JPH08220775A - Developer for photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE: To provide a developer and a development replenisher soln. excellent in stability in development, shelf stability and developing ability and capable of processing positive type and negative type PS plates in common with each other and to provide a developing method using them. CONSTITUTION: This developer has buffer action at pH11.5-13.5 and contains at least one kind of compd. selected from among silicic acid, phenol, saccharides, oximes and fluorinated alcohols and a compd. represented by formula I or II. In the formulae I, II, each of R<1> -R<10> is 1-12C alkyl, cycloalkyl, hydroxyalkyl, unsubstd. or alkyl substd. benzyl or optionally substd. phenyl, each of Z1 -Z3 is N<+> , P<+> , S, As, Sb, I, Sn or B<-> , when each of Z1 -Z3 is N<+> or P<+> , each of X<1> -X<3> is an anion other than OH<-> , when each of Z1 -Z3 is B<-> , each of X<1> -X<3> is a cation, and (n) is an integer of 1-5.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a developing solution for a photosensitive lithographic printing plate.

[0002]

2. Description of the Related Art Conventionally widely used positive-working photosensitive lithographic printing plates have an aluminum plate as a support provided with a photosensitive layer such as an o-quinonediazide compound. It is known that an o-quinonediazide compound is converted to a carboxylic acid by exposure to ultraviolet light,
Therefore, when this is developed with an alkaline aqueous solution, only the exposed portion of the photosensitive layer is removed and the surface of the support is exposed. Since the surface of the aluminum support is hydrophilic, the portion where the surface of the support is exposed by development (non-image area) retains water and repels the oil-based ink. On the other hand, the area (image area) where the photosensitive layer was not removed by development repels water because it is lipophilic,
Accept ink. Various alkaline aqueous solutions used as a developer for such a positive photosensitive lithographic printing plate are known, but most preferred is sodium silicate,
An aqueous solution of silicate such as potassium silicate. The reason is that the developability can be adjusted to some extent by changing the ratio of silicon oxide, which is a component of the silicate, and the alkali metal oxide, and the in-liquid concentration of both.

It is known that, in a developer containing these silicates as a main component, if the alkali strength is increased, a high processing ability can be obtained, but the development stability is insufficient.

On the other hand, these silicates are not only the above-mentioned positive type photosensitive lithographic printing plates, but also the reversal type negative type photosensitive lithographic printing plates using an o-quinonediazide photosensitive layer described in Japanese Patent Publication No. 56-14970. Or a negative photosensitive lithographic printing plate using a negative photosensitive lithographic printing plate developer using an alkali-soluble diazonium salt as a photosensitive layer and a photosensitive layer using a resin having a dimethylmaleimide group as a side chain as a photocrosslinking agent. However, in recent years, negative and positive photosensitive lithographic printing plates have been commonly processed in one automatic developing machine for the purpose of space saving, resource saving and labor saving. There is. However, when the alkali strength is increased in order to obtain a high processing capacity for the positive working photosensitive lithographic printing plate, there is a problem that the developability of the negative working photosensitive lithographic printing plate is significantly lowered and common processing cannot be performed.

[0005]

Therefore, the object of the present invention is to provide excellent development stability and development processing ability over a long period of time.
The object is to provide a developer for a photosensitive lithographic printing plate which is particularly suitable for use with an automatic processor. Another object of the present invention is to provide a developing solution suitable for common processing of negative-working and positive-working photosensitive lithographic printing plates.

[0006]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors in order to achieve the above-mentioned object, a developer and / or replenisher for a photosensitive lithographic printing plate (hereinafter also referred to as “PS plate”) In the liquid, the pH is adjusted to 11.5 to 13.5,
And at least one compound selected from silicic acids, phenols, saccharides, oximes and fluorinated alcohols and having a buffering action, and a compound represented by the following general formula (A) or (B) It was found that the development stability is improved by the above, and the present invention has been accomplished.

[0007]

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In the formula, R ^{1 to} R ¹⁰ are each independently an alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group, a hydroxyalkyl group, an unsubstituted or alkyl-substituted benzyl group, or a substituted or unsubstituted A phenyl group, Z _{1 to} Z ₃ represent N ⁺ , P ⁺ , S, As, Sb, I, Sn or B ^−, and when Z _{1 to} Z ₃ is N ⁺ or P ⁺ , X ^{1 to} X ³ Represents an anion other than a hydroxyl group, X ^{1 to} X ³ represent cations when Z _{1 to} Z ₃ are B ⁻ , and n represents an integer of 1 to 5.

Further, when X ^{1 to} X ³ are halogen ions (for example, chlorine ion, bromine ion), development stability is further improved, which is preferable. Further, when the sum of carbon numbers of R ^{1 to} R ^{4 in} the general formula (A) is ⁴ to 24, development stability is further improved, which is preferable. In addition, the general formula (B)
When the sum of carbon numbers of R ^{5 to} R ¹⁰ is 6 to 48, development stability is further improved, which is preferable. Furthermore, the compound having a buffering action has an acid dissociation constant of 5 × 10 ⁻¹⁴ to 1 × 10 ⁻¹¹ and is at least selected from silicic acids, phenols, sugars, oximes, and fluorinated alcohols. When it is one kind of compound, development stability is further improved, which is preferable.

Hereinafter, the present invention will be described in detail. In the compound represented by the general formula (A) or (B), R
^{1 to} R ¹⁰ are each independently an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms (eg, methyl group, ethyl group, n-propyl group, n-butyl group), cyclic alkyl group (eg, cyclohexyl). Group, 3-methylcyclohexyl group), hydroxyalkyl group (eg hydroxymethyl group, hydroxyethyl group), unsubstituted or alkyl-substituted benzyl group (eg benzyl group, isopropylbenzyl group), or substituted or unsubstituted phenyl group ( For example, 2-methoxyphenyl group, 3,5-dichlorophenyl group), Z _{1 to} Z ₃ are N ⁺ , P ⁺ , S, As, Sb,
I, Sn or B ^−, and when Z _{1 to} Z ₃ are N ⁺ or P ⁺ , X ^{1 to} X ³ represent anions other than hydroxyl group, for example, halogen ion, nitrate ion, sulfate ion, phosphate ion, P
F ₅ ⁻ or BF ₄ ^{− and the} like, and when Z _{1 to} Z ₃ are B ⁻ , X ^{1 to} X ³ represent a cation, for example, Li ⁺ , Na ⁺ ,
K ⁺ or NH ₄ ⁺ is included, and n is 1 to 5, preferably 1
Indicates an integer of ˜3.

Hydroxide ions as X ^{1 to} X ³ are not suitable because they change the pH of the liquid. As X ^{1 to} X ³ , halogen ions (eg, chlorine ion, bromine ion) are preferable from the viewpoint of development stability and the like.

