JP3506291B2 - Processing method of photosensitive lithographic printing plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to a photosensitive lithographic printing plate.
Regarding the processing method, use a developer with a relatively low pH.
It is easy to use, hardly generates insolubilized matter, and has good developability and image quality.
Regarding processing method of photosensitive lithographic printing plate to achieve image intensity
Things. [0002] 2. Description of the Related Art Conventionally, a positive feeling has been widely used.
The light-sensitive lithographic printing plate is placed on an aluminum plate as a support.
-Provided with a photosensitive layer comprising a quinonediazide compound
is there. The o-quinonediazide compound is exposed to ultraviolet light.
It is known to convert to rubonic acid and therefore
Is developed with an alkaline aqueous solution, only the exposed portion of the photosensitive layer
Is removed to expose the support surface. Aluminum support
Since the surface of the body is hydrophilic, the surface of the support is exposed during development.
Part (non-image part) retains water and repels oil-based ink
You. On the other hand, areas where the photosensitive layer was not removed by development
(Image area) is lipophilic, so it repels water and receives ink
Put on. For the photosensitive layer of these positive photosensitive lithographic printing plates
Is a binder of the above-mentioned o-quinonediazide compound (hereinafter referred to as ba)
Usually called cresol novolak tree
Fat has been used. Therefore, as a developer,
Strong pH around pH 13 that can dissolve sol novolak resin
It was common to use a lukalic silicate. Heel
Used as a developer for positive-type photosensitive lithographic printing plates
Various types of lukari aqueous solutions are known, but
Preferred is silicate water such as sodium silicate and potassium silicate.
Solution. The reason is that silicon oxide S which is a component of silicate
iO_TwoAnd alkali metal oxide M_Two O ratio (generally [S
iO_Two] / [M_TwoO] molar ratio) and concentration
This is because the developability can be adjusted to some extent. Only
However, such a high pH developer may not adhere to the skin or mucous membranes.
Is very irritating and requires careful handling.
Was. In order to solve this problem, a positive photosensitive photosensitive
Various studies have been made to lower the pH of the developer for printing plates.
Has been developed, but currently it can be developed at pH 12.5 or less.
Positive PS plate and its developer are not found in the market
No. The main reason is that the developability of the photosensitive layer and the image strength
Difficulty in balancing. That is, at pH 12.5 or less
The unexposed area (image area) of the photosensitive layer that can be imaged is physically
It is fragile, wears quickly during printing, and provides sufficient press life.
Not. Also, the image area is chemically weak,
Area that has been wiped with an ink cleaning solvent, plate cleaner, etc.
Image is damaged and as a result
Below, referred to as chemical resistance). On the other hand,
60-143345, JP-A-61-107352.
JP, JP-A-62-133452, JP-A-62-133452
No. 133461 and Japanese Patent Publication No. 3-15176
There are various reports on improving the physical and chemical strength of the image area.
O-quinonediazide compounds and binders are described
However, all of the photosensitive layers described above are present at pH around 13.
Only things that can be imaged. Further, Japanese Patent Application Laid-Open No. 61-205933 discloses
Is an o-quinonediazide compound for the purpose of improving printing durability.
Product and weight average molecular weight 6.0 × 10^Three~ 2.0 × 10^FourIn
A photosensitive composition comprising a novolak resin is disclosed.
You. However, the novolak resin is more like cresol.
Normally no monomer with chemical resistance is co-condensed
Phenol-formaldehyde resin, especially
On a support provided with a hydrophilic undercoat layer or on a hydrophilic silicate
Sufficient chemical resistance on the treated support
Not work, and increase sensitivity and development of photosensitive layer
Acid anhydride, etc. as a development accelerator was added to improve
In some cases, it is not possible to obtain sufficient chemical resistance
Had. On the other hand, in recent years, plate making and printing industries have
For the photosensitive lithographic printing plate to streamline and standardize
Dynamic developing machines are widely used. This automatic processor
Generally, a device for transporting a photosensitive lithographic printing plate, a developer tank and
And exposed lithographic printing plate
While transporting the developer horizontally, remove the developer pumped up by the pump.
The developing process is performed by spraying from a play nozzle.
Also, recently, a submerged gas is placed in a developing tank filled with developer.
The photosensitive lithographic printing plate is immersed and transported by an
Also, a method of performing development processing is known. Such automatic development
A positive-type photosensitive lithographic printing plate using a printing machine
And SiO 2 as a developing solution_Two/ Na_TwoWhen the molar ratio of O is 1.0 to 1.0
1.5 (ie [SiO_Two] / [Na _TwoO] is 1.0 to 1.5)
And SiO_TwoContent of sodium silicate of 1 to 4% by weight
Uses an aqueous solution of thorium and has a positive photosensitive lithographic stamp
Continuous or intermittent SiO 2 depending on the throughput of the printing plate_Two/
Na_TwoThe molar ratio of O is 0.5-1.5 (ie [SiO_Two] /
[Na_TwoO] is 0.5 to 1.5) aqueous sodium silicate solution
(Replenisher) to the developer for a longer
A large amount of positive-type photosensitivity without changing the developing solution
Japanese Patent Application Laid-Open No. 54-6 / 1979 discloses that a lithographic printing plate can be processed.
2004. Also,
No. 7427 discloses [SiO_Two] / [M] is 0.5 to 0.7
5 (ie [SiO_Two] / [M_TwoO] is 1.0 to 1.5)
What is SiO_TwoAlkali metal with a concentration of 1 to 4% by weight
Alkali gold used as replenisher using silicate developer
The group silicate [SiO_Two] / [M] is 0.25 to 0.75 (immediately
Chi [SiO_Two] / [M_TwoO] is 0.5 to 1.5),
Both the developer and the replenisher are present therein.
At least based on gram atoms of all alkali metals
Development method comprising 20% potassium
Is disclosed. However, silicic acid, which is a main component of the developer,
Salts are stable in the alkaline region, but gel in neutral
Like hydrofluoric acid when converted to insolubilized and evaporated to dryness
It has the disadvantage of being soluble only in strong acids. Real
Of the solidified matter due to liquid splash around the developing tank of the automatic developing machine
Precipitation of insolubles due to neutralization when disposing of waste developer
Outing is one of the real harms. JP-A-58-95
No. 349 discloses a photosensitive layer in a non-image portion of a photosensitive plate.
A sensor that electrically measures the degree of elution of
When the level drops to the specified level, replenish the developer
A method is disclosed. If the developer is silicate based
In this case, silicate insolubilized matter accumulates on this sensor and
Normal replenishment was not possible due to the decrease in the degree of
There was a problem that it deteriorated. To solve this problem
The positive type photosensitive lithographic printing plate
Attempts have been made to use it as a developer for
Strong combination of sodium hydroxide and trisodium phosphate
Alkali was evaluated as a developer, but all of them had a buffer action
, And stable development was not possible. [0007] SUMMARY OF THE INVENTION Accordingly, an object of the present invention is as follows.
Is relatively less irritating to the skin and mucous membranes and increases safety
With sufficient image strength (press life and printing durability)
Processing of photosensitive lithographic printing plates that can obtain chemical properties)
Is to provide the law. It is a further object of the present invention to
Photosensitive flat material that is less likely to generate debris and is suitable for cleaning of automatic developing machines
An object of the present invention is to provide a printing plate processing method. Eye of the invention
The target is a photosensitive plate with high development stability without using silicate.
An object of the present invention is to provide a printing plate processing method. Eye of the invention
It is also important to perform extremely stable processing over a long period of time.
And the conductivity of the developer or the impedance
Insoluble material is unlikely to adhere to sensors for measuring
Planographic printing plate that can ensure easy maintenance
An object of the present invention is to provide a method of processing a printing plate. [0008] Means for Solving the Problems The present inventors have achieved the above object.
As a result of intensive studies to achieve this, aromatic groups are contained in one molecule.
When the content of the component having three or more
Specific phenol with a weight average molecular weight of 10,000 or more
Formaldehyde resin, weight average molecular weight 2,000 or less
Above, the o-naphthoquinonediadi of the polyhydroxy compound
Having a photosensitive layer containing dosulfonic acid ester
Use lithographic printing plates to prepare sugars, oximes, phenols,
At least one compound selected from fluorinated alcohols
PH value of the solution is in the range of 10.0 to 12.7
Sufficient image strength (press life)
And chemical resistance), hardly generate insoluble matter, and
The present invention was found to exhibit high development stability and completed the present invention.
It has led to. That is, the present invention provides (a) an aromatic compound in one molecule.
90% by weight or more of the component having three or more group groups
Phenol with a weight average molecular weight of 10,000 or more
A formaldehyde resin and (b) a weight average molecular weight of 2,0
O-naphthoquinone as a polyhydroxy compound
Having a photosensitive layer containing diazidosulfonic acid ester
Use photosensitive lithographic printing plates to prepare sugars, oximes, phenols
And fluorinated alcohols
It contains at least one compound and has a pH value of 10.0-1.
Developed with a developer in the range of 2.7
This is a method for processing an optical planographic printing plate. The present invention also provides
The layer further contains a cyclic acid anhydride as a development accelerator.
And a method for processing the photosensitive lithographic printing plate.
You. Further, the object of the present invention is to provide an o-naphthoquinone diazine
Having a photosensitive layer containing dosulfonic acid ester
Use lithographic printing plates to prepare sugars, oximes, phenols,
At least selected from the group consisting of fluorinated alcohols
It contains one compound and the pH value of the solution is 10.0 to 12.
7 with the developer in the range of 7
Deterioration of the developer caused by the processing of the lithographic printing plate,
By measuring the conductivity or impedance of the developer
And replenish the replenisher based on the detection result.
Thereby keep the activity of the developer almost constant.
Achieved by the processing method of photosensitive lithographic printing plate
You. Hereinafter, the photosensitive lithographic printing plate of the present invention (hereinafter referred to as PS plate).
The details of the PS plate used for the processing method
You. [0009] [Photosensitive composition] Photosensitivity in PS plate used in the present invention
O-quinonediazide compound and polymer
Consists of a binder. [Binder] Characterizing the PS plate used in the present invention
Molecular binder has three or more aromatic groups in one molecule
Is 90% by weight or more and the weight average molecular weight is
10,000 or more novolak-type phenol-forma
It is a aldehyde resin. Hereinafter, in the present specification, the above one minute
A component having three or more aromatic groups in the
Called minutes. Here, the weight average molecular weight is gel permeation.
Polystyrene exchange for chromatography (GPC)
It is defined with an arithmetic value. Such phenol formua
Phenol and formaldehyde or aldehyde resin
Use aldehydes such as paraformaldehyde with an acidic catalyst.
It is synthesized by condensation using Especially for the present invention
Phenol with weight average molecular weight of 10,000 or more
1 mole of phenol to obtain a formaldehyde resin
0.7 to 0.9 mole of aldehyde is used
preferable. Aldehydes less than 0.7 mol are sufficient molecules
When the amount is not obtained and the amount exceeds 0.9 mol, a gel is formed.
It is not preferable because it is easy to perform. Acid catalyst used for condensation reaction
Use hydrochloric acid, sulfuric acid, formic acid, acetic acid and oxalic acid
Oxalic acid is preferred. [0010] The phenol formal thus obtained
If the aldehyde resin contains 10% by weight or more of a component having a binuclear content or less,
Low molecular weight components, e.g., fractional precipitation,
2 or less nuclei
Must be 10% by weight or less. 2 or less nucleolus
Phenol formaldehyde containing at least 10% by weight of
Hyd resin has high solubility and does not provide sufficient chemical resistance.
No. Also, phenol having a weight average molecular weight of less than 10,000
Sufficient image strength can be obtained even with Le formaldehyde resin
Therefore, the object of the present invention cannot be achieved. In particular, the photosensitive layer
Acid anhydride, etc. to increase the sensitivity of
When added, hydrophilic silica is used as a surface treatment for the support described below.
When a salt treatment has been performed, various additional treatments may be performed on the support.
Even when a coating layer is provided, 10% by weight
Or containing less than 10,000
Phenol-formaldehyde resin
Image intensity is not obtained. In addition, conventional positive-type photosensitive lithographic plates
Cresol phor used for binders in printing plates
Develop with a developer of pH 12.5 or less for mualdehyde resin
Cannot achieve the object of the present invention. In the total amount of photosensitive composition
The phenol / phore having a molecular weight of 10,000 or more
An appropriate amount of the aldehyde resin is 30 to 90% by weight.
