JP2003091076A - Processing device for planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an automatic processing device which is free of generation of fur and mold in each processing tank even when planographic printing plates are processed over a long period of time, can minimize the amounts of chemicals to be used and the amount of waste liquor and can be efficiently cleaned in a short time. SOLUTION: The formula of a replenisher solution and the amount of the solution added to each processing tank of the automatic processing device can be made optimum by connecting two or more replenishing pumps to each processing tank, accordingly an operator can cope with any peculiar problem which arises in each processing tank.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an automatic developing device for a lithographic printing plate, and more particularly to a structure of an automatic developing device for a lithographic printing plate that is environmentally friendly and can be improved in handleability.

[0002]

2. Description of the Related Art A plate making method of a lithographic printing plate from a photosensitive lithographic printing plate having a photosensitive layer whose solubility in alkali is changed by light on a hydrophilic support is basically A).
Image exposure of the photosensitive layer with laser light, B) development treatment,
C) The process is such that the registration marks are read, a punch bender is used to open punch holes for attachment to the printing machine, and both sides are bent. In this case, the B) developing process is often performed by using an automatic developing device, which aims at saving labor, speeding up, and improving quality. Examples of the structure of the automatic developing device are disclosed in JP-A-6-236041 and JP-A-200200.
0-221697 and JP-A-8-202046.

Typical examples of the above photosensitive lithographic printing plate include a compound having an ethylenically unsaturated double bond on a support such as an aluminum plate (also referred to as an ethylenically unsaturated compound), a photopolymerization initiator and There is a photopolymerizable lithographic printing plate having a photosensitive layer of a photopolymerizable photosensitive composition comprising a polymer binder. In such a photopolymerizable lithographic printing plate, when the photosensitive layer is exposed, the exposed portion is polymerized and cured by the action of the ethylenically unsaturated compound and the photopolymerization initiator. After that, when development processing is performed with a developer such as an alkaline aqueous solution, the unexposed portion is dissolved and removed to become a hydrophilic non-image, and the exposed portion remains undissolved because it is polymerized and cured, and the lipophilic It becomes the image part.

Further, in order to prevent the photopolymerizable lithographic printing plate from inhibiting the polymerization of the photosensitive layer by oxygen in the air,
An oxygen barrier protective layer is provided on the photosensitive layer. The details of the development processing method of the photopolymerizable lithographic printing plate having such an oxygen-blocking protective layer are as follows: after image exposure, the protective layer is removed with a protective layer eluent such as water in the pre-water washing section, and then the developing section. To remove the unexposed part of the photosensitive layer with a developer, and then
It is common practice to wash the plate surface with a water washing section, and then further carry out a finishing treatment with a rinse solution containing a surfactant or the like and a desensitizing solution containing gum arabic or a starch derivative in the finishing section. As a simpler method, after image exposure, the oxygen barrier protective layer and the unexposed photosensitive layer are removed with a developing solution in the developing section, then the plate surface is washed in the water washing section, and further finishing treatment is performed in the finishing section. The method of doing is also used.

Further, in recent years, in order to print a large number of sheets, it has been required to increase the mechanical strength of the photosensitive layer image portion of the lithographic printing plate. In order to increase the mechanical strength (printing durability) of the image area of the photosensitive layer, a heat treatment is performed after the image exposure and before the protective layer removal treatment to accelerate the polymerization and increase the curing degree. The heating temperature is preferably as high as possible, and 100 ° C. or higher is necessary to obtain desired mechanical strength (printing durability). Further, as a method of improving printing durability, the curing reaction at the time of exposure with the ethylenically unsaturated compound in the image area is 1
A method of further advancing the polymerization and curing by exposing the front surface of the portion which has not been completed to 00% with active light such as ultraviolet rays (UV) after finishing is often used. FIG. 5 shows an example of the structure of a conventional automatic developing apparatus that performs the above series of processing. The overall configuration includes processing units 1 to 7, a replenishing device 8, and a control device 9. The processing units 1 to 7 include a preheating unit 1, a prewashing unit 2, a developing unit 3, a washing unit 4, a finishing unit 5, in the order of processing. The drying unit 6 and the post-exposure unit 7 are included.

In this case, the number of replenishment pumps (P1 to P6) for replenishing the treatment liquid (including washing water) to each treatment tank is 1
One to two per treatment tank was used for supplementing the stock solution of each treatment solution and dilution water, or washing water. However, for example, in the pre-water washing part and the water washing part, scales and spoilage often occur during processing, the scales adhere to the printing plate surface to deteriorate the quality, clog the processing liquid circulation pump, and develop automatically. There was a problem that it took longer to clean the device. On the other hand, a method of adding an antiscaling agent or an antiseptic agent to the wash water is known, but in that case, the specific method is to manually add the water directly to the treatment tank by an operator or to prepare a stock tank for the wash water. It is known that manual addition, or automatic addition by a replenishment pump (P7) as in the configuration described in Japanese Patent Application No. 2000-092062. The addition by the replenishment pump P7 is also effective in preventing the generation of mold and bacteria in the stock tank. In the above example, manual addition would be complicated, and addition to the water storage tank would result in dilution water containing an antiseptic agent being added to the developing section or the finisher section, which may cause waste or an adverse effect on processing performance. is there. Further, since the dissolved / mixed substances in the pre-water washing section, the water washing section, and the finishing section are different for each tank, the optimum addition amount to each tank may not be realized. These problems can be avoided by increasing the replenishing amount of the washing water without using the preservative, and the problem can be avoided by decreasing the concentration of dissolved substances / contaminated substances, but the amount of waste liquid increases and it is desirable from the viewpoint of environmental measures. Absent.

Further, when the oxygen-blocking protective layer is dissolved in the water of the pre-washed portion, or when the components of the photosensitive layer are mixed in the water of the washed portion, bubbles may often occur. In such a case, addition of an antifoaming agent is effective. It is desirable to add the optimum amount for each treatment tank. In some cases, it may be more effective to add the same additive to each treatment tank, or it may be more effective to add different additives to each treatment tank. The method of batch addition to the tank is inconvenient.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to overcome the drawbacks of the above-mentioned conventional techniques, to obtain a high-quality processed plate surface, and to add various additives to each processing tank in an optimum amount to eliminate waste. It is an object of the present invention to provide an automatic developing device for a lithographic printing plate which is capable of preventing and reducing the amount of waste liquid and shortening the cleaning time of the developing device.

[0009]

As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by adopting the following constitution. That is, the present invention is as follows.