Specific examples of the compound represented by the general formula (A) or (B) include the following compounds. (1) Tetrabutylammonium bromide (2) Tetrabutylammonium chloride (3) Triethylbenzylammonium chloride (4) Tetramethylammonium chloride (5) Tetramethylammonium bromide (6) Tetraethylammonium chloride (7) Tetraethylammonium bromide (8) Tetrapropylammonium chloride (9) Tetrapropylammonium bromide (10) Tributylbenzylammonium chloride (11) Octyldimethylammonium chloride (12) Tetraphenylphosphonium iodide (13) Tetraphenylphosphonium bromide (14) Tetraphenylphosphonium chloride (15) Tetraphenylphosphonium sulfate (16) Tetraphenylphosphonium nitrate (17) Tetraphenylboron Natri (18) Tetra n-butylphosphonium iodide (19) Tetra n-butylphosphonium bromide (20) Tetra n-butylphosphonium chloride (21) Tetra n-butylphosphonium sulfate (22) Tetra n-butylphosphonium nitrate (23) ) Tetrabutylammonium sulfate (24) Tetrabutylammonium nitrate (25) Ethyltriphenylphosphonium bromide (26) Benzyltriphenylphosphonium chloride (27) Tetrabutylphosphonium phosphate (28) Butyltriphenylphosphonium bromide (29) Tetrabutylammonium Trilyphosphonium bromide (30) Triethylbenzylammonium bromide (31) Triethylbenzylammonium iodide (32) Octyldimethylbenzylammonium chloride (33) Octyldimethylbenzylammonium bromide De (34) lauryl dimethyl benzyl ammonium chloride (35) lauryl dimethyl benzyl ammonium bromide (36) 1,2-bis (diphenylphosphino) ethane bromide

The above general formula (A) or (B) of the present invention
The compound represented by is available as a commercial product. The amount of the compound represented by the general formula (A) or (B) used is 0.00 per 1 liter of the developer and the replenisher.
It is preferably 5 g or more, more preferably 0.0
It is 1 g / liter or more. Increasing the amount of quaternary ammonium salt used increases the stability of the developer and replenisher. Therefore, the upper limit of the quaternary ammonium salt is not particularly limited as long as it dissolves in the developer or the replenisher, but it is preferably 10% by weight or less.

In the developer and replenisher of the present invention, the compound represented by the general formula (A) or (B) is added together with p.
A compound having a buffering effect at H 11.5-13.5 is used. The compound having such a buffering action is preferably 5 × 10 5 because of the effect of improving the development stability.
A compound having an acid dissociation constant of ⁻¹⁴ to 1 × 10 ⁻¹¹ and selected from silicic acids, phenols, sugars, oximes, and fluorinated alcohols can be mentioned.

The silicic acid used in the developing solution and the replenishing solution of the present invention includes alkali metal silicates (SiO ₂ / M ₂
O; M is an alkali metal), and more specifically, sodium silicate, potassium silicate, and lithium silicate. In the present invention, these may be used alone or in combination. Preferably sodium silicate,
It is potassium silicate. SiO _{2 of} alkali metal silicate /
M ₂ O molar ratio (M represents an alkali metal) is 0.5 to
It is preferably 2.0. The concentration of the alkali metal silicate in the developer is preferably 1 to 10%, particularly preferably 1.5 to 5%. In any of the above developing solutions and replenishing solutions, the pH value is preferably 11.5 to 13.5, and more preferably the developing solution pH of 12.2 to 13.
3, pH of the replenisher is 12.5-13.5. When the pH value is less than 11.5, the developability is remarkably deteriorated, whereas when the pH value is more than 13.5, the corrosiveness of the PS plate for the aluminum support and the automatic developing machine parts becomes remarkable. Therefore, it is not preferable.

An alkaline agent can be used in combination with the developer and replenisher of the present invention. Examples thereof include tribasic sodium phosphate, potassium phosphate, ammonium phosphate, dibasic sodium phosphate, potassium phosphate, ammonium phosphate, sodium carbonate, potassium phosphate, ammonium phosphate, sodium hydrogen carbonate, potassium salt, ammonium salt, sodium borate salt, Examples thereof include inorganic alkali agents such as potassium, ammonium, sodium hydroxide, ammonium, potassium and lithium. In addition, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine,
n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxy An organic alkaline agent such as deoxidizer is also used. These alkaline agents can be used in combination of two or more kinds.

The compounds having a buffer action for use in the present invention, especially 5 × 10 ^-14 ~1 × 10 ^- is a compound having an acid dissociation constant of ^11, which 0.01 mol / l or more, in particular 0. By adding 0. 3 to 1 mol / l, the sensitivity of the PS plate to be developed can be stably obtained. The acid dissociation constant as used herein means that any one of the first, second, third, etc. is a compound having a concentration of 5 × 10 ⁻¹⁴ to 1 × 10 ⁻¹¹ . If the addition amount is less than 0.01 mol / l, the development stabilizing effect is insufficient, and if it exceeds 1 mol / l,
It is not preferable because it may deteriorate the solubility of the photosensitive layer.

Next, saccharides (particularly those represented by the following general formula (I) or (II)) and oximes (particularly the following general formula) used as the compound having a buffering action of the present invention.
(III)), phenols (especially those represented by the following general formula (IV)) and fluorinated alcohols (especially those represented by the following general formula (V)) will be described. The saccharides represented by the general formula (I) or (II) are as follows.

[0019]

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X ₁ , X ₂ and X ₃ each represent a hydrogen atom, a hydroxyl group, an amino group, a halogen atom, an acyloxy group, an alkoxy group, an acylamino group or a phosphoryloxy group.
R ₁₁ and R ₁₂ are each a hydrogen atom, an alkyl group (eg, methyl group), a substituted alkyl group (eg, hydroxymethyl group, 1,2-dihydroxyethyl group, acetoxymethyl group, benzoyloxymethyl group, methoxymethyl, benzyl). Oxymethyl or the like) or a carboxyl group. Y represents a hydrogen atom, an acyl group, an alkoxycarbonyl group, a carbamoyl group or an alkyl group. Further X
_{When the} substituent represented by ₁ , X ₂ , X ₃ , R ₁₁ , R ₁₂ and Y is a hydroxyl group or a hydroxyl group-containing group, formation of an ether bond between any two hydroxyl groups or further addition of acetone or benzaldehyde A 5- or 6-membered ring may be formed by acetalization by adding a carbonyl compound. Y in the general formula (I) or (II) is further a hydroxyl group represented by X ₁ , X ₂ , X ₃ , R ₁₁ , R ₁₂ and Y of other (I) or (II) and (n-1) ) N (I) completed by forming Glucoxide bonds
Alternatively, an oligosaccharide composed of the unit (II) may be formed. Here, n represents an integer of 2 to 6.

Preferred as X ₁ , X ₂ and X ₃ are a hydrogen atom or a hydroxyl group, more preferably a hydroxyl group.
Preferred as R ₁₁ and R ₁₂ are a hydrogen atom, a hydroxymethyl group, a 1,2-dihydroxyethyl group or a carboxyl group, more preferably a hydrogen atom, a hydroxymethyl group or a 1,2-dihydroxyethyl group. Y
Is preferably a hydrogen atom.

