JP2000089474A - Plate making method of photosensitive lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress production of insoluble scum in a finishing bath after a photosensitive lithographic printing plate having an aluminum plate as a supporting body is developed with a developer containing no silicate, to permit continuous stable developing and finishing treatment, and further to produce a lithographic printing plate without printing contamination or failure in ink deposition for a long time. SOLUTION: The aluminum supporting body used for the photosensitive lithographic printing plate shows <=100 mg/m2 elution amt. of aluminum ion when the plate is developed with a developer containing non-reducing sugar and base (except silicate). The photosensitive lithographic printing plate is developed with the developer above described, and then treated with a finishing liquid containing at least one kind of oxycarboxylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate, and more particularly to a method for making a photosensitive lithographic printing plate suitable for long-term stable development and finishing.

[0002]

2. Description of the Related Art Conventionally, a photosensitive lithographic printing plate widely used comprises an aluminum plate as a support and a photodegradable or photocurable photosensitive layer provided thereon. These photosensitive layers are solubilized in a developing solution by an actinic ray and become insoluble in the latter by an actinic ray. Therefore, when this is developed, only the developer-soluble portion of the photosensitive layer is removed, and the surface of the support is exposed. Since the surface of the aluminum support is hydrophilic, a portion (non-development portion) where the surface of the support is exposed by development retains water and repels oil-based ink. on the other hand,
Area where the photosensitive layer was not removed by development (image area)
Is lipophilic and repels water and accepts ink.

As a developer for such a photosensitive lithographic printing plate, an alkaline aqueous solution has been generally used. Among them, aqueous silicate solutions such as sodium silicate and potassium silicate have been generally used. However, silicates are stable in an alkaline region, but have a disadvantage that they are neutral, gel and insolubilize, and are soluble only in strong acids such as hydrofluoric acid when evaporated to dryness. Actually, there has been a problem that aluminum silicate adheres to the developing tank or the developing solution replenishment sensor and cleaning is difficult, and silica gel is generated when neutralizing the waste liquid of the developing solution.

[0004] In order to solve such problems, attempts have been made to use an alkali agent other than silicate, and for example, a developer containing a non-reducing sugar and a base other than silicate has been proposed (Japanese Patent Application Laid-Open No. Hei 8 (1996)). -160631, JP-A-8-23
4447, JP-A-8-305039). According to the developer containing the non-reducing sugar and the base, the disadvantage caused by the developer comprising the silicate is eliminated. on the other hand,
A developer containing a non-reducing sugar and a base other than silicate is more likely to attack the aluminum support of the photosensitive lithographic printing plate than a conventional developer comprising an alkali metal silicate, and has a larger elution amount of aluminum ions. When aluminum ions eluted during development are brought into the usually acidic finishing solution (a desensitizing solution containing a water-soluble resin or an aqueous solution containing a surfactant) by the plate being processed, insoluble residues (aluminum oxide) Occurs. After the insoluble residue is deposited on the transport roller, it adheres to the plate surface, causing printing stains and poor ink deposition. In addition, it precipitates even in the finishing liquid, causing clogging of filters and sprays, making long-term stable processing impossible. This problem could not be satisfactorily solved even if the plate was washed with water after development and before finishing.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photosensitive lithographic printing plate using an aluminum plate as a support in a finishing bath after development with a silicate-free developer. An object of the present invention is to provide a method for making a photosensitive lithographic printing plate capable of suppressing the occurrence of a lithographic printing plate and capable of continuing stable development and finishing processes. Still another object of the present invention is to provide a method for making a photosensitive lithographic printing plate capable of producing a lithographic printing plate free from printing stains and defective ink deposition over a long period of time.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have suppressed the amount of aluminum ions eluted when developed with a developer containing no silicate, In addition, it has been found that the use of a finishing treatment solution containing a specific component suppresses the generation of insoluble scum, and the present invention has been completed.
That is, the present invention relates to a non-reducing sugar and a base (excluding silicate).
A photosensitive lithographic printing plate using an aluminum support having an aluminum ion elution amount of 100 mg / m ² or less when developed with a developer containing, is developed with the above developer and contains at least one oxycarboxylic acid. A method for making a photosensitive lithographic printing plate, characterized by treating with a finishing solution.

The method of making a photosensitive lithographic printing plate according to the present invention comprises:
As described above, the amount of eluted aluminum ions when developed with a developer containing no silicate is 0 to 100 mg /
m ² , preferably 0 to 60 mg / m ² , more preferably 0 to 3 mg / m ² .
By adjusting the aluminum support to a concentration of 0 mg / m ² by aluminum ion elution prevention treatment, the amount of aluminum ion eluted is suppressed, and furthermore, finishing is performed by treating with a finishing solution containing at least one oxycarboxylic acid. In the processing step, generation of insoluble residue is suppressed, clogging of the filter and the spray is prevented, and stable development and finishing can be continued.
As a result, a lithographic printing plate free from printing stains and defective ink deposition can be obtained over a long period of time. Here, the finishing treatment means a desensitization treatment or a rinsing treatment. The finishing liquid may be a desensitizing liquid containing a water-soluble resin or an aqueous solution containing a surfactant (hereinafter referred to as a rinsing liquid).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The method of making a photosensitive lithographic printing plate according to the present invention will be described in detail in the order of developer, photosensitive lithographic printing plate, finishing solution and automatic developing machine. [Developer] Unless otherwise specified, the developer and the replenisher are collectively referred to as a developer. The developer used in the plate making method of the present invention is a developer containing a non-reducing sugar and a base (excluding silicate) as main components. Examples of such a developing solution are disclosed in
Developers described in JP-A-160631 and JP-A-8-234647 are preferably used. Among them, preferred examples include a developer described in JP-A-8-305039. Specific description of a preferred developer is as follows.
It contains at least one compound selected from non-reducing sugars and at least one base (excluding silicate), and has a pH of 9.
The developer ranges from 0 to 13.8.

Such non-reducing sugars are saccharides having no free aldehyde group or ketone group and exhibiting no reducing property. Trehalose-type oligosaccharides in which reducing groups are bonded to each other, or a non-saccharide in which a reducing group of a saccharide is bonded to a non-saccharide. Glycosides and saccharides are classified as sugar alcohols that have been reduced by hydrogenation, and all are suitably used in the present invention. Trehalose-type oligosaccharides include saccharose and trehalose, and examples of glycosides include alkyl glycosides, phenol glycosides, and mustard oil glycosides. As sugar alcohols, D, L-arabit,
Rebit, Xylit, D, L-Sorbit, D, L-
Mannit, D, L-idit, D, L-talit, zuricit and allozurcit. Further, maltitol obtained by hydrogenating disaccharide maltose and a reductant (reduced starch syrup) obtained by hydrogenating oligosaccharide are preferably used. Among these, the non-reducing sugars preferred in the present invention are sugar alcohols and trehalose-type oligosaccharides. Among them, D-sorbitol, saccharose and reduced starch syrup have a buffering action in an appropriate pH range and are low in price. preferable.

These non-reducing sugars can be used alone or in combination of two or more, and their ratio in the developing solution is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight. is there. Below this range, a sufficient buffering effect cannot be obtained, and at concentrations higher than this range, it is difficult to achieve high concentration and the problem of increased cost arises. As the base to be combined with the non-reducing sugar, a conventionally known alkali agent can be used. For example, sodium hydroxide, potassium, lithium, trisodium phosphate, potassium, ammonium, disodium phosphate, potassium,
Inorganic alkali agents such as ammonium, sodium carbonate, potassium, ammonium, sodium hydrogencarbonate, potassium, ammonium, sodium borate, potassium, and ammonium can be used. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine,
Organic alkali agents such as ethyleneimine, ethylenediamine and pyridine are also used.

These alkaline agents are used alone or in combination of two or more. Among these, sodium hydroxide and potassium hydroxide are preferred. The reason is,
This is because adjusting these amounts with respect to the non-reducing sugar enables pH adjustment in a wide pH range. Trisodium phosphate, potassium phosphate, sodium carbonate, potassium phosphate, etc. are also preferable because they have a buffering action by themselves. These alkaline agents adjust the pH of the developer composition to 9.0-1.
It is added so as to be in the range of 3.8, and the amount of addition is determined depending on the desired pH, the type of non-reducing sugar and the amount added, but a more preferred pH range is 10.0 to 13.2. In the developer used in the plate making method of the present invention, an alkali metal salt of a non-reducing sugar can be used as a main component instead of the combination of the non-reducing sugar and the alkali agent. The non-reducing sugar salt is prepared by mixing a 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, or by drying a mixed aqueous solution of the non-reducing sugar and the alkali metal hydroxide. can get.

The developing solution is further described in JP-A-8-160631.
Or an alkaline buffer solution comprising a weak acid other than a saccharide and a strong base described in JP-A-8-13447. The weak acid used as such a buffer is preferably one having a dissociation constant (PKa) of 10.0 to 13.2. Examples of such weak acids include Pergamon Press
IONISATION CONSTANTS OF ORGANIC ACIDS IN AQUEOUS S
OLUTION and the like, for example, 2,2,3,3-tetrafluoropropanol-1 (P
Ka 12.74), trifluoroethanol (12. Ka).
37), alcohols such as trichloroethanol (12.24) and pyridine-2-aldehyde (12.6).
8), aldehydes such as pyridine-4-aldehyde (12.05), salicylic acid (13.0), 3-hydroxy-2-naphthoic acid (12.84), catechol (12.6), Gallic acid (12.4), sulfosalicylic acid (11.7), 3,4-dihydroxysulfonic acid (12.2), 3,4-dihydroxybenzoic acid (11.94), 1,2,2 4-trihydroxybenzene (11.82), hydroquinone (11.56),
Pyrogallol (11.34), o-cresol (1)
0.33), resorcinol (11.27), p-cresol (10.27), m-cresol (10.
09) a compound having a phenolic hydroxyl group,

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) and adenosine (12.5
6), inosine (12.5) and guanine (12.
3), cytosine (12.2), hypoxanthine (1)
2.1), nucleic acid-related substances such as xanthine (11.9), and diethylaminomethylphosphonic acid (12.
32), 1-amino-3,3,3-trifluorobenzoic acid (12.29), isopropylidene diphosphonic acid (12.10), 1,1-ethylidene diphosphonic acid (11.54) , 1,1-ethylidene diphosphone-1
-Hydroxy (11.52), benzimidazole (12.86), thiobenzamide (12.8),
Weak acids such as picoline thioamide (12.55) and barbituric acid (12.5).

Among these weak acids, preferred are sulfosalicylic acid and salicylic acid. As the base to be combined with these weak acids, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide are preferably used.
These alkali agents are used alone or in combination of two or more. The above-mentioned various alkaline agents are used by adjusting the pH within a preferred range depending on the concentration and combination.

