JP2001166488A - Plate making method for planographic printing plate and automatic developing machine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a plate making method for planographic printing plates which allows the always adequate setting of at least one regulation conditions among the replenishing amount of a removing liquid, temperature of the removing liquid and removing process time when removing an oxygen shielding layer according to the sizes and kinds of the PS plates provided with photopolymerization layers having the over-coating layers on the uppermost layers and eliminates the possibility of operation errors, etc., in the removing process of over-coating layers to be executed before the development processing of the PS plates. SOLUTION: A processor control section 30 of an automatic developing machine 16 online acquires various kinds of set information on the kinds, sizes, etc., of the PS plates inputted to a plate setter 14, determines the removal conditions for the over-coating layers in accordance with various kinds of the acquired set information and regulates the replenishing amount of the washing water, the temperature of the washing water and the process time in such a manner that the determined removal conditions may be attained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for making a lithographic printing plate and to an automatic developing machine.
A method of making a lithographic printing plate capable of so-called direct plate making,
And an automatic developing machine.

[0002]

2. Description of the Related Art In general, a photosensitive lithographic printing plate (hereinafter referred to as "PS
Plate) is a photosensitive lithographic printing plate processing apparatus (hereinafter referred to as “P”).
S "processor").
The developing process in the PS plate processor is performed by immersing the PS plate on which the image is recorded in the developing solution stored in the developing solution while transporting the PS plate into the developing solution, and rubbing with a rotating brush roller or the like provided in the developing solution. This is performed by removing the photosensitive layer in the non-image portion of the PS plate.

[0003] The PS plate that has been processed with the developer is washed with washing water in a washing section (washing treatment), and then subjected to a desensitizing treatment by applying a gum solution in a desensitizing section. Then, the processing such as the plate surface protection is continuously performed.

As the photosensitive layer of the PS plate, diazo resin,
A photocrosslinking type and a photopolymerization type are used. Above all, the polymerization reaction of the photopolymerizable photosensitive layer is inhibited by oxygen in the air. Therefore, in general, an oxygen barrier layer is provided on the photopolymerizable photosensitive layer to prevent the polymerization reaction from being inhibited. are doing.

In the prior art, since the oxygen-blocking layer is removed simultaneously with the development, the life of the developer is significantly shortened, and the developing layer is replenished in order to perform sufficient development processing. There is a disadvantage that it is necessary to increase the replenishment amount of the replenisher.

Therefore, there has been proposed a method of removing the oxygen barrier layer on the PS plate before development. In this method, before the development of the PS plate, the PS plate is immersed in a removing liquid such as water, or the surface of the PS plate is rubbed with a rubbing means such as a rotating brush roller while immersed in the removing liquid, so that the oxygen barrier property is improved. Remove the layer.

According to this method, since the oxygen-blocking layer is removed before development, it is not necessary to increase the replenishment amount of the developer, and there is no possibility that the life of the developer is significantly shortened. It is becoming mainstream.

[0008]

However, in the prior art, the oxygen barrier layer is removed under certain conditions regardless of the amount of the oxygen barrier layer to be removed. Therefore, although the plate size is small and the amount of the oxygen-blocking layer to be removed is small, the removing solution is replenished in accordance with the PS plate having a large plate size, and the removing solution is wasted by that amount. In some cases, an incomplete removal process in which the removal process of the oxygen-barrier layer is terminated even if the insulating layer is not completely removed.

In the case of excessive treatment, the PS plate which does not need to remove the oxygen barrier layer is treated with a large amount of the removing liquid, so that the removing liquid is wasted and the amount of waste liquid is reduced. When the amount becomes unnecessary, or when a rubbing member such as a rotating brush roller is provided in the removal tank, the photopolymer layer on the lower layer side of the oxygen barrier layer is rubbed by the rubbing member, thereby deteriorating the quality of the plate. There is fear. In addition, when the incomplete removal treatment is performed, a portion of the oxygen-blocking layer that has not been removed is removed in a subsequent development step, so that there is a problem that the life of the developer is shortened.

Furthermore, in recent years, there has been an increasing demand for energy saving, and it has become an important issue to eliminate wasteful use of the removing liquid and to reduce the running cost of the apparatus.

From the above, the present invention provides a method of making a lithographic printing plate in which the conditions for adjusting the removal of the oxygen-blocking layer applied to the PS plate before development can always be appropriately set according to the PS plate to be processed. , And an automatic developing machine.

[0012]

In order to achieve the above object, the invention of claim 1 is to provide a lithographic printing plate having an oxygen barrier layer on the uppermost layer and a photopolymerizable photosensitive layer on the lower side. After exposure based on the data, the oxygen-blocking layer is removed by a removing solution, and a plate-making method of a lithographic printing plate for further developing, wherein a replenishing amount of the removing solution when removing the oxygen-blocking layer, At least one condition for adjusting the temperature of the removal liquid and the removal processing time is determined based on the plate information used in the previous step.

According to a second aspect of the present invention, there is provided an automatic developing machine suitable for the method of making a lithographic printing plate according to the first aspect of the present invention. Before the development of the lithographic printing plate having a polymerizable photosensitive layer, the lithographic printing plate is transported into a removing tank, and a removing means for removing the oxygen barrier layer with a removing solution supplied into the removing tank; Condition determining means for determining adjustment conditions for removing the oxygen-barrier layer based on the plate information used in the apparatus, and a removing liquid supplied to the removing tank so that the adjusting conditions are determined by the condition determining means. Adjusting means for adjusting at least one of the replenishing amount, the temperature of the removing solution, and the processing time.

In other words, according to the first and second aspects of the present invention, before developing an exposed lithographic printing plate having an oxygen-blocking layer on the uppermost layer and a photopolymerizable photosensitive layer below the oxygen-blocking layer, Determining at least one adjustment condition of the replenishing amount of the removing solution to be added to the removing tank, the temperature of the removing solution, and the processing time when removing the oxygen barrier layer based on the plate information used in the previous step. I do. Then, after adjustment is made so as to satisfy the adjustment conditions, a removal process is performed, and then development is performed.

As the plate information, at least one of a plate size and a plate type can be used.

Since the larger the plate size, the larger the amount of the oxygen-blocking layer, the replenishing amount of the removing solution is increased as the plate size increases, and conversely, decreased as the plate size decreases. It can be determined according to the size of the plate size.

[0017] With this, the replenisher is replenished in a replenishing amount corresponding to the amount of the remover necessary for removing the oxygen-blocking layer of the lithographic printing plate to be actually processed. The amount of waste liquid can be reduced without wasting.

The temperature of the removing solution can be determined by using a predetermined temperature for each type of plate used in the preceding step.

Further, the removal processing time can be determined in advance for each plate type. The removal processing time can be adjusted by controlling the transport speed of the lithographic printing plate.

Since such adjustment conditions are determined by using the version information used in the previous step, there is no need for the user to input the adjustment conditions, and therefore, the user is prevented from forgetting to change or input mistakes. Eliminate operation mistakes. Therefore, it is possible to always determine the optimum adjustment condition for the planographic printing plate to be removed.

As described above, according to the first and second aspects of the present invention, at least one of the replenishing amount of the removing solution, the temperature of the removing solution, and the removing processing time is determined based on the plate information used in the preceding step.
In order to determine the two adjustment conditions, the oxygen barrier layer can be removed in accordance with the lithographic printing plate that is actually being processed.

If the type of the lithographic printing plate currently being removed is different from the type of the lithographic printing plate to be removed next, the lithographic printing plate currently being processed is processed during or before the lithographic printing plate being processed. Adjustment conditions suitable for the type of lithographic printing plate to be processed next are determined in advance, and after the processing of the lithographic printing plate currently being processed, the adjustment conditions are immediately adjusted to the type of lithographic printing plate to be processed next. It can be configured to change to the adjusted condition. As a result, the waiting time can be reduced, which is efficient.

The "previous step" is a step before removing the oxygen-blocking layer, and is one or more steps selected from a plurality of steps before removing the oxygen-blocking layer. is there. As the plate information, the information used in the previous step may be used. For example, the plate type used in the exposure step and the plate size used in the step before the exposure step may be used. Such as those used in a plurality of previous steps may be used.

Before removing the oxygen barrier layer, the lithographic printing plate may be heated. In this case, since the surface temperature of the lithographic printing plate before the development processing is made uniform, it is possible to prevent the reaction unevenness due to the ambient temperature and the time difference after the exposure, to improve the printing durability of the photosensitive layer, and to improve the halftone dot. Can be formed uniformly, so that plate making with better image quality can be obtained.

[0025]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. In the present embodiment,
As shown in FIG. 1, a personal computer 10, a workstation 1
2. A case where the present invention is applied to a plate making system including a plate setter (exposure device) 14 and a PS plate processor (automatic developing machine) 16 will be described.

The photosensitive lithographic printing plate (hereinafter, referred to as PS plate) used in the present embodiment has an organic undercoat layer on the surface of an aluminum support having a back coat layer on the back surface, and a photopolymerizable photosensitive layer. An optical layer and an overcoat layer (oxygen barrier layer) are sequentially provided. The details of the PS plate will be described later.

The plate making system according to the present embodiment includes a personal computer 10, a work station 12, a plate setter 1
4 and the PS version processor 16 are all connected online, and the image data input to the personal computer 10 and the
Plate information such as plate thickness, plate size, and PS plate type (plate type) can be output online as various setting information to the plate setter 14 and the PS plate processor 16.

The personal computer 10 includes, for example, an application for editing an image read from an image reading means such as a scanner while displaying the image on a display, or creating a new character or image on the display and creating an image to be printed. Is installed.

This application outputs an image created by a user to the workstation 12 as vector-format image data such as an outline, a drawing command for designating an area ratio of a filled area, a transmittance of a filled area, and the like. I do. Further, various setting information such as the type, thickness and size of the PS plate to be exposed, which is input by the user from the keyboard at the same time as the creation of the image, is converted into text data together with the vector format image data. Output to the workstation 12.

The workstation 12 has a raster image processor (hereinafter, referred to as RIP) and driver software for the platesetter 14 installed therein.

The RIP interprets vector-format image data and develops it as an array of dots having gradations.
FF format file (hereinafter referred to as TIFF file)
In this embodiment, the image data is converted from a vector format image data into a TIFF file including a tag format header portion and an image data portion.

The driver software of the plate setter 14 is a TIFF file and a PS version in a text format.
This is software that converts various setting information such as plate thickness and plate size into an image format that can be analyzed by the platesetter 14, and outputs the image format to the platesetter 14.

Therefore, the workstation 12 converts the vector-format image data such as the drawing command input from the personal computer 10 into a TIFF file, and then converts the TIFF file and the PS plate into a plate type, a plate thickness, a plate size, and the like. Various setting information of the plate setter 1
4 is converted into an image format that can be analyzed by the platesetter 14, and then output to the platesetter 14.

The plate setter 14 includes a ROM and a RAM.
And a setter control section 18 composed of a CPU.
Various programs for controlling the plate setter 14 are stored in the ROM, and a TIFF in an image format that can be analyzed by the plate setter 14 is stored in the RAM.
The file and various setting information are temporarily stored.

The CPU calls various programs from the ROM, and reads T from the RAM based on the programs.
Based on the IFF file and the various kinds of setting information described above, for example, a control signal for controlling a transport speed of a transport unit (not shown) of the plate setter 14, an on / off drive signal of a laser light source (not shown), and a light amount A variety of control signals such as a laser drive signal for performing the adjustment are generated, and the driving of the platesetter 14 is controlled by the various control signals. As a result, the plate setter 14 can use the personal computer 1
The exposure processing of the PS plate is performed under the optimum adjustment condition according to the image selected on the image plane 0.

As the plate setter 14, an external drum (outer drum) type, a flat bed type, or an inner drum type can be used. Above all, an ultraviolet to visible light region (360 nm to 450 nm)
nm) of an inner drum type plate setter using a semiconductor laser. The semiconductor laser of this inner drum type plate setter includes I
An nGaN-based semiconductor laser is preferable. By adopting such a configuration, even in the case of an inner drum type plate setter, the occurrence of fog can be reduced and the exposure amount can be increased, so that there is an advantage that the printing durability can be improved.

Although the reason is not clear, it can be estimated as follows. That is, the laser light that cannot be absorbed by the photosensitive layer of the PS plate is emitted as reflected light from the surface of the PS plate. The longer the wavelength of the reflected light, the higher the regular reflection efficiency, and the shorter the wavelength of the reflected light, the shorter the wavelength. , And the specular reflection efficiency is reduced. Therefore, by using an inner drum type plate setter using a semiconductor laser in the ultraviolet to visible light region, it is considered that the regular reflection efficiency is reduced and the occurrence of fog due to the regular reflected light is suppressed to a low level.

As a light source to be used, the above-mentioned I
Ultraviolet to visible light region such as nGaN semiconductor laser
(360 nm to 450 nm) semiconductor lasers, for example, 488 nm or 514.5 nm Ar lasers, 532
The use of an FD-YAG laser of nm or the like is preferable in terms of output, life, stability, cost, and the like. In addition, since the exposure processing of the plate setter 14 is publicly known, detailed description is omitted here.

Further, the driver software of the PS plate processor 16 is installed in the ROM of the setter control unit 18, and various setting information such as plate type, plate thickness, and plate size are stored in the driver software of the PS plate processor 16. After that, the data is converted into a format that can be analyzed by the PS plate processor 16 and output to the PS plate processor 16 together with the PPF data.

As shown in FIG. 2, the PS plate processor 16 is roughly divided into a heating section 20, a first washing section 22, a developing section 24, a second washing section 26, a finisher section 28, a drying section 29, and a processor control section. The PS plate is moved from the heating unit 20 to the first washing unit 22, the developing unit 24, the second washing unit 26, the finisher unit 28, and the drying unit 29 by a transport mechanism including a plurality of pairs of transport rollers. Are transported in this order.

The heating unit 20 includes a pair of pull-in rollers 31 to which the driving force of a driving unit (not shown) is transmitted, and a heating device 32.
The pull-in roller pair 31 pulls the PS plate 110 into the PS plate processor 16 by rotating along the transport direction of the PS plate 110 while holding the exposed PS plate 110 therebetween. The heating device 32
PS version 11 drawn inside S version processor 16
Heat 0.

By heating the PS plate 110 before the development processing, the curing of the image forming area (that is, the exposed area) in the photopolymerizable photosensitive layer of the PS plate 110 is promoted. In the present embodiment, the various setting information for determining the heating condition of the heating unit 20 is also acquired online from the preceding device, temporarily stored in the RAM, and then based on the stored various setting information. The heater drive voltage is controlled.

As a result, the surface temperature of the PS plate is adjusted under the optimum heating conditions for the combination of the type, thickness and size of the PS plate 110, and the temperature in the exposed portion of the plate setter 14 or the temperature before the heat treatment. The uniformity can be achieved irrespective of the temperature of the PS plate 110, problems such as insufficient heat treatment and excessive heat treatment can be eliminated, and favorable heat treatment can be performed.
Further, since there is no need for the user to input various setting information, it is possible to avoid the occurrence of loss due to an operation error or the like, and it is possible to efficiently switch to the next heating condition. Efficiency can also be improved.

In the heating section 20, the heat-treated PS
The plate 110 is provided with a first washing unit (removing means) provided at a later stage.
22.

The first washing section 22 has a first washing tank (removal tank) 60 as shown in FIG. First washing tank 60
Contains cleaning water (removal liquid), and a temperature adjusting device for adjusting the temperature of the cleaning water is provided in the tank. As the washing water, here, water (tap water or pure water having a low impurity content) is used, but if necessary,
Those to which a surfactant, a preservative and the like are added can also be used.

The temperature control device includes a heater 34a, a chiller 3
4b, and a temperature sensor 34c. Based on the temperature detected by the temperature sensor 34c, one of the heater 34a and the chiller 34b is driven by an instruction signal output from the processor control unit 30 described later, and The temperature is adjusted so that the temperature becomes an optimum temperature according to the type of the PS plate 110 to be processed.

Further, a first overflow pipe 61 is provided in the first washing tank 60, and when the liquid level of the washing water accumulated in the tank exceeds a predetermined level, the first overflow pipe 61 is provided. Waste liquid tank 80 flowing into 61
And adjusted so that the liquid level in the tank is always constant.

The first washing tank 60 has a PS plate 110
And a replenishing cylinder 64c, a first water supply nozzle 64a, a first rotating brush roller 66, a backup roller 67, a second water supply nozzle 64b, a conveyance roller pair 68, and a conveyance roller 68. A delivery roller pair 72 is provided.

Wash water is supplied to the first water supply nozzle 64a and the second water supply nozzle 64b from a pipe line 37 provided with a circulation device constituted by a pump P4 and a filter F. One end of the conduit 37 is open at the bottom of the first washing tank 60, and the other end is bifurcated and connected to the first water supply nozzle 64 a and the second water supply nozzle 64 b. The cleaning water is pumped up by the pump P4 and supplied to the first water supply nozzle 64a and the second water supply nozzle 64b to circulate the cleaning water.

The replenishing cylinder 64c is connected to a water storage tank 84 which will be described later, and replenishes the first washing tank 60 with clean washing water from the water storage tank 84 by a replenishing pump P1. The driving of the refill pump P1 is controlled by the processor control unit 30.

In this embodiment, the clean water from the water storage layer 84 is used as the replenishing washing water.
A washing water replenishing layer storing the replenishing washing water may be separately provided. The replenishing washing water includes a first washing tank 60
Water (tap water or pure water having a small content of impurities) or water obtained by adding a surfactant, a preservative, or the like can be used in the same manner as the washing water in the above.

The two pairs of transport rollers 62 and 68 are provided above the first washing tank 60 and form a transport path for the PS plate 110. The transport rollers 62 and 68 rotate under the driving force of a driving unit (not shown). The PS plate 110 sent from the heating unit 20 is nipped and conveyed.

The first water supply nozzle 64a supplies cleaning water to the first water supply nozzle 64a.
It is supplied to the PS plate 110 before being rubbed by the rotating brush roller 66. The first rotating brush roller 66 is paired with the first backup roller 67, and removes the uppermost overcoat layer by polishing the surface of the PS plate 110 being transported. Further, the second water supply nozzle 64b supplies cleaning water to the PS plate 110 after being rubbed by the first rotating brush roller 66.

In addition, clean water for replenishment is stored in the water storage tank 84. In addition to the second water supply nozzle 64b, the dilution water injection nozzle 7 for replenishing water for dilution into the developing tank 70 is provided.
6 and a second spray pipe 96 for refilling water in the second washing tank 90 are connected.

The processor control unit 30 (condition determining means,
The adjusting means) includes a CPU, a ROM, and a RAM. Various setting information and PPF data obtained online from the plate setter 14 are temporarily stored in the RAM. The ROM controls the replenishment amount of the washing water to be supplied to the first washing section 22, the temperature of the washing water, and the washing time (removal time) based on at least one of the plate size and the plate type included in the various setting information. A condition adjustment program, a replenishment amount Q corresponding to the plate size, a processing temperature corresponding to the plate type, and a processing time corresponding to the plate type are stored.

The replenishment amount Q stored in the ROM is, for example,
The standard replenishment amount Q1 for a medium plate of 650 mm × 550 mm in height and width, the replenishment amount Q2 (Q1> Q2) for a small plate of 254 mm × 391 mm in height and width, and 113 for height and width.
For a large plate of 0 mm x 930 mm, the replenishment amount Q3 (however,
Q3> Q1),... Are determined for each plate size. The plate size and the replenishment amount Q are examples, and the present invention is not limited to these.

The processing temperature is stored in the ROM in advance for each plate type, for example, 30 ° C. for plate type A, which is a high printing life product, 25 ° C. for plate type B, which is a normal product. The processing temperature is the same as that of commonly used photopolymer CT.
For P, a temperature range of 20 ° C. to 45 ° C., preferably 2 ° C.
It can be set within a temperature range of 5 ° C. or more and 35 ° C. or less.

The processing time is, for example, 30 seconds for plate type A, which is a high printing durability product, at a transport speed of 760 mm / min, and 20 seconds for plate type B, which is a normal product, at a transport speed of 1000 mm / min.
For example, seconds,... Are stored in the ROM in advance for each version type. The processing time of the commonly used photopolymer CTP can be determined in the range of 5 seconds to 120 seconds, preferably in the range of 7 seconds to 60 seconds.

As the plate type, for example, a newspaper PS
Plate, a high printing plate, a high quality PS plate, and the like. The present invention is not limited to only the processing temperature and the processing time corresponding to the plate type A and the plate type B described above. It may be determined for each version type.

The CPU calls the condition adjustment program stored in the ROM, obtains various setting information online from the plate setter 14, which is the apparatus at the preceding stage, and acquires the various setting information in the RAM.
After that, the replenishment amount of the washing water is determined based on the plate size included in the various setting information stored in the RAM, and the temperature of the washing water is determined based on the plate type stored in the RAM.
Each adjustment condition of the cleaning time (removal time) is determined, and the replenishing pump P1, the temperature adjusting device,
And the transport mechanism.

Here, the CPU of the processor control unit 30
Will be described with reference to the flowchart of FIG. First, in step 100, R
Read various setting information from AM. Next step 102
Then, it is determined whether or not the various setting information includes the plate size. When it is determined that the plate size is included in the various setting information, the process proceeds to step 104, and when it is determined that the plate size is not included, the process proceeds to step 112.