Specific examples of the saccharide represented by the general formula (I) or (II) include the following compounds. I-1 D-Erythrose ^* I-2 D-Threose ^* I-3 D-Arabinose I-4 D-Ribose I-5D -Xylose I-6 D-Erythro-penturose (D-Eryth)
ro-Pentulose) ^* I-7 D-Allose I-8 D-Galactose I-9 D-Glucose I-10 D-Mannose I -11 D-Talose I-12 β-D-Fructose I-13 α-L-Sorbose I-14 6-deoxy-D-glucose (6-deoxy
-D-Glucose) I-15 D-glycero-D-galacto-Heptose I-16 α-D-allo-heptulose (α-D-
allo-Heptulose) I-17 β-D-Altro-3-heptulose (β
-D-altro-3-Heptulose) I-18 Sucrose I-19 Lactose I-20 D-Maltose I-21 Solmaltose I-22 Inulobiose ^* I-23 Hyalbiouronic acid I-24 Maltotriose

[0023]

[Chemical 4]

The compounds marked with * belong to the general formula (II). Most of these compounds are commercially available and easily available. Those that are not on the market,
(1) "Large Organic Chemistry Volume 3, Aliphatic Compound II" Supervised by Mitsuo Kotake, published by Asakura Shoten, 1957, or (2) "Th
e Carbonhydrates, Chemistry and Biochemistry "2nd
Ed IA (1972), and IIA (1970), W. Pibgm
It can be easily synthesized by referring to an and D. Horton's supervision, Academic Press. The oximes represented by the general formula (III) are as follows.

[0025]

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R ₁₃ and R ₁₄ represent a hydrogen atom, an alkyl group (which may have a substituent), an aryl group (which may have a substituent), an acyl group or a heterocycle. A 5- or 6-membered ring in which R ₁₃ and R ₁₄ are bonded to each other (especially a cycloalkyl ring)
May be formed.

The alkyl group has 1 to 18 carbon atoms and includes straight chain, branched chain and cycloalkyl groups. Examples of the substituent include a hydroxy group, a carboxyl group, an alkoxy group, a halogen atom, a sulfo group, a sulfamoyl group,
Examples thereof include a carbamoyl group, a sulfonylamino group, an acylamino group, a cyano group, and an acyloxy group. The aryl group is, for example, a phenyl group or a naphthyl group, and the substituents are, for example, those mentioned as the substituents of the alkyl group. Examples of the heterocycle include thiazole, oxazole, imidazole, triazole,
Examples thereof include tetrazole, thiadiazole, oxadiazole, tetrahydrofuran, morpholine, pyridine, piperidine, benzothiazole, benzoxazole, and benzimidazole. Specific examples of the compound represented by the general formula (III) include the following.

[0028]

[Chemical 6]

[0029]

[Chemical 7]

These compounds are commercially available or are available in "Organic Functional Group Preparations Vol. 3" Pa.
ge 365 Ed. by SRSandler and W.Karo, Academic Pre
It can be easily obtained by synthesizing by the method described in ss (1972). Next, the phenols of general formula (IV) will be described.

[0031]

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Here, R ₁₅ , R ₁₆ , R ₁₇ , and R ₁₈ are the same or different and each represents a hydrogen atom, an amino group, a carboxylic acid group,
It represents a sulfonic acid group, an alkyl group having 1 to 4 carbon atoms (which may have a substituent), and an alkoxy group (which may have a substituent). As the substituent, R in the general formula (III) is used.
_{The same} as the substituents of the alkyl group or aryl group of ₁₃ and R ₁₄ can be mentioned. The following are specific examples of the compound represented by the general formula (IV).

[0033]

[Chemical 9]

Many of these compounds are commercially available,
Other compounds are known and can be easily synthesized. Next, the fluorinated alcohol of the general formula (V) will be described.

[0035]

[Chemical 10]

In the formula, R represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group; n represents 1 or 2, and J represents n. In the case of 1, it represents a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, and n is 2 In the case of a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted arylene group,
It represents a substituted or unsubstituted aralkylene group.

In the preferred compounds represented by the general formula (V), R represents a hydrogen atom, a fluorine-substituted alkyl group, a carboxylic acid group or an alkylcarboxylic acid group, n represents 1 or 2, and J When n is 1, it represents a hydrogen atom or a fluorine-substituted alkyl group, and when n is 2, it is a fluorine-substituted alkylene group. Among these preferable compounds, those having 6 or less carbon atoms per hydrophilic group such as a hydroxyl group, a carboxylic acid group and a sulfonic acid group are preferable in terms of having sufficient solubility in the treatment liquid. Specific examples of the compound represented by formula (V) are shown below.

[0038]

[Chemical 11]

Many of these compounds are commercially available,
Other compounds are known and can be easily synthesized.

Among the compounds of the general formulas (I) to (V),
Preferred are sugars of general formula (I) or (II), phenols of general formula (IV), more preferably non-reducing sugars such as saccharose of general formula (I) or (II) or sulfosalicylic acid. Is. When the above-mentioned development stabilizer is added to the alkaline developer and / or the replenisher in the present invention, the acidic substance may be added in the form of a salt which is previously reacted with various alkaline compounds.

The developer and replenisher obtained as described above may contain various surfactants, if necessary, for the purpose of promoting the developability, dispersing the development residue and enhancing the ink affinity of the image portion of the printing plate. Organic solvents can be added.

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 ester. , Sorbitan fatty acid partial esters,
Pentaerythritol fatty acid partial ester, 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 , Polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial ester, fatty acid diethanolamide,
Nonionic surfactants such as N, N-bis-2-hydroxyalkylamines, polyoxyethylenealkylamines, triethanolamine fatty acid esters, trialkylamine oxides; fatty acid salts, abietic acid salts,
Hydroxyalkane sulfonates, alkane sulfonates, dialkylsulfosuccinate ester salts, linear alkylbenzene sulfonates, branched chain alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkylphenoxypolyoxyethylenepropyl sulfonates, polyoxy Ethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium salt, N-alkyl sulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated tallow oil, sulfate ester salts of fatty acid alkyl esters, alkyl sulfate esters Salts, polyoxyethylene alkyl ether sulfate ester salts, fatty acid monoglyceride sulfate ester salts, polyoxyethylene alkylphenyl ether sulfate ester salts, Oxyethylene styryl phenyl ether sulfate ester salts, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphate ester salts, polyoxyethylene alkylphenyl ether phosphate ester salts, partial saponification products of styrene / maleic anhydride copolymers, Anionic surfactants such as partially saponified products of olefin / maleic anhydride copolymers and naphthalene sulfonate formalin condensates; alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, polyethylene polyamine derivatives, etc. Cationic surfactants; amphoteric surfactants such as carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfates, and imidazolines. Among the above-mentioned surfactants, the term "polyoxyethylene" can be replaced with polyoxyalkylenes such as polyoxymethylene, polyoxypropylene and polyoxybutylene, and these surfactants are also included.

