JP2000352826A - Method for developing planographic printing original plate and apparatus for the method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developing method by which a printing plate is stably manufactured using a planographic printing original plate capable of a direct photomechanical process by heat-mode image recording from the digital information of a computer or the like independently of the span of preservation, the state of a developing solution and intraday and day-to-day changes of throughput and to provide a developing apparatus suitable for the developing method. SOLUTION: A positive type photosensitive planographic printing original plate for IR laser containing (A) an alkali-soluble high molecular compound, (B) a compound which is compatible with the alkali-soluble high molecular compound, lowers the solubility of the high molecular compound to an aqueous alkali solution and reduces its solubility lowering action when heated, and (C) a photothermal conversion compound is developed with an alkaline developing solution while retaining the activity of the developing solution by supplying electric current between the electrodes of a current supplying means with anode and cathode chambers by way of the developing solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plate making method of a heat mode photosensitive image recording material which can be used as an offset printing master, and more particularly to a so-called direct plate making infrared laser which can make a plate directly from a digital signal of a computer or the like. The present invention relates to a method for making a lithographic printing plate provided with a photosensitive layer comprising a positive photosensitive composition.

[0002]

2. Description of the Related Art In general, starting with a photosensitive lithographic printing original plate,
In the step of developing the photosensitive resin composition provided on the substrate, a part of the composition such as a printing original plate is developed by being eluted in an alkaline developer, so that the alkaline developer in the developing tank is developed. Consumes the alkali component,
Activity decreases. Also, during the downtime when development of the original printing plate is not performed, the surface of the developer is always in contact with air, so the developer absorbs carbon dioxide gas in the air and the alkaline agent component contained in the solution. Is consumed, and the activity similarly decreases. That is, in the development processing apparatus, the processing fatigue accompanying the development processing of the printing original plate and the aging deterioration (or the aging fatigue) caused by the contact between the developing solution and the air are progressing at the same time, though the degree is different. . If the deterioration proceeds beyond a certain level, proper development processing cannot be performed. Therefore, a method of performing development while appropriately preventing deterioration by replenishing a development replenisher at an appropriate time is generally used.

In order to prevent a decrease in the activity of a developer,
In general, a method of correcting the alkali consumption by supplying a replenisher containing an alkali agent or a buffer at a higher concentration than the developing solution in the developing tank is adopted. This so-called replenishment method is necessary to stably develop a large amount of the photosensitive resin composition using a developing apparatus, but also has the following problems.

[0004] 1) With the replenishment, the overflow is discharged from the developing tank and becomes a developing waste liquid. However, since it cannot be discharged to the sewer, it is necessary to take measures for disposal of the waste liquid. The disposal of the waste liquid is costly, and the disposal itself
With environmental impact. 2) Performing replenishment results in wasteful discharge of developer components such as an alkali agent in addition to the problem described in the preceding paragraph, and is economically burdensome. 3) The photosensitive resin composition eluted in the developing solution precipitates in the developing solution having a high salt concentration and adheres to a transport system such as a roller, which causes an abnormal transportability in the developing device or a stop of the developing device. . When the cleaning is performed to remove the precipitates, the development processing device is stopped, so that the productivity is reduced and the labor of the operation is increased. 4) Chemicals added as alkali agents or buffers (silicates, phosphates, etc.) increase the salt concentration, and the components dissolved from the photosensitive resin composition in the transport system or tank are likely to precipitate (especially silicates). .

On the other hand, in recent years, a system for directly making a plate from digital data of a computer without passing through a squirrel film or the like has attracted attention. In recent years, the development of lasers has been remarkable. Particularly, solid-state lasers and semiconductor lasers that emit light in the near-infrared to infrared regions have become easily available in high-power and small-sized products. These lasers are very useful as exposure light sources for such systems.

An image recording material suitable for laser writing is used as a photosensitive printing plate for this purpose. Japanese Patent Application Laid-Open No. 7-285275 discloses a printing plate for this purpose, which includes a binder such as a cresol resin and a substance that absorbs light to generate heat, and is thermally decomposable such as quinonediazide; Positive-type image recording materials have been proposed that contain substances that substantially reduce the solubility of the binder when not decomposed. In this method, a substance that absorbs the light and generates heat generates heat in an exposed portion by exposure to an infrared laser, thereby expressing the solubility of the exposed portion.

[0007] By the way, the photosensitive lithographic printing original plate, which can be directly made in the heat mode, has a disadvantage that when the developing process is performed,
The environmental, economic, quality maintenance, and work problems associated with the development of the lithographic printing plate described above appear as particularly serious defects. That is, the heat mode printing plate
Since the discrimination due to the exposure is small, the discrimination is liable to be affected by a variation factor that does not cause a problem in the related art. One of them is deterioration of developability during storage over time. When this type of printing original plate is stored for a long period of time, the developability of the photosensitive layer gradually deteriorates, and a remarkable difference in developability occurs immediately after application and after storage. Cause quality fluctuations.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to make a plate in a heat mode directly from digital information of a computer or the like, without being affected by a change over time during the storage period of a lithographic printing plate. And within the day of the development conditions,
It is an object of the present invention to provide a developing method capable of stably producing a printing plate without being affected by daily fluctuation. Another object of the present invention is to provide a suitable development processing apparatus for the lithographic printing original plate, which can maintain the developability stably for a long period of time.

[0009]

Means for Solving the Problems The inventors of the present invention have developed a photosensitive lithographic printing plate capable of directly making a plate in a heat mode. As a result of intensive studies on the means for maintaining the performance of the developer, the use of hydroxyl ions generated by the electrolysis of water enables the activity of the developer to be stably maintained with high accuracy, and the developability of the original printing plate over time. Of the present invention, and found that storage stability of developability was improved, and the present invention was achieved.

The present invention provides a method for developing a photosensitive lithographic printing plate precursor as described in claim 1, wherein the photosensitive lithographic printing plate precursor comprises at least (A) an alkali-soluble polymer compound, (B) compatibilizing with the alkali-soluble polymer compound, thereby reducing the solubility of the polymer compound in an aqueous alkali solution, heating, and reducing the solubility-reducing action of the compound by heating; and (C) absorbing light. A lithographic printing original plate having a photosensitive layer obtained by applying a positive photosensitive composition for an infrared laser containing a compound that generates heat on a support, and a developing method for processing the original plate uses an alkaline developer. A method, comprising: maintaining the activity of a developing solution by applying a current between electrodes through a developing solution in a cathode chamber of an energizing means having a cathode chamber and an anode chamber associated with the developing means. A photosensitive lithographic printing plate precursor development processing method of the symptoms. That is, the development processing method of the present invention
It is characterized in that it is of an electrolytically activated type, and prevents the hydroxyl ions generated by energization from lowering the activity of the developing solution, thereby maintaining stable development quality. The above photosensitive printing plate is
It has the property that the developability deteriorates with time, and the degree of the deterioration varies depending on the storage period of the original plate used, but when the development treatment is performed by the above-described electrolytic activation method of the present invention,
The defect does not appear. Also, during the day of the development conditions,
Similarly, it is hardly affected by daily fluctuations, and stable development can be maintained.

According to a second aspect of the present invention, the photosensitive lithographic printing plate to which the development processing method of the present invention is applied further comprises the above components (A), (B) and (C). (D) It is stated that a lithographic printing plate having a photosensitive layer containing a cyclic acid anhydride represented by the following general formula (I) is preferably used.

[0012]

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Where R¹, R^TwoIs independently hydrogen
Atom, alkyl having 1 to 12 carbons which may have a substituent
Group, alkenyl group, alkoxy group, cycloalkyl group,
Aryl group, carbonyl group, carboxy group, carboxylic acid
Represents an ester group. Note that R ¹, R^TwoAre connected to each other
A ring structure may be formed.

In the development method of the present invention of the electrolytic activation type,
As described in claim 3, when the photosensitive lithographic printing original plate is immersed in the developing solution and the developing process is performed, an electric current is applied between the electrodes via the developing solution according to the degree of fatigue of the developing solution accompanying the development. By controlling the amount of current to be supplied, the amount of hydroxyl ions supplied to the developing solution is controlled, whereby the activity of the developing solution is stably maintained. The method for detecting the fatigue of the developer accompanying the development is selected from the following three, and more effective when two or more are used in combination. (1) Reading of the processing area of the photosensitive lithographic printing original plate (2) Integration of time during which the developing process of the photosensitive lithographic printing original plate is not performed in the developing device (3) Developer stored in the developing device Of electrical conductivity (abbreviated as conductivity), specific gravity or opacity.

When the electrolytic activation method is employed, hydroxyl ions generated in the cathode chamber are used to maintain the activity of the developer, while hydrogen ions are generated in the anode chamber. According to claim 5 of the present invention, the hydrogen ions are guided to the treatment bath in the washing / stopping step following the development step, thereby lowering the pH to promote the washing / stopping action, and at the same time, reducing the load on the wastewater treatment of the development wastewater. This is a description of an embodiment in which the above-described operation is performed.

[0016] The developing device according to claim 6 is a developing means for sequentially processing the photosensitive lithographic printing original plate with a developing solution, a detecting means for detecting fatigue of the developing solution accompanying the development or the aging of the developing solution, A developing means for the photosensitive lithographic printing original plate of the present invention, comprising: an energizing means for generating hydroxyl ions by energizing between electrodes through a liquid; and a circulating means for coupling the developing means and the energizing means. Of the developing device. The energizing means is an electrolysis device including a cathode chamber, an anode chamber, a porous membrane or a liquid junction for allowing electricity to flow between the cathode chamber and the anode chamber, and an electrode provided in each chamber. Hydrogen ions are generated in the chamber and hydrogen ions are generated in the anode chamber.

A developing device according to a seventh aspect of the present invention is a device for use in a mode in which hydrogen ions generated in an anode chamber are used in a washing / stopping step. And a liquid feeding means for coupling with the anode chamber.

The image forming mechanism in the plate making method of the present invention is based on (A) an alkali-soluble polymer compound (hereinafter, referred to as “A”).
(Sometimes referred to as "(A) component")), (B) a molecule having a group that interacts with the alkali-soluble polymer compound in the molecule, and being compatible with the polymer compound, Reduces solubility in aqueous alkaline solutions,
Compounds that decrease the solubility lowering effect by heating (hereinafter, referred to as
By combining "(B) component") and (C) a compound that absorbs light and generates heat,
The component (B) is homogeneously compatible with the component (A) during the formation of a coating film, and reduces the solubility of the component (A) in an aqueous alkaline solution. , The compound which absorbs (C) light and generates heat in the exposed portion generates heat.
It is considered that the component (A) and the component (B) are separated, the dissolution inhibiting ability by the interaction is reduced, and the exposed portion is removed by the alkali developing solution in the developing step. Therefore, in the photosensitive original plate, the component (B) changes due to the aging of the original plate, and the pH of the photosensitive composition of the original plate changes. Due to the inferiority of the photosensitive original plate, there is an inherent property that even a slight change in the activity of the developer greatly affects the effect. It is estimated that this variation is prevented.

The electrolytic activation type developing method is known for developing silver halide photosensitive materials. Is ineffective and not practical.

When the heat mode master plate is stored for a long period of time, the developability of the exposed portion of the photosensitive layer gradually deteriorates.
When the cyclic acid anhydride represented by the general formula (I) is added, the structure has a bond conjugated with the carbonyl group of the carboxylic acid anhydride, thereby increasing the stability of the carbonyl group, and increasing the decomposition rate during storage. And the acid is gradually decomposed at an appropriate rate to gradually generate an acid, so that the developability in the photosensitive layer is always maintained at a constant level, and the solubility in an alkali developing solution can be maintained for a long time. Guessed.
Therefore, if the developing method of the present invention is applied to the development of a printing plate containing the component (D), the development quality can be further stabilized.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A photosensitive lithographic printing original plate, an exposure for image recording, a developing method, a developing apparatus, and a plate making method used in the present invention will be sequentially described below.

[Lithographic printing plate precursor] First, the photosensitive lithographic printing plate precursor used in the present invention will be described. This printing plate has a photosensitive layer formed by coating a positive photosensitive composition for an infrared laser (hereinafter, may be simply referred to as a “photosensitive composition”) on a support. Depending on the other layers.

(Photosensitive Layer) The positive photosensitive composition for an infrared laser contained in the photosensitive layer is (A) an alkali-soluble polymer compound, and (B) the high-sensitivity compound is compatible with the alkali-soluble polymer compound. A compound that reduces the solubility of a molecular compound in an aqueous alkali solution and decreases the solubility-lowering effect by heating; (C) a compound that absorbs light and generates heat; and (D) a compound that is expressed by the general formula (I) And, if necessary, other components.

The components of the photosensitive composition used in the lithographic printing plate of the present invention will be described below. — (A) Alkali-Soluble Polymer Compound— The alkali-soluble polymer compound used in the present invention is not particularly limited as long as it is a conventionally known one. (A-1) a phenolic hydroxyl group, A sulfonamide group, (A
-3) It is preferable that the polymer compound has any functional group of the active imide group in the molecule. For example, the following are exemplified, but the present invention is not limited thereto.