(Surfactant) Various surfactants and organic solvents can be added to the developer as required for the purpose of accelerating the developability, dispersing the development residue, and increasing the ink affinity of the printing plate image area. Preferred surfactants include anionic,
Cationic, nonionic and amphoteric surfactants are included. Preferred examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, and sorbitan. Fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol monofatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, poly Glycerin fatty acid partial esters, polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters,

Nonionic surfactants such as fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides, fatty acid salts, abieticin Acid salts, hydroxyalkanesulfonates, alkanesulfonates, dialkylsulfosuccinates, α-olefinsulfonates, linear alkylbenzenesulfonates, branched alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylphenoxypoly Oxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-
Oleyltaurine sodium salt, N-alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonates,
Sulfated tallow oil, fatty acid alkyl ester sulfate salts, alkyl sulfate salts, polyoxyethylene alkyl ether sulfate salts,

Fatty acid monoglyceride sulfates,
Polyoxyethylene alkyl phenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, styrene / anhydrous Anionic surfactants such as partially saponified maleic acid copolymers, partially saponified olefin / maleic anhydride copolymers, and naphthalenesulfonate formalin condensates; alkylamine salts;
Quaternary ammonium salts such as tetrabutylammonium bromide, cationic surfactants such as polyoxyethylene alkylamine salts and polyethylene polyamine derivatives, carboxybetaines, alkylaminocarboxylic acids, sulfobetaines, aminosulfates, and imidazolines And other amphoteric surfactants. Among the surfactants listed above, those with polyoxyethylene,
Polyoxyalkylene such as polyoxymethylene, polyoxypropylene, polyoxybutylene, etc. can be read, and their surfactants are also included.

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

(Development Stabilizer) Various development stabilizers are used in the developer. Preferred examples thereof include polyethylene glycol adducts of sugar alcohols described in JP-A-6-282079, tetraalkylammonium salts such as tetrabutylammonium hydroxide, phosphonium salts such as tetrabutylphosphonium bromide, and iodonium such as diphenyliodonium chloride. Salts are mentioned as preferred examples. Further, anionic or amphoteric surfactants described in JP-A-50-51324, water-soluble cationic polymers described in JP-A-55-95946,
There is a water-soluble amphoteric polymer electrolyte described in Japanese Patent No. 42528.

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

(Organic Solvent) An organic solvent is further added to the 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, 2-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 liquid.
It is. 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 when the amount of the surfactant is small and the amount of the organic solvent is large, the organic solvent is not completely dissolved, and therefore, it is impossible to expect good developing property.

(Reducing Agent) A reducing agent may be further added to the developer. This is to prevent the printing plate from being stained. Preferred organic reducing agents include phenolic compounds such as thiosalicylic acid, hydroquinone, methol, methoxyquinone, resorcin, and 2-methylresorcin; and amine compounds such as phenylenediamine and phenylhydrazine. More preferred inorganic reducing agents include sodium salts, potassium salts, and ammonium salts of inorganic acids such as sulfurous acid, bisulfite, phosphorous acid, bisulfite, diphosphite, thiosulfate and dithionite. Salts and the like can be mentioned. Among these reducing agents, sulfites are particularly excellent in the stain prevention effect. These reducing agents are preferably used in a developing solution at the time of use.
It is contained in the range of 0.5 to 5% by weight.

(Organic carboxylic acid) An organic carboxylic acid can be further added to the developer. Preferred organic carboxylic acids are aliphatic and aromatic carboxylic acids having 6 to 20 carbon atoms. Specific examples of the aliphatic carboxylic acid include caproic acid, enantiic acid, caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, and particularly preferred are alkanoic acids having 8 to 12 carbon atoms. . Further, unsaturated fatty acids having a double bond in the carbon chain or branched fatty acids may be used. The aromatic carboxylic acid is a compound in which a carboxyl group is substituted on a benzene ring, a naphthalene ring, an anthracene ring, or the like. Specifically, o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p- Hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4
-Dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, 3 -Hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid,
There are 1-naphthoic acid and 2-naphthoic acid, and hydroxynaphthoic acid is particularly effective.

The above aliphatic and aromatic carboxylic acids are preferably used as a sodium salt, a potassium salt or an ammonium salt in order to increase the water solubility. The content of the organic carboxylic acid in the developer is not particularly limited, but may be 0.1% by weight.
If it is lower, the effect is not sufficient, and if it is 10% by weight or more, not only the effect cannot be further improved but also dissolution may be hindered when another additive is used in combination. Therefore, the preferred amount is 0.1 to 10% by weight, more preferably 0.5 to 4% by weight, based on the amount of the developing solution used.

(Others) The developer may further contain a preservative, a coloring agent, a thickener, an antifoaming agent, a water softener and the like, if necessary. Examples of the water softener include polyphosphoric acid and its sodium salt, potassium salt and ammonium salt, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic acid. Aminopolycarboxylic acids such as acetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts;
Aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), hydroxyethylethylenediaminetri (methylenephosphonic acid) and 1-
Hydroxyethane-1,1-diphosphonic acid and its sodium, potassium and ammonium salts can be mentioned.

The optimum value of such a water softener varies depending on the chelating power thereof, the hardness of the hard water used and the amount of the hard water. 01 to 5% by weight, more preferably 0.01 to 5% by weight
It is in the range of 0.5% by weight. If the added amount is less than this range, the intended purpose is not sufficiently achieved, and if the added amount is larger than this range, an adverse effect on an image portion such as color omission appears. The remaining component of the developer is water. It is advantageous from the viewpoint of transportation that the developing solution is a concentrated solution having a smaller content of water than at the time of use, and is diluted with water at the time of use. The degree of concentration in this case is suitably such that each component does not cause separation or precipitation. Further, a solidified developer in which water is removed by a spray drying method or the like or a solid material is mixed is also a preferred embodiment.

[Photosensitive lithographic printing plate] The photosensitive lithographic printing plate will be described below. The photosensitive lithographic printing plate used in the method of making a photosensitive lithographic printing plate of the present invention is not particularly limited as long as the aluminum ion elution amount is 100 mg / m ² or less, preferably 60 mg / m ² or less, more preferably 30
mg / m ² or less. In order to suppress the aluminum ion elution amount to the specified value, it is achieved by performing the aluminum ion elution prevention treatment described below after performing a surface roughening treatment, an anodic oxidation treatment and the like described below on the aluminum support described below. You.

(Aluminum ion elution prevention treatment) The aluminum ion elution prevention treatment of the present invention is carried out on an aluminum plate which has been subjected to anodization treatment described later, and the anodic oxide film is eluted during development. The amount is 0 to 100 mg / m ² , preferably 0 to 60 mg / m
² , and more preferably, any of various conventionally-known sealing methods so as to obtain 0 to 30 mg / m ² . For example, an alkali metal silicate treatment (for example, sodium silicate) as disclosed in U.S. Pat. No. 3,181,461 or the like, or JP-B-36-2206.
No. 3, etc., can be used. Further, a method of treating with an aqueous solution containing a phosphate and an inorganic fluorine compound disclosed in JP-A-9-244227 can be used. Further, a method of treating with an aqueous solution containing a sugar disclosed in JP-A-9-134002 can be used.

(Treatment with phosphate and inorganic fluorine compound) Further, a method of treating with an aqueous solution containing a phosphate and an inorganic fluorine compound disclosed in JP-A-9-244227 can be used. The phosphate and the inorganic fluorine compound can be used alone, but when used in combination, there is the effect of further reducing the elution amount of aluminum ions. Examples of the phosphate used in the present invention include phosphates of metals such as alkali metals and alkaline earth metals. Specifically, zinc phosphate, aluminum phosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, monoammonium phosphate, monopotassium phosphate, monosodium phosphate, potassium dihydrogen phosphate, Dipotassium hydrogen phosphate, calcium phosphate, ammonium sodium hydrogen phosphate, diammonium hydrogen phosphate, magnesium hydrogen phosphate, magnesium phosphate, ferrous phosphate, ferric phosphate, sodium dihydrogen phosphate, sodium phosphate , Disodium hydrogen phosphate, lead phosphate, diammonium phosphate, calcium dihydrogen phosphate, lithium phosphate, phosphotungstic acid, ammonium phosphotungstate, sodium phosphate tungstate, ammonium phosphomolybdate, sodium phosphomolybdate Is mentioned. In addition, sodium phosphite, sodium tripolyphosphate and sodium pyrophosphate can be exemplified. Preferably, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, and dipotassium hydrogen phosphate can be used.

The inorganic fluorine compound used in the present invention is preferably a metal fluoride. Specifically, sodium fluoride, potassium fluoride, calcium fluoride, magnesium fluoride, sodium hexafluorozirconium, potassium hexafluorozirconium, sodium hexafluorotitanate, potassium hexafluorotitanate, hexafluorozirconium hydrogen acid, hexafluorozirconium Examples thereof include hydrofluorotitanic acid, ammonium hexafluorozirconium, ammonium hexafluorotitanate, hexafluorosilicic acid, nickel fluoride, iron fluoride, phosphoric acid phosphoric acid, and ammonium fluoride phosphate. In the present invention, the aqueous solution may contain one or more phosphate salts and one or more inorganic fluorine compounds.

The concentration of phosphate in the above aqueous solution is
10 g / l to 1000 g / l is suitable, preferably 50 g / l to 200 g / l. The concentration of the inorganic fluorine compound is suitably from 0.1 g / L to 10 g / L, preferably from 0.1 g / L to 10 g / L.
5 g / liter to 2 g / liter. P at 25 ° C
These aqueous solutions having an H of 2 to 6, preferably a pH of 3 to 5, are added at a temperature of 30 ° C. or more and less than 100 ° C., preferably 6
The contact is performed at 0 to 90 ° C. for 2 seconds to 5 minutes, preferably for 5 seconds to 30 seconds. The contacting method may be any method, such as immersion or spraying. After the above-described treatment with an aqueous solution containing a phosphate or an inorganic fluorine compound, the treatment with an acidic aqueous solution disclosed in Japanese Patent Application Laid-Open No. Priming, and Japanese Patent Application Laid-Open No. 4-282637 and Japanese Patent Application No. 6-108.
It is preferable to provide an organic layer disclosed in Japanese Patent Application No. 678 or Japanese Patent Application No. 9-089664.

