JP2009162993A - Developing method of photosensitive planographic printing plate and automatic developing machine for photosensitive planographic printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide the developing method of a photosensitive planographic printing plate and an automatic developing machine for a photosensitive planographic printing plate, with which, even when a temperature in a preheating section is sufficiently increased to improve plate wear resistance, a plate is free from occurrence of wrinkles (occurrence of preheat ripples) caused by deformation in a subsequent pre-rinsing section where the plate is brought into contact with rinsing water and rapidly cooled, and a planographic printing plate having an excellent plate wear resistance can be obtained in a subsequent developing section. <P>SOLUTION: The developing method of a photosensitive planographic printing plate includes at least, a preheating step of preliminarily heating and curing a photosensitive planographic printing plate to improve plate wear resistance, a pre-rinsing step of rinsing the plate with water to remove an oxygen shielding layer, and a developing step of developing the plate with an aqueous developer solution containing an alkali agent, and the method further includes a heat radiating means between the preheating step and the pre-rinsing step. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a development processing method and an automatic processor for a photosensitive lithographic printing plate having a photopolymerizable photosensitive layer containing a compound having an ethylenically unsaturated bond capable of addition polymerization represented by a photopolymer type CTP plate. Specifically, there is no generation of wrinkles (preheat ripple) in the pre-water washing section (pre-water washing section), and the next development in the development section can provide a lithographic printing plate having excellent printing durability. The present invention relates to a development processing method for a photosensitive lithographic printing plate and an automatic developing machine for a photosensitive lithographic printing plate.

In the field of printing that requires a relatively high printing durability, it is known to use a negative photosensitive lithographic printing plate material having a polymerizable photosensitive layer containing a polymerizable compound. In the development processing of a photosensitive lithographic printing plate having a photopolymerizable photosensitive layer containing a compound having an addition-polymerizable ethylenically unsaturated bond typified by a photopolymer type CTP plate, light is applied to the image area. A method is generally used in which the exposed portion is cured by generating radicals and then heating to 100 ° C. or higher to promote polymerization. This photopolymerization type photosensitive lithographic printing plate material is usually subjected to image exposure and heat treatment (preheating), followed by washing with water for removing the oxygen blocking layer, and dissolution removal of unexposed portions (non-image portions). A lithographic printing plate is obtained by performing a development process, a water washing process, and a finisher gum process for making the non-image area hydrophilic. (For example, refer to Patent Document 1.)
However, when an aluminum plate heated to 100 ° C. or more is washed with water, the temperature of the plate suddenly decreases, causing the aluminum support to shrink, and a phenomenon of wrinkling may occur (hereinafter referred to as preheat ripple). When the temperature of the heat treatment part (preheating part) is lowered to 100 ° C. or lower, the occurrence of preheat ripple is reduced, but there is a problem that polymerization of the exposed part does not proceed sufficiently and printing durability is poor.
JP 2006-047633 A

The present invention has been made in view of the above problems, and an object of the present invention is to provide a photopolymerizable photosensitive layer containing a compound having an ethylenically unsaturated bond capable of addition polymerization represented by a photopolymer type CTP plate. In a developing method and an automatic developing machine for a photosensitive lithographic printing plate having
Even if the temperature in the preheating part (preheating part) is sufficiently increased in order to improve the printing durability, it is brought into contact with the washing water in the next prewashing part (prewashing part) and rapidly cooled and deformed. Photosensitive lithographic printing plate development processing method and photosensitive lithographic printing plate capable of obtaining a lithographic printing plate which is free of wrinkles (preheat ripples) and has excellent printing durability by the development in the developing section. Is to provide an automatic developing machine.

  The above object of the present invention can be achieved by the following constitution.

1. A photosensitive layer of a photopolymerizable photosensitive resin composition containing a compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a polymer binder on an aluminum support, and oxygen on the photosensitive layer In the method of developing a photosensitive lithographic printing plate, the photosensitive lithographic printing plate having a blocking layer is subjected to image exposure and then developed with an aqueous developer containing an alkaline agent using an automatic developing machine.
The development method of the photosensitive lithographic printing plate is such that the photosensitive lithographic printing plate is first heated to be cured and brought to an improvement in printing durability (preheating step), and then washed with washing water. A pre-water washing step (pre-water washing step) for removing the oxygen blocking layer, and then a development step for developing with an aqueous solution containing an alkaline agent,
And,
A heat dissipating means is provided between the preheating step and the pre-water washing step;
A development processing method of a photosensitive lithographic printing plate characterized by the above.

2. A photosensitive layer of a photopolymerizable photosensitive resin composition containing a compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a polymer binder on an aluminum plate support, and on the photosensitive layer In the method of developing a photosensitive lithographic printing plate in which a photosensitive lithographic printing plate having an oxygen blocking layer is subjected to image exposure and then developed with an aqueous developer containing an alkaline agent using an automatic developing machine.
The development method of the photosensitive lithographic printing plate is such that the photosensitive lithographic printing plate is first heated to be cured and brought to an improvement in printing durability (preheating step), and then washed with washing water. A pre-water washing step (pre-water washing step) for removing the oxygen blocking layer, and then a development step for developing with an aqueous solution containing an alkaline agent,
And,
As a heat dissipating means between the pre-heating step and the pre-washing step, the washing water does not contact the transport roller at the entrance of the pre-washing step.
A development processing method of a photosensitive lithographic printing plate characterized by the above.

  3. The heat radiating means is provided with a roller for preventing backwashing of the washing water between the roller at the entrance of the pre-washing step and the washing treatment part of the pre-washing step, so that the washing water that has flowed to the plate surface flows into the entrance of the pre-washing portion. 3. The method for developing a photosensitive lithographic printing plate as described in 1 or 2, which is a means which does not contact a roller.

  4). The heat radiating means is a means in which the washing water that has flowed on the plate surface does not contact the roller at the entrance of the pre-washing section by making the entrance of the pre-washing process higher than the washing treatment part of the pre-washing process. The method for developing a photosensitive lithographic printing plate as described in 1 or 2 above.

  5). The heat radiating means is provided with a roller for preventing backwash of washing water between the roller at the entrance of the pre-washing process and the washing treatment part of the pre-washing process, so that the washing water that has flowed to the plate surface is the roller at the entrance of the pre-washing process. And means that the washing water that has flowed on the plate surface does not come into contact with the roller at the entrance of the pre-washing process by making the entrance of the pre-washing process higher than the washing treatment part of the pre-washing process. 3. The method for developing a photosensitive lithographic printing plate as described in 1 or 2 above.

6). The above-mentioned `` means that the washing water that has flowed on the plate surface does not come into contact with the roller at the entrance of the pre-washing process by making the entrance of the pre-washing process higher than the washing treatment part of the pre-washing process '',
6. The photosensitive lithographic plate according to 4 or 5, which is “means for inclining the traveling direction portion of the conveyance path of the photosensitive lithographic printing plate in contact with the roller at the entrance of the pre-washing step so as to form a depression with the horizontal direction”. Development method of printing plate.

7). The above-mentioned `` means that the washing water that has flowed on the plate surface does not come into contact with the roller at the entrance of the pre-washing process by making the entrance of the pre-washing process higher than the washing treatment part of the pre-washing process '',
6. “Means in which the included angle θ between the traveling direction portion of the conveyance path of the photosensitive lithographic printing plate contacting the roller at the entrance of the pre-water washing step and the horizontal direction is 5 ° or more and 30 ° or less” Development processing method for photosensitive lithographic printing plate.

8). The above-mentioned `` means that the washing water that has flowed on the plate surface does not come into contact with the roller at the entrance of the pre-washing process by making the entrance of the pre-washing process higher than the washing treatment part of the pre-washing process '',
6. “Means in which the included angle θ between the traveling direction portion of the conveyance path of the photosensitive lithographic printing plate contacting the roller at the entrance of the pre-water washing step and the horizontal direction is 15 ° or more and 20 ° or less” Development processing method for photosensitive lithographic printing plate.

  9. The photosensitive lithographic printing plate in the preheating step (preheating step) is heated to reach a temperature on the plate surface of 100 ° C. or higher and 150 ° C. or lower. Development processing method for photosensitive lithographic printing plate.

  10. The photosensitive lithographic printing plate in the preheating step (preheating step) is heated to reach a temperature on the plate surface of 120 ° C. or higher and 140 ° C. or lower. Development processing method for photosensitive lithographic printing plate.

11. A photosensitive layer of a photopolymerizable photosensitive resin composition containing a compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a polymer binder on an aluminum support, and oxygen on the photosensitive layer In an automatic developing machine for photosensitive lithographic printing plates, a photosensitive lithographic printing plate having a blocking layer is subjected to image exposure and then developed with an aqueous developer containing an alkaline agent using an automatic developing machine.
The automatic processor first heats and cures the photosensitive lithographic printing plate so as to improve the printing durability, and then rinses with washing water to remove the oxygen barrier layer. A pre-water washing section (pre-water washing section), and then a developing section that develops with an aqueous developer containing an alkaline agent, and at least,
And,
A heat dissipating means is provided between the pre-heating unit and the pre-water washing unit.
An automatic developing machine for photosensitive lithographic printing plates.

12 A photosensitive layer of a photopolymerizable photosensitive resin composition containing a compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a polymer binder on an aluminum plate support, and on the photosensitive layer In an automatic developing machine for a photosensitive lithographic printing plate, a photosensitive lithographic printing plate having an oxygen blocking layer is subjected to image exposure and then developed with an aqueous developer containing an alkaline agent using an automatic developing machine.
The automatic processor first heats and cures the photosensitive lithographic printing plate so as to improve the printing durability, and then rinses with washing water to remove the oxygen barrier layer. A pre-water washing section (pre-water washing section), and then a developing section that develops with an aqueous developer containing an alkaline agent, and at least,
And,
As a heat radiating means between the pre-heating unit and the pre-washing unit, there is a means that the washing water does not contact the transport roller at the entrance of the pre-washing unit.
An automatic developing machine for photosensitive lithographic printing plates.

