formed in this order (FIG. 8B). Next, the portion of the heat-fusible fine particle layer 1 corresponding to the wiring portion is melt-fixed to form a melt-fixing layer 3 (FIG. 8C). Subsequently, the hot-melt fine particle layer 1 and the non-wiring soluble resin layer 2 in the non-wiring portion are removed with an alkaline liquid (FIG. 8D). The heat-fusible fine particle layer 1 that has not been fused and fixed is in a very sparse state, so that the liquid can easily penetrate, and can be removed together with the lower layer of the soluble resin layer 2. It is possible. The remaining melt-fixing layer 3, alkali-soluble resin layer 2, and filling ink 5 are used as an etching resist layer 25a.

FIG. 9 is a conceptual diagram showing a method of forming an etching resist layer in the method (38) of manufacturing a printed wiring board of the present invention. After the conductive layer 24 is formed, the alkali-soluble dry film 4 is attached to the laminate (Fig. 11C) (Fig. 9 A) Next, the heat-meltable fine particle layer 1 is formed on the soluble dry film 4 (FIG. 9B), and the heat-meltable fine particle layer 1 corresponding to the wiring portion is melt-fixed. (Fig. 9C). Subsequently, the heat-fusible fine particle layer 1 and the non-wiring soluble dry film 4 at the non-wiring portion are removed with an alkaline solution (FIG. 9D). The remaining resist layer 3 and the alkali-soluble dry film 4 are used as an etching resist layer 25b.

The heat-fusible fine particle layer according to the image forming material, the image forming method, the lithographic printing plate manufacturing method and manufacturing apparatus, the lithographic printing plate plate making method, and the printed wiring board manufacturing method of the present invention is a fine particle layer at normal temperature. It has the property of forming a dense film structure by fusing and fixing. Examples of the material forming such heat-fusible fine particles include (meth) acrylic resin, vinyl acetate resin, polyethylene resin, polypropylene resin, polybutadiene resin, vinyl chloride resin, vinyl acetal resin, vinylidene chloride resin, styrene resin, and polyester. Examples include resin, polyamide resin, phenol resin, xylene resin, alkyd resin, gelatin, cellulose, wax, and the like.

The image forming material, the image forming method, the lithographic printing plate manufacturing method and manufacturing apparatus of the present invention, the lithographic printing plate plate making method, and the method for forming a heat-fusible fine particle layer according to the method for manufacturing a printed wiring board include at least: The hot-melt fine particles are dispersed in an appropriate dispersion medium, and are dipped, spin-coated, bar-coated, white-coated, roll-coated, spray-coated, force-coated, air-knife-coated, It can be formed by using a coating method such as a blade coating method and an electrodeposition method. Among them, the electrodeposition method has good adherence to base materials, alkali-soluble resin layers, photosensitive lithographic printing plates, alkali-soluble dry films, etc., good adhesion, and very few defects such as pinholes. Further, since a thin film to which the heat-fusible fine particles are uniformly attached can be obtained, it can be used most advantageously. Further, even when the concentration of the heat-meltable fine particle dispersion is low, the heat-meltable fine particle layer can be efficiently formed.

The image forming material, the image forming method, the lithographic printing plate manufacturing method and manufacturing apparatus, the lithographic printing plate plate making method, and the method for forming a heat-fusible fine particle layer according to the method of manufacturing a printed wiring board according to the present invention include: As a liquid that does not dissolve Water, linear, branched or cyclic hydrocarbons, their halogen-substituted products, silicone oils, and the like. When the electrodeposition method is used, a material having a high electric resistivity is preferable, and a material having a low dielectric constant is preferable. Examples of the dispersion medium that can be used in the electrodeposition method include aliphatic hydrocarbons. In order to quickly remove the dispersion medium after the formation of the heat-fusible fine particle layer, it is more preferable to use a low-fraction aliphatic hydrocarbon. Examples of commercially available products include Shellsol 71 (manufactured by Shell Petroleum), Biopar G, Biopar H and Biopar L (manufactured by Exxon Chemical), and IP Solvent IP_1620 (manufactured by Idemitsu Petroleum). Considering safety and the environment, hydrocarbon-based petroleum solvents having a low vapor pressure and hydrocarbons having a high molecular weight can be used.

The heat-meltable fine particle layer according to the image forming material, the image forming method, the lithographic printing plate manufacturing method and manufacturing apparatus, the lithographic printing plate making method, and the printed wiring board manufacturing method of the present invention is formed by an electrodeposition method. In this case, a charge control agent is contained in the heat-fusible fine particle layer dispersion in order to keep the heat-fusible fine particle layer charged. Examples of the charge control agent include metal salts of fatty acids such as naphthenic acid, octenoic acid, and oleic acid, metal salts of sulfosuccinate esters, metal salts of oil-soluble sulfonic acids, metal salts of phosphoric acid esters, and aromatic carboxylic acids. Metal salts of sulfonic acids, ionic or nonionic surfactants, polymeric surfactants, quaternary ammonium salts, organic borates, lipophilic and hydrophilic block or graft polymers, lecithin, etc. Can be mentioned.

The heat-meltable fine particle layer according to the image forming material, the image forming method, the lithographic printing plate manufacturing method and manufacturing apparatus, the lithographic printing plate making method, and the printed wiring board manufacturing method of the present invention is formed by an electrodeposition method. In such a case, a commercially available toner (wet developer) for an electrophotographic lithographic printing plate can be used. In this toner, the above-mentioned heat-meltable fine particle layer, dispersion medium, charge control agent, dispersant, dispersion stabilizer and the like are prepared in advance and can be used easily.

In the method for forming a heat-meltable fine particle layer according to the image forming material, the image forming method, the lithographic printing plate manufacturing method and the manufacturing apparatus, the lithographic printing plate making method, and the printed wiring board manufacturing method of the present invention, To disperse the conductive fine particles in the dispersion medium, use a mechanical or ultrasonic disperser or stirrer such as an agitator, ball mill, homogenizer, etc. Can be used. At this time, a dispersion stabilizer and a dispersant such as a surfactant and a resin soluble in a dispersion medium can be used. When a dispersing medium-soluble resin is used as the dispersing (stabilizing) agent, the dispersing medium-soluble resin is contained in the heat-meltable fine particle layer. When the content of the dispersing medium-soluble resin is increased, the resin acts as a binder and may reduce image resolution. Therefore, the content of the dispersing medium-soluble resin is preferably 0.1 to 30% by weight based on the weight of the heat-meltable fine particles. Further, the image forming method (4) of the present invention having a step of removing a non-image portion with an alkaline solution, the plate making method of a lithographic printing plate of the present invention (29), the method of manufacturing a printed wiring board (37) and (37) In 38), the resin soluble in a dispersion medium is preferably alkali-resistant, more preferably hydrophobic, in order not to lower the alkali resistance of the heat-meltable fine particle layer.

The heat-meltable fine particle layer according to the image forming material, the image forming method, the lithographic printing plate manufacturing method and the manufacturing apparatus, the lithographic printing plate making method, and the printed wiring board manufacturing method of the present invention is obtained by applying the above-described coating method. Then, the dispersion medium is dried in an atmosphere temperature range equal to or lower than the softening point of the heat-meltable fine particle layer, and the dispersion medium is removed by evaporation. The softening point of the heat-meltable fine particles is the temperature at which a film is formed by heating, and the numerical value is that when the heat-meltable fine particle dispersion is sealed and gradually heated, the heat-meltable fine particles melt to form a film. The temperature can be obtained by a simple experiment.

The alkali-soluble resin that can be used in the alkali-soluble resin layer according to the image forming material (2), the image forming method (4), and the method for manufacturing a printed wiring board (37) of the present invention. In order to express alkali solubility, at least a monomer having an anionic group such as a carboxylic acid group, a sulfoxyamide group, a sulfonic acid group, a sulfonamide group, a sulfonimide group, a phosphonic acid group, etc. Contains as an ingredient. In addition, various monomers may be copolymerized to control alkali solubility, film strength, heat melting temperature, and the like. Further, two or more kinds of alkali-soluble resins may be mixed.

The alkali-soluble resin layer according to the image-forming material (2), the image-forming method (4) and the method for manufacturing a printed wiring board (37) of the present invention comprises at least an alkali-soluble resin in an appropriate medium. Disperse or dissolve, dipping, spin coating, bar coating, roll coating, spray coating, curtain coating, air knife coating It can be formed by using a coating method such as a coating method, a blade coating method, and an electrodeposition method. In particular, the electrodeposition method can be advantageously used because it has good followability and adhesion to a substrate to be coated, has very few defects such as pinholes, and can provide a good thin film. .

The main component of the Alkali soluble soluble film according to the method (38) for producing a printed wiring board of the present invention is an alkali-soluble resin. The alkali-soluble resin includes at least one monomer component having a monomer having an anionic group such as a carboxylic acid group, a carboxyamide group, a sulfonic acid group, a sulfonamide group, a sulfonimide group, and a phosphonic acid group. Contained as In addition, various monomers may be copolymerized to control alkali solubility, film strength, adhesion, softening temperature, glass transition point, and the like. Also, two or more kinds of soluble resins may be mixed and used.

The alkali-soluble dry film according to the method (38) for producing a printed wiring board of the present invention is generally formed by dissolving the above-mentioned alkali-soluble resin in a medium and coating it on a substrate. As the substrate, films of polytetrafluoroethylene, polyethylene terephthalate, alamide, Kapton, polymethylpentene, polyethylene, polypropylene, polyvinyl chloride, etc. can be used.

In the method of forming an image, the method of making a lithographic printing plate, and the method of manufacturing a printed wiring board of the present invention, the method of fusing and fixing the image portion of the heat-fusible fine particle layer includes heat fixing, light fixing, pressure fixing, and solvent. There are methods such as fixing. In order to perform a direct drawing method using a computer chip plate to increase productivity, it is desirable to use a laser for fusing and fixing. Lasers include gas lasers such as carbon dioxide laser, nitrogen laser, Ar laser, HeZNe laser, HeZCd laser, Kr laser, solid lasers such as liquid (dye) laser, ruby laser, NdZY AG laser, GaAsZGaAlAs, I nG a a s a semiconductor laser such as a laser, K r F laser, XEC l laser, XeF laser, the use of excimer laser or the like of the Ar ² laser or the like leaving at.

In the image forming material (1), the image forming method (3), and the plate making method (22) of the lithographic printing plate of the present invention, in order to improve the melting and fixing ability of the heat fusible fine particle layer, the heat fusible fine particle layer is used. Preferably contains a light absorbing agent. This allows PT 7

2 1 It becomes possible to fuse and fix the thermofusible fine particle layer with small heat or light energy. As the light absorber, for example, carbon black, cyanine, metal-free or metal phthalocyanine, metal dithiolene, anthraquinone and the like can be used. When performing laser exposure, it is preferable to select a light absorber having the maximum absorption at the wavelength of the laser. For example, when fixing a heat-meltable fine particle layer using a semiconductor laser of 830 nm, a cyanine dye having a heptamethine skeleton can be suitably used. Ripbon black is a light absorber that can be used most preferably because it has a wide light absorption wavelength range and high heat absorption efficiency. Also in the image forming material (2), the image forming method (4) and the method for manufacturing a printed wiring board (37) of the present invention, similarly to the above, it is selected from an alkali-soluble resin layer or a heat-meltable fine particle layer. Preferably, at least one layer contains a light absorber. Also, in the method (38) for producing a printed wiring board of the present invention, it is preferable that at least one layer selected from the group consisting of a soluble dry film and a heat-meltable fine particle layer contains a light absorber.

In the method (32) and (35) of making a lithographic printing plate of the present invention, a negative PS plate is used in the method (29) to (31) of making a lithographic printing plate of the present invention. In this case, it is preferable that the plate surface is irradiated with ultraviolet light after elution and removal of the non-image portion. Therefore, a light absorber having low absorption in a wavelength region of 600 nm or less is desirable.

In the image forming method (4) and the printed wiring board manufacturing methods (37) and (38) according to the present invention, the alkali-soluble resin layer or the alkali-soluble dry film in the non-image portion or the non-circuit portion, and The hot-melt fine particle layer formed on the substrate is removed using an alkaline solution. The heat-fusible fine particle layer that is not melt-fixed is in a very sparse state, and the alkali solution can easily penetrate and is removed together with the underlying alkali-soluble resin layer or Al-soluble dry film. It is possible. As the alkaline liquid, water can be advantageously used as a solvent. In addition, as the base compound, alkali metal gayate, alkali metal hydroxide, phosphoric acid and alkali metal carbonate and ammonium salt, ethanolamine, ethylenediamine, propanediamine, triethylenetetramine, morpholine and the like are used. be able to. In order to further enhance the dissolving ability, a water-soluble alcohol / surfactant may be contained.

A commercially available PS plate developer can be used as the photosensitive layer eluting solution in the plate making method (29) of the present invention. If there is a dedicated or recommended developer for the PS plate to be used, it can be suitably used. Further, for example, a negative / positive common developer as described in JP-A-6-282709 can be used. Furthermore, it can be treated with an alkaline solution containing water as a main solvent. Examples of such an alkaline liquid include the alkaline liquids relating to the above-described image forming method (4) and methods (37) and (38) for producing a printed wiring board of the present invention.

As the substrate relating to the image forming materials (1) and (2) and the image forming methods (3) and (4) of the present invention, for example, in the case of producing a printing plate, polyethylene terephthalate, polyethylene naphthalate, A metal plate such as a plastic plate such as polyphenylene sulfide, paper, an aluminum plate, a zinc plate, and a copper Z aluminum plate can be used. In the case of manufacturing printed wiring boards, epoxy resin-impregnated glass substrate, epoxy resin-impregnated paper substrate, phenol resin-impregnated glass substrate, phenol resin-impregnated paper substrate, polyimide film And an insulating substrate such as a polyester film, a laminated plate or a metal plate provided with a conductive layer of copper, aluminum, silver, iron, gold, or the like on at least one surface of the insulating substrate.

As the photosensitive lithographic printing plate according to the method and apparatus for manufacturing a lithographic printing plate of the present invention, and the method of making a lithographic printing plate according to the present invention, a commercially available PS plate is not limited to a negative type or a positive type, and It can be used without being affected by the type and thickness of the support. In addition, in order to cope with mass production of lithographic printing plates, it is possible to use web (rolled) ones before being cut into sheets. Also, an elution type printing plate that forms an image by an electrophotographic method can be used.

When the photosensitive lithographic printing plate according to the lithographic printing plate making method (29) of the present invention is a negative type, as described in the lithographic printing plate making methods (32) and (35) of the present invention, By irradiating the plate surface with ultraviolet light such as a mercury lamp after removing the non-image area, the photosensitive layer is polymerized and hardened, and the image area can be made stronger. In order to increase the efficiency of UV light irradiation, use a solvent or the like that dissolves only the melt-fixing layer in the image area. After separating the fixing layer, ultraviolet light irradiation can be performed.

When the photosensitive lithographic printing plate according to the lithographic printing plate making method (29) of the present invention is of a positive type, the lithographic printing plate making method of the present invention (33) and (36) are as follows. Before providing the heat-meltable fine particle layer, the surface of the photosensitive lithographic printing plate is irradiated with ultraviolet light such as a mercury lamp in advance to improve the solubility of the photosensitive layer, and a plate-making process using the heat-meltable fine particles is performed. . By irradiating with ultraviolet light, the solubility of the photosensitive layer of the photosensitive lithographic printing plate in the elution treatment liquid increases, and the photosensitive layer in the non-image area can be removed very easily.

In the method of making a lithographic printing plate according to the present invention (34) to (36), a non-image portion of the photosensitive lithographic printing plate is eluted and removed, and then a burning process is performed to further strengthen the image portion. Can be. As the burning treatment, a method generally applied to a PS plate, such as heating at 200 to 250 ° C. for several minutes, can be used. Such a burning process is described in, for example, “PS Version Overview” (by Yonezawa Teruhiko, published by The Printing Society of Japan, pp. 107-108).

As the hole filling ink relating to the method (37) for producing a printed wiring board of the present invention, for example, a dry (air-drying) type hole filling ink, an ultraviolet light curing type hole filling ink, or a thermosetting type hole filling ink can be used. As a method of filling the filling hole inside the through hole, a roll coating method, a squeegee method, a multi-pin injection method, or the like can be used. The filling ink that has adhered to the outside of the through-hole may be left as it is, or may be removed by wiping or puffing.

Examples of the laminated board provided with a conductive layer on at least one surface of an insulating substrate according to the method for manufacturing a printed wiring board of the present invention include, for example, “Printed Circuit Technology Handbook-Second Edition 1”

((Corporation) Printed Circuit Society, edited by Nikkan Kogyo Shimbun) can be used. Examples of the insulating substrate include a paper substrate or a glass substrate impregnated with an epoxy resin or a phenol resin, a polyester film, a polyimide film, and the like. Examples of the material of the conductive layer include copper, silver, and aluminum.

As a method for forming a plated conductive layer according to the method for manufacturing a printed wiring board of the present invention, for example, when the plated conductive layer is copper, “Surface mounting technology” (June 1993, June, Electroless plating step, electroless plating-one electrolytic plating step, direct electrolytic plating step, etc. described in Nikkan Kogyo Shimbun, etc.) can be used.

In the method for manufacturing a printed wiring board of the present invention, as a method of removing the conductive layer and the plated conductive layer of the non-wiring portion after forming the etching resist layer, see “Printed Circuit Technology Handbook-Second Edition 1” Etching equipment, etchant, etc. described in "Printed Circuit Handbook, Original Edition, Third Edition" (edited by C. F. Coombs, Jr., 1991, edited by The Printed Circuit Society, published by Modern Science Co., Ltd.) Can be used. In the method for manufacturing a printed wiring board according to the present invention, the etching resist layer after removing the unnecessary conductive layer and the plated conductive layer may be left as it is, but is unnecessary when loading and connecting circuit components and the like. If it becomes, remove it. To remove the etching resist layer, an alkali solution can be advantageously used. In the case where the solubility of the etching resist layer in the alkaline solution is low, a force for appropriately adding an organic solvent or only the organic solvent may be used.

FIG. 10 is a schematic side sectional view showing an example of the lithographic printing plate manufacturing apparatus (24) of the present invention. First, the printing plate 4 14 with its surface facing upward is introduced into a gap formed by the electrode 41 and the guide plate 42 by a pair of feed rolls 4 3 and 4 4 whose surface is formed of rubber. At this time, the liquid supply section attached to the recovery tank 410, the pump 41, and the electrode 41, which constitutes the hot-melt fine particle-containing coating liquid supply means, sends the liquid to the gap. Is discharged. At the same time, a voltage is supplied from a voltage supply unit 413, which is a charge application unit connected to the electrode 41, the conductive grounding piece 47, and the plate guide 49. The polarity of the supplied voltage is the same as the polarity of the charged electrode of the hot-melt particles in the coating liquid, and the hot-melt particles are electrodeposited on the surface of the printing plate 4 14.

Subsequently, the printing plate 4 14 is a gas blowing means in which excess coating liquid is squeezed by a pair of squeezing rolls 4 5 and 4 6 which are squeezing means, and at the same time, is connected to a high-pressure air source (not shown). High-pressure air is blown from the air knife 48 to the gap formed by the printing plate 4 14 and the squeezing roll pairs 45, 46.

Further, the printing plate 4 14 is suctioned on its back surface by suction conveyance means composed of a conveyance belt 4 24 suspended on four rotating shafts 4 23 and a suction box 4 22. Conveyed. The suction box 4 22 has a plurality of suction ports on its upper surface for sucking the printing plate 4 14, and the air inside the suction box 4 22 is exhausted by an exhaust fan (not shown) installed inside. It is being discharged. In the upper part, two drying fans 420 are arranged as a means for promoting the evaporation of the dispersion medium, so that the dispersion medium in the coating liquid that has not been squeezed on the printing plate 4 14 is sealed. I have.

Note that, depending on the softening point of the heat-fusible fine particles used, air cooled or heated by an air temperature control unit (not shown) is introduced into the drying fan 420. Further, an exhaust duct 421 is provided at the upper part as an evaporation promoting means, so that the evaporated dispersion medium can be discharged as required. By discharging the dispersion medium vapor, the vapor pressure can be reduced and the evaporation speed of the dispersion medium on the plate surface can be increased. The transport speed of the printing plate 4 14 can be arbitrarily set according to the evaporation speed of the dispersion medium used.

The printing plate 4 14 processed as described above reaches a buffer unit composed of a transport belt 4 31 suspended on two rotating shafts 4 30. Here, the printing plate 4 14 may be taken out, or may be transported to a stocker capable of stocking a plurality of printing plates. In addition, it is also possible to connect a device that performs heating and drawing subsequently, and perform drawing processing continuously with the formation of the heat-meltable fine particle layer.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples unless departing from the gist thereof.

Example 1

Fabrication of base material

A JIS 1550 aluminum sheet was immersed in an aqueous solution of 10% NaOH at 60 ° C, and the surface was etched so that the amount of aluminum dissolved was 6 gZm ² . After washing with water, it was immersed in a 30% aqueous nitric acid solution for 1 minute to neutralize, and washed thoroughly with water. Thereafter, electrolytic surface roughening was performed in a 2.0% aqueous nitric acid solution for 25 seconds, and the surface was washed by immersion in a 20% aqueous sulfuric acid solution at 50 ° C., and then washed with water. Furthermore, the substrate (printing plate support, A3 size) is prepared by anodizing in a 20% sulfuric acid aqueous solution, washing with water, and drying.

: S

Formation of hot-melt fine particle layer The coating solution of Table 1 was applied by a curtain coating method and then air-dried at 40 ° C for 2 minutes to obtain a heat-meltable fine particle layer (thickness: 3.0 urn).

Table 1 Compositions Polyuryl lauryl methacrylate (molecular weight: 200000) 5 Polyvinyl acetate emulsion (average particle size: 0.2〃m) 25 Saturated hydrocarbons (IP-1620; Idemitsu Petrochemical Co., Ltd.) 2) Formation of fusing and fixing layer

The heat-meltable fine particle layer corresponding to the image area was fused and fixed by a semiconductor laser exposure device (780 nm) to obtain a printing plate. Using this printing plate, printing was performed with an offset printing machine (Ryobi 3200 MCD). At the initial stage of printing (approximately 10 sheets), a layer of heat-meltable fine particles that had not been fused was fixed. Was completely removed, and the hydrophilically treated surface of the substrate was exposed. By using the remaining melt-fixing layer as the ink receiving layer, it was possible to obtain good printed matter free of stains and the like up to 60,000 sheets.

Storage test

After storing the substrate with the heat-meltable fine particle layer in a light room at 30 ° C for 6 months, a printing plate was tried in the same manner as above to obtain a printing plate without defects. I was able to do it.

Example 2

Formation of hot-melt fine particle layer

A substrate having the same specifications as in Example 1 (hydrophilic aluminum sheet, 110 × 398 mm) was coated with a coating solution having the composition shown in Table 2 by a curtain coating method, and the coating was performed at 30 °. After drying for 5 minutes at C, a heat-meltable fine particle layer (2.5 m thick) was formed. Table 2 Compositions Polyuryl methacrylate (molecular weight 2,000,000) 5 Polyvinyl acetate emulsion (average particle size 0.2 μm) 25 Carbon black 5 Saturated hydrocarbons (IP-1620; Idemitsu Petrochemical) 2 1 5 Formation of fusing layer

The printing plate was obtained by fusing and fixing the heat-meltable fine particle layer corresponding to the image area with a semiconductor laser exposure device (780 nm). Using this printing plate, we performed printing with an offset printing machine (Ryobi 320 MCD). At the initial stage of printing (about 10 sheets), the heat-fusible fine particles that had not been fused and fixed were used. The layer was completely removed, exposing the hydrophilized surface of the substrate. By using the remaining melt-fixing layer as the ink receiving layer, it was possible to obtain good printed matter free of stains and the like up to 60,000 sheets.

Storage test

Example 3

Formation of hot-melt fine particle layer

Using a coating solution having the composition shown in Table 3 on a base material (hydrophilic aluminum sheet, A3 size) having the same specifications as in Example 1 and applying it by electrodeposition (applied voltage: 150 V), 40 ° After drying at C for 2 minutes, a heat-meltable fine particle layer (film thickness 2.0 urn) was formed. Table 3 Composition Polyradiryl methacrylate (weight average molecular weight 200000)

Polyvinyl acetate emulsion (average particle size 0.2〃m)

Octadecyl vinyl ether Z maleic anhydride copolymer

Amount composition ratio 3/1, maleic anhydride hydrolysis rate 54%, weight average

0.01 Carbon: Rack 0.5 Saturated hydrocarbon (IP-1620; manufactured by Idemitsu Petrochemical Co., Ltd.) 744 Formation of fusion fixing layer

The heat-meltable fine particle layer corresponding to the image area was fused and fixed by a semiconductor laser exposure device (780 nm) to obtain a printing plate. Using this printing plate, we performed printing with an offset printing machine (Ryobi 320 MCD). At the initial stage of printing (about 10 sheets), the heat-fusible fine particles that had not been fused and fixed were used. The layer was completely removed, exposing the hydrophilized surface of the substrate. By using the remaining melt-fixing layer as the ink receiving layer, no stains or the like were generated up to 70,000 sheets, and good printed matter was obtained.

Storage test

Example 4

Formation of Al-soluble resin layer and hot-melt fine particle layer

After applying the coating solution shown in Table 4 to a substrate (hydrophilic aluminum sheet, 1110 x 398 mm) having the same specifications as in Example 1 by the curtain coating method, it was heated at 90 ° C to 10 ° C. After drying for an minute, an alkali-soluble resin layer (4.6 m thick) was obtained. Furthermore, after applying the coating solution shown in Table 5 by the curtain coating method, it was air-dried at 40 ° C. for 2 minutes to obtain a heat-meltable fine particle layer (film thickness: 1.5 // m). Composition Ryu of methacrylic acid / Metakurinore acid n- off ^f chill / Ryo acrylic acid n- Petit

Copolymer (weight ratio: 3/3/4, weight-average molecular weight: 350,000) 10 carbon black 5 butyl cellulose sorb 8 5 Table 5 Composition Polyuryl lauryl methacrylate (molecular weight 2,000,000) 5 polyacetic acid Vinylemulsion (average particle size 0.2 zm) 25 Saturated hydrocarbon (IP-1620; manufactured by Idemitsu Petrochemical Co., Ltd.) 270 Formation of image layer

A semiconductor laser exposure device (780 nm) melts and fixes the heat-meltable fine particle layer corresponding to the image area, and then sprays 5.0% sodium carbonate solution (liquid temperature 35 ° C) (2.0 kg / cm ² ) to remove the hot-melt fine particle layer and the alkali-soluble resin layer in the non-image area to obtain a printing plate. Observation with a microscope of the image layer composed of the alkali-soluble resin layer and the heat-meltable fine particle layer revealed that the image had a high resolution without any missing image portions and no stain on non-image portions. When printing was performed using this printing plate with an offset printing machine (Hamaduster 600 CD), it was possible to obtain up to 80,000 sheets of good printed matter free of stains and the like.

Storage test

After storing the printing plate substrate on which the soluble resin layer and the heat-fusible fine particle layer were formed in a bright room at 30 ° C for 6 months, an attempt was made to form an image layer using the same method as above. At that time, a clear and defect-free image layer could be obtained.

Example 5 Formation of Al-soluble resin layer and hot-melt fine particle layer

One-sided copper-clad laminate with copper foil laminated on one side of a paper-based epoxy resin plate (Matsushita Electric Works

Coating Co., Ltd., 200 x 300 x 1.6 mm, copper thickness 18 〃m) using a coating solution having the composition shown in Table 6 by dipping and then 90 ° After drying at C for 5 minutes, an alkali-soluble resin layer (5.2 m in thickness) was obtained. Next, using a coating solution having the composition shown in Table 7, coating was performed by a curtain coating method to form a heat-meltable fine particle layer (thickness: 1.2 m).

Table 6 Composition Crotonic acid Z-vinyl acetate copolymer (weight ratio: 3Z97, weight average)

Equivalent molecular weight: 350,000) 1 5

Composition by weight Polyuryl methacrylate (molecular weight: 2,000,000) 5 Polyvinyl acetate emulsion (average particle size: 0.2 m) 25 Carbon black 5 Saturated hydrocarbon (IP-1620; Idemitsu Petrochemical Co., Ltd.) 2) 70 Image layer formation

A semiconductor laser exposure device (780 nm) melts and fixes the heat-meltable fine particle layer corresponding to the image area, and then sprays 5.0% sodium carbonate solution (liquid temperature of 35 ° C) (2.0 kg / cm ² ) to remove the heat-meltable fine particle layer and the non-imageable resin layer in the non-image area. Observation with a microscope of the image layer comprising the resin layer and the heat-meltable fine particle layer revealed a high-resolution image with no missing image portions and no stain on non-image portions. In addition, the copper-clad laminate on which the image layer was formed was prepared using a commercially available ferric chloride solution. (45 ° C, spray pressure: 3.0 kg / cm ² ) to remove the copper foil in the area not covered by the image layer. Then, treatment with a 3.0% sodium hydroxide solution at 40 ° C. was performed to remove the remaining image layer, thereby obtaining a printed wiring board. Observation of the obtained printed wiring board with a microscope revealed that the circuit pattern had high resolution and no defects such as disconnection during the course o

Storage test

After storing the copper-clad laminate を on which the resin layer and the heat-fusible fine particle layer were formed for 4 months in a light room at 30 ° C, an attempt was made to form an image layer in the same manner as above. In this case, a clear and defect-free image layer could be obtained.

Example 6

Formation of Al-soluble resin layer and hot-melt fine particle layer

Table 8 shows a single-sided copper-clad laminate (Matsushita Electric Works, Ltd., 200 mm x 300 mm, copper thickness 18 mm, copper thickness 18〃m) with copper foil laminated to one side of a paper-based epoxy resin plate. Using a coating solution having the following composition, apply by electrodeposition (applied current: 100 mA), and then dry at 90 ° C for 10 minutes to obtain an alkali-soluble resin layer (thickness 3.2 μm). ). Furthermore, using a coating solution having the composition shown in Table 3, coating was carried out by the electrodeposition method (applied voltage: 180 V), and then air-dried at 40 ° C for 2 minutes. 0 um).

Table 8 Compositions Acrylic acid Z-N-butyl methacrylate / N-butyl acrylate

Chill copolymer (weight ratio: 2/3/4, weight average molecular weight

5.50000) 20 Triethylamine 1 butyl sesolve 9 0 Deionized water 9 0 Image layer formation

A semiconductor laser exposure device (780 nm) melts and fixes the heat-meltable fine particle layer corresponding to the image area, and then sprays 5.0% sodium carbonate solution (liquid temperature 35 ° C) (2.0 kg / cm ² ) to remove the hot-melt fine particle layer and the alkali-soluble resin layer in the non-image area. Observation with a microscope of the image layer composed of the alkali-soluble resin layer and the heat-meltable fine particle layer revealed a high-resolution image with no missing image portions and no stain on non-image portions. The copper-clad laminate on which the image layer was formed was treated with a commercially available ferric chloride solution (45 ° C, spray pressure: 3.0 kg / cm ² ), and the portion not covered with the image layer was treated. Was removed. Then, treatment with a 3.0% sodium hydroxide solution at 40 ° C. was performed to remove the remaining image layer, thereby obtaining a printed wiring board. Observation of the obtained printed wiring board with a microscope revealed a high-resolution circuit pattern without any defects such as disconnection in the middle.

Storage test

After storing the copper-clad laminate on which the resin layer and the heat-fusible fine particle layer were formed for 4 months in a light room at 30 ° C, an attempt was made to form an image layer in the same manner as above. In this case, a clear and defect-free image layer could be obtained.

Comparative Example 1

Drift film photoresist (Nippon Gohsei Chemical Co., Ltd.) as a photopolymer was thermocompression-bonded on the copper-clad laminate having the same specifications as in Examples 5 and 6. This photopoly Exposure was performed with the same semiconductor laser exposure apparatus as in Examples 1 and 2, but no photopolymerization reaction could be caused and no image could be obtained. Further, when a dry film photoresist was thermocompression-bonded on a copper-clad laminate and stored for 30 months in a bright room, the polymerization reaction proceeded and the photosensitive properties were deactivated.

Example 7

Using a coating solution having the composition shown in Table 9, a curtain coating method was applied to a commercially available unexposed negative PS plate (Fuji Photo Film, FNS), followed by air drying at 40 ° C for 2 minutes. A thermally fusible fine particle layer (thickness: 3.0 fim) was obtained.

Table 9 Compositions Polyuryl lauryl methacrylate (Molecular weight 200000) 5 Polyvinyl acetate emulsion (average particle size 0.2 m) 50 Carbon black 5 Saturated hydrocarbons (IP-1620; Idemitsu Petrochemical) 220) The softening point of the polyvinyl acetate fine particle layer produced using this coating solution was 62.

A semiconductor laser exposure device (830 nm) melts and fixes the hot-melt fine particle layer corresponding to the image area, and then uses a commercially available negative-type PS plate developer (Fuji Photo Film, DN 3C). The heat-meltable fine particle layer and the PS plate photosensitive layer in the non-image area were removed. The plate surface was once subjected to gumming treatment and subjected to burning treatment in an oven heated to 200 ° C to obtain a lithographic printing plate. Observation of the plate surface with a microscope revealed that the image had high resolution without any missing image portions and poor elution in non-image portions. Offset printing was performed using this lithographic printing plate. As a result, good scumming property and printing durability were obtained, and good printed matter was obtained.

Example 8

Using a coating solution with the composition shown in Table 10 on a commercially available unexposed negative PS plate (FNS, FNS) using the curtain coating method, air-dry at 40 ° C for 2 minutes. Then, a heat-meltable fine particle layer (thickness: 3.0 fim was obtained).

Table 10 Composition Polyuryl lauryl methacrylate (molecular weight 200000) 5 Polyvinyl acetate emulsion (average particle size 0.2〃m) 50 0 Heptamethine cyanine dye represented by the following formula I 6 Saturated hydrocarbon (IP-1620; manufactured by Idemitsu Petrochemical) 2 20

A semiconductor laser exposure device (830 nm) melts and fixes the heat-meltable fine particle layer corresponding to the image area, and then uses a commercially available negative-type PS plate developer (Fuji Photo Film, DN 3C). The heat-meltable fine particle layer and the PS plate photosensitive layer in the non-image area were removed. Further, the plate surface was irradiated with ultraviolet light from a mercury lamp, the plate surface was once subjected to gumming treatment, and subjected to burning treatment in an oven heated to 200 ° C. to obtain a lithographic printing plate. Observation of the plate surface with a microscope revealed that the image had high resolution without any missing image areas and poor elution in non-image areas. Offset printing was performed using this lithographic printing plate. As a result, it was possible to obtain a printed matter that had good scumming properties and printing durability, and was good even with the 50,000th print.

Example 9

After exposing the commercially available positive PS plate (manufactured by Fuji Photo Film, VS) with a mercury lamp, applying the coating solution shown in Table 11 by the force coating method and then air-drying at room temperature for 10 minutes. As a result, a heat-fusible fine particle layer (film thickness 2.5 u) was obtained. Table 11 1 Composition Polyradiryl methacrylate (molecular weight 2,000,000) 5 Polyvinyl acetate emulsion (average particle size 0.2〃m) 2 5 Power black 5 Saturated hydrocarbon (IP-160; Idemitsu Petrochemical Co., Ltd. 2 15 A semiconductor laser exposure device (830 nm) fuses and fixes the heat-meltable fine particle layer corresponding to the image area, and then a commercially available positive PS plate developer (Fuji Photo Film, Using DP 4), the heat-fusible fine particle layer and the PS plate photosensitive layer in the non-image area were removed, and a gumming treatment was performed. Thereafter, a lithographic printing plate was obtained by performing a burning treatment in an oven heated to 200 ° C. Observation of the plate surface with a microscope revealed that the image had high resolution without any missing image portions and poor elution in non-image portions. Offset printing was performed using this lithographic printing plate. As a result, it was possible to obtain a printed matter having good scumming property and printing durability, and having a printability of 50,000 sheets.

Example 10

After irradiating the entire surface of a commercially available positive PS plate (manufactured by Fuji Photo Film, VS) with ultraviolet light using the following manufacturing equipment, heat was applied using a commercially available liquid toner (manufactured by Mitsubishi Paper Mills, ODP-TW). A fusible fine particle layer was formed. The softening point of the heat-fusible fine particle layer produced using this coating solution was 65 ° C.

The manufacturing apparatus of this embodiment will be described with reference to FIG. First, a printing plate 4 1 4 with its surface facing upwards by means of a feed roller pair 43, 44 formed of nitrile butadiene rubber (NBR) having a hardness of 45 degrees (in this example, a positive PS plate) Is introduced into a gap formed by an electrode 41 made of SUS304 (JIS stainless steel) and a guide plate 42 made of polycarbonate. At this time, the liquid is fed from the collection tank 4 10 to the gap by the pump 4 12 from the recovery tank 4 10 to the liquid discharge portion 4 11 1 attached to the electrode 41, and is applied. At the same time, the voltage supply unit 4 1 3 connected to the electrode 1 and the phosphor bronze ground strip 47 and the SUS 304 pass-through guide 49 Are supplied with a voltage. In the present example, the polarity of the supplied voltage was set to + (plus) because the heat-fusible fine particles in the coating liquid had a positive charge, and a voltage of 180 V was applied.

Subsequently, the printing plate 4 14 is squeezed out of the excess coating liquid by the squeezing roll pairs 45, 46, and at the same time, the air nip 48, which is a gas blowing means connected to a high-pressure air source (not shown), is provided. Then, high-pressure air (pressure 2 kgZcm ² ) is blown toward the gap formed by the printing plate 4 14 and the squeezing roll pairs 45, 46.

Further, the printing plate 4 14 is conveyed while its back surface is adsorbed by the adsorbing / conveying means composed of the conveying belt 4 24 suspended on the four rotating shafts 4 2 3 and the suction box 4 22. Inside the suction box 4 2 2, two exhaust fans (not shown) with a maximum air flow of 500 1 / min are provided. Above this, two drying fans (maximum static pressure 6 mm A q), which are means for accelerating the dispersion medium evaporation, are arranged. It is designed to air dry. In this example, the blowing temperature of the drying fan was measured and found to be 20 ° C.

Subsequently, the printing plate 4 14 is conveyed to a buffer section comprising a conveying belt 4 31 suspended on two rotating shafts 4 30. Here, the printing plate 4 14 was taken out.

The PS plate treated as described above is melt-fixed with a semiconductor laser exposure apparatus (830 nm) to a hot-melt fine particle layer corresponding to the image area, and then a commercially available positive PS plate developer (Fuji Using a photographic film, DP4), the heat-meltable fine particle layer and the PS plate photosensitive layer in the non-image area were removed. The lithographic printing plate was obtained by performing a gumming treatment on the plate surface and a burning treatment in an oven heated to 200 ° C. Observation of the plate surface with a microscope revealed that the image had high resolution without any missing image portions and poor elution in non-image portions. Offset printing was performed using this lithographic printing plate. As a result, it was possible to obtain a printed material that had good scumming resistance and printing durability from the start of printing, and was good for the 50,000th print.

Example 1 1

A heat-meltable fine particle layer was formed in the same manner as in Example 7, except that a commercially available electrophotographic lithographic printing plate (ODP ND-300, manufactured by Mitsubishi Paper Mills) was used as the printing plate. The processed printing plate is melt-fixed with a semiconductor laser exposure device (830 nm) to a heat-fusible fine particle layer corresponding to the image area, and then an electrophotographic lithographic printing plate eluent (Mitsubishi Paper, Using ODP-DF), the fusible fine particle layer and the photosensitive layer in the non-image area were removed to obtain a lithographic printing plate. Observation of the plate surface with a microscope revealed that the image had high resolution without any missing image portions and poor elution in non-image portions. Offset printing was performed using this lithographic printing plate. As a result, it was possible to obtain a printed matter which had good soiling properties and printing durability from the start of printing, and was satisfactory even on the 100,000th print. Example 1 2

Formation of through holes and filling of filling ink

On a double-sided copper-clad laminate (200 x 300 x 0.8 mm, copper thickness 18 / m, manufactured by Mitsubishi Gas Chemical Co., Ltd.) After drilling 100 through holes of 0.4 mm0 and 0.6 mm0 each, a copper plating process (Okuno Pharmaceutical Co., Ltd., 0PC process M) is applied to the surface of the laminated board including the inside of the through holes. A copper plating layer having a thickness of 8 m was provided. Next, a hole-filling ink (SER-450W, manufactured by San-ei Chemical Co., Ltd.) was applied to the inside of the through-hole by a roll coating method, followed by heat curing. Filling ink on the copper plating layer other than inside the through holes was removed by buffing and washing.

Formation of Al-soluble resin layer and hot-melt fine particle layer

After the filling of the through-hole filling ink into the through-hole is completed, the coating solution having the composition shown in Table 4 is applied by the curtain coating method, and the coating is dried at 90 ° C for 10 minutes. A layer (film thickness 4.5) was obtained. Furthermore, using a coating solution having the composition shown in Table 5, the composition was applied by curtain coating, and then air-dried at 40 ° C for 2 minutes to obtain a heat-meltable fine particle layer (film thickness: 1.5 / m). .

Formation of etching resist layer

A semiconductor laser exposure apparatus (780 nm) melts and fixes the heat-meltable fine particle layer corresponding to the wiring section to form a fusion-fixed layer, and then sprays 5.0% sodium carbonate solution (liquid temperature of 35 ° C) ( 2.0 kg / cm ² ) to remove the heat-fusible fine particle layer and the alkali-soluble resin layer in the non-wiring area, and form an etching resist layer consisting of the alkali-soluble resin layer, the fusion fixing layer, and the ink for filling the hole. Obtained. Observe this etching resist layer with a microscope. From the observation, it was a high-resolution wiring image with no missing wiring parts and no stain on non-image parts.

Etunk:

After the etching resist layer is formed, it is treated with a ferric chloride solution (45 ° C, spray pressure: 3.0 kg / cm ² ), and the copper plating layer and the copper that are not covered with the etching resist layer The layer was removed. Then, the substrate was treated with a 3.0% sodium hydroxide solution at 40 ° C. to remove the remaining etching resist layer, thereby obtaining a printed wiring board. Observation of the obtained printed wiring board with a microscope showed no defects such as disconnection. No defects such as pinholes were found inside the through holes. Storage test

After storing the laminated board on which the ink for filling the hole, the formation of the alkali-soluble resin layer, and the formation of the heat-meltable fine particle layer have been stored for 4 months in a light room at 30 ° C, the etching resist layer is formed in the same manner as above. As a result, a wiring image free from defects was obtained.

Example 13

Forming through holes

To a double-sided copper-clad laminate (Mitsubishi Gas Chemical Co., Ltd., 200 x 300 x 0.8 mm, copper thickness 18 〃 m) with copper foil laminated on both sides of a glass base epoxy resin plate, 0.

After opening 100mm through holes of 4mm0 and 0.6mm0 each, copper plating treatment (Okuno Pharmaceutical Co., Ltd., 0PC process M) is applied and the thickness of the laminated board surface including the inside of the through holes is increased. An 8 zm copper plating layer was provided.

Coating of soluble dry film

The coating solution having the composition shown in Table 12 was applied to a polyester film having a thickness of 15 m by the roll coating method, and then dried at 60 ° C for 20 minutes to obtain an alkali-soluble dry film (thickness 15). fim). After the formation of the through holes, an alkali-soluble dry film was thermocompression-bonded to the surface of the copper plating layer of the laminate, the polyester film was removed, and the plating conductive layer was covered with the dry film. CT /

3 9

Table 1 2 Composition methacrylic acid Z-methacrylic acid n-butyl / acrinoleic acid n—

Butyl copolymer (weight ratio: 3 / 3Z'4, weight average molecular weight

3.50,000) 10 methacrylic acid / methacrylic acid n—butyl acrylic acid n—

Lauryl copolymer (weight ratio 1/1 / 1'3, weight average molecular weight 15

1.20,000)

Carbon black 5 Solvent with butyl mouth 7 0 Formation of heat-meltable fine particle layer

After coating the copper plating layer with a soluble dry film, use a coating solution having the composition shown in Table 5 and apply it by the roll coating method, and then air dry at 40 ° C to obtain an alkali-soluble dry film. A hot-melt fine particle layer (film thickness 2.1 ^ m) was formed on the film.

Formation of etching resist layer

A semiconductor laser exposure apparatus (780 nm) melts and fixes the heat-meltable fine particle layer corresponding to the wiring section to form a fusion-fixed layer, and then sprays 5.0% sodium carbonate solution (liquid temperature of 35 ° C) ( 2.0 kg / cm ² ) to remove the heat-meltable fine particle layer and the soluble dry film in the non-wiring area to obtain an etching resist layer consisting of the soluble dry film and the fusion fixing layer. Was. Observation of this etching resist layer with a microscope revealed a high-resolution wiring image with no missing wiring portions and no stain on non-image portions.

Etchinchini

After the etching resist layer is formed, it is treated with a ferric chloride solution (45 ° C, spray pressure: 3.0 kg / cm ² ). The copper layer was removed. Next, the printed wiring board is obtained by removing the remaining etching resist layer by treating it with a 3.0% hydroxylamine solution at 40 ° C. Was. Observation of the obtained printed wiring board with a microscope showed no defects such as disconnection. No defects such as pinholes were found inside the through holes. Storage test

After storing the laminated plate on which the dry film coating with heat flux and the heat-meltable fine particle layer were formed for 4 months in a light room at 30 ° C, an etching resist layer was formed in the same manner as above. As a result, a wiring image free from defects was obtained.

Example 14

Formation of through hole and filling of filling ink

To a double-sided copper-clad laminate (Mitsubishi Gas Chemical Co., Ltd., 200 x 300 x 0.8 mm, copper thickness 18 〃 m) with copper foil laminated on both sides of a glass base epoxy resin plate, After drilling 100 through holes of 0.4 mm0 and 0.6 mm0 each, a copper plating process (Okuno Pharmaceutical Co., Ltd., 0PC process M) is applied to the surface of the laminated board including the inside of the through holes. A copper plating layer having a thickness of 8 m was provided. Next, the hole filling ink used in Example 1 was filled in the through holes by a squeegee method, and was thermally cured. Filling ink on the copper plating layer other than inside the through hole was removed by buffing and washing.

Formation of Al-soluble resin layer and hot-melt fine particle layer

After the filling of the through-hole with the filling ink is completed, it is applied by a dipping method using a coating solution having the composition shown in Table 6, and then dried at 90 ° C for 10 minutes to obtain an alkali-soluble resin layer ( A film thickness of 3.2 / zm) was obtained. Furthermore, using a coating solution having the composition shown in Table 3, coating was performed by an electrodeposition method (applied voltage: 150 V), followed by air-drying at 40 ° C for 2 minutes to obtain a heat-meltable fine particle layer (film thickness 2. 0 zm).

Formation of etching resist layer

A semiconductor laser exposure device (780 nm) melts and fixes the heat-meltable fine particle layer corresponding to the wiring section to form a melt-fixed layer. Then, a 5.0% sodium carbonate solution (liquid temperature 35

° C) was sprayed ^{(2. 0 kg / cm 2)} , the heat melting particles layer and alkali-soluble resin layer of non Rooster himself wire unit is removed, the alkali-soluble resin layer, fusing layer, filling An etching resist layer composed of the ink and was obtained. Observation of this etching resist layer with a microscope revealed a high-resolution wiring image with no missing wiring parts and no stain on non-image parts. Hot o

Etching

After forming the etching resist layer, it is treated with a ferric chloride solution (45 ° C, spray pressure: 3.0 kg / cm ² ), and the copper plating layer and the copper that are not covered with the etching resist layer The layer was removed. Next, treatment with a 3.0% sodium hydroxide solution at 40 ° C. was performed to remove the remaining etching resist layer, thereby obtaining a printed wiring board. Observation of the obtained printed wiring board with a microscope showed no defects such as disconnection. No defects such as pinholes were found inside the through holes. Storage test

After storing the laminate having been filled with the ink for filling in holes, forming the alkali-soluble resin layer, and forming the heat-meltable fine particle layer in a light room at 30 ° C for 4 months, the etching resist layer is formed in the same manner as described above. As a result, no defect was found and a wiring image could be obtained.

Example 15

Forming through holes

To a double-sided copper-clad laminate (Mitsubishi Gas Chemical Co., Ltd., 200 mm x 300 mm x 0.8 mm, copper thickness 18 mm) After opening 100 through holes of 0.4 mm ø and 0.6 mm ø each, and then performing copper plating (Okuno Pharmaceutical Co., Ltd., PC process M), the product including the inside of the through holes A copper plating layer having a thickness of 8 zm was provided on the surface of the layer plate.

Coating of alkali-soluble dry film

After forming the through holes, an alkali-soluble dry film was coated on the copper plating layer surface in the same manner as in Example 2.

Formation of hot-melt particulate layer

After coating the copper plating layer with an Al-soluble dry film, apply it by the electrodeposition method using a coating solution having the composition shown in Table 3, then air-dry at 40 ° C to obtain an alkali-soluble film. A hot-melt fine particle layer (2.6 m thick) was formed thereon.

Formation of etching resist layer

Using a semiconductor laser exposure device (780 nm), a layer of heat-meltable fine particles CT / JP 7 3 1

4 2 Fusing and fixing to form a fusing layer, then spraying (2.0 kg / cm ² ) with 5.0% sodium carbonate solution (liquid temperature 35 ° C) The soluble dry film was removed to obtain an etching resist layer composed of the soluble dry film and the fusion fixing layer. Observation of this etching resist layer with a microscope revealed a high-resolution wiring image with no missing wiring portions and no stain on non-image portions.

Etching

The laminated plate on which the soluble dry film coating and the heat-fusible fine particle layer were formed was stored for 4 months in a light room at 30 ° C, and then an etching resist layer was formed in the same manner as above. However, a defect-free wiring image could be obtained.

Example 16

Formation of through holes and filling of fill holes

A double-sided copper-clad laminate with copper foil laminated on both sides of a glass-based epoxy resin plate (Mitsubishi Gas Chemical Co., Ltd., 200 x 300 x 0.8 mm, copper thickness 18 zm) After opening 100 through holes of 4 mm0 and 0.6 mm0 each, a copper plating treatment (Okuno Pharmaceutical Co., Ltd., 0PC process M) is applied, and the thickness of the laminated board surface including the inside of the through holes is increased. An 8 m copper plating layer was provided. Next, the filling ink used in Example 12 was filled in the inside of the through-hole by a roll coating method, and was thermally cured. Filling ink on the copper-plated layer other than inside the through hole was removed by buffing and washing.

Formation of Al-soluble resin layer and hot-melt fine particle layer

After filling the through-hole with filling ink, fill with the composition shown in Table 8 The solution was applied by electrodeposition (applied current: 10 O mA) and dried at 90 ° C for 10 minutes to obtain an alkali-soluble resin layer (thickness: 3.2 fim). Furthermore, using a coating solution having the composition shown in Table 3, coating was performed by an electrodeposition method (applied voltage: 180 V), and then air-dried at 40 ° C for 2 minutes to obtain a heat-meltable fine particle layer (film thickness 2. 0 τη was obtained.

Formation of etching resist layer

A semiconductor laser exposure apparatus (780 nm) melts and fixes the heat-meltable fine particle layer corresponding to the wiring section to form a fusion-fixed layer, and then sprays 5.0% sodium carbonate solution (liquid temperature of 35 ° C) ( 2.0 kg / cm ² ) to remove the heat-fusible fine particle layer and the alkali-soluble resin layer in the non-wiring area, and form an etching resist layer consisting of the alkali-soluble resin layer, the fusion fixing layer, and the ink for filling the hole. Obtained. Observation of this etching resist layer with a microscope revealed that it was a high-resolution wiring image with no missing wiring parts and no stain on non-image parts.o

Etchin

After the etching resist layer is formed, it is treated with a ferric chloride solution (45 ° C, spray pressure: 3.0 kg / cm ² ), and the copper plating layer and the copper that are not covered with the etching resist layer The layer was removed. Next, the substrate was treated with a 3.0% sodium hydroxide solution at 40 ° C. to remove the remaining etching resist layer, thereby obtaining a printed wiring board. Observation of the obtained printed wiring board with a microscope showed no defects such as disconnection. No defects such as pinholes were found inside the through holes. Storage test

After storing the laminated board on which the ink for filling the hole, the formation of the alkali-soluble resin layer, and the formation of the heat-meltable fine particle layer have been stored for 4 months in a light room at 30 ° C, the etching resist layer is formed in the same manner as described above. After forming, a wiring image without any defects could be obtained ο

Comparative Example 2

To a double-sided copper-clad laminate (Mitsubishi Gas Chemical Co., Ltd., 200 x 300 x 0.8 mm, copper thickness 18 〃 m) with copper foil laminated on both sides of a glass base epoxy resin plate, After drilling 100 through holes of 0.4 mm0 and 1.6 mm0 at a time, copper plating treatment (Okuno Pharmaceutical Co., Ltd., 0PC process M) is applied to the product including the inside of the through holes. Layer plate A copper plating layer with a thickness of 8 m was provided on the surface. A dry polymer photoresist (manufactured by Nippon Synthetic Chemical Co., Ltd.), which is a photopolymer, was thermocompression-bonded on the copper plating layer. This photopolymer was exposed to light using the same semiconductor laser exposure apparatus as in Examples 12 to 16 above, but no photopolymerization reaction could be caused. After the dry finolem photoresist was thermocompressed and stored in a light room at 30 ° C for 3 months, the polymer was inactivated.

Industrial applicability

As described above, the image forming material of the present invention has better storage stability than the conventional image forming material using a photopolymer. Further, in the image forming method, the lithographic printing plate making method, and the printed wiring board manufacturing method of the present invention, it is possible to easily form an image by a direct drawing method using a low-output laser, and to use a computer. It is also compatible with a flat plate, and has an excellent effect that an image having high resolution can be obtained easily and at low cost.

Claims

The scope of the claims

1. An image-forming material comprising a base material and a layer of heat-meltable fine particles.

2. An image forming material having an alkali-soluble resin layer and a heat-meltable fine particle layer in this order on a substrate.

3. An image forming method in which a heat-meltable fine particle layer is provided on a base material, and the heat-meltable fine particle layer in a portion to be imaged is heated and melted and fixed on the base material surface.

4. An image forming material having an alkali-soluble resin layer and a heat-fusible fine particle layer in this order on a base material is melt-fixed at a portion corresponding to the image area of the heat-fusible fine particle layer, and then the non-image is formed. An image forming method for forming an image on a base material by removing a hot-melt fine particle layer and a soluble resin layer corresponding to a part by a concentrated liquid.

5. The image forming material according to claim 1, wherein the heat fusible fine particle layer contains a light absorbing agent.

6. The image forming material according to claim 2, wherein at least one of the resin layer and the thermofusible fine particle layer contains a light absorbing agent.

7. The image forming method according to claim 3, wherein the heat-meltable fine particle layer contains a light absorbing agent.

8. The image forming method according to claim 4, wherein at least one of the resin layer and the thermofusible fine particle layer contains a light absorbing agent.

9. The image forming method according to claim 4, wherein the soluble resin layer is formed by an electrodeposition method.

10. The image forming method according to any one of claims 3, 4, 7, and 8, wherein the thermofusible fine particle layer is fused and fixed by a laser.

11. The image forming method according to claim 4, wherein the alkali-soluble resin layer is formed by an electrodeposition method, and the thermofusible fine particle layer is fused and fixed by a laser.

1 2. The image forming method according to claim 3, wherein the heat-meltable fine particle layer is formed by an electrodeposition method.

The image according to claim 4 or 8, wherein the alkali-soluble resin layer is formed by an electrodeposition method, the heat-meltable fine particle layer is formed by an electrodeposition method, and the heat-meltable fine particle layer is fused and fixed by a laser. Forming method.

1 4. The image according to any one of claims 1, 2, 5, and 6, wherein the substrate is a support for a printing plate. Imaging material.

1 5. The image forming method according to claim 3, wherein the substrate is a support for a printing plate.

1 6. The image forming method according to claim 4 or 8, wherein the base material is a support for a printing plate, the alkali-soluble resin layer is formed by an electrodeposition method, and the heat-meltable fine particle layer is fused and fixed by a laser. Method.

1 7. The substrate is a printing plate support, the alkali-soluble resin layer is formed by electrodeposition, the heat-meltable fine particle layer is formed by electrodeposition, and the heat-meltable fine particle layer is formed by laser. 9. The image forming method according to claim 4, wherein the fixing is performed by fusing.

1 8. The image forming material according to any one of claims 1, 2, 5, and 6, wherein the substrate is a support for manufacturing a printed wiring board.

1 9. The image forming method according to any one of claims 3, 4, 7, and 8, wherein the substrate is a support for manufacturing a printed wiring board.

20. The substrate according to claim 4, wherein the base material is a support for manufacturing a printed wiring board, wherein the resin layer is formed by an electrodeposition method, and the layer of the heat-meltable fine particles is fused and fixed by a laser. Image forming method.

2 1. The base material is a substrate for the production of printed Tokki Line Co., Ltd., and the resin layer that can be dissolved is formed by electrodeposition, and the layer of heat-meltable fine particles is formed by electrodeposition. 9. The image forming method according to claim 4, wherein the conductive fine particle layer is fused and fixed by a laser.

2 2. On the photosensitive layer of the photosensitive lithographic printing plate before image exposure, apply a coating solution containing a dispersion medium and heat-meltable fine particles, and apply the dispersion medium at an ambient temperature equal to or lower than the softening point of the heat-meltable fine particles. A method for producing a lithographic printing plate wherein the heat-fusible fine particle layer is formed into a layer by evaporating.

2 3. The coating liquid is heat-fusible fine particles having a charge dispersed in a dispersion medium having a high electric resistivity, and the heat-fusible fine particles are deposited on a photosensitive lithographic printing plate before image exposure by an electrodeposition method. The method for producing a lithographic printing plate according to claim 22, wherein the particles are applied.

2 4. A coating liquid containing a dispersion medium and heat-meltable fine particles is applied, and the dispersion medium is evaporated at an ambient temperature equal to or lower than the softening point of the heat-meltable fine particles to form the heat-meltable fine particles in a layer. An apparatus, comprising: a guide plate and an electrode disposed opposite to the guide plate; and a gap formed between the guide plate and the electrode, having a charge dispersed in a dispersion medium having a high electrical resistivity. A lithographic printing plate having means for supplying a coating liquid containing heat-fusible fine particles, a means for applying a voltage from the electrode to a lithographic printing plate, and a means for squeezing excess coating liquid downstream of the electrode. Printing plate manufacturing equipment.

2 5. The means for squeezing the excess coating liquid is a squeezing roll pair, and means for blowing gas toward a gap formed between the squeezing roll pair and an end of the photosensitive lithographic printing plate. 25. The lithographic printing plate manufacturing apparatus according to claim 24, wherein:

26. The lithographic printing plate manufacturing apparatus according to claim 24, further comprising means for adsorbing and transporting the back surface of the photosensitive lithographic printing plate downstream of the squeezing roll pair.

27. The lithographic printing plate manufacturing apparatus according to claim 24 or 25, further comprising a dispersion medium evaporation promoting means downstream of the squeezing roll pair.

28. The lithographic printing method according to claim 24, further comprising means for adsorbing and transporting the back surface of the photosensitive lithographic printing plate downstream of the pair of squeezing rolls, and further comprising means for accelerating dispersion medium evaporation. Plate manufacturing equipment.

2 9. Heat-fusible fine particles are provided in a layer on the photosensitive layer of the photosensitive lithographic printing plate, and the hot-melt fine particle layer in a portion to be an image is heated and melted and fixed on the photosensitive lithographic printing plate. A plate making method for lithographic printing plates that elutes and removes non-image areas.

30. The method of making a lithographic printing plate according to claim 29, wherein the heat-fusible fine particle layer contains a light absorbing agent.

31. The lithographic printing plate according to claim 30, wherein the light absorber has an absorption maximum in a wavelength region of 600 nm or more, and the absorption is a half of a maximum value at a wavelength of less than 600 nm. Plate making method.

32. The method of making a lithographic printing plate according to any one of claims 29 to 31, wherein the photosensitive lithographic printing plate is a negative type, and the plate surface is irradiated with ultraviolet light after removing a non-image portion.

3 3. The lithographic printing plate according to any one of claims 29 to 31, wherein the photosensitive lithographic printing plate is a positive type, and the plate surface is irradiated with ultraviolet light before providing the heat-fusible fine particle layer. Method.

31. The plate making method for a lithographic printing plate according to any one of claims 29 to 31, wherein a burning treatment is performed after a non-image portion of the photosensitive lithographic printing plate is eluted and removed.

3 5. The photosensitive lithographic printing plate is negative type, and after removing the non-image area, 32. The method of making a lithographic printing plate according to any one of claims 29 to 31, wherein a burning treatment is performed after irradiating external light to elute and remove a non-image portion of the photosensitive lithographic printing plate.

3 6. The photosensitive lithographic printing plate is of a positive type, after irradiating the plate surface with ultraviolet light before providing the heat-meltable fine particle layer, and eluting and removing a non-image portion of the photosensitive lithographic printing plate. 31. The method of manufacturing a lithographic printing plate according to claim 29, wherein the lithographic printing plate is subjected to a burning treatment.

3 7. After making a through hole in the laminated board provided with a conductive layer on at least one side of the insulating substrate, a plated conductive layer is formed on the laminated board surface including the inside of the through hole, and then an etching resist layer corresponding to the wiring part A method of manufacturing a printed wiring board in which the adhered conductive layer and the conductive layer which are not covered with the etching resist layer are removed by etching, and the remaining etching resist layer is removed as the case may be. After filling with an ink, an Al-soluble resin layer and a heat-fusible fine particle layer are formed in this order on the plating conductive layer, and the heat-fusible fine particle layer at the portion corresponding to the wiring portion is fused and fixed. A printed wiring board in which an etching resist layer is formed by removing the heat-meltable fine particle layer and the alkali-soluble resin layer in a portion corresponding to the non-wiring portion. Production method.

3 8. After opening a through hole in the laminated board provided with a conductive layer on at least one side of the insulating substrate, form a plated conductive layer on the laminated board surface including the inside of the through hole, and then etch resist corresponding to the wiring section A method of manufacturing a printed wiring board, wherein a conductive layer and a conductive layer which are not covered with the etching resist layer are removed by etching, and the remaining etching resist layer is removed as the case may be. After coating the conductive layer with a film, a heat-meltable fine particle layer is formed on the alkali soluble dry film, and then the heat-meltable fine particle layer in a portion corresponding to the wiring portion is melted and fixed. An etching resist layer is formed by removing the heat-meltable fine particle layer and the Al-soluble soluble dry film in the part corresponding to the non-wiring part Manufacturing method of printed wiring board.

39. The method according to claim 37, wherein at least one layer selected from the group consisting of a soluble resin layer and a thermally fusible fine particle layer contains a light absorbing agent.

40. Small amount selected from alkali-soluble dry film and hot-melt fine particle layer 39. The method for producing a printed wiring board according to claim 38, wherein at least one layer contains a light absorbing agent.

41. The method for producing a printed wiring board according to claim 37, wherein the soluble resin layer is formed by an electrodeposition method.

42. The method for producing a printed wiring board according to any one of claims 37 to 40, wherein the thermofusible fine particle layer is fused and fixed by a laser.

40. The method for producing a printed wiring board according to claim 37, wherein the soluble resin layer is formed by an electrodeposition method, and the heat-meltable fine particle layer is fused and fixed by a laser.

4 4. The method for producing a printed wiring board according to any one of claims 37 to 40, wherein the heat-meltable fine particle layer is formed by an electrodeposition method.

40. The method for producing a printed wiring board according to claim 37, wherein the soluble resin layer is formed by an electrodeposition method, and the thermofusible fine particle layer is formed by an electrodeposition method.

46. The method for producing a printed wiring board according to any one of claims 37 to 40, wherein the heat-meltable fine particle layer is formed by an electrodeposition method, and the heat-meltable fine particle layer is fused and fixed by a laser.

4 7. Claim 37 or 39, wherein the alkali-soluble resin layer is formed by an electrodeposition method, the heat-meltable fine particle layer is formed by an electrodeposition method, and the heat-meltable fine particle layer is fused and fixed by a laser. Manufacturing method of printed wiring board.