(Sugar aqueous solution treatment) and JP-A-9-13400
2, the method of treating with an aqueous solution containing a sugar can be used. As the saccharide used in the present invention, monosaccharides include trioses such as glycerol, tetroose and sugar alcohols such as threose and erythritol, pentoses and sugar alcohols such as arabinose and arabitol, and hexoses and sugars such as glucose and sorbitol. Alcohols, heptose and sugar alcohols such as D-glycero-D-galactoheptose and D-glycero-D-galactoheptitol, D-erythro-D
Octose, such as -galactooctitol, and nonose, such as D-erythro-L-gluco-nonulose. Oligosaccharides include disaccharides such as saccharose, trehalose and lactose, and trisaccharides such as raffinose and cyclodextrin. Polysaccharides include amylose, arabinan, cellulose alginate and the like.

The sugar used in the present invention also includes glycosides. The glycoside used in the present invention refers to a compound in which a sugar moiety and a non-sugar moiety are bonded via an ether bond or the like. These glycosides can be classified by non-sugar moieties, such as alkyl glycosides, phenol glycosides, coumarin glycosides, oxycoumarin glycosides, flavonoid glycosides,
Examples include anthraquinone glycosides, triterpene glycosides, steroid glycosides and mustard oil glycosides. Examples of the sugar moiety include monosaccharides, oligosaccharides, and polysaccharides. Examples of the monosaccharides include trioses such as glycerol, tetroose and sugar alcohols such as threose and erythritol, pentoses and sugar alcohols such as arabinose and arabitol, hexoses and sugar alcohols such as glucose and sorbitol, and D-glycero-D.
-Heptose and sugar alcohols such as -galactoheptose and D-glycero-D-galactoheptitol; octose such as D-erythro D-galactoctitol;
Nonose such as -erythro-L-gluco-nonulose. Saccharose as an oligosaccharide,
Examples include disaccharides such as trehalose and lactose, and trisaccharides such as raffinose and cyclodextrin.
Examples of the polysaccharide include amylose and arabinan. The saccharide moiety is preferably a monosaccharide or an oligosaccharide, and more preferably a monosaccharide or a disaccharide. Preferred examples of glycosides include compounds of the following general formula [I].

[0034]

Embedded image

(In the formula, R represents a linear or branched alkyl group, alkenyl group or alkynyl group having 1 to 20 carbon atoms.) 1 carbon atom represented by R in the general formula [I] As the alkyl group of -20, for example, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl And the like. These alkyl groups may be linear or branched, or may be cyclic alkyl groups. Examples of the alkenyl group include an allyl and a 2-butenyl group, and examples of the alkynyl group include a 1-pentynyl group.

Specific compounds represented by the above general formula [I] include, for example, methyl glucoside, ethyl glucoside, propyl glucoside, isopropyl glucoside, butyl glucoside, isobutyl glucoside, n-hexyl glucoside, octyl glucoside, caprylic glucoside, decyl Glucoside, 21-ethylhexyl glucoside, 2-pentyl nonyl glucoside, 2-hexyl decyl glucoside, lauryl glucoside, myristyl glucoside, stearyl glucoside, cyclohexyl glucoside, and 2-butynyl glucoside. These compounds are glucooxides, which are a kind of glycosides, in which the hemiacetal hydroxyl group of glucose is bonded to another compound in an ether-like manner, and can be obtained, for example, by a known method of reacting glucose with alcohols. . Some of these alkyl glycosides are marketed under the trade name GLUCOPON by Henkel, Germany, and can be used in the present invention. Other examples of preferred glycosides include saponins, rutin trihydrate, hesperidin methyl chalcone, hesperidin, nalidin hydrate, phenol-β-D-glucoviranoside, salicin, 3 ′, 5,7-methoxy-7-. Rutinosides can be mentioned.

In the present invention, one or more of the above sugars can be used together to form an aqueous solution. The concentration of the sugar in the aqueous solution is generally from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight. 0.01
Less than 100% by weight of aluminum ion eluted at 100mg / m
² and insoluble scum is likely to be generated. After the insoluble residue deposits on the transport roller, it adheres to the plate surface, causing printing stains and poor ink deposition. If the content exceeds 20% by weight, the effect of reducing the elution amount of aluminum ions does not change, but stains during printing tend to occur.

PH at 25 ° C. is 2 to 12, preferably 8
To 10 to 100 ° C., preferably 40 to 70 ° C., for 2 seconds to 5 minutes, preferably 5 seconds to 3
Contact for 0 seconds. The contacting method may be any method, such as immersion or spraying. If the temperature is lower than 20 ° C., the elution amount of aluminum ions is 10
The concentration is increased to more than 0 mg / m ² , and insoluble residue is likely to be generated.
After the insoluble residue deposits on the transport roller, it adheres to the plate surface, causing printing stains and poor ink deposition. In addition, even when the temperature is 100 ° C. or more, the effect of reducing the elution amount of aluminum ions is saturated, and stains during printing are likely to occur. If the pH is lower than 2, the effect of reducing the elution amount of aluminum ions is reduced, insoluble scum is likely to be generated, and scum deposited on the transport roller adheres to the plate surface, resulting in printing stains. On the other hand, if the pH is higher than 12, there is a concern that the anodic oxide film may be dissolved during the treatment with the aqueous solution containing sugar, which is not preferable. To adjust the pH of the aqueous solution, p
Any one that can adjust the H can be used.
Specific examples include sodium hydroxide, potassium hydroxide, sulfuric acid, sodium sulfate, carbonic acid, sodium carbonate, potassium carbonate, phosphoric acid, and sodium phosphate.

(Alkali metal silicate treatment) In this aluminum ion elution prevention treatment, the alkali metal silicate is treated with 0.1%.
001 to 30% by weight, preferably 0.01 to 10% by weight, particularly preferably 0.05 to 3% by weight, and an alkali metal silicate aqueous solution having a pH of 10 to 13 at 25 ° C.
Anodized aluminum support at 4-40 ° C,
Preferably 10 to 30 ° C, particularly preferably 10 to 20 ° C
The aluminum ion elution amount is 100 mg / m ² by a method of immersion for 0.5 to 120 seconds, preferably for 2 to 30 seconds.
The treatment can be preferably carried out by appropriately selecting the treatment conditions such as the alkali metal silicate concentration, the treatment temperature, the treatment time and the like as described below. In performing this hydrophilization treatment, if the pH of the alkali metal silicate aqueous solution is lower than 10, the solution gels,
Attention should be paid to this point because if it is higher than 13.0, the anodic oxide film will be dissolved. As the alkali metal silicate used in the hydrophilization treatment of the present invention, sodium silicate, potassium silicate, lithium silicate and the like are used.

In the hydrophilization treatment of the present invention, a hydroxide may be added, if necessary, to adjust the pH of the alkali metal silicate aqueous solution to a high value. Examples of the hydroxide include sodium hydroxide and water hydroxide. Examples include potassium oxide and lithium hydroxide. If necessary, an alkaline earth metal salt or a Group IVB metal salt may be added to the aqueous alkali metal silicate solution. Examples of the alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate, and barium nitrate, and sulfates, hydrochlorides, phosphates, acetates, oxalates, and borates of these alkaline earth metals. And water-soluble salts such as salts. Examples of Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, titanium potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride, and zirconium tetrachloride. be able to. Alkaline earth metal salts or Group IVB metal salts can be used alone or in combination of two or more. The preferred use amount range of these metal salts is 0.01 to 10% by weight, and the more preferred range is 0.05 to 5.0% by weight.

[Support] The aluminum support of the photosensitive lithographic printing plate used in the method of making a photosensitive lithographic printing plate of the present invention will be described. (Aluminum Plate) The aluminum plate used in the present invention is a plate-like body such as pure aluminum or an aluminum alloy containing aluminum as a main component and containing a small amount of a different atom. The hetero atoms include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. As the alloy composition, a content of different atoms of 10% by weight or less is appropriate. Aluminum that is suitable for the present invention is pure aluminum, but it is preferable that completely pure aluminum contains as little foreign atoms as possible because it is difficult to produce due to refining technology. Further, any aluminum alloy having a different atomic content of the above-described level can be said to be a material that can be used in the present invention. The composition of the aluminum plate used in the present invention is not particularly limited, and conventionally known and publicly available materials can be appropriately used. Preferred materials are JIS A1050, JIS 1100, JIS 1200, JIS 3003, JIS 3103, and JIS A3
005 materials. The thickness of the aluminum plate used in the present invention is suitably about 0.1 mm to 0.6 mm. Prior to the surface roughening treatment of the aluminum plate, a degreasing treatment for removing a rolling oil on the surface, for example, a treatment with a surfactant or an alkaline aqueous solution is performed as necessary.

[Roughening and Anodizing Treatment] The surface of the above-mentioned aluminum plate is subjected to a roughening treatment and an anodic oxidation treatment prior to the treatment for preventing the elution of aluminum ions. (Roughening treatment) The surface of the aluminum plate as described above is subjected to a roughening treatment. As a method of the surface roughening treatment, there are a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening the surface, and a method of chemically selectively dissolving the surface. As the mechanical method, a known method called a ball polishing method, a brush polishing method, a blast polishing method, a buff polishing method, or the like can be used. 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, Japanese Patent Application Laid-Open No. 54-6390
A method combining both of them, such as that disclosed in Japanese Patent Application Laid-Open Publication No. 2 (1994), can be used.

(Anodic Oxidation Treatment) The aluminum plate roughened as described above is subjected to an alkali etching treatment and a neutralization treatment as necessary, and then anodized to improve the water retention and abrasion resistance of the surface. Processing is performed. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, any electrolyte that forms 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 to be used and cannot be specified unconditionally. However, in order to reduce the elution amount of aluminum ions during development, it is desirable to select conditions that reduce the surface area. The concentration of the electrolyte is a 1-50% solution, preferably a 5-30%, particularly preferably a 7-20% solution. The liquid temperature is 5 to 70 ° C, preferably 20 to 60 ° C, particularly preferably 30 to 50 ° C. Current density is 5-60A
/ Dm ² , preferably 10 to 60 A / dm ² , particularly preferably 20 to 60 A / dm ² . It is desirable that the current density be as high as possible without burning. As the current density is lower, the surface area of the anodic oxide film increases, and the elution amount of aluminum ions increases.

[0044] The amount of anodized film, 1 to 5 g / m ² but is preferred, more preferably 1.5 to 4 g / m ^2, particularly preferably 2 to 3 g / m ^2. When the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient, and 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. If the amount exceeds 5 g / m ² , the elution amount of aluminum ions increases, or the substances contained in the photosensitive layer are irreversibly adsorbed on the non-image areas of the lithographic printing plate obtained by development, contaminating the non-image areas. Therefore, a so-called residual color occurs, it is difficult to distinguish between an image portion and a non-image portion in a correction process, a correction mark is clearly left on a non-uniform plate surface, and when the degree is severe, the printing plate becomes dirty. Can no longer be used.