Further preferred surfactants are fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Such fluorine-based surfactants include perfluoroalkylcarboxylates, perfluoroalkylsulfonates, anionic types such as perfluoroalkyl phosphates, amphoteric types such as perfluoroalkylbetaines,
Power thione type and perfluoroalkylamine oxides such as perfluoroalkyltrimethylammonium salts, perfluoroalkylethylene oxide adducts, perfluoroalkyl group- and hydrophilic group-containing oligomers,
Nonionic type oligomers such as perfluoroalkyl group- and lipophilic group-containing oligomers, perfluoroalkyl groups, hydrophilic group- and lipophilic group-containing oligomers, and perfluoroalkyl group- and lipophilic group-containing urethanes can be mentioned.
The above surfactants can be used alone or in combination of two or more kinds. It is added to the developer and the replenisher in the range of 0.001 to 10%, preferably 0.01 to 5%.

An organic solvent can be optionally added to the developing solution and the replenishing solution of the present invention. As the organic solvent, those having a solubility in water of about 10% or less are suitable, and those having a solubility of 5% or less are preferable. For example,
1-phenyl ethanol, 2-phenyl ethanol, 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, 4-methylcyclohexanol, N-phenylethanol Mention may be made of amines and N-phenyldiethanolamine. The content of the organic solvent is 0.1 to 5% based on the total weight of the used liquid. 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 it is therefore impossible to expect to secure good developability.

The developer and replenisher of the present invention may further contain an antifoaming agent and a water softener, 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,
Aminopolycarboxylic acids such as hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts, aminotri (methylene) Phosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), hydroxyethylethylenediaminetri (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphone. Mention may be made of acids and their sodium, potassium and ammonium salts.

The optimum value of such a water softener varies depending on its chelating power, the hardness of hard water used, and the amount of hard water. 0.01 to 5%, more preferably 0.01
Is in the range of 0.5%. If the addition amount is less than 0.01%, the intended purpose cannot be sufficiently achieved, and if the addition amount exceeds 5%, the image area is adversely affected such as color loss.

The remaining component of the developing solution and the replenishing solution of the present invention is water, but various additives known in the art can be further added if necessary. For example, JP-A-5
NaCl, KCl, KBr described in JP-A-8-75152
Neutral salts, etc., complexes such as [Co (NH ₃ ) ₆ ] Cl ₃ described in JP-A-58-121336, JP-A-55-2
5100, ionizable compounds of elements of Group IIa, Group IIIa or Group IIIb of the Periodic Table, tetramethyldecynediol described in US Pat. No. 4,374,920, JP-A-60- Nonionic surfactants described in JP 213943 A, cationic polymers such as a methyl chloride quaternary compound of p-dimethylaminomethyl polystyrene described in JP 55-95946 A, JP 56-142528 A. Amphoteric polyelectrolytes such as copolymers of vinylbenzyltrimethylammonium chloride and sodium acrylate, JP-A-57-19295
No. 2, an alkali-soluble mercapto compound or a thioether compound, an inorganic lithium compound such as lithium chloride described in JP-A-58-59444, JP-B-5.
Organic lithium compounds such as lithium benzoate described in JP-A No. 0-34442, organometallic surfactants containing Si, Ti, etc. described in JP-A-59-75255, JP-A-5-75.
Organoboron compounds described in JP-A-9-84241, quaternary ammonium salts such as tetraalkylammonium oxide described in EP 101010, and bactericides such as sodium dehydroacetate described in JP-A-63-226657. To be It is advantageous in terms of transportation that the developer and the replenisher of the present invention are concentrated solutions containing less water than when used and diluted with water when used. In this case, the degree of enrichment should be such that each component does not separate or precipitate. In addition, JP-A-5
When it is solidified and used as described in JP-A-142786, it can be further advantageously used for transportation.

The PS plate to which the developer and replenisher of the present invention are preferably used is a PS plate having a positive type (which may be inverted and used as a negative type) photosensitive layer containing an o-quinonediazide compound as a photosensitizer. Examples include a plate and a negative PS plate having various photocurable photosensitive layers. In particular, the developer and replenisher of the present invention are particularly suitable in the case where a positive PS plate and a negative PS plate are commonly processed, because a sufficient development speed can be obtained with the negative PS plate.

The PS plate to which the developer and replenisher of the present invention can be preferably applied will be described in detail below. (Support) PS to which the developer and replenisher of the present invention are applied
The plate support is a dimensionally stable plate. As such a support, the effect of the present invention is remarkably exhibited on a metal plate such as an aluminum plate. Suitable aluminum plates are a pure aluminum plate and an alloy plate containing aluminum as a main component and containing a slight amount of a foreign element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The thickness of the aluminum plate used is about 0.1 mm to 0.6 mm. First, the surface of the aluminum plate is subjected to degreasing treatment if desired, and then roughened. As the method, a method of mechanically roughening the surface,
There are methods of electrochemically dissolving and roughening the surface and methods of chemically selectively dissolving the surface. As a 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 graining method, there is a method of performing alternating current or direct current in a hydrochloric acid or nitric acid electrolytic solution.
Further, as disclosed in Japanese Patent Application Laid-Open No. 54-63902, a method in which both are combined can be used.

The thus roughened aluminum plate is optionally subjected to alkali etching treatment and neutralization treatment, and then, if desired, subjected to anodizing treatment in order to enhance water retention and abrasion resistance of the surface. It As the electrolyte used for anodizing 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 electrolyte. The amount of the anodized film is preferably 1.0 g / m ² or more, more preferably 2.
It is in the range of 0 to 6.0 g / m ² . After being subjected to anodizing treatment, the aluminum surface is optionally subjected to hydrophilic treatment. As hydrophilic treatment, US Pat. No. 2,714,0
No. 66, No. 3,181,461, No. 3,280,73
4 and 3,902,734, there are alkali metal silicate (eg sodium silicate aqueous solution) methods. In this method, the support is immersed or electrolyzed in an aqueous sodium silicate solution. In addition, potassium fluorozirconate disclosed in Japanese Patent Publication No. 36-22063 and U.S. Pat. Nos. 3,276,868, 4,153,461 and 4,689,272 are disclosed. For example, a method of treating with polyvinylphosphonic acid is used.

The aluminum plate is optionally provided with an organic undercoat layer or an intermediate layer before coating the photosensitive layer.
Examples of the organic compound used in this organic undercoat layer include phosphonic acids having an amino group such as carboxymethyl cellulose, dextrin, gum arabic, and 2-aminoethylphosphonic acid, phenylphosphonic acid which may have a substituent, and naphthyl. Organic phosphonic acids such as phosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, phenylphosphoric acid which may have a substituent, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid Phosphoric acid, optionally substituted phenylphosphinic acid, naphthylphosphinic acid, organic phosphinic acids such as alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and triethanolamine hydrochloride The hydroxy Although selected from such as hydrochloric acid salt of an amine having a group it may be used as a mixture of two or more. The undercoat layer coating solution may be used in a pH range of 1 to 12 by adjusting the pH with a basic substance such as ammonia, triethylamine, potassium hydroxide or the like or an acidic substance such as hydrochloric acid or phosphoric acid. Further, a yellow dye may be added to improve the tone reproducibility of the photosensitive lithographic printing plate. The coating amount of the organic undercoat layer after drying is appropriately ² to 200 mg / m ² . An intermediate layer may be provided to enhance the adhesion between the support and the photosensitive layer. In order to improve the adhesion, the intermediate layer is generally made of a diazo resin, a phosphoric acid compound adsorbed on aluminum, or the like.

(Backcoat Layer) Since the developing solution and the replenishing solution of the present invention have relatively high alkali strength, a PS plate having a backcoat layer is preferably used in order to suppress elution of aluminum oxide from the back surface. As such a back coat layer, those described in detail in JP-A-5-45885, JP-A-5-210235 and JP-A-6-35174 can be used.

(Photosensitive layer) A photosensitive layer made of a known photosensitive composition is provided on the thus obtained aluminum plate having a hydrophilic surface to obtain a photosensitive lithographic printing plate. Examples of the photosensitive composition include a positive type containing an o-quinonediazide compound as a main component, a diazonium salt, an alkali-soluble diazonium salt, a photopolymerizable compound containing an unsaturated double bond-containing monomer as a main component, and a cinnamic acid or a dimethylmaleimide group. A negative type photosensitizer containing a photocrosslinkable compound containing a compound is used.

(Positive-type photosensitive layer) Of these, an o-naphthoquinonediazide compound used as a positive-type photosensitive composition is 1,2-diazonaphthoquinonesulfonic acid described in JP-B-43-28403. Esters with pyrogallol-acetone resin are preferred. Other suitable orthoquinonediazide compounds include, for example:
US Pat. Nos. 3,046,120 and 3,18
There is an ester of 1,2-diazonaphthoquinone-5-sulfonic acid and a phenol-formaldehyde resin described in Japanese Patent No. 8,210, which is disclosed in JP-A-2-96163.
Japanese Patent Application Laid-Open No. 2-96165 and Japanese Patent Application Laid-Open No.
There is an ester of 1,2-diazonaphthoquinone-4-sulfonic acid and a phenol-formaldehyde resin described in Japanese Patent No. 96761. Other useful o-naphthoquinonediazide compounds include those known in numerous patents and the like. For example, JP-A-47-5303
48-63802, 48-63803, 48-96575, 49-38701, 48-.
No. 13854, Japanese Examined Patent Publication No. 37-18015, No. 41-1
No. 1222, No. 45-9610, No. 49-17481
Publications, US Pat. Nos. 2,797,213 and 3,4.
No. 54,400, No. 3,544,323, No. 3,
573,917, 3,674,495, 3,785,825, and British Patents 1,227,602.
No. 1,251,345, No.1,267,00
No. 5, No. 1,329,888, No. 1,330,9
32, German Patent No. 854,890 and the like can be mentioned. More particularly preferred o-naphthoquinonediazide compounds are polyhydroxy compounds having a molecular weight of 1,000 or less and 1,2-
It is a compound obtained by a reaction with diazonaphthoquinone sulfonic acid. Specific examples of such compounds are described in JP-A-5-58
1-139402, 58-150948, 58
-203434, 59-165053, 60-
121445, 60-134235, 60-1
No. 63043, No. 61-118744, No. 62-10.
No. 645, No. 62-10646, No. 62-15395.
No. 0, No. 62-178562, No. 64-76047
U.S. Pat. Nos. 3,102,809 and 3,12.
No. 6,281, No. 3,130,047, No. 3,1
No. 48,983, No. 3,184,310, No. 3,
No. 188,210, No. 4,639,406, etc., and those described in the specification can be mentioned. The amount of these positive-working photosensitive compounds (including the above combinations) in the photosensitive composition is appropriately 10 to 50%, more preferably 15 to 50%.
40%.

The o-quinonediazide compound alone can form the photosensitive layer, but it is preferable to use a resin soluble in alkaline water together as a binder. As such a resin soluble in alkaline water, there is a novolak type resin such as phenol formaldehyde resin, o-, m- and p-cresol formaldehyde resin, m / p-mixed cresol formaldehyde resin, phenol / cresol ( o-, m-, p-, m / p
Mixed formaldehyde resin and the like). Further, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, and an acrylic resin containing a phenolic hydroxyl group as disclosed in JP-A-51-34711 can also be used. Examples of other suitable binders include copolymers having various monomers as structural units and usually having a molecular weight of 10,000 to 200,000 as described in JP-A-6-35184. Acrylic acid, methacrylic acid,
It is preferable to contain unsaturated carboxylic acids such as maleic anhydride and itaconic acid, and the preferable acid value of the copolymer is 0 to 10 meq / g, more preferably 0.2 to 5.0 m.
eq / g. The preferred molecular weight of the above copolymer is 10,000 to
It is 100,000. Also, if necessary, the above-mentioned copolymer,
Polyvinyl butyral resin, polyurethane resin, polyamide resin and epoxy resin may be added. One kind or two kinds of such alkali-soluble polymer compounds are used.
8 or more kinds of all photosensitive compositions can be combined.
It is used in an addition amount of 0% or less. Furthermore, US Pat.
123,279, t-
The combined use of a condensate of phenol and formaldehyde having a C3-8 alkyl group as a substituent, such as butylphenol formaldehyde resin and octylphenol formaldehyde resin, is preferable in order to improve the oil sensitivity of the image.

Further, cyclic acid anhydrides, phenols, and organic acids are preferably added to the positive photosensitive composition in order to enhance sensitivity. As the cyclic acid anhydride, those described in US Pat. No. 4,115,128 can be used. Examples of phenols include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone,
2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 4,4 ', 4 "-trihydroxy-triphenylmethane, 4,4', 3", 4 "-tetrahydroxy-3,5,3 ' , 5'-tetramethyltriphenylmethane, etc. Further, as organic acids, JP-A-60-88942 and JP-A-2-9675 are available.
There are various acids described in Japanese Patent Publication No. 5 and the like. The proportion of the cyclic acid anhydrides, phenols and organic acids in the photosensitive composition is preferably 0.05 to 15%, more preferably 0.1 to 5%.

Further, in order to broaden the stability of processing (so-called development latitude) in developing conditions in the above-mentioned photosensitive composition, a nonionic surfactant as described in JP-A-62-251740. JP-A-59-12
Amphoteric surfactants such as those described in JP-A-1044 and JP-A-4-13149 can be added. The proportion of the nonionic surfactant and the amphoteric surfactant in the photosensitive composition is preferably 0.05 to 15%, more preferably 0.1 to 5%. A printout agent for obtaining a visible image immediately after exposure and a dye or pigment as an image colorant can be added to the positive photosensitive composition. Typical examples of the printout agent include a combination of a compound that releases an acid upon exposure (photoacid releasing agent) and an organic dye capable of forming a salt. Specifically, o-naphthoquinonediazide-4 described in JP-A Nos. 50-36209 and 53-8128 are disclosed.
-A combination of a sulfonic acid halogenide and a salt-forming organic dye, and JP-A-53-36223 and 54-74728.
No. 60-3626, No. 61-143748, No. 61-151644, and No. 63-58440, the combination of the trihalomethyl compound and the salt-forming organic dye can be mentioned. Such trihalomethyl compounds include oxazole compounds and triazine compounds, both of which have excellent stability over time,
Gives a clear printout. As the image colorant,
Other dyes besides the salt-forming organic dyes mentioned above can be used. Suitable dyes, including salt-forming organic dyes, include oil-soluble dyes and basic dyes. Specifically, those described in JP-A-6-35184 can be used. Also, JP-A-62-2932
The dyes described in Japanese Patent No. 47 are particularly preferable.