(A-1) Examples of the high molecular compound having a phenolic hydroxyl group include phenol formaldehyde resin, m-cresol formaldehyde resin and p-formaldehyde resin.
Novolak resins such as cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p-, or m- / p-mixture) and mixed formaldehyde resin, and pyrogallol acetone resin are exemplified. Can be As the high molecular compound having a phenolic hydroxyl group, a high molecular compound having a phenolic hydroxyl group in a side chain is preferably used. As the high molecular compound having a phenolic hydroxyl group in the side chain, a polymerizable monomer composed of a low molecular weight compound having at least one unsaturated bond capable of polymerizing with the phenolic hydroxyl group is homopolymerized, or another polymerizable monomer is used. Examples include a polymer compound obtained by copolymerizing a monomer.

Examples of the polymerizable monomer having a phenolic hydroxyl group include acrylamide, methacrylamide, acrylate, methacrylate, and hydroxystyrene having a phenolic hydroxyl group. Specifically, N- (2-hydroxyphenyl) acrylamide, N- (3-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) acrylamide, N- (2-hydroxyphenyl) methacrylamide, N- (3 -Hydroxyphenyl) methacrylamide, N- (4-hydroxyphenyl) methacrylamide, o-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate, p-hydroxyphenyl acrylate, o-hydroxyphenyl methacrylate,
m-hydroxyphenyl methacrylate, p-hydroxyphenyl methacrylate, o-hydroxystyrene,
m-hydroxystyrene, p-hydroxystyrene, 2
-(2-hydroxyphenyl) ethyl acrylate, 2
-(3-hydroxyphenyl) ethyl acrylate, 2
-(4-hydroxyphenyl) ethyl acrylate, 2
-(2-hydroxyphenyl) ethyl methacrylate,
2- (3-hydroxyphenyl) ethyl methacrylate, 2- (4-hydroxyphenyl) ethyl methacrylate and the like can be suitably used. Such resins having a phenolic hydroxyl group may be used in combination of two or more.

(A-2) As the alkali-soluble polymer compound having a sulfonamide group, a polymer obtained by homopolymerizing a polymerizable monomer having a sulfonamide group or copolymerizing the monomer with another polymerizable monomer can be used. Molecular compounds. As the polymerizable monomer having a sulfonamide group, at least 1
Sulfonamide group -NH-SO with two hydrogen atoms bonded
_2- and a polymerizable monomer comprising a low-molecular compound having at least one polymerizable unsaturated bond.
Among them, a low-molecular compound having an acryloyl group, an allyl group, or a vinyloxy group and a substituted or monosubstituted aminosulfonyl group or a substituted sulfonylimino group is preferable. As such a compound, for example, the following general formula (I
Compounds represented by I) to (VI) are mentioned.

[0028]

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In the formula, X ¹ and X ² each represent —O— or —NR ⁷ —. R ¹ and R ⁴ each represent a hydrogen atom or —CH ₃ . R ² , R ⁵ , R ⁹ , R ¹² and R
¹⁶ has 1 to 1 carbon atoms each of which may have a substituent.
2 represents an alkylene group, a cycloalkylene group, an arylene group or an aralkylene group. R ³ , R ⁷ and R ¹³ each represent a hydrogen atom, each having 1 to 5 carbon atoms which may have a substituent;
12 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. R ⁶ and R ¹⁷ each represent an optionally substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. R ^8, R ¹⁰ and R ¹⁴ represents a hydrogen atom or -CH _3. R ¹¹ and R ¹⁵ each represent a single bond or an optionally substituted alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, an arylene group or an aralkylene group. Y ¹ and Y ² each represent a single bond or —CO—. Specifically, m-aminosulfonylphenyl methacrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl)
Acrylamide and the like can be suitably used.

(A-3) The alkali-soluble polymer compound having an active imide group is preferably one having an active imide group represented by the following formula in the molecule. An active imide group represented by the following formula and a polymerizable monomer composed of a low-molecular compound having at least one polymerizable unsaturated bond are homopolymerized, or obtained by copolymerizing another monomer with the monomer. High molecular compounds are exemplified.

[0031]

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As such a compound, specifically,
N- (p-toluenesulfonyl) methacrylamide, N
-(P-Toluenesulfonyl) acrylamide and the like can be suitably used.

Further, as the alkali-soluble polymer compound of the present invention, two or more of the above-mentioned polymerizable monomers having a phenolic hydroxyl group, polymerizable monomers having a sulfonamide group, and polymerizable monomers having an active imide group are provided. It is preferable to use a polymer compound obtained by polymerizing the above, or a polymer compound obtained by copolymerizing another polymerizable monomer with two or more polymerizable monomers. When a polymerizable monomer having a sulfonamide group and / or a polymerizable monomer having an active imide group is copolymerized with a polymerizable monomer having a phenolic hydroxyl group, the mixing weight ratio of these components is from 50:50 to 5: It is preferably in the range of 95, particularly preferably in the range of 40:60 to 10:90.

In the present invention, the alkali-soluble polymer compound is a polymerizable monomer having a phenolic hydroxyl group, a polymerizable monomer having a sulfonamide group, or a polymerizable monomer having an active imide group and another polymerizable monomer. In the case of a copolymer, it is preferable that the monomer for imparting alkali solubility is contained in an amount of 10 mol% or more,
Those containing 20 mol% or more are more preferable. When the amount of the copolymer component is less than 10 mol%, alkali solubility tends to be insufficient, and the effect of improving development latitude may not be sufficiently achieved.

Examples of the monomer component to be copolymerized with the polymerizable monomer having a phenolic hydroxyl group, the polymerizable monomer having a sulfonamide group, or the polymerizable monomer having an active imide group include the following (1) to (12)
The following monomers can be used, but are not limited thereto.

(1) Acrylic esters and methacrylic esters having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. (2) Alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, glycidyl acrylate and N-dimethylaminoethyl acrylate. (3) Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, glycidyl methacrylate, and N-dimethylaminoethyl methacrylate. (4) acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-
Acrylamide or methacrylamide such as hydroxyethylacrylamide, N-phenylacrylamide and N-ethyl-N-phenylacrylamide. (5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether and phenyl vinyl ether. (6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate.

(7) Styrenes such as styrene, α-methylstyrene, methylstyrene and chloromethylstyrene. (8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone. (9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene. (10) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like. (11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, and N- (p-chlorobenzoyl) methacrylamide. (12) acrylic acid, methacrylic acid, maleic anhydride,
Unsaturated carboxylic acids such as itaconic acid;

In the present invention, the alkali-soluble polymer compound may be a homopolymer or a copolymer of the polymerizable monomer having a phenolic hydroxyl group, the polymerizable monomer having a sulfonamide group, or the polymerizable monomer having an active imide group. In this case, those having a weight average molecular weight of 2,000 or more and a number average molecular weight of 500 or more are preferable. More preferably, the weight average molecular weight is from 5,000 to 300,000.
And the number average molecular weight is 800 to 250,000, and the degree of dispersion (weight average molecular weight / number average molecular weight) is 1.1 to 10
belongs to. Further, in the present invention, when the alkali-soluble polymer compound is a resin such as a phenol formaldehyde resin or a cresol aldehyde resin, the compound having a weight average molecular weight of 500 to 20,000 and a number average molecular weight of 200 to 10,000. Is preferred.

Each of these alkali-soluble polymer compounds may be used alone or in combination of two or more. 30 to 99% by weight, preferably 40 to 95% by weight based on the total solid content of the photosensitive composition. Particularly preferably 50
It is used in an amount of up to 90% by weight. If the amount of the alkali-soluble polymer compound is less than 30% by weight, the durability of the photosensitive layer deteriorates, and if it exceeds 99% by weight, both sensitivity and durability are not preferred.

-(B) a compound which, by being compatible with the above-mentioned alkali-soluble polymer compound, reduces the solubility of the polymer compound in an aqueous alkali solution and reduces the action of lowering the solubility by heating. Has good compatibility with the alkali-soluble polymer compound (A) due to the function of the hydrogen-bonding functional group present in the molecule, can form a uniform coating solution, and has good compatibility with the component (A). It refers to a compound having a function of suppressing the alkali solubility of the component (A) through interaction. In addition, this compound loses its solubility lowering effect by heating, but when the component (B) itself is a compound that decomposes by heating, sufficient energy for decomposition is not provided depending on conditions such as laser output and irradiation time. In addition, the effect of inhibiting the solubility is insufficiently reduced, and the sensitivity may be reduced. Therefore, the thermal decomposition temperature of the component (B) is preferably 150 ° C. or higher.

Suitable components (B) for use in the present invention include compounds that interact with component (A), such as sulfone compounds, ammonium salts, phosphonium salts, and amide compounds. The component (B) should be appropriately selected in consideration of the interaction with the component (A) as described above. Specifically, for example, when a novolak resin is used alone as the component (A) The cyanine dye A exemplified below is preferably used.

The mixing ratio of component (A) to component (B) is usually preferably in the range of 99/1 to 75/25. When the amount of the component (B) is less than 99/1, the interaction with the component (A) becomes insufficient, so that the alkali solubility cannot be inhibited and good image formation is difficult. Also, 75/25
When the amount of the component (B) is larger than that, the interaction is excessive, and the sensitivity is remarkably lowered.

-(C) Compound that absorbs light and generates heat-The compound that absorbs light and generates heat in the present invention is 70%.
0 or more, preferably a light absorption region in the infrared region of 750 to 1200 nm, which indicates light / heat conversion capability in light having a wavelength in this range, and specifically absorbs light in this wavelength region. Various pigments or dyes that generate heat can be used. Examples of the pigment include commercially available pigments and color index (CI) handbook, "Latest Pigment Handbook"
(Edited by Japan Pigment Technology Association, 1977), “Latest Pigment Application Technology” (CMC Publishing, 1986), and “Printing Ink Technology”, CMC Publishing, 1984) can be used.

Examples of the pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and polymer-bound pigments. . Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelated azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments And quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like.

These pigments may be used without surface treatment, or may be used after surface treatment. Methods of surface treatment include a method of surface-coating a resin or wax, a method of attaching a surfactant, and a reactive substance (for example, a silane coupling agent, an epoxy compound, or a polyisocyanate).
Can be conceived on the surface of the pigment. The above surface treatment methods are described in "Properties and Applications of Metallic Soap" (Koshobo),
It is described in "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986).

The particle size of the pigment is preferably in the range of 0.01 to 10 μm, more preferably in the range of 0.05 to 1 μm, and particularly preferably in the range of 0.1 to 1 μm. . When the particle size of the pigment is less than 0.01 μm, the dispersion is not preferred in terms of stability in the coating solution for the photosensitive layer, and when it exceeds 10 μm, the uniformity of the photosensitive layer is not preferred. As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. See “Latest Pigment Application Technology” (CMC
Publishing, 1986).

Examples of the dye include commercially available dyes and literatures (for example, “Dye Handbook” edited by The Society of Synthetic Organic Chemistry, Showa 45)
Known publications described in the annual publication can be used. Specific examples include azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, and cyanine dyes. In the present invention, among these pigments or dyes, those that absorb infrared light or near-infrared light are particularly preferable because they are suitable for use in lasers that emit infrared light or near-infrared light.

As such a pigment absorbing infrared light or near infrared light, carbon black is suitably used. Dyes that absorb infrared light or near infrared light include, for example, cyanine dyes described in JP-A-59-202829 and JP-A-60-78787, Methine dyes described in JP-A-194595 and the like; naphthoquinone dyes described in JP-A-59-48187, JP-A-59-73996, JP-A-60-52940 and the like; 1958
Examples include squarylium dyes described in publications such as No. 12792, cyanine dyes described in British Patent No. 434,875, and dihydroperimidine squarylium dyes described in U.S. Pat. No. 5,380,635.

Also, US Pat.
The near-infrared absorption sensitizer described in US Pat. No. 6,938 is also preferably used, and substituted arylbenzo (thio) pyrylium salts described in U.S. Pat. No. 57-142645 (U.S. Pat.
7,169)), trimethinethiapyrylium salts described in JP-A-58-220143 and JP-A-59-146063.
, A pyranium compound described in JP-A-59-146061, a cyanine dye described in JP-A-59-216146, and a pentamethinethiopyrylium salt described in U.S. Pat. No. 4,283,475. Etc. 5
Nos. 13514 and 5-19702, a pyrylium compound, Epollight III-17
8, Epollight III-130, Epollight
III-125, Epolight IV-62A and the like are particularly preferably used.

Another particularly preferred example of the dye is a near-infrared absorbing dye described as formulas (I) and (II) in US Pat. No. 4,756,993. . These pigments or dyes are used in an amount of 0.01 to 50% by weight, preferably 0.1 to 10% by weight based on the total solid content of the photosensitive layer, particularly preferably 0.5 to 10% by weight in the case of dyes, and in the case of pigments. Particularly preferred is 3.1.
It can be added to the photosensitive composition in a proportion of 10 to 10% by weight. If the amount of the pigment or dye is less than 0.01% by weight, the sensitivity is lowered. If the amount exceeds 50% by weight, the uniformity of the photosensitive layer is lost and the durability of the photosensitive layer is deteriorated. These dyes or pigments may be added to the same layer as other components, or another layer may be provided and added to the layer. In the case of a separate layer, it is desirable to add the layer to a layer adjacent to the layer containing a substance which substantially reduces the solubility of the alkali-soluble polymer compound in the state of being thermally decomposable and not decomposed in the present invention. The dye or pigment and the alkali-soluble polymer compound are preferably in the same layer, but may be in different layers.