At step 104, the replenishment amount corresponding to the plate size is read from the ROM, and the routine proceeds to step 106. If the size of the plate read from the preceding device is medium, Q1 is read, if it is small, Q2, if it is large, Q3, ROM
Read from On the other hand, if the plate size is not included in the various setting information, the standard replenishment amount Q1 is
After reading from M, the process proceeds to step 106.

In step 106, a drive signal for the replenishing pump P1 is generated and output to the replenishing pump P1 so that the replenishing amount of washing water read from the ROM is supplied from the second water supply nozzle 64b.

In the next step 108, it is determined whether or not the various kinds of setting information include the version type. If it is determined that the version type is included in the various setting information, the process proceeds to step 110, and if it is determined that the version type is not included, step 11 is performed.
Move to 4.

In step 110, first, the processing temperature and processing time corresponding to the plate type are read from the ROM. In other words, the plate type read from the preceding device is a high printing
, The processing temperature is 30 ° C. and the transport speed is 760 mm /
Minutes and a processing time of 30 seconds, and for plate type B which is a normal product, the processing temperature is 25 ° C. and the transport speed is 1000 mm /
Minutes and processing time are 20 seconds.

Thereafter, the temperature adjusting device (the heater 34a and the chiller 34b) is controlled based on the temperature from the temperature sensor 34c provided in the first washing tank 60 so that the washing water in the first washing tank 60 becomes the read temperature. ) And PS
After the transport speed of the PS plate 110 by the transport mechanism, that is, the number of rotations of each transport roller, is controlled so that the plate is immersed in the cleaning water for the read processing time, the routine ends.

In step 114, a standard processing temperature (25 ° C.) and processing time (20 seconds at 1000 mm / min)
Is read from the ROM, and a temperature adjusting device (the heater 34a and the chiller 34a) in the first washing tank 60 is adjusted so as to reach the temperature.
b) and controlling the PS plate 1 by the transport mechanism so that the PS plate is immersed in the cleaning water for a treatment time corresponding to the type of the plate.
After controlling the transfer speed of No. 10, the present routine ends.

Although the standard processing temperature is set at 25 ° C. here, the standard processing temperature is generally a temperature at which the overcoat can be removed. The standard processing time is 1000 mm / min for 20 seconds, but the standard processing time is generally a time during which overcoat removal processing is possible.

As described above, the first water washing section 22 controls the temperature adjusting device based on the plate information obtained from the plate setter 14 to obtain various setting information online so that the temperature becomes optimum for the PS plate to be processed. At the same time, the number of rotations of each transport roller is controlled so that the immersion time is reached, the PS plate 110 is drawn in by the pull-in roller pair 62, and the washing water is supplied from the first water supply nozzle 64a to the surface of the PS plate 110,
After rubbing with the first rotating brush roller 66, scum and the like rubbed off by the brush roller 66 are removed from the PS plate 110 with clean cleaning water supplied from the second water supply nozzle 64 b, and the cleaning water is transferred by the transport roller pair 68. And PS version 1
10 is delivered to the delivery roller pair 72. The feed roller pair 72 sends out the PS plate 110 that has been subjected to the water-washing process to the developing unit 24 provided at a stage subsequent to the first water-washing unit 22.

As shown in FIG. 2, the developing section 24 includes a developing replenisher stock solution injection nozzle 74, a dilution water injection nozzle 76, and a first The developing device includes a spray pipe 78, a second rotating brush roller 71a, a third rotating brush roller 71b, and a delivery roller pair 75, and performs development processing by immersing the PS plate 110 in a developing solution.

The PS plate 110 delivered by the delivery roller pair 72 of the first washing section 22 is drawn into the developing section 24 at an angle in the range of about 15 ° to 31 ° with respect to the horizontal direction. The developing replenisher stock injection nozzle 74 injects the developing replenisher stock pumped up from the developing replenisher stock reservoir 82 by the developing replenisher stock pump P2 into the developing tank 70. The drive of the developing replenisher stock solution replenishing pump P2 is controlled by the processor controller 30.

Similarly, the dilution water injection nozzle 76 injects the dilution water pumped up from the water storage tank 84 by the water replenishing pump P3 into the developing tank 70. The drive of the water replenishment pump P3 is also controlled by the processor control unit 30.

The processor control unit 30 controls the ratio of the amount of the developing replenisher stock solution jetted from the developing replenisher stock jet nozzle 74 to the amount of the dilution water jetted from the dilution water jetting nozzle 76 to a predetermined ratio. The drive of the development replenisher stock solution replenishment pump P2 and the water replenishment pump P3 is controlled.

A liquid surface cover 73 is arranged on the developer liquid surface of the developing section 24. The liquid surface cover 73 is arranged so that the lower surface is lower than the liquid surface of the developer stored in the developing tank 70. The liquid level cover 73 allows the developing tank 70
The area where the liquid level of the developing solution in the inside comes into contact with air is narrowed, thereby suppressing the deterioration of the developing solution and the evaporation of moisture in the developing solution due to carbon dioxide in the air.

In the developing tank 70, a second overflow pipe 7 for collecting the developing solution overflowing from the developing tank 70 is provided.
When the liquid level of the developer accumulated in the developing tank 70 exceeds a predetermined level, the developing liquid flows into the second overflow pipe 79, is guided to the waste liquid tank 80, and the developing tank 70 is provided. Is adjusted so that a constant amount of the developing solution is always held in the inside.

In the developing solution in the developing tank 70, there is provided a guide plate 77 having a substantially inverted mountain shape with an inner surface protruding downward at the center of the bottom. The guide plate 77 has a configuration in which a plurality of freely rotating rollers (small rollers; not shown) are arranged with their rotating shafts arranged in parallel in a direction orthogonal to the transport direction of the PS plate 110. The fed PS plate 110 is transported while being guided by rollers. At this time, since the rollers rotate, the PS plate 110 is not damaged by sliding.

A first spray pipe 78 is provided in the developing solution on the way to the lowest position of the guide plate 77. The first spray pipe 78 is composed of a plurality of spray pipes arranged along a direction orthogonal to the transport direction of the PS plate 110, and sprays a developer from each spray pipe onto the surface of the PS plate 110, thereby forming a PS. Edition 11
In addition to promoting the development process of No. 0, it plays a role of circulating the developer in the developing tank 70.

The second rotary brush roller 71a and the third rotary brush roller 71a are located at positions corresponding to the upper surface of the PS plate 110 along the downstream side from the lowest position of the guide plate 77.
The second rotating brush roller 71a and the third rotating brush roller 71b are driven by driving means (not shown) to rotate in the transport direction of the PS plate 110.

At the final stage position of the developing section 24, there is provided a pair of delivery rollers 75 having a clamping section disposed above the liquid level of the developing solution.
, Sandwiches the PS plate 110 conveyed along the guide plate 77 provided in the developing solution and sends it out from the developing unit 24.
At this time, the developer adhering to the surface of the PS plate 110 is squeezed.

That is, the PS plate 110 sent out from the first rinsing section 22 is supplied to the delivery roller pair 72 of the developing section 24.
Is drawn into the developing unit 24 at an angle in the range of about 15 ° to 31 ° with respect to the horizontal direction, and is conveyed along the surface of the guide plate 77 provided in the developing solution. At this time, PS
The plate 110 is immersed in the developing solution, and then the undeveloped portion of the photopolymerizable photosensitive layer is reliably swollen by the developing solution sprayed by the first spray pipe 78 provided on the way to the lowest position of the guide plate 77. (Ie, developed).

When the PS plate 110 moves downstream from the lowest position of the guide plate 77, the second rotating brush roller 71a,
The surface is rubbed in the order of the third rotating brush roller 71b, and the undeveloped portion of the swollen photopolymerizable photosensitive layer is rubbed off. Further, the PS plate 110 is pulled out from the developing solution by being held by the feed roller pair 75 from the final end position of the guide plate 77, and the developing solution attached to the front and back surfaces when being sent to the feed roller pair 75 is squeezed. And the developing unit 24
To the second washing section 26 provided at the subsequent stage.

Here, the developer suitable for the present invention will be described below.

(Alkali agent) The developer and the developing replenisher used in the developing step are preferably an alkaline aqueous solution having a pH of 9.0 to 13.5, more preferably 10.0 to 13.3.

As such a developing solution and a developing replenishing solution, conventionally known alkaline aqueous solutions can be used. For example, sodium silicate, potassium, tribasic sodium, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium bicarbonate, potassium, ammonium, sodium carbonate, potassium, potassium Inorganic alkaline agents such as ammonium, sodium bicarbonate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, ammonium, potassium, and lithium. Also, 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.

Preferred among these alkaline agents are aqueous solutions of silicates such as sodium silicate and potassium silicate. The reason is that silicon oxide Si
The ratio of O ₂ to alkali metal oxide M ₂ O (generally [SiO 2
₂ ] / [M ₂ O] molar ratio) and the concentration allow adjustment of pH and developability. For example, Si
When the molar ratio of O ₂ / K ₂ O is 0.5 to 2.0 (that is, [Si
O ₂ ] / [K ₂ O] is 0.5 to 2.0) and SiO 2
Alkali metal silicate comprising an aqueous solution of potassium silicate having a content of ₂ to 4% by weight is suitably used in the present invention. Still another preferred alkaline agent includes a buffer solution comprising a weak acid and a strong base. . The weak acid used as such a buffer includes an acid dissociation constant (pKa) of 10.0 to 1
Those having 3.3 are preferred, and particularly those having a pKa of 11.0 to 1.0.
13.1 is preferred. In the case of sulfosalicylic acid, for example, the third dissociation constant is 11.7, which can be suitably used in the present invention. That is, in the case of a polybasic acid, it can be used in the present invention if at least one acid dissociation constant is within the above range.

[0086] Such weak acids include Pergamo.
IONISATION CON issued by nPress
STANTS OF ORGANIC ACIDS I
Selected from those described in NAQUEOUS SOLUTION, etc., for example, 2,2,3,3-tetrafluoropropanol-1 (pKa 12.74), trifluoroethanol (12.37), and trichloroethanol (12 .24), aldehydes such as pyridine-2-aldehyde (12.68) and pyridine-4-aldehyde (12.05), sorbitol (13.0), and saccharose (12.7). ), 2
-Deoxyribose (12.61), 2-deoxyglucose (12.51), glucose (12.4)
6), galactose (12.35), arabinose (12.34), xylose (12.29), fructose (12.27), ribose (12.22), mannose (12.08) , L-ascorbic acid (1)
Saccharides such as 1.34), salicylic acid (13.0), 3-
Hydroxy-2-naphthoic acid (12.84), catechol (12.6), gallic acid (12.4), sulfosalicylic acid (11.7), 3,4-dihydroxybenzenesulfonic acid (12) .2), 3,4-dihydroxybenzoic acid (11.94), 1,2,4-trihydroxybenzene (11.82), hydroquinone (11.5)
6), compounds having a phenolic hydroxyl group such as pyrogallol (11.34) and resorcinol (11.27), 2-butanone oxime (12.45), acetoxime (12.42), 1,2- Cycloheptanedione dioxime (12.3), 2-hydroxybenzaldehyde oxime (12.10), dimethylglyoxime (11.9), ethanediamide dioxime (11.37), acetophenone oxime (11) .3
Oximes such as 5) and 2-quinolones (11.7
6), 2-pyridone (11.65), 4-quinolone (11.28), 4-pyridone (11.12), 5-
Aminovaleric acid (10.77), 2-mercaptoquinoline (10.25), 3-aminopropionic acid (10.77)
Amino acids such as 24), fluorouracil (13.
0), guanosine (12.6), uridine (12.6).
6), adenosine (12.56) and inosine (12.56).
5), Guanine (12.3), Citizin (12.4)
2), cytosine (12.2), hypoxanthine (1)
2.1), nucleic acid-related substances such as xanthine (11.9), and diethylaminomethylphosphonic acid (11.2).
32), 1-amino-3,3,3-trifluorobenzoic acid (12.29), isopropylidene diphosphonic acid (12.10), 1,1, -ethylidene diphosphonic acid (11.54) ), 1,1-ethylidene diphosphonic acid 1
-Hydroxy (11.52), benzimidazole (12.86), thiobenzamide (12.8), picoline thioamide (12.55), barbituric acid (12.5) and the like. .

As the strong base to be combined with these weak acids, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide are used.

These alkaline agents are used alone or in combination of two or more.

Preferred among these alkaline buffers are those obtained by combining sulfosalicylic acid, salicylic acid, saccharose and sorbitol with sodium hydroxide and potassium hydroxide. Among them, a preferred combination is sorbitol and potassium hydroxide or sodium hydroxide.

The above-mentioned various alkaline agents are used after adjusting the pH within a preferred range by the concentration and combination.

(Surfactant) The developer and replenisher suitable for the present invention may contain various surfactants as necessary for the purpose of accelerating developability, dispersing development scum, and increasing the ink affinity of the printing plate image area. Agents and organic solvents can be added. 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, and glycerin fatty acid partial esters. , Sorbitan fatty acid partial esters,
Pentaerythritol fatty acid partial esters, propylene glycol monofatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters , Polyoxyethylenated castor oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides,
Nonionic surfactants such as N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, and trialkylamine oxides, fatty acid salts, abietic acid salts,
Hydroxyalkanesulfonates, alkanesulfonates, dialkylsulfosuccinates, linear alkylbenzenesulfonates, branched alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylphenoxypolyoxyethylenepropylsulfonates, polyoxy Ethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyltaurine sodium salt, N-alkyl sulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated tallow oil, sulfate salts of fatty acid alkyl esters, alkyl sulfates Salts, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkyl phenyl ether sulfates, Oxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, partially saponified styrene / maleic anhydride copolymers, Partially saponified olefin / maleic anhydride copolymers, anionic surfactants such as naphthalene sulfonate formalin condensates, quaternary ammonium salts such as alkylamine salts, tetrabutylammonium bromide, polyoxyethylene alkylamine Salts, cationic surfactants such as polyethylene polyamine derivatives, amphoteric surfactants such as carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfates, and imidazolines. . Among the surfactants listed above, those with polyoxyethylene,
It can be read as a polyoxyalkylene such as polyoxymethylene, polyoxypropylene, polyoxybutylene, and their surfactants are also included.

More preferred surfactants are fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Such fluorosurfactants include perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, anionic type such as perfluoroalkyl phosphate, amphoteric type such as perfluoroalkyl betaine,
Cationic and perfluoroalkylamine oxides such as perfluoroalkyltrimethylammonium salts, perfluoroalkylethylene oxide adducts, oligomers containing perfluoroalkyl and hydrophilic groups,
Non-ionic forms such as oligomers containing perfluoroalkyl groups and lipophilic groups, oligomers containing perfluoroalkyl groups, hydrophilic groups and lipophilic groups, and urethanes containing perfluoroalkyl groups and lipophilic groups.

The above surfactants can be used alone or in combination of two or more.
001 to 10% by weight, more preferably 0.01 to 5% by weight.

(Development Stabilizer) Various development stabilizers are used in the developer and replenisher suitable for the present invention. As preferred examples thereof, polyethylene glycol adducts of sugar alcohols described in JP-A-6-282079,
Preferred examples include tetraalkylammonium salts such as tetrabutylammonium hydroxide, phosphonium salts such as tetrabutylphosphonium bromide, and iodonium salts such as diphenyliodonium chloride.

Further, anionic 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 disclosed. There is a water-soluble amphoteric polyelectrolyte described in the gazette.

Further, an organic boron compound to which an alkylene glycol has been added described in JP-A-59-84241, and a polyoxyethylene / polyoxypropylene block polymerization type water-soluble surfactant described in JP-A-60-111246. Japanese Patent Application Laid-Open No. Sho 60-129750, polyoxyethylene / polyoxypropylene-substituted alkylenediamine compounds, Japanese Patent Application Laid-Open No. Sho 61-215554, polyethylene glycol having a weight average molecular weight of 300 or more, and Japanese Patent Application Laid-Open No. Sho 63-175858. JP-A-2-39157 discloses a fluorine-containing surfactant having a cationic group, a water-soluble ethylene oxide addition compound obtained by adding 4 mol or more of ethylene oxide to an acid or alcohol, and a water-soluble polyalkylene compound. No.

(Organic Solvent) An organic solvent is further added to the developing solution and the developing replenisher, if necessary. As such an organic solvent, those having a solubility in water of about 10% by weight or less are suitable, and preferably selected from those having a solubility of 5% by weight 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-phenoxyethanol, Benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol, N-phenylethanol Examples include amines and N-phenyldiethanolamine. The content of the organic solvent is 0.1 to 5% by weight based on the total weight of the used solution. The amount used is closely related to the amount of surfactant used, and as the amount of organic solvent increases,
Preferably, the amount of surfactant is increased. This is because when the amount of the surfactant is small and the amount of the organic solvent is large, the organic solvent is not completely dissolved, and therefore, it is impossible to expect good developing property.

(Reducing Agent) A reducing agent is further added to the developer and replenisher suitable for the present invention. This is to prevent stains on the printing plate, and is particularly effective when developing a negative photosensitive lithographic printing plate containing a photosensitive diazonium salt compound. Preferred organic reducing agents include thiosalicylic acid,
Examples thereof include phenol compounds such as hydroquinone, metol, methoxyquinone, resorcin and 2-methylresorcin, and amine compounds such as phenylenediamine and phenylhydrazine. Further preferred inorganic reducing agents include sodium salts, potassium salts, and ammonium salts of inorganic acids such as sulfurous acid, bisulfite, phosphorous acid, bisulfite, diphosphite, thiosulfate and dithionite. Salts and the like can be mentioned. Among these reducing agents, sulfites are particularly excellent in the stain prevention effect. These reducing agents are preferably used in a developing solution at the time of use.
It is contained in the range of 0.5 to 5% by weight.

(Organic Carboxylic Acid) The developing solution and replenisher suitable for the present invention may further contain an organic carboxylic acid. Preferred organic carboxylic acids are aliphatic and aromatic carboxylic acids having 6 to 20 carbon atoms. Specific examples of the aliphatic carboxylic acid include caproic acid, enantiic 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, unsaturated fatty acids having a double bond in the carbon chain or branched fatty acids may be used.

The aromatic carboxylic acid is a compound in which a carboxyl group is substituted on a benzene ring, a naphthalene ring, an anthracene ring or the like, and specifically, 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, 3,5-dihydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-naphthoic acid And 2-naphthoic acid, and hydroxynaphthoic acid is particularly effective.

The above aliphatic and aromatic carboxylic acids are preferably used as a sodium salt, a potassium salt or an ammonium salt 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 the content is less than 0.1% by weight, the effect is not sufficient.
If it is 0% by weight or more, not only the effect cannot be further improved but also dissolution may be hindered when another additive is used in combination. Therefore, the preferred amount of addition is 0.1 to 10% by weight, more preferably 0.5 to 10% by weight, based on the developer used.
4% by weight.

(Others) The developer and replenisher suitable for the present invention may further contain an antifoaming agent and a water softener, if necessary. Examples of water softeners include polyphosphoric acid and its sodium, potassium and ammonium salts, ethylenediaminetetraacetic acid,
Aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium salts , Potassium and ammonium salts, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), hydroxyethylethylenediaminetri (methylenephosphonic acid) and Examples thereof include 1-hydroxyethane-1,1-diphosphonic acid and their sodium, potassium and ammonium salts.

The optimum value of such a water softener varies depending on the chelating power, the hardness of the hard water used, and the amount of the hard water. 01 to 5% by weight, more preferably 0.01 to 5% by weight
It is in the range of 0.5% by weight. If the added amount is less than this range, the intended purpose is not sufficiently achieved, and if the added amount is larger than this range, an adverse effect on an image portion such as color omission appears.

The remaining component of the developer and replenisher is water, but may further contain various additives known in the art, if necessary.

Further, it is advantageous from the viewpoint of transportation that the developing solution and the replenishing solution are prepared as concentrated solutions in which the content of water is smaller than at the time of use, and are diluted with water at the time of use. The degree of concentration in this case is suitably such that each component does not cause separation or precipitation.

The temperature of the developing solution is preferably from 15 to 40 ° C., more preferably from 20 to 35 ° C. Development time is 5-60
Seconds are preferred, and more preferably 7 to 40 seconds.

The PS plate 110 developed in the developing section 24 and sent to the second washing section 26 is subjected to a washing process in the second washing section 26. As shown in FIG. 2, the second washing section 26 includes a second washing tank 90 and two pairs of transport rollers 92 and 9.
4, a second spray pipe 96 and a third spray pipe 98 are provided, and the developed PS plate 110 is washed with cleaning water to completely remove the developer adhering to the PS plate 110.

The two transport roller pairs 92 and 94 are located above the second washing tank 90 and in the PS plate 11 of the second washing section 26.
It is provided at the zero retract position and the feed position. The transport roller pairs 92 and 94 form a transport path for the PS plate 110, rotate by receiving a driving force of a driving unit (not shown), and pinch and transport the PS plate 110 sent from the developing unit 24.

Between the two pairs of transport rollers 92 and 94,
A second spray pipe 96 and a third spray pipe 98 are provided above and below the PS plate 110 conveyance path, respectively.
Are arranged.

The second spray pipe 96 pumps up water from the water storage tank 84 by the pump P, and replenishes the water in the second washing tank 90. The third spray pipe 98
It is constituted by a plurality of spray pipes arranged along a direction orthogonal to the transport direction of the PS plate 110,
By injecting the cleaning water onto the surface of the PS plate 110 in synchronization with the transport of the S plate 110, the cleaning water is jetted across the width of the PS plate 110.

The third spray pipe 98 injects washing water pumped up by the pump P from a storage tank 93 described later toward the surface of the PS plate 110. As a result, the PS plate 110 is washed with water, and the developer is completely removed.

The cleaning water sprayed from the third spray pipe 98 spreads quickly on the surface of the PS plate 110, and when the PS plate 110 is washed with water, the PS plate 110 is transported by the conveying roller pair 94 to the finisher at the subsequent stage. When it is sent out, it is squeezed from the PS plate 110.

The second washing tank 90 is provided with a third overflow pipe 91. The third overflow pipe 91 guides the washing water flowing into the pipe by raising the water level in the second washing tank 90 to the storage tank 93,
The water level in the second washing tank 90 is always kept constant. The storage tank 93 is provided with a pump P, and the stored cleaning water is pumped up by the pump P and supplied to the third spray pipe 98.

That is, P sent from the developing unit 24
The S plate 110 is drawn into the second washing unit 26 by the pair of conveying rollers 92 provided at the position where the second washing unit 26 is drawn in, and passes through the conveying path formed in the upper layer of the second washing tank. 2 spray pipe 96 and third spray pipe 9
8 is washed on both sides by the washing water sprayed from the second washing unit 26, and a pair of transport rollers 94 provided at the delivery position of the second washing unit 26.
The washing water that adheres to the second washing section 26
Sent out from.

A finisher unit 28 is provided at a stage subsequent to the second washing unit 26. This finisher section 28
Are a gum solution tank 100 and a gum solution spray nozzle 102 for spraying the gum solution onto the surface of the PS plate 110;
The gum solution is applied to the PS plate 110 after washing with water to desensitize it. The gum solution tank 100 is provided with an overflow pipe similarly to the other tanks, and is adjusted so that the water level in the tank is always kept constant.

The PS plate 1 sent from the second washing section 26
Reference numeral 10 denotes a gum that is ejected from the gum solution ejecting nozzle 102 to the image forming side of the surface when passing through the finisher unit 28, and then adheres to the conveying roller pair 104 provided at the delivery position of the finisher unit 28. The liquid is squeezed and sent out from the finisher unit 28.

A drying section 29 is provided downstream of the finisher section 28. When the PS plate 110 passes through the drying section 29, the PS plate 110 is dried and discharged to the outside. In addition,
Since a known configuration can be applied to the drying unit 29, the description is omitted here.

The PS plate used in the plate making system of the present embodiment may be any as long as it includes a photopolymerizable photosensitive layer and an overcoat layer (oxygen barrier layer) for protecting the photosensitive layer. Preferably, a compound having an addition-polymerizable ethylenic double bond, a photopolymerization initiation system activated by light having a wavelength of 450 nm or more, and a crosslinkable group are provided on a support obtained by subjecting an aluminum plate to a hydrophilic treatment. It is preferable to use a material having a photopolymerizable photosensitive layer containing the polymer having the above.

Hereinafter, a preferred PS plate will be described in detail.

[Aluminum Support] The aluminum support of the PS plate is a dimensionally stable metal containing aluminum as a main component, and is made of aluminum or an aluminum alloy. In addition to a pure aluminum plate, it is selected from an alloy plate containing aluminum as a main component and containing a trace amount of a different element, or a plastic film or paper on which aluminum (alloy) is laminated or evaporated. Further, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in JP-B-48-18327 may be used.

In the following description, the above-mentioned substrates made of aluminum or aluminum alloy are collectively used as aluminum substrates. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium, and the content of the foreign elements in the alloy is 10% by weight or less. In the present invention, a pure aluminum plate is preferable, but completely pure aluminum is difficult to produce due to refining technology, and therefore may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and any of conventionally known and used materials such as JIS A 1050 and JISA 110 can be used.
0, JIS A 3103, JIS A 3005, and the like can be used as appropriate.

The thickness of the aluminum substrate used in the present invention is about 0.1 mm to 0.6 mm. This thickness can be appropriately changed according to the size of the printing press, the size of the printing plate, and the user's request.

[Hydrophilic treatment] The above-mentioned aluminum substrate is appropriately subjected to a treatment such as graining, which will be described later, and then the surface of the substrate is subjected to a hydrophilic treatment with silicate or polyvinylphosphonic acid or the like. The film has a Si or P element content of ^{2 to} 40 mg / m ² , more preferably 4 to 30 mg / m ² .
mg / m ² . In addition, the coating amount can be measured by a fluorescent X-ray analysis method.

In the above-mentioned hydrophilization treatment, the alkali metal silicate or polyvinylphosphonic acid is 1 to 30% by weight, preferably 2 to 15% by weight, and the pH at 25 ° C. is 10 to 10% by weight.
The aluminum substrate on which the anodized film is formed is immersed in the aqueous solution of No. 13 at, for example, 15 to 80 ° C. for 0.5 to 120 seconds.

As the alkali metal silicate, sodium silicate, potassium silicate, lithium silicate and the like can be used. Hydroxides used to increase the pH of the aqueous alkali metal silicate solution include sodium hydroxide, potassium hydroxide, and lithium hydroxide.

Incidentally, an alkaline earth metal salt or a Group IVB metal salt may be added to the above-mentioned treatment liquid. Alkaline earth metal salts include nitrates such as calcium nitrate, strolentium nitrate, magnesium nitrate and barium nitrate, and aqueous solutions such as sulfates, hydrochlorides, phosphates, acetates, oxalates and borates. Salts.

As a Group IVB metal salt, titanium tetrachloride,
Examples thereof include titanium trichloride, potassium titanium fluoride, potassium potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride, and zirconium tetrachloride.

The alkaline earth metal salts or Group IVB metal salts can be used alone or in combination of two or more. The preferred range of these metal salts is 0.01 to 10
% By weight, and a more preferred range is 0.05 to 5.0% by weight.

Electrodeposition of silicate as described in US Pat. No. 3,658,662 is also effective. Further, JP-B-46-27481 and JP-A-52-5
No. 8602 and Japanese Patent Application Laid-Open No. 52-30503 are also useful in combination with a support provided with electrolytic grains and a surface treatment combining the above-described anodic oxidation treatment and hydrophilic treatment.

[Hydrophilic undercoat layer] The following hydrophilic undercoat layer can be provided on the silicate-treated aluminum substrate as needed.

Water-soluble resins, for example, polyvinylphosphonic acid, polymers and copolymers having a sulfonic acid group in the side chain, polyacrylic acid, water-soluble metal salts (for example, zinc borate)
Alternatively, a primer coated with a yellow dye, an amine salt or the like is also suitable.

Examples of the organic compound used in the organic (resin) undercoat layer include carboxymethyl cellulose and
Dextrin, gum arabic, phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, phenylphosphonic acid which may have a substituent, naphthylphosphonic acid,
Organic phosphonic acids such as alkyl phosphonic acid, glycerophosphonic acid, methylene diphosphonic acid and ethylene diphosphonic acid, phenylphosphoric acid which may have a substituent, naphthyl phosphoric acid, organic phosphoric acid such as alkyl phosphoric acid and glycerophosphoric acid, Organic phosphines such as phenylphosphinic acid, naphthylphosphinic acid, alkylphosphinic acid and glycerophosphinic acid which may have a substituent, amino acids such as glycine and β-alanine, and hydroquinol such as triethanolamine hydrochloride It is selected from hydrochlorides of amines having a group, but may be used as a mixture of two or more kinds.

The organic undercoat layer can be provided by the following method. That is, a method in which a solution obtained by dissolving the above organic compound in water or an organic solvent such as methanol, ethanol, or methyl ethyl ketone or a mixed solvent thereof is applied to an aluminum substrate and dried to form a solution, and water or methanol, ethanol, methyl ethyl ketone, or the like. An aluminum substrate is immersed in a solution obtained by dissolving the above organic compound in an organic solvent or a mixed solvent thereof to adsorb the organic compound, and then washed with water and dried to form an organic undercoat layer. Is the way. In the former method, a solution of the above organic compound having a concentration of 0.005 to 10% by weight can be applied by various methods. For example, any method such as bar coater coating, spin coating, spray coating, and curtain coating may be used. In the latter method, the concentration of the solution is 0.01 to 20% by weight, preferably 0.05 to 5% by weight, and the immersion temperature is 20 to 90 ° C.
Preferably, the temperature is 25 to 50 ° C., and the immersion time is 0.1 second to
20 minutes, preferably 2 seconds to 1 minute.

The solution used for this may be a basic substance such as ammonia, triethylamine or potassium hydroxide, hydrochloric acid,
The pH is adjusted with an acidic substance such as phosphoric acid,
2 can be used. Further, a yellow dye can be added for improving the tone reproducibility of the photopolymerizable lithographic printing plate.

The coated amount of the organic undercoat layer after drying is from 2 to 20.
0 mg / m ² is suitable, preferably 5 to 100 mg.
/ M ² . If the coating amount is less than 2 mg / m ² , sufficient printing durability cannot be obtained. The same is true even if it is larger than 200 mg / m ² .

The aluminum support may be further subjected to a surface treatment such as immersion in an aqueous solution of potassium fluorozirconate, phosphate or the like.

[Photopolymerizable Photosensitive Layer] The main components of the photopolymerizable photosensitive layer used in the present invention include compounds containing an addition-polymerizable ethylenic double bond, a photopolymerization initiator, an organic polymer binder and the like. Various compounds such as a coloring agent, a plasticizer, and a thermal polymerization inhibitor are added as necessary.

The compound containing a double bond capable of addition polymerization is
It can be arbitrarily selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds.

For example, those having a chemical form such as a monomer, a prepolymer, ie, 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, etc.) and aliphatic polyhydric alcohol compounds. And amides of unsaturated carboxylic acids and aliphatic polyamine compounds.

Specific examples of the monomer of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3
-Butanediol diacrylate, 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 Triacry Over DOO, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipesitaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, sorbitol trimethacrylate, sorbitol natramethacrylate , There is bis [p- (3--methacryloxy-2-hydroxypropoxy) phenyl] dimethyl methane, bis [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
There are 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like.

The crotonates include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Sorbitol tetradicrotonate and the like.

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.

Further, a mixture of the above-mentioned ester monomers can also be mentioned.

Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples include diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like.

Another example is described in JP-B-48-417.
08 polyisocyanate compound having two or more isocyanate groups in one molecule described in
A bierurethane compound containing two or more polymerizable vinyl groups in one molecule to which a hydroxyl group-containing vinyl monomer represented by the following general formula (A) is added is exemplified.

CH ₂ ＣC (R ⁵ ) COO ₂ CH (R ⁶ ) OH (A) (where R ⁵ and R ⁶ represent H or CH ₃ )

Also, urethane acrylates described in JP-A-51-37193,
64183, JP-B-49-43191, JP-B-52
And polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in JP-A-30490. Further, the Journal of the Adhesion Society of Japan vol. 20, no. 7, 300-
Those introduced as photocurable monomers and oligomers on page 308 (1984) can also be used. In addition, these usage amounts are 5 to all components.
70% by weight (hereinafter abbreviated as%), preferably 10 to
50%.

Examples of the photopolymerization initiator include various photoinitiators known in patents and literatures, depending on the wavelength of the light source used.
Alternatively, a combination system (photoinitiating system) of two or more photoinitiators can be appropriately selected and used.

Various light-initiating systems have also been proposed when using visible light of 450 nm or more, an Ar laser, the second harmonic of a semiconductor laser, or an SHG-YAG laser as a light source. For example, US Pat. No. 2,850. Certain photoreducing dyes, for example, rose bengal, eosin, erythrosine, and the like, or a system using a combination of a dye and an initiator, for example, a complex starting system of a dye and an amine (Japanese Patent Publication No. 44-20189). ), A combination of hexaarylbiimidazole, a radical generator and a dye (Japanese Patent Publication No. Sho 4)
5-37377), a system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (JP-B-47-2528, JP-A-54-155292), and a system of a cyclic cis-α-dicarbonyl compound and a dye ( Kaisho 4
8-84183), a system of a cyclic triazine and a merocyanine dye (JP-A-54-151024), a system of 3-ketocoumarin and an activator (Tokikai Sho 52-112681, JP-A 58-15503), A system of imidazole, a styrene derivative, and a thiol (JP-A-59-140203);

Organic peroxide and dye system (Japanese Unexamined Patent Publication No.
No. 504, JP-A-59-140203, JP-A-59-140203
No. 189340, JP-A-62-174203, JP-B-62-1641, U.S. Pat. No. 4,766,055), a system of a dye and an active halogen compound (JP-A-63-17181).
No. 05, JP-A-63-258903, Japanese Patent Application No. 2-63
No. 054), a system of a dye and a borate compound (JP-A-6
2-143044, JP-A-62-150242, JP-A-64-13140, JP-A-64-13141,
JP-A-64-13142, JP-A-64-13143
JP-A-64-13144, JP-A-64-1704
8, JP-A-1-229003, JP-A-1-2983
No. 48, JP-A-1-138204, etc., and a system of a dye having a rhodanine ring and a radical generator (JP-A No. 2-17)
No. 9643, JP-A-2-244050), a system of titanocene and 3-ketocoumarin dye (JP-A-63-22111).
No. 0), a system in which a titanocene is combined with a xanthene dye and an addition-polymerizable ethylenically unsaturated compound containing an amino group or a urethane group (JP-A-4-221958)
JP-A-4-219756), a system of titanocene and a specific merocyanine dye (JP-A-6-295061),
A dye system having a titanocene and a benzopyran ring (Japanese Patent Application No. Hei 7-164585) can be exemplified.

The titanocene compound used as a photopolymerizable initiation system in the present invention may be any titanocene compound which can generate an active radical when irradiated with light in the presence of the above-mentioned sensitizing dye. For example, JP-A-59-152396, JP-A-61-151197
A known compound described in JP-A No. 5-211 can be appropriately selected and used.

More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,3 4,5,6-pentafluorophenyl-1-yl (hereinafter also referred to as “A-1”), di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1- Yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl
1-yl, di-cyclopentadiphenyl-Ti-bis-
2,6-difluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4-difluorophenyl
1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-
Yl (hereinafter also referred to as “A-2”), di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti -Bis-2,4-difluorophenyl-1-
Il, bis (cyclopentadieel) -bis (2,6-
And difluoro-3- (pyrid-1-yl) phenyl) titanium (hereinafter also referred to as “A-3”).

The titanocene compounds used in the photopolymerizable composition can be used alone or in combination of two or more.

These photopolymerization initiators are used in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the ethylenically unsaturated compound.
0 parts by weight, preferably 0.1 to 70 parts by weight, and more preferably 0.2 to 50 parts by weight.

The photopolymerizable composition usually contains an organic polymer as a binder. In the present invention, a polymer having a crosslinkable group in a side chain is used. Such an organic high molecular polymer (hereinafter also simply referred to as a polymer) itself has a crosslinkable group (also referred to as an unsaturated group) and a carboxyl group in a side chain, and the crosslinkable group has the following general formula: [I]

[0161]

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[Wherein R _{1 to} R ₅ are hydrogen, halogeno, carboxyl, sulfo, nitro, cyano, amide, amino, alkyl, aryl, each of which may have a substituent,
Alcoquin, aryloquin, alkylamino, arylamino, cyclic alkyl, alkylsulfonyl, arylsulfonyl, wherein Z is oxygen, sulfur, N
H or NR (R is an alkyl group)].

Further, polymers having a crosslinkable group in a side chain used as a binder for the photopolymerizable photosensitive layer are described in US Pat. Nos. 3,376,138 and 3,556,792.
No. 3,556,793, the disclosed polymer is a polymer itself,
It is used as a photocrosslinkable resist, and has a clear difference from the method of using the photopolymerizable composition described in this embodiment as a binder.

The methods for synthesizing the above polymers are roughly classified into the following two methods.

(Method A): A compound represented by the following general formula [Ia] is subjected to a polymer reaction with a carboxylic acid, a carboxylic acid halide, and a backbone polymer having a carboxylic anhydride group as a side chain.

[0166]

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(Wherein, R _{1 to} R ₅ have the same meanings as in the general formula [I]).
-, -CONH- or -CONR- a method of introducing via each connecting group.

(Method B): A monomer having a crosslinkable group represented by the above general formula [I] and an ethylenically unsaturated group having a higher addition polymerization reactivity than the crosslinkable group is converted into an unsaturated carboxylic acid. A method of obtaining a polymer by copolymerization.

[0169]

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[Wherein, R _{1 to} R ₅ have the same meanings as in formula [I], and Y is OH, —SH, —NH ₂ , —NHR
(R is an alkyl group) or a halogen atom. The alkyl group of R _{1 to} R _{5 in} the general formula [Ia] is
It may be linear, branched, or cyclic, and has 1 to 7 carbon atoms.
Preferably has, even in these alkyl group, an alkoxy group having from 1 to 2 carbon atoms, an alkoxycarbonyl group having 1 to 3 carbon atoms, a phenyl group may have a substituent such as hydroxy group, R ₁ As the aryl group represented by R ₅ to R _5, a phenyl group and a furyl group are preferable, including a halogeno group (eg, chloro, bromo, etc.), a hydroxy group,
May have a substituent such as an alkyl group, an aryl group (e.g., phenyl and methkinphenyl), an alkoxy group having 1 to 7 carbon atoms, a nitro group, an amino group, and an N, N-dialkylamino group. . The alkoxy group of R _{1 to} R ₅ is preferably a group having 1 to 7 carbon atoms, and the aryloxy group is preferably a phenyl okine group, which has a substituent such as an alkyl or alkoxy group having 1 to 7 carbon atoms. May be. The alkylamino group of R _{1 to} R ₅ is preferably a group having 1 to 15 carbon atoms, and the arylamino group is preferably a phenylamino group or a naphthylamino group. The alkylsulfonyl group represented by R _{1 to} R ₅ is preferably a group having 1 to 15 carbon atoms, and the arylsulfonyl group is preferably a phenylsulfonyl group. May have a substituent such as an alkoxy group and an amino group.

If the method A is described in more detail, examples of the trunk polymer include a copolymer of acrylic acid or methacrylic acid and a copolymer in which the copolymer is an acid halide by a polymer reaction. Further, copolymers such as maleic anhydride and itaconic anhydride can be used. Examples of the comonomer to be copolymerized include styrene or an alkyl-substituted derivative thereof, an alkyl acrylate, an aryl acrylate, an alkyl methacrylate, an aryl methacrylate, or an aliphatic vinyl ester. Preferably acrylic acid or methacrylic acid and methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, methyl methacrylate,
Copolymers with ethyl methacrylate, butyl methacrylate, and benzyl methacrylate are exemplified. In order to introduce a crosslinkable group into these copolymers, a crosslinkable alcohol, an amine, a thiol, or a halide represented by the general formula [Ia] is reacted with the above copolymer in a reaction solvent under predetermined reaction conditions. It is obtained by mixing and dissolving, adding a reaction catalyst and a polymerization inhibitor, and heating. Specifically, a copolymer of methacrylic acid and benzyl methacrylate is shown below as an example.

A poly (methacrylic acid / benzyl methacrylate = 27/73) was placed in a 300 ml three-necked flask equipped with a stirring rod and stirring blades, a reflux condenser and a thermometer.
19.8 g), 40.2 g of ethylene glycol monomethyl ether acetate as a reaction solvent, 6.0 g of allyl bromide as a reagent containing a crosslinkable group, and 10.4 g of trimethylbenzylammonium hydroxide as a catalyst.
g of paramethoxyphenol and 0.1 g of paramethoxyphenol as a polymerization inhibitor.
And mixed and dissolved at 70 ° C. in a nitrogen atmosphere.
Heating and stirring were performed for hours. After cooling, methyl ethyl ketone is added to remove free quaternary salts. Further, the mixture is diluted with methanol and poured into dilute hydrochloric acid to precipitate. After washing with water, suction filtration and vacuum drying, the yield of polymer obtained is 1
It was 3.6 g. Allyl groups were introduced at 35% relative to the carboxylic acid of the backbone polymer.

[0173]

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A synthesis example in which the crosslinkable group is introduced into a copolymer of maleic anhydride can be carried out by the method described in US Pat. No. 2,047,398, whereby the maleic anhydride moiety is formed. A ring-opened unsaturated ester, amide, thioester or the like is introduced. As a method for introducing a crosslinkable group into a maleic anhydride copolymer, JP-A-48-82
A similar example described in Japanese Patent Application Laid-Open No. 902/1990 is mentioned, but the crosslinkable group by this method is bonded to the nitrogen atom of maleic imide, and is clearly a compound different from the above-mentioned polymer, and is used in the present invention. Polymer having a crosslinkable group in the side chain.

On the other hand, the method B will be described in more detail. A monomer containing at least two carbon-carbon double bonds having a crosslinkable group can be obtained by a known synthesis method using an alcohol, amine or thiol having the crosslinkable group. And unsaturated carboxylic acids,
Preferably, it is synthesized by a condensation reaction with acrylic acid or methacrylic acid. By copolymerizing the monomer containing at least two or more unsaturated groups with an unsaturated carboxylic acid, preferably acrylic acid or methacrylic acid, a copolymer having the crosslinkable group is obtained. The monomer to be copolymerized may further be copolymerized with another monomer in addition to the unsaturated carboxylic acid, for example, alkyl acrylate, alkyl methacrylate, benzyl methacrylate, 2-hydroquinethyl methacrylate, acrylonitrile, and the like. No.

The following is an example of copolymerization of allyl methacrylate and methacrylic acid. As a similar synthesis method, a method described in US Pat. No. 2,047,398 can be mentioned.

1.68 liters of 1,2-dichloroethane as a reaction solvent was placed in a 3 liter four-necked flask equipped with a stirring rod and a stirring blade, a reflux condenser, a dropping funnel and a thermometer, and heated to 70 ° C. while purging with nitrogen. did. 100.8 g of allyl methacrylate, 7.6 g of methacrylic acid, and 1.68 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator were added to a dropping funnel in an amount of 0.1 g.
The mixture was dissolved in 44 liters of 1,2-dichloroethane, and the mixed solution was dropped into the flask over 2 hours with stirring.

After completion of the dropwise addition, the mixture was further stirred at a reaction temperature of 70 ° C. for 5 hours to complete the reaction. After the completion of heating, 0.04 g of paramethokine phenol was added as a polymerization inhibitor, and the reaction solution was added to 50 parts.
The solution was concentrated to 0 ml, and the concentrated solution was added to 4 liters of hexane to precipitate. After vacuum drying, 61 g (yield 56%) of a copolymer was obtained. At this time, the viscosity was [η] = 0.068 for methyl ethyl ketone at 80 ° C.

Representative compounds represented by the above general formula [Ia] include allyl alcohol, 2-methylallyl alcohol, crotyl alcohol, 3-chloro-2-propen-1-ol, and 3-phenyl-2. -Propen-1-ol, 3- (hydroquinphenyl) -2-propen-1-
All, 3- (2-hydroxyphenyl) -2-propen-1-ol, 3- (3.4-dihydroxyphenyl) -2-propen-1-ol, 3- (2.4-dihydroxyphenyl-2-ol Propen-1-ol, 3-
(3,4-5-trihydroquinphenyl) -2-propen-1-ol, 3- (3-methoxy-4-hydroquinphenyl) -2-propen-1-ol, 3- (3.4
-Dihydroxy-5-methoxyphenyl) -2-propen-1-ol, 3- (3.5-dimethoxy-4-hydroxyphenyl) -2-propen-1-ol, 3-
(2-hydroxy-4-methylphenyl) -2-propen-1-ol, 3- (4-methoxyphenyl) -2-
Propen-1-ol, 3- (4-ethoxyquinphenyl)
-2-propen-1-ol, 3- (2-methoxyphenyl) -2-propen-1-ol, 3- (3-4-dimethoxyphenyl) -2-propen-1-ol, 3-
(3-methoxy-4-propoxyphenyl) -2-propen-1-ol,

3- (2-4,6-trimethoxyphenyl) -2-propen-1-ol, 3- (3-methoxy-4-benzyloxyphenyl) -2-propen-1-
All, 3-1- (3′-methokinphenyl) -4-benzyloxyphenyl) -2-propen-1-ol,
3-phenoxy-3-phenyl-2-propen-1-ol, 3- (3.4.5-trimethoxyphenyl) -2
-Propen-1-ol, 3- (4-methylphenyl)
-2-propen-1-ol, 3-phenyl-3- (2
* 4,6-trimethylphenyl) -2-propene-1-
All, 3,3- {di- (2,4,6-trimethylphenyl)}-2-propen-1-ol, 3-phenyl-
3- (4-methylphenyl) -2-propen-1-ol, 3,3-diphenyl-2-propen-1-ol,
3- (2-chlorophenyl) -2-propen-1-ol, 3- (3-chlorophenyl) -2-propen-1-
All, 3- (4-chlorophenyl) -2-propene-
1-ol, 3- (2.4-dichlorophenyl) -2-
Propen-1-ol, 3- (2-bromophenyl)-
2-propen-1-ol, 3-bromo-3-phenyl-2-propen-1-ol, 3-chloro-3-phenyl-2-propen-1-ol, 3- (4-nitrophenyl) -2 -Propen-1-ol,

3- (2-nitrophenyl) -2-propen-1-ol, 3- (3-nitrophenyl) -2-propen-1-ol, 2-methyl-3-phenyl-2-
Propen-1-ol, 2-methyl-3- (4-chlorophenyl) -2-propen-1-ol, 2-methyl-
3- (4-nitrophenyl) -2-propen-1-ol, 2-methyl-3- (4-aminophenyl) -2-propen-1-ol, 2-methyl-3-3.3-diphenyl-2- Propen-1-ol, 2-ethyl-1 / 3-diphenyl-2-propen-1-ol, 2-ethoxymethylene-3-phenyl-2-propen-1-ol, 2
-Phenoxy-3-phenyl-2-propen-1-ol, 2-methyl-3- (4-methoxyphenyl) -2-
Propen-1-ol, 2,3-diphenyl-2-propen-1-ol, 1,2,3-triphenyl-2-propen-1-ol, 2,3,3-triphenyl-2-
Propen-1-ol, 2-ethoxy-3-phenyl-
2-propen-1-ol, 1.3-diphenyl-2-
Propen-1-ol, 1- (4-methylphenyl)-
3-phenyl-2-propen-1-ol, 1-phenyl-3- (4-methylphenyl) -2-propen-1-
All, 1-phenyl-3- (4-methoxyphenyl)
-2-propen-1-ol, 1- (4-methoxyphenyl) -3-phenyl-2-propen-1-ol,

1,3-di (4-chlorophenyl) -2-
Propen-1-ol, 1- (4-bromophenyl)-
3-phenyl-2-propen-1-ol, 1-phenyl-3- (4-nitrophenyl) -2-propen-1-
All, 1,3-di (2-nitrophenyl) -2-propen-1-ol, 1- (4-dimethylaminophenyl) -3-phenyl-2-propen-1-ol, 1-
Phenyl-3- (4-dimethylaminophenyl) -2-
Propen-1-ol, 1,1-di (4-dimethylaminophenyl) -3-phenyl-2-propen-1-ol, 1.1,3-triphenyl-2-propen-1-ol, 1. 1,3,3-tetraphenyl-2-propen-1-ol, 1- (4-methylphenyl) -3-phenyl-2-propen-1-ol, 1- (dodecylsulfonyl) -3-phenyl-2 -Propen-1-ol,
1-phenyl-2-propen-1-ol, 1,2-diphenyl-2-propen-1-ol, 1-phenyl-
2-methyl-2-propen-1-ol, 1-cyclohexyl-2-propen-1-ol, 1-phenoxy-
2-propen-1-ol, 2-benzyl-2-propen-1-ol, 1.1-di (4-chlorophenyl)-
2-propen-1-ol, 1-carboxy-2-propen-1-ol,

1-carboxamido-2-propene-1
-Ol, 1-cyano-2-propen-1-ol, 1
-Sulfo-2-propen-1-ol, 2-ethoxy-
2-propen-1-ol, 2-amino-2-propen-1-ol, 3- (3-amino-4-methoxyphenylsulfonyl) -2-propen-1-ol, 3- (4
-Methylphenylsulfonyl) -2-propen-1-ol, 3-phenylsulfonyl-2-propen-1-ol, 3-benzylsulfonyl-2-propen-1-ol, 3-anilinosulfonyl-2-propene- 1-ol, 3- (4-methoxyanilinosulfonyl) -2-
Propen-1-ol, 8-anilino-2-propene-
1-ol, 3-naphthylamino-2-propene-1-
All, 3-phenoxy-2-propen-1-ol,
3- (2-methylphenyl) -2-propen-1-ol, 3- (3-methylphenokine) -2-propen-1
-Ol, 3- (2,4-dimethylphenyl) -2-propen-1-ol, 1-methyl-3-carboxy-2
-Propen-1-ol, 3-carboxy-2-propen-1-ol, 3-bromo-3-carboxy-2-propen-1-ol, 1-carboxy-3-chloro-3
-Methyl-2-propen-1-ol, 1-carboxy-3-methyl-2-propen-1-ol,

1- (2-carbethoxyisopropyl)-
3-methyl-2-propen-1-ol, 1- (1-carbethoxypropyl) -2-propen-1-ol,
-(1-carbethoxyethyl) -3-methyl-2-propen-1-ol, 1-carbethoxy-3-chloro-3
-Methyl-2-propen-1-ol, 1-carbethoxymethylene-3-methyl-2-propen-1-ol,
1-amido-2 / 3-dimethyl-2-propen-1-ol, 1-cyano-3-methyl-2-propen-1-ol, 3-sulfo-2-propen-1-ol, 3-butoxy- 2-propen-1-ol, 1-cyclohexyl-3- (2-hydroxycyclohexyl) -2-propen-1-ol, 3-cyclobenzyl-2-propen-1-ol, 3-furyl-2- Propen-1-ol, 3-chrom-2-propen-1-ol, 3-bromo-2-propen-1-ol, 2-methyl-3-chloro-2-propen-1-ol, 2-methyl- 3-bromo-2-propen-1-ol, 1-carboisobutoxy-3-chloro-3-methyl-2-propen-1-ol, 2-chloro-3-phenyl-2-propen-1-ol ( 2-chlorosi Cinnamyl alcohol), 2-bromo-3-phenyl-2-propen-1-ol (2-bromo cinnamyl alcohol),

2-bromo-3- (4-nitrophenyl)
-2-propen-1-ol, 2-fluoro-3-phenyl-2-propen-1-ol (2-fluorocinnamyl alcohol), 2-fluoro-3- (4-methoxyphenyl) -2-propene- 1-ol, 2-nitro-
3-chloro-3-phenyl-2-propen-1-ol, 2-nitro-3-phenyl-2-propen-1-ol (2-nitrocinnamyl alcohol), 2-cyano-3-phenyl-2-ol Propen-1-ol (2-cyanocinnamyl alcohol), 2-chloro-2-propen-1-ol (2-chloroallyl alcohol), 2-bromo-2-propen-1-ol (2-bromoallyl alcohol) ), 2-carboxy-2-propen-1-ol (2-carboxyallyl alcohol), 2-carbethoxy-2-propen-1-ol (2-carbethoxyallyl alcohol), 2-sulfonic acid-2-propene- 1
-Ol (2-allyl alcohol sulfonate), 2-nitro-2-propen-1-ol (2-nitroallyl alcohol), 2-bromo-3 / 3-difluoro-2-propen-1-ol, 2- Chlor-3-3-difluoro-2-propen-1-ol, 2-fluoro-3-chloro-2-propen-1-ol, 2,3-dibromo-3
-Carboxy-2-propen-1-ol,

2,3-diiodo-3-carboxy-2-
Propen-1-ol, 2,3-dibromo-2-propen-1-ol, 2-chloro-3-methyl-2-propen-1-ol. In the above specific examples, a compound in which the alcohol at the 1-position is replaced with a thioalcohol, an amine or a halogen can of course be used.

The preferable range of the crosslinkable group content in the polymer is 10 to 90 mol%,
60 mol%, a more preferable range is 20 to 70 mol%,
0 to 40 mol%.

Similarly, there are acidic cellulose derivatives having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful. In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer and [allyl (meth) acrylate (meth) acrylic acid / optionally Other addition-polymerizable vinyl monomers) copolymers are preferred. In addition, as the water-soluble organic polymer, polybierpyrrolidone, polyethylene oxide and the like are useful. In order to increase the strength of the cured film, alcohol-soluble polyamides and polyethers of 2,2-bis- (4-hydroquinphenyl) -propane and epichlorohydrin are also useful.
These organic high-molecular polymers can be mixed in an arbitrary amount in the entire composition. However, if it exceeds 90% by weight, no favorable result is obtained in view of the strength of the formed image and the like. Preferably 10 to 90%, more preferably 30 to 8
0%. The weight ratio of the photopolymerizable ethylenically unsaturated compound and the organic high molecular weight polymer is preferably in the range of 1/9 to 9/1. A more preferred range is 2/8 to 8 /
2, more preferably 3/7 to 7/3.

In the present invention, in addition to the above basic components, a small amount of thermal polymerization is inhibited in order to prevent unnecessary thermal polymerization of a polymerizable ethylenically unsaturated compound during the production or storage of the photosensitive composition. It is desirable to add an agent. Suitable thermal polymerization inhibitors include haloid quinone, p-
Methkinphenol, 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), cerium N-nitrosophenylhydroxylamine, aluminum aluminum N-nitrosophenylhydroxylamine and the like.
The addition amount of the thermal polymerization inhibitor is preferably from about 0.01% to about 5% based on the weight of the whole 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 in a 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 preferred.

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 15:
3, 15: 4, 15: 6), 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 inorganic fillers and plasticizers such as dioctyl phthalate, dimethyl phthalate and tricresyl phosphate may be added to improve the physical properties of the cured film.

The amount of these additives is preferably 10% or less of the total composition.

When the photopolymerizable composition is coated on a support, it is used after being dissolved in various organic solvents. 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 Ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-meth Kin-propyl acetate, N, N- dimethylformamide, dimethyl sulfoxide, .gamma.-butyrolactone, methyl lactate and ethyl lactate. These solvents can be used alone or as a mixture. The appropriate concentration of the solid content in the coating solution is 1 to 50% by weight.

A surfactant can be added to the photopolymerizable composition of the present invention to improve the coated surface quality.

The coating amount is about 0. lg /
range of m ² ~ about 10 g / m ² are suitable. More preferably, it is 0.3 to 5 g / m ² . More preferably 0.5 to
3 g / m ² .

[Overcoat layer] The overcoat layer of the present invention (C) is an oxygen-blocking overcoat layer.
This overcoat layer contains a water-soluble vinyl polymer. The water-soluble vinyl polymer contained in the overcoat layer contains polyvinyl alcohol and its partial esters, ethers and acetal, or a substantial amount of terminally substituted vinyl alcohol units that have the necessary water solubility. The copolymer is mentioned. Examples of the polyvinyl alcohol include those having a hydrolysis degree of 71 to 100% and a polymerization degree of 300 to 2400. Specifically, Kuraray's PVA-105, Pv
A-110, PVA-117, PVA-117H, PV
A-120, PVA-124, PVA-124H, PV
A-CS, PVA-CST, PVA-HC, PVA-2
03, PVA-204, PVA-205, PVA-21
0, PVA-217, PVA-220, PVA-22
4, PVA-217EE, PVA-220, PVA-2
24, PVA-217EE, PVA-217E, PVA
-220E, PVA-224, PVA-405, PVA
-420, PVA-613, L-8 and the like. The above-mentioned copolymers include polyvinyl acetate chloroacetate or propionate, polybierformal and polybieracetal hydrolyzed 88 to 100%, and copolymers thereof. Other useful polymers include polyvinylpyrrolidone, gelatin and gum arabic, which may be used alone or in combination.

The solvent used for applying the overcoat layer is preferably pure water, but alcohols such as methanol and ethanol, and ketones such as acetone and methyl ethyl ketone may be mixed with the pure water. The concentration of the solid content in the coating solution is suitably from 1 to 20% by weight.

In addition, known additives such as a surfactant for improving coating properties and a water-soluble plasticizer for improving physical properties of the film may be added to the overcoat layer. Examples of the water-soluble plasticizer include propionamide, cyclohexanediol, glycerin, and sorbitol. Further, a water-soluble (meth) acrylic polymer or the like may be added.

The amount of the coating was about 0.1 / m 2 after drying.
A range from ² to about 15 / m ² is suitable. More preferably, it is 1.0 / m ² to about 5.0 / m ² .

In this embodiment, for the sake of explanation, one personal computer is connected to the workstation 12 online. However, the number of personal computers is not limited to one, and a plurality of personal computers can be connected online. Similarly,
In the present embodiment, for the sake of explanation, one PS plate processor 16 is connected online to the plate setter 14, but the present invention is not limited to one, and a plurality of personal computers can be connected online to the plate setter 14.

When a plurality of personal computers are connected to the plate setter 14 online, conditions such as changing adjustment conditions can be set more efficiently, so that the loss time can be reduced and the efficiency is improved.

In the present embodiment, the image data output from the workstation is a TIFF file. However, the present invention is not limited to a TIFF file. A standard PPF file containing image data such as a PPF file composed of transfer characteristic curves, types of registration marks, color density information for quality control of position data, and information of trimming marks and cutting. Formatted image data can be used.

In the present embodiment, the plate setter 14 and the PS plate processor 16 are connected online. However, the present invention is not limited to the online connection. The information of the plate setter 14 may be stored on the medium as setter information, and the storage medium may be read by the PS version processor 16 to transfer the setter information.

Further, in the present embodiment, the condition adjustment program is stored in the ROM of the processor control unit 30, but the present invention is not limited to this, and the condition adjustment program may be stored in the ROM of the setter control unit 18 or in the preceding stage. PC ROM
May be stored.

Further, the condition adjusting program may be stored on a floppy disk, a hard disk may be provided in the computer main body, and the condition adjusting program may be read from the floppy disk and installed on the hard disk. Further, the condition adjustment program may be transmitted to a wired or wireless network by a transmission means such as a telephone line and installed.

The condition adjusting program is not limited to being stored on a floppy disk, but may be stored on a CD-RO.
M, the program is stored on a magnetic tape, and the CD-RO
M, a magnetic tape may be installed on the hard disk of the personal computer. Further, a hard disk storing the condition adjustment program may be provided. Further, the condition adjustment program may be directly written in the hard disk or RAM of the personal computer. As described above, the condition adjustment program can be distributed by at least one of a tangible recording medium and a transmission unit.

In the above description, the stock solution for developing replenishment and the dilution water are separately supplied to the developing tank. However, the stock solution for developing replenishment and the diluting water are once mixed in the mixing tank, and the mixed solution is supplied to the developing tank. It can also be configured to supply.

[0208]

As described above, according to the present invention, it is possible to always appropriately set the adjustment conditions in the removal process of the oxygen-blocking layer applied to the PS plate before development, according to the PS plate to be processed. This has the effect.

Further, since the adjustment condition is determined using the data used in the previous step, there is no possibility that the temperature adjustment condition set by an operation error or the like becomes inappropriate, and the processing efficiency can be improved. There is.

Further, there is an effect that the use of the removing liquid can be eliminated and the running cost of the apparatus can be reduced.

[0211] Further, since the time until the temperature of the removal liquid reaches an appropriate temperature can be switched efficiently, the loss time can be shortened, and the processing efficiency can be increased. As a result, energy saving can be achieved. This has the effect.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory diagram showing a data flow of a plate making system according to an embodiment.

FIG. 2 is an explanatory diagram showing a schematic configuration of the automatic developing machine shown in FIG.

FIG. 3 is a flowchart illustrating an operation of a CPU of a processor control unit illustrated in FIG. 2;

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Personal computer 12 Workstation 14 Plate setter 16 PS plate processor 18 Setter control part 20 Heating part 22 First rinsing part 24 Developing part 26 Second rinsing part 28 Finisher part 29 Drying part 30 Processor control part 31 Pull-in roller pair 32 Heating device 34b Chiller 34a Heater 34c Temperature sensor 37 Pipeline 60 First washing tank (removal tank) 61, 79, 91 Overflow pipe 62, 68, 92, 94, 104 Transport roller pair 63, 80 Waste liquid tank 64a First water supply nozzle 64b First 2 water supply nozzle 64c replenishing cylinder 66, 71a, 71b rotating brush roller 67 backup roller 68 transport roller pair 70 developing tank 72, 75 delivery roller pair 73 liquid level cover 74 development replenisher stock solution injection nozzle 76 dilution water injection nozzle 77 guy Plate 78, 96, 98 Spray pipe 82 Developing replenisher stock tank 84 Water tank 90 Second washing tank 93 Storage tank 110 PS plate

Continued on the front page F term (reference) 2H025 AA04 AB03 AC01 AC08 AD01 BC13 BC34 BC43 DA04 FA12 FA17 2H096 AA07 BA05 EA02 EA04 EA23 FA05 FA10 GA08

Claims (2)

[Claims] 1. A lithographic printing plate having an oxygen barrier layer on the uppermost layer and a photopolymerizable photosensitive layer on the lower side thereof is exposed based on image data, and the oxygen barrier layer is removed by a remover. And a plate making method of a lithographic printing plate for further developing, wherein at least one adjustment condition of a replenishing amount of a removing solution, a removing solution temperature, and a removing treatment time when removing the oxygen barrier layer, A lithographic printing plate making method determined based on the plate information used in the previous step. 2. Prior to development of a lithographic printing plate having an oxygen-blocking layer as an uppermost layer and a photopolymerizable photosensitive layer below the lithographic printing plate, transporting the lithographic printing plate into a removal tank, Removing means for removing the oxygen-blocking layer with the removing liquid supplied to the apparatus, and a replenishing amount of the removing liquid when removing the oxygen-blocking layer based on the plate information used in the preceding apparatus, a temperature of the removing liquid. An automatic developing machine comprising: a condition determining unit that determines at least one adjustment condition of the removal processing time; and an adjusting unit that performs adjustment so as to satisfy the adjustment condition determined by the condition determining unit.