More preferably, it is 40 to 70% by weight. The PS plate photosensitive composition used in the present invention is
In some cases, other alkali-soluble resins other than novolak
Can be used together. With such an alkali-soluble resin
Is soluble in alkaline water of pH 12.5 [here, p
H12.5 resin soluble in alkaline water is sodium hydroxide
0.11 mol of potassium and 0.4 mol of potassium chloride dissolved in water
Aqueous solution (pH 12.5 alkaline water)
Solution) 1 liter was prepared, and 30.0 g of resin was added thereto.
And a resin that dissolves in 30 minutes.]
And the weight average molecular weight is 10,000 to 100,000.
Containing the alkali-soluble groups of (1) to (4) shown below.
At least one selected from monomers as a polymerization component
Are preferred. (1) N- (4-hydroxyphenyl) a
Acrylamide or N- (4-hydroxyphenyl) meth
Tacrylamide, o-, m- or p-hydroxysty
Len, o- or m-bromo-p-hydroxystyrene
O- or m-chloro-p-hydroxystyrene,
o-, m- or p-hydroxyphenyl acrylate
Or an acrylic resin having an aromatic hydroxyl group such as methacrylate.
Luamides, methacrylamides, acrylates
, Methacrylates and hydroxystyrene
, (2) acrylic acid, methacrylic acid, maleic acid, none
Water maleic acid and its half ester, itaconic acid,
Unsaturation such as itaconic anhydride and its half ester
carboxylic acid, (3) N- (o-aminosulfonylphenyi)
L) acrylamide, N- (m-aminosulfonylfe)
Nyl) acrylamide, N- (p-aminosulfonyl)
Enyl) acrylamide, N- [1- (3-aminosulfur)
Honyl) naphthyl] acrylamide, N- (2-amino
Acrylamide such as sulfonylethyl) acrylamide
Compounds, N- (o-aminosulfonylphenyl) methacryl
Luamide, N- (m-aminosulfonylphenyl) meth
Crylamido, N- (p-aminosulfonylphenyl)
Methacrylamide, N- [1- (3-aminosulfoni
Ru) naphthyl] methacrylamide, N- (2-aminos
Methacrylures such as ruphonylethyl) methacrylamide
Amides and o-aminosulfonylphenyl acryle
, M-aminosulfonylphenyl acrylate, p
-Aminosulfonylphenyl acrylate, 1- (3-
Aminosulfonylphenylnaphthyl) acrylate
Unsaturated sulphonamides such as acrylates of
o-Aminosulfonylphenyl methacrylate, m-a
Minosulfonylphenyl methacrylate, p-aminos
Rufonylphenyl methacrylate, 1- (3-aminos
Meta such as rufonylphenylnaphthyl) methacrylate
Unsaturated sulfonamides such as acrylates, (4) Substitution as in tosylacrylimide
Phenylsulfonylacrylimide which may have a group,
And substituents such as tosyl methacrylimide
Phenylsulfonyl methacrylimide. In addition,
In addition to these alkali-soluble group-containing monomers,
(5) A film-forming resin obtained by copolymerizing the monomers of (14) to (14).
Fat is preferably used. (5) A having an aliphatic hydroxyl group
Crylate and methacrylate esters, eg
For example, 2-hydroxyethyl acrylate or 2-
Droxyethyl methacrylate, (6) methyl acrylate
, Ethyl acrylate, propyl acrylate, acrylic
Butyl acrylate, amyl acrylate, hexyl acrylate,
Cyclohexyl acrylate, octyl acrylate, acrylic
Phenyl luate, benzyl acrylate, acrylic acid-2-
Chloroethyl, 4-hydroxybutyl acrylate, gly
Sidyl acrylate, N-dimethylaminoethylacryl
(Substituted) acrylates such as acrylates, (7) meta
Methyl acrylate, ethyl methacrylate, methacrylate
Ropyl, butyl methacrylate, amyl methacrylate,
Hexyl methacrylate, cyclohexyl methacrylate,
Octyl acrylate, phenyl methacrylate, methacrylate
Benzyl acrylate, 2-chloroethyl methacrylate, meta
4-hydroxybutyl acrylate, glycidyl methacrylate
And N-dimethylaminoethyl methacrylate
(Substituted) methacrylates, (8) Acrylamide, methacrylamid
, N-methylolacrylamide, N-methylolmethyl
Tacrylamide, N-ethylacrylamide, N-ethyl
Rumethacrylamide, N-hexylacrylamide, N
-Hexylmethacrylamide, N-cyclohexylac
Rilamide, N-cyclohexyl methacrylamide, N
-Hydroxyethyl acrylamide, N-hydroxy
Tylacrylamide, N-phenylacrylamide, N
-Phenylmethacrylamide, N-benzylacrylia
Amide, N-benzyl methacrylamide, N-nitrophen
Nylacrylamide, N-nitrophenyl methacrylate
Amide, N-ethyl-N-phenylacrylamide and
An accelerator such as N-ethyl-N-phenylmethacrylamide
Rilamide or methacrylamide, (9) ethyl bi
Nyl ether, 2-chloroethyl vinyl ether, hydr
Roxyethyl vinyl ether, propyl vinyl ether
Butyl vinyl ether, octyl vinyl ether,
Vinyl ethers such as phenyl vinyl ether, (10) Vinyl acetate, vinyl chloro
Acetate, vinyl butyrate, vinyl benzoate, etc.
Vinyl esters, (11) styrene, α-methylstyrene
Styrene, methylstyrene, chloromethylstyrene, etc.
Tylenes, (12) methyl vinyl ketone, ethyl vinyl
Ketone, propyl vinyl ketone, phenyl vinyl ketone
Vinyl ketones such as (13) ethylene, propylene
Olefin such as butane, isobutylene, butadiene, isoprene
Fins, (14) N-vinylpyrrolidone, N-vinyl
Carbazole, 4-vinylpyridine, acrylonitrile
And methacrylonitrile. Such alkali soluble
One or more types of conductive film-forming resins
Can be used in combination, from 1 to 50 of the total photosensitive composition.
It is used in a weight% addition amount. In addition, other than the above copolymers
In addition, polyvinyl butyral resin, polyurethane resin,
A amide resin and an epoxy resin are also used. [O-Quinonediazide compound]
In the PS plate to be used, the other main component of the photosensitive composition
O-naphthoquinonediazide compound having a molecular weight of
2,000 or more polyhydroxy compound o-quinone
Consists of diazidesulfonic acid esters. The polyhydroxy
Compounds include pyrogallol-acetone resin, pheno
-Formaldehyde resin, cresol formaldehyde
Hydresin, hydroxystyrene resin and halogenated arsenic
Doxystyrene resin and the like. In the present invention
If the molecular weight is 2,000 or less, sufficient image intensity
Can not be obtained. From these polyhydroxy compounds, o-
When synthesizing naphthoquinonediazide compounds,
1,2-diazo to hydroxyl group of roxy compound
0.2 to 1.2 equivalent reaction of naphthoquinone sulfonic acid chloride
It is preferable to react 0.3 to 1.0 equivalent.
Is more preferred. 1,2-diazonaphthoquinone sulfone
Examples of the acid chloride include 1,2-diazonaphthoquinone-5.
-Sulfonic acid chloride or 1,2-diazonaphthoxy
Non-4-sulfonic acid chloride can be used.
Further, the obtained o-naphthoquinonediazide compound is
Position of 1,2-diazonaphthoquinonesulfonic acid ester group
A mixture of components with different placement and introduction amounts is obtained.
All of the droxyl groups are 1,2-diazonaphthoquinone sulf
Phosphonated compounds account for this mixture.
Ratio (content of completely esterified compound) is 5
Mol% or more, and more preferably 20 mol% or more.
~ 99 mol%. This accounts for the total amount of the photosensitive composition
The amount of the o-quinonediazide compound is 10 to 50% by weight.
Is suitable, more preferably 15 to 40% by weight.
You. In the photosensitive composition of the PS plate used in the present invention,
In addition to the above-mentioned o-quinonediazide compound,
A polyhydroxy compound having a molecular weight of less than 2,000 and 1,2
-Obtained by reaction with diazonaphthoquinone sulfonic acid
Compounds can be used in combination as long as the effects of the present invention are not impaired.
You. Specific examples of such an o-quinonediazide compound include:
JP-A-51-139402 and JP-A-58-150948.
No. 58-203434, No. 59-165053
No., No. 60-112445, No. 60-134235
No., No. 60-163443, No. 61-118744
No. 62-10645, No. 62-10646, No.
No. 62-153950, No. 62-178562, No. 6
4-76047, U.S. Pat. No. 3,102,809,
No. 3,126,281, No. 3,130,047
No. 3,148,983, No. 3,184,31
No. 0, No. 3,188,210, No. 4,639, 4
What is described in each gazette or specification such as No. 06
Can be mentioned. In this case, o-quinone di
The ratio of the azide compound is based on the total o-quinonediazide compound.
It is preferably at most 50% by weight, more preferably
It is preferably at most 30% by weight. [Oil Sensitizer] Further, US Pat.
As described in US Pat. No. 3,279, t-butyl
Lephenol formaldehyde resin, octyl phenol
Alkyl having 3 to 8 carbon atoms, such as formaldehyde resin
And formaldehyde having a phenyl group as a substituent
The use of a condensate with a compound improves the oil sensitivity of the image.
It is preferable in terms of performance. [Development accelerator] The PS accelerator used in the present invention
In the photosensitive composition, the sensitivity is improved and the developability is improved.
Acid anhydrides, phenols and organic acids
It is preferred to add. In particular, use cyclic acid anhydrides.
Preferably. U.S. Pat.
No. 115,128, anhydrous phthalate
Acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride
Luic acid, 3,6-endooxy- △^Four-Tetrahydroanhydride
Phthalic acid, tetrachlorophthalic anhydride, maleic anhydride
Acid, chloromaleic anhydride, α-phenylmaleic anhydride
Acid, succinic anhydride, pyromellitic anhydride etc. can be used
You. Examples of phenols include bisphenol A, p-d
Trophenol, p-ethoxyphenol, 2,4
4'-trihydroxybenzophenone, 2,3,4-to
Lihydroxybenzophenone, 4-hydroxybenzoph
Enone, 4,4 ', 4 "-trihydroxy-triphenyl
Methane, 4,4 ', 3 ", 4" -tetrahydroxy-
3,5,3 ', 5'-tetramethyltriphenylmethane
And the like. Further, as organic acids, JP-A-60-8
8942 and JP-A-2-96755.
Sulfonic acids, sulfinic acids, alkyl sulfur
Acids, phosphonic acids, phosphate esters and carboxyls
Acids and the like, specifically, p-toluene sulfone
Acid, dodecylbenzene sulfonic acid, p-toluene sulf
Acid, ethyl sulfate, phenylphosphonic acid, phenylpho
Sphinic acid, phenyl phosphate, diphenyl phosphate, benzoate
Perfume acid, isophthalic acid, adipic acid, p-toluic acid,
3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid
Acid, 1,4-cyclohexene-2,2-dicarboxylic acid,
Erucic acid, lauric acid, n-undecanoic acid, ascorbic
Acid and the like. The above cyclic acid anhydrides, pheno
Of Photochemicals and Organic Acids in Photosensitive Composition
Is preferably 0.05 to 15% by weight, more preferably 0.05 to 15% by weight.
1 to 5% by weight. [Development Stabilizer] The P used in the present invention
In the photosensitive composition of the S plate, the processing stability with respect to the developing conditions is included.
To expand the qualitative (so-called development latitude)
62-251740 and JP-A-4-68355.
Non-ionic surfactant as described in Japanese Patent Application Publication
JP-A-59-121044, JP-A-4-13149
Add an amphoteric surfactant as described in the gazette
be able to. Specific examples of the nonionic surfactant include:
Sorbitan tristearate, sorbitan monopalmites
Salt, sorbitan triolate, monoglyceryl stearate
Cerides, polyoxyethylene sorbitan monooleate,
And polyoxyethylene nonyl phenyl ether.
Can be Specific examples of amphoteric surfactants include alkyl
(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 alkylimi
Dazoline type (for example, trade name Levon 15, Sanyo Chemical
(Manufactured by Co., Ltd.). The above nonionic surfactant
Of Photosensitive Compositions of Ammonium and Amphoteric Surfactants
Is preferably 0.05 to 15% by weight, more preferably 0.05 to 15% by weight.
1 to 5% by weight. [Print-out agent and dye] P used in the present invention
In the S-plate photosensitive composition, a visible image is obtained immediately after exposure.
Printing agents and dyes and pigments as image colorants
Can be added. As a printing-out agent,
Can form a salt with a compound that releases an acid (photoacid releasing agent)
Combinations of organic dyes can be mentioned as representatives. Ingredient
Physically, JP-A-50-36209 and 53-812
No. 8, the o-naphthoquinone diazine described in each publication
Combination of do-4-sulfonic acid halogenide and salt-forming organic dye
And JP-A-53-36223 and JP-A-54-7472.