Component (B + C) In the present invention, the solubility of the polymer compound in an aqueous alkali solution is reduced by being compatible with the alkali-soluble polymer compound (B), and the solubility is reduced by heating. One compound having both properties (hereinafter, may be referred to as “(B + C) component”) in place of the compound having reduced action and the compound (C) which absorbs light and generates heat. The compound may be, for example, a compound represented by the following general formula (VII).

[0052]

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In the general formula (VII), R _{1 to} R ₄ each independently represent a hydrogen atom or a carbon atom having 1 to 5 carbon atoms which may have a substituent.
12 represents an alkyl group, an alkenyl group, an alkoxy group, a cycloalkyl group, or an aryl group, and R ₁ and R ₂ , and R ₃ and R ₄ may be bonded to each other to form a ring structure.
Here, as R _{1 to} R ₄ , specifically, a hydrogen atom,
Examples include a methyl group, an ethyl group, a phenyl group, a dodecyl group, a naphthyl group, a vinyl group, an allyl group and a cyclohexyl group. When these groups have a substituent, examples of the substituent include a halogen atom, a carbonyl group, a nitro group, a nitrile group, a sulfonyl group, a carboxyl group, a carboxylic acid ester, and a sulfonic acid ester.
R _{5 to} R ₁₀ each independently represent an alkyl group having 1 to 12 carbon atoms which may have a substituent, wherein R _{5 to} R ₁₀
Specific examples include a methyl group, an ethyl group, a phenyl group, a dodecyl group, a naphthyl group, a vinyl group, an allyl group, and a cyclohexyl group. When these groups have a substituent, examples of the substituent include a halogen atom, a carbonyl group, a nitro group, a nitrile group, a sulfonyl group, a carboxyl group, a carboxylic acid ester, and a sulfonic acid ester.

R _{11 to} R ₁₃ each independently represent a hydrogen atom,
Represents a halogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent, wherein R ₁₂ may be bonded to R ₁₁ or R ₁₃ to form a ring structure, and m> In the case of 2, a plurality of R ₁₂ may be bonded to each other to form a ring structure. Specific examples of R _{11 to} R ₁₃ include a chlorine atom, a cyclohexyl group, a cyclopentyl ring and a cyclohexyl ring formed by bonding R ₁₂ to each other. When these groups have a substituent, examples of the substituent include a halogen atom, a carbonyl group, a nitro group, a nitrile group, a sulfonyl group, a carboxyl group, a carboxylic acid ester, and a sulfonic acid ester. M represents an integer of 1 to 8, preferably 1 to 3. R _{14 to} R ₁₅ each independently represent a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 8 carbon atoms, and R ₁₄ is bonded to R ₁₅ to form a ring structure. When m> 2, a plurality of R ₁₄ may be bonded to each other to form a ring structure. Specific examples of R _{14 to} R ₁₅ include a chlorine atom, a cyclohexyl group, a cyclopentyl ring and a cyclohexyl ring formed by bonding R ₁₄ to each other. When these groups have a substituent, examples of the substituent include a halogen atom, a carbonyl group, a nitro group, a nitrile group, a sulfonyl group, a carboxyl group, a carboxylic acid ester, and a sulfonic acid ester. M represents an integer of 1 to 8, preferably 1 to 3.

In the general formula (VII), X ⁻ represents an anion. Specific examples of the anion include perchloric acid, tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 5-sulfosalicylic acid, 2,5-dimethylbenzene Sulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol- 5-sulfonic acid, 2-
Methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, p-toluenesulfonic acid and the like can be mentioned. Of these, alkyl aromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid are particularly preferably used.

The compound represented by the general formula (VII) is a compound generally called a cyanine dye. Specifically, the following compounds are suitably used, but the present invention is not limited to these specific examples. Not something.

[0057]

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The component (B + C) has a property of absorbing light to generate heat (that is, the characteristic of the component (C)), has an absorption range in the infrared region of 700 to 1200 nm, and is further alkali-soluble. Good compatibility with high molecular compounds,
It is a basic dye and has a group that interacts with an alkali-soluble polymer compound such as an ammonium group or an iminium group in the molecule (that is, it has the characteristics of the component (B)), so that it interacts with the polymer compound. Thus, its alkali solubility can be controlled and can be suitably used in the present invention.

In the present invention, when a compound (B + C) having both properties like the above-mentioned cyanine dye is used instead of the components (B) and (C), the amount of the compound added is (A) 99/1 to 70/3 based on the components
The range of 0 is preferable from the viewpoint of sensitivity, and 99/1 to 75 /.
A range of 25 is more preferred.

-(D) Cyclic Acid Anhydride- It is preferable to add a cyclic acid anhydride as an additional additive component to the photosensitive lithographic printing original plate used in the present invention. A preferred cyclic anhydride is represented by the following general formula (I), and has a bond conjugated to the carbonyl group of the carboxylic acid anhydride in its structure, controls the decomposition rate by increasing the stability of the carbonyl group, During storage, it decomposes at an appropriate rate and generates an acid, which suppresses the deterioration of developability over storage time. Can be reached.

[0061]

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Where R¹, R^TwoIs independently hydrogen
Atom, alkyl having 1 to 12 carbons which may have a substituent
Group, alkenyl group, alkoxy group, cycloalkyl group,
Aryl group, carbonyl group, carboxy group, carboxylic acid
Represents an ester group. Note that R ¹, R^TwoAre connected to each other
A ring structure may be formed. R¹, R^TwoAs a hydrogen source
, Unsubstituted alkyl group having 1 to 12 carbon atoms, aryl
Groups, alkenyl groups, and cycloalkyl groups are preferred
Specific examples include a hydrogen atom, a methyl group,
Tyl, phenyl, dodecyl, naphthyl, vinyl
Group, allyl group, cyclohexyl group and the like.

When R ¹ and R ² are linked to each other to form a ring structure, the formed group includes a phenylene group, a naphthylene group, a cyclohexene group, a cyclopentene group and the like. When these groups in R ¹ and R ² have a substituent, examples of the substituent include a halogen atom, a hydroxy group, a carbonyl group, a sulfonate, a nitro group, and a nitrile group.

Among the above acid anhydrides, the following general formula (I)
Compounds having a structure represented by -2) are preferred.

[0065]

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In the formula, R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom, a hydroxy group, a halogen atom such as chlorine, a nitro group, a nitrile group, or a carbon atom which may have a substituent. And 1 to 12 alkyl groups, alkenyl groups, alkoxy groups, cycloalkyl groups, aryl groups, carbonyl groups, carboxy groups, carboxylic acid ester groups, and the like. R ³ , R
^4, the R ^5, R ^6, a hydrogen atom, a halogen atom, an unsubstituted alkyl group having 1 to 12 carbon atoms, are mentioned as the alkenyl group, an aryl group having 6 to 12 carbon atoms are preferred, specifically Represents a methyl group, a vinyl group, a phenyl group,
Allyl groups and the like.

When these groups in R ³ , R ⁴ , R ⁵ and R ⁶ have a substituent, the substituent may be a halogen atom, a hydroxy group, a carbonyl group, a sulfonic acid ester, a nitro group, a nitrile group, And a carboxy group.

Specific examples of the cyclic acid anhydride preferably used in the present invention include phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, 3-hydroxyphthalic anhydride, -Methyl phthalic anhydride, 3-phenylphthalic anhydride, trimetic anhydride, pyromethic anhydride, maleic anhydride, phenylmaleic anhydride, dimethylmaleic anhydride, dichloromaleic anhydride, chloromaleic anhydride and the like are mentioned as preferable ones. Can be

The proportion of the cyclic acid anhydride in the solid content of the photosensitive composition is preferably 0.5 to 20% by weight,
15% by weight is more preferable, and 1 to 10% by weight is particularly preferable. If the content is less than 0.5% by weight, the effect of maintaining developability becomes insufficient, and if it exceeds 20% by weight, no image is formed, and both are not preferred.

-Other Components- Various additives can be further added to the photosensitive composition of the lithographic printing plate used in the present invention, if necessary. For example, an onium salt, an o-quinonediazide compound, an aromatic sulfone compound, an aromatic sulfonic acid ester compound or the like, which is thermally decomposable, and is used in combination with a substance that substantially reduces the solubility of an alkali water-soluble polymer compound when not decomposed. This is preferable from the viewpoint of improving the dissolution inhibiting property of the image area in the developer. Examples of onium salts include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts, and the like.

As the onium salt used in the present invention, known compounds can be widely used. Representative examples of each of the known compound groups include the following, but other known compounds can also be used for the original printing plate that is the object of the present invention. That is, for example, SI
Schlesinger, Photogr. Sci. Eng., 18, 387 (1974),
TS Bal et al, Polymer, 21, 423 (1980), diazonium salts, ammonium salts described in the specification of JP-A-3-140140, DC Necker et al, Macromolecules,
17, 2468 (1984) Phosphonium salts described in U.S. Pat.No. 4,069,055, JVCrivello et al, Macromorecules, 10
(6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31.
(1988) JP-A-2-150848, iodonium salts described in JP-A-2-296514, JV Crivello et al, Polymer J. 1
7, 73 (1985), U.S. Patent No. 4,933,377, German Patent No. 3,
Nos. 604,580 and 3,604,581, sulfonium salts,
JV Crivello et al, J. Polymer Sci., Polymer Che
m. Ed., 17, 1047 (1979).
S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA,
p478 Tokyo, Oct (1988). In the present invention, diazonium salts are particularly preferred. Particularly preferred diazonium salts include those described in JP-A-5-158230.

Suitable quinonediazides include o-quinonediazide compounds. The o-quinonediazide compound used in the present invention is a compound having at least one o-quinonediazide group, which increases alkali solubility by thermal decomposition, and may be a compound having various structures. In other words, o-quinonediazide assists the solubility of the light-sensitive material system by both the effect of losing the ability to suppress the dissolution of the binder by thermal decomposition and the fact that o-quinonediazide itself changes to an alkali-soluble substance. Examples of the o-quinonediazide compound used in the present invention include those described in J. Am. The compounds described in "Light-Sensitive Systems" (John Wiley & Sons. Inc.), pp. 339-352, can be used. Sulfonic acid esters or amides of quinonediazides are preferred. Also, benzoquinone (1,2)-as described in JP-B-43-28403.
Diazidesulfonic acid chloride or naphthoquinone-
Esters of (1,2) -diazide-5-sulfonic acid chloride with pyrogallol-acetone resin, U.S. Pat.
Esters of benzoquinone- (1,2) -diazidosulfonic acid chloride or naphthoquinone- (1,2) -diazido-5-sulfonic acid chloride and phenol-formaldehyde resin described in 046,120 and 3,188,210 are also used. It is preferably used.

Further, esters of naphthoquinone- (1,2) -diazide-4-sulfonic acid chloride with phenol formaldehyde resin or cresol-formaldehyde resin, naphthoquinone- (1,2) -diazide-
Esters of 4-sulfonic acid chloride with pyrogallol-acetone resin are likewise preferably used. Other useful o-quinonediazide compounds are reported and known in numerous patents. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48-63803, JP-A-48-96
No. 575, JP-A-49-38701, JP-A-48-13354, JP-B-41-11222, JP-B-45-9610, JP-B-49-17481
U.S. Pat.Nos. 2,797,213, 3,454,400, 3,544,323, 3,573,917, and 3,674,495
No. 3,785,825; British Patent No. 1,227,602;
Nos. 1,251,345, 1,267,005, 1,329,888,
No. 1,330,932, German Patent No. 854,890, etc. can be mentioned.

An onium salt, an o-quinonediazide compound,
The amount of the aromatic sulfonic acid ester or the like is preferably 0.1 to 50% by weight, more preferably 0.5 to 30% by weight, and particularly preferably 0.5 to 50% by weight, based on the total solids of the photosensitive composition.
It is in the range of 20% by weight. These compounds can be used alone, but may be used as a mixture of several kinds.

For the purpose of improving the sensitivity, for example,
General-purpose cyclic acid anhydrides other than those shown in the general formula (I),
Phenols, organic acids, and sulfonyl compounds can also be used in combination. As the cyclic acid anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic anhydride and the like described in U.S. Pat. No. 4,115,128 can be used. Examples of phenols include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-phenol
Hydroxybenzophenone, 4,4 ', 4 "-trihydroxytriphenylmethane, 4,4', 3", 4 "-tetrahydroxy-3,5,3 ', 5'-tetramethyltriphenylmethane and the like. As organic acids,
Examples thereof include sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphate esters, and carboxylic acids described in JP-A-60-88942 and JP-A-2-96755. P-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, adipic acid, p-toluic acid, 3, 4-
Examples include dimethoxybenzoic acid, phthalic acid, erucic acid, lauric acid, n-undecanoic acid, ascorbic acid, methylphenylsulfone, diphenyldisulfone and the like. The proportion of the above-mentioned cyclic acid anhydride, phenols, organic acids, and sulfonyl compounds in the solid content of the photosensitive composition is preferably 0.05 to 20% by weight, more preferably 0.1 to 15% by weight. , 0.1 to 10% by weight is particularly preferred.