(1) The invention of an automatic developing device for a lithographic printing plate according to claim 1 is a lithographic printing plate developing device having at least a developing part and a water washing part, which automatically develops a lithographic printing plate. In a lithographic printing plate developing apparatus in which a developing tank and a water washing tank are respectively provided in the developing unit and the water washing unit, two or more processing liquid replenishing pumps for replenishing at least two types of liquids in the respective tanks are provided. It is characterized in that it is provided near each tank. (2) The invention according to claim 2 is the automatic developing apparatus for a lithographic printing plate according to claim 1, which is provided with a pre-heat treatment section for heating the photosensitive layer or two or more processing solution replenishing pumps. A pre-water washing section having a processing tank in which two or more kinds of liquids are replenished by a liquid replenishing pump is provided in the preceding stage of the developing tank. (3) The invention according to claim 3 is the automatic developing apparatus for a lithographic printing plate according to claim 1 or 2, wherein the two kinds of liquids to be replenished in the pre-washing section or the washing section are water and a preservative solution. Is characterized in that. (4) The invention according to claim 4 is the automatic developing apparatus for a lithographic printing plate according to any one of claims 1 to 3, wherein the two kinds of liquids to be replenished in the pre-washing section or the washing section are water and water. It is characterized in that it is a solution containing a foaming agent. (5) The invention of an automatic developing method for a lithographic printing plate according to claim 5 is a lithographic printing plate developing method in which the lithographic printing plate is automatically developed through a lithographic printing plate at least in a developing tank of a developing section and a washing tank of a water washing section, In a lithographic printing plate developing method in which each tank is replenished with at least two kinds of liquids of water and a solution containing a preservative, the lithographic printing plate comprises an ethylenically unsaturated compound, a photopolymerization initiator and a polymer binder. It is characterized in that a photopolymerizable lithographic printing plate containing a photopolymerizable photosensitive composition in the photosensitive layer of the lithographic printing plate is used. (6) The invention of an automatic developing method for a lithographic printing plate according to claim 6 is a lithographic printing plate developing method in which a lithographic printing plate is automatically developed at least through a developing tank of a developing section and a washing tank of a water washing section. In a lithographic printing plate developing method in which each tank is replenished with at least two kinds of liquids of water and a solution containing an antiseptic, the developing tank is replenished with a development replenishing stock solution and a solution containing diluting water and a surfactant. Is characterized by.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The lithographic printing plate automatic developing apparatus of the present invention will be described in detail below with reference to FIGS.
1 to 4 are processing units 1 to 7 in FIG. 5 of the conventional device.
Is divided into four figures in the order of processing and is shown in FIG.
Is the first pre-heating unit 1 and pre-washing unit 2 among the processing units 1 to 7.
FIG. 2 shows the next developing unit 3 among the processing units 1 to 7.
3 shows the next washing section 4 and finishing section 5 among the processing sections 1 to 7, and FIG. 4 shows the final drying section 6 and the post-exposure section of the processing sections 1 to 7. 7 is shown.
In addition, in each drawing, a replenishing device 8 provided in each processing section is also provided.
And a control device 9 commonly used for each process. Thus, this automatic developing device is
Pre-water washing section 2, developing section 3, water washing section 4, finishing section 5,
The drying unit 6 and the post-exposure unit 7 constitute a processing unit in this order, and in addition, a replenishing device 8 and a control device 9 are included. The exposed printing plate starts processing from the preheating unit 1 and is placed on a printing machine after the post-exposure processing is completed. Of these, the developing section 3, the water washing section 4,
The finishing unit 5 is an essential processing unit, and the other processing units are appropriately provided depending on the type of lithographic printing plate and printing conditions.
The processing width dimension is preferably 0.5 to 2.0 m, and is 0.
8 to 1.5 m is more preferable.

In FIG. 1, the preheating unit 1 guides the plate S to the inside by the transport rolls 11a and 11b, and the heater 12 heats the plate surface to accelerate polymerization and increase the curing degree of the photosensitive layer. A ceramic heater is preferably used as the structure of the heater 12. During the heating, the conveyance guide 13 keeps the distance between the heater 12 and the plate constant to keep the heating temperature stable. The heated plate S is guided to the pre-water washing unit 2 by the transport rolls 14a and 14b. In order to stabilize the temperature in the pre-heating section, it is effective to take in an appropriate amount of outside air with the blower fan 15. The temperature of the heat treatment for promoting polymerization is 8
It must be 0 ° C or higher. Preferably 100-170
C., more preferably 110 to 150.degree. If the temperature is lower than 80 ° C., the polymerization is not promoted sufficiently and the lithographic printing plate obtained has a lower printing durability and is unsuitable for printing on a large number of sheets. The heating time is not particularly limited, but is preferably 1 to 20 seconds, more preferably 2 to 10 seconds. In the pre-water washing section 2, the transport roll 21
The washing water supplied from the washing water discharge spray 22 and the pre-washing brush roll 2 are guided to the inside by the a and 21b.
At 3, the oxygen barrier protective layer on the top of the photosensitive layer is removed. During washing with water, the plate S is supported by the transport guide 24 and the pressing pressure of the brush is kept constant. The rinsing water is stored in the rinsing tank 20, is supplied to the rinsing water discharge spray 22 by the circulation pump 26, and the rinsing water after cleaning is returned to the rinsing tank 20 again and is circulated. The circulation rate is preferably 10 to 20 liters / minute, and the capacity of the washing tank 20 is preferably 2 to 10 liters. The plate S that has been washed with water is guided to the developing unit 3 while squeezing excess water for washing with transport rollers 25a and 25b. The treatment time is preferably 3 to 20 seconds, more preferably 5 to 10 seconds. The liquid temperature is preferably 15 to 70 ° C., more preferably 25 to 40 degrees. Dissolution of the oxygen barrier protective layer is delayed at low temperatures,
It is dangerous to handle at high temperature, and water vaporization becomes great.

In the developing section 3 shown in FIG.
The plate S is guided obliquely downward by 1a and 31b, and the developing tank 3
While the plate S passes through the developer stored in 0, the plate surfaces are rubbed by the developing brushes 33a and 33b to remove the non-image portion and develop. The capacity of the developing tank 30 is preferably 20 to 50 liters from the viewpoint of the apparatus size, the amount of waste liquid, the development stability, and the like. After the development is completed, the plate S is guided to the water washing section 4 (FIG. 3) while removing excess developer by the transport rolls 36a and 36b. During the development, the plate S is conveyed on the correct conveying line by the conveying guides 32 and 35 and the submerged conveying roll 34 so that the pressing force of the developing brushes 33a and 33b is kept constant.
Further, the developing spray is ejected toward the plate surface by the developing spray 39c to efficiently remove the photosensitive layer in the non-image area, and a fresher developing solution is supplied to the plate surface. Further, by supplying the developing solution to the developing spray 39c by the circulation pump 38, the developing solution is agitated and circulated to make the developing solution activity in the tank uniform. The circulation rate is preferably 10 to 30 liters / minute. Further, since the developing performance depends on the developing temperature, a data signal of a liquid thermometer (not shown) is sent to the microcomputer 91 in the control device 9 to control the liquid temperature heating heater 39a and the cooling device 39b to obtain a proper liquid. Keep it warm. The developer activity can be maintained constant for a long period of time by appropriately adding a developer replenisher, and a sensor 39d is provided in the middle of the circulation system to control the replenisher amount of the developer replenisher.
The electric conductivity of the developing solution is measured, and the computer 91 operates the developing solution replenishing pump P3a and the diluting water replenishing pump P3b so as to always maintain the optimum developing solution activity. In addition, a floating lid 37 is provided on the surface of the developing solution in close contact with the surface of the developing solution to prevent evaporation of water and deterioration of the developing solution due to oxygen and carbon dioxide in the air. The development time is preferably 5 to 40 seconds, more preferably 10 to 30 seconds. The conveying speed is determined by the length of the developing section and a value that realizes the developing time, but is preferably 0.5 to 3 m / min, more preferably 1 to 3 m / min.
It is preferably 2 m / min. The developer temperature is 20
The temperature is preferably -40 ° C, more preferably 25-35 ° C.