No. 8, No. 60-3626, No. 61-143748,
Nos. 61-151644 and 63-58440
Trihalomethyl compounds described in each publication and salt formation
And organic dyes. Such birds
Halomethyl compounds include oxazole-based compounds and
There are riadin-based compounds, both of which have excellent stability over time.
To give clear print-out images. As the colorant for the image, the above-mentioned salt-forming agent is used.
Other dyes besides mechanical dyes can also be used. Salt-forming
Suitable dyes, including organic dyes, are oil-soluble dyes and bases.
Dyes. Specifically, oily
Row # 101, Oil Yellow # 103, Oil Pink
# 312, Oil Green BG, Oil Blue BOS,
Oil blue # 603, oil black BY, oil black
Rack BS, Oil Black T-505 (or more, Orie
Chemical Pure Chemical Co., Ltd.), Victoria Pure Blue,
Listal Violet (CI42555), methylbi
Olet (CI42535), ethyl violet, b
-Damine B (CI145170B), Malachite Glee
(CI42000), methylene blue (CI5201)
5) and the like. Also, Japanese Unexamined Patent Publication No.
The dyes described in JP-A-93247 are particularly preferred.
No. [0025] [Coating solvent] Photosensitive group in PS plate used in the present invention
The product is dissolved in a solvent that dissolves the above components, and
It is applied on an aluminum plate. Solvent used here
As described in JP-A-61-95463,
Organic solvents such as
You. The photosensitive composition generally has a solid content of 2 to 50% by weight.
It is dissolved and dispersed at different temperatures, coated and dried on a support. [Coating amount] The layer of the photosensitive composition to be coated on the support (sensitivity)
The coating amount of the optical layer varies depending on the application, but in general,
0.3 to 4.0 g / m in weight after drying^TwoIs preferred. Application
The smaller the amount, the smaller the exposure to obtain an image
However, the film strength is reduced. As the amount of application increases
As a result, the amount of exposure is required, but the photosensitive film becomes stronger.
For example, when used as a printing plate, the number of printable sheets is high (high
A (durable) printing plate is obtained. [0026] [Improvement of coating surface quality] In the photosensitive composition, the coating surface quality is improved.
Surfactants, for example, JP-A-62-170
No. 950, fluorinated surfactant
Agents can be added. The preferred addition amount is
0.001 to 1.0% by weight of the hydrophilic composition, more preferably
Is 0.005 to 0.5% by weight. [Matte layer] The surface of the photosensitive layer provided as described above
In the case of vacuum evacuation during contact exposure using a vacuum
A mat layer is provided to shorten the interval and prevent baking.
Preferably. Specifically, JP-A-50-1258
No. 05, Japanese Patent Publication No. 57-6582, No. 61-28986
To provide a mat layer as described in each gazette
The method is described in Japanese Patent Publication No. 62-62337.
And a method of thermally fusing such a solid powder. [0027] [Support] The support in the PS plate used in the present invention includes:
It is a dimensionally stable plate. As such a support,
Paper, plastics (eg polyethylene, polypropylene
Paper laminated with pyrene, polystyrene, etc.)
For example, aluminum (including aluminum alloy),
Metal plates such as lead, iron, and copper are used.
The effect of the present invention is remarkable in metal plates such as minium plates.
Be demonstrated. The preferred aluminum plate is pure aluminum
Plate and aluminum as main components and trace amounts of foreign elements
Alloy plate, and aluminum may be laminated or
May be a deposited plastic film. Armini
The different elements contained in the alloys are silicon, iron, and manga.
, Copper, magnesium, chromium, zinc, bismuth, nickel
Kel, titanium and the like. High content of foreign elements in alloy
At most 10% by weight. Aluminum suitable for the present invention
Is pure aluminum, but completely pure aluminum
Is difficult to manufacture due to refining technology,
May be contained. Thus applied to the present invention
The composition of aluminum plates is not specified.
In addition, use materials of publicly known and publicly known materials as appropriate.
Can be done. The thickness of the aluminum plate used in the present invention
Is about 0.1 mm to 0.6 mm. Before roughening the aluminum plate,
If desired, e.g. surfactants to remove rolling oil on the surface
Degreasing with a surfactant, organic solvent or alkaline aqueous solution
Processing is performed. First, the surface of the aluminum plate is roughened
Processed, but the method is mechanically roughening
Method and surface roughening method for electrochemically dissolving and roughening a surface
There is a method of chemically dissolving the surface. Mechanical methods and
Then, ball polishing method, brush polishing method, blast polishing
A known method called a buffing method or buffing method should be used.
Can be. Hydrochloric acid is used as an electrochemical roughening method.
Alternatively, there is a method that uses AC or DC in nitric acid electrolyte.
is there. Further, Japanese Patent Application Laid-Open No. 54-63902 discloses
It is also possible to use a method that combines the two as
I can do it. The aluminum plate thus roughened
Is alkali etching and neutralization if necessary
After the surface treatment, if necessary, increase the water retention and abrasion resistance of the surface
Anodizing is performed for this purpose. Aluminum plate anode
A porous oxide film is used as the electrolyte used for the oxidation treatment.
Anything that forms can be used
Generally sulfuric acid, phosphoric acid, oxalic acid, chromic acid or
These mixed acids are used. The concentration of those electrolytes
It is determined as appropriate depending on the type of quality. Anodizing treatment conditions
Varies depending on the electrolyte used, so it cannot be specified
However, generally, the concentration of the electrolyte is 1 to 80% by weight solution,
Liquid temperature is 5 to 70 ° C, current density is 5 to 60 A / dm^Two,Voltage
1 to 100 V, electrolysis time 10 seconds to 5 minutes
That's right. The amount of anodized film is 1.0 g / m^TwoAbove is preferred
But more preferably from 2.0 to 6.0 g / m^TwoIn the range
is there. Anodized film is 1.0g / m^TwoLess press life
Is insufficient or the non-image area of the lithographic printing plate is scratched.
It is easy for ink to adhere to scratches during printing.
Loose "scratch dirt" is likely to occur. After being subjected to anodizing treatment, aluminum
The surface is subjected to a hydrophilic treatment if necessary. Suitable for the present invention
US Pat. No. 2,71
4,066, 3,181,461, 3,28
0,734 and 3,902,734
Alkali metal silicates such as sodium silicate
Aqueous solution) method. In this method, the support is
Immersion in sodium silicate aqueous solution
It is solved. In addition, Japanese Patent Publication No. 36-22063
Disclosed potassium fluoride zirconate and US patents
Nos. 3,276,868, 4,153,461 and
And poly as disclosed in U.S. Pat. No. 4,689,272.
For example, a method of treating with vinylphosphonic acid is used. [0031] [Organic undercoat layer] In the PS plate used in the present invention,
It is not possible to provide an organic subbing layer before applying the photosensitive layer to the body.
This is preferable for reducing the remaining photosensitive layer in the image area. Such organic
Organic compounds used in the undercoat layer include, for example,
Xymethylcellulose, dextrin, gum arabic,
E having an amino group such as 2-aminoethylphosphonic acid;
Sulfonic acids, optionally substituted phenylphosphone
Glyceroacid, naphthylphosphonic acid, alkylphosphonic acid
Phosphonic acid, methylene diphosphonic acid and ethylene dipho
Organic phosphonic acids such as sulfonic acid, which may have a substituent
Phenyl phosphate, naphthyl phosphate, alkyl phosphate and
And organic phosphoric acids such as glycerophosphoric acid
Good phenylphosphinic acid, naphthylphosphinic acid,
Such as rukyphosphinic acid and glycerophosphinic acid
Amino acids such as organic phosphinic acid, glycine and β-alanine
Acids and triethanolamine hydrochloride
Selected from hydrochlorides of amines having a droxyl group
However, two or more kinds may be used in combination. This organic undercoat layer is provided by the following method.
I can do it. That is, water or methanol, ethanol
Or organic solvents such as methyl ethyl ketone or
A solution of the above organic compound dissolved in a mixed solvent of
Coating and drying on a minium plate, water or
Yes, such as methanol, ethanol, methyl ethyl ketone
The above organic compounds in organic solvents or their mixed solvents
An aluminum plate is immersed in the dissolved solution to
Absorb the compound, then wash with water and dry.
This is a method of drying to provide an organic undercoat layer. In the former way
Has a concentration of 0.005 to 10% by weight of the above organic compound.
The solution can be applied in various ways. For example, a bar coater
Coating, spin coating, spray coating, curtain coating, etc.
These methods may be used. In the latter method, the solution
Is 0.01 to 20% by weight, preferably 0.05 to 5 weight%.
%, And the immersion temperature is 20 to 90 ° C., preferably 25 to 90 ° C.
５０50 ° C., and the immersion time is 0.1 second to 20 minutes, preferably
Is 2 seconds to 1 minute. The solution used for this was ammonia
A, basic substances such as triethylamine and potassium hydroxide
PH adjusted by quality and acidic substances such as hydrochloric acid and phosphoric acid
However, it can be used in a pH range of 1 to 12. Ma
Yellow dye to improve the tone reproducibility of photosensitive lithographic printing plates.
Additives can also be added. Coating of organic undercoat after drying
The amount is 2-200 mg / m^TwoIs suitable, preferably
5-100mg / m^TwoIt is. The above coating amount is 2 mg /
m^TwoIf the amount is smaller, sufficient printing durability cannot be obtained. Also,
200mg / m^TwoThe same is true for larger values. [0033] [Back coat] The back of the support
A coat is provided. As such a back coat,
An organic polymer compound described in JP-A-5-45885 and
And organic or inorganic gold described in JP-A-6-35174
Acid obtained by hydrolysis and polycondensation of genus compounds
A coating layer made of a compound is preferably used. These
Of the covering layers, Si (OCH_Three)_Four, Si (OC_TwoH_Five)_Four,
Si (OC _Three H₇)_Four, Si (OC_FourH₉)_Four, Such as silicon
Alkoxy compounds are inexpensive and readily available, and
Metal oxide coating layer is excellent in developer resistance
Good. [0034] [Development processing] The PS plate thus obtained passes through the transparent original image
Carbon arc lamp, mercury lamp, metal halide lamp,
Xenon lamp, tungsten lamp, etc. as the light source
After being exposed to actinic rays, it is developed. The developer used in the present invention may be a saccharide,
Shims, phenols and fluorinated alcohols
At least one compound selected from the group consisting of
It contains one base and has a pH of 10.0 to 12.7.
It is characterized by that. The photosensitive lithographic printing plate of the present invention
The developer used in the processing method will be described in detail. [Sugars, oximes, phenols, fluorinated alcohol
Saccharides and oxic acid contained in the developer used in the present invention.
Shims, phenols and fluorinated alcohols are
5 × 10^-14~ 1 × 10^-11With an acid dissociation constant of
Things are preferred. The acid dissociation constant here is the first
Any of the second, third, etc. is 5 × 1
0^-14~ 1 × 10^-11Means the compound is
You. That is, in the case of the compound polybasic acid, at least one
Is preferably within the above range. Acid dissociation determination
If the number is within this range, the pH stable holding power becomes stronger.
You. The amount of these compounds added in the developer is generally
0.01 mol / l or more is suitable, and preferably 0.03 mol / l.
３3 mol / liter. If the added amount is less than 0.01 mol / liter,
Insufficient development stabilizing effect and more than 3 mol / l
In this case, the solubility of the photosensitive layer may be deteriorated.
I don't. [Saccharides] Examples of the saccharide include the following general formula (I) or (I)
And I). [0036] Embedded image In the above formula, X₁, X_Two, X_ThreeAre each independently
Hydrogen atom, hydroxyl group, amino group, halogen atom, acyloxy
Si, alkoxy, acylamino or phosphoryl
Represents an oxy group. R₁, R_TwoIs independently a hydrogen atom,
Alkyl group (eg, methyl group), substituted alkyl group (eg,
For example, a hydroxymethyl group, a 1,2-dihydroxyethyl group,
Sethoxymethyl group, benzoyloxymethyl group, methoxy
(Simethyl, benzyloxymethyl, etc.)
Represents a xyl group. Y is a hydrogen atom, an acyl group, an alkoxy
Represents carbonyl, carbamoyl or alkyl groups
You. Further X₁, X_Two, X_Three, R₁, R_TwoAnd in Y
When the substituent represented is a hydroxyl group or a hydroxyl group-containing group
The formation of an ether bond between any two hydroxyl groups.
Or even acetone or benzaldehyde
By adding a bonyl compound and acetalizing, a 5-member or
A six-membered ring may be formed. In the general formula (I) or (II), Y
X of (I) or (II)₁, X_Two, X_Three, R₁, R_Two
And the hydroxyl group represented by Y and (n-1)
By forming the oxide bond, the n completed
Forming small sugars consisting of units (I) or (II)
You may. Here, n represents an integer from 2 to 6.
X₁, X_Two, X_ThreeIs preferably a hydrogen atom or water
It is an acid group, more preferably a hydroxyl group. R₁, R_TwoWhen
Are preferably a hydrogen atom, a hydroxymethyl group,
1,2-dihydroxyethyl group or carboxyl group
And more preferably a hydrogen atom or a hydroxymethyl group.
Or a 1,2-dihydroxyethyl group. Good as Y
Preferred is a hydrogen atom. Formula (I) or (I
Specific examples of the saccharide represented by I) include the following compounds
Can be [0039] I-1 D-Erythrose^* I-2 D-Threose^* I-3 D-Arabinose I-4 D-Ribose I-5 D-Xylose I-6 D-Erythro-Pentulose
entulose)^* 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
lucose) I-15 D-glycero-D-galactose
-D-galacto-Heptose) I-16 α-D-Alluro-Heptulose (α-D-all
o-Heptulose) I-17 β-D-Altro-3-hepturose (β
-D-altro-3-Heptulose) I-18 Sucrose I-19 Lactose I-20 D-maltose I-21 Isomaltose I-22 Inulobiose^* I-23 Hyalbiouronic acid I-24 Maltotriose [0040] Embedded image Compounds marked with * belong to the general formula (II)
Things. Most of these compounds are commercially available
It is readily available. Those not on the market are (1)
"Large Organic Chemistry Vol. 3, Aliphatic Compounds II" by Kouji Takeshi
Osamu, Asakura Shoten, published in 1957, or (2) `` The Carbonhy
drates, Chemistry and Bicchemistry '' 2nd EdIA (197
2), and IIA (1970), W. Pibman and D. Horton
Osamu Osamu, you can easily synthesize by referring to Academic Press. As the saccharide, a non-reducing sugar is preferably used.
it can. Such non-reducing sugars include free aldehyde groups and
A saccharide that does not have a reducing group
Trehalose-type oligosaccharides linked to each other,
Hydrogenation and reduction of glycosides and sugars to which non-saccharides are bound
Sugar alcohols, all of which are used in the present invention.
It is suitably used for a developer. Trehalose-type oligosaccharides
Has saccharose and trehalose, and as a glycoside
Means alkyl glycoside, phenol glycoside, mustard oil glycoside
Body and the like. D and L are sugar alcohols.
-Arabit, Rebit, Xylit, D, L-Sorbi
D, L-mannit, D, L-idit, D, L
-Talit, Zuricit and Allozurshit
I can do it. Multi-toe obtained by hydrogenation of disaccharides
Reduced product obtained by hydrogenation of
Is preferably used. More preferred among these
Non-reducing sugars are sugar alcohols and saccharose, especially D
-PH suitable for sorbitol, saccharose and reduced starch syrup
It is preferable that the area has a buffering effect and that the price is low.
New Reducing sugar turns brown over time when combined with a base
There is a problem that the color changes to and the pH gradually decreases,
Non-reducing sugars are stable over time. These non-reducing sugars
Can be used alone or in combination of two or more.
The proportion of these in the developer is preferably 0.1 to 30% by weight.
And more preferably 1 to 20% by weight. This range
Below, sufficient buffering action cannot be obtained, and above this range
Concentration, it is difficult to achieve high concentration, and the problem of cost increase
Come out. [Oximes] Examples of oximes
Examples include oximes represented by the following general formula (III).
You. [0044] Embedded image In the above formula, R_Three, R_FourAre each independently a hydrogen source
, An alkyl group (which may have a substituent), an aryl group
(Optionally having a substituent), an acyl group or a heterocyclic ring
You. R_Three, R_FourAre bonded to each other to form a 5- or 6-membered ring
To form a cycloalkyl ring). Alkyl group and
Straight-chain, branched and cyclic compounds having 1 to 18 carbon atoms
Including a low alkyl group. As the substituent, for example, hydroxy
Group, carboxyl group, alkoxy group, halogen atom,
Ruho group, sulfamoyl group, carbamoyl group, sulfoni
Ruamino, acylamino, cyano, or acylo
And a xy group. Examples of the aryl group include, for example,
Phenyl, naphthyl, and the like.
Are, for example, the same as the above-mentioned substituents of the alkyl group.
Is included. Acyl groups include formyl group and acetyl group.
Tyl group, propionyl group, butyryl group, oxalyl group,
Malonyl group, benzoyl group, toluoyl group, salicyloi
And a furyl group. As a heterocycle
For example, thiazole, oxazole, imidazole,
Triazole, tetrazole, thiadiazole, oxa
Diazole, tetrahydrofuran, morpholine, pyridi
, Piperidine, benzothiazole, benzoxazo
Or benzimidazole. General
Specific examples of the compound represented by the formula (III) are as follows
There is. [0046] Embedded image [0047] Embedded imageThese compounds are commercially available or
"Organic Functional Group Preparations Volume 3" 36
Page 5 S.R.Sandler and W. Karo, Academic Pre
ss (1972).
It is easily available. [Phenols] As phenols,
For example, phenols of the following general formula (IV) can be mentioned. [0050] Embedded image In the above formula, R_Five, R₆, R₇, R₈Is German
First, hydrogen atom, amino group, carboxylic acid group, sulfonic acid
Group, an alkyl group having 1 to 4 carbon atoms (even if it has a substituent
Good), an alkoxy group (which may have a substituent)
Represent. As the substituent, R of the general formula (III)_ThreeAnd R_Fourof
The same substituents as the alkyl or aryl group include
I can do it. Specific examples of the compound represented by the general formula (IV)
The following are available. [0052] Embedded imageMany of these compounds are commercially available,
Other compounds are known and can be easily synthesized.
it can. [Fluorinated alcohols] Fluorinated alcohols
For example, fluorinated alcohols of the following general formula (V)
For example. [0055] Embedded image In the above formula, R is a hydrogen atom, substituted or unsubstituted
An alkyl group, a substituted or unsubstituted cycloalkyl group,
Represents a substituted or unsubstituted aryl group, wherein n is 1 or 2
J represents a hydrogen atom, a fluorine atom when n is 1,
A substituted or unsubstituted alkyl group,
Chloroalkyl group, substituted or unsubstituted aryl group, substituted
Or represents an unsubstituted aralkyl group, a carboxy group,
When n is 2, a substituted or unsubstituted alkylene group,
Substituted or unsubstituted cycloalkylene group, substituted or unsubstituted
Substituted arylene group, substituted or unsubstituted aralkylene
Represents a group. These substituents include those represented by the general formula (III)
May be mentioned. General formula (V)
In a preferable compound represented by the formula, R is
Represents a hydrogen atom or a fluorine-substituted alkyl group;
J represents a hydrogen atom or fluorine when n is 1.
Represents an atom-substituted alkyl group, and when n is 2, fluorine
Represents a substituted alkylene group. These preferred compounds
Where the number of carbon atoms is hydroxyl, carboxylic, sulfonic
The treatment liquid is less than 6 per hydrophilic group such as
It is preferable in that it has a sufficient solubility for General formula
Specific examples of the compound represented by (V) are shown below. [0057] Embedded imageMany of these compounds are commercially available,
Other compounds are known and can be easily synthesized. Above
Of the above compounds, saccharides and phenols are preferably used.
Wear. Particularly preferred are D-saccharose and D-sorbitol.
And compounds represented by IV-1, IV-2 and V-8.
In the developer used in the present invention, the saccharide and ox
Among shims, phenols and fluorinated alcohols
These can be used alone or in combination of two or more. The above sugars, oximes, phenols,
Combine with fluorinated alcohols to adjust pH to 10.0-1
Alkali agent conventionally known as a base for 2.7
Can be used. For example, sodium hydroxide, potassium hydroxide
Lithium, ammonium, trisodium phosphate,
Same potassium, same ammonium, disodium phosphate, same
Lium, ammonium, sodium carbonate, potassium
Ammonium, sodium bicarbonate, potassium
Ammonium, sodium borate, potassium,
An inorganic alkali agent such as ammonium is exemplified. Ma
Monomethylamine, dimethylamine, trimethyla
Min, monoethylamine, diethylamine, triethyl
Amine, monoisopropylamine, diisopropylamido
, Triisopropylamine, n-butylamine, mono
Ethanolamine, diethanolamine, triethanol
Luamine, monoisopropanolamine, diisopropa
Nolamine, ethyleneimine, ethylenediamine,
Lysine, tetramethylammonium hydroxide, tet
Laethylammonium hydroxide, tetrapropyla
Ammonium hydroxide, tetrabutyl ammonium arsenide
Droxide, triethylbutylammonium hydroxy
An organic alkali agent such as metal is also used. These alkali agents may be used alone or in combination of two or more.
Used in combination with the above, partially halogenated
It may be added in the form of such a salt. These alkaline agents
Of these, sodium hydroxide and potassium hydroxide are preferred.
Therefore, by adjusting the amount, pH can be adjusted over a wide pH range.
This is because preparation becomes possible. Also, trisodium phosphate
And potassium, sodium carbonate, potassium, etc.
This is preferable because it has a buffering effect. These arca
The dispersant is adjusted so that the pH of the developer is in the range of 10.0 to 12.7.
At the desired pH, the sugars described above,
Of oximes, phenols and fluorinated alcohols
It is determined by the type and the amount added. More preferred pH range
The box is 11.5 to 12.5. If the pH is below 10.0, the current
Insufficient image easily causes print stains, and pH is 12.7
If it exceeds, over-development occurs and the image area is damaged,
A large number of prints cannot be obtained. The developer used in the present invention further comprises
Sugars, oximes, phenols and fluorinated alcohols
Alkaline buffers consisting of weak acids and strong bases other than
You may use together. With a weak acid used as such a buffer
Therefore, those with a dissociation constant (pKa) of 10.0 to 13.2
preferable. Examples of such weak acids include Pergamon Press
Issued IONISATION CONSTANTS OF ORGANIC ACIDS IN AQU
EOUS SOLUTION
For example, trichloroethanol (pKa12.24), pyri
Gin-2-aldehyde (12.68) and pyridine-4-
Aldehydes such as aldehyde (12.05), 3-Hydro
Roxy-2-naphthoic acid (12.84) and catechol (12
12.6), gallic acid (12.4), 3,4-dihydroxys
Sulfonic acid (12.2), 3,4-dihydroxybenzoic acid (1)
11.94), 1,2,4-trihydroxybenzene (11.94)
2), hydroquinone (11.56), pyrogallol
(11.34) and resorcinol (11.27)
Noron (11.76), 2-pyridone (11.65),
4-quinolone (11.28) and 4-pyridone (11.1.1)
2), 5-aminovaleric acid (10.77), 2-mercap
Toquinoline (same as 0.25), 3-aminopropionic acid
Amino acids such as (10.24) and fluorouracil
(13.0), guanosine (12.6), uridine (same as above)
12.6), adenosine (12.56) and inosine (1)
2.5), guanine (12.3), cytidine (12.
2), cytosine (12.2), hypoxanthine (11.2)
1), nucleic acid-related substances such as xanthine (11.9), etc.
In addition, diethylaminomethylphosphonic acid (12.32),
1-amino-3,3,3-trifluorobenzoic acid (12.2
9), isopropylidene diphosphonic acid (12.10.)
1,1-ethylidene diphosphonic acid (11.54), 1,1-ethyl
1-hydroxy lidendiphosphonic acid (11.52), ben
Zimidazole (12.86), thiobenzamide (12)
12.8), picolinethioamide (12.55), barbi
And weak acids such as turic acid (12.5). As a strong base combined with these weak acids
Are sodium hydroxide, ammonium hydroxide, potassium
And the same lithium is used. These alkaline agents are simply
It is used alone or in combination of two or more. above
Various alkaline agents have a pH of 1 depending on the concentration and combination.
Used to be 0.0-12.7. [0063] [Surfactant] The developer used in the present invention has a developing property.
Of ink, dispersion of development residue, and ink affinity for the printing plate image area
Various surfactants and organics as needed to enhance
Solvents can be added. Preferred surfactants include aniline
On, cationic, nonionic and amphoteric surfactants
Is mentioned. Preferred examples of the surfactant include poly
Oxyethylene alkyl ethers, polyoxyethylene
Alkyl phenyl ethers, polyoxyethylene
Listyryl phenyl ethers, polyoxyethylene poly
Lioxypropylene alkyl ethers, glycerin fat
Fatty acid partial esters, sorbitan fatty acid partial esters
, Pentaerythritol fatty acid partial esters, pro
Pyrene glycol monofatty acid esters, sucrose fatty acids
Partial esters, polyoxyethylene sorbitan fatty acid
Partial esters, polyoxyethylene sorbitol fat
Acid partial esters, polyethylene glycol fatty acid esters
Ters, polyglycerin fatty acid partial esters, polio
Xyethylenated castor oil, polyoxyethylene glycer
Phosphoric acid partial esters, fatty acid diethanolamide
, N, N-bis-2-hydroxyalkylamines,
Polyoxyethylene alkylamine, triethanol alcohol
Min fatty acid ester, trialkylamine oxide, etc.
A nonionic surfactant, Fatty acid salts, abietic acid salts, hydroxy
Sialkanesulfonates, alkanesulfonates,
Dialkyl sulfosuccinates, straight-chain alkyl
Benzene sulfonates, branched-chain alkylbenzene sulfo
Acid salts, alkyl naphthalene sulfonates, alkyl
Rufenoxy polyoxyethylene propyl sulfonate
, Polyoxyethylene alkyl sulfophenylate
Salts, N-methyl-N-oleyltaurine sodium
Salt, disodium N-alkyl sulfosuccinate monoamide
Salt, petroleum sulfonates, sulfated tallow oil, fatty acid alk
Sulfates of alkyl esters, alkyl sulfates
Salts, polyoxyethylene alkyl ether sulfate
Salts, fatty acid monoglyceride sulfate salts, poly
Oxyethylene alkyl phenyl ether sulfate
Salts, polyoxyethylene styryl phenyl ether sulfur
Acid ester salts, alkyl phosphate ester salts, polio
Xylethylene alkyl ether phosphate salts,
Lioxyethylene alkyl phenyl ether phosphate
Ter salts, styrene / maleic anhydride copolymer partial soap
Compounds, partial soap of olefin / maleic anhydride copolymer
And naphthalene sulfonate formalin condensates
Which anionic surfactants, alkylamine salts, tetra
Quaternary ammonium salts such as butyl ammonium bromide
, Polyoxyethylene alkylamine salts, polyethylene
Cationic surfactants such as lenpolyamine derivatives,
Ruboxitanes, aminocarboxylic acids, sulfobeta
Ins, aminosulfates, imidazolines, etc.
Amphoteric surfactants are included. Of the surfactants listed above
Among them, polyoxyethylene refers to polyoxymethyl
, Polyoxypropylene, polyoxybutylene, etc.
Can also be read as polyoxyalkylene,
These surfactants are also included. A further preferred surfactant is a perfume in the molecule.
Fluorosurfactants containing fluoroalkyl groups
You. Such fluorosurfactants include perfluoro
Alkyl carboxylate, perfluoroalkyl sulfone
Salts such as acid salts and perfluoroalkyl phosphates
On-type, amphoteric type such as perfluoroalkyl betaine,
Such as perfluoroalkyltrimethylammonium salts
Cationic and perfluoroalkylamine oxides
Perfluoroalkyl ethylene oxide adduct,
-Fluoroalkyl group and hydrophilic group-containing oligomer,
Oligomers containing perfluoroalkyl groups and lipophilic groups
-, Perfluoroalkyl group, hydrophilic group and lipophilic group
Containing oligomers, perfluoroalkyl groups and lipophilicity
Non-ionic types such as group-containing urethanes are included. above
Surfactants may be used alone or in combination of two or more.
0.001 to 10% by weight in the developer,
More preferably, it is added in the range of 0.01 to 5% by weight. [0066] [Organic solvent] The developer used in the present invention
An organic solvent is added. Such an organic solvent includes water
With a solubility of about 10% by weight or less
And preferably 5% by weight or less. example
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-methoxybenz
Zyl alcohol, m-methoxybenzyl alcohol, p
-Methoxybenzyl alcohol, benzyl alcohol,
Cyclohexanol, 2-methylcyclohexanol,
3-methylcyclohexanol and 4-methylcyclo
Hexanol, N-phenylethanolamine and N
-Phenyldiethanolamine, etc.
You. The content of the organic solvent is 0.1% based on the total weight of the used solution.
~ 5% by weight. The amount used depends on the amount of surfactant used.
There is a close relationship, and as the amount of organic solvent increases,
It is preferable to increase the amount of the activating agent. This is a surfactant
If the amount of the agent is small and the amount of the organic solvent is large,
Does not completely dissolve, and therefore good developability is expected
It is not possible. [0067] [Development stabilizer] Various types of developers are used in the present invention.
Development stabilizers may be used. Preferred examples of them
As sugar alcohols described in JP-A-6-282079.
Polyethylene glycol adduct, tetrabutyl alcohol
Tetraalkylammonium such as ammonium hydroxide
Potassium salt, tetrabutylphosphonium bromide, etc.
Suphonium salt and diphenyliodonium chloride
Preferred examples thereof include iodonium salts.
Further, an anion described in JP-A-50-51324
Surfactants or amphoteric surfactants and JP-A-55-9
No. 5946, water-soluble cationic polymer,
Water solubility described in JP-A-56-142528
There is an amphoteric polymer electrolyte. Further, Japanese Patent Application Laid-Open No. 59-842
No. 41, an organic resin to which an alkylene glycol is added.
Iodine compounds described in JP-A-60-111246
Lioxyethylene / polyoxypropylene block polymerization
Type water-soluble surfactant, JP-A-60-129750
Polyoxyethylene and polyoxypropylene
Alkylene diamine compound, JP-A-61-2155
No. 54, a polyethylene having a weight average molecular weight of 300 or more
Len glycol, described in JP-A-63-175858.
Fluorinated surfactant having a thionic group, JP-A 2-3
No. 9157, acid or alcohol of 4 moles or more
Water-soluble ethylene oxide obtained by adding tylene oxide
Sid addition compound, water-soluble polyalkylene compound, etc.
No. [0068] [Reducing agent] The developing solution used in the present invention further contains a reducing agent.
May be added. This is to prevent the printing plate from becoming dirty.
Negative photosensitive, especially containing photosensitive diazonium salt compounds
It is effective when developing a lithographic printing plate. Preferred organic
Reducing agents include thiosalicylic acid, hydroquinone,
Thor, methoxyquinone, resorcinol, 2-methylreso
Phenolic compounds such as rusin, phenylenediamine,
Examples include amine compounds such as phenylhydrazine.
Further preferred inorganic reducing agents include sulfurous acid and sulfurous acid aqueous solution.
Acid, phosphorous acid, hydrogen phosphite, dihydrogen phosphite,
Sodium of inorganic acids such as thiosulfuric acid and dithionous acid
Salts, potassium salts, ammonium salts, etc.
Wear. Among these reducing agents, the stain prevention effect is particularly excellent.
It is sulfite. These reducing agents are used at the time of use.
Preferably, it is contained in the range of 0.05 to 5% by weight with respect to the image liquid.
Have. [0069] [Organic carboxylic acid] The developer used in the present invention further comprises
Organic carboxylic acids can also be added. Preferred organic mosquito
Rubonic acid is an aliphatic carboxylic acid having 6 to 20 carbon atoms and
And aromatic carboxylic acids. Specific of aliphatic carboxylic acid
Examples are caproic acid, enantiic acid, capryl
Acids, lauric, myristic, palmitic and sulfuric acids
And the like. Particularly preferred are those having 8 to 1 carbon atoms.
2 alkanoic acids. Also has a double bond in the carbon chain
Unsaturated fatty acids or branched carbon chains
No. As aromatic carboxylic acids, benzene ring, naphthalene
Ring, anthracene ring, etc. substituted with carboxyl group
Compounds, specifically, o-chlorobenzoic acid, p-chloro
B-benzoic acid, o-hydroxybenzoic acid, p-hydroxy
Benzoic acid, o-aminobenzoic acid, p-aminobenzoic acid,
2,4-dihydroxybenzoic acid, 2,5-dihydroxy
Benzoic acid, 2,6-dihydroxybenzoic acid, 2,3-di
Hydroxybenzoic acid, 3,5-dihydroxybenzoic acid,
Gallic acid, 1-hydroxy-2-naphthoic acid, 3-hydrid
Roxy-2-naphthoic acid, 2-hydroxy-1-naphtho
Acetic acid, 1-naphthoic acid, 2-naphthoic acid and the like.
Droxynaphthoic acid is particularly effective. The above aliphatic and
And aromatic carboxylic acids are sodium to increase water solubility
Used as salts, potassium salts or ammonium salts
preferable. The developer used in the present invention contains an organic carboxylic acid.
There is no special restriction on the amount, but it is effective if it is less than 0.1% by weight.
Is not enough, and more than 10% by weight has more effect
Not only cannot be improved, but also when using other additives
May hinder dissolution. Therefore, the preferred amount is
0.1 to 10% by weight with respect to the developing solution when used.
More preferably, it is 0.5 to 4% by weight. [0070] [Others] The developer used in the present invention further requires
If necessary, contain antifoaming agent and water softener
You can also. Examples of water softeners include polyphosphoric acid and
And its sodium, potassium and ammonium salts
Salt, ethylenediaminetetraacetic acid, diethylenetriami
Pentaacetic acid, triethylenetetramine hexaacetic acid,
Droxyethylethylenediaminetriacetic acid, nitrilot
Acetic acid, 1,2-diaminocyclohexanetetraacetic acid
And 1,3-diamino-2-propanoltetraacetic acid
Which aminopolycarboxylic acids and their sodium
Salts, potassium and ammonium salts, aminotri
Tylene phosphonic acid), ethylene diamine tetra (methyle
Phosphonic acid), diethylene triamine penta (methyle
Phosphonic acid), triethylenetetraminehexa (meth
Lenphosphonic acid), hydroxyethylethylenediamine
Tri (methylene phosphonic acid) and 1-hydroxy eta
1,1-diphosphonic acid and their sodium salts,
Lium and ammonium salts can be mentioned.
Such water softeners are used with their chelating power
The optimum value changes depending on the hardness of hard water and the amount of hard water
However, if the general usage amount is shown, 0.01% is used for the developer at the time of use.
To 5% by weight, more preferably 0.01 to 0.5% by weight.
It is. If the amount is less than this range, the intended purpose is not sufficient.
If this is not achieved in minutes and the amount added is
An adverse effect on the image portion, such as omission, appears. Residual developer
The component is water, but it is also known in the art as needed.
And various additives. For use in the present invention
The developer contains less water than when used
Keep as a concentrate and dilute with water before use.
Is advantageous for transportation. In this case, the concentration of each component
Is suitable so that no separation or precipitation occurs. [0071] [Development and post-processing] The photosensitive lithographic printing plate of the present invention
Is carried out according to a conventional method using a developer having the composition described above.
I can. The PS plate developed with a developer is washed with water
Rinse solution containing water, surfactant, etc., gum arabic and
Finishers and protective gums based on starch derivatives
The liquid is post-treated. The processing method of the PS plate of the present invention
In post-processing, these processes are used in various combinations.
Can be In recent years, the plate making and printing industry has
Automatic processing machines for PS plates are widely used for rationalization and standardization.
Commonly used. This automatic processor generally has a developing section
A post-processing unit that transports PS plates and each processing solution
Consists of a bath and a spray device, and exposes the exposed PS plate to water
While transporting flat, each processing solution pumped up by the pump is
Is developed and post-processed by spraying from a laser nozzle.
is there. Also, recently, a processing solution tank filled with
The PS plate is immersed and transported by a middle guide roll, etc.
The image processing method, and a certain amount of small amount of washing water after development
And wash it with water, and use the wastewater as dilution water for the undiluted developer solution.
There is also known a method of reuse. Automatic processing like this
In each case, the amount of each processing solution depends on the processing amount, operating time, etc.
Processing can be performed while replenishing each replenisher.
In addition, the so-called use of treating with a substantially unused treating solution
A discarding method can also be applied. Use of such an automatic developing machine
The processing method of the photosensitive lithographic printing plate of the present invention is
It can be applied advantageously. Lithographic printing obtained by the above process
The plate is set on an offset printing machine and used for printing many sheets.
Can be [0072] Next, an embodiment of the present invention will be described.
Automatic developing machine to which the processing method of photosensitive lithographic printing plate is applied,
This will be described with reference to FIG. In FIG. 1, a sheet-like feeling
The light-sensitive lithographic printing plate (hereinafter, referred to as PS plate) 10 includes a photosensitive layer.
In a predetermined transport direction (direction of arrow A) with
The developing unit 2 is transported horizontally or continuously while being curved.
0, in the washing section 50 and the finisher section 60
Each is subjected to a predetermined process. In the developing tank 21 of the developing unit 20
The activity of the developer stored in the controller is controlled by a control unit (not shown).
By supplying the developing replenisher to the developing tank 21 based on the
It is kept almost constant. In the developing section 20, the developer is stored in a developing tank 21.
Due to the action of the developed developer, the photosensitive layer of the PS plate 10
Image processing is performed. The developing roller 20 includes a transport roller 22,
Squeeze rollers 23 and 24 sandwich PS plate 10 respectively
And the rotating brush roller 25
The PS plate 10 is sandwiched between the guide plate 26 and the guide roller 26 or 28.
Provided. The transport roller 22 holds the PS plate 10 therebetween.
By rotating the PS plate 10 in the state, the PS plate 10 is
And guided by the guide plate 27 and the guide plate 30 while being curved.
Then, it is immersed in the developing solution in the developing tank 21. Squeeze
The roller 23 is disposed substantially at the center of the developing tank 21 and has a developer
The PS plate 10 that is immersed in
The PS plate 10 is transported by rotating while holding it
Of the PS plate 10
Removal of waste and the like in the image liquid. The squeeze roller 24
It is arranged downstream of the transport direction A in the developing tank 21 and
And rotate while holding the PS plate 10 that has passed through the developing solution.
By rotating, the PS plate 10 is transported,
Excess developer adhering to the surface of the PS plate 10 is removed. B
The lash rollers 25 are respectively immersed in the developer.
The brush roller motor (not shown)
Therefore, the elution of the surface of the PS plate 10 is caused by the rotation.
Scrape layer. The lower end of the guide plate 30 in the developing tank 21
Around the squeeze roller 23 and the guide roller 26
A spray pipe 31 is provided at each of the sandwiched positions.
Can be Each spray pipe 31 has a number of discharge ports (shown in FIG.
No), and each outlet is individually
Communicating with the developing tank 21 through the pump 32 and the circulation pump 33
ing. Each spray pipe 31 is controlled based on the control of the control unit.
With the operation of the circulation pump 33, suction from the developing tank 21 is performed.
The raised developer is again supplied from each discharge port to the bottom of the developing tank 21.
The developer in the developing tank 21
Circulate. Each spray pipe 31 and circulation pump 33
A sensor 34 is provided in the communicating pipe 32.
You. The sensor 34 indicates the conductivity or impedance of the developer.
Of the PS plate 10 that has been image-exposed,
The deterioration of the developer caused by the process is detected. The developing tank 21 contains a stock solution for developing replenisher 3
5 is connected via a connecting pipe 36 and a stock solution replenishing pump 37
The stock solution replenishment pump 3 which is
7, the replenisher stock solution tank 35
The tank 21 is supplied with a required amount of a stock solution of the developing replenisher. In addition
In the image tank 21, a liquid surface cover 38 is brought into contact with the stored developer.
And it is arranged so that the surface may be covered. Liquid cover 3
8 is polyvinyl chloride, polyethylene or polyamide, etc.
Made of lightweight material. The liquid level cover 38 is at both ends in the transport direction A.
Part is supported by a body frame (not shown) so that it can move up and down.
And moves up and down in response to changes in the developer level.
This minimizes contact between the developer surface and air. Liquid lid
In the vicinity of both ends in the conveyance direction A of the blade 38, a blade 39 is provided.
Each is provided between the liquid level cover 38 and the outer panel 11.
Can be Each blade 39 is in contact with the upper surface in FIG.
The space surrounded by the inner surface of the outer panel 11 is
By completely isolating the developer, evaporation of the developer is minimized
I do. In the washing section 50, the PS plate 10 is required.
Is performed. The washing unit 50 includes the transport roller 5
When two pairs of 1 are provided so as to sandwich the PS plate 10 respectively.
In both cases, a spray pipe 5
2 are provided. The spray pipe 52 is made up of a number of
Each outlet has a connecting pipe
53 and a washing water tank 55 through a washing pump 54.
Through. The spray pipe 52 is connected to the downstream conveying row.
A large amount of water is placed on the upper surface of the
By spraying water from the discharge port, P
The surface of the S plate 10 is washed with water via the transport roller 51. Transport
The rollers 51 respectively correspond to the lower transport rollers 51 in FIG.
It is arranged to be immersed in the water stored in the saucer 56
By rotating the PS plate 10 while holding it,
To transport the PS plate 10 almost horizontally,
The bottom surface of PS plate 10 in Fig. 1
Is washed with water. The receiving tray 56 is provided at the lower transport roller 5 in FIG.
1 is provided so as to cover the lower half of the PS plate 10.
The water from the spray pipe 52 whose upper surface is washed with water in FIG. 1 is stored.
To stay. A washing tank 57 is provided below the receiving tray 56.
And stores the water overflowing from the tray 56. Washing
The tank 57 is connected via a connecting pipe 58 and a water replenishing pump 59.
To the developing tank 21. That is, in the washing tank 57
Of the water supply pump 59 based on the control of the control unit.
A required amount is supplied to the developing tank 21 with the
It becomes dilution water. In the finisher section 60, the gum solution
The required finishing treatment is applied to the PS plate 10 by the action of
You. The finisher section 60 includes a spray pipe 61.
However, a pair is provided above and below the PS plate 10 and
The squeeze roller 6 is located downstream of the spray pipe 61.
A pair 2 is provided above and below the PS plate 10. The spray pipes 61 are not shown.
It has a large number of outlets, and each outlet
The gum liquid tank is connected via the connecting pipe 63 and the gum liquid pump 64.
６５65 is connected. Spray pipe 61
With the operation of the gum solution pump 64 and facing the discharge port.
Gum solution (finishing solution) toward each guide plate 66
By spraying, the PS plate 10 after the water washing process is shown in FIG.
A gum solution is sprayed on the middle upper surface and the lower surface via each guide plate 66.
wear. Each of the squeeze rollers 62 holds the PS plate 10
The PS plate 10 is transported by rotating while holding it.
Attached to the surface of PS plate 10 after finishing
Remove excess gum solution. By the squeeze roller 62
The gum solution thus removed is collected in the gum solution tank 67.
The lower half of the squeeze roller 62 in FIG.
It is immersed in the gum solution in the solution tank 67,
Apply the lubricated gum solution to the lower surface of PS plate 10 in FIG.
You. The developing unit 20, the washing unit 50, and the finish
In the shear section 60, the developing tank 21, the washing tank 57 and the
Each of the liquid tanks 67 is provided with an overflow pipe 12.
Can be Each overflow pipe 12 has a connecting pipe 13
Through the waste liquid tank 14, and the liquid level in each tank is
When the height exceeds a certain level, the liquid overflowing from each tank is
The liquid is discharged to a waste liquid tank 14 via a pump 13. The controller controls the conduction of the developer by the sensor 34.
Replenisher volume based on degree or impedance detection results
Calculate m and dilution ratio. And the control unit replenishes the stock solution
By controlling the pump 37 and the water refill pump 59
And replenish the required amount of developer replenisher diluted at the calculated ratio.
Supply to the developing tank 21, that is, a stock solution for developing replenisher
From 35, a required amount of the undiluted replenisher is supplied to the developing tank 21.
And the required amount of water from the washing tank 57 to the developing tank 21.
Supply. As a result, the control unit stores the image in the developing tank 21.
The activity of the developer is kept almost constant at all times. FIG. 2 is a view showing the development in the developing tank 21 by the control unit.
It is a control flowchart of replenisher replenishment. Hereinafter, FIG.
Along the way (refer to FIG. 1 for symbols)
The control will be described. Automatic processor starts operation
And the brush roller motor operates in step S1
Then, the brush roller 25 rotates. This allows development
The developer in the tank 21 is stirred. And to step S2
Then, the circulation pump 33 is operated, and the current in the developing tank 21 is changed.
The circulation of the image liquid is started. Like immediately after starting operation
Since the developer is stirred and circulated,
The unevenness in the concentration of the developer caused during the
Can be eliminated. Next, in step S3, the electric conductivity (or
It is determined whether it is time to measure impedance)
If so, the process proceeds to step S4. On the other hand, when measuring
If not, the determination in step S3 is repeated.
You. In step S4, the developing solution is detected by the sensor 34.
The conductivity (or impedance) of the
In S5, measured value of electric conductivity (or impedance)
The electrical conductivity (or impedance) is
The replenishment of the developer replenisher is required.
It is determined whether it is necessary. In step S5, replenishment of the developer replenisher is performed.
If it is determined that is necessary, proceed to step S6.
Based on conductivity (or impedance) measurements
From the map stored in the memory of the control unit.
Read the replenishment amount n per liter of liquid, and
In step S7, the development stored in the developing tank 21
The liquid amount D is read. On the other hand, in step S5,
If it is determined that is not necessary, the process proceeds to step S13.
move on. In step S8, the current value corresponding to the developer amount D
The image replenisher amount m is calculated (m = n × D), and step S9 is performed.
At the calculated replenisher volume m and the dilution ratio
The replenisher stock solution and dilution water volume respectively
Then, in step S10, the stock solution replenishing pump 3
7 and the water replenishment pump 59 are activated, and the calculated ratio is
A required amount of the diluted developing replenisher is supplied into the developing tank 21.
Is done. In step S11, the inside of the developing tank 21 is
It is determined whether the replenishment of the predetermined developer replenisher amount m has been completed.
It is. If it is determined that replenishment has been completed, step S
Then, in step S12, the stock solution replenishment pump
37 and the water refill pump 59 are stopped. Meanwhile, replenish
If it is determined that the processing has not been completed, the process proceeds to step S11.
The judgment is repeated. In step S13,
After a predetermined time has passed since the degree (or impedance) was measured
It is determined whether or not it has passed. Conductivity (or impedance
S) If it is determined that a predetermined time has elapsed after measurement,
Proceed to step S14, and in step S14,
The motor for the roller is stopped, and the rotation of the brush roller 25 is stopped.
Is stopped. Further, in step S15, the circulation pump
After the step 33 is stopped, it is reset. On the other hand,
In step S13, conductivity (or impedance) measurement
Later, if it is determined that the predetermined time has not passed,
The determination in step S13 is repeated. In the above-mentioned replenishment control, the second and subsequent times
For the conductivity (or impedance) measurement of
The drive of the brush roller 25 by the brush roller motor is P
It is performed only during the passage of the S plate, and the circulation pump 3
3 is activated every time the conductivity (or impedance) is measured
Is controlled to be [0089] The method for processing a photosensitive lithographic printing plate according to the present invention is described below.
According to this, it can be developed with a safe developer having a relatively low pH,
Both developability and image strength (printing and chemical resistance) are compatible
It works. Also, since insolubilized substances are hardly generated,
Suitable for processing using an image machine. Also according to the invention
For example, if the photosensitive lithographic printing plate is
When developed with a developer in the range of 10.0 to 12.7
The development caused by the processing of a photosensitive lithographic printing plate
Measures the deterioration of the solution and the conductivity or impedance of the developer
To perform replenishment based on the detection result.
By replenishing, the activity of the developer becomes almost constant.
keep. Therefore, extremely stable processing over a long period of time
And the conductivity of the developer or the
It is difficult for insolubles to accumulate on sensors that measure impedance.
And good maintainability can be secured. [0090] The present invention will be described in detail with reference to the following Examples and Comparative Examples.
explain. Example 1 0.24mm thick aluminum plate and nylon brush
Surface using 400 mesh pumicestone-water suspension
Was grained and washed well with water. 10% hydroxide
Etched in thorium at 70 ° C for 20 seconds
After that, it is washed with running water and then 20% HNO_ThreeWith neutralization washing,
Washed with water. Under the condition of VA = 12.7V, the sine wave
400 coulombs in 0.7% nitric acid aqueous solution using waveform current
In / dm^TwoThe electrolytic surface roughening treatment was performed with the quantity of electricity. This group
The aluminum plate of the surface is placed in a 10% aqueous sodium hydroxide solution.
0.9 g / m^TwoIt was processed to become. water
After washing, neutralize and wash in a 20% nitric acid solution to remove smut.
18% H_TwoSO_FourIn aqueous solution, the amount of oxide film is 3
g / m^TwoAnodized so that Then, at 35 ° C,
Hydrophilic treatment was performed with a 2% aqueous solution of sodium silicate. Or
After drying the undercoat liquid a of the following composition on the support thus manufactured
10mg / m in weight^Two90
It dried at 1 degreeC for 1 minute, and provided the undercoat layer. Undercoat liquid a   Phenylphosphonic acid 0.06 g   0.12 g of sulfuric acid   100 g of methanol Subsequently, a photosensitive solution having the following composition was prepared, and
1.8 g / m in weight after drying on the substrate^TwoSo that
A photosensitive layer was provided. Photosensitive liquid   Phenol-formaldehyde resin   (95.5% by weight of trinuclear or higher component content,     Molecular weight 13,500) 1.9 g   1,2-diazonaphthoquinone-5-sulfonyl chloride and   Esterified product with pyrogallol-acetone resin   (Molecular weight 2,500) 0.76 g   0.2 g of tetrahydrophthalic anhydride   4- [p-N- (p-hydroxybenzoyl) aminophenyl]   -2,6-bis (trichloromethyl) -s-triazine 0.02 g   Victoria Pure Blue BOH   (Manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.03 g   Mega Fuck F-177   (Fluorine surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.006 g   15 g of methyl ethyl ketone   Propylene glycol monomethyl ether 15g The surface of the photosensitive layer thus prepared is
Spray the mat layer forming resin liquid as described above
Layers were provided. Methyl methacrylate as a resin solution for mat layer formation
Relate / ethyl acrylate / acrylic acid (charged weight
Ratio 65:20:15) Part of the copolymer is sodium salt
A 12% aqueous solution was prepared and sprayed with a rotary atomizing electrostatic coating machine.
The head rotation speed is 25,000 rpm, and the amount of resin solution sent is 40
ml / min, the applied voltage to the atomizing head is -90 kv,
Ambient temperature is 25 ° C and relative humidity is 50%, after application 2.5
In a second, steam is applied to the surface to be wetted, and then moistened.
After 3 seconds, blow hot air at a temperature of 60 ° C and a humidity of 10% for 5 seconds.
And dried. The height of the mat is about 6μm and the size is
Approximately 30 μm, the number is 150 / mm^TwoMet. This
The PS plate A obtained in this way is 1,003 mm x 800 mm
Prepare the paper cut to the size of
3km metal halide run from 1m distance
Exposure was performed for 60 seconds using a pump. Next, an immersion type developing tank
Commercial automatic processor PS-900D (Fuji Photo File
The following developer a (pH 12.5)
Was charged and kept at 30 ° C. PS-90
8 liters of tap water in the second bath of 0D, and in the third bath
FP-2 (Fuji Photo Film Co., Ltd.): Water = 1: 1 diluted
8 liters of the finished finishing solution was charged. [0093] Developer a   D-saccharose 5.1% by weight   0.51% by weight of sodium hydroxide   0.74% by weight of sodium carbonate   Tetrabutylammonium bromide 0.03% by weight   93.62% by weight of water Pass the exposed PS plate through this PS-900D,
Developed. At this time, a step tablet (one stage
(15 steps with an optical density difference of 0.15)
Change the amount of light and print on the PS plate at the same time
After developing, the number of steps of the remaining image corresponding to the amount of light on the plate
(Clear / solid number) and read the value of PS version A
The sensitivity was defined as that obtained when the film was developed with the developer A and is shown in Table 1. Or
The lithographic printing plate obtained in this way is offset printing press spring
To 25 (Komori Printing Machine Manufacturing Co., Ltd.)
went. Each time 5,000 sheets are printed, half of the printing plate
Ultra Plate Cleaner (ABC Chemica
wiped with a sponge soaked in
Was. Table 1 shows the printing results at this time. Relatively low pH
PS plate A that can be developed at (pH 12.5)
Printing durability and chemical resistance equivalent to commonly used high pH systems
Sex was obtained. Embodiment 2 Example 1 was repeated except that the following photosensitive solution was used.
Except that a PS plate B was prepared in the same manner as in
All were processed and evaluated in the same manner as in Example 1. Same as Example 1
Thus, good printing durability and chemical resistance were obtained. Photosensitive liquid   Phenol-formaldehyde resin   (95.5% by weight of trinuclear or higher component content,     Molecular weight 13,500) 1.7 g   Methyl methacrylate / methacrylic acid copolymer   (Polymer charge ratio during polymerization: 76/24, molecular weight: 60,000) 0.2 g   1,2-diazonaphthoquinone-5-sulfonyl chloride and   Esterified product with pyrogallol-acetone resin   (Molecular weight 2,500) 0.76 g   0.2 g of tetrahydrophthalic anhydride   4- [p-N- (p-hydroxybenzoyl) aminophenyl]   -2,6-bis (trichloromethyl) -s-triazine 0.02 g   Victoria Pure Blue BOH   (Manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.03 g   Mega Fuck F-177   (Fluorine surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.006 g   15 g of methyl ethyl ketone   Propylene glycol monomethyl ether 15g Embodiment 3 Example 1 was repeated except that the following developer B was used.
The PS plate A was processed and evaluated in the same manner as described above. Example 1 and
Similarly, good printing durability and chemical resistance were obtained. Developer b   D-Sorbit 3.41% by weight   0.28% by weight of sodium hydroxide   Sodium carbonate 1.05% by weight   Tetrabutylammonium bromide 0.03% by weight   95.23% by weight of water Embodiment 4 The o-quinonediazide compound of the photosensitive solution of Example 1 was replaced with 1,
2-diazonaphthoquinone-5-sulfonyl chloride and m
-Esterified product with cresol formaldehyde resin
(Molecular weight 3,200), except that all were the same as in Example 1.
PS plate C produced in the same manner as in Example 1
The lithographic printing plate was processed and evaluated. Example 1
As in the above, good printing durability and chemical resistance were obtained. Comparative Example 1 Phenol formaldehyde novola in the photosensitive solution of Example 1
The content of the tri- or higher nucleus component is 88.6% by weight.
%, Except that the molecular weight was changed to 8,400.
PS plate D produced in the same manner as
The resulting lithographic printing plate was evaluated by the method described above. P
Insufficient printing and chemical resistance of the printing plate obtained from S-plate D
In particular, the chemical resistance was significantly poor. Embodiment 5 Support prepared in the same manner as in Example 1 up to anodizing treatment
10 mg of the undercoat liquid b having the following composition as a weight after drying
/ M^TwoAnd dried at 90 ° C for 1 minute.
A coating layer was provided. Undercoating liquid b 0.5 g of triethanolamine hydrochloride 95 g of methanol 5 g of water Subsequently, a photosensitive solution having the following composition was prepared, and
1.8 g / m in weight after drying on the substrate^TwoSo that
A photosensitive layer was provided. Photosensitive liquid   Phenol-formaldehyde resin   (The content of components of 3 or more nuclei is 94.6 wt%,   Molecular weight 12,500) 1.9g   1,2-diazonaphthoquinone-5-sulfonyl chloride and   Esterified product with pyrogallol-acetone resin   (Molecular weight 2,500) 0.76 g   0.2 g of tetrahydrophthalic anhydride   4- [p-N- (p-hydroxybenzoyl) aminophenyl]   -2,6-bis (trichloromethyl) -s-triazine 0.02 g   Victoria Pure Blue BOH   (Manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.03 g   Mega Fuck F-177   (Fluorine surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.006 g   15 g of methyl ethyl ketone   Propylene glycol monomethyl ether 15g The surface of the photosensitive layer thus prepared was applied as in Example 1.
Spray the mat layer forming resin liquid
A PS plate E provided with was prepared.
And the resulting printing plate was evaluated.
Excellent printing durability and chemical resistance were obtained. Comparative Example 2 The o-quinonediazide compound of the photosensitive solution of Example 5 was replaced with 1,2
-Diazonaphthoquinone-5-sulfonyl chloride and tri
Esterified product with hydroxybenzophenone (average molecule
Except that the amount was changed to 870).
The prepared PS plate F was treated in exactly the same manner as in Example 5,
The obtained lithographic printing plate was evaluated. Obtained from PS version F
The resulting printing plates had significantly poorer press and chemical resistance. Comparative Example 3 Phenol formaldehyde novola of the photosensitive solution of Example 5
M-cresol formaldehyde resin (trinuclear)
With a molecular weight of 4,80 at a content of 86.5% by weight
Except for changing to (0), all were made in the same manner as in Example 5.
The produced PS plate G was treated in exactly the same manner as in Example 5.
At this time, the exposed portion was not dissolved and could not be developed. Embodiment 6 Excluding tetrahydrophthalic anhydride from the photosensitive solution of Example 5
Otherwise, a PS plate H produced in the same manner as in Example 5 was used.
Treated in exactly the same way as in Example 5. To the developer in the exposed area
Was delayed, resulting in a slight decrease in sensitivity.
The lithographic printing plate showed good printing durability and chemical resistance. Example 7 The tetrahydrophthalic anhydride of the photosensitive solution of Example 5 was
Except for changing to the maleic acid, all were prepared in the same manner as in Example 5.
The treated PS version I was treated in exactly the same way as in example 5. This
PS plate was excellent in developability, had sufficient sensitivity, and was obtained.
As a result of evaluating the printing plate, sufficient printing durability and chemical resistance were obtained.
Was. Tables 1 and 2 below show the above Examples and Comparative Examples.
The results are summarized. All embodiments of the present invention are relatively low
Both pH developability and film strength (printing and chemical resistance)
Printable, almost equivalent to conventional high pH development system
Performance was obtained. In the table, each component is as follows
Show. binder a-1: Phenol-formaldehyde resin a-2: m-cresol-formaldehyde resin Polyhydroxy compound b-1: Pyrogallol-acetone resin b-2: m-cresol-formaldehyde resin b-3: trihydroxybenzophenone pH12.5 soluble resin MMA / MA: Methyl methacrylate / methacrylic acid copolymer Development accelerator THPA: Tetrahydrophthalic anhydride MALA: Maleic anhydride Developer A and B are described in Examples 1 and 3, respectively.
thing [0103] [Table 1]                   Example 1 Example 2 Example 3 Example 4 Comparative Example 1 ─────────────────────────────────── PS version A B A C D ─────────────────────────────────── (Support) Hydrophilic treatment silicate silicate silicate silicate silicate silicate Organic undercoat layer Phenylphosphon phenyl phosphon phenyl phosphon phenyl phosphon phenyl phosphone                   Acid Acid Acid Acid Acid ─────────────────────────────────── (Photosensitive layer) Binder a-1 a-1 a-1 a-1 a-1 Trinuclear or higher components   95.5 95.5 95.5 95.5 88.6 Weight average molecular weight 13,500 13,500 13,500 13,500 8,400 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− pH12.5 soluble resin − MMA / MA − − − Weight average molecular weight-60,000--- −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Polyhydroxy         Compound b-1 b-1 b-1 b-2 b-1 o-Naphthoquinone thiocyanate compound Weight average molecular weight 2,500 2,500 2,500 3,200 2,500 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Development accelerator THPA THPA THPA THPA THPA ─────────────────────────────────── Developer solution   Buffer D-Saccharose D-Saccharose D-Sorbid D-Saccharose D-Saccharose   pH 12.5 12.5 12.5 12.5 12.5 ─────────────────────────────────── Sensitivity (clear / solid) 4.5 / 11.5 4.5 / 11.5 4.5 / 11.5 4.5 / 11.5 4.8 / 12.0 ─────────────────────────────────── Printing durability (number of sheets) 100,000 100,000 100,000 100,000 83,000 ─────────────────────────────────── Chemical resistance (number) 80,000 80,000 80,000 83,000 56,000 ─────────────────────────────────── [0104] [Table 2]                   Example 5 Comparative Example 2 Comparative Example 3 Example 6 Example 7 ─────────────────────────────────── PS version EFGHI ─────────────────────────────────── (Support) Hydrophilic treatment----- Organic undercoat layer Triethanol triethanol Triethanol triethanol triethanolamine hydrochloride Amine hydrochloride Amine hydrochloride Amine hydrochloride Amine hydrochloride ─────────────────────────────────── (Photosensitive layer) Binder a-1 a-1 a-2 a-1 a-1 Trinuclear or higher components   94.6 94.6 86.5 94.6 94.6 Weight average molecular weight 13,500 13,500 4,800 13,500 13,500 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− pH12.5 soluble resin − − − − − Weight average molecular weight----- −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Polyhydroxy         Compound b-1 b-3 b-1 b-1 b-1 o-Naphthoquinone thiocyanate compound Weight average molecular weight 2,500 870 2,500 2,500 2,500 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Development accelerator THPA THPA THPA − MALA ─────────────────────────────────── Developer solution   Buffer D-Saccharose D-Saccharose D-Saccharose D-Saccharose D-Saccharose   pH 12.5 12.5 12.5 12.5 12.5 ─────────────────────────────────── Sensitivity (clear / solid) 4.5 / 11.5 4.5 / 11.5 Not developable 4.0 / 11.0 4.7 / 11.7 ─────────────────────────────────── Printing durability (number of sheets) 100,000 87,000 − 100,000 100,000 ─────────────────────────────────── Chemical resistance (number) 82,000 68,000 − 82,000 82,000 ─────────────────────────────────── Embodiment 8 0.24mm thick aluminum plate and nylon brush
Surface using 400 mesh pumicestone-water suspension
Was grained and washed well with water. 10% hydroxide
Etched in thorium at 70 ° C for 20 seconds
After that, it is washed with running water and then 20% HNO_ThreeWith neutralization washing,
Washed with water. Under the condition of VA = 12.7V, the sine wave
400 coulombs in 0.7% nitric acid aqueous solution using waveform current
In / dm^TwoThe electrolytic surface roughening treatment was performed with the quantity of electricity. This group
The aluminum plate of the surface is placed in a 10% aqueous sodium hydroxide solution.
0.9 g / m^TwoIt was processed to become. water
After washing, neutralize and wash in a 20% nitric acid solution to remove smut.
18% H_TwoSO_FourIn aqueous solution, the amount of oxide film is 3
g / m^TwoAnodized so that Then, at 35 ° C,
Hydrophilic treatment was performed with a 2% aqueous solution of sodium silicate. What
Note that the hydrophilic treatment may not be performed. Thus produced
On the support, the undercoating liquid a having the following composition was converted into a weight of 1 after drying.
0mg / m^TwoAnd dried at 90 ° C for 1 minute
Then, an undercoat layer was provided. Undercoat liquid a   Phenylphosphonic acid 0.06 g   0.12 g of sulfuric acid   100 g of methanol Subsequently, a photosensitive solution having the following composition was prepared, and
1.8 g / m in weight after drying on the substrate^TwoSo that
A photosensitive layer was provided. Photosensitive liquid   Phenol-formaldehyde resin   (95.5% by weight of trinuclear or higher component content,     Molecular weight 13,500) 1.9 g   1,2-diazonaphthoquinone-5-sulfonyl chloride and   Esterified product with pyrogallol-acetone resin   (Molecular weight 2,500) 0.76 g   0.2 g of tetrahydrophthalic anhydride   4- [p-N- (p-hydroxybenzoyl) aminophenyl]   -2,6-bis (trichloromethyl) -s-triazine 0.02 g   Victoria Pure Blue BOH   (Manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.03 g   Mega Fuck F-177   (Fluorine surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.006 g   15 g of methyl ethyl ketone   Propylene glycol monomethyl ether 15g The surface of the photosensitive layer thus formed is
Spray the mat layer forming resin liquid as described above
Layers were provided. Methyl methacrylate as a resin solution for mat layer formation
Relate / ethyl acrylate / acrylic acid (charged weight
Ratio 65:20:15) Part of the copolymer is sodium salt
A 12% aqueous solution was prepared and sprayed with a rotary atomizing electrostatic coating machine.
The head rotation speed is 25,000 rpm, and the amount of resin solution sent is 40
ml / min, the applied voltage to the atomizing head is -90 kv,
The ambient temperature was 25 ° C. and the relative humidity was 50%.
Spray steam on the coated surface in 5 seconds to wet, then wet
After 3 seconds, blow hot air at a temperature of 60 ° C and a humidity of 10% for 5 seconds.
Squeezed and dried. The height of the mat is about 6μm and the size
Is about 30 μm, the number is 150 / mm^TwoMet. this
PS plate A obtained in this way is 1,003 mm x 800 m
m, and prepare a manuscript file
3km metal halide rider from 1m distance through LUM
Exposure was performed for 60 seconds using a pump. Next, immersion type developing tank
Has a commercially available automatic processor PS-900V (Fuji Photo
Lum Co., Ltd.) in the developing tank
18 liters of pH 12.5 developer solution diluted 9 times with water
The mixture was heated to 30 ° C. Automatic developing machine PS-90
Tap water is automatically supplied to the washing bath, which is the second bath of 0V.
It is supplied so that the PS plate can be washed. 3rd bath
FP-2 (Fuji Photo Film)
Finishing liquid obtained by diluting (made by) with tap water
4 liters. Separately, the developer replenisher stock solution tank
Was prepared by charging 5 liters of the following stock solution 1 of a replenisher. Ma
Automatic developing machine PS-900V, PS plate processing and air
Built-in reduction of developer activity due to carbon dioxide gas inside
Is detected by a conductivity sensor that is
With the feedback control of the computer, the stock solution of the developing replenisher
Developing replenisher diluted with water at a ratio of 5 to 1
Replenish. As a result, the developer solution stored in the developing tank is removed.
Is kept almost constant. The automatic processor PS-
900V has a conductivity setting range of 4
0.0 to 80.0 ms / cm.
Modified to an automatic processor PS-900V to measure conductivity.
Construction. The set value of the conductivity is 25.0 ms / c.
m. Other conditions are standard conditions of PS-900V
And [0108] <Developer stock solution 1>   D-saccharose 45.0% by weight   4.5% by weight of sodium hydroxide   6.5% by weight of sodium carbonate   Tetrabutylammonium bromide 0.27% by weight   43.73% by weight of water <Development replenisher stock solution 1>   D-saccharose 45.0% by weight   Sodium hydroxide 7.1% by weight   4.7% by weight of sodium carbonate   Tetrabutylammonium bromide 0.3% by weight   42.9% by weight of water Under these conditions, the above-described exposed
120 editions per day, Saturday, Sunday and holidays
Every day, except for days, treatment was performed for 6 months. Activity che
The tablet is a step tablet (the optical density difference of one stage is 0.
15 and 15 steps), and the light amount is changed stepwise.
The PS plate is baked and developed,
Read the number of remaining image steps corresponding to the amount of light and start processing
This was done by comparing with the number of stages at the time. 6 month test
Solid portion of the step tablet (image remaining portion)
Was maintained at 11 stages, and stable processing was maintained.
After processing, the developer A was removed from the developing tank,
No insoluble deposits were found at the bottom. Also, conductivity
When I checked the surface of the sensor,
In good condition. Comparative Example 4 The surface of an aluminum plate with a thickness of 0.30 mm is
Using a brush and an aqueous suspension of 400 mesh pamistone
After sanding, it was washed well with water. 10% hydroxide
Etched by dipping in thorium at 70 ° C for 60 seconds
After washing with running water, 20% HNO_ThreeNeutralizing and washing with water
Was. This is V_A= 12.7V alternating wave of sine wave under the condition of 12.7V
160 coulomb / d in 1% nitric acid aqueous solution
m^TwoThe electrolytic surface roughening treatment was performed with the amount of electricity at the time of anode. The table
When the surface roughness was measured, it was 0.6 μ (Ra display).
Was. Subsequently, 30% H_TwoSO_FourDipped in aqueous solution 5
After desmutting at 5 ° C for 2 minutes, 20% H_TwoSO_FourWater soluble
In the solution, place the cathode on the grained surface,
A / dm^Two2.7 g / m in thickness^TwoTo be
Anodizing was performed to produce a substrate. In addition, the sun on the back side at this time
The extreme oxide film is approximately 0.2 g / m2 at the center of the substrate.^Two,edge
About 0.5g / m^TwoMet. Next, the surface of the substrate
The following photosensitive solution I was applied to the mixture, and the applied weight after drying was 2.5 g.
/ M^TwoThe photosensitive layer was provided so that [0111] Photosensitive solution I   1,2-diazonaphthoquinone-5-sulfonyl chloride and   Esterified product with pyrogallol-acetone resin   (As described in Example 1 of U.S. Pat. No. 3,635,709)                                                           45 parts by weight   Cresol formaldehyde novolak resin 110 parts by weight   2- (p-methoxyphenyl) -4,6-   Bis (trichloromethyl) -s-triazine 2 parts by weight   Oil blue $ 603   (Orient Chemical Industry Co., Ltd.) 1 part by weight   Mega Fuck F-177   (Dai Nippon Ink Chemical Industry Co., Ltd., fluorine surfactant) 0.4 parts by weight   1000 parts by weight of methyl ethyl ketone   Propylene glycol monomethyl ether 1000 parts by weight On the surface of the photosensitive layer thus prepared,
Spray the mat layer forming resin liquid as follows and
Thus, a PS plate J provided with a cut layer was obtained. Mat layer forming resin liquid
As methyl methacrylate / ethyl acrylate /
Acrylic acid (65:20:15 charged weight ratio) copolymer
Prepare a 12% aqueous solution with a part of
Atomizing head rotation speed of 25,000 rpm with atomizing electrostatic coating machine,
40 ml / min of resin solution flow rate, applied voltage to atomization head -9
0kv, ambient temperature at the time of application 25 ° C, relative humidity 50%
2.5 seconds after application, steam is sprayed on the application surface
3 seconds after wetting, at a temperature of 60 ° C and a humidity of 10%
Hot air was blown for 5 seconds to dry. The height of the mat is flat
Average 6μm, average size 30μm, coating amount 150
mg / m^TwoMet. PS plate J obtained in this way
Was cut into a size of 1,003 mm x 800 mm.
1m
Using a 3 kw metal halide lamp from a distance of 6
Exposure was for 0 seconds. Next, the following developer 2 and development replenishment were performed.
A concentrated stock solution of Liquid 2 was prepared. <Developer stock solution 2>   [SiO_Two] / [K_TwoO] molar ratio 1.2,     SiO_Two1000 parts by weight of 12.2% by weight aqueous potassium silicate solution   2 parts by weight of polyoxyethylene (additional mole number n = 12) sorbitol <Development replenisher stock solution 2>   [SiO_Two] / [K_TwoO] molar ratio 1.0,     SiO_Two1000 parts by weight of 19.9% by weight aqueous solution of potassium silicate   Polyoxyethylene (additional mole number n = 12) sorbitol 4 parts by weight Commercially available automatic developing machine P having an immersion type developing tank
Developing tank for S-900V (Fuji Photo Film Co., Ltd.)
The pH of the above-mentioned undiluted developer 2 was diluted 9 times with tap water.
18 liters of the developer C of 13.1 was charged. Separately,
The image replenisher stock solution supply tank contains the above-described developer replenisher stock solution 2
Was charged in 5 liters. Under these conditions,
Exposed PS plate J processed 120 plates per day
did. During the treatment, the treatment of PS plate J and carbon dioxide in air
Built-in PS900-V reduces developer activity drop
Detected by the conductivity sensor that is
Replenishment by computer feedback control
Developing replenisher diluted at a ratio of water 6.5 to liquid stock solution 2
To the developer tank to reduce the activity of the developer C in the developer tank.
Kept constant. The set value of the conductivity is 62.5 ms /
cm. Activity check, step tablet
(One step optical density difference of 0.15 and 15 steps)
Change the amount of light step by step and print on the PS plate J
Is developed, and the remaining image corresponding to the amount of light on the plate
Is read and compared with the number of stages at the start of processing.
I did it. From about 3 months, step tablet
The number of stages started to rise gradually. So we developed from the developing tank
When the solution was removed, a deposit of insoluble material was found at the bottom of the developing tank.
Product was seen. In addition, the surface of the conductivity sensor
Had adhered.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic sectional view of an automatic developing machine to which a method for processing a photosensitive lithographic printing plate according to an embodiment of the present invention is applied. FIG. 2 is a control flowchart of replenishment of a developing replenisher to a developing tank by a control unit. FIG. 3 is a control flowchart of replenishment of a developing replenisher to a developing tank by a control unit. [Description of Signs] 10 Photosensitive lithographic printing plate (PS plate) 20 Developing unit 21 Developing tank 33 Circulating pump 34 Sensor 35 Developing replenisher stock solution tank 37 Stock solution replenishing pump 50 Washing unit 57 Washing tank 59 Water refilling pump 60 Finisher unit

Continuation of the front page (56) References JP-A-60-143345 (JP, A) JP-A-2-96164 (JP, A) JP-A-55-25100 (JP, A) JP-A-63-200154 (JP) JP-A-61-162049 (JP, A) JP-A-7-114178 (JP, A) JP-A-8-272092 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) G03F 7/00-7/42

Claims (1)

(57) Claims 1. A photosensitive lithographic printing plate having a photosensitive layer containing o-naphthoquinonediazidesulfonic acid ester,
It contains no silicate, contains at least one compound selected from the group consisting of sugars, oximes, phenols, and fluorinated alcohols, and has a pH of 10.0 to 1
While developing with the developing solution in the range of 2.7, the deterioration of the developing solution caused by the processing of the photosensitive lithographic printing plate is detected by measuring the conductivity or impedance of the developing solution. A method for processing a photosensitive lithographic printing plate, wherein the activity of the developer is maintained substantially constant by replenishing the replenisher based on the replenisher.