(Backcoat) In the present invention, a backcoat is provided on the back surface of the aluminum support.
Examples of the back coat include organic polymer compounds described in JP-A-5-45885 and JP-A-6-3517.
A coating layer composed of a metal oxide obtained by hydrolyzing and polycondensing an organic or inorganic metal compound described in JP-A No. 4 (1994) is preferably used. Of these coating layers, Si (O
CH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , Si (O
Alkoxy compounds of silicon such as C ₄ H ₉ ) ₄ are inexpensive and readily available, and a coating layer of a metal oxide provided therefrom is particularly preferred because of its excellent development resistance.

[Intermediate Layer] In the photosensitive printing plate used in the plate making method of the present invention, a photosensitive layer can be provided directly on the aluminum support which has been subjected to the above-mentioned aluminum ion elution prevention treatment. An intermediate layer may be provided on each of the supports, and a photosensitive layer may be provided on the intermediate layer. Amino acids and their salts (such as alkali metal salts such as Na salt and K salt) disclosed in JP-A-60-149491;
Ammonium salts, hydrochlorides, oxalates, acetates, phosphates and the like), amines having a hydroxyl group disclosed in JP-A-60-232998 and salts thereof (hydrochlorides, oxalates, phosphates, etc.) ), A compound having an amino group and a phosphonic acid group or a salt thereof disclosed in JP-A-63-165183 can be used as the intermediate layer. Further, a compound having a phosphonic acid group disclosed in JP-A-4-282637 can be used as the intermediate layer. Further, after the alkali metal silicate treatment, it is desirable to use a polymer compound containing an acid group and an onium group described in Japanese Patent Application No. 9-26439 as the intermediate layer.

[Photosensitive Layer] In the present invention, a photosensitive layer is provided on the aluminum support on which the above-mentioned aluminum ion elution prevention treatment has been performed or on the aluminum support on which an intermediate layer described later is provided. As the photosensitive composition used in the photosensitive layer, solubility in a developer before and after exposure,
Alternatively, any material that changes its swelling property can be used. Hereinafter, a typical positive photosensitive composition will be described, but the present invention is not limited thereto.

(Photosensitive compound) Examples of the photosensitive compound of the photosensitive composition include an o-quinonediazide compound.
A typical example is an o-naphthoquinonediazide compound. As the o-naphthoquinonediazide compound,
1, 2 described in JP-B-43-28403.
Those which are esters of diazonaphthoquinonesulfonic acid chloride with pyrogallol-acetone resin are preferred.

Other suitable o-quinonediazide compounds include those described in US Pat. Nos. 3,046,120 and 3,188,210.
There are esters of diazonaphthoquinone sulfonic acid chloride with phenol formaldehyde resin.

Other useful o-naphthoquinonediazide compounds include those reported and known in numerous patents. For example, JP-A-47-5303
No. 48-63802, No. 48-63803, No. 48-96575, No. 49-38701, No. 48-
13354, JP-B-37-18015, 41-1
No. 1222, No. 45-9610, No. 49-17481
JP-A-5-11444, JP-A-5-19477
JP-A-5-19478, JP-A-5-107755
No. 2,797,213 and No. 3,45.
No. 4,400, No. 3,544,323, No. 3,5
No. 73,917, No. 3,674,495, No. 3,
785,825, British Patent No. 1,227,602,
Nos. 1,251,345 and 1,267,005
No. 1,329,888, No. 1,330,93
No. 2, German Patent No. 854,890, etc. or those described in the specification.

As other o-quinonediazide compounds, o-naphthoquinonediazide compounds obtained by reacting a polyhydroxy compound having a molecular weight of 1,000 or less with 1,2-diazonaphthoquinonesulfonic acid chloride can be used. For example, JP-A-51-1394
No. 02, No. 58-150948, No. 58-20343
No. 4, No. 59-165053, No. 60-112445
No. 60-134235, No. 60-16343
No. 61-118744, No. 62-10645,
No. 62-10646, No. 62-153950, No. 6
2-178562, 64-76047, U.S. Pat. Nos. 3,102,809 and 3,126,281,
No. 3,130,047, No. 3,148,983
No. 3,184,310, No. 3,188,21
No. 0, No. 4,639,406 and the like, and those described in each gazette or specification.

When synthesizing these o-naphthoquinonediazide compounds, it is preferable to react 0.2-1.2 equivalents of 1,2-diazonaphthoquinonesulfonic acid chloride with respect to the hydroxyl groups of the polyhydroxy compound. More preferably, the reaction is performed in an amount of 0.3 to 1.0 equivalent. As the 1,2-diazonaphthoquinone sulfonic acid chloride, 1,2-diazonaphthoquinone-5-sulfonic acid chloride is preferable, but 1,2-diazonaphthoquinone-sulfonic acid chloride is preferred.
4-sulfonic acid chloride can also be used. The resulting o-naphthoquinonediazide compound is a mixture of various 1,2-diazonaphthoquinonesulfonic acid ester groups having different positions and introduced amounts, but all of the hydroxyl groups are converted to 1,2-diazonaphthoquinonesulfonic acid ester. Of the compound in the mixture (content of completely esterified compound) is 5 mol%
Or more, more preferably 20 to 9
9 mol%.

Examples of the photosensitive compound which acts positively without using an o-naphthoquinonediazide compound include, for example, a polymer compound containing an o-nitrile carbinol ester group described in JP-B No. 52-2696 and pyridinium. Group-containing compounds (for example, JP-A-4-365049) and diazonium group-containing compounds (for example, JP-A-5-2496).
No. 64, JP-A-6-83047, JP-A-6-3244
No. 95, JP-A-7-72621) can also be used. Further, a compound which generates an acid by photolysis is disclosed in JP-A-4-121748 and JP-A-4-365043.
No.), a C—O—C group or C—O dissociated by an acid
A combination system with a compound having a -Si group can also be used. For example, a combination of a compound capable of generating an acid by photolysis with an acetal or an O, N-acetal compound (Japanese Patent Application Laid-Open No. 48-89003), a combination of an orthoester or an amide acetal compound (Japanese Patent Application Laid-open No.
Combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-1).
No. 33429) and a combination with an enol ether compound (JP-A-55-12959, JP-A-4-1974).
No. 8, JP-A-6-230574), a combination with an N-acylimino carbon compound (JP-A-55-12623)
No. 6, etc.), a combination with a polymer having an orthoester group in the main chain (JP-A-56-17345, etc.), and a combination with a polymer having a silyl ester group (JP-A-6-17345).
No. 0-10247) and a combination with a silyl ether compound (JP-A-60-37549, JP-A-60-37549).
No. 112446, JP-A-63-236028, JP-A-63-236029, JP-A-63-276046, and the like. The amount of these positive-acting photosensitive compounds (including the above combinations) in the photosensitive composition is suitably from 10 to 50% by weight, more preferably from 15 to 40% by weight.

(Binder) Although the o-quinonediazide compound alone can form the photosensitive layer, it is preferably used together with a resin soluble in alkaline water as a binder. Such a resin soluble in alkaline water includes a novolak resin having this property, such as phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin,
Phenol / cresol (m-, p-, o- or m-
/ P- / o-mixture) and cresol formaldehyde resins such as mixed formaldehyde resins. These alkaline soluble high molecular compounds preferably have a weight average molecular weight of 500 to 100,000. In addition, resol type phenol resins are also preferably used, and phenol / cresol (m-, p-,
o- or m- / p- / o-mixture). A mixed formaldehyde resin is preferred.
Phenolic resins described in Japanese Patent No. 217034 are preferred.

Further, a phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, an acrylic resin containing a phenolic hydroxyl group as disclosed in JP-A-51-34711, and JP-A-2-866. Patent Publication No. 7-28244, a vinyl resin or urethane resin having a sulfonamide group described in
JP-A-7-36184, JP-A-7-36185
JP-A-7-248628, JP-A-7-26139
No. 4, JP-A-7-333839, etc., various alkali-soluble polymer compounds such as vinyl resins having a structural unit can be contained. In particular, in the case of a vinyl resin, a film-forming resin having as a polymerization component at least one selected from the following alkali-soluble group-containing monomers (1) to (4) is preferable.

(1) N- (4-hydroxyphenyl) acrylamide or N- (4-hydroxyphenyl) methacrylamide, o-, m- or p-hydroxystyrene, o- or m-bromo-p-hydroxystyrene, o- or m-chloro-p-hydroxystyrene,
Acrylamides, methacrylamides, acrylates, methacrylates and vidroxystyrenes having an aromatic hydroxyl group such as o-, m- or p-hydroxyphenyl acrylate or methacrylate, (2) acrylic acid, methacrylic acid , Maleic acid, maleic anhydride and its half esters, itaconic acid,
Unsaturated carboxylic acids such as itaconic anhydride and its half esters,

(3) N- (o-aminosulfonylphenyl) acrylamide, N- (m-aminosulfonylphenyl) acrylamide, N- (p-aminosulfonylphenyl) acrylamide, N- [1- (3-aminosulfonyl) Naphthyl] acrylamide, acrylamides such as N- (2-aminosulfonylethyl) acrylamide, N- (o-aminosulfonylphenyl) methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonyl) Phenyl)
Methacrylamides such as methacrylamide, N- [1- (3-aminosulfonyl) naphthyl] methacrylamide, N- (2-aminosulfonylethyl) methacrylamide, and o-aminosulfonylphenyl acrylate and m-aminosulfonylphenyl Acrylate, p
-Aminosulfonylphenyl acrylate, 1- (3-
Unsaturated sulfonamides such as acrylates such as aminosulfonylphenylnaphthyl) acrylate;
unsaturated sulfonamides such as methacrylic esters such as o-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, 1- (3-aminosulfonylphenylnaphthyl) methacrylate;
(4) Phenylsulfonylacrylamide which may have a substituent such as tosylacrylamide, and phenylsulfonylmethacrylamide which may have a substituent such as tosylmethacrylamide.

Further, in addition to these alkali-soluble group-containing monomers, a film-forming resin obtained by copolymerizing the following monomers (5) to (14) is preferably used. (5)
Acrylic esters and methacrylic esters having an aliphatic hydroxyl group, for example, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, (6) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid Amyl, hexyl acrylate, cyclohexyl acrylate,
Octyl acrylate, phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, 4-hydroxybutyl acrylate, glycidyl acrylate, N-
(Substituted) acrylates such as dimethylaminoethyl acrylate, (7) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, methacrylic acid (Substituted) methacrylates such as phenyl, benzyl methacrylate, 2-chloroethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate,

(8) Acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-ethyl acrylamide, N-ethyl methacrylamide, N-hexyl acrylamide, N
-Hexyl methacrylamide, N-cyclohexyl acrylamide, N-cyclohexyl methacrylamide, N
-Hydroxyethylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N
Acrylamides such as -phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenylmethacrylamide, N-ethyl-N-phenylacrylamide and N-ethyl-N-phenylmethacrylamide Or methacrylamide, (9) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether,
Vinyl ethers such as phenyl vinyl ether,

(10) vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate; (11) styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and (12) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone; (13) olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene; (14) N-vinylpyrrolidone, N-vinylcarbazole; 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like.