Further, in the photosensitive composition of the present invention, JP-A-62-251740 and JP-A-3-208514 are used in order to widen the stability of processing under development conditions.
Non-ionic surfactants described in JP-A-59-121044, JP-A-4-13149.
An amphoteric surfactant such as that described in JP-A No. 2-211 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, monoglyceride stearic acid, and polyoxyethylene nonyl phenyl ether. Specific examples of the amphoteric surfactant include:
Alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-N, N-betaine type (for example, trade name "Amogen K ": Manufactured by Dai-ichi Kogyo Co., Ltd.). The proportion of the nonionic surfactant and the amphoteric surfactant in the solid content of the photosensitive composition is 0.05 to 15%.
% By weight, more preferably 0.1 to 5% by weight.

In the photosensitive composition of the present invention, a printing-out agent for obtaining a visible image immediately after heating by exposure,
Dyes and pigments as image colorants can be added.
Representative examples of the printing-out agent include a combination of a compound that releases an acid by heating upon exposure (photoacid releasing agent) and an organic dye that can form a salt. Specifically, combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and salt-forming organic dyes described in JP-A-50-36209 and JP-A-53-8128, No. 36223, No. 54-74728, No. 60-
No. 3626, No. 61-143748, No. 61-151
And combinations of trihalomethyl compounds and salt-forming organic dyes described in JP-A Nos. 644 and 63-58440. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent temporal stability and give clear print-out images.

As the image coloring agent, other dyes can be used in addition to the above-mentioned salt-forming organic dyes. Suitable dyes, including salt-forming organic dyes, include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 10
1, oil yellow # 103, oil pink # 312,
Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black B
S, Oil Black T-505 (all manufactured by Orient Chemical Industries, Ltd.), Victoria Pure Blue, Crystal Violet (CI. 42555), Methyl Violet (CI. 42535), Ethyl Violet, Rhodamine B (C.I. I. 145170B), malachite green (C.I. 42000), methylene blue (C.I.
I. 52015) and the like. Also, JP-A-62-293247 and JP-A-5-3133
The dye described in JP-A-59-59 is particularly preferred. These dyes are used in an amount of 0.01 to 0.01% based on the solid content of the photosensitive composition.
It can be added to the photosensitive composition at a ratio of 10 to 10% by weight, preferably 0.1 to 3% by weight.

Further, a plasticizer may be added to the photosensitive composition according to the present invention, if necessary, in order to impart flexibility to the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid Oligomers and polymers are used. Further, if necessary, compounds decomposable by light, such as quinonediazides and diazo compounds, may be added to the photosensitive composition according to the present invention. The addition amount of these compounds is preferably 1 to 5% by weight based on the solid content of the photosensitive composition.

-Preparation of photosensitive layer- The photosensitive layer of the lithographic printing original plate used in the present invention is usually prepared by the above-mentioned method.
Dissolve the components in a solvent and coat on a suitable support
Can be manufactured. The solvent used here
Ethylene dichloride, cyclohexanone, methyl
Ethyl ketone, methanol, propanol, ethylene
Glycol monomethyl ether, 2-methoxyethyl alcohol
Acetate, 1-methoxy-2-propyl acetate, di
Methoxyethane, ethyl lactate, N, N-dimethylaceto
Amide, N, N-dimethylformamide, tetramethyl
Urea, N-methylpyrrolidone, dimethylsulfoxy
, Γ-butyrolactone, toluene and the like.
It is not limited to this. These solvents are
Used alone or as a mixture. The above components in the solvent
The concentration of the total solids including additives) is preferably 1 to 50 times
%. The coating on the support obtained after coating and drying
The amount of cloth (solid content) varies depending on the application, but photosensitive printing
Generally speaking about the plate, 0.5-5.0 g / m ^TwoIs good
Good.

Various methods can be used for coating, examples of which include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, roll coating and the like. Can be. As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the photosensitive film deteriorate.

A surfactant for improving coating properties, for example, a fluorine-based surfactant as described in JP-A-62-170950 can be added to the photosensitive layer. A preferable addition amount is 0.01 to 1% by weight, more preferably 0.05 to 1% by weight based on the total solid content of the photosensitive layer.
0.5% by weight.

(Support) As the support used in the present invention, a dimensionally stable plate can be used. For example, paper, plastic (eg, polyethylene, polypropylene, polystyrene, etc.) is laminated. Paper, metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene) , Polypropylene, polycarbonate, polyvinyl acetal, etc.),
Examples thereof include paper on which a metal is laminated or vapor-deposited, or a plastic film.

As the support, a polyester film or an aluminum plate is preferable, and among them, an aluminum plate which has good dimensional stability and is relatively inexpensive is particularly preferable. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and a trace amount of a different element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The content of the foreign element in the alloy is at most 10% by weight or less. Particularly preferred aluminum in the present invention is
Although it is pure aluminum, 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 an aluminum plate of a conventionally known and used material can be appropriately used. The thickness of the aluminum plate is approximately 0.1 to 0.6 mm, preferably 0.15 to 0.4 mm.
mm, particularly preferably 0.2 to 0.3 mm.

Prior to roughening the aluminum plate, if necessary, a degreasing treatment with, for example, a surfactant, an organic solvent or an aqueous alkaline solution is performed to remove rolling oil on the surface. The surface roughening treatment of the aluminum plate is performed by various methods, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of selectively dissolving the surface chemically. It is performed by the method of causing. Known mechanical methods such as a ball polishing method, a brush polishing method, a blast polishing method, and a buff polishing method can be used as the mechanical method. Further, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in a hydrochloric acid or nitric acid electrolyte. Also,
As disclosed in JP-A-54-63902, a method in which both are combined can also be used. The aluminum plate thus surface-roughened is subjected to an alkali etching treatment and a neutralization treatment as required, and then subjected to an anodic oxidation treatment, if desired, in order to increase the water retention and abrasion resistance of the surface. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, various electrolytes for forming a porous oxide film can be used, and generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of the electrolyte.

The anodizing treatment conditions vary depending on the electrolyte used and cannot be specified unconditionally. However, in general, the concentration of the electrolyte is a 1 to 80% by weight solution, the liquid temperature is 5 to 70 ° C.,
Current density 5 to 60 A / dm ^2, voltage 1 to 100 V, which is an electrolyzing time of 10 seconds to 5 minutes. If the amount of the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient or the non-image area of the lithographic printing plate is easily damaged, and the ink adheres to the damaged area during printing. So-called "scratch dirt" tends to occur. After the anodizing treatment, the aluminum surface is subjected to a hydrophilic treatment as necessary. US Pat. No. 2,714,066 describes the hydrophilic treatment.
No. 3,181,461, No. 3,280,734
And an alkali metal silicate (for example, an aqueous solution of sodium silicate) disclosed in Japanese Patent No. 3,902,734. In this method, the support is immersed in an aqueous solution of sodium silicate or electrolytically treated. In addition, potassium fluoride zirconate disclosed in JP-B-36-22063 and U.S. Pat.
276,868, 4,153,461, and 4,689,272, a method of treating with polyvinyl phosphonic acid, or the like is used.

(Other Layers) The lithographic printing plate precursor of the present invention comprises a support and provided thereon a photosensitive layer obtained by coating a positive photosensitive composition for infrared laser. An undercoat layer can be provided between them. As the component of the undercoat layer, various organic compounds are used, for example, carboxymethylcellulose, dextrin, gum arabic, phosphonic acids having an amino group such as 2-aminoethylphosphonic acid, and phenyl which may have a substituent. Organic phosphonic acids such as phosphonic acid, naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, phenylphosphoric acid, naphthylphosphoric acid, alkylphosphoric acid and alkylglycerol optionally having a substituent Organic phosphoric acids such as acids, organic phosphinic acids 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 triethanolamine Amides with hydroxy groups such as hydrochloride Although selected from the hydrochloride or the like, they may be used alone or may be used in admixture of two or more.

The coating amount of the organic undercoat layer is 2 to 200 mg /
m ² is appropriate, and 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 . In the lithographic printing plate of the present invention,
If necessary, an overcoat layer may be provided on the photosensitive layer. Examples of the overcoat layer component include polyvinyl alcohol, methacrylate, acrylate, and a mat material used for a normal photosensitive lithographic printing original plate.

[Exposure Step] The lithographic printing original plate produced as described above is subjected to exposure in an appropriate heat mode, preferably exposure to an infrared laser, and development processing using an alkali developing solution, and is subjected to plate making. . The photosensitive layer according to the present invention has an advantage that a positive type image can be formed by an infrared laser. Therefore, in the exposure step (imagewise exposure step), the light source of the actinic ray used for image exposure is 700 n in the near infrared to infrared region.
Light sources having an emission wavelength of at least m are preferred. The light source in the plate making method of the present invention is preferably 700 to 1200 nm.
Solid-state lasers and semiconductor lasers capable of irradiating infrared rays having the above-mentioned emission wavelength are particularly preferable. The lithographic printing plate may be exposed by a heat mode light source other than the infrared laser. For example, high-intensity xenon flash light, xenon arc light, light from a tungsten halogen lamp, laser light oscillating in the visible wavelength range, or the like that acts as a heat ray can be used.

[Developing Step] The developing step of the photosensitive lithographic printing original plate of the present invention will be described in detail in the order of a developing solution and a replenishing method developing apparatus. (Developing solution) Preferred examples of the developing solution (referred to as a developing solution) to which the developing method of the present invention can be applied include:
pH is in the range of 9.0 to 14.0, preferably 12.0 to
The developer is in the range of 13.5. In this specification, unless otherwise specified, the developing solution means both the developing solution and the developing replenisher in the state of the working solution filled in the developing tank. As a developing solution used for such a developing process, a conventionally known alkaline aqueous solution can be used. For example, sodium silicate, potassium, tribasic sodium, potassium, ammonium, dibasic sodium, potassium, ammonium, sodium carbonate,
Inorganic alkali agents such as potassium, 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-
Organic alkali agents such as butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine and pyridine are also used. These alkali agents are used alone or in combination of two or more.

Among the above-mentioned aqueous alkali solutions, the developing solution in which the effect of the present invention is further exerted contains an alkali silicate as a base or an alkali silicate obtained by mixing a base with a silicon compound. An aqueous solution having a pH of 12 or more, called a “silicate developer”, and a so-called “non-silicate developer” containing a non-reducing sugar and a base without containing alkali silicate.

In the former, the aqueous solution of the alkali metal silicate is prepared by mixing the ratio of silicon oxide SiO ₂ and the alkali metal oxide M ₂ O (generally [SiO ₂ ] /
[Expressed in the molar ratio of [M ₂ O]) and the concentration can be adjusted. For example, the molar ratio of SiO ₂ / Na ₂ O as disclosed in JP-A-54-62004 can be adjusted. Is 1.0 to 1.5 (that is, [SiO ₂ ] / [Na ₂ O] is 1.0 to 1.5), and the content of SiO ₂ is 1 to 4
Wt.% Aqueous solution of sodium silicate,
No. 427, [SiO ₂ ] /
[M] is 0.5 to 0.75 (that is, [SiO ₂ ] / [M
₂ O] is 1.0 to 1.5) and the concentration of SiO ₂ is 1
-4% by weight and the developer is at least 20% based on gram atoms of total alkali metal present therein.
Aqueous solutions of alkali metal silicates containing% potassium are preferably used.

Further, a so-called "non-silicate developer" containing no non-reducing sugar and a base without containing alkali silicate is also preferable for applying to the developing method of the present invention. Using this developer, the photosensitive lithographic printing plate is developed,
The surface of the photosensitive layer is not deteriorated, and the inking property of the photosensitive layer can be maintained in a good state. In addition, the photosensitive lithographic printing plate generally has a narrow developing latitude and a large change in image width and the like depending on the developer pH. Since it is contained, it is more advantageous than the case where a developing solution containing silicate is used. Furthermore, non-reducing sugars are less likely to contaminate a conductivity sensor, a pH sensor, and the like for controlling the liquid activity than silicates. Therefore, a non-silicate developer is also advantageous in this respect. That is,
The silicate developer and the non-silicate developer each have an excellent point, and are preferably applicable to the present invention.

The non-reducing sugar is a saccharide which does not have a free aldehyde group or ketone group and does not exhibit a reducing property. Glycosides and sugar alcohols obtained by hydrogenating and reducing saccharides can be suitably used in the present invention. In the present invention,
Non-reducing sugars described in JP-A-8-305039 can be suitably used.