(Negative-Type Photosensitive Layer) The photosensitive composition of the negative PS plate to which the developer and replenisher of the present invention are preferably applied is a photosensitive layer containing a photosensitive diazo compound, a photopolymerizable photosensitive layer. Examples thereof include those having a layer, a photocrosslinkable photosensitive layer, and the like. Among these, a photocurable photosensitive copying material containing a photosensitive diazo compound and a photosensitive copying material having a photocrosslinkable photosensitive layer will be described. As the photosensitive diazo compound,
A diazo resin obtained by condensing an aromatic diazonium salt and a reactive carbonyl group-containing organic condensing agent, particularly aldehydes such as formaldehyde and acetaldehyde, or acetals in an acidic medium is preferably used. The most typical one is a condensate of p-diazophenylamine and formaldehyde. The synthesis method of these diazo resins is described in, for example, US Pat.
No. 0,502, No. 3,311,605 and No. 3,277,074. Further, Japanese Patent Publication No. 49-48,001 and Japanese Patent Laid-Open No. 4-18
559, 4-190361 and 4-1723.
54, JP-A-3-2846, 3-5754, 3-240061, 3-253857, 4-1.
72354, 4-2112253, 4-2197.
The photosensitive diazo compounds described in JP-A No. 59, JP-A No. 4-2744429, and JP-A No. 5-5984 are also used. Suitable counter anions for these diazonium salts include Japanese Patent Publication No. 47-1167, U.S. Pat. No. 3,300,
309, JP-A-54-98613, and JP-A-56-1.
21031, JP-A-58-209733, and JP-A-58-209733.
It is possible to use a diazonium salt using the compounds listed in JP-A Nos. 2-175731 and 63-262642. 5 in the photosensitive layer
-50%, preferably 8-20%.

The above-mentioned photosensitive diazo compound is preferably used in combination with a lipophilic polymer compound soluble or swellable in alkaline water as a binder. As such a lipophilic polymer compound, a copolymer having a molecular weight of 10,000 to 200,000 and having the same monomer as the constituent unit used in the positive photosensitive composition described above as a constitutional unit is exemplified. However, polymer compounds obtained by copolymerizing the following monomers as constituent units can also be used. Maleimide, N-acryloyl acrylamide, N-acetyl acrylamide, N-propionyl acrylamide, N-
Unsaturated imides such as (p-chlorobenzoyl) acrylamide, N-acetylacrylamide, N-acryloylmethacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide, N- [ 2- (Acryloyloxy) -ethyl] -2,3-dimethylmaleimide, N- [2- (methacryloyloxy) -ethyl]-
Unsaturated monomers having a crosslinkable group in the side chain such as 2,3-dimethylmaleimide and vinylcinnamate. Further, a monomer copolymerizable with the above monomer may be copolymerized. Further, a copolymer obtained by copolymerizing the above-mentioned monomers may be modified with, for example, glycidyl acrylate or glycidyl methacrylate, but is not limited thereto. The above copolymer preferably contains an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic anhydride or itaconic acid, and the preferred acid value of the copolymer is 0 to 10 meq / g, more preferably It is 0.2 to 5.0 meq / g. The preferred molecular weight of the above copolymer is 10,000 to 100,000. Further, polyvinyl butyral resin, polyurethane resin, polyamide resin and epoxy resin may be added to the above-mentioned copolymer, if necessary. Further, novolac type resins, phenol-modified xylene resins, polyhydroxystyrene, polyhalogenated hydroxystyrene, JP-A-51-34711.
It is also possible to use an alkali-soluble resin containing a phenolic hydroxyl group as disclosed in JP-A No. Such alkali-soluble polymer compounds may be used alone or in combination of two or more, and are usually contained in the solid content of the entire photosensitive composition in an amount of 40 to 95%.

Next, as the photocrosslinkable polymer used for the photocrosslinkable photosensitive layer, a polymer having a maleimide group, a cinnamyl group, a cinnamoyl group, a cinnamylidene group, a cinnamylidene acetyl group, a chalcone group or the like in its side chain or main chain is used. Can be mentioned. As a polymer having a maleimide group in the side chain,
JP-A-52-988 (corresponding US Pat. No. 4,079,04)
1), German Patent 2,626,769, European Patent 21,019, European Patent 3,
No. 552 or Die Angewandte Makromolekulare
Chemie) 115 (1983), pages 162 to 182, and polymers having a maleimide group in the side chain, JP-A-49-128991 and JP-A-49-12899.
No. 2, No. 49-128993, No. 50-5376,
No. 50-5377, No. 50-5379, No. 50-5
No. 378, No. 50-5380, No. 53-5298,
No. 53-5299, No. 53-5300, No. 50-5
No. 0197, No. 51-47940, No. 52-1390
No. 7, No. 50-45076, No. 52-121700
No. 50-10884, No. 50-45087, and German Patent Nos. 2,349,948 and 2,616,27.
The polymer etc. which have the maleimide group in the side chain which are described in each Unexamined-Japanese-Patent No. 6 can be mentioned. The average molecular weight of these polymers is 1000 or more, preferably 30,000 to 40,000. Further, these polymers have an average of 2 or more maleimide groups in the side chain per molecule.

In order to make these polymers having maleimide groups in their side chains soluble or swellable in alkaline water, acid groups may be included in the polymers. Specific examples of the acid group include carboxylic acid, sulfonic acid, phosphoric acid, phosphonic acid and their alkali metal salts and ammonium salts, and acid groups having a pKa of 6 to 12 which are difficult to dissolve in alkaline water, and specifically, _{, -SO 2 NHCO -, - CONHCO} -, - S
O ₂ NHCOO-, and a 4-hydroxyphenyl group. For example, the monomer having an acid group and the monomer having a maleimide group may be mixed in an amount of 10/90 to 50/5.
The above polymer can be easily obtained by copolymerizing at a ratio of 0, preferably 20/80 to 40/60 (molar ratio). The acid value of the maleimide polymer having an acid group is 3
The range of 0 to 300 is preferable, and 50 to 50 is more preferable.
200. Preferred examples of the monomer having a copolymerizable acid group include vinyl monomers having a carboxyl group such as acrylic acid and methacrylic acid, maleic anhydride, and itaconic anhydride. Among the polymers containing these acid groups, Die Angewandte
Makromolekulare Chemie) 128 (1984) 71
Copolymers such as those described on page 91 are useful. There are also photosensitive polyesters described in U.S. Pat. No. 3,030,208. Those obtained by solubilizing these polymers with alkaline water are disclosed in JP-A-60-191.
244, JP-A-62-175729, JP-A-62-
175730, JP 63-25443, JP 6
Those described in JP-A-3-218944 and JP-A-63-218945 can be used. The photo-crosslinkable polymer used in the present invention has a molecular weight of 1,000 or more, preferably 10,000 to 500,000, and particularly preferably 20,000 to 3
It is desirable to use the one of 0,000. The amount of the photo-crosslinkable polymer added to the total composition of the photosensitive layer is 10 to 99%, preferably 50 to 99%.