These alkali-soluble polymer compounds are
Those having a weight average molecular weight of 500 to 500,000 are preferred. Such alkali-soluble polymer compounds may be used alone or in combination of two or more. The proportion of the polymer compound in the photosensitive composition is suitably 80% by weight or less, and preferably 30 to 8% by weight.
0% by weight, more preferably 50 to 70% by weight. This range is preferred from the viewpoint of developability and printing durability.

Further, as described in US Pat. No. 4,123,279, an alkyl group having 3 to 8 carbon atoms such as a t-butylphenol formaldehyde resin or an octylphenol formaldehyde resin is used as a substituent. Condensates of phenol and formaldehyde or o-naphthoquinonediazidosulfonic acid esters of these condensates (for example, JP-A-61-243446).
It is preferable to use the above-mentioned compounds in combination in order to improve the oil sensitivity of the image.

(Development Accelerator) It is preferable to add cyclic acid anhydrides, phenols and organic acids to the photosensitive composition in order to increase sensitivity and improve developability.
As cyclic acid anhydrides, US Pat. No. 4,115,128
Pat has been and phthalic anhydride described, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ - tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic acid anhydride, chlorosulfonic maleic anhydride , Α-phenyl maleic anhydride, succinic anhydride,
Pyromellitic anhydride and the like can be used. As phenols, bisphenol A, p-nitrophenol, p
-Ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ',
4 "-trihydroxy-triphenylmethane, 4,
4 ', 3 ", 4"-tetrahydroxy-3,5,3',
5'-tetramethyltriphenylmethane and the like. Further, as organic acids, JP-A-60-8894
2, sulfonic acids, sulfinic acids, alkyl sulfates, and the like described in JP-A-2-96755 and the like.
Examples include phosphonic acids, phosphoric esters and carboxylic acids, and specifically, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid,
Ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 1,4 −
Cyclohexene-2,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, ascorbic acid and the like. The proportion of the above cyclic acid anhydrides, phenols and organic acids in the photosensitive composition is from 0.05 to
It is preferably 15% by weight, more preferably 0.1 to 5% by weight.

(Development Stabilizer) Further, in the photosensitive composition, JP-A-62-251740 and JP-A-4-68355 may be used in order to widen the stability of processing under development conditions (so-called development tolerance). Nonionic surfactants as described in JP-A-59-121044,
An amphoteric surfactant as described in JP-A-4-13149 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate,
Sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, polyoxyethylene sorbitan monooleate, polyoxyethylene nonyl phenyl ether and the like can be mentioned. Specific examples of the amphoteric surfactant include alkyldi (aminoethyl) glycine,
Alkyl polyaminoethyl glycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine or N-tetradecyl-N, N-betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Co., Ltd.) ) And alkyl imidazolines (eg, Levon 15, trade name, manufactured by Sanyo Chemical Co., Ltd.). The proportion of the nonionic surfactant and amphoteric surfactant in the photosensitive composition is preferably from 0.05 to 15% by weight, and more preferably from 0.1 to 5% by weight.

(Print-out agent, dye, etc.) In the photosensitive composition, a print-out agent for obtaining a visible image immediately after exposure,
Dyes and other fillers as image colorants can be added. As the dye, JP-A-5-31335
No. 9, a cation having a basic dye skeleton,
A basic dye comprising a salt with an organic anion having 10 or more carbon atoms and having a sulfonic acid group as a sole exchange group and having 1 to 3 hydroxyl groups can be given. The amount of addition is 0.2 to 5% by weight of the total photosensitive composition.

Further, compounds capable of generating a photo-decomposed product which changes the color tone by interacting with the dye described in JP-A-5-313359 are disclosed, for example, in JP-A-50-36209 (US Pat. No. 3,969,118). O) -naphthoquinonediazide-4-sulfonic acid halogenide described in
No. 3-36223 (U.S. Pat. No. 4,160,671) discloses trihalomethyl-2-pyrone and trihalomethyltricidin, and JP-A-55-62444 (U.S. Pat.
38,801), various o-naphthoquinonediazide compounds described in JP-A-55-77742 (U.S. Pat.
279, 982).
An aryl 1,3,4-oxadiazole compound or the like can be added. These compounds can be used alone or as a mixture. 400 of these compounds
A compound having an absorption at nm may be used as the yellow dye.

As a colorant for an image, the above-mentioned Japanese Patent Application Laid-Open No.
Other dyes besides the dyes described in JP 13359 can be used. Suitable dyes, including salt-forming organic dyes, include oil-soluble dyes and basic dyes.
Specifically, Oil Green BG, Oil Blue BO
S, Oil Blue # 603 (orientated by Orient Chemical Co., Ltd.), Victoria Pure Blue BOH, Victoria Pure Blue NAPS, Ethyl Violet 6H
NAPS (above, manufactured by Hodogaya Chemical Industry Co., Ltd.), Rhodamine B (C145170B), Malachite Green (C1
42000), methylene blue (C152015) and the like.

In the photosensitive composition, 417n represented by the following general formula [II], [III] or [IV] is used.
A yellow dye having an absorbance at m of 70% or more of the absorbance at 436 nm can be added.

[0069]

Embedded image

In the formula [II], R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group or an alkenyl group. R ₁ and R ₂ may form a ring. R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. G ₁ , G ₂
Are each independently an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an arylcarbonyl group,
It represents an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or a fluoroalkylsulfonyl group. G ₁ and G ₂ may form a ring. Moreover _{R 1, R 2, R 3} , R 4, R 5, G 1, G 2
One or more of which has at least one sulfonic acid group, carboxyl group, sulfonamide group, imide group, N-sulfonylamide group, phenolic hydroxyl group, sulfonimide group, or a metal salt thereof, or an inorganic or organic ammonium salt. . Y is O, S, NR (R is a hydrogen atom or an alkyl group or an aryl _{group), Se, -C (CH 3} ) 2 -, -
CH = CH- represents a divalent atomic group, wherein n ₁ is 0
Or 1 is indicated.

[0071]

Embedded image

In the formula [III], R₆ And R₇ Are each
Independently hydrogen, alkyl, substituted alkyl, aryl
Group, substituted aryl group, heterocyclic group, substituted heterocyclic group,
An allyl group or a substituted allyl group;₆ And R
₇ Together form a ring with the carbon atom to which it is attached
You may. n_Two Represents 0, 1 or 2. G_Three And
And G_Four Are each independently a hydrogen atom, a cyano group, an alcohol
Xycarbonyl group, substituted alkoxycarbonyl group, ant
Oxycarbonyl group, substituted aryloxy carbonyl
Group, acyl group, substituted acyl group, arylcarbonyl
Group, substituted arylcarbonyl group, alkylthio group, ant
Thiol, alkylsulfonyl, arylsulfonyl
And a fluoroalkylsulfonyl group. However
Then G_Three And G _Four Are not simultaneously hydrogen atoms. Ma
G_Three And G_Four Is with the carbon atom to which it is attached
A ring composed of non-metallic atoms may be formed. Further R₆ ,
R₇ , G_Three , G_Four One or more of one or more sulfones
Acid group, carboxyl group, sulfonamide group, imide group,
N-sulfonylamide group, phenolic hydroxyl group, sulfo
Imido group or its metal salt, inorganic or organic ammonium
Has a sodium salt.

[0073]

Embedded image

In the formula [IV], R ₈ , R ₉ , R ₁₀ , R ₁₁ , R
₁₂ and R ₁₃ may be the same or different, and each may be a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkoxy group, a hydroxyl group, an acyl group,
Represents a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a nitro group, a carboxyl group, a chloro group, or a bromo group.

(Formation of Photosensitive Layer, etc.) The positive type photosensitive layer is obtained by dissolving the components of each of the above-mentioned photosensitive compositions in a solvent that dissolves them and coating the solution on a support. As the solvent used here, γ-butyrolactone, ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propanol Propyl acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide,
Dimethylacetamide, dimethylformamide, water, N
-Methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methanol, ethanol, isopropanol, diethylene glycol dimethyl ether and the like, and these solvents can be used alone or in combination. The concentration (solid content) of the photosensitive composition component in the solution is suitably from 2 to 50% by weight. 0.5g / m ² ~4.0g / m ² is preferred as the coating amount. When the amount is less than 0.5 g / m ² , the printing durability deteriorates. When the amount is more than 4.0 g / m ² , the printing durability is improved, but the sensitivity is lowered. The method for forming the photosensitive layer, such as coating the photosensitive composition solution on a support, can be based on various conventionally known methods.

A surfactant for improving the coating method, for example, a fluorine-based surfactant described in JP-A-62-170950 may be added to the photosensitive composition. it can. A preferable addition amount is 0.01 to 1% by weight of the total photosensitive composition, and more preferably 0.01% by weight.
5 to 0.5% by weight. With the planographic printing plate obtained as described above, a printed matter faithful to the original picture film can be obtained, but the print blurring and the feeling of coarseness of the printed matter are poor. As a method for improving the burning blur, there is a method of making the surface of the photosensitive layer thus provided uneven. For example, as described in Japanese Patent Application Laid-Open No. 61-258255, there is a method in which particles of several μm are added to a photosensitive composition solution and the particles are coated. Roughness is not improved at all.

However, for example, Japanese Patent Application Laid-Open No. 50-12580
No. 5, JP-B-57-6582, JP-B-61-28986
And Japanese Patent Application Laid-Open No. 62-62337, a method of forming a component having irregularities on the surface of a photosensitive layer can improve bokeh blur and improve the roughness of printed matter. Furthermore, as described in JP-B-55-30619, when a light absorbing agent having absorption in the photosensitive wavelength region of the photosensitive material is contained in the mat layer, the burning blur and the roughness are further improved. In addition, an original film having a line number of 300 lines or more per inch and an original film obtained by FM screening, which is more easily burned out than an original film having a line number of 175 lines per inch and which easily gives a sense of roughness of a printed material, is used. Thus, a good printed matter can be obtained. As described above, the following minute patterns are desirably provided on the surface of the photosensitive layer of the photosensitive printing plate. That is, the height of the application portion is preferably in the range of 1 to 40 μm, particularly 2 to 20 μm, and the size (width) is 10 to 10000 μm, particularly 2 μm.
The range of 0 to 200 μm is preferred. The amount is 1 to 100
0 / mm ² , preferably in the range of 5 to 500 / mm ² .

(Infrared-sensitive lithographic printing plate) As the infrared-sensitive lithographic printing plate, a positive-type infrared-sensitive lithographic printing plate as described below is preferably used, but the invention is not limited thereto. As a conventionally known positive-type infrared-sensitive lithographic printing plate material, for example, described in JP-A-7-285275, an alkali-soluble resin having a phenolic hydroxyl group such as a novolak resin, a substance that absorbs light and generates heat. And image recording materials to which various onium salts, quinonediazide compounds and the like are added. On the other hand, a substance that absorbs light and generates heat, a resin soluble in an aqueous alkaline solution having a phenolic hydroxyl group, and a copolymer containing at least one of the following (a) to (c) as a copolymer component in an amount of 10 mol% or more: And a positive type infrared-sensitive lithographic printing plate comprising: In this system, the strong interaction of the two resins makes them insoluble in aqueous alkaline solutions, but when heated,
It is presumed that the heat weakens the interaction and solubilizes in the aqueous alkaline solution. (A) A monomer having a sulfonamide group in which at least one hydrogen atom is bonded to a nitrogen atom in one molecule. (B) A monomer having an active imino group in one molecule. (C) Acrylamide having a phenolic hydroxyl group. , Methacrylamide, acrylate, methacrylate, or hydroxystyrene. In the present invention, these positive-working infrared-sensitive lithographic printing plates are preferably used.

[Finishing Solution] The finishing solution used in the present invention will be described in detail below. Unless otherwise specified, the finishing liquid and the finishing replenisher are collectively referred to as a finishing liquid. As a specific example of the oxycarboxylic acid to be contained in the finishing solution,
Gluconic acid, glycolic acid, lactic acid, hydroacrylic acid,
Glyceric acid, tartronic acid, tartaric acid, citric acid, malic acid and the like can be mentioned. Among them, citric acid, gluconic acid,
Malic acid and tartaric acid are preferred. The amount of oxycarboxylic acid added to the finishing solution depends on the amount of aluminum ions eluted into the developing solution and the amount of the eluted aluminum ions carried into the finishing solution, but is generally 0.1% based on the total weight of the finishing solution. 001 to 2.0% by weight is suitable, and a more preferable range is 0.01 to 0.5% by weight.
% By weight. If the amount is less than 0.001% by weight, the generation of insoluble residue due to aluminum ions cannot be sufficiently suppressed. On the other hand, if it exceeds 2.0% by weight,
There is a tendency that the ink deposition at the start of printing is reduced.

It is generally advantageous to use the finishing solution in a pH range of 3 to 12, which is lower than that of the developing solution. p
In order to adjust H to 3 to 12, a mineral acid, an organic acid, an inorganic salt, or the like is generally added to the finishing solution and adjusted. The addition amount is 0.01 to 2% by weight. For example, mineral acids include nitric acid, sulfuric acid, phosphoric acid, and metaphosphoric acid. Examples of the organic acid include acetic acid, oxalic acid, malonic acid, p-toluenesulfonic acid, levulinic acid, phytic acid, organic phosphonic acid, and amino acids such as glycine, α-alanine and β-alanine. Magnesium nitrate as an inorganic salt,
Sodium monophosphate, sodium phosphate dibasic, nickel sulfate, sodium hexametaphosphate, sodium tripolyphosphate and the like. At least one kind or two or more kinds of mineral acids, organic acids or inorganic salts may be used in combination.

When the finishing liquid used in the present invention is a rinsing liquid containing a surfactant, it may contain a lipophilic substance, a preservative, a fungicide, an antifoaming agent, etc. in addition to the above-mentioned pH adjuster. Can be kept. Examples of the surfactant that is a main component of the rinsing liquid include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. Fatty acid salts as anionic surfactants,
Abietic acid salts, hydroxyalkanesulfonates, alkanesulfonates, α-olefinsulfonates, dialkylsulfosuccinates, alkyldiphenyletherdisulfonates, linear alkylbenzenesulfonates, branched-chain alkylbenzenesulfonates, alkylnaphthalenesulfones Acid salts, alkylphenoxy polyoxyethylene propyl sulfonates,
Polyoxyethylene alkylsulfophenyl ether salts, N-methyl-N-oleyltaurine sodium,
N-alkylsulfosuccinic acid monoamide disodium salts,

Petroleum sulfonates, sulfated castor oil, sulfated tallow oil, sulfates of fatty acid alkyl esters, alkyl sulfates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkyl Phenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, styrene-maleic anhydride copolymer Examples include saponified compounds, partially saponified olefin-maleic anhydride copolymers, and naphthalene sulfonate formalin condensates. Among them, dialkyl sulfosuccinates, alkyl sulfates, alkyl naphthalene sulfonates and α-
Olefin sulfonates and alkyl diphenyl ether disulfonates are particularly preferably used. As the cationic surfactant, alkylamine salts, quaternary ammonium salts and the like are used.

As the amphoteric surfactant, alkyl carboxy betaines, alkyl imidazolines, alkyl amino carboxylic acids and the like are used. Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ether, polyoxyethylene polyoxypropylene alkyl ether, glycerin fatty acid partial esters, sorbitan fatty acid partial esters Pentaerythritol fatty acid partial esters, propylene glycol monofatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid partial ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid partial ester ,

Polyoxyethylated castor oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, triethanolamine Examples thereof include alkylamine oxide, polypropylene glycol having a molecular weight of 200 to 5,000, trimethylolpropane, glycerin or sorbitol polyoxyethylene or polyoxypropylene adducts, and acetylene glycol. Also, fluorine-based and silicon-based nonionic surfactants can be used in the same manner. Two or more surfactants can be used in combination. The amount used is not particularly limited, but is preferably in the range of 0.01 to 20% by weight, preferably 0.05 to 10% by weight, based on the total weight of the rinsing liquid.

As the preservative used for the rinsing solution, known substances used in the fields of fiber, wood processing, food, medicine, cosmetics, agrochemicals and the like can be used. For example, quaternary ammonium salts, monohydric phenol derivatives, dihydric phenol derivatives, polyhydric phenol derivatives, imidazole derivatives, pyrazolopyrimidine derivatives, monovalent naphthols, carbonates, sulfone derivatives, organic tin compounds, cyclopentane derivatives, phenyl derivatives , Phenol ether derivatives, phenol ester derivatives, hydroxylamine derivatives, nitrile derivatives, naphthalenes, pyrrole derivatives, quinoline derivatives, benzothiazole derivatives, secondary amines, 1,3,5 triazine derivatives, thiadiazole derivatives, anilide derivatives, pyrrole derivatives , Halogen derivatives, dihydric alcohol derivatives, dithiols, cyanic acid derivatives, thiocarbamic acid derivatives, diamine derivatives, isothiazole derivatives, monohydric alcohols, saturated aldehydes, Sum monocarboxylic acids, saturated ethers, unsaturated ethers,

Lactones, amino acid derivatives, hydantoin, cyanuric acid derivatives, guanidine derivatives, pyridine derivatives, saturated monocarboxylic acids, benzenecarboxylic acid derivatives, hydroxycarboxylic acid derivatives, biphenyl, hydroxamic acid derivatives, aromatic alcohols, halogenophenol derivatives, Benzenecarboxylic acid derivative, mercaptocarboxylic acid derivative, quaternary ammonium salt derivative, triphenylmethane derivative, hinokitiol, furan derivative, benzofuran derivative, acridine derivative, isoquinoline derivative, arsine derivative, thiocarbamic acid derivative, phosphate ester, halogenobenzene Derivatives, quinone derivatives,
Benzenesulfonic acid derivative, monoamine derivative, organic phosphate, piperazine derivative, phenazine derivative,
Known preservatives among pyrimidine derivatives, thiophanate derivatives, imidazoline derivatives, isoxazole derivatives, ammonium salt derivatives and the like can be used.

As particularly preferred preservatives, salts of pyridinethiol-1-oxide, salicylic acid and its salts,
1,3,5-trishydroxyethylhexahydro-S
-Triazine, 1,3,5-trishydroxymethylhexahydro-S-triazine, 1,2-benzisothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-bromo- 2-nitro-1,
3-propanediol is exemplified. The preferable addition amount is an amount that exerts a stable effect on bacteria, molds, yeasts, and the like, and varies depending on the types of bacteria, molds, and yeasts. 01-4% by weight
Is preferable, and it is preferable to use two or more preservatives in combination so as to be effective against various molds and bacteria.

The rinsing liquid may also contain a lipophilic substance. As a result, the image area of the lithographic printing plate becomes more oil-sensitive, and the development ink is used (emulsion-type ink (usually used to make the image easier to see after development and to increase the oil sensitivity of the image and maintain it). Black)
Not only on the image) but also after the treatment with the aqueous solution, a plate surface protective agent treatment is performed.
A decrease in the oil sensitivity of the image area can be strongly suppressed. Preferred lipophilic substances include, for example, oleic acid, lanolinic acid,
Organic carboxylic acids having 5 to 25 carbon atoms, such as valeric acid, nonylic acid, capric acid, myristic acid, and palmitic acid, and castor oil are included. These lipophilic substances can be used alone or in combination of two or more. The lipophilic substance contained in the rinsing liquid is 0.005 to 10% by weight, more preferably 0.05% by weight, based on the total weight thereof.
It is in the range of 5-5% by weight. An antifoaming agent can be added, and a silicone antifoaming agent is particularly preferable. Among them, an emulsified dispersion type and a solubilized type can be used. Preferably, the range is 0.001 to 1.0% by weight with respect to the rinsing liquid at the time of use.

If the finishing liquid used in the present invention is a desensitizing liquid containing a water-soluble resin,
Conditioning agents, preservatives, fungicides, and antifoaming agents can be similarly contained. As the desensitizing solution, basically, an aqueous solution of about 15 to 20% of gum arabic is often used. Various water-soluble resins other than gum arabic are used as the main components of the desensitizing solution. For example, dextrin, stellavic, structan, alginates, polyacrylates, hydroxyethylcellulose, polyvinylpyrrolidone, polyacrylamide, methylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, carboxyalkylcellulose salts, water-soluble polysaccharides extracted from soybean okara Is preferable, and pullulan, a pullulan derivative, and polyvinyl alcohol are also preferable.

Further, modified starch derivatives such as roasted starch such as British gum, enzyme-modified dextrins such as enzyme dextrin and Shardinger dextrin, oxidized starch shown in solubilized starch, modified pregelatinized starch and non-denatured pregelatinized starch, etc. Esterified starch such as alpha starch, phosphate starch, fat starch, sulfate starch, nitrate starch, xanthate starch and carbamic acid starch, carboxyalkyl starch, hydroxyalkyl starch, sulfoalkyl starch, cyanoethyl starch, allyl starch, benzyl starch Carbamylethyl starch, etherified starch such as dialkylamino starch, crosslinked starch such as methylol crosslinked starch, hydroxyalkyl crosslinked starch, phosphoric acid crosslinked starch, dicarboxylic acid crosslinked starch, starch polyacrylamide copolymer, starch polyacrylic Acid copolymer, starch-polyvinyl acetate copolymer, starch polyacrylonitrile copolymer, cationic starch polyacrylic acid ester copolymer,

A chaotic starch-vinyl polymer copolymer,
Starch graft polymers such as starch polystyrene maleic acid copolymer, starch polyethylene oxide copolymer and starch polypropylene copolymer are preferred. Examples of natural polymer compounds include starches such as potato starch, potato starch, tapioca starch, wheat starch and corn starch, and those obtained from algae such as carrageenan, laminaran, sea sour mannan, seaweed, Irish moss, agar and sodium alginate. , Trollo mallow, mannan, quince seed, pectin, tragacanth gum, karaya gum,
Vegetable mucilage such as xanthin gum, guabing gum, locust bingham, carob gum, benzoin gum,
Homopolysaccharides such as dextran, glucan, levan and the like, and microbial mucous substances such as hetropolysaccharide such as succinoglucan and suntan gum, glue, proteins such as gelatin, casein and collagen are preferred. These water-soluble resins can be used in combination of two or more, and preferably 5 to 40.
%, More preferably 10 to 30% by weight.

The desensitizing solution may contain the surfactant described for the rinsing solution. The content is 0.01 to 20 based on the total weight of the desensitizing liquid.
A suitable amount is about weight%. In addition, glycerin, ethylene glycol, and humectant as necessary
Triethylene glycol or the like can be added. The preferred use amount of these wetting agents is 0.1 to 5% by weight.

Further, a chelate compound may be added to the desensitizing solution. Usually, the desensitized liquid is commercially available as a concentrated liquid, and is diluted with tap water, well water, or the like at the time of use. The calcium ions and the like contained in the diluted tap water or well water adversely affect the printing, and may cause the printed matter to be easily stained. . Preferred chelating compounds include, for example, ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; diethylenetriaminepentaacetic acid, its potassium salt, its sodium salt; triethylenetetraminehexaacetic acid, its potassium salt, its sodium salt; Acetic acid, its potassium salt, its sodium salt; nitrilotriacetic acid, its sodium salt; 1-hydroxyethane-1,1-diphosphonic acid, its potassium salt;
Organic salts such as aminotri (methylenephosphonic acid), potassium salt and sodium salt thereof, and phosphonoalkanetricarboxylic acids can be exemplified. Organic amine salts are also effective in place of the sodium and potassium salts of the above chelating agents. These chelating agents are selected from those which are stably present in the desensitizing solution composition and do not inhibit printability. The amount of addition is suitably from 0.001 to 1.0% by weight based on the desensitizing solution used. The desensitizing liquid may be of an emulsified dispersion type, in which an organic solvent is used as the oil phase, and may be of a solubilized type with the aid of a solubilizing agent.

The remaining component of the finishing liquid is water. It is advantageous from the viewpoint of transportation that the finishing liquid is a concentrated liquid having a smaller water content than at the time of use, and is diluted with water at the time of use. The degree of concentration in this case is suitably such that each component does not cause separation or precipitation.
Further, a solidified finishing agent in which water is removed by a spray drying method or the like or a solid raw material is mixed is also a preferred embodiment.

[Common Processing] In the method of making a photosensitive lithographic printing plate according to the present invention, a positive-working / negative-working photosensitive lithographic printing plate, a light-curing photosensitive lithographic printing plate, and a negative-working and positive-working infrared-sensitive lithographic printing plate are used. The printing plate can be commonly processed by the same automatic developing machine using the same processing solution.

[Exposure / Development / Post-treatment] The infrared-sensitive lithographic printing plate is exposed by a plate setter equipped with a laser having an emission wavelength in the near infrared to infrared region.
As such a laser, a solid-state laser or a semiconductor laser that emits infrared light having a wavelength of 760 nm to 1200 nm is preferable. In the present invention, the development treatment may be performed immediately after the laser irradiation, but it is preferable to perform the heat treatment between the laser irradiation step and the development step. The condition of the heat treatment is 80 ° C.
It is preferable to carry out for 10 seconds to 5 minutes within the range of -150 ° C. By this heat treatment, the laser energy required for recording at the time of laser irradiation can be reduced. After performing a heat treatment as needed, it is developed and post-processed by the plate making method of the present invention. Further, the ultraviolet / visible light-sensitive lithographic printing plate is exposed through a transparent original image, for example, by a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a tungsten lamp, a carbon arc lamp, etc., and then developed by the plate-making method of the present invention. Post-processed. Further, the photopolymerizable photosensitive lithographic printing plate is subjected to a scanning treatment with an argon laser and a YAG laser, followed by a heating treatment if necessary, followed by development and post-treatment by the plate making method of the present invention.

[Automatic Developing Machine] In the method of making a photosensitive lithographic printing plate according to the present invention, it may or may not be washed with water after development and before finishing treatment. By washing with water, the amount of aluminum ions dissolved in the developing solution on the plate after development into the finishing bath can be somewhat reduced. Therefore, the plate-making process according to the method of the present invention includes, for example, development → (washing) → desensitization, development → (washing) → rinse, development → (washing) → desensitization → desensitization, development → (washing) → rinse → Rinse and development → (Washing) → Rinse → Desensitization etc.

The method of making a photosensitive lithographic printing plate according to the present invention comprises:
It is preferably carried out using an automatic developing machine. Further, it is preferable to use the developing solution and the finishing solution while replenishing them. The automatic developing machine comprises a developing bath and a post-processing bath (rinsing bath, desensitizing bath, etc.), a device for transporting a photosensitive lithographic printing plate, each processing bath and a spray device, and a post-processing bath for the latter stage. It consists of an overflow section to the post-processing bath from the previous stage, etc., while developing and post-processing by spraying each processing solution pumped up by a pump from a spray nozzle while transporting the exposed photosensitive lithographic printing plate horizontally. is there. Recently, a method has been known in which a photosensitive lithographic printing plate is immersed and conveyed in a processing bath filled with a processing solution using a submerged guide roll or the like to perform development processing. In such automatic processing, processing can be performed while replenishing the developing bath and the post-processing bath with respective replenishers according to the processing amount, the operating time, and the like.

In the method of the present invention, after the photosensitive lithographic printing plate is exposed and developed, desensitizing treatment or rinsing treatment is performed in two or more processing baths, and a replenisher is replenished to the final processing bath. The embodiment can be carried out in such a manner that the overflow wastewater is discharged to the preceding treatment bath, and the overflow wastewater is sequentially replenished to the preceding treatment bath in the same manner. For example, in the case of desensitizing treatment, after development, desensitizing treatment is performed in two or more processing baths, a resensitizing replenisher is replenished to the final desensitizing bath, and the overflow drainage is added to the preceding stage. , And the overflow wastewater is successively replenished to the preceding treatment bath in the same manner. By such a method, the amount of waste liquid of the processing liquid can be suppressed, and stable processing can be performed for a long time. From the viewpoint of simplification of the automatic developing machine, installation space, manufacturing cost, and the like, it is preferable that the automatic developing machine has a two-stage desensitizing bath or a rinsing bath.

[0100]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. In addition, all percentages in the following examples indicate percentages by weight unless otherwise specified. Example 1 The following treatments were continuously performed using a JIS1050 aluminum plate formed by a continuous casting method having a thickness of 0.3 mm and a width of 1030 mm. (A) While supplying a suspension of abrasive pumistone having a specific gravity of 1.12 and water to the surface of an aluminum plate as a polishing slurry, mechanical surface roughening was performed with a rotating roller-shaped nylon brush. Nylon brush material is 6.1
Using 0 nylon, the hair length was 50 mm and the hair diameter was as shown in Table 1. Nylon brushes were made by drilling holes in a stainless steel cylinder with a diameter of 300 mm and densely implanting them.
Three rotating brushes were used. The distance between the two support rollers (Φ200 mm) below the brush was 300 mm. The brush roller was pressed until the load of the drive motor for rotating the brush became 7 kW plus the load before pressing the brush roller against the aluminum plate. The direction of rotation of the brush was the same as the direction of movement of the aluminum plate.

(B) The aluminum plate was subjected to a sodium hydroxide concentration of 2
The aluminum plate was subjected to an etching treatment by spraying at 6% by weight, an aluminum ion concentration of 6.5% by weight, and a liquid temperature of 75 ° C. to dissolve 15 g / m ^{2 of the} aluminum plate. Thereafter, washing with water was performed by spraying. (C) 1% by weight aqueous solution of nitric acid at a liquid temperature of 30 ° C. (containing 0.5% by weight of aluminum ion)
Then, a desmut treatment by spraying was performed, and then, the substrate was washed with water by spraying. As the nitric acid aqueous solution used for the desmutting, a waste liquid from a step of performing electrochemical surface roughening using an alternating current in a nitric acid aqueous solution was used.

(D) Electrochemical surface roughening treatment was continuously performed using a triangular alternating current having a frequency of 60 Hz. The electrolytic solution at this time was a 1% by weight aqueous nitric acid solution (containing 0.5% by weight of aluminum ion and 0.007% by weight of ammonium ion), and the temperature of the solution was 35 ° C. In the AC power supply waveform, the time TP until the current value reaches the peak from zero is 2 msec,
Electrochemical surface roughening treatment was performed using a carbon electrode as a counter electrode using a trapezoidal rectangular wave alternating current with a ty ratio of 1: 1. The quantity of electricity was as shown in Table 1 as the sum of the quantity of electricity when the aluminum plate was the anode. Thereafter, washing with water was performed by spraying.

(E) The aluminum plate was treated with caustic soda concentration 2
6 wt%, aluminum ion concentration was etched by spraying with 6.5% by weight, the aluminum plate 1.3 g / m ² was dissolved, when subjected to electrochemical surface roughening by using alternating current in the prior step The generated smut component mainly composed of aluminum hydroxide was removed, and the edge portion of the generated pit was dissolved to smooth the edge portion. Then, it was washed with water by spraying.

(F) Desmut treatment was performed by spraying with a 25% by weight aqueous solution of sulfuric acid (containing 0.5% by weight of aluminum ion) at a liquid temperature of 60 ° C., followed by washing with water by spraying. Anodized at 50 ° C. in a 10% H ₂ SO ₄ aqueous solution so as to have a current density of 30 A / dm ² and an anodized film amount of 2.2 g / m ² , washed with water, and washed with 0.1% by weight of No. 3 sodium silicate The substrate was treated with an aqueous solution at 20 ° C. for 8 seconds and washed with water to form a substrate. The polymer compound [a] shown below was applied to the surface of the substrate thus treated, and dried at 90 ° C. for 10 seconds. The coating amount after drying was 6.5 mg / m ² .

Polymer compound [a] (see formula below) 0.15 g methanol 100 g water 1 g

[0106]

Embedded image

Thus, the substrate [A] was prepared. A photosensitive layer was formed by applying the following photosensitive solution [A] on the substrate [A]. The coating amount of the photosensitive layer after drying was 1.8 g / m ² .

Photosensitive Solution [A] Esterified product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (described in Example 1 of US Pat. No. 3,635,709). 0.8 g Binder Novolak I (see formula below) 1.5 g Novolak II (see formula below) 0.2 g Resin other than novolak III (see formula below) 0.4 g p-N-octylphenol-formaldehyde resin (US Patent No. 4,123,279) 0.02 g naphthoquinone-1,2-diazide-4-sulfonic acid chloride 0.01 g tetrahydrophthalic anhydride 0.02 g benzoic acid 0.02 g pyrogallol 05g 4- [p-N, N-bis (ethoxycarbonylmethyl) aminophenyl]- , 6-Bis (trichloromethyl) -S-triazine 0.07 g Victoria Pure Blue BOH (a dye manufactured by Hodogaya Chemical Co., Ltd. in which the counter anion was changed to 1-naphthalenesulfonic acid) 0.045 g F176PF (fluorinated surfactant) Agent) (manufactured by Dainippon Ink and Chemicals, Inc.) 0.01 g methyl ethyl ketone 15 g 1-methoxy-2-propanol 10 g

[0109]

Embedded image

Further, in order to shorten the vacuum contact time, a mat layer was formed by the following method. A 12% aqueous solution in which a part of a copolymer of methyl methacrylate / ethyl acrylate / acrylic acid (weight ratio 65:20:15) was prepared as a resin solution for forming a mat layer was prepared. , The number of rotations of the atomizing head is 25,000 rpm, the amount of the resin solution fed is 40 ml / min, and the voltage applied to the atomizing head is -9.
0kV, ambient temperature during application is 25 ℃, relative humidity is 50%
2.5 seconds after application, steam was sprayed on the application surface to wet it.
Was blown for 5 seconds to dry. The height of the mat is about 6 μm, the size is about 30 μm, and the number is 150 pieces / mm ²
Met. Thus, a positive photosensitive lithographic printing plate was prepared.

(Measurement method of aluminum ion elution amount) The photosensitive lithographic printing plate 0.1 m ² prepared as described above was used for 1 m
Image exposure for 1 minute with a 3 kW metal halide lamp from the distance of
C., 12 seconds dish development.

Developer [A] D-Sorbit 2.5% Potassium hydroxide 1.3% Diethylenetriaminepenta (methylenephosphonic acid) 5Na salt 0.1% Water 96.1%

The in-situ treatment solution was diluted 10-fold with pure water, and then inductively coupled plasma atomic emission spectrometer (ICP-AES: Inductively Cou
The emission intensity of aluminum atoms in the liquid was measured by pled plasma-atomic emission spectroscopy). The developer was diluted 10 times with pure water, and an Al standard solution for atomic absorption was added to prepare a calibration curve solution, and the emission intensity of aluminum atoms was measured in the same manner. Yttrium ion (Y standard solution for atomic absorption) was added as an internal standard substance to the measurement sample and the calibration curve solution to correct the fluctuation of the sample introduction amount. The aluminum ion elution concentration in the dish processing solution was determined from the aluminum atom emission intensity of the dish processing solution and the calibration curve solution. The aluminum ion elution amount per 1 m ^{2 of the} plate was calculated from the aluminum ion elution concentration in the dish solution.

Analytical conditions for measuring aluminum ion elution amount Measurement device: High frequency plasma emission spectrometer (ICPS-1000IV) manufactured by Shimadzu Corporation Plasma: High frequency inductively coupled plasma Frequency: 27.120 MHz High frequency output: 1.2 kW Coolant gas: Ar 14L / Min Plasma gas: Ar 1.2 L / min Carrier gas: Ar 1.0 L / min Purge gas: Ar 3.5 L / min Measurement wavelength: Aluminum atom emission wavelength 396.
The elution amount of 153 nm aluminum ion was 40 mg / m ² .

The photosensitive lithographic printing plate thus prepared was
It was cut into 030 mm x 800 mm, and many sheets were prepared. After performing image exposure for 1 minute with a 3 kW metal halide lamp from a distance of 1 m, a first desensitizing bath and a second desensitizing bath are provided after the immersion type developing bath, and a developing bath and a second desensitizing bath are provided. It has a mechanism for replenishing the desensitizing bath with a replenisher, a mechanism for discharging an overflow solution of the second desensitizing bath to the first desensitizing bath, and a mechanism for transporting a photosensitive lithographic printing plate. In an automatic processor having the following rollers. At that time, 20 liters of the developing solution [A] was charged into the developing bath and adjusted to 30 ° C., and 4 liters of the following desensitizing solution [A] was charged into the first desensitizing bath, and the second 4 liters of the desensitizing solution [A] was also charged into the desensitizing bath.

Desensitizing solution [A] Gum arabic 1.6% Enzyme-modified potato starch 8.8% Phosphorylated waxy corn starch 0.80% Dioctyl sulfosuccinate sodium salt 0.10% Citric acid 0.14% α-alanine 0.11% EDTA-tetrasodium salt 0.10% dodecyl diphenyl ether disulfonic acid 2Na salt 0.18% ethylene glycol 0.72% benzyl alcohol 0.87% sodium dehydroacetate 0.04% emulsion silicone defoamer 0.01% Water 86.53%

The processing was performed at a speed of passing through the developing bath in 12 seconds, and was continuously performed for 160 plates per day for three months.
The following developer replenisher [A] was added to the developing bath at 26 c / m ^2.
c Replenished. The desensitizing solution [A] was replenished to the ^second desensitizing bath at 20 cc per 1 m ² .

Development Replenisher [A] D-Sorbit 5.6% Potassium hydroxide 2.5% Diethylenetriaminepenta (methylenephosphonic acid) 5Na salt 0.2% Water 91.7%

No deposits were found on the processed plate, and printing could be performed without any problem. After the completion of the processing, the inside of the automatic developing machine was observed. As a result, no precipitate was found in the first desensitizing bath, and no clogging was observed in the spray pipe.

Example 2 In Example 1, the treatment with No. 3 sodium silicate was performed at 2.5% at 25 ° C. for 8 seconds. 15mg / m ²
Other than the above, the treatment was performed in the same manner as in Example 1. The aluminum ion elution amount during development was 10 mg / m ² . Good results were obtained as in Example 1.

Polymer compound (a) 0.3 g Methanol 100 g Water 1 g

[Example 3] In Example 1, the treatment with saponin in place of No. 3 sodium silicate was performed at 1%, at 40 ° C, and at 30 ° C.
The procedure was performed in the same manner as in Example 1 except that the application was performed in seconds and the application of the polymer compound was not performed. The aluminum ion elution amount during development was 40 mg / m ² . Good results were obtained as in Example 1.

Example 4 The procedure of Example 3 was repeated, except that glucopon was used instead of saponin at 1% at 50 ° C. for 30 seconds. The aluminum ion elution amount during development was 50 mg / m ² . Good results were obtained as in Example 1.

[Example 5] In Example 3, a mixed solution of 10% NaH ₂ PO ₄ and 0.1% NaF was used at 70 ° C instead of saponin.
The same processing as in Example 3 was performed except that the processing was performed for 30 seconds. The aluminum ion elution amount during development was 30 mg / m ² . Good results were obtained as in Example 1.

Example 6 The procedure of Example 1 was repeated, except that the treatment with K ₂ ZrF ₆ was performed at 0.1%, 20 ° C. for 5 seconds instead of the treatment with saponin. . The aluminum ion elution amount during development was 90 mg / m ² . Good results were obtained as in Example 1.

Comparative Example 1 The procedure of Example 3 was repeated except that the treatment with saponin was not carried out. The aluminum ion elution amount during development was 120 mg / m ² .
As a result of observing the inside of the automatic developing machine, a precipitate was observed in the first desensitizing bath, a deposit was observed on the processed plate, and printing stains occurred. Also, slight contamination of the roller was observed.

[Comparative Example 2] In Comparative Example 1, the anodic oxidation was carried out by 20%.
The same treatment as in Comparative Example 1 was performed, except that the treatment was performed for 50 seconds at H ₂ SO ₄ , a current density of 5 A / dm ² , a temperature of 33 ° C. The aluminum ion elution amount during development was 160 mg / m ² . As a result of observing the inside of the automatic developing machine, a precipitate was observed in the first desensitizing bath, a deposit was observed on the processed plate, and printing stains occurred. Further, dirt on the roller and clogging of the spray were observed.

Comparative Example 3 The same treatment as in Comparative Example 2 was carried out except that after the anodizing treatment in Comparative Example 2, the treatment was carried out at 2% of polyvinylphosphonic acid at 60 ° C. for 30 seconds. The aluminum ion elution amount during development was 140 mg / m ² . As a result of observing the inside of the automatic developing machine, a precipitate was observed in the first desensitizing bath, a deposit was observed on the processed plate, and printing stains occurred. Also, dirt on the roller was observed.

Comparative Example 4 The procedure of Comparative Example 3 was repeated, except that a treatment with boiling water at 100 ° C. for 20 seconds was carried out with pure water in place of the polyvinylphosphonic acid treatment. The aluminum ion elution amount during development was 140 mg / m ² .
As a result of observing the inside of the automatic developing machine, a precipitate was observed in the first desensitizing bath, a deposit was observed on the processed plate, and printing stains occurred. Also, dirt on the roller was observed.

As is clear from the above results, the plate making methods of the photosensitive lithographic printing plates of the examples according to the present invention each obtained satisfactory results. A precipitate was observed in the desensitizing bath, and a deposit was observed on the treated plate, resulting in printing stains. Also, dirt on the roller was recognized, which was unsatisfactory.

[0131]

The method of making a photosensitive lithographic printing plate according to the present invention suppresses the generation of insoluble scum in a finishing bath and prevents clogging of filters and sprays.
Stable development and finishing can be continued. Further, it is a highly practical lithographic printing plate free from printing stains and defective ink deposition over a long period of time.

Claims (1)

[Claims] 1. A photosensitive lithographic printing plate using an aluminum support having an aluminum ion elution amount of 100 mg / m ² or less when developed with a developer containing a non-reducing sugar and a base (excluding silicate), A plate making method for a photosensitive lithographic printing plate, comprising developing with a developer and then treating with a finishing solution containing at least one oxycarboxylic acid.