The trehalose-type oligosaccharides include, for example, saccharose, trehalose and the like. Examples of the glycoside include an alkyl glycoside, a phenol glycoside, and a mustard oil glycoside. Examples of the sugar alcohol include D, L-arabit, ribit, xylit, D, L-sorbit, D, L-mannit, D, L-idit, D, L-tallit, zuricit, allozurcit and the like. . Furthermore, maltitol obtained by hydrogenating disaccharide maltose, reductant (reduced starch syrup) obtained by hydrogenating oligosaccharide, and the like are preferably mentioned. Among these non-reducing sugars, trehalose-type oligosaccharides and sugar alcohols are preferable. Among them, D-sorbitol, saccharose, reduced starch syrup, and the like are preferable because they have a buffering action in an appropriate pH range and are inexpensive.

In the present invention, these non-reducing sugars may be used alone or in a combination of two or more. The content of the non-reducing sugar in the non-silicate developer is preferably 0.1 to 30% by weight,
-20% by weight is more preferred. If the content is less than 0.1% by weight, a sufficient buffering effect cannot be obtained.

Examples of the base used in combination with the non-reducing sugar include conventionally known alkali agents such as inorganic alkali agents and organic alkali agents.
As the inorganic alkali agent, for example, sodium hydroxide,
Potassium hydroxide, lithium hydroxide, trisodium phosphate, tripotassium phosphate, triammonium phosphate, disodium phosphate, dipotassium phosphate, diammonium phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate , Potassium bicarbonate, ammonium bicarbonate, sodium borate, potassium borate, ammonium borate and the like.

Examples of the organic alkali agent include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine ,
Monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine and the like can be mentioned.

The bases may be used alone or in combination of two or more. Among these bases, sodium hydroxide and potassium hydroxide are preferred. The reason is that adjusting these amounts enables pH adjustment in a wide pH range. Trisodium phosphate, tripotassium phosphate, sodium carbonate, potassium carbonate and the like are also preferable because they have a buffering action by themselves. The content of the base used in the non-silicate developer is appropriately determined according to the desired pH, the type of the non-reducing sugar, the amount added, and the like. When the reducing sugar is used in combination with the base, the reducing sugar is browned, the pH is gradually lowered, and the developing property is lowered.

In the present invention, as the non-silicate developer, instead of using a non-reducing sugar and a base together,
Those containing an alkali metal salt of a non-reducing sugar as a main component can also be used. The alkali metal salt of the non-reducing sugar is obtained by mixing the non-reducing sugar with an alkali metal hydroxide and heating the mixture to a temperature equal to or higher than the melting point of the non-reducing sugar to dehydrate the non-reducing sugar. It is obtained by drying the aqueous solution mixed with the substance.

In the present invention, an alkaline buffer consisting of a weak acid other than the non-reducing sugar and a strong base can be used in combination with the non-silicate developer. The weak acid is preferably one having a dissociation constant (pKa) of 10.0 to 13.2, for example, Ionizati published by Pergmon Press.
on Constants of Organic Acidsin Aqueous Solution
And so on.

Specifically, 2,2,3,3-tetrafluoropropanol-1 (pKa 12.74), trifluoroethanol (12.37), trichloroethanol (12.24) and the like Alcohols, pyridine-2-
Aldehydes such as aldehyde (12.68) and pyridine-4-aldehyde (12.05), salicylic acid (13.0) and 3-hydroxy-2-naphthoic acid (1)
2.84), catechol (12.6), gallic acid (12.4), sulfosalicylic acid (11.7), 3, 4
-Dihydroxysulfonic acid (12.2), 3,4-dihydroxybenzoic acid (11.94), 1,2,4-trihydroxybenzene (11.82), hydroquinone (11.56), pyrogallol (Id. 11.34),
o-cresol (10.33), resorsonol (11.27), p-cresol (10.27), m-
Compounds having a phenolic hydroxyl group such as cresol (10.09);

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) and acetophenone oxime (11.37).
Oximes such as 35), adenosine (id. 12.56),
Inosine (12.5), guanine (12.3), cytosine (12.2), hypoxanthine (12.5).
1) nucleic acid-related substances such as xanthine (11.9);

In addition, diethylaminomethylphosphonic acid (12.32), 1-amino-3,3,3-trifluorobenzoic acid (12.29), isopropylidene diphosphonic acid (12.10), 1 1,1-ethylidene diphosphonic acid (11.54), 1,1-ethylidene diphosphonic acid 1-hydroxy (11.52), benzimidazole (12.86), thiobenzamide (12.86).
8), picoline thioamide (12.55), barbituric acid (12.5) and the like are preferred. Among these weak acids, sulfosalicylic acid and salicylic acid are preferred.

As the strong base to be combined with these weak acids, for example, sodium hydroxide, ammonium hydroxide,
Preferable examples include potassium hydroxide and lithium hydroxide. These strong bases may be used alone,
Two or more kinds may be used in combination. The strong base is used after adjusting the pH to a preferred range by appropriately selecting the concentration and combination.

In the present invention, in order to improve the developability, it is preferable to increase the alkali concentration of the alkali developing solution and perform the processing under so-called over conditions.
What is necessary is just to adjust the addition amount of the said base. That is, the base, the alkali developing solution is strongly alkaline, for example,
Preferably, p is adjusted so that the pH is between 12.5 and 13.5.
What is necessary is just to add to the said alkali developing solution so that H may be set to 12.8-13.3.

Various surfactants and organic solvents can be added to the developing solution, if necessary, for the purpose of accelerating the developing property, dispersing the developing residue and increasing the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. The surfactants can be used alone or in combination of two or more, and are added to the developer in an amount of 0.001 to 10% by weight, more preferably 0.01 to 5% by weight.

An organic solvent is further added to the developer 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-benzyloxyethanol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol,
-Methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol, N-phenylethanolamine, N-phenyldiethanolamine and the like can be mentioned. 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 used of the surfactant, and it is preferable to increase the amount of the surfactant as the amount of the organic solvent increases. This is because if the amount of the surfactant is small and the amount of the organic solvent is large, the organic solvent does not completely dissolve, and therefore, it is impossible to expect good developability.

The developer may further contain a preservative, if necessary.
Coloring agents, thickeners, defoamers, water softeners and the like can be included. Examples of water softeners include polyphosphoric acid and its sodium, potassium and ammonium salts, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and their alkali metal and ammonium salts, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylene Phosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), hydroxyethylethylenediaminetri (methylenephosphonic acid)
And 1-hydroxytaene-1,1-diphosphonic acid and their sodium, potassium and ammonium salts.

The appropriate addition amount of such a water softener varies depending on its chelating ability, the hardness of the hard water used and the amount of the hard water. 0.01 to 5% by weight, more preferably 0.0
It is in the range of 1-0.5% by weight. If the added amount is less than this range, the intended purpose is not sufficiently achieved, and if the added amount is more than this range, adverse effects on the image area such as color omission appear.

(Replenishment) In the development of the original plate for a photosensitive printing plate, the developer composition is consumed by consuming the developer components during the development reaction, dissolving the composition of the original plate, and contacting air during storage over time before development of the original plate. Is replenished to compensate for the change in.
In normal development processing, the pH of the developer is usually selected as a representative characteristic that is a guide for replenishment, and replenishment is performed so as to keep the pH value constant, or replenishment management based on the representative characteristic is not appropriate. Replenishment is performed with the replenishment amount increased to the required level. However, in the latter method, the discharge amount of the developing waste liquid is increased. In the former method, the heat mode type photosensitive lithographic printing plate used in the present invention has a pH value of
However, as described above, the fluctuation which cannot correspond to the photographic performance is large, which is not preferable. As a means for solving this problem, in the present invention, as described above, activation is performed by supplying hydroxyl ions to supplement the replenishment by applying a current between the electrodes via the developer. In the present invention, it is preferable that the supply of hydroxyl ions by energization is also performed according to the degree of fatigue of the developer. Therefore, there is a need for a detection means which does not depend on pH and which correctly reflects the degree of fatigue, and the present invention can be achieved by finding such a detection means.

Preferred detection means for detecting the fatigue of the developer, which is the key to the present invention, include the following three means. (1) Reading the processing area of the photosensitive lithographic printing original plate. For example, when a photosensitive lithographic printing original plate is exposed to light, the components (A), (B), and (C) are dissolved in a developing solution, so that alkali is consumed. In a developer system with poor buffering capacity, the relationship between the consumption of alkali and the fluctuation of pH is not uniquely determined, whereas the amount of the photosensitive material processed corresponds to the amount of alkali agent consumed during development. Moreover, it is an index that can be read accurately. Therefore, when the processing amount of the photosensitive material is used as an index, the degree of fatigue of the developer can be accurately detected.

(2) An integrated value of the time during which the development processing is not performed in the development processing apparatus. The developer for the photosensitive lithographic printing plate is usually pH 12 or higher,
Most of them have high alkalinity of 12.5 or more, and have a low salt concentration, so that the absorption rate of carbon dioxide in the air is high. As a result, the development activity is reduced correspondingly to the amount of the absorbed carbon dioxide gas. Therefore, the deterioration with time of the developing solution due to carbon dioxide gas progresses in proportion to the time during which the developing process is not performed in the developing device. Under these circumstances,
Since the salt concentration of the developer is low and the hydroxide ion concentration is high, the pH value is not an indicator of the deterioration over time due to absorption of carbon dioxide gas, and the integration time of the time when the development process is not performed is the alkali time. It is an index for controlling the supply amount, that is, an appropriate means for detecting the degree of fatigue. Here, "the development processing is not performed" means that the development is performed when the power of the development processing apparatus is turned on, the temperature and the replenishment system are ready, and the material of the photosensitive lithographic printing original plate is fed, that is, This is the sum of both the case of the so-called standby state and the case of the rest state where the power of the developing device is not turned on. There is no significant difference in the absorption rate of carbon dioxide between the standby state and the idle state where neither temperature control nor stirring of the developer is performed, so ignoring the slight difference between the two. Even if the total is integrated, there is no significant effect on the accuracy of the developer management. The detection of the degree of fatigue of the developer due to the development processing is performed according to the above (1), and the detection of the degree of fatigue of the developer due to the aging of the developer when the development processing is not performed is performed according to the above (2). The degree of fatigue of the developer due to both the development processing and the aging (standby and stop of the apparatus) can be detected by the method (3) described below.

(3) Detection of degree of fatigue based on physical property values other than pH value. On the other hand, physical property values other than the pH value can be used as physical property detection means. In the developer for the photosensitive lithographic printing plate, the alkali component is consumed by the development process, and this should appear as a decrease in hydroxyl ions, that is, a decrease in pH, conductivity, an increase in specific gravity, and an increase in opacity. However, as described repeatedly, the pH value does not correctly reflect the degree of fatigue of the developer due to various confounding factors, whereas physical properties other than the pH value respond in accordance with the degree of fatigue. Can be used as detecting means. Preferred physical properties that can be used for this purpose are electrical conductivity (hereinafter conductivity), specific gravity and opacity. Among them, the electrical conductivity unexpectedly reflects the fatigue level well. Probably, the high alkali and low salt concentrations greatly contribute to the conductivity of the hydroxide ions, and it is considered to be advantageous as a detection means that the concentration is in a condition substantially corresponding to the conductivity. The advantage of this method over the above (1) and (2) is that the degree of fatigue of the developer can be directly read regardless of the type of the photosensitive lithographic printing plate to be developed or the storage time after production. is there.

The fatigue of the developer is caused by both the processing fatigue caused by the processing of the photosensitive lithographic printing original plate and the temporal fatigue caused by the absorption of carbon dioxide in the environment when the development processing is not performed. The alkali supply accuracy can be further improved by obtaining a combination of the processing area of the photosensitive lithographic printing original plate and the integrated time over time in a state where development processing is not performed even during standby.

The electrolytic solution used for supplying electricity for supplying alkali is:
Although an aqueous salt solution may be prepared separately from the developing solution, it is unnecessary to use an actually used developing solution for at least the catholyte, since preparation of the electrolytic solution is unnecessary (or the amount can be significantly reduced). It can be directly connected to the bath, and therefore, it is also possible to guide the tired developer to the current-carrying tank and circulate the developer while activating the developer in the current-carrying tank. This is particularly advantageous because the amount of the developer discharged as waste can be greatly reduced within a range in which the organic substances (polymer compounds and the like) eluted in the developer do not occur.

During energization, hydroxyl ions are generated in the cathode chamber to activate the developer, while hydrogen ions are generated in the anode chamber. This hydrogen ion can also be used for the development processing. That is, as explained later,
In the washing step following development of the photosensitive lithographic printing plate,
It can be used for accelerating washing with water, or for neutralization as a preliminary treatment before discharging the waste developer.

The defect relating to the development stability of the photosensitive lithographic printing original plate due to the activation of the developer by the current supply through the developer can be solved as follows. (1) The amount of chemicals used in the developer is reduced, and the amount of waste liquid discharged is reduced. (2) supply of alkali is controlled by an appropriate index,
The development quality is also maintained, and stable operation without precipitation of eluted components is performed in the developer circulation system. (3) When anodic water is used as a replenisher for washing with water, particularly for washing with low replenishment, the strength of the relief image in the non-eluted region increases.
Further, it is possible to reduce the influence of a decrease in developability of the photosensitive lithographic printing original plate over time on the fatigue of the developer.

Regarding the above-mentioned organic contamination of the electrode, that is, poisoning, in the method of the present invention, deterioration of electrolysis efficiency due to poisoning is not recognized. This surprising effect is attributed to the fact that the method of the present invention for controlling the supply of alkali with an appropriate index stabilizes the developing solution in the developing tank.