The plate S guided to the rinsing section 4 in FIG. 3 is guided inside by the transport rolls 41a and 41b, and is washed by the rinsing water and the rinsing brush roll 44 supplied from the rinsing water supply spray 43 to the plate surface. The remaining developing component is washed off. The plate S is supported by the conveyance guide 42 during washing with water, and the pressing pressure of the washing brush roll 44 is kept constant. The rinsing water is stored in the rinsing tank 40, is supplied to the rinsing water discharge spray 43 by the circulation pump 46, and the rinsing water after cleaning is returned to the rinsing tank 40 again and repeated circulation. Circulation volume is 2-10 liters /
Minutes are preferred. The washing tank 40 preferably has a capacity of 2 to 10 liters. The plate S that has been washed with water is transported by the transport roll 45.
Excessive rinsing water is squeezed by a and 45b and is guided to the finishing section 5. The washing time is preferably 3 to 20 seconds, more preferably 5 to 10 seconds. The liquid temperature is preferably 15 to 70 ° C,
More preferably, it is 25 to 40 ° C. As a method of guiding the plate S to the finishing portion, a method of transporting the water in the washing portion transporting rolls 45a and 45b in a diagonally downward direction is adopted, and the number of rolls is reduced to reduce the size of the device and the cost of the device. The finishing liquid is supplied from the finishing liquid supply spray 51 to the plate surface to desensitize the non-image area (to make it difficult for fingerprints and printing ink to adhere). It is necessary to apply an appropriate amount of the finishing liquid to the plate surface, and this is achieved by leaving an appropriate amount by squeezing with the transport rolls 52a and 52b. The transport rolls 52a and 52b also have a function of guiding the plate S that has finished the finishing process to the drying unit 6 (FIG. 4). The finishing liquid is stored in the finishing tank 50 and is discharged by the circulation pump 53.
And the treated finishing liquid is returned to the treatment tank 50 and the circulation is repeated. Circulation volume is 2-10 liters /
Minutes are preferred. The capacity of the processing tank 50 is preferably 2 to 10 liters. The finishing treatment time is preferably 3 to 15 seconds, more preferably 5 to 10 seconds.
The liquid temperature is preferably 15 to 50 ° C, more preferably 25 to 40 ° C.

The plate S guided to the drying unit 6 in FIG. 4 is dried on the plate surface by the hot air blown from the hot air duct 62 and discharged to the outside of the apparatus by the transport roll 63, or has a higher printing durability. If required, the sheet is conveyed to the post-exposure section 7, where the curing processing of the image section is completed, and then sent to the printing step. In the post-exposure unit 7, the plate surface is uniformly exposed by an ultraviolet (UV) lamp 71 and then discharged by the transport rollers 73a and 73b. During exposure, the plate surface is supported on the guide roll 72, and the distance between the ultraviolet lamp 71 and the plate surface (S) is kept constant.

Next, the replenishing device 8 will be described. The replenishing device 8 includes a replenishing pump (P2a, P2b, ... P5a, P5b) for feeding a replenishing liquid (including water) to each processing unit, a replenishing tank (T1 to T5) for storing each replenishing liquid, and It is composed of a replenisher hose 81. The liquid feed capacity of each replenishment pump is preferably 30 to 300 cc / min, and accuracy is 5%
It must be within the range, and a bellows type or tube type is suitable for the structure. The computer 91 in the control device controls the drive time of the replenishment pump to add the optimum amount of liquid to be fed. The replenishing device 8 of the pre-water washing unit 2 of FIG. 1 is provided with a replenishing pump P2a for replenishing an additive such as an antiseptic and a replenishing pump P2b for replenishing washing water, and the additive storage tank T2 and the water storage respectively. A required amount is sent from the tank T1 to the processing tank 20.
It is preferable that the amount of liquid to be sent is added in proportion to the amount of the oxygen-blocking protective layer dissolved in the treatment liquid, and therefore, the amount of liquid may be added in proportion to the area of the plate S to be treated. Specifically, the additive replenishment pump P2a is 0.01 to 10 per area of the plate S.
cc / m ² range, wash water replenishment pump P2b is 30-200
The range of cc / m ² is suitable, and the driving time of the pump per refilling operation stored in advance in a storage device (not shown) in the control device is determined by controlling the computer 91. Sensor 1 for detecting plate passage
When starting addition based on the 00 signal (each specified number of sheets is possible), or when only P2b is driven by the cumulative elapsed time while plate processing is not performed and the cumulative elapsed time when the power of the automatic developing device is turned off to compensate for water evaporation There is. Specific examples of additives include preservatives described in JP-A-10-10754 and JP-A-8-27.
There are organic solvents described in 8636.

The replenishing device 8 of the developing section 3 of FIG. 2 is provided with a replenishing pump P3a for replenishing the developing replenishing stock solution and a replenishing pump P3b for replenishing the diluting water, and a developing replenishing stock solution storage tank T3 and a water reserve, respectively. The required amount of each is sent from the tank T1 (FIG. 1) to the processing tank 30. The amount of liquid fed is 3 to 30 cc / per plate area for the developing replenishment stock solution replenishment pump P3a
The m ² and diluted m water P3b are suitable in the range of 10 to ²⁰⁰ cc / m ² , and an appropriate amount is sent by the pump drive signal from the controller. An appropriate amount can be determined by (1) replenishment pump P3 so as to keep the developer activity constant according to a control program which is measured by measuring sensor 39d and the computer 91 in the controller inputs the signal based on the signal.
a) and a method of driving P3b, (2) a signal of the sensor 100 for detecting the passage of the plate S, operation information of the automatic developing device (cumulative elapsed time of power-on and power-off), and a storage device (not shown) in the control device. There is a method of issuing a required pump drive signal from the computer 91 to replenish the pump based on the drive time of the pump per one replenishment operation stored in (1). Also, in any of the methods, it is possible to appropriately compensate for water evaporation by the elapsed time during which plate processing is not performed. In the developing unit 3,
Depending on the type of printing plate, in addition to the above two replenishment pumps, a third replenishment pump and a tank for storing a third additive may be provided, and three types of addition may be performed in one processing section. It is described in detail in Japanese Patent Publication No. 2000-141329.
In the same application, the inventors diligently studied the fluctuation of the performance of the developing solution, and as a result, by adding a high-concentration aqueous surfactant solution each time the developing processing of a predetermined plate area was performed, It has been found that the solubility of the image area and the dissolution resistance of the image area can be maintained, and stable development can be achieved for a long period of time. That is, the method of replenishing the lithographic printing plate developer of the invention is an infrared ray containing (A) a water-insoluble and alkali-soluble polymer compound and (B) a compound which absorbs light and generates heat on the support. After exposing the lithographic printing plate precursor, which is formed with a positive photosensitive layer for laser, with an infrared laser, the method of replenishing the alkaline developing solution when developing, every time when developing a predetermined amount of lithographic printing plate precursor It is characterized in that an aqueous solution of a surfactant is added to the alkali developing solution. In this case, it is also possible to cite addition of an alkaline agent to the alkaline developing solution, independently of the addition of the aqueous surfactant solution, as a preferred embodiment. In this mode, during the time when the developing process is not performed, the alkaline developer in the processing tank absorbs carbon dioxide gas in the air to compensate for so-called air deterioration that causes a pH decrease. This means adding replenisher. Explaining this in accordance with the embodiment of the present invention, the replenishing pump for the developing tank is composed of a developing replenishing stock solution replenishing pump, a diluting water replenishing pump, and a surfactant aqueous solution adding pump.
Will have two.