The photosensitive layer made of a photocrosslinkable polymer preferably contains a photosensitive diazo resin in order to improve the adhesion to the support. The above-mentioned diazo resin can be used as such a photosensitive diazo resin. When the diazo resin is contained in the photosensitive layer, the content is
It is 0.1 to 30%, preferably 1 to 10%. In addition,
In addition to the above-mentioned diazo resins, diazo resins such as those described in JP-B-47-1167, JP-A-50-118802, JP-B-52-7364 and JP-A-59-222834 may be used. You may use together 50% or less with respect to a diazo resin. For the negative photosensitive layer used in the present invention, a sensitizer, an oil sensitizer, a plasticizer, a printout agent, an image colorant and the like as described in JP-A-6-35184 are used. It is preferable. Further, cyclic acid anhydrides, phenols, organic acids and higher alcohols can be added to enhance the developability. The photosensitive composition of the present invention is dissolved in a solvent that dissolves the above components and applied on an aluminum plate of a support. Examples of the solvent used here include JP-A-62-251739.
Organic solvents such as those described in Japanese Patent Laid-Open Publication can be used alone or in combination. The photosensitive composition is 2 to 50%.
Is dissolved and dispersed at a solid content concentration of, and coated and dried on a support. The coating amount of the layer of the photosensitive composition (photosensitive layer) coated on the support varies depending on the use, but generally, the weight after drying is preferably 0.3 to 4.0 g / m ^2. . A surfactant for improving the coated surface quality, for example, a fluorinated surfactant as described in JP-A-62-170950 can be added to the photosensitive composition. The preferable addition amount is 0.00 of the total photosensitive composition.
1 to 1.0%, more preferably 0.005 to 0.
5%.

(Matte Layer) On the surface of the photosensitive layer provided as described above, the matte layer is formed in order to shorten the vacuuming time during contact exposure using a vacuum baking frame and prevent baking blur. Is provided. Specifically, JP-A-50-125
No. 805, Japanese Examined Patent Publication No. 57-6582, No. 61-2898.
No. 6, JP-B No. 62-62337 and the like are mentioned, and a PS plate having a water-soluble, alkaline water developer-soluble matte layer is more preferable.

(Development Treatment) The PS plate thus obtained is exposed through a transparent original image to actinic rays having a carbon arc lamp, a mercury lamp, a metal halide lamp, a xenon lamp, a tungsten lamp or the like as a light source, and then developed. The developer and replenisher of the present invention are particularly advantageous for use in a development processing method using an automatic processor,
A method of guaranteeing a decrease in the activity of the developer with a replenisher is preferable. A known technique is used as the replenishment method. For example, a method of continuously or intermittently replenishing the deterioration of developability due to the treatment of a PS plate and aging described in JP-A-55-115039, a photosensitive layer in the middle of a development zone described in JP-A-58-95349. The elution degree of
A method for replenishing a replenisher according to a decrease in elution degree
The method of computer-processing the measured impedance value of the developing solution described in JP-A-21451 and JP-A-1-180548 and replenishing it according to the detected deterioration of the developing solution is preferably used. The PS plate thus developed is post-treated with washing water, a rinse solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and a starch derivative. Furthermore, these treatments can be used in various combinations. In recent years, in the plate making / printing industry, automatic developing machines for PS plates have been widely used in order to rationalize and standardize the plate making work. This automatic developing machine is generally composed of a developing section and a post-processing section, and is composed of an apparatus for conveying a PS plate, each processing solution tank and a spraying apparatus, and while conveying an exposed PS plate horizontally, it was pumped up by a pump. Each processing solution is sprayed from a spray nozzle for development processing. Further, recently, a method has also been known in which a PS plate is dipped and conveyed by a submerged guide roll or the like in a treatment liquid tank filled with the treatment liquid for treatment. In such automatic processing, it is possible to perform processing while supplementing each replenisher with each replenisher according to the treatment amount, operating time, and the like. Further, the developing solution of the present invention can be applied to a so-called disposable processing method in which processing is carried out with a substantially unused processing solution. The planographic printing plate obtained by such treatment is set on an offset printing machine and used for printing a large number of sheets.

[0065]

The present invention will be described in detail with reference to the following examples. Example The surface of an aluminum plate having a thickness of 0.30 mm was grained with a nylon brush and 400 mesh pumice water suspension, and then thoroughly washed with water. It was immersed in 10% sodium hydroxide at 70 ° C. for 60 seconds for etching, washed with running water, neutralized with 20% HNO ₃ and washed with water. This was subjected to 160 coul / d in a 1% aqueous nitric acid solution using a sinusoidal alternating current under the condition of V _A = 12.7V.
The electrolytic surface-roughening treatment was performed with the amount of electricity at m ^{2 as} an anode. The surface roughness was measured and found to be 0.6 μm (Ra indication). Continue to soak in a 30% H ₂ SO ₄ aqueous solution for 5
After desmutting at 5 ° C for 2 minutes, place the cathode on the grained surface in a 20% H ₂ SO ₄ aqueous solution to obtain a current density of 2A.
Anodization was performed so that the thickness would be equal to 2.7 g / m ² at / dm ² , and a substrate was prepared. Subsequently, the following Photosensitive Solution I or Photosensitive Solution II was applied to the surface of the above substrate, and a photosensitive layer was provided so that the coating weight after drying was 2.5 g / m ² .

Photosensitive Solution I 1,2-Diazonaphthoquinone-5-sulfonyl chloride esterified product of pyrogallol-acetone resin (described in Example 1 of US Pat. No. 3,635,709) 45 parts by weight Cresol formaldehyde novolac resin 110 parts by weight 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine 2 parts by weight Oil blue # 603 (manufactured by Orient Chemical Industry Co., Ltd.) 1 part by weight Part Megafac F-177 (Dainippon Ink and Chemicals, Incorporated Fluorosurfactant) 0.4 parts by weight Methyl ethyl ketone 1000 parts by weight Propylene glycol monomethyl ether 1000 parts by weight Photosensitive solution II Cresol formaldehyde novolak resin of photosensitive solution I Change to phenol novolac resin Photosensitive solution

A mat layer-forming resin liquid was sprayed onto the surface of the photosensitive layer thus produced in the following manner to obtain a PS plate having a mat layer. A 12% aqueous solution of methyl methacrylate / ethyl acrylate / acrylic acid (weight ratio of 65:20:15) copolymer with a part of sodium salt was prepared as a mat layer forming resin liquid, and a rotary atomizing electrostatic coating machine was prepared. The atomizing head rotation speed is 25,000 rpm, the resin liquid feed rate is 40 ml / min, the voltage applied to the atomizing head is -90 kV, the ambient temperature during application is 25 ° C, and the relative humidity is 50%. Steam was sprayed onto the coated surface for 2.5 seconds to wet the surface, and 3 seconds after the surface was wet, warm air with a temperature of 60 ° C. and a humidity of 10% was sprayed for 5 seconds to dry the surface. PS thus obtained
The plate was exposed through the original film for 60 seconds using a 3 kW metal halide lamp from a distance of 1 m.

A method for confirming the effects of the present invention will be shown below. The developing solution was charged into a developing tank of a commercially available automatic developing machine PS-900NP (manufactured by Fuji Photo Film Co., Ltd.) having an immersion developing tank in an amount of 22 liters. Separately, 5 liters of developing replenisher was charged in the developing replenisher stock solution supply tank. Under such conditions, the exposed PS plate was subjected to a developing process while automatically replenishing, and 50 plates per day were processed for 1 week. After that, the step number of the solid portion (image remaining portion) of the step number remaining after the development of the image printed with the step tablet (15 steps with the optical density difference of 0.15 per step) is forced to the high sensitivity side. The replenisher was excessively replenished in a fixed amount so as to vary, and the number of fluctuation stages was compared for each developer / replenisher combination. As an excessive replenishment standard for comparison, a developer AN and a development replenisher GN obtained by removing a quaternary ammonium salt from the following developer A and development replenisher G respectively.
The PS plates developed by the combination of No. 1 and No. 2 were arranged under the condition that the number of steps of the solid portion (image remaining portion) of the number of steps varies by 2.0.

The developing solutions A to F and the developing replenishing solutions G to L are described below.
showed that.

Developer A [SiO ₂ ] / [K ₂ O] molar ratio 1.2, SiO ₂ 1.4
% Potassium silicate aqueous solution, tetrabutylammonium bromide (0.2 g / liter) was added to adjust the pH to 13.
A developing solution set to 0. (PS Plate Used; Photosensitive Solution I) Developer B Developer in which triethylbenzylammonium chloride (0.2 g / liter) was added to sulfosalicylic acid (0.15 mol / liter) and the pH was adjusted to 13.0 with KOH. (PS plate used; Photosensitive solution I) Developer C Tetrabutylammonium chloride (0.2 g / liter) was added to saccharose (0.15 mol / liter), and KOH was added.
Developer with pH adjusted to 13.0. (PS plate used; Photosensitive solution I)

Developer D [SiO ₂ ] / [K ₂ O] molar ratio 1.7, SiO ₂ 1.4
% Potassium silicate aqueous solution, tetrabutylammonium bromide (0.2 g / liter) was added to adjust the pH to 12.
A developer of 5. (PS plate used; Photosensitive solution II) Developer E Tetrabutylammonium bromide (0.2 g / liter) was added to sulfosalicylic acid (0.15 mol / liter), and K
Developer with pH adjusted to 12.5 with OH. (PS plate used; Photosensitive solution II) Developer F Tetrabutylammonium bromide (0.2 g / liter) was added to 25.0 g / liter of sodium carbonate, and KOH was added.
Developer with pH adjusted to 12.5. (PS plate used; Photosensitive solution II)

Development replenisher G [SiO ₂ ] / [K ₂ O] molar ratio 0.9, SiO ₂ 1.6
% Potassium silicate aqueous solution, tetrabutylammonium bromide (0.8g / l) was added and the pH was adjusted with KOH.
Development replenisher of 13.4. (PH is maintained at 13.0 during development test) Development replenisher H Sulfosalicylic acid (0.15 mol / liter) is added with triethylbenzylammonium chloride (0.8 g / liter), and pH is adjusted to 13.4 with KOH. Developer replenisher. (PH is maintained at 13.0 during development test) Development replenisher I Tetrabutylammonium chloride (0.8 g / liter) is added to saccharose (0.15 mol / liter), and KOH is added.
Development replenisher with pH of 13.4. (PH is maintained at 13.0 during development test)

Development replenisher J [SiO ₂ ] / [K ₂ O] molar ratio 0.9, SiO ₂ 1.6
% Potassium silicate aqueous solution to which tetrabutylammonium bromide (0.8 g / liter) was added and KOH was added to adjust the pH to 13.4. (The pH is maintained at 12.5 during the development test.) Development replenisher K Tetrabutylphosphonium bromide (0.8 g / liter) is added to sulfosalicylic acid (0.15 mol / liter) to obtain K.
Development replenisher whose pH is adjusted to 13.4 with OH. (The pH is maintained at 12.5 during the development test.) Development replenisher L Tetrabutylammonium bromide (0.8 g / liter) is added to sodium carbonate 25.0 g / liter, and KOH is added.
Development replenisher with pH of 13.4. (PH is maintained at 12.5 during development test)

Comparative Example The same tests as in the examples were carried out using the developers A to F and the development replenishers G to L used in the examples, which did not contain the quaternary ammonium salt.

A developer without a quaternary ammonium salt of developer A was designated as AN, and BN to FN without a quaternary ammonium salt of a developer corresponding to the following Examples and GN to FN without a quaternary ammonium salt of a developer replenisher. LN. The above test results are summarized in Table A.

[0076]

[Table 1]

[0077]

[Table 2]

From the results shown in Table A, the developer / replenisher containing the quaternary ammonium salt of the present invention has a smaller number of sensitivity fluctuation stages than the developer / replenisher of the comparative example containing no quaternary ammonium salt. It is understood that there is.

Further, it was shown that the addition of the quaternary ammonium salt has a great effect that the gradation of the step number becomes harder (the difference in the number of steps between the image remaining portion and the non-image portion is small).

[0080]

The developing solution and the developing replenisher of the present invention are excellent in development stability, storage stability, development processing ability and contrast enhancement ability, and can commonly process positive-working and negative-working PS plates.

Claims (1)

[Claims] 1. At least one compound selected from silicic acids, phenols, saccharides, oximes and fluorinated alcohols, which has a buffering action at a pH of 11.5-13.5, and the following general formula: A developer for a photosensitive lithographic printing plate, which comprises a compound represented by (A) or (B). Embedded image In the formula, each of R ^{1 to} R ¹⁰ independently has 1 to 1 carbon atoms.
12 alkyl group, cyclic alkyl group, hydroxyalkyl group, unsubstituted or alkyl-substituted benzyl group, or substituted or unsubstituted phenyl group, Z _{1 to} Z ₃ are N ⁺ , P ⁺ , S, As, Sb , I, Sn or B ⁻ ,
When Z _{1 to} Z ₃ are N ⁺ or P ⁺ , X ^{1 to} X ³ represent anions other than the hydroxyl group, and when Z _{1 to} Z ₃ are B ⁻ , X ^{1 to} X ³ represent cations and n is 1 Indicates an integer of ˜5.