As a mode of using the hydroxide ions obtained by energization between the electrodes via the developer as an alkali component for replenishment, a developer energized in a cathode chamber is introduced into a replenishing tank.
Either a method of replenishing the developing tank with a current supplied in the cathode chamber or a method of replenishing a circulating route of the developing tank with a liquid supplied in the cathode chamber may be employed, but a particularly preferable embodiment is used.

(Development Processing Apparatus) In the present invention, apart from the part related to the power supply apparatus (also referred to as electrolysis apparatus), any general-purpose or known development processing apparatus (also referred to as development apparatus) on the market can be used. . Usually, a developing tank necessary for dissolving an image-like alkali-soluble region of a photosensitive lithographic printing original plate in a developing solution is indispensable, but usually, a rinsing tank (washing tank) for washing after development is further required. , A desensitizing tank and a drying unit. Further, an apparatus in which the post-processes described above are combined is also used. In the present invention, it is preferable to use hydroxide ions as an alkali agent for replenishment by energization and to use p
Since it is a preferable mode to use a detecting means that does not depend on H, the developing device will be mainly described.

FIG. 1 is a schematic diagram showing the structure of an energizing device (electrolytic device) used in one embodiment of the present invention. In FIG. 1, an electrolysis apparatus 1 includes an electrolysis tank 2, a pipe 12 for feeding catholyte to a development tank (not shown), and, in the present embodiment, an anolyte to a development stop tank of the development apparatus. It comprises a pipe 13 for liquid supply, a pipe 10 for replenishing the electrolytic solution to the electrolytic device, and the like. The electrolytic cell 2 is divided into an anode chamber 3 and a cathode chamber 4 by a diaphragm 5, and an anode 14 and a cathode 15 are provided in each of the electrolytic chambers. The flow of the liquid between the developing tank and the electrolytic chamber is indicated by an arrow. A direct current energizing voltage is applied to the anode 14 and the cathode 15 by voltage applying means 17 (a rectifier and an AC power supply, a battery, and applied voltage control, etc.). The control unit 16 manages energization. Fresh water 11 is piped to the liquid preparation tank 6 via a switching valve 8, and this pipe is also connected to an electrolytic cell via a level sensor 7. The liquid preparation tank is provided with a valve 9.
To the electrolysis chamber.

The diaphragm 5 has liquid permeability enough to secure conductivity between the cathode chamber and the anode chamber, but the liquids in both tanks are not excessively mixed, and are not mixed with the developing solution or the anolyte. What is necessary is not to be invaded. Preferred diaphragm materials include:
Neutral porous membrane film (eg, unglazed pottery plate) which is not affected by the developing solution or anolyte, or polymer hydrophobic polyporous membrane [eg, commercially available Gore-Tex film (manufactured by Gore-Tex Corporation) ], Polymer permeable membrane [for example, commercially available MF (microfilter) membrane, UF (ultrafiltration) membrane, RO (reverse osmosis)
Membrane] can be used. In addition, an ion exchange membrane may be used, and an anion exchange membrane (product names include Selemion AMV / AMR, anion type Aciplex manufactured by Asahi Glass Co., Ltd.)
Cation exchange membranes (such as Nafion manufactured by DuPont, Flemion manufactured by Asahi Glass Co., Ltd., and cation type Aciplex) are all suitable for the purpose of the present invention. In particular, a bivalent selective anion exchange membrane is preferable because the anolyte solution and the catholyte solution are less likely to cross each other and the electric resistance is less increased.

As the electrode, any material can be used as long as it is an electrolysis inactive material. Preferred anode materials include, for example, lead dioxide, graphite, lead, platinum and the like, for example, a commercially available carbon sheet (Cresheet, manufactured by Kureha Chemical Industry Co., Ltd.). As the cathode material, stainless steel (SUS303, 316 or the like), copper, silver, graphite, lead, platinum or the like, for example, commercially available SUS316 (NTK316, manufactured by Nippon Metal Industry Co., Ltd.) can be used. Each of these electrode materials is commercially available. The electrolyte for the cathode compartment is
As described above, the developing solution is suitable, but it may be used after being diluted to some extent with water for the purpose of correcting the amount of evaporation while the development is continued.

Next, the operation of the electrolysis apparatus will be described. When a voltage is applied between the anode 14 and the cathode 15 and energization is performed, hydroxyl ions are generated in the cathode chamber and hydrogen ions are generated in the anode chamber, and change in the alkaline and acidic directions, respectively. The catholyte is supplied to the developing tank via the pipe 12 as a replenisher, and the developing activity in the developing tank is maintained and stable development is performed. On the other hand, in one embodiment of the present invention, in the apparatus shown in FIG. 1, the acidic electrolytic solution in the anode chamber is supplied to the developing stop tank in the developing apparatus and the alkaline electrolyte adhered to the developed photosensitive resin composition. , And the composition film is de-swelled to achieve physical strengthening. Further, washing may be performed at the same time. The anode compartment and the cathode compartment are separated by a diaphragm, so that direct mixing is prevented.

The liquid preparation tank 6 substantially serves as both a liquid preparation tank for preparing fresh developer and a storage tank for storing used developer for reuse. That is, fresh water 11 is supplied via the valve 8 and a developer is charged therein to prepare a developing solution. In addition, an overflow solution (not shown) returned from the developing tank may be stored. In any case, the developing solution prepared or stored in this tank is sent to the cathode chamber via the valve 10 and energized, and the alkali component (hydroxyl ion) is supplied to be in a replenishing solution state. Tube 1
The liquid is sent to the developing tank by 2 and replenishment is performed. on the other hand,
The anolyte can be adjusted in the solution adjusting tank 6 and supplied to the anode chamber by switching the piping system with a switching valve. Further, the level of the liquid in the anode chamber and the level of the cathode chamber are maintained constant by switching the level sensor 7 and the valve so that the fresh water 11 or the liquid in the liquid adjusting tank 6 is sent. A preferred embodiment is a developing method in which a used developing solution is stored in the solution preparation tank 6, activated in the composition of the replenisher in the electrolytic tank, and reused.

As the electrolyte for the anode compartment, a developer can be used, but a solution prepared by dissolving only the inorganic salt component in the developer composition in water may be used. May be used. In the latter case, there is also an advantage that the disposal cost can be reduced by disposing of the waste developer as the pH is already low. Energization is performed at a current density of 1 to 100 A / dm ² , preferably 1 to 50 A / d
m ² , more preferably in the range of ^{2 to} 20 A / dm ² . The applied voltage is adjusted so that the current density falls within this range. The value varies depending on the shape of the apparatus, particularly the distance between the electrodes, and the electrolyte concentration of the developing solution.
0V, preferably 3-10V. The electrode area varies depending on the substantial volume of the developing tank to be processed. However, it is almost appropriate to obtain the electrode area per 1 liter of the developing tank by proportional calculation, assuming that the electrode area is 1 dm ² . Under such a relationship between the electrode area and the amount of liquid in the developing tank, the energizing time is about 40 seconds with respect to the developing amount of 1 m ² of the photosensitive resin composition.

Next, the management of the developer by energization will be described. As described above, the fatigue detection means for reading the degree of the fatigue of the developer and leading to the replenishment is based on the development processing amount, the integration time during which the developing device is in the standby and rest states, Physical properties of the developer other than
Preferably, the reading is performed by one of the electric conductivity, the specific gravity, and the opacity, or one of the three methods for reading the electric conductivity, or a combination thereof.

In the case where the detection of the degree of fatigue of the developer is based on the development processing amount, a processing amount integrating device for the photosensitive resin composition is installed in the development processing device by measurement using an infrared sensor or contact measurement. The processing amount is obtained as an area from the time during which the composition is sent into the developing tank, the width of the composition, and the transport speed, and is integrated. The information on the development processing amount obtained here is sent to the control unit 16 of the electrolysis apparatus shown in FIG. Such a processing amount integrating device is known,
It has also been adopted.

When the detection of the degree of fatigue of the developer is based on the integrated time of the elapsed time during which the developing process is not performed, the pH of the developer and the amount of the alkaline component of the developer due to carbon dioxide gas in the air are substantially reduced. Is a correction to This correction is performed by a timer that records the operating state of the developing device, the time when the developing device is turned on and in a standby state,
And the time during which the developing device is stopped is integrated and recorded. In a typical embodiment of the present invention, in the operation for correcting the influence of carbon dioxide, a voltage is applied to the electrolytic layer every time the integrated value of the standby time exceeds 4 hours, and an electrolytic current is supplied. If the development processing apparatus is in a halt, the halt time is accumulated, and when the power of the development processing apparatus is turned on next, power is supplied for a length corresponding to the integration time up to that time.

When the electric conductivity is selected and managed as the physical property value, the electric conductivity meter is installed at an appropriate place in the circulation system of the developer, but is installed in the developing tank or in the stirring and circulating portion of the developing tank. Is preferred. The information related to the fatigue of the developer is sent to the control unit 16 in FIG. 1 to manage the voltage application time to the electrodes.

When the energizing time is controlled by the processing amount of the lithographic printing original plate, the voltage application time should be approximately 600 coulombs for the processing amount of 1 m ² . Of course, it depends on the thickness of the coating layer of the photosensitive composition on the original plate and the amount of the eluted components (therefore, the exposure amount, etc.)
Needless to say, it is necessary to adjust according to the actual working conditions. When the energization time is controlled by the integration time of the standby time and the halt time of the developing device, the voltage application time is set to 4 hours for the integration time of both the standby time and the halt time in the average-scale development processing device. The standard is to set the amount to 600 coulombs. Since the concentration of carbon dioxide in the indoor environment varies depending on the seasonal variation, the content of the work being performed in parallel, the ventilation of the work place, and the like, it goes without saying that further fine adjustment is necessary in the actual place.

When the energization time is controlled by the electric conductivity of the developing solution in use, the change in the electric conductivity is within 5% of the standard value, preferably within 2%, more preferably within 1%. It is desirable to control the electrolysis time. In the average composition of the developer to which the present invention is applied, the conductivity is 40,000 to 6
10,000 μs / cm. The conductivity of the developer is 50,000 μs / cm
In the case of (1), the fluctuation in 1% is 500 μs / cm, which is a value that can be accurately read by a conductivity meter.
Fluctuations in electrical conductivity are accompanied by an increase or decrease in alkali metal ions accompanying the dissolution of the photosensitive resin composition, so that they correspond only to changes in hydrogen ion concentration, and are more logarithmic as a measure of fatigue of the developer than the corresponding pH value. Sensitive. To explain the specific energization operation and replenishment management, the conductivity meter constantly monitors the conductivity of the developing solution during the operation of the developing apparatus.
Is transmitted to the control device. Conductivity value is 1 of standard value
1, that is, 500 μs / cm, the controller of FIG. 1 applies a voltage between the electrodes 14 and 15 according to the information. When the energization time reaches 20 seconds, the energization amount becomes 300 coulombs. At this point, if the conductivity returns to within 1% of the standard value, the applied voltage is cut off.
If it has not returned to within%, energization is continued until the next control cycle. The energization and replenishment management are performed by such a control sequence.

The above three replenishment management methods may be performed alone or in combination. From the viewpoint of the stability of the developing process, it is most preferable to use three types of replenishment control in combination. Next, it is preferable to combine the management based on the conductivity management, or the management based on the information on the development processing amount and the information on the accumulated time of the operable time. When the specific gravity or opacity, which is a physical property value other than the electric conductivity, is used for detecting the degree of fatigue of the developer, since all of these physical property values change with development, the first physical property value is used. A change value from that value is read based on (initial value), and the energization time is adjusted according to the value.

During energization, hydroxyl ions are generated in the cathode chamber to activate the developer, while hydrogen ions are generated in the anode chamber. This hydrogen ion can also be used for the development processing. That is, in the washing / stopping step following the development of the photosensitive lithographic printing original plate, when the anolyte containing hydrogen ions generated on the anode chamber side by energization is used as part or all of the washing water (also a stop solution), Excessive swelling of the insoluble portion of the photosensitive resin composition is suppressed, the physical strength is also enhanced, and washing with water is performed effectively. At this time, the components eluted during the development process may become insoluble in the washing wastewater and precipitate, in which case the components are separated from the waste liquid as far as the sediment is concerned, and disposal of the waste liquid is easy. become. A more specific description of this type of apparatus that also utilizes hydrogen ions generated by energization will be given in Examples. As another method of using the anolyte, a used developer can be used as the anolyte to neutralize the alkali component and reduce the addition at the time of disposal of the waste liquid.