The replenishing device 8 of the water washing section 4 of FIG. 3 is provided with a replenishing pump P4a for replenishing an additive such as an antiseptic and a replenishing pump P4b for replenishing washing water. A required amount is sent from the water storage tank T1 (FIG. 1) to the processing tank 40. The feed amount of the additive replenishment pump P2a is in the range of 0.01 to 10 cc / m ² per plate area,
A suitable range of the flush water replenishment pump P2b is from 20 to 200 cc / m ² , and a storage device (not shown) in the control device is provided in advance.
The driving time of the pump for each replenishment operation stored in the above is determined by controlling the computer 91. As the timing of addition, there are cases where the addition is started based on the signal from the sensor 100 that detects the passage of the plate (each specified number of sheets is also possible), and there is a case where P4b is driven by the elapsed time during which the plate processing is not performed to compensate for water evaporation. . The pre-washing unit 2 (FIG. 1) and the washing unit 4 (FIG. 3) described above have the same structure of the replenishing device 8, but different solutes to be dissolved in each processing liquid. That is, the oxygen-blocking protective layer is dissolved in the processing solution in the pre-water washing section 2, and the photosensitive layer components brought in by the plate are dissolved in the processing solution in the water washing section 4. Polyvinyl alcohol is often used as the main component in the oxygen-blocking protective layer, and its aqueous solution is prone to bacteria and mold growth. In addition, bacteria and molds often proliferate in the treatment liquid of the water washing section 4, and it is desirable to add an appropriate amount of preservative. In general, the amount added to the water washing section is often smaller than that in the previous water washing section. Further, the above-mentioned Japanese Patent Laid-Open No. 2000-
No. 221697 shown in FIG. 12 does not have a pre-water washing section, and the oxygen blocking protective layer and the non-image area photosensitive layer are removed in the developing section 140. Layer components and photosensitive layer components are mixed, and bacteria and fungi easily propagate. For this reason, it is desirable to add a large amount of preservative to the water washing part.

The replenishing device 8 of the finishing section 5 of FIG. 3 includes a replenishing pump P5a for replenishing the stock solution for finishing.
A replenishing pump P5b for replenishing the diluting water is arranged, and the necessary amount is sent from the finishing stock solution storage tank T5 and the water storage tank T1 (FIG. 1) to the treatment tank 50. The amount of liquid to be sent is 1 to 3 per plate area for the additive replenishment pump P2a.
0cc / m ² range, rinse water replenishment pump P2b is 10 to 10
The range of 0 cc / m ² is suitable, and the drive time of the pump per replenishment operation stored in the storage device 92 in the control device in advance is determined by controlling the computer 91.
As for the timing of addition, when addition is started based on a signal from the sensor 100 that detects plate passage (each specified number of sheets is possible), or when the replenishment pump P5b is driven by the elapsed time before plate processing to compensate for water evaporation There is.

Next, the control device 9 will be described. The control device 9 is for operating various electric devices built in the automatic developing device as designed based on various input signals, and has a circuit board, an operation panel, a microcomputer 91, a storage device 92, It consists of a timer and a relay. As the electrical equipment to control, the transport roll drive motor,
There are various processing liquid circulation pumps and replenishment pumps, processing liquid heating heaters, processing liquid cooling chillers, drying unit heaters, blower fans, and the like. As the input signal, signals from a plate detection sensor, a developing solution temperature sensor, a developing solution activity measuring sensor, a dry air temperature sensor, etc., which detect that the printing plate is inserted into the entrance of the automatic developing device, are used. The developer activity measuring sensor measures pH, electrical conductivity, AC impedance, etc. of the developer, and based on the signals, the microcomputer 91 performs a developer replenishing stock solution replenishing pump and a diluting water replenishing pump according to a control program preprogrammed. To keep the developer activity constant. Regarding the technique, Japanese Patent Laid-Open No. 64-214
No. 51 for details.

Next, the photopolymerizable lithographic printing plate used in the method for making a lithographic printing plate of the present invention will be described. The photopolymerizable photosensitive composition constituting the photosensitive layer of the photopolymerizable lithographic printing plate used in the plate making method of the present invention is an addition-polymerizable ethylenically unsaturated compound, a photopolymerization initiator, an essential component of a polymer binder. If necessary, various compounds such as a colorant, a plasticizer and a thermal polymerization inhibitor can be used in combination.

The ethylenically unsaturated compound is an ethylenically unsaturated bond which undergoes addition polymerization by the action of a photopolymerization initiator when the photopolymerizable photosensitive composition is irradiated with an actinic ray to cause crosslinking and curing. Is a compound having The addition-polymerizable compound containing an ethylenic double bond can be arbitrarily selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. For example, it has a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.

Examples of monomers and copolymers thereof include esters of unsaturated carboxylic acids (eg acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid) with aliphatic polyhydric alcohol compounds. , Amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and the like. Specific examples of monomers of the ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester There are acrylate oligomers and the like.

Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate , Bis [p- (3--methacryloxy-2-hydroxypropoxy) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

The itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate and sorbitol tetramaleate. Furthermore, a mixture of the above-mentioned ester monomers can also be mentioned. Specific examples of the amide monomer of the aliphatic polyvalent amine compound and the unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1,6-hexamethylenebis. −
Methacrylamide, diethylenetriamine tris acrylamide, xylylene bis acrylamide, xylylene bis methacrylamide and the like.

As another example, Japanese Patent Publication No. 48-417.
In the polyisocyanate compound having two or more isocyanate groups in one molecule described in JP-A-08,
Examples thereof include vinyl urethane compounds having two or more polymerizable vinyl groups in one molecule to which a vinyl monomer having a hydroxyl group represented by the following general formula (A) is added. CH ₂ ═C (R ₅ ) COOCH ₂ CH (R ₆ ) OH (A) (provided that R ₅ and R ₆ represent H or CH ₃ ). 3229
Urethane acrylates as described in No. 3,
JP-A-48-64183, JP-B-49-43191
And polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-B No. 52-30490 and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid. Furthermore, the Japan Adhesive Association Magazine Vol. 20, No.
Those introduced as photocurable monomers and oligomers on pages 7,300-308 (1984) can also be used. The amount of these ethylenically unsaturated compounds used is 5-80% by weight, preferably 30-70% by weight, based on the total components of the photosensitive layer.

As the photopolymerization initiator to be contained in the photosensitive layer of the photopolymerizable lithographic printing plate of the present invention, various photoinitiators known in patents, literatures, etc., depending on the wavelength of the light source used,
Alternatively, a combination system of two or more photoinitiators (photoinitiator system) can be appropriately selected and used. Specific examples are listed below, but the invention is not limited thereto. Various photoinitiating systems have been proposed even when a visible light of 400 nm or more, an Ar laser, a second harmonic of a semiconductor laser, or an SHG-YAG laser is used as a light source. For example, US Pat. No. 2,850,445 is proposed. Photoreducible dyes such as rose bengal, eosin, erythrosine, etc., or a combination of a dye and an initiator, for example, a complex initiation system of a dye and an amine (Japanese Patent Publication No. 44-2018).
No. 9), a system in which a hexaarylbiimidazole, a radical generator and a dye are used in combination (Japanese Patent Publication No. 45-37377), a system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (Japanese Patent Publication No. 47-2528, JP-A-47-2528). 54-155292), a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-84183), a system of a cyclic triazine and a merocyanine dye (JP-A-54-1).
51024), a system of 3-ketocoumarin and an activator (JP-A-52-112681, JP-A-58-15503).
No.), biimidazole, styrene derivative, thiol system (JP-A-59-140203), organic peroxide and dye system (JP-A-59-1504, JP-A-59-1402).
03, JP-A-59-189340, JP-A-62-1.
74203, Japanese Examined Patent Publication No. 62-1641, US Pat. No. 4
766055), a system of a dye and an active halogen compound (JP-A-63-258903, JP-A-2-63054, etc.), a system of a dye and a borate compound (JP-A-62-1430).
44, JP-A-62-150242, JP-A-64-1
3140, JP-A-64-13141, JP-A-64-
13142, JP-A-64-13143, JP-A-64
-13144, JP-A-64-17048, JP-A-1
-229003, JP-A-1-298348, JP-A-1-138204, etc.) A system of a dye having a rhodanine ring and a radical generator (JP-A-2-179643, JP-A-2-244050), titanocene and 3- A system of ketocoumarin dyes (JP-A-63-221110), a system in which a titanocene and a xanthene dye, and an addition-polymerizable ethylenically unsaturated compound containing an amino group or a urethane group are combined (JP-A-4-221958, JP-A-4-221958). -21
9756), a system of titanocene and a specific merocyanine dye (JP-A-6-295061), and a system of titanocene and a dye having a benzopyran ring (JP-A-8-334897).
No.) and the like.

Recently, a laser (violet laser) having a wavelength of 400 to 410 nm has been developed, and a photoinitiating system showing high sensitivity to a wavelength of 450 nm or less, which is sensitive to it, has been developed. These photoinitiating systems are also used. It For example, a cationic dye / borate system (JP-A-11-8464)
No. 7), a merocyanine dye / titanocene system (JP-A-200
No. 0-147763), a carbazole type dye / titanocene type (Japanese Patent Application No. 11-22480). In the present invention, a system using a titanocene compound is particularly preferable in terms of sensitivity.

As the titanocene compound, various compounds can be used, and examples thereof include JP-A-59-1523.
It can be appropriately selected and used from various titanocene compounds described in JP-A-96 and JP-A-61-151197. More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, 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-di-fluorophen-1-
Di-cyclopentadienyl-Ti-bis-2,4
-Di-fluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti- Bis-2,6-difluorophenyl-1
-Yl, di-cyclopentadienyl-Ti-bis-2,
6-difluoro-3- (pyr-1-yl) -phenyl-1
-Ill and the like can be mentioned. Further, if necessary, a thiol compound such as 2-mercaptobenzthiazole, 2-mercaptobenzimidazole and 2-mercaptobenzoxazole, N-phenylglycine,
It is known that the photoinitiating ability can be further enhanced by adding a hydrogen donating compound such as an amine compound such as N, N-dialkylamino aromatic alkyl ester. The amount of these photopolymerization initiators (system) used is 0.05-100 parts by weight, preferably 0.1-70 parts by weight, more preferably 0.2-, based on 100 parts by weight of the ethylenically unsaturated compound.
Used in the range of 50 parts by weight.

The polymer binder used in the photosensitive layer of the photopolymerizable lithographic printing plate of the present invention is not only used as a film-forming agent for the composition, but also needs to be dissolved in an alkali developing solution. An organic high molecular weight polymer that is soluble or swellable is used. The organic high molecular polymer can be developed in water by using, for example, a water-soluble organic high molecular polymer. As such an organic polymer, an addition polymer having a carboxylic acid group in its side chain, for example, JP-A-59-4
4615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-
No. 12577, Japanese Examined Patent Publication No. 54-25957, and Japanese Unexamined Patent Publication No. 54
-92723, JP-A-59-53836, JP-A-5-
9-71048, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer,
There are partially esterified maleic acid copolymers and the like.

Similarly, there is an acidic cellulose derivative having a carboxylic acid group in its side chain. In addition to these, a product obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group is useful. In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomer] copolymer and [allyl (meth) acrylate (meth) acrylic acid / optional Other Addition Polymerizable Vinyl Monomers] Copolymers are preferred. In addition, polyvinylpyrrolidone, polyethylene oxide and the like are useful as the water-soluble organic polymer. Further, alcohol-soluble polyamide, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful for increasing the strength of the cured film.
In addition, Japanese Patent Publication No. 7-120040 and Japanese Patent Publication No. 7-2004
1, No. 7-120042, No. 8-1242
4, JP-A-63-287944, JP-A-63-28
7947, JP-A 1-271741, JP-A 11-
The polyurethane resin described in 352691 is also useful for the purpose of the present invention.

These high molecular weight polymers can improve the strength of the cured film by introducing a radical reactive group into the side chain. The functional group capable of addition polymerization reaction is an ethylenically unsaturated bond group, an amino group, an epoxy group or the like, and the functional group capable of becoming a radical by light irradiation is a mercapto group, a thiol group, a halogen atom, a triazine structure, an onium salt structure. Examples of the polar group include a carboxyl group and an imide group. The functional group capable of undergoing the addition polymerization reaction is particularly preferably an ethylenically unsaturated bond group such as an acrylic group, a methacrylic group, an allyl group and a styryl group, but also an amino group, a hydroxy group, a phosphonic acid group, a phosphoric acid group, a carbamoyl group. A functional group selected from an isocyanate group, an ureido group, a ureylene group, a sulfonic acid group and an ammonio group is also useful.

In order to maintain the developability of the composition, the polymer binder of the present invention preferably has an appropriate molecular weight and acid value. The weight average molecular weight is 5000 to 300,000 and the acid value is 2.
High molecular weight polymers of 0-200 are effectively used. These organic high molecular weight polymers can be mixed in arbitrary amounts in the entire composition. However, when it exceeds 90% by weight, favorable results are not obtained in terms of the strength of the formed image. It is preferably 10-90%, more preferably 30-80%. The weight ratio of the photopolymerizable ethylenically unsaturated compound to the organic polymer is preferably 1 / 9-9 / 1. A more preferable range is 2 / 8-8 / 2, and a further preferable range is 3 / 7-7 / 3.

In the present invention, in addition to the above basic components, a small amount of thermal polymerization is prohibited in order to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during the production or storage of the photosensitive composition. It is desirable to add agents. Suitable thermal polymerization inhibitors include haloid quinone, p-
Methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl) −
6-t-butylphenol), N-nitrosophenylhydroxylamine primary cerium salt, N-nitrosophenylhydroxylamine aluminum salt and the like.
The amount of the thermal polymerization inhibitor added is preferably about 0.01% to about 5% based on the weight of the entire composition. Further, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. . The amount of the higher fatty acid derivative added is about 0.5% to about 1 of the total composition.
0% is preferable.

Further, a coloring agent may be added for the purpose of coloring the photosensitive layer. As the colorant, for example, a phthalocyanine-based pigment (CI Pigment Blue 1
5: 3, 15: 4, 15: 6, etc.), azo pigments, carbon black, pigments such as titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The amount of dye and pigment added is preferably about 0.5% to about 20% of the total composition.
In addition, additives such as an inorganic filler and a plasticizer such as dioctyl phthalate, dimethyl phthalate and tricresyl phosphate may be added to improve the physical properties of the cured film. The addition amount of these is preferably 10% or less of the total composition.

When the photosensitive layer composition of the photopolymerizable lithographic printing plate of the present invention is coated on a support described below, it is dissolved in various organic solvents before use. As the solvent used here, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran,
Toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol Monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-
Methoxypropanol, methoxymethoxyethanol,
Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate-3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, lactic acid Examples include methyl and ethyl lactate. These solvents can be used alone or as a mixture. And, the concentration of the solid content in the coating solution is appropriately 1 to 50% by weight.

A surfactant may be added to the photopolymerizable composition in the photosensitive layer of the photopolymerizable lithographic printing plate of the invention in order to improve the quality of the coated surface. The coating weight of about 0.1 g / m ² in weight after drying - is suitably ranges from about 10 g / m ^2. It is more preferably 0.3-5 g / m ² . More preferably, it is 0.5-3 g / m ² .

Further, an oxygen-blocking protective layer is required on the photosensitive layer in order to prevent an oxygen polymerization inhibiting action. Examples of the water-soluble vinyl polymer contained in the oxygen barrier protective layer include polyvinyl alcohol, and partial esters, ethers, and acetals thereof, or a substantial amount of an unsubstituted vinyl alcohol unit such that they have the necessary water solubility. And its copolymers containing Examples of polyvinyl alcohol include those that are 71-100% hydrolyzed and have a degree of polymerization in the range of 300-2400. Specifically, PVA-105, P manufactured by Kuraray Co., Ltd.
VA-110, PVA-117, PVA-117H, P
VA-120, PVA-124, PVA-124H, P
VA-CS, PVA-CST, PVA-HC, PVA-
203, PVA-204, PVA-205, PVA-2
10, PVA-217, PVA-220, PVA-22
4, PVA-217EE, PVA-220, PVA-2
24, PVA-217EE, PVA-217E, PVA
-220E, PVA-224E, PVA-405, PV
A-420, PVA-613, L-8 etc. are mentioned.
The above copolymers include polyvinyl acetate chloroacetate or propionate, polyvinyl formal and polyvinyl acetal which are 88-100% hydrolyzed, and copolymers thereof. Other useful polymers include polyvinylpyrrolidone, gelatin and gum arabic, which may be used alone or in combination.

In the photopolymerizable lithographic printing plate of the present invention, pure water is preferably used as a solvent for coating the oxygen-blocking protective layer, but alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone are preferred. It may be mixed with pure water. Then, the concentration of the solid content in the coating solution is appropriately 1 to 20% by weight. The oxygen-blocking protective layer of the present invention may further contain known additives such as a surfactant for improving coating properties and a water-soluble plasticizer for improving physical properties of the film. Examples of the water-soluble plasticizer include propionamide, cyclohexanediol, glycerin, sorbitol and the like. Also, a water-soluble (meth) acrylic polymer or the like may be added. The amount of clothing is about 0.1 g / m ² after drying. ~ About 15g /
A range of m ² is suitable. More preferably 1.0 g / m
² to about 5.0 g / m ² .

Next, the support of the photopolymerizable lithographic printing plate of the present invention will be described. In order to obtain the photopolymerizable lithographic printing plate of the present invention, the photosensitive layer is provided on a support having a hydrophilic surface. As the hydrophilic support, conventionally known hydrophilic supports used for lithographic printing plates can be used without limitation. The support used is preferably a dimensionally stable plate-like material, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc). , Copper, etc.), plastic films (for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), Such materials include paper or plastic film laminated or vapor-deposited with a metal, and the surface thereof may be subjected to appropriate known physical and chemical treatments for the purpose of imparting hydrophilicity or improving strength, if necessary. May be given.

Particularly preferable supports include paper, polyester film and aluminum plate, and among them, they have good dimensional stability, are relatively inexpensive, and have excellent hydrophilicity and strength by surface treatment as required. Aluminum plates that can provide a surface are particularly preferred. A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable.

Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a trace amount of a foreign element, and a plastic film laminated or vapor-deposited with aluminum may be used. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium. The content of foreign elements in the alloy is at most 10% by weight. Aluminum which is particularly preferred in the present invention is pure aluminum, but completely pure aluminum is difficult to produce in terms of refining technology, and thus may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and conventionally known and publicly known aluminum plates can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, and particularly preferably 0.2 mm to 0.3 mm.

In the case of a support having a surface of metal, especially aluminum, roughening (graining) treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodization. Surface treatment such as treatment is preferably performed. Roughening treatment of the surface of the aluminum plate is performed by various methods, for example,
It is carried out by a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening the surface, and a method of chemically and selectively melting the surface. As the mechanical method, known methods such as a ball polishing method, a brush polishing method, a blast polishing method, a buffing method and a polishing method can be used. Further, as an electrochemical graining method, there is a method of performing alternating current or direct current in an electrolytic solution such as hydrochloric acid or nitric acid. Further, as disclosed in Japanese Patent Application Laid-Open No. 54-63902, a method in which both are combined can also be used. In addition, prior to roughening the aluminum plate, if desired, in order to remove the rolling oil on the surface,
For example, degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution, or the like is performed.

Further, an aluminum plate which has been roughened and then immersed in an aqueous sodium silicate solution can be preferably used. As described in JP-B-47-5125, an aluminum plate subjected to anodizing treatment and then immersed in an aqueous solution of an alkali metal silicate is preferably used. The anodizing treatment is carried out, for example, in an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or an aqueous solution or a non-aqueous solution of a salt thereof, or an electrolytic solution obtained by combining two or more kinds. It is carried out by passing a current through the aluminum plate as an anode.

Further, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective. Further, JP-B-46-27481 and JP-A-52-5860
No. 2, JP-A No. 52-30503, and a surface treatment in which a support subjected to electrolytic graining is combined with the anodizing treatment and the sodium silicate treatment are also useful. Further, those subjected to mechanical surface roughening, chemical etching, electrolytic graining, anodizing treatment and sodium silicate treatment in this order as disclosed in JP-A-56-28893 are also preferable.

Furthermore, after these treatments are carried out, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having a sulfonic acid group in the side chain, polyacrylic acid, water-soluble metal salts (eg zinc borate). ) Alternatively, a yellow dye, amine salt or the like undercoat is also suitable. Further, a sol-gel treated substrate having a functional group capable of causing an addition reaction by a radical covalently bonded thereto as disclosed in JP-A-7-159983 is also suitably used.

Other preferable examples include those in which a water-resistant hydrophilic layer is provided as a surface layer on an arbitrary support. As such a surface layer, for example, US3
No. 055295, a layer comprising an inorganic pigment and a binder described in JP-A-56-13168, a hydrophilic swelling layer described in JP-A-9-80744, titanium oxide and polyvinyl described in JP-A-8-507727. Examples thereof include a sol-gel film made of alcohol and silicic acid. These hydrophilization treatments are performed in order to make the surface of the support hydrophilic, prevent the harmful reaction of the photopolymerizable composition provided thereon, and improve the adhesion of the photosensitive layer. And so on. The photopolymerizable lithographic printing plate of the present invention is prepared by forming a photosensitive layer made of the above photopolymerizable composition on the support, but if necessary before coating the photosensitive layer. An organic or inorganic undercoat layer may be provided.

The photosensitive layer in the photopolymerizable lithographic printing plate of the present invention is formed, for example, by 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, FD / YAG laser, helium neon laser, semiconductor laser (350 nm
An image can be formed on the surface of the support by imagewise exposure with a conventionally known actinic ray such as (-600 nm). Further, on the photosensitive layer of the photopolymerizable lithographic printing plate of the present invention, as described above, an oxygen barrier protective layer is provided, and the protective layer is first excluded with water or warm water,
After that, a method of removing the photosensitive layer in the unexposed area with a developing solution is often used. Further, more simply, a method of simultaneously removing the oxygen-blocking protective layer and the photosensitive layer in the unexposed area at the time of development processing is also used. The development of the photopolymerizable lithographic printing plate in the present invention with the above-mentioned developing solution is carried out according to a conventional method at a temperature of about 0 to 60 ° C, preferably about 15 to 40 ° C, for example, an exposed photopolymerizable lithographic printing plate. Is immersed in a developer and rubbed with a brush. Furthermore, when developing with an automatic processor, the developing solution becomes tired depending on the amount processed, so
Replenisher or fresh developer may be used to restore throughput.

Next, the chemicals used in the present invention will be described. The developer for use in the development of the photopolymerizable lithographic printing plate of the present invention is not particularly limited, but preferably, a developer as described in JP-B-57-7427 can be mentioned, and silicic acid can be used. Sodium, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium phosphate tribasic, sodium phosphate dibasic, ammonium phosphate tribasic, ammonium phosphate dibasic, sodium metasilicate, sodium bicarbonate, Aqueous solutions of inorganic alkaline agents such as aqueous ammonia and organic alkaline agents such as monoethanolamine or diethanolamine are suitable. The concentration of such an alkaline solution is 0.1-10.
%, Preferably 0.5-5% by weight.

Further, in such an alkaline aqueous solution,
If necessary, a small amount of a surfactant or an organic solvent such as benzyl alcohol, 2-phenoxyethanol or 2-butoxyethanol may be contained. Examples thereof include those described in US Pat. Nos. 3,375,171 and 3,615,480. Furthermore, JP-A-5
No. 0-26601, No. 58-54341, Japanese Patent Publication No. 56
The developers described in JP-A-39464 and JP-A-56-42860 are also excellent.

The photopolymerizable lithographic printing plate thus developed is disclosed in JP-A-54-8002 and JP-A-55-1150.
No. 45, No. 59-58431, etc., it is post-treated with washing water, a rinse solution containing a surfactant, a desensitizing solution containing gum arabic, a starch derivative and the like. . Further, after the development processing, the entire surface may be exposed to UV light for the purpose of improving printing durability. Various combinations of these treatments can be used in the post-treatment of the photopolymerizable lithographic printing plate of the present invention.

As the antiseptic in the present invention, there is disclosed in Japanese Patent Laid-Open No.
The compound described in No. -12340 is suitable, and specifically, pyridinethiol-1-oxide, salicylic acid, 1,
3,5-Trishydroxyethylhexahydro-S-triazine, 1,3,5-trishydroxymethylhexahydro-S-triazine, 1- (3-chloroallyl)-
3,5,7-Triaza-1-azonia adamantan chloride, 2-phenoxyethanol, α-bromocinnamaldehyde, methyl 2-benzimidazolylcarbamate, 3-methyl-4-isopropylphenol, N-methyldithiocarbamic acid, 5- Methyl-1,2,4-triazolo [3.4-b] benzothiazole, N-lauroyl-sarcosine, N-lauroyl-N-methyl-β-
Aminopropionic acid, resorcinol, pyrogallol,
Resorcinol monoacetate, alginic acid, ethylenebisdithiocarbamic acid, 10,10'-oxybisphenoxaarsine, cresol, phenol, 2,5-dichloro-4-bromophenol, 2- (4'-thiazolyl) -benzimidazole, 2 , 4,4'-Trichloro-2'-hydroxydiphenyl ether, 2-benzyl-4-chlorophenol, N- (2-hydroxypropyl) -aminomethanol, allylmethanol-hemiformal, (2,2'-dihydroxy- 5,5'-dichloro) -diphenylmethane, 2-phenylphenol,
Any or a mixture of 2,4,6-trichlorophenol, 2- (4-thiazolyl) -benzimidazole, P-chloro-m-cresol, and alkali metal salts thereof is used. Besides, 5-chloro-2-
Methyl-4-isothiazolin-3-one, 2-bromo-
2-nitro-1,3-propanediol may be mentioned.
The preferable addition amount is an amount that exerts a stable effect on bacteria, molds, yeasts and the like, and although it varies depending on the type of bacteria, molds, yeasts, etc., it is 0 as a concentration when used in a treatment tank. 0.01 to 5% by mass is preferable, and it is also preferable to use two or more kinds of preservatives together so as to be effective.

As the surfactant to be added to the developing tank in the present invention, compounds and concentrations described in JP-A-8-234448 are preferably used. Examples of the defoaming agent in the present invention include JP-A Nos. 62-73270 and 2-24.
The compounds and concentrations described in 4143 are preferably used. As the additive in the present invention, a mixture of the above preservative, surfactant, and defoaming agent can also be preferably used,
An optimum composition can be formulated as an additive to each treatment tank.

The planographic printing plate obtained by such treatment is read by a register mark, punched for attachment to the printing machine by a punch bender, hung on an offset printing machine in a process of bending both sides, and the like. Used for printing sheets.

[0056]

The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited by these examples. [Preparation of photopolymerizable lithographic printing plate] An aluminum plate of material 1S having a thickness of 0.30 mm was used with a No. 8 nylon brush and an 800 mesh pumicestone water suspension, and after graining the surface thereof, it was thoroughly rinsed with water. Washed. It was immersed in 10% sodium hydroxide at 70 ° C. for 60 seconds for etching, washed with running water, neutralized with 20% HNO ₃ and washed with water. This was subjected to electrolytic surface-roughening treatment in an aqueous 1% nitric acid solution under the condition of V _A = 12.7 V in an aqueous 1% nitric acid solution at an anode electricity of 300 coulomb / dm ² . When the surface roughness was measured, it was 0.45 μm (Ra indication).
Continue to soak in 30% H ₂ SO ₄ aqueous solution,
After desmutting for 2 minutes at ° C, 33 ° C, 20% H ₂
In an SO ₄ aqueous solution, place the cathode on the grained surface,
When the film was anodized at a current density of 5 A / dm ² for 50 seconds, the thickness was 2.7 g / m ² .

An undercoat layer was provided on the thus treated aluminum plate by the following procedure. The following liquid composition for undercoating was mixed and stirred at 30 ° C. Exotherm was observed after about 5 minutes, and after reacting for 60 minutes, the contents were transferred to another container, and 30,000 parts by mass of methanol was further added to prepare a liquid coating solution.

[0058] (Liquid composition for undercoat)   50 parts by mass of the following compound [Chemical formula 1]   130 parts by mass of methanol   20 parts by mass of water   Paratoluenesulfonic acid 5 parts by mass   Tetraethoxysilane 50 parts by mass   3-methacryloxypropyltrimethoxysilane 50 parts by mass

[0059]

[Chemical 1]

This liquid coating solution was coated on the treated aluminum plate so that the amount of Si was about 0.003 g / m ^2, and dried at 100 ° C. for 1 minute.

On the undercoat layer thus obtained, the high-sensitivity photopolymerizable composition 1 having the following composition was applied in a dry coating weight of 1.5.
The photosensitive layer was formed by coating so as to have a g / m ² and drying at 100 ° C. for 1 minute.

[0062] (Photopolymerizable composition)   2.0 parts by weight of ethylenically unsaturated bond-containing compound (A1)   Linear organic high molecular polymer (B1) 2.0 parts by weight   Sensitizer (C1) 0.15 parts by weight   Photopolymerization initiator (D1) 0.2 part by weight   Sensitization aid (E1) 0.2 parts by weight   ε-phthalocyanine (F1) dispersion 0.02 parts by weight   Fluorine-based nonionic surfactant Megafac F177 0.03 parts by weight     (Manufactured by Dainippon Ink and Chemicals, Inc.)   Methyl ethyl ketone 15.0 parts by weight   Propylene glycol monomethyl ether acetate 15.0 parts by weight

[0063]

[Chemical 2]

A 3% by weight aqueous solution of polyvinyl alcohol (saponification degree: 98 mol%, polymerization degree: 500) was coated on the photosensitive layer so that the dry coating weight was 2.5 g / m ² .
Dry for 3 minutes at 120 ° C and finish dimension is 0.7 ×
A photopolymerizable lithographic printing plate was obtained by cutting to 1.0 m ² .

[Examples and Comparative Examples] This photopolymerizable lithographic printing plate was applied to an FD / YAG laser (Fuji Photo Film Co., Ltd.).
Made Luxel Plate Setter P-960
0 CTP NEWS) with an exposure amount of 150 μJ / cm ² and scanning exposure of a solid image and a 1-99% halftone dot image (in 1% increments) under the condition of 100 lines / inch at 909 dpi. ． The automatic development device shown in (the processing width is 0.8
m), and preheated to the conditions shown in Table 1 below.
Pre-washing, development, washing, and finishing were appropriately performed.
In this example, the post heat treatment was omitted. Pre-heating temperature is 10
0 ° C, preheating time is about 10 seconds. Developer temperature is 25 ° C,
The immersion time in the developing solution was about 22 seconds. Washing part liquid temperature is room temperature, washing process time is 7 seconds, finishing liquid temperature is room temperature,
Finishing time is 5 seconds, drying section is 50 ° C, 10
It was seconds.

(Water Replenishing Amount by Replenishing Pump P2b of Pre-Washing Section) 70 cc (same as 100 cc / m ² ) every time plate detection signal is given (composition and concentration of solution in stock tank T2 of pre-washing section) Preservative: Pyridinethiol-1-oxide 1000 ppm aqueous solution (replenishing amount of preservative solution by replenishing pump P2a in the pre-washing section and concentration of preservative at the time of replenishment) 30 cc for every 20 plates detected (same as about ² cc / m ² It becomes 20 ppm because it is mixed with 100 cc / m ² of water. (Composition and amount of developer initially charged) DV-1 (manufactured by Fuji Photo Film Co., Ltd.) 10 wt% water 90 wt% Charge amount 20 liters (development replenisher stock solution storage tank T3 as composition and replenisher) Composition) DV-1R (manufactured by Fuji Photo Film Co., Ltd.) 10 wt% water (supplemented by replenishment pump P3b) 40 wt% (development replenisher replenishment amount) 70 cc (100 cc / m ² same as plate detection signal) Replenishment rate according to the elapsed time when the power is turned on 150 cc / hour Replenishment rate according to the elapsed time when the power is turned off 20 cc / hour (Water replenishment rate by the replenishing pump P4b in the washing section) 70 cc (100 cc / m ² ) every time a plate detection signal is issued. (The same as the above) (Composition and concentration of solution in additive storage tank of water washing part) Preservative: Pyridinethiol-1-oxide 20000ppm Agents: the SM-5512 (trade name Toray Silicone Co. Porijimechi Le siloxane-containing emulsion) 10000 ppm (replenishing amount of additive solution according replenishing pump P4a of washing section) Version detection 20 sheets each in 10 cc (about 0.7 cc / m ² Same) (Composition of solution in stock tank of finishing liquid and composition at the time of replenishment) FP-2W (manufactured by Fuji Photo Film Co., Ltd.) 10 wt% water (by replenishing pump P5b) 30 wt% (replenishing pump for finishing liquid) Amount of replenishment by P5a and P5b) 35 cc (same as 50 cc / m ² each time plate detection signal is sent)

In the above example, 10 per day for one month
When 0 plates were processed, a high quality printing plate was obtained without any foreign matter on the plate surface. In addition, no bubbles or scales are generated in each processing unit during processing, and the processing tank of each processing unit after one month is free from sedimentation, mold, and other stains, so the equipment can be cleaned in a short time. done.

Comparative Example The replenishing device and the control device of the automatic developing device used in the above-mentioned examples were changed to the conventional type shown in FIG. 5, and a preservative: 500 ppm aqueous solution of pyridinethiol-1-oxide was added as an additive. After charging the stock tank and processing the printing plate under the same period and conditions as in the example,
Although a high quality printing plate was obtained without foreign matter on the plate surface,
Foaming was so severe in the water wash section that an antifoaming agent had to be added manually. In addition, when the treatment tanks of each treatment unit were inspected one month later, a large amount of water stains had adhered to the inner wall of the treatment tank because the concentration of the preservative to be replenished as the pre-water washing unit was insufficient. It took a long time to wash. It is considered that the preservatives could be prevented by increasing the concentration, but this would wastefully supply them to the washing section and the finishing section. As described above, the conventional developing apparatus, which does not have two replenishing pumps in each processing section, is difficult to use.

[0069]

As described above, in the automatic developing machine for a lithographic printing plate of the present invention, the number of replenisher replenishing pumps for each processing tank is set to two or more, so that a trouble occurs in each processing tank. Since it is possible to realize the optimum additive composition to prevent the development, the development quality of the printing plate will not be impaired, and there will be no bubbles during processing and no stains such as water stains or mold on the inner wall of the processing tank. You can keep the consumption of as much as you need,
Since the equipment can be easily cleaned, it is possible to provide a processing environment that is very easy to use.

[Brief description of drawings]

FIG. 1 is a diagram showing a structural example of a first pre-heating unit and a pre-water washing unit of an automatic developing apparatus including each processing unit according to the present invention.

FIG. 2 is a diagram showing a structural example of a developing unit according to the present invention connected to the downstream side of FIG.

3 is a diagram showing a structural example of a water washing section and a finishing section according to the present invention, which are connected to the downstream side of FIG.

FIG. 4 is a diagram showing a structural example of a drying unit and a post-exposure unit according to the present invention, which are connected to the downstream side of FIG.

FIG. 5 is a diagram showing an example of the structure of a conventional automatic developing device including each processing unit.

[Explanation of symbols]

1 Pre-heating section 11a, 11b transport rolls 12 heater 13 Transport guide 14a, 14b Transport rolls 15 Blower fan 2 front water washing section 20 water washing tank 21a, 21b transport rolls 22 Washing water discharge spray 23 Pre-washing brush roll 24 Transport guide 25a, 25b transport rolls 26 Circulation pump 3 development department 30 developer tank 31a, 31b transport rolls 32, 35 transport guide 33a, 33b Development brush 34 transport rolls 36a, 36b Transport roll 37 Floating lid 38 Circulation pump 39a Liquid temperature heater 39b Cooling device 39c Development spray 39d measurement sensor 4 Washing department 40 water washing tank 41, 41b Transport roll 42 Transport guide 43 Flushing water supply spray 44 Washing brush roll 45a, 45b transport rolls 5 Finishing section 50 finishing tank 51 Finishing liquid supply spray 52a, 52b transport rolls 53 Circulation pump 6 Drying section 62 hot air duct 63 Conveyor roll 7 Post exposure section 71 Ultraviolet (UV) lamp 73a, 73b Transport rolls 8 Replenishing device 81 Replenisher hose 9 Control device 91 Microcomputer 92 storage device 100 sensors S version P2a, P2b to P5a, P5b replenishment pump T1 water storage tank T2-T5 replenishment tank

Claims (6)

[Claims] 1. At least a developing section and a washing section,
A lithographic printing plate developing apparatus for automatically developing a lithographic printing plate, comprising: a developing tank and a washing tank respectively provided in the developing section and the water washing section, wherein at least two types are provided in each tank. 2. An automatic developing device for a lithographic printing plate, comprising two or more processing liquid replenishing pumps for replenishing the above liquid in the vicinity of each tank. 2. A pre-water washing unit having a pre-heat treatment section for heating a photosensitive layer, or a treatment tank provided with two or more treatment liquid replenishing pumps and replenishing two or more types of liquids by the treatment liquid replenishing pumps. 2. The automatic developing device for a lithographic printing plate as claimed in claim 1, wherein a part is provided in the preceding stage of the developing tank. 3. The automatic developing device for a lithographic printing plate as claimed in claim 1, wherein the two kinds of liquids to be replenished in the pre-washing section or the washing section are solutions containing water and a preservative. 4. The lithographic printing plate according to claim 1, wherein the two kinds of liquids to be replenished in the pre-washing section or the washing section are solutions containing water and an antifoaming agent. Automatic developing device. 5. A lithographic printing plate developing method in which a lithographic printing plate is automatically developed by passing through a lithographic printing plate at least in a developing tank of a developing section and a washing tank of a water washing section, wherein each tank comprises water and a solution containing a preservative. In a lithographic printing plate development method in which at least two kinds of liquids are replenished, a photopolymerizable photosensitive composition comprising an ethylenically unsaturated compound, a photopolymerization initiator and a polymer binder is used as the lithographic printing plate. An automatic developing method for a lithographic printing plate, comprising using a photopolymerizable lithographic printing plate contained in a photosensitive layer. 6. A lithographic printing plate developing method for automatically performing development processing by passing a lithographic printing plate through at least a developing tank of a developing section and a washing tank of a water washing section, wherein each tank comprises water and a solution containing a preservative. An lithographic printing plate developing method of replenishing at least two kinds of liquids, wherein the developing tank is replenished with a developing replenishing stock solution and a solution containing dilution water and a surfactant.