  13. The heat radiating means is provided with a roller for preventing backwashing of the washing water between the roller at the entrance of the pre-washing section and the washing treatment part of the pre-washing section, so that the washing water that has flowed to the plate surface flows into the entrance of the pre-washing section. The automatic developing machine for a photosensitive lithographic printing plate as described in 11 or 12, characterized in that the means is a means which does not contact a roller.

  14 The heat radiating means is a means in which the washing water that has flowed on the plate surface does not contact the roller at the entrance of the pre-washing section by making the entrance of the pre-washing section higher than the washing process portion of the pre-washing section. The automatic developing machine for photosensitive lithographic printing plates according to 11 or 12.

  15. The heat radiating means is provided with a roller for preventing backwashing of washing water between a roller at the entrance of the pre-washing section and a washing treatment portion of the pre-washing section, so that the washing water that has flowed to the plate surface is a roller at the entrance of the pre-washing section. And means that the washing water that has flowed on the plate surface does not contact the roller at the entrance of the pre-washing section by making the entrance of the pre-washing section higher than the washing treatment section of the pre-washing section. 13. An automatic developing machine for photosensitive lithographic printing plates as described in 11 or 12 above.

16. Said `` means that the washing water that has flowed on the plate surface does not contact the roller at the entrance of the pre-washing part by making the entrance of the pre-washing part higher than the washing treatment part of the pre-washing part '',
The photosensitive lithographic plate according to 14 or 15, which is "means for inclining an advancing direction portion of a conveyance path of a photosensitive lithographic printing plate in contact with a roller at the entrance of the pre-washing section to form a depression with the horizontal direction" Automatic developing machine for printing plates.

17. Said `` means that the washing water that has flowed on the plate surface does not contact the roller at the entrance of the pre-washing part by making the entrance of the pre-washing part higher than the washing treatment part of the pre-washing part '',
16. “Means in which the included angle θ between the traveling direction portion of the conveyance path of the photosensitive lithographic printing plate in contact with the roller at the entrance of the pre-washing section and the horizontal direction is 5 ° or more and 30 ° or less” Automatic developing machine for photosensitive lithographic printing plates.

18. Said `` means that the washing water that has flowed on the plate surface does not contact the roller at the entrance of the pre-washing part by making the entrance of the pre-washing part higher than the washing treatment part of the pre-washing part '',
16. “Means in which the included angle θ between the traveling direction portion of the conveyance path of the photosensitive lithographic printing plate contacting the roller at the entrance of the pre-washing section and the horizontal direction is 15 ° or more and 20 ° or less” Automatic developing machine for photosensitive lithographic printing plates.

  19. The photosensitive lithographic printing plate is heated in the preheating section (preheating section), and the temperature reached on the plate surface is 100 ° C. or more and 150 ° C. or less, characterized in that any one of 11 to 18 Automatic developing machine for photosensitive lithographic printing plates.

  20. The photosensitive lithographic printing plate is heated in the preheating unit (preheating unit), and the temperature reached on the plate surface is 120 ° C. or higher and 140 ° C. or lower. Automatic developing machine for photosensitive lithographic printing plates.

The present invention has been made in view of the above problems, and according to the present invention, a photopolymerizable photosensitive layer containing a compound having an ethylenically unsaturated bond capable of addition polymerization represented by a photopolymer type CTP plate. In a developing method and an automatic developing machine for a photosensitive lithographic printing plate having
Even if the temperature in the preheating part (preheating part) is sufficiently increased in order to improve the printing durability, it is brought into contact with the washing water in the next prewashing part (prewashing part) and rapidly cooled and deformed. Photosensitive lithographic printing plate development processing method and photosensitive lithographic printing plate capable of obtaining a lithographic printing plate which is free of wrinkles (preheat ripples) and has excellent printing durability by the development in the developing section. An automatic processor can be provided.

  Hereinafter, although the best mode for carrying out the present invention will be described, the present invention is not limited to these.

<< Development method of photosensitive lithographic printing plate >>
Hereinafter, the present invention will be described in detail.

<exposure>
In the present invention, the photopolymerization type photosensitive layer in the photosensitive lithographic printing plate is, for example, a carbon arc lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a halogen lamp, a helium cadmium laser, an argon ion laser. An image is formed on the support surface by image development with a well-known actinic ray such as FD / YAG laser, helium neon laser, semiconductor laser (350 nm to 600 nm) or (700 nm to 1000 nm), followed by development. be able to.

<Development processing>
In the development processing method of the photosensitive lithographic printing plate of the present invention,
The photosensitive lithographic printing plate development method is such that the photosensitive lithographic printing plate is first heated to be cured and pre-heated to improve printing durability (preheating step), and then washed with washing water to block oxygen. A pre-water washing step for removing the layer (pre-water washing step), and then a development step for developing with an aqueous solution containing an alkaline agent, and at least the pre-heating step and the pre-water washing step There is a heat dissipation means in between. Further, as a heat radiating means between the preheating step and the pre-water washing step, there is a means for preventing the washing water from contacting the transport roller at the entrance of the pre-development water washing step.

or,
In the automatic processor for the photosensitive lithographic printing plate of the present invention,
An automatic processor first heats and cures the photosensitive lithographic printing plate to pre-heat part (preheating part) that brings about improvement in printing durability, and then rinses with water to remove the oxygen barrier layer. Part (pre-water washing part), and next, a developing part developed with an aqueous developer containing an alkaline agent, and a heat radiating means between the pre-heating part and the pre-water washing part . Moreover, as a heat radiating means between the pre-heating part and the pre-washing part, there is a means for preventing the washing water from contacting the transport roller at the entrance of the pre-development washing part.

And
As "a heat dissipating means between the preheating step and the prewashing step" or "a heat dissipating means between the preheating unit and the prewashing unit", the washing water is supplied to the transport roller at the entrance of the prewashing unit. Consider non-contact means, i.e., usually the washing water is in contact with the entrance roller of the pre-washing process or pre-washing section, but the washing water does not touch the roller at the entrance of the pre-washing process or pre-washing section. It has been found that ripples are suppressed by considering the means to perform the present invention, and the present invention has been achieved.

  In the present invention, a process means a process in the development processing method, and a part means a part in an automatic processor corresponding to the process. Hereinafter, for the sake of convenience, the present invention will be described mainly with respect to a part, but it means that the process corresponding to the part has also been described.

  Examples of means for preventing the washing water from contacting the roller at the entrance of the pre-washing section include the following means.

(1). By installing a roller for preventing backwashing of the washing water between the roller at the entrance of the pre-washing unit and the washing process part of the pre-washing unit, the washing water that has flowed on the plate surface will not come into contact with the roller at the entrance of the pre-washing unit. Means (for example, see FIG. 3),
(2). Means (for example, refer to FIG. 2) for preventing the flush water flowing on the plate from coming into contact with the roller at the entrance of the pre-washing unit by making the entrance of the pre-washing unit higher than the washing process part of the pre-washing unit.
(3). Provide a roller for preventing backflow of flush water between the roller at the entrance of the pre-rinsing section and the washing section of the pre-rinsing section, and make the entrance of the pre-rinsing section higher than the flush section of the pre-wash section. Means for preventing the washing water flowing on the printing plate from contacting the roller at the entrance of the pre-washing section (for example, see FIG. 4),
It has been found that the object of the present invention can be achieved by the above-mentioned means that the contact of the washing water with the entrance roller can be suppressed and prevented.

In the present invention, by making the entrance of the pre-washing section higher than the washing treatment part of the pre-washing section, the means for preventing the washing water flowing on the plate surface from contacting the roller at the entrance of the pre-washing section,
It is preferable that the traveling direction portion of the conveyance path of the photosensitive lithographic printing plate in contact with the roller at the entrance of the pre-washing section is inclined so as to form a depression with the horizontal direction. Furthermore, it is preferable that the included angle θ between the traveling direction portion of the conveyance path of the photosensitive lithographic printing plate contacting the roller at the entrance of the pre-washing section and the horizontal direction is 5 ° or more. The inclination is preferably set to be 5 ° to 30 °, that is, the angle θ is preferably 5 ° to 30 °, and the depression angle θ is more preferably 15 ° to 20 °.

  When the angle θ is in the above range, the washing water flowing on the plate surface does not come into contact with the roller at the entrance of the pre-washing section, and the effects of the present invention can be favorably achieved.

  In the present invention, the temperature reached on the plate surface by heating in the preheating section for heating and curing the photopolymerization type photosensitive layer of the photosensitive lithographic printing plate to bring about improvement in printing durability is 100 ° C. The temperature is preferably 150 ° C. or lower. Furthermore, it is more preferable that the temperature reached on the plate surface is 120 ° C. or more and 140 ° C. or less.

  When the temperature reached on the plate surface by heating in the preheating section is not less than the above range, the photopolymerization type photosensitive layer of the photosensitive lithographic printing plate can be heated and cured to improve printing durability. . Moreover, it is preferable that it is below the above range because the photosensitive lithographic printing plate can exhibit performance without deterioration.

  Hereinafter, the developing method of the photosensitive lithographic printing plate of the present invention will be described using the automatic developing machine shown in FIGS. 1 to 3 exemplifying an example of the automatic developing machine used in the present invention. Also, a conventional photosensitive lithographic printing plate developing method will be described using the automatic developing machine shown in FIG. 4 used in the prior art.

  FIG. 1 is a schematic view of an automatic developing machine 1 showing an example of an automatic developing machine used in the present invention, in which the entrance of a pre-water washing section (pre-water washing section) is made higher than the water washing treatment part of the pre-water washing section.

  In FIG. 1, a photosensitive lithographic printing plate 1 is first heated by heaters 2 and 3 in a preheating section (preheating section), and is cured to improve printing durability. Next, “the rollers 4 and 5 provided at the entrance of the pre-water washing section in the pre-water washing section (pre-water washing section) are higher than the brush roller 8 and the roller 7 (water washing treatment portion) of the pre-water washing section (angle θ). By doing so, the washing water that has flowed to the plate surface is not contacted with the rollers 4 and 5 at the entrance of the pre-washing section ”, and is washed with washing water by the shower 6 and rubbed by the brush roller 8 to block oxygen. The layer is removed. Next, development processing is performed with an aqueous developer containing an alkaline agent in the developing section. Next, there is no generation of wrinkles (preheat ripple) in the pre-water washing section (pre-water washing section) after passing through the alkali processing section, post-development washing section, finishing section, and drying section. An excellent lithographic printing plate can be obtained.

  FIG. 2 shows an example of an automatic processor used in the present invention, in which a roller for preventing backwash of washing water is provided between the roller at the entrance of the pre-washing section (pre-washing section) and the washing treatment section of the pre-washing section. It is the schematic of the automatic processor 2 shown.

  In FIG. 2, first, although not shown, the photosensitive lithographic plate is heated by the heaters 2 and 3 in the same preheating part (preheating part) as in FIG. 2 and cured to improve the printing durability. Next, the printing plate 1 is provided with "rollers 4 'and 5' for preventing backflow of washing water between the rollers 4 and 5 at the entrance of the prewashing section and the washing section (shower 6) of the prewashing section. This prevents the washing water flowing on the plate surface from coming into contact with the rollers 4 and 5 at the entrance of the pre-washing section ”, and is washed with washing water by the shower 6 and rubbed by the brush roller 8 to remove the oxygen barrier layer. . Although not shown, in the same manner as in FIG. 2, next, development processing is performed with an aqueous developer containing an alkaline agent in the developing section. Next, there is no generation of wrinkles (preheat ripple) in the pre-water washing section (pre-water washing section) after passing through the alkali processing section, post-development washing section, finishing section, and drying section. An excellent lithographic printing plate can be obtained.

  FIG. 3 shows an embodiment of the present invention, in which a roller for preventing backwashing of washing water is provided between the roller at the entrance of the pre-washing section (pre-washing section) and the washing treatment section of the pre-washing section. It is the schematic of the automatic processor 3 which shows an example of the automatic processor which made the entrance higher than the water washing process part of a pre-water-washing part.

  In FIG. 3, although not shown, the photosensitive lithographic plate is heated by the heaters 2 and 3 in the same preheating unit (preheating unit) as in FIG. Next, the printing plate 1 was "flowed to the plate surface by providing a roller 4 'for preventing backwashing of the washing water between the rollers 4 and 5 at the entrance of the prewashing section and the washing section of the prewashing section. “While the washing water does not come into contact with the rollers 4 and 5 at the entrance of the pre-washing section”, and further, “the rollers 4 and 5 provided at the entrance of the pre-washing section at the pre-washing section (pre-washing section)” Is made higher (angle θ) than the brush roller 8 and the roller 7 (water-washed portion, etc.) of the pre-wash section so that the wash water flowing on the plate surface does not contact the roller at the entrance of the pre-wash section. "While it is washed with water by shower 6" Rubbed by Rashirora 8 is removed oxygen barrier layer. Although not shown, in the same manner as in FIG. 2, next, development processing is performed with an aqueous developer containing an alkaline agent in the developing section. Next, there is no generation of wrinkles (preheat ripple) in the pre-water washing section (pre-water washing section) after passing through the alkali processing section, post-development washing section, finishing section, and drying section. Excellent lithographic printing plates can be obtained particularly well.

  FIG. 4 is a schematic view of an automatic developing machine 4 showing an example of an automatic developing machine that has been conventionally used and has a conventional pre-water washing section (pre-water washing section).

  In FIG. 4, first, although not shown, a photosensitive lithographic plate which is heated by the heaters 2 and 3 in the same preheating part (preheating part) as in FIG. 2 and cured to improve the printing durability. Next, the printing plate 1 is washed with washing water by the shower 6 between the “rollers 4 and 5 at the entrance of the pre-washing section wet with the washing water by the shower 6” and the brush rollers 8 and 7. The oxygen barrier layer is removed by rubbing with the brush roller 8. Although not shown, in the same manner as in FIG. 2, next, development processing is performed with an aqueous developer containing an alkaline agent in the developing section. Next, a lithographic printing plate was obtained through an alkali treatment section, a post-development washing section, a finishing section, and a drying section. However, in this case, a lithographic printing plate in which wrinkles in the pre-water washing section (pre-water washing section) occurred (preheat ripple occurred) was obtained.

  The automatic processor used in the present invention can have any mechanism provided in the automatic processor applied to the processing of the photosensitive lithographic printing plate in addition to the above-described essential mechanism. For example, a mechanism for automatically replenishing a required amount of replenisher is preferably provided in the developer tank. Further, preferably a mechanism for automatically replenishing the developer tank with a necessary amount of water is provided, and preferably a mechanism for detecting the passage of the photosensitive lithographic printing plate (detection of plate passing) is provided, Preferably, a mechanism for estimating the processing area of the plate based on the detection of the plate is provided, and preferably a replenisher to be replenished based on the detection of the plate and / or the estimation of the processing area and / or A mechanism for controlling the replenishment amount and / or replenishment timing of water is provided, preferably a mechanism for controlling the temperature of the developer is provided, and preferably a mechanism for detecting the pH and / or conductivity of the developer. Preferably, a mechanism for controlling the replenishment amount and / or replenishment timing of the replenisher and / or water to be replenished based on the pH and / or conductivity of the developer is provided. That.

<Developer>
The developer according to the present invention is an aqueous developer containing an alkaline agent, and is an aqueous alkaline developer.

  The developer according to the present invention will be described below.

(Alkaline agent)
The main component of the developer and replenisher used in the processing method of the present invention is at least one compound selected from silicic acid, phosphoric acid, carbonic acid, boric acid, phenols, saccharides, oximes and fluorinated alcohols, or an alkali metal thereof. It is preferable to contain a salt or a salt of an organic cation. These compounds can be used as an alkaline agent by coexisting with an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide, etc., to make an alkaline aqueous solution having a pH higher than 8.5 and lower than 13.0. It is preferable to use it. More preferably, the pH is 8.5-12.

  The developer referred to in the present invention is not only an unused solution that is used at the start of development, but also a replenisher that is replenished in order to correct the activity of the developer that decreases due to the processing of the photosensitive lithographic printing plate. In addition, a liquid whose activity is maintained (so-called running liquid) is included. The replenisher therefore needs to have a higher activity (alkali concentration) than the developer, so the pH of the replenisher may exceed 13.0.

  Among these alkaline agents, as weakly acidic substances such as phenols, saccharides, oximes and fluorinated alcohols, those having a dissociation index (pKa) of 10.0 to 13.2 are preferable. Such an acid is selected from those described in IONISATION CONSTANTS OF ORGANIC ACIDS INAQUEOUS SOLUTION published by Pergamon Press, and specifically salicylic acid (pKa13.0), 3-hydroxy-2-naphthoic acid ( 12.84), catechol (12.6), gallic acid (12.4), sulfosalicylic acid (11.7), 3,4-dihydroxysulfonic acid (12.2), 3,4- Dihydroxybenzoic acid (11.94), 1,2,4-trihydroxybenzene (11.82), hydroquinone (11.56), pyrogallol (11.34), o-cresol (10.33) ), Resorsonol (11.27), p-cresol (10. 7), m-cresol (phenol having a phenolic hydroxyl group, such as the 10.09) and the like.

  As the saccharide, a non-reducing sugar that is stable even in an alkali is preferably used. Such non-reducing sugars are saccharides that do not have a free aldehyde group or ketone group and do not exhibit reducing properties, and are trehalose-type oligosaccharides in which reducing groups are bonded to each other, and glycosides in which a reducing group of saccharides and non-saccharides are bonded. These are classified into sugar alcohols reduced by hydrogenation of the body and saccharides, both of which are preferably used in the present invention. Trehalose type oligosaccharides include saccharose and trehalose. Examples of glycosides include alkyl glycosides, phenol glycosides, mustard oil glycosides, and the like. Examples of the sugar alcohol include D, L-arabit, rebit, xylit, D, L-sorbit, D, L-mannit, D, L-exit, D, L-talit, durisit and allozulcit. Furthermore, maltitol obtained by hydrogenation of a disaccharide and a reduced form (reduced water candy) obtained by hydrogenation of an oligosaccharide are preferably used. Furthermore, 2-butanone oxime (pKa 12.45), acetoxime (12.42), 1.2-cycloheptanedione oxime (12.3), 2-hydroxybenzaldehyde oxime (12.10), dimethylglycol Oximes such as oxime (11.9), ethanediamide dioxime (11.37), acetophenone oxime (11.35), such as 2,2,3,3-tetrafluoropropanol-1 (12. 74), fluorinated alcohols such as trifluoroethanol (12.37) and trichloroethanol (12.24). In addition, aldehydes such as pyridine-2-aldehyde (12.68) and pyridine-4-aldehyde (12.05), adenosine (12.56), inosine (12.5), guanine ( 12.3), nucleic acid-related substances such as cytosine (12.2), hypoxanthine (12.1), xanthine (11.9), diethylaminomethylsulfonic acid (12.32), 1-amino-3,3,3-trifluorobenzoic acid (12.29), isopropylidenedisulfonic acid (12.10), 1,1-ethylidene diphosphonic acid (11.54), 1,1 -1-hydroxyethylidene disulfonate (11.52), benzimidazole (12.86), thiobenzamide (12.8), picolinethioamide (12.55), barbi It includes weak acid, such as Le acid (same 12.5). These acidic substances may be used alone or in combination of two or more.

  Among these acidic substances, phosphoric acid, carbonic acid, sulfosalicylic acid, salicylic acid, and sugar alcohols and saccharose of non-reducing sugar are preferable, and D-sorbite, saccharose, and reduced starch candy have a buffering action in an appropriate pH range. That is preferable because of its low price.

  The proportion of these acidic substances in the developer is preferably from 0.1 to 30% by mass, and more preferably from 1 to 20% by mass. Below this range, a sufficient buffering effect cannot be obtained, and when the concentration is above this range, it is difficult to achieve high concentration, and the problem of increased costs arises. As the base to be combined with these acids, sodium hydroxide, ammonium, potassium and lithium are preferably used. These alkali agents are used alone or in combination of two or more. When the pH of the developer is 8.5 or less, the image portion of the printing plate obtained from the photosensitive lithographic printing plate that can be developed with such a developer is physically fragile, and the wear during printing is sufficient. Printing durability cannot be obtained. Further, the image portion is chemically weak, and an image of a portion wiped with an ink washing solvent or a plate cleaner is damaged during printing, and as a result, sufficient chemical resistance cannot be obtained. A developer having a high pH such that the pH exceeds 13.0 is strongly irritating when adhering to the skin or mucous membrane, and is not preferable because it requires sufficient care in handling.

  Other examples include tripotassium phosphate, trisodium phosphate, trilithium phosphate, triammonium phosphate, dipotassium phosphate, disodium phosphate, dilithium phosphate, diammonium phosphate, potassium carbonate, sodium carbonate, lithium carbonate, ammonium carbonate, carbonate Examples include potassium hydrogen carbonate, sodium hydrogen carbonate, lithium hydrogen carbonate, ammonium hydrogen carbonate, potassium borate, sodium borate, lithium borate, ammonium borate and the like, and may be added in the form of a preformed salt. Again, sodium hydroxide, ammonium, potassium and lithium can be added to the pH adjustment. Moreover, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine, and pyridine are also used in combination.

Most preferred are potassium silicate and sodium silicate. The concentration of silicate is preferably 1.0 to 3.0% by mass in terms of SiO ₂ concentration. Further, SiO ₂ and mol ratio of the alkali metal M (SiO ₂ / M) is still preferably be in the range of 0.25 to 2.

  To the developer and replenisher used in the present invention, various surfactants and organic solvents can be added as necessary for the purpose of promoting developability, dispersing development residue, and improving ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants.

  Preferred examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan Fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, poly Glycerin fatty acid partial esters, polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, polio Siethylene-polyoxypropylene block copolymer, ethylenediamine polyoxyethylene-polyoxypropylene block copolymer adduct, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamine, Nonionic surfactants such as triethanolamine fatty acid esters and trialkylamine oxides, fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinic acid ester salts, linear alkylbenzene sulfonic acid salts Branched alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl diphenyl ether sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, Lioxyethylene alkylsulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated beef oil, sulfate esters of fatty acid alkyl esters, alkyl Sulfuric acid ester salts, polyoxyethylene alkyl ether sulfuric acid ester salts, fatty acid monoglyceride sulfuric acid ester salts, polyoxyethylene alkylphenyl ether sulfuric acid ester salts, polyoxyethylene styryl phenyl ether sulfuric acid ester salts, alkyl phosphoric acid ester salts, polyoxyethylene alkyl ether Phosphoric acid ester salts, polyoxyethylene alkylphenyl ether phosphoric acid ester salts, partially saponified products of styrene / maleic anhydride copolymer, olefin / none Anionic surfactants such as partially saponified products of water maleic acid copolymer, naphthalene sulfonate formalin condensates, alkylamine salts, quaternary ammonium salts such as tetrabutylammonium bromide, polyoxyethylene alkylamine salts, Examples include cationic surfactants such as polyethylene polyamine derivatives, and amphoteric surfactants such as carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric esters, and imidazolines. Among the surfactants listed above, those having polyoxyethylene can be read as polyoxyalkylenes such as polyoxymethylene, polyoxypropylene and polyoxybutylene, and these surfactants are also included. A more preferred surfactant is a fluorosurfactant containing a perfluoroalkyl group in the molecule. Such fluorosurfactants include perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, anionic types such as perfluoroalkyl phosphates, amphoteric types such as perfluoroalkyl betaines, and perfluoroalkyltrimethylammonium salts. Cationic and perfluoroalkylamine oxides, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl group and hydrophilic group-containing oligomers, perfluoroalkyl group and lipophilic group-containing oligomers, perfluoroalkyl groups, hydrophilic groups and lipophilic groups Nonionic types such as group-containing oligomers, perfluoroalkyl groups, and lipophilic group-containing urethanes can be mentioned.

  Said surfactant can be used individually or in combination of 2 or more types, and is added in 0.001-10 mass% in a developing solution, More preferably, it is added in 0.01-5 mass%.

(Development stabilizer)
A development stabilizer is preferably used for the developer and replenisher used in the present invention. Preferred examples thereof include polyethylene glycol adducts of sugar alcohols described in JP-A-6-282079, tetraalkylammonium salts such as tetrabutylammonium hydroxide, phosphonium salts such as tetrabutylphosphonium bromide, and iodonium such as diphenyliodonium chloride. A salt is a preferred example. Further, anionic surfactants or amphoteric surfactants described in JP-A-50-51324, water-soluble cationic polymers described in JP-A-55-95946, and JP-A-56-142528 are described. And water-soluble amphoteric polymer electrolytes. Further, an organoboron compound to which an alkylene glycol is added as described in JP-A-59-84241, a polyoxyethylene-polyoxypropylene block polymerization type water-soluble surfactant as described in JP-A-60-111246, An alkylenediamine compound substituted with polyoxyethylene-polyoxypropylene disclosed in JP-A-60-129750, a polyethylene glycol having a weight average molecular weight of 300 or more described in JP-A-61-215554, and a cation described in JP-A-63-175858 And a water-soluble ethylene oxide addition compound obtained by adding 4 mol or more of ethylene oxide to an acid or alcohol disclosed in JP-A-2-39157, a water-soluble polyalkylene compound, and the like.

(Organic solvent)
If necessary, an organic solvent is added to the developer and the development replenisher. As the organic solvent, those having a solubility in water of about 10% by mass or less are suitable, and preferably selected from those having 5% by mass or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol, 4-phenyl-2-butanol, 2-phenyl-1-butanol, 2-phenoxyethanol, 2- Benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol, N-phenylethanol Examples thereof include amines and N-phenyldiethanolamine.

  The content of the organic solvent is 0.1 to 5% by mass with respect to the total mass of the liquid used, but it is preferably substantially not contained, and particularly preferably not contained at all. Here, “substantially not contained” means 1% by mass or less.

(Reducing agent)
A reducing agent is added to the developer and replenisher used in the present invention as necessary. This prevents stains on the printing plate, and is particularly effective when developing a negative photosensitive lithographic printing plate containing a photosensitive diazonium salt compound. Preferable organic reducing agents include phenol compounds such as thiosalicylic acid, hydroquinone, metol, methoxyquinone, resorcin, and 2-methylresorcin, and amine compounds such as phenylenediamine and phenylhydrazine.

  More preferable inorganic reducing agents include sodium, potassium and ammonium salts of inorganic acids such as sulfurous acid, bisulfite, phosphorous acid, hydrogen phosphite, dihydrogen phosphite, thiosulfuric acid and dithionite. A salt etc. can be mentioned. Among these reducing agents, sulfites are particularly excellent in the antifouling effect. These reducing agents are preferably contained in the range of 0.05 to 5% by mass with respect to the developer at the time of use.

(Organic carboxylic acid)
If necessary, an organic carboxylic acid can be further added to the developer and replenisher used in the present invention. Preferred organic carboxylic acids include aliphatic carboxylic acids and aromatic carboxylic acids having 6 to 20 carbon atoms.

  Specific examples of the aliphatic carboxylic acid include caproic acid, enanthylic acid, caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, and particularly preferred are alkanoic acids having 8 to 12 carbon atoms. . Further, it may be an unsaturated fatty acid having a double bond in the carbon chain or a branched carbon chain. The aromatic carboxylic acid is a compound in which a carboxyl group is substituted on a benzene ring, naphthalene ring, anthracene ring or the like, and specifically includes o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p- Hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3, There are 5-dihydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-naphthoic acid, 2-naphthoic acid and the like. Naphthoic acid is particularly effective. The aliphatic and aromatic carboxylic acids are preferably used as sodium salts, potassium salts or ammonium salts in order to enhance water solubility.

  The content of the organic carboxylic acid in the developer used in the present invention is not particularly limited, but if it is less than 0.1% by mass, the effect may not be sufficient, and if it is 10% by mass or more, the effect is further improved. In some cases, it is not observed, and therefore, the preferable addition amount is 0.1 to 10% by mass, and more preferably 0.5 to 4% by mass with respect to the developing solution in use.

(Other additives)
In addition to the above, the following additives can be added to the developer and replenisher used in the present invention in order to improve the development performance. For example, neutral salts such as NaCl, KCl and KBr described in JP-A-58-75152, complexes such as [Co (NH ₃ )] ₆ Cl ₃ described in JP-A-59-121336, JP-A-56 Ampholytic polymer electrolytes such as a copolymer of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A-142258, organometallic surfactants containing Si, Ti, etc. described in JP-A-59-75255, JP And organic boron compounds described in JP-A-59-84241. The developer and replenisher used in the present invention may further contain a preservative, a colorant, a thickener, an antifoaming agent, a hard water softener, and the like, if necessary. Examples of the antifoaming agent include mineral oil, vegetable oil, alcohol, surfactant, silicone and the like described in JP-A-2-244143. Examples of water softeners include polyphosphoric acid and its sodium, potassium and ammonium salts, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetra Aminopolycarboxylic acids such as acetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylene Phosphonic acid), triethylenetetramine hexa (methylenephosphonic acid), hydroxyethylethylenediaminetri (methylenephosphonic acid) and - hydroxyethane-1,1-diphosphonic acid and their sodium salts, potassium salts and ammonium salts.

  The optimum value of such a hard water softening agent varies depending on its chelating power, the hardness of the hard water used and the amount of hard water. % By mass, more preferably in the range of 0.01 to 0.5% by mass.

  If the addition amount is less than this range, the intended purpose is not sufficiently achieved. If the addition amount is more than this range, adverse effects on the image area such as color loss will occur. The remaining component of the developer and replenisher is water.

(Concentrated liquid)
It is advantageous in terms of transportation that the developer and replenisher used in the present invention are concentrated solutions in which the water content is less than in use, and diluted with water during use. The degree of concentration in this case is appropriate so that each component does not separate or precipitate, but it is preferable to add a solubilizing agent if necessary. As such a solubilizer, a so-called hydrotrope such as toluenesulfonic acid, xylenesulfonic acid and alkali metal salts thereof described in JP-A-6-32081 is preferably used.

<Post-processing after development>
The plate developed with the developer having such a composition is subjected to post-processing with washing water, a rinsing solution containing a surfactant, a finisher mainly composed of gum arabic or starch derivatives, or a protective gum solution. These treatments can be used in various combinations for the post-treatment after development. For example, a rinse solution or finisher solution can be used after the development → washing with water → processing with a rinsing liquid containing a surfactant or development → water washing → finishing liquid. This is preferable because of less fatigue. Furthermore, a countercurrent multistage process using a rinse liquid or a finisher liquid is also a preferred embodiment. These post-processing are generally performed using an automatic developing machine including a developing unit and a post-processing unit. As the post-treatment liquid, a method of spraying from a spray nozzle or a method of immersing and conveying in a treatment tank filled with the treatment liquid is used. There is also known a method in which a small amount of washing water after development is supplied to the plate surface and washed, and the waste solution is reused as dilution water for the developer stock solution. In such automatic processing, each processing solution can be processed while being replenished with each replenisher according to the processing amount, operating time, and the like. In addition, a so-called disposable processing method in which treatment is performed with a substantially unused post-treatment liquid can also be applied. The lithographic printing plate obtained by such processing is loaded on an offset printing machine and used for printing a large number of sheets.

《Photosensitive planographic printing plate》
The photosensitive lithographic printing plate used in the present invention will be described.

  The photosensitive lithographic printing plate used in the present invention is a photosensitive lithographic printing plate having a photopolymerizable photosensitive layer containing a compound having an ethylenically unsaturated bond capable of addition polymerization represented by a photopolymer type CTP plate. A photosensitive layer of a photopolymerizable photosensitive resin composition containing at least a compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a polymer binder on an aluminum support, and the photosensitive layer It has an oxygen barrier layer on it.

<Photosensitive layer>
The main components of the photopolymerization type photosensitive layer according to the present invention of the photosensitive lithographic printing plate used in the present invention are compounds having an addition-polymerizable ethylenically unsaturated bond, a photopolymerization initiator, and a polymer bond. It is a photopolymerization type photosensitive resin composition containing a material.

(Compound having an ethylenically unsaturated bond)
Examples of the compound having an addition-polymerizable ethylenically unsaturated bond used as the compound having an ethylenically unsaturated bond according to the present invention include general radical polymerizable monomers and molecules generally used for ultraviolet curable resins. Polyfunctional monomers having a plurality of addition-polymerizable ethylenic double bonds or polyfunctional oligomers can be used. Preferred examples include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, Monofunctional acrylic esters such as acrylate of 1,3-dioxane alcohol ε-caprolactone adduct, 1,3-dioxolane acrylate, or methacrylic acid, itaconic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate , Crotonic acid, maleic acid esters such as ethylene glycol diacrylate, triethylene glycol Diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcinol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, hydroxypentylate neopentyl glycol diacrylate, neopentyl glycol adipate di Acrylate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, Tricyclodecane dimethylol acrylate, ε-caprolactone adduct of tricyclodecane dimethylol acrylate, 1,6-hexanediol Difunctional acrylates such as diacrylates of diglycidyl ethers, or methacrylic acid, itaconic acid, crotonic acid, maleic acid esters such as trimethylolpropane triacrylate in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate Ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ε-caprolactone of dipentaerythritol hexaacrylate Additives, pyrogallol triacrylate, propionic acid / dipipe Polyfunctional acrylic acid such as taerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, or methacrylic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate , Itaconic acid, crotonic acid, maleic acid ester and the like.

  Prepolymers can also be used as described above. Examples of the prepolymer include compounds as described below, and a prepolymer obtained by introducing acrylic acid or methacrylic acid into an oligomer having an appropriate molecular weight and imparting photopolymerizability can be preferably used. These prepolymers may be used alone or in combination of two or more, and may be used by mixing with the above-mentioned monomers and / or oligomers.

  Examples of prepolymers include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, pimelic acid, Polybasic acids such as sebacic acid, dodecanoic acid, tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, trimethylol Polyester obtained by introducing (meth) acrylic acid into a polyester obtained by combining polyhydric alcohols such as propane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol Chlorates such as bisphenol A, epichlorohydrin, (meth) acrylic acid, and epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as phenol novolac, epichlorohydrin, (meth) acrylic acid, such as ethylene glycol, adipine Acid / tolylene diisocyanate / 2-hydroxyethyl acrylate, polyethylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate, hydroxyethylphthalyl methacrylate / xylene diisocyanate, 1,2-polybutadiene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate , Trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate In addition, urethane acrylates in which (meth) acrylic acid is introduced into urethane resin, for example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate, etc., and (meth) acryloyl in oil-modified alkyd resins Examples thereof include prepolymers such as alkyd-modified acrylates having introduced groups and spirane resin acrylates.

  Also, phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) modified diacrylate, isocyanuric acid EO modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane acrylic acid benzoate, alkylene glycol type acrylic acid Addition-polymerizable oligomers and prepolymers having monomers such as modified and urethane-modified acrylates and structural units formed from the monomers can be used.

  Furthermore, examples of the ethylenic monomer that can be used in combination include a phosphate ester compound containing at least one (meth) acryloyl group. The compound is not particularly limited as long as it is a compound in which at least part of the hydroxyl group of phosphoric acid is esterified and has a (meth) acryloyl group.

  In addition, JP-A-58-212994, 61-6649, 62-46688, 62-48589, 62-173295, 62-187092, 63- 67189, JP-A-1-244891, and the like. Further, “11290 Chemical Products”, Chemical Industry Daily, p. 286-p. 294, “UV / EB Curing Handbook (raw material)”, Kobunshi Publishing Co., p. The compounds described in 11 to 65 can also be suitably used in the present invention. Of these, compounds having two or more acrylic groups or methacryl groups in the molecule are preferred in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are preferred.

  In addition, it is preferable to use an addition-polymerizable ethylenic double bond-containing monomer containing a tertiary amino group in the molecule. Although there is no particular limitation on the structure, a tertiary amine compound having a hydroxyl group modified with glycidyl methacrylate, methacrylic acid chloride, acrylic acid chloride or the like is preferably used. Specifically, collectable compounds described in JP-A-1-165613, JP-A-1-203413, and JP-A-1-197213 are preferably used.

  Furthermore, it is preferable to use a reaction product of a polyhydric alcohol containing a tertiary amino group in the molecule, a diisocyanate compound, and a compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule.

  Examples of the polyhydric alcohol containing a tertiary amino group in the molecule include triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-tert-butyldiethanolamine, N, N-di (hydroxyethyl) aniline, N, N, N ′, N′-tetra-2-hydroxypropylethylenediamine, p-tolyldiethanolamine, N, N, N ′, N′-tetra-2-hydroxyethylethylenediamine, N, N-bis (2-hydroxypropyl) aniline, allyldiethanolamine, 3- (dimethylamino) -1,2-propanediol, 3-diethylamino-1,2-propanediol, N, N-di (n -Propyl) amino-2,3-propanediol, N, N-di iso- propyl) amino-2,3-propanediol, 3- (N-methyl--N- benzylamino) -1,2-propanediol - but Le and the like, but are not limited thereto.

  Examples of the diisocyanate compound include butane-1,4-diisocyanate, hexane-1,6-diisocyanate, 2-methylpentane-1,5-diisocyanate, octane-1,8-diisocyanate, 1,3-diisocyanate methyl-cyclohexanone. 2,2,4-trimethylhexane-1,6-diisocyanate, isophorone diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene- Examples include 2,5-diisocyanate, tolylene-2,6-diisocyanate, 1,3-di (isocyanatomethyl) benzene, 1,3-bis (1-isocyanato-1-methylethyl) benzene, and the like. Limited to Not.

  Examples of the compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule include compounds such as MH-1 to MH-13, but are not limited thereto.

  Preferable examples include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropylene-1,3-dimethacrylate, 2-hydroxypropylene-1-methacrylate-3-acrylate, and the like.

  These reactions can be carried out in the same manner as a method for synthesizing urethane acrylate by a reaction of a normal diol compound, diisocyanate compound, and hydroxyl group-containing acrylate compound.

Specific examples of reaction products of polyhydric alcohols containing tertiary amino groups in the molecule, diisocyanate compounds, and compounds containing ethylenic double bonds capable of addition polymerization with hydroxyl groups in the molecule are shown below. Shown in
M-1: reaction product of triethanolamine (1 mol), hexane-1,6-diisocyanate (3 mol), 2-hydroxyethyl methacrylate (3 mol) M-2: triethanolamine (1 mol), isophorone Reaction product of diisocyanate (3 mol) and 2-hydroxyethyl acrylate (3 mol) M-3: Nn-butyldiethanolamine (1 mol), 1,3-bis (1-isocyanate-1-methylethyl) Reaction product of benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) M-4: Nn-butyldiethanolamine (1 mol), 1,3-di (isocyanatomethyl) ) Reaction of benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) Product M-5: Reaction product of N-methyldiethanolamine (1 mol), tolylene-2,4-diisocyanate (2 mol), 2-hydroxypropylene-1,3-dimethacrylate (2 mol) The acrylates or alkyl acrylates described in JP-A-1-105238 and JP-A-2-127404 can be used.

(Photopolymerization initiator)
As the photopolymerization initiator, for example, J.P. Carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo, diazo compounds, halogen compounds, and photoreductive dyes as described in Chapter 5 of “Light Sensitive Systems” by J. Kosar Etc. More specific compounds are disclosed in British Patent 1,459,563.

  That is, the following can be used as a photopolymerization initiator that can be used in combination.

  Benzoin derivatives such as benzoin methyl ether, benzoin-i-propyl ether, α, α-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4′-bis (dimethyl) Benzophenone derivatives such as amino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-i-propylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N-methylacridone, N-butylacridone and the like In addition to α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone and uranyl compounds, JP-B-59-1281, JP-A-61-9621 and JP-A-60-60104 Triazine derivatives described in JP-A-59-1504 and JP-A-61-243807; JP-B-43-23684, JP-A-44-6413, JP-A-44-6413, No. 47-1604 and U.S. Pat. No. 3,567,453; diazonium compounds; U.S. Pat. Nos. 2,848,328, 2,852,379 and 2,940,853 Organic azide compounds described in Japanese Patent Publication Nos. 36-22062, 37-13109, 38-18015, and 45-9610; 55-39162; JP-A-59-14023 and “Macromolecules”, Vol. 10, p. 1307 ( 977); azo compounds described in JP-A-59-142205; JP-A-1-54440, European Patents 109,851, 126,712, and “Journal Of Imaging Science (J. Imag. Sci.), Vol. 30, page 174 (1986); (oxo) sulfonium organic compounds described in JP-A-5-213861 and JP-A-5-255347 Boron complexes; transition metal complexes containing transition metals such as ruthenium described in “Coordination Chemistry Review”, 84, 85-277 (1988) and JP-A-2-182701; No. 3-209477 Roh triarylimidazole dimer; carbon tetrabromide, organic halogen compounds in JP 59-107344 JP like.

  Of these, preferred are titanocenes. Specific examples of titanocenes include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, and di-cyclopentadienyl-Ti-bis-2,3,4. , 5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis -2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2, 4-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bi -2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis ( 2,6-difluoro-3- (pyridin-1-yl) phenyl) titanium (IRGACURE784: manufactured by Ciba Specialty Chemicals Co., Ltd.) and the like are exemplified, but not limited thereto.

(Sensitizing dye)
The photosensitive lithographic printing plate used in the present invention contains a sensitizing dye in the photopolymerizable photosensitive layer.

  Examples of compounds for wavelength sensitization from visible light to near infrared include cyanine, phthalocyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, polyene, azo compound, diphenylmethane, triphenyl Ketone alcohol borate complexes such as methane, polymethine acridine, coumarin, coumarin derivatives, ketocoumarin, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, etc. Further, European Patent No. 568,993, U.S. Pat. No. 4,508,811, No. 5,227,227, JP-A-2001-1252. 5 discloses, compounds described in JP-A 11-271969 Patent Publication also used.

  Among the sensitizing dyes, particularly preferred are pyromethene compounds, and specific examples thereof include compounds described as sensitizers in JP-A-11-271969.

  Although the compounding quantity of these polymerization initiators is not specifically limited, Preferably, it is 0.1-20 mass parts with respect to 100 mass parts of compounds which have an ethylenically unsaturated bond in which addition polymerization is possible. The mixing ratio of the photopolymerization initiator and the sensitizing dye is preferably in the range of 1: 100 to 100: 1 in terms of molar ratio.

(Polymer binder)
The polymer binder used in the photosensitive layer according to the present invention includes acrylic polymer, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin. Shellac and other natural resins can be used. Two or more of these may be used in combination.

  A vinyl copolymer obtained by copolymerization of acrylic monomers is preferred. The copolymer composition of the polymer binder is preferably a copolymer of (a) carboxyl group-containing monomer, (b) methacrylic acid alkyl ester, or acrylic acid alkyl ester.

  Specific examples of the carboxyl group-containing monomer include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like. In addition, carboxylic acids such as phthalic acid and 2-hydroxymethacrylate half ester are also preferable. Specific examples of alkyl methacrylates and alkyl esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate. , Decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, acrylic In addition to unsubstituted alkyl esters such as decyl acid, undecyl acrylate and dodecyl acrylate, cyclic alkyl esters such as cyclohexyl methacrylate and cyclohexyl acrylate Substituted alkyl esters such as benzyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate, benzyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, and glycidyl acrylate Also mentioned.

Furthermore, in the polymer binder of the present invention, monomers described in the following 1) to 14) can be used as other copolymerization monomers.
1) Monomers having an aromatic hydroxyl group, such as o- (or p-, m-) hydroxystyrene, o- (or p-, m-) hydroxyphenyl acrylate and the like.
2) Monomers having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl methacrylate , 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether and the like.
3) A monomer having an aminosulfonyl group, such as m- (or p-) aminosulfonylphenyl methacrylate, m- (or p-) aminosulfonylphenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p -Aminosulfonylphenyl) acrylamide and the like.
4) Monomers having a sulfonamide group, such as N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide and the like.
5) Acrylamide or methacrylamides such as acrylamide, methacrylamide, N-ethylacrylamide, N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl-N- Phenylacrylamide, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide and the like.
6) Monomers containing fluorinated alkyl groups such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N- Butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.
7) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether and the like.
8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate and the like.
9) Styrenes such as styrene, methyl styrene, chloromethyl styrene and the like.
10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
11) Olefins such as ethylene, propylene, i-butylene, butadiene, isoprene and the like.
12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine and the like.
13) Monomers having a cyano group, such as acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o- (or m-, p-) cyanostyrene.
14) A monomer having an amino group, such as N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropyl acrylamide, N, N-dimethylacrylamide, acryloylmorpholine, Ni-propylacrylamide, N, N-diethylacrylamide and the like.

  Further, other monomers that can be copolymerized with these monomers may be copolymerized.

  Furthermore, an unsaturated bond-containing vinyl copolymer obtained by addition-reacting a compound having a (meth) acryloyl group and an epoxy group in the molecule to a carboxyl group present in the molecule of the vinyl copolymer. Is also preferred as a polymer binder. Specific examples of the compound containing both an unsaturated bond and an epoxy group in the molecule include glycidyl acrylate, glycidyl methacrylate, and an epoxy group-containing unsaturated compound described in JP-A No. 11-271969.

  These copolymers preferably have a weight average molecular weight of 1 to 200,000 as measured by gel permeation chromatography (GPC), but are not limited to this range.

  The content of the polymer binder in the photosensitive layer is preferably in the range of 10 to 90% by weight, more preferably in the range of 15 to 70% by weight, and particularly in terms of sensitivity to be used in the range of 20 to 50% by weight. preferable.

  Further, the acid value of the polymer binder is preferably in the range of 10 to 150, more preferably in the range of 30 to 120, and the use in the range of 50 to 90 balances the polarity of the entire photosensitive layer. It is particularly preferable from the viewpoint of taking. Thereby, when a pigment is contained in the photopolymerization type photosensitive layer coating solution, aggregation of the pigment can be prevented.

<Oxygen barrier layer>
The photosensitive lithographic printing plate used in the present invention has an oxygen blocking layer on the photosensitive layer. For the oxygen barrier layer, a water-soluble polymer capable of forming a film having low oxygen permeability is used. Specifically, it contains polyvinyl alcohol and polyvinyl pyrrolidone. Polyvinyl alcohol has an effect of suppressing permeation of oxygen, and polyvinyl pyrrolidone has an effect of ensuring adhesion with an adjacent photosensitive layer.

  In addition to the above two polymers, polysaccharides, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, ammonium alginate, sodium alginate as required Water-soluble polymers such as polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, and water-soluble polyamide can also be used in combination.

  The photosensitive lithographic printing plate used in the present invention can be provided with an overcoat layer. The peeling force between the photosensitive layer and the overcoat layer is preferably 35 g / 10 mm or more, more preferably 50 g / 10 mm or more, still more preferably 75 g / 10 mm or more. The peeling force is the force when an adhesive tape of a predetermined width having a sufficiently large adhesive force is applied on the overcoat layer and peeled off with the overcoat layer at an angle of 90 degrees with respect to the plane of the photosensitive lithographic printing plate. Can be measured.

  Preferred overcoat layer compositions include those described in JP-A-10-10742. The overcoat layer can further contain a surfactant, a matting agent and the like as required. The overcoat layer composition is dissolved in a suitable solvent, applied onto the photosensitive layer and dried to form an overcoat layer. The main component of the coating solvent is particularly preferably water or alcohols such as methanol, ethanol, i-propanol. The thickness of the overcoat layer is preferably from 0.1 to 5.0 μm, particularly preferably from 0.5 to 3.0 μm.

<Aluminum support>
As the support, an aluminum support of an aluminum plate is used in the present invention.

  The aluminum support is obtained from an aluminum plate material using pure aluminum or an aluminum support material using an aluminum alloy. As the aluminum plate material using an aluminum alloy, for example, an alloy of aluminum and a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, and iron is used. The surface has a rough surface shape of a double structure in which small pits are superimposed on large undulations.

  The aluminum plate is usually used after degreasing with an alkali, an acid, a solvent or the like in order to remove oil used during rolling and winding existing on the surface. As the degreasing treatment, degreasing with an alkaline aqueous solution is particularly preferable. Moreover, in order to improve adhesiveness with a coating layer, it is preferable to perform an easily bonding process and undercoat layer application | coating to an application surface. For example, there may be mentioned a method of immersing in a liquid containing a coupling agent such as a silane coupling agent or applying a liquid and then sufficiently drying. Anodizing treatment is also considered as a kind of easy adhesion treatment and can be used. Moreover, it can also be used combining an anodizing process and the said immersion or application | coating process. Moreover, the aluminum plate roughened by the well-known method can also be used.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these. Unless otherwise specified, “part” or “%” in the examples represents “part by mass” or “% by mass”.

Example 1
(Binder synthesis)
(Synthesis of acrylic copolymer 1)
A three-necked flask under a nitrogen stream is charged with 30 parts of methacrylic acid, 50 parts of methyl methacrylate, 20 parts of ethyl methacrylate, 500 parts of isopropyl alcohol and 3 parts of α, α'-azobisisobutyronitrile. The reaction was carried out in an oil bath at 0 ° C. for 6 hours. Then, after refluxing at the boiling point of isopropyl alcohol for 1 hour, 3 parts of triethylammonium chloride and 25 parts of glycidyl methacrylate were added and reacted for 3 hours to obtain an acrylic copolymer 1. The weight average molecular weight measured using GPC was about 35,000, and the glass transition temperature (Tg) measured using DSC (differential thermal analysis) was about 85 ° C.

(Production of support)
An aluminum plate (material 1050, tempered H16) having a thickness of 0.3 mm was immersed in a 5% by mass aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. This degreased aluminum plate was neutralized by immersing it in a 10% by mass hydrochloric acid aqueous solution maintained at 25 ° C. for 1 minute, and then washed with water. Next, the aluminum plate was subjected to electrolytic surface roughening with an alternating current for 60 seconds under conditions of 25 ° C. and a current density of 100 A / dm ^{2 in} a 0.3% by mass nitric acid aqueous solution, and then kept at 60 ° C. The desmutting treatment was performed for 10 seconds in a 5% by weight aqueous sodium hydroxide solution. The surface-roughened aluminum plate subjected to desmut treatment was anodized in a 15% by weight sulfuric acid solution at 25 ° C., a current density of 10 A / dm ² and a voltage of 15 V for 1 minute, and further 1% by weight polyvinylphosphone. Hydrophilic treatment was performed with acid at 75 ° C. to prepare a support.

  At this time, the center line average roughness (Ra) of the surface was 0.65 μm.

<< Preparation of photosensitive lithographic printing plate >>
On the above support, a photopolymerizable photosensitive layer coating solution having the following composition was applied with a wire bar so that the drying rate was 1.5 g / m ² , and dried at 95 ° C. for 1.5 minutes. A sample was obtained.

(Photopolymerizable photosensitive layer coating solution)
Compound containing addition-polymerizable ethylenic double bond: M-3 25.0 parts Compound-containing monomer containing addition-polymerizable ethylenic double bond: NK ester 4G (polyethylene glycol manufactured by Shin-Nakamura Chemical Co., Ltd.) Dimethacrylate) 25.0 parts Polymerization initiator T-1 (below) 2.0 parts Polymerization initiator T-2 (below) 2.0 parts Polymerization initiator BR22 (below) 1.0 part Polymerization host BR43 (below) ) 1.0 part Spectral sensitizing dye D-5 (below) 1.5 parts Spectral sensitizing dye D-7 (below) 1.5 parts Acrylic copolymer 1 (above) 40.0 parts N-phenylglycine Benzyl ester 4.0 parts Phthalocyanine pigment (MHI454: manufactured by Mikuni Dye Co.) 6.0 parts 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (Sumilyzer GS: manufactured by Sumitomo 3M Co., Ltd.) 0.5 parts Fluorosurfactant (F-178K; manufactured by Dainippon Ink and Co., Ltd.) 0.5 parts Methyl ethyl ketone 80 parts Cyclohexanone 820 parts M-3: Nn-butyldiethanolamine ( 1 mol), 1,3-bis (1-isocyanate-1-methylethyl) benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) reaction product (in general description) Is described in.)

On the photopolymerization photosensitive layer coating sample, an oxygen barrier layer coating solution having the following composition was coated with an applicator so as to be 1.8 g / m ² when dried, and dried at 75 ° C. for 1.5 minutes. A photosensitive lithographic printing plate sample having an oxygen blocking layer on the photosensitive layer was prepared.

(Oxygen barrier coating liquid)
Polyvinyl alcohol (GL-05: Nippon Synthetic Chemical Co., Ltd.) 89 parts Water-soluble polyamide (P-70: Toray Industries, Inc.) 10 parts Surfactant (Surfinol 465: Nissin Chemical Industry Co., Ltd.) 0.5 parts Water 900 Part 《Evaluation Method》
(Exposure, development)
The photosensitive lithographic printing plate sample was exposed at 1200 dpi (dpi represents the number of dots per 2.54) using a plate setter (News CTP: manufactured by ECRM) equipped with a light source of 405 nm. . As the exposure pattern, a 100% solid image portion and 5% square dots at 100 lpi were used.

  Next, a CTP automatic developing machine (Raptor polymer 85HW (Glunz and Jensen) provided with a preheating part, a pre-water washing part (pre-water washing part), a developing part, a water washing part, and a gum solution processing part. The modified lithographic printing plate 6 is subjected to development processing and post-treatment using the developer, developer replenisher, and gum solution described below. Obtained.

<Ripple generation prevention>
The presence or absence of wrinkles (ripples) occurring in the lithographic printing plate obtained by the development treatment was visually observed, and the ripple prevention properties were evaluated according to the following criteria.

(Evaluation criteria)
◎: No wrinkle on the lithographic printing plate after development ○: Wrinkles on the lithographic printing plate after development appear slightly due to reflection on the plate surface of room light △: Wrinkles on the lithographic printing plate after development on the plate surface of room light Visible through reflection (level of aesthetic problems)
×: Wrinkles can be immediately confirmed on the lithographic printing plate after development from the front.
<Developer (1 liter formulation)>
Polyoxyethylene (13) naphthyl ether 50.0 g / L
Ethylenediaminetetraacetic acid 0.5g / L
Potassium hydroxide The following pH level The remaining component is water. pH: 11.8
<Development replenisher (1 liter formulation)>
Polyoxyethylene (13) naphthyl ether 50.0 g / L
Ethylenediaminetetraacetic acid 0.5g / L
Potassium hydroxide The following pH level The remaining component is water. pH: 12.6
<Gum liquid (Finisher liquid) (100g prescription)>
White dextrin 5.0% by mass
Hydroxypropyl etherified starch 10.0% by mass
Gum arabic 1.0% by mass
1st Ammon Phosphate 0.1% by mass
Sodium dilauryl succinate 0.15% by mass
Polyoxyethylene naphthyl ether 0.5% by mass
Polyoxyethylene polyoxypropylene block copolymer (ethylene oxide ratio 50 mol%, molecular weight 5000) 0.3 mass%
Ethylene glycol 1.0% by mass
Ethylenediaminetetraacetic acid disodium 0.005 mass%
1,2 benzoisothiazolin-3-one 0.005 mass%
The remaining component is water.

<Ripple generation prevention>
The lithographic printing plate obtained by the development treatment as described above was visually observed for the occurrence of wrinkles (ripple) generated in the lithographic printing plate, and the ripple prevention property was evaluated according to the following criteria.

(Evaluation criteria)
◎: No wrinkle on the lithographic printing plate after development ○: Wrinkles on the lithographic printing plate after development appear slightly due to reflection on the plate surface of room light △: Wrinkles on the lithographic printing plate after development on the plate surface of room light Visible through reflection (level of aesthetic problems)
×: Wrinkles can be immediately confirmed on the lithographic printing plate after development from the front.
《Prevention of ripple pattern in printed matter》
A lithographic printing plate obtained by developing and developing a lithographic printing plate obtained by exposing and developing a front 50% halftone image of 1200 dpi 100 lpi at 50 μJ / cm ² was developed into a printing press (Mitsubishi Heavy Industries, Ltd.). ) DAIYA1F-1), coated paper, printing ink (manufactured by Dainippon Ink & Chemicals, soybean oil ink “Naturalis 100”) and fountain solution (Tokyo ink Co., Ltd. H liquid SG-51 concentration 1) .5%) was printed, the printed matter was visually observed, and the ripple pattern generation preventing property of the printed matter was evaluated according to the following evaluation criteria.

Evaluation criteria ○: No unevenness is observed in the printed matter △: Slightly unevenness is visible in the printed matter ×: Clearly unevenness is visible in the printed matter << Print durability >>
A lithographic printing plate produced by exposing and developing a 1200 dpi, 100 lpi image at 50 μJ / cm ² , is coated paper, printing ink (Dainippon Ink & Chemicals, Inc.) using a printing press (DAIYA1F-1 manufactured by Mitsubishi Heavy Industries, Ltd.). Produced using soybean oil ink “Naturalis 100”) and fountain solution (Tokyo Ink Co., Ltd., H solution SG-51 concentration 1.5%), and dots appear to be highlighted. The number of printed sheets was used as an index of printing durability.

A: 400,000 or more: A,
○: 300,000 or more and less than 400,000 sheets Δ: 200,000 or more and less than 300,000 sheets ×: Less than 200,000 sheets The results are shown in Table 1.

  As is apparent from Table 1, in the case of the present invention, it is found that the lithographic printing plate is excellent in ripple generation prevention, the printed matter is prevented from generating ripple patterns, and is excellent in printing durability.

According to the present invention, in the development processing method of a photosensitive lithographic printing plate having a photopolymerizable photosensitive layer containing a compound having an ethylenically unsaturated bond capable of addition polymerization represented by a photopolymer type CTP plate,
Even if the temperature in the preheating section (preheating section) is sufficiently increased, there is no problem (preheat ripple) that the photosensitive lithographic printing plate is deformed by washing with water in the next prewashing section (prewater washing section). It can be seen that it is possible to provide a method for developing a photosensitive lithographic printing plate that can obtain a lithographic printing plate having excellent printing durability by development in the developing section.

It is the schematic of the automatic processor 1 which shows an example of the automatic processor which can be used for this invention and made the entrance of the pre-washing part (pre-washing part) higher than the washing process part of the pre-washing part. Automatic showing an example of an automatic processor which can be used in the present invention and has a roller for preventing backwashing of washing water between the roller at the entrance of the pre-washing section (pre-washing section) and the washing treatment section of the pre-washing section. 2 is a schematic diagram of a developing machine 2. FIG. A roller for preventing backwashing of washing water is provided between the roller at the entrance of the pre-washing section (pre-washing section) and the washing treatment section of the pre-washing section, and the entrance of the pre-washing section can be used in the present invention. It is the schematic of the automatic processor 3 which shows an example of the automatic processor made higher than the water washing process part of a pre-water-washing part. It is the schematic of the automatic processor 4 which shows an example of the conventional automatic processor which has been used conventionally and has a pre-washing part (pre-washing part).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photosensitive lithographic printing plate 2 Heater of a preheating part 3 Heater of a preheating part 4 Roller provided in the entrance of the pre-washing part (pre-washing part) 5 Roller provided in the entrance of the pre-washing part (pre-washing part) 6 Shower 7 Roller 8 Brush roller, Washing treatment part

Claims (20)

A photosensitive layer of a photopolymerizable photosensitive resin composition containing a compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a polymer binder on an aluminum support, and oxygen on the photosensitive layer In the method of developing a photosensitive lithographic printing plate, the photosensitive lithographic printing plate having a blocking layer is subjected to image exposure and then developed with an aqueous developer containing an alkaline agent using an automatic developing machine.
The development method of the photosensitive lithographic printing plate is such that the photosensitive lithographic printing plate is first heated to be cured and brought to an improvement in printing durability (preheating step), and then washed with washing water. A pre-water washing step (pre-water washing step) for removing the oxygen blocking layer, and then a development step for developing with an aqueous solution containing an alkaline agent,
And,
A heat dissipating means is provided between the preheating step and the pre-water washing step;
A development processing method of a photosensitive lithographic printing plate characterized by the above. A photosensitive layer of a photopolymerizable photosensitive resin composition containing a compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a polymer binder on an aluminum plate support, and on the photosensitive layer In the method of developing a photosensitive lithographic printing plate in which a photosensitive lithographic printing plate having an oxygen blocking layer is subjected to image exposure and then developed with an aqueous developer containing an alkaline agent using an automatic developing machine.
The development method of the photosensitive lithographic printing plate is such that the photosensitive lithographic printing plate is first heated to be cured and brought to an improvement in printing durability (preheating step), and then washed with washing water. A pre-water washing step (pre-water washing step) for removing the oxygen blocking layer, and then a development step for developing with an aqueous solution containing an alkaline agent,
And,
As a heat dissipating means between the pre-heating step and the pre-washing step, the washing water does not contact the transport roller at the entrance of the pre-washing step.
A development processing method of a photosensitive lithographic printing plate characterized by the above. The heat radiating means is provided with a roller for preventing backwashing of the washing water between the roller at the entrance of the pre-washing step and the washing treatment part of the pre-washing step, so that the washing water that has flowed to the plate surface flows into the entrance of the pre-washing portion. The method for developing a photosensitive lithographic printing plate according to claim 1, wherein the developing method is a means that does not contact a roller. The heat radiating means is a means in which the washing water that has flowed on the plate surface does not contact the roller at the entrance of the pre-washing section by making the entrance of the pre-washing process higher than the washing treatment part of the pre-washing process. The method for developing a photosensitive lithographic printing plate according to claim 1 or 2. The heat radiating means is provided with a roller for preventing backwash of washing water between the roller at the entrance of the pre-washing process and the washing treatment part of the pre-washing process, so that the washing water that has flowed to the plate surface is the roller at the entrance of the pre-washing process. And means that the washing water that has flowed on the plate surface does not come into contact with the roller at the entrance of the pre-washing process by making the entrance of the pre-washing process higher than the washing treatment part of the pre-washing process. The method for developing a photosensitive lithographic printing plate according to claim 1 or 2, characterized in that The above-mentioned `` means that the washing water that has flowed on the plate surface does not come into contact with the roller at the entrance of the pre-washing process by making the entrance of the pre-washing process higher than the washing treatment part of the pre-washing process '',
6. The photosensitive according to claim 4 or 5, which is "means for inclining an advancing direction portion of a conveyance path of a photosensitive lithographic printing plate in contact with a roller at an entrance of a pre-water washing step so as to form a depression with a horizontal direction". A development processing method for a photolithographic printing plate. The above-mentioned `` means that the washing water that has flowed on the plate surface does not come into contact with the roller at the entrance of the pre-washing process by making the entrance of the pre-washing process higher than the washing treatment part of the pre-washing process '',
7. A means in which a depression angle θ between a traveling direction portion of a conveyance path of a photosensitive lithographic printing plate in contact with a roller at an entrance in a pre-water washing step and a horizontal direction is 5 ° or more and 30 ° or less. The development processing method of the photosensitive lithographic printing plate as described in 1 above. The above-mentioned `` means that the washing water that has flowed on the plate surface does not come into contact with the roller at the entrance of the pre-washing process by making the entrance of the pre-washing process higher than the washing treatment part of the pre-washing process '',
7. A means in which a depression angle θ between a traveling direction portion of a conveyance path of a photosensitive lithographic printing plate in contact with a roller at an entrance in a pre-water washing step and a horizontal direction is 15 ° or more and 20 ° or less. The development processing method of the photosensitive lithographic printing plate as described in 1 above. The photosensitive lithographic printing plate in the preheating step (preheating step) is heated so that the temperature reached on the plate surface is 100 ° C. or higher and 150 ° C. or lower. The development processing method of the photosensitive lithographic printing plate as described in 1 above. The photosensitive lithographic printing plate in the preheating step (preheating step) is heated so that the temperature reached on the plate surface is 120 ° C. or higher and 140 ° C. or lower. The development processing method of the photosensitive lithographic printing plate as described in 1 above. A photosensitive layer of a photopolymerizable photosensitive resin composition containing a compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a polymer binder on an aluminum support, and oxygen on the photosensitive layer In an automatic developing machine for photosensitive lithographic printing plates, a photosensitive lithographic printing plate having a blocking layer is subjected to image exposure and then developed with an aqueous developer containing an alkaline agent using an automatic developing machine.
The automatic processor first heats and cures the photosensitive lithographic printing plate so as to improve the printing durability, and then rinses with washing water to remove the oxygen barrier layer. A pre-water washing section (pre-water washing section), and then a developing section that develops with an aqueous developer containing an alkaline agent, and at least,
And,
A heat dissipating means is provided between the pre-heating unit and the pre-water washing unit.
An automatic developing machine for photosensitive lithographic printing plates. A photosensitive layer of a photopolymerizable photosensitive resin composition containing a compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a polymer binder on an aluminum plate support, and on the photosensitive layer In an automatic developing machine for a photosensitive lithographic printing plate, a photosensitive lithographic printing plate having an oxygen blocking layer is subjected to image exposure and then developed with an aqueous developer containing an alkaline agent using an automatic developing machine.
The automatic processor first heats and cures the photosensitive lithographic printing plate so as to improve the printing durability, and then rinses with washing water to remove the oxygen barrier layer. A pre-water washing section (pre-water washing section), and then a developing section that develops with an aqueous developer containing an alkaline agent, and at least,
And,
As a heat radiating means between the pre-heating unit and the pre-washing unit, there is a means that the washing water does not contact the transport roller at the entrance of the pre-washing unit.
An automatic developing machine for photosensitive lithographic printing plates. The heat radiating means is provided with a roller for preventing backflow of flush water between the roller at the entrance of the pre-wash section and the washing treatment portion of the pre-wash section, so that the flush water that has flowed to the plate surface is at the entrance of the pre-wash section. The automatic developing machine for a photosensitive lithographic printing plate according to claim 11 or 12, wherein the automatic developing machine is a means that does not contact a roller. The heat radiating means is a means in which the washing water that has flowed on the plate surface does not contact the roller at the entrance of the pre-washing section by making the entrance of the pre-washing section higher than the washing treatment part of the pre-washing section. An automatic developing machine for a photosensitive lithographic printing plate according to claim 11 or 12. The heat radiating means is provided with a roller for preventing back flow of washing water between the roller at the entrance of the pre-washing section and the washing process portion of the pre-washing section, so that the washing water that has flowed to the plate surface is the roller at the entrance of the pre-washing section. And means that the washing water that has flowed on the plate surface does not contact the roller at the entrance of the pre-washing section by making the entrance of the pre-washing section higher than the washing treatment section of the pre-washing section. The automatic developing machine for photosensitive lithographic printing plates according to claim 11 or 12, characterized in that: Said `` means that the washing water that has flowed on the plate surface does not contact the roller at the entrance of the pre-washing part by making the entrance of the pre-washing part higher than the washing treatment part of the pre-washing part '',
16. The photosensitive according to claim 14, wherein the means is a means for forming an inclination in which the traveling direction portion of the conveyance path of the photosensitive lithographic printing plate in contact with the roller at the entrance of the pre-washing section forms a depression with the horizontal direction. Automatic processing machine for sex lithographic printing plates. Said `` means that the washing water that has flowed on the plate surface does not contact the roller at the entrance of the pre-washing part by making the entrance of the pre-washing part higher than the washing treatment part of the pre-washing part '',
17. A means in which a depression angle θ between a traveling direction portion of a conveyance path of a photosensitive lithographic printing plate in contact with a roller at an entrance of a pre-washing section and a horizontal direction is 5 ° or more and 30 ° or less. An automatic developing machine for photosensitive lithographic printing plates as described in 1. Said `` means that the washing water that has flowed on the plate surface does not contact the roller at the entrance of the pre-washing part by making the entrance of the pre-washing part higher than the washing treatment part of the pre-washing part '',
17. A means in which a depression angle θ between a traveling direction portion of a conveyance path of a photosensitive lithographic printing plate in contact with a roller at an entrance of a pre-washing section and a horizontal direction is 15 ° or more and 20 ° or less. An automatic developing machine for photosensitive lithographic printing plates as described in 1. The photosensitive lithographic printing plate is heated in the preheating section (preheating section), and the temperature reached on the plate surface is 100 ° C. or higher and 150 ° C. or lower. An automatic developing machine for photosensitive lithographic printing plates as described in 1. The photosensitive lithographic printing plate is heated in the preheating unit (preheating unit), and the temperature reached on the plate surface is 120 ° C. or more and 140 ° C. or less, 19. An automatic developing machine for photosensitive lithographic printing plates as described in 1.

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