In another embodiment of the present invention, two electrolytic cells are provided, one of which is sufficient to compensate for the deterioration over time due to the absorption of carbon dioxide gas in the air when the developing process is not performed. The amount of current to be applied is always set to the amount
The base may be of a function-sharing type in which two electrolytic cells are energized only when the development processing is performed so as to compensate for fatigue caused by the development processing. By making the system cope with the fatigue of the developing process and the fatigue of the developing solution over time, it is possible to design a developing device with an electrolytic device having a low electric capacity. In this case, the electrolytic device for compensating for the influence of carbon dioxide gas absorption is always energized irrespective of whether the developing process is in progress or not, so that the electrolytic device for compensating for the fatigue of the developing solution accompanying the developing process requires the developing device. No compensation is made for the absorption of carbon dioxide that occurs during processing. In addition, the electrolytic device for compensating for the fatigue of the developing solution accompanying the developing process, even if the amount of the developing process is adopted as the means for detecting the degree of fatigue of the developing solution, the physical properties such as conductivity, specific gravity, opacity, etc. May be adopted.

[Plate making process following development] The printing base plate subjected to development processing is described in JP-A-54-8002 and JP-A-55-1504.
No. 5, No. 59-58431, etc., a rinsing solution containing washing water, a surfactant and the like,
It is post-treated with a desensitizing solution containing gum arabic and starch derivatives. The processing apparatus used in the present invention can perform these processes in various combinations. The lithographic printing plate obtained by such a process is mounted on an offset printing press and used for printing a large number of sheets. As a plate cleaner used for removing stains on the plate at the time of printing, a conventionally known plate cleaner for a PS plate is used. For example, CL-1, CL-2, CP, CN-4,
CN, CG-1, PC-1, SR, IC (all manufactured by Fuji Photo Film Co., Ltd.) and the like.

The lithographic printing plate obtained as described above is optionally washed with washing water, a rinsing solution containing a surfactant, etc., coated with a desensitized gum containing gum arabic and a starch derivative, and then subjected to a printing step. However, when a lithographic printing plate having a higher printing durability is desired, a burning treatment is performed. When the lithographic printing plate is to be subjected to a burning treatment, the lithographic printing plate must be burned before the burning treatment.
No. 55-28062, JP-A-62-31859.
And JP-A-61-159655. As a method, with a sponge or absorbent cotton impregnated with the surface conditioning liquid,
A method of applying on a lithographic printing plate, or by dipping the printing plate in a vat filled with a surface-regulating liquid, and applying by an automatic coater or the like is applied. Also, after applying squeegee,
Alternatively, making the application amount uniform with a squeegee roller gives more preferable results.

The coating amount of the surface-conditioning solution is generally 0.03 to 0.3.
8 g / m ² (dry weight) is suitable. The lithographic printing plate coated with the surface conditioning liquid is dried if necessary, and then burned (for example, a burning processor sold by Fuji Photo Film Co., Ltd .: "BP-13").
00 ”). The heating temperature and time in this case depend on the type of the component forming the image,
The temperature is preferably in the range of 180 to 300 ° C. for 1 to 20 minutes.

The burned lithographic printing plate can be subjected to a conventional treatment such as washing with water or gumming, if necessary, but the surface preparation containing a water-soluble polymer compound or the like can be performed. When a liquid is used, a so-called desensitizing treatment such as gumming can be omitted. The lithographic printing plate obtained by such a process is set on an offset printing machine or the like and used for printing a large number of sheets.

[0141]

(Preparation of photosensitive lithographic printing plate sample)

(Production of alkali-soluble polymer compound) 31.0 g (0.36 mol) of methacrylic acid, 39.1 g (0.36 mol) of ethyl chloroformate and acetonitrile 2 were placed in a 500 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel.
The mixture was stirred while cooling in an ice-water bath. 36.4 g of triethylamine (0.3
6 mol) was dropped by a dropping funnel over about 1 hour.
After the addition, the ice-water bath was removed, and the mixture was stirred at room temperature for 30 minutes.

To the reaction mixture was added 51.7 g (0.30 mol) of p-aminobenzenesulfonamide, and the mixture was stirred for 1 hour while warming to 70 ° C. in an oil bath. After completion of the reaction, the mixture was added to 1 liter of water while stirring the water, and the resulting mixture was stirred for 30 minutes. The mixture was filtered to remove the precipitate, which was then washed with 500 m of water.
Then, the slurry was filtered and the obtained solid was dried to obtain a white solid of N- (p-aminosulfonylphenyl) methacrylamide (yield 46.9 g).

Next, 5.04 g of N- (p-aminosulfonylphenyl) methacrylamide was placed in a 100 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel.
210 mol), and 2.05 g (0.05 g) of ethyl methacrylate.
180 mol), acrylonitrile 1.11 g (0.02
1 mol) and 20 g of N, N-dimethylacetamide, and the mixture was stirred while being heated to 65 ° C. in a hot water bath. This mixture was mixed with “V-65” (manufactured by Wako Pure Chemical Industries, Ltd.).
0.15 g was added, and the mixture was stirred for 2 hours under a nitrogen stream while maintaining at 65 ° C. The reaction mixture was further added to N- (p-aminosulfonylphenyl) methacrylamide 5.04
g, 2.05 g of ethyl methacrylate, 1.11 g of acrylonitrile, 20 g of N, N-dimethylacetamide, and 0.15 g of "V-65" were dropped by a dropping funnel over 2 hours. After the addition was completed, the resulting mixture was further stirred at 65 ° C. for 2 hours. After completion of the reaction, 40 g of methanol
Was added to the mixture, and the mixture was cooled. The obtained mixture was poured into 2 liters of water while stirring the water. After stirring the mixture for 30 minutes, the precipitate was taken out by filtration and dried to obtain 15 g of a white solid ( Alkali-soluble polymer compound 1
Called). The weight average molecular weight (polystyrene standard) of this alkali-soluble polymer compound was measured by gel permeation chromatography to find that it was 53.0.
00.

(Preparation of Substrate (Support)) Thickness 0.3 mm
After the aluminum plate (material 1050) was washed with trichlorethylene and degreased, the surface was grained with a nylon brush and a 400 mesh Pumice-water suspension,
Washed well with water. This plate was etched by immersing it in a 25% aqueous solution of sodium hydroxide at 45 ° C. for 9 seconds, washed with water, further immersed in 20% nitric acid for 20 seconds, and washed with water. At this time, the etching amount of the grained surface was about 3 g / m ² . Next, the plate was subjected to a current density of 15% using 7% sulfuric acid as an electrolyte.
To provide a DC anodic oxide film of 3 g / m ² in A / dm ^2, washed with water and dried. This was treated with a 2.5% by weight aqueous solution of sodium silicate at 30 ° C. for 10 seconds, the following undercoating solution was applied, and the coating film was dried at 80 ° C. for 15 seconds.
I got The coating amount of the coating film after drying was 15 mg / m ² . <Undercoat liquid> The following copolymer having a molecular weight of 28,000 0.3 g methanol 100 g water 1 g

[0145]

Embedded image

(Coating) The following coating solution 1 for forming a photosensitive layer was applied to the obtained substrate so that the coating amount was 1.8 g / m ² , to obtain a lithographic printing original plate sample 1. <Coating solution 1 for forming photosensitive layer>-Alkali-soluble polymer compound 1 [(A) component] 0.7 g-Cyanine dye A [(B + C) component] 0.1 g-Phthalic anhydride [(D) component] M, p-cresol novolak (m / p ratio = 6/4, 0.1 g weight average molecular weight: 3500, unreacted cresol 0.5% by weight) 4-diazo-3-methoxydiphenylamine PF ₆ salt 01g ・ p-toluenesulfonic acid 0.002g ・ Dye in which the counter anion of Victoria Pure Blue BOH is changed to 1-naphthalenesulfonic acid anion 0.02g ・ Fluorinated surfactant (MegaFac F-177, Dainippon Ink & Chemicals, Inc.) Co., Ltd.) 0.05 g ・ γ-butyl lactone 8 g ・ Methyl ethyl ketone 8 g ・ 1-Methoxy-2-propanol 4 g

[Exposure, Development and Evaluation] The obtained lithographic printing original plate sample 1 was stored at room temperature for 7 days after production, and then output 500 mW, wavelength 830 nm, and beam diameter 17 μm (1 μm).
/ E ² ), and exposed to light at a main scanning speed of 5 m / sec with a semiconductor laser, and then developed using the following developing apparatus and an alkali developing solution. Next, the image forming property of the developed sample was evaluated. The evaluation was made by visually observing the drawing properties of thin lines and the residual film (insufficient solubility).

(Preparation of Alkaline Developing Solution) An alkali developing solution used in the developing step was prepared as follows. <Formulation of alkaline developing solution> Potassium hydroxide 2.4% by weight 1.8% by weight of silicon dioxide Nonionic surfactant (PEG-1000, manufactured by Wako Pure Chemical Industries) 0.8% by weight 3.0% by weight of potassium citrate Water 92.0% by weight The pH of the developer was 13.03. Its conductivity is 49
It was 500 μs / cm.

(Developing Apparatus) The developing apparatus is the same as that of the fourth to fourth embodiments.
Except for the sample No. 6, a commercially available PS plate development processing device connected to an electrolysis device with a control device (16 in FIG. 1) shown in FIG. 1 was used. This developing apparatus has an immersion type developing tank, a washing tank, and a desensitizing tank, and the respective processing times are 15, 10 and 10 seconds in the order described above. Further, a part of the developing solution is returned from the developing tank to the cathode chamber of the electrolytic tank.

(Example 1) In this example, the degree of fatigue of the developing solution due to the developing process was determined based on the developing amount obtained from the developing amount integrating device provided in the developing device. Each time 3 m ² (depending on the type of the photosensitive resin composition) of the printing original plate sample 1 was developed, a voltage was applied to the electrode by a signal from a control device (16 in FIG. 1) attached to the electrolytic cell, and the current density was increased. Current value 1 at 5 A / dm ²
After electrolysis at 5 A for 2 minutes (electricity of 1800 coulombs), the circuit is cut off. The development processing was performed with a total processing amount of 60 m ² while taking out a development sample for evaluation every time the development processing was performed by 15 m ² by this apparatus. As a result of the visual evaluation of the image forming property of the developed sample, from the beginning to the end of the development, the drawing property of the fine line and the presence or absence of the residual film were good. In addition, no precipitate was observed in the developer circulated and used while being electrolytically activated.

(Embodiment 2) In this embodiment, the degree of fatigue of the developing solution when the developing processing apparatus is in a halt state is determined.
The developer was managed by the electrolysis apparatus based on the integrated pause time obtained from the pause time integrating device provided in the developing apparatus, and based on this value. The PS processing was stopped for 2 days without developing the PS plate sample by turning off the power of the developing apparatus. Each time the standing time reaches 5 hours, a voltage is applied to the electrode by a signal from a control device (16 in FIG. 1) attached to the electrolytic cell, and a current density of 5 A / dm ² and a current value of 15 A, 2
After electrolysis for 1 minute (electricity 1800 coulombs),
The circuit breaks. After performing the development processing of the reference original sample 1 as a reference, after leaving the apparatus in a resting state for 2 days, immediately developing the original sample 1 of the same lot without adjusting the developing solution in the developing tank,
A comparison of both samples was made. In both cases, the visual evaluation results were good, and no difference was observed between the two.

Embodiment 3 In this embodiment, the degree of fatigue of the developing solution due to the developing process is determined by the value of the electric conductivity of the developing solution obtained from the electric conductivity meter provided in the developing tank of the developing apparatus. went. Each time the conductivity changes (decreases) by 495 μs / cm with the development of the master sample 1, a voltage is applied to the electrode by a signal from a control device (16 in FIG. 1) attached to the electrolytic cell, and a current density of 5 A / Current value 1 at dm ²
After electrolysis at 5 A for 2 minutes (electricity of 1800 coulombs), the circuit is cut off. During this time, the change in the electric conductivity is 495 μs / cm of the initial electric conductivity of the developer.
If it does not recover within this time, further voltage application is automatically performed every two minutes. The development processing was performed with a total processing amount of 60 m ² while taking out a development sample for evaluation every time the development processing was performed by 15 m ² by this apparatus. When the developed master sample 1 was evaluated, it was good from the beginning to the end of the development, and no deterioration of the image quality on the master sample due to the continuous processing was observed. In addition, no precipitation of components dissolved in the developer used in circulation while being electrolytically activated was observed.

(Example 4) In this example, an embodiment in which a method for developing a material having a photosensitive resin composition of the present invention is performed by using an integrated apparatus of an electrolysis (energization) apparatus and a development processing apparatus. Write. FIG. 2 is a diagram showing an integrated apparatus of the electrolysis apparatus and the development processing apparatus used in the present invention.
The same display numbers are used for the same portions as those in FIG. 1 and FIGS. 3 and 4 described later. Electrolysis device 2
The cathode chamber 4 also serves as a developing tank, and the developing solution filled in this tank is also a catholyte, and is used for developing the photosensitive resin composition which is sent through the transport path shown by the arrow AA ′. At the same time, the reaction is also performed in which water is reduced by the cathode 15 to generate hydroxyl ions, and as a result, the mechanism in which the consumption at the cathode compensates for the consumption of hydroxyl ions due to development is made. The anode compartment 3 is separated from the cathode compartment by a diaphragm 5, and the catholyte flows into the anode compartment over the upper part of the diaphragm serving as a weir and undergoes electrolytic oxidation. As a result, electrolytic oxidation of organic components and generation of hydrogen ions occur, which is accompanied by a decrease in pH. The anolyte is discharged from the electrolysis device as a waste developer through the discharge hole 45. on the other hand,
The developer in the cathode chamber 4 is circulated by a circulation pump 40 into a circulation path 4.
The circulation with stirring is performed by 1 to adjust the temperature and stir the developer.

In this example, the development of the original sample 1 was performed in the same manner as in Example 3 except that the apparatus shown in FIG. 2 was used. 15
Each time the m ² development processing was performed, the development processing for a total processing amount of 60 m ² was performed while taking out the development sample for evaluation, but the developed original plate had good image formability by visual observation from the beginning to the end of the development. No precipitation of dissolved components was observed in the circulated developer.

Embodiment 5 This embodiment is an example in which the method of developing a lithographic printing plate of the present invention is applied to coating development (also referred to as coating and developing), and hydrogen ions generated in an anode chamber are formed. Is also used in the washing / stopping step. FIG. 3 is a schematic diagram showing only the development processing section of the coating and developing apparatus according to the embodiment of the present invention. The processing web 21 is
In FIG. 3, the original sample 1 is transported from left to right on the web 21, and is provided with an applicator roller 24 incorporated in the developer application unit 22. At the contact 28, the developer is applied. The coating thickness is adjusted by adjusting the distance between the lower end surface of the mantle 23 and the original plate. In the present embodiment, the thickness is set to 0.5 mm. The original sample 1 is moved from the developer coating contact 28 to the washing / stop liquid coating contact 29
Is the developing time, and the coating developer on the original plate is removed by forming the squeegee blade for removing the coating liquid on the lower end surface of the jacket 26 of the washing / stopping liquid coating unit 25. The used developer is returned to the electrolytic cell by a return pipe (not shown), and then sent to the cathode chamber.
The original sample 1 that has passed through the squeegee blade is applied with the washing / stop liquid at the contact point 29 with the applicator roller 27 incorporated in the washing / stop liquid applying section 25. The coating thickness is adjusted by adjusting the distance between the lower end surface of the mantle 26 and the original plate.
mm. After the original sample 1 has been transported on the web for another 20 seconds, the rinsing and stopping liquid is removed by the squeegee, and the development processing is completed. The developing solution is supplied from the cathode chamber of the electrolytic cell (not shown) to the developer applying section 22 by the liquid sending pipe 12, and the washing / stopping liquid is supplied from the anode chamber (not shown) to the washing / stopping liquid applying section 25 by the liquid sending pipe 13. Supplied to The electrolytic cell has the configuration described in FIG.
The developer returned from the squeegee blade at the lower end of the jacket 26 of the rinsing / stopping liquid applying unit 25 in FIG. 3 is mixed with a newly prepared developer (tank 6 in FIG. 1) to form the cathode chamber 4.
After the power is supplied to the developing device shown in FIG. On the other hand, the anolyte is an aqueous solution containing 0.5% by weight of sodium sulfate and 0.5% by weight of sodium bicarbonate and 0.1% by weight of glacial acetic acid. After that, it is sent to the washing / stop liquid applying section 25 of the developing device of FIG. This anolyte is supplied to the original sample 1 at the contact 29.
And used for washing, and then discharged from the electrolytic device as a developing waste liquid.

In this example, the development of the original sample 1 was performed in the same manner as the development in Example 3 except that the apparatus shown in FIG. 3 was used. 15
While developing samples for evaluation were taken out every time the m ² developing process was performed, a developing process was performed with a total processing amount of 60 m ² , but the developed original plate sample 1 maintained good image forming properties from the beginning to the end of the development. However, no precipitation of the components dissolved in the developer was observed.

(Embodiment 6) This embodiment is an embodiment in which the method for developing a lithographic printing plate precursor of the present invention is applied to slit development. FIG. 4 is a schematic structural view of a slit developing device employing an energization process via a developer according to the present invention.
The transport of the original sample is performed along the paths 38 and 38 '.
The developing tank 33 is provided with a conveying path for the developed sample at the entrance 3 by a conveying roller group, a facing roller for driving, and a liquid lid 34.
7 to form a slit. The original plate developed through the slit-shaped path is subsequently conveyed to a washing / stop unit 35 having substantially the same structure as the developing tank 33. Also in the washing / stop unit 35, the transport path is formed in a slit shape by the transport roller group, the drive roller, and the liquid lid 36,
The developed plate is sent out of the developing device via an outlet 37 '. The developer circulates through the circulation path 42,
In the circulation path, a circulation pump 40 with a built-in filter and a switching cock 39 for switching to the control unit 43 for removing precipitates and deposits that may occur during development are provided. The switching cock 39 controls the circulation path 42 by the timer control.
The circulating liquid is supplied to the control unit 43 by operating at different time intervals during the pause time and during the development processing. An electrolysis device 44 is incorporated in the control unit 43, and after the electric power of the developing solution guided to the cathode chamber recovers to a predetermined value, the developing solution is returned and returned from the switching cock 39 to the developing tank 33 via the circulation path 42. .
Therefore, the developer in the developing tank is separated from the developing tank 33 by the circulation path 4.
While circulating, the temperature is adjusted and sent to the control unit 43 according to a program so that the electric conductivity is kept constant. When the amount of the developing solution in the developing tank is reduced, a new liquid is replenished from a replenishing device (not shown), and the liquid level in the developing tank 33 is kept constant. In the present embodiment, in the washing / stop tank 35, washing water is supplied independently of the anolyte in the electrolytic tank 44 to perform washing. Although both the developing tank 33 and the washing / stop tank 35 have a sufficiently large liquid volume in the tank, the stirring effect is enhanced by narrowing the original sheet conveying path into a slit shape by the conveying roller and the liquid lid described above. .

In the present embodiment, except that the apparatus shown in FIG. 4 was used, the original plate sample 1 was subjected to the development processing while maintaining the conductivity by the same method as the development processing method of the third embodiment. The development processing of a total processing amount of 60 m ² was performed while taking out a development sample for evaluation every time the development processing was performed by 15 m ² by this apparatus. The developed original sample 1 showed good image generation from the beginning to the end of development. The composition maintained its properties, and no precipitation of the components dissolved in the developer was observed.

(Example 7) The coating solution for forming the photosensitive layer of the photosensitive lithographic printing original plate sample 1 in Example 1 was changed to the following coating solution 2, and the other conditions were not changed and the photosensitive lithographic printing original plate was changed. Sample 2 was prepared. Exposure, development, and evaluation were performed in the same manner as in Example 1 except that this master sample 2 was used. In this example in which the original sample was changed, the developed original sample 2 maintained good image forming properties from the beginning to the end of development, and no precipitation of components dissolved in the developer was observed.

<Coating solution 2 for forming photosensitive layer> m, p-cresol novolak [component (A)] 1.0 g (m / p ratio = 6/4, weight average molecular weight 8,000, unreacted cresol 0.5 weight) %) ・ Cyanine dye A [(B + C) component] 0.1 g ・ Phthalic anhydride [(D) component] 0.05 g ・ P-toluenesulfonic acid 0.002 g ・ Counter ion of ethyl violet is 6-hydroxy-β -Naphthalenesulfonic acid 0.02 g-Esterified product of naphthoquinone 1,2-diazide-5-sulfonyl chloride and pyrogallol-acetone resin 0.01 g-Fluorinated surfactant (MegaFac F-177, Dainippon Ink.) Chemical Industry Co., Ltd.) 0.05 g ・ Methyl ethyl ketone 8 g ・ 1-methoxy-2-propanol 4 g

[0161]

According to the developing method and the developing device of the present invention for conducting development while maintaining the activity of the developing solution by supplying electricity through the developing solution in the cathode chamber, a conventional processing apparatus or printing apparatus can be used as it is. The heat mode image described in this specification had the disadvantage that the conventional developing method had the disadvantage that fluctuations in the developing conditions and the aging conditions of the original plate became apparent while having the advantage of being able to make a plate directly from digital information such as It is possible to stably develop a recording type photosensitive lithographic printing original plate to make a plate. Further, according to the present invention, it is possible to provide a method which is advantageous in terms of environment and economy, such as reduction of development waste liquid and reduction of development chemicals.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a configuration of a water electrolysis apparatus according to the present invention.

FIG. 2 is a schematic view of an integrated apparatus of an electrolysis apparatus and a development processing apparatus used in one embodiment of the present invention.

FIG. 3 is a schematic view of a developing apparatus incorporating an electrolytic device used in another embodiment of the present invention.

FIG. 4 is a schematic view of a developing apparatus incorporating an electrolysis apparatus used in still another embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Electrolyzer 2 Electrolysis tank 3 Anode chamber 4 Cathode chamber 5 Diaphragm 6 Liquid regulating tank 7 Level sensor 8 Valve 9 Valve 10 Switching cock 11 Water 12 Catholyte liquid supply pipe 13 Anolyte liquid supply pipe 14 Anode 15 Cathode 16 Control part 17 Power supply device 21 Processing web 22 Developer application section 23 Developer application section outer jacket 24 Applicator roller 25 Rinse / stop liquid application section 26 Rinse / stop liquid apply outer jacket 27 Applicator roller 28 Developer liquid application contact 29 Rinse / stop Liquid application contact 33 Developing tank 34 Liquid lid 35 Rinse / stop tank 36 Liquid lid 37, 37 'Slit entrance, exit 38, 38' Transport path 39 Switching cock 40 Circulation pump 41 Circulation path 42 Circulation path 43 Control unit 44 Electrolytic tank 45 Discharge holes A, A 'Conveyance path of photosensitive lithographic printing original plate

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Koji Oishi 4000F, Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture F-term in Fujisha Shin Film Co., Ltd. (Reference) 2H096 AA06 BA11 BA20 EA04 GA01 GA09 GA21

Claims (7)

[Claims] At least (A) the alkali-soluble polymer compound and (B) the solubility of the polymer compound in an aqueous alkali solution are reduced by being compatible with the alkali-soluble polymer compound, and the solubility is increased by heating. A lithographic printing original plate having a photosensitive layer obtained by coating a support with a positive photosensitive composition for infrared laser containing a compound capable of decreasing the solubility lowering effect and (C) a compound that absorbs light and generates heat is used. A method of performing development processing using an alkaline developer,
Photosensitive lithographic printing characterized by maintaining the activity of the developing solution by applying a current through the developing solution in the cathode chamber between the electrodes of the conducting means having a cathode chamber, an anode chamber, and an electrode attached to the developing means. Development method for the original plate. 2. The method according to claim 1, wherein the photosensitive lithographic printing plate is (A)
In addition to the components (B) and (C), (D)
A photosensitive composition containing a cyclic acid anhydride represented by the general formula (I)
A lithographic printing plate having a layer
Item 6. A method for developing a photosensitive lithographic printing plate according to Item 1. Embedded imageWhere R¹, R^TwoAre each independently a hydrogen atom, a substituent
An alkyl group having 1 to 12 carbon atoms which may have
Group, alkoxy group, cycloalkyl group, aryl group,
Carbonyl group, carboxy group, carboxylate group
Represent. Note that R ¹, R^TwoConnect to each other to form a ring structure
May be. 3. A method according to claim 1, wherein the amount of current flowing between the electrodes via the developer in the cathode chamber is adjusted in accordance with the degree of fatigue of the developer accompanying the development, thereby generating hydroxyl ions supplied to the developer. 3. The method for developing a photosensitive lithographic printing original plate according to claim 1, wherein the amount is controlled to maintain the activity of the developing solution. 4. The photosensitive material according to claim 1, wherein the method for detecting the fatigue of the developer accompanying the development is at least one selected from the following three: A method for developing a lithographic printing plate. (1) Reading of the processing area of the photosensitive lithographic printing original plate (2) Integration of time during which the developing process of the photosensitive lithographic printing original plate is not performed in the developing device (3) Developer stored in the developing device Of electrical conductivity (abbreviated as conductivity), specific gravity or opacity. 5. The method according to claim 1, wherein the anolyte is taken out of the anode chamber of the power supply means and used as part or all of the washing water used in the washing or stopping step following the developing step. 3. The method for developing a photosensitive printing plate according to claim 1. 6. A developing means for developing a photosensitive lithographic printing original plate, a detecting means for detecting fatigue of the developing solution accompanying the development or the aging of the developing solution, and a cathode chamber and an anode attached to the developing means. An energizing means having a chamber and generating electricity by applying an electric current between the electrodes through a developing solution in the cathode chamber, and a liquid feeding means for coupling the developing means and the energizing means. Developing apparatus for developing a photosensitive lithographic printing plate. 7. A developing means for treating a photosensitive lithographic printing original plate with a developing solution, a washing / stopping means for stopping or washing the original plate after the developing step, and a developing solution accompanying the development or the aging of the developing solution Detecting means for detecting fatigue of the battery, and a cathode chamber and an anode chamber attached to the developing means. When a current is passed between the two electrodes through a developing solution in the cathode chamber to generate hydroxyl ions in the cathode chamber. At the same time, having an energizing unit for generating hydrogen ions in the anode chamber, a liquid sending unit for coupling the developing unit and the energizing unit, and a liquid sending unit for coupling the washing / stopping unit and the energizing unit. An apparatus for developing a photosensitive lithographic printing original plate, comprising: