JP2003084450A - Plate making method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plate making method which is economical because separate development-processing lines for a photopolymerizable photosensitive planographic printing plate and a key plate are not prepared, diminishes waste liquor owing to a reduced replenishment amount to contribute toward solving environmental problem, ensures stable developability for both the photopolymerizable photosensitive planographic printing plate and the key plate and can be appropriately applied to a planographic printing plate for newspaper free of printing stain and ensuring satisfactory printing resistance. SOLUTION: In the plate making method in which a photopolymerizable photosensitive planographic printing plate obtained by disposing a photopolymerizable photosensitive layer and an oxygen intercepting layer in order on an aluminum support having a hydrophilic surface and a key plate obtained by disposing a non-photosensitive resin layer on an aluminum support having a hydrophilic surface are development-processed in the same automatic developing machine, replenishment amounts to the prewashing tank and developing tank of the automatic developing machine are automatically varied according to the plate material to be processed.

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a photopolymerizable photosensitive lithographic plate.
Automatic development of printing plate (hereinafter also referred to as photosensitive material) and discarded plate
It relates to a plate making method characterized by processing with a machine
is there. More specifically, a separate development processing line is prepared.
It is economical without waste, and it reduces waste liquid by reducing the replenishment amount.
Responding to environmental problems and photopolymerizable photosensitive lithographic printing
Stable developability is obtained for both the plate and the discarded plate, and printing stains
Lithographic printing plate for newspapers with sufficient printing durability
It relates to a plate making method that can be suitably used for
is there. [0002] [0002] When performing color newspaper printing, all
Since the paper surface is often not colored, it is simply not colored.
On cyan, magenta, and yellow cylinders on colored paper
Requires a full non-image part. Conventionally, CTP
(Puputer to Plate)
When performing color printing in newspapers, develop the photosensitive material unexposed.
Or a discard version for the conventional PS version
It was developed with an automatic machine for conventional PS plates.
However, it is uneconomical and the development system has two lines.
There was a need to prepare and a place. In addition, the same automatic developing machine can be used for the photopolymerizable photosensitive flat plate.
Even if the printing plate and the discarding plate are processed, the layer structure of both
The material and amount applied are different, and depending on the day
Use newspaper photopolymerizable photosensitive lithographic printing plates and discarded plates
Replenishment same as photopolymerizable photosensitive lithographic printing plate due to different amount
The pre-washing section is unnecessary for the discarded plate, so the waste liquid increases.
In addition, the pH of the developer could not be controlled to be constant. That
Therefore, when the pH rises, the damage to the image area increases and
When the printability decreases and the pH decreases, the developability decreases and the dots
There were problems such as gain and printing stains. [0004] SUMMARY OF THE INVENTION The problem of the present invention is that light weight
Separate development processes for photosensitive photosensitive lithographic printing plates and discarded plates
Economical without preparing a line, to reduce the replenishment amount
Responding to environmental problems by reducing waste liquid and photopolymerization
Stable developability was obtained for both photolithographic printing plates and discarded plates
Newspaper that does not cause printing stains and provides sufficient printing durability
A plate making method that can be suitably used for lithographic printing plates
Is to provide. [0005] [Means for Solving the Problems] The hydrophilicity of the present invention
On an aluminum support having a surface, at least in order
Next, a photopolymerizable photosensitive layer and an optical layer provided with an oxygen blocking layer
Compatible photosensitive lithographic printing plate and aluminum having hydrophilic surface
Discarded plate with non-photosensitive resin layer provided on the um support
In the plate making method of developing with the same automatic processor,
Depending on the plate material to be processed, the pre-washing tank and development of the automatic processor
By the plate making method that automatically changes the tank replenishment amount,
The problem can be solved. [0006] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Details on plate making method of photosensitive photosensitive lithographic printing plate and discarded plate
Explained. FIG. 1 shows an automatic processor 1 used in the present invention.
It is explanatory drawing which shows one form. First, CTP system
Basically, from laser exposure setter and automatic processor 1
Computer for linking to higher-level systems.
It consists of a computer system. First photopolymerizable photosensitive lithographic printing
Both the plate and the discarded plate in the cassette of the laser exposure setter
Housed and photopolymerizable photosensitive lithographic printing according to instructions from the host
The plate is image-exposed and automatically conveyed to the automatic processor 1,
Developed. On the other hand, the discarded plate is laser-exposed.
It is automatically conveyed through the setter without any change.
Sent to the automatic processor 1. Automatic developing machine for photopolymerizable photosensitive lithographic printing plates
1 includes, for example, a heating unit 11, a pre-washing tank 12,
From image tank 13, washing tank 14, gum tank 15, and drying unit 16
Become. The heating unit 11 may be omitted in some cases.
Yes. In the pre-washing tank 12, a photopolymerizable photosensitive lithographic plate.
Remove the oxygen barrier layer of the printing plate with water. As the development process proceeds
As a result, the concentration of the water-soluble resin dissolved in the pre-washing tank 12 increases.
In addition, the dissolution and removal properties are inferior and waste is generated.
Replenishment is necessary. On the other hand, the discarded version had no oxygen barrier
Therefore, no replenishment of water is required when discarding plates are processed.
In the present invention, photopolymerizable photosensitive lithographic printing plate and disposal
Change the replenishment amount of water etc. according to the processing amount of each plate material.
By maintaining the pre-wash tank 12 in an appropriate state
can do. Note that the power of the automatic processor 1 is turned on.
Pre-wash tank 12 when it is turned off
Because water volatilizes naturally from the photopolymerizable photosensitive lithographic stamp
Separately from the processing amount of printing plates and discarded plates,
It is preferable to replenish water. In the developing tank 13, light is generated by an alkali developer.
Removing unexposed areas of the polymerizable photosensitive lithographic printing plate
Then, the non-photosensitive resin layer of the discarded plate is removed. Photopolymerizable photosensitivity
Material and coating amount applied to lithographic printing plates and discarded plates
The pH can be kept constant with the same replenishment amount.
Absent. In the present invention, a photopolymerizable photosensitive lithographic printing plate and
Depending on the processing amount of each plate material,
By changing the replenishment amount of the stock solution etc.
The pH and the like can be maintained in an appropriate state. Automatic
When the power of the developing machine 1 is ON or OFF
The pH will drop naturally with carbon dioxide in the atmosphere.
What is the processing amount of photopolymerizable photosensitive lithographic printing plates and discarded plates?
In addition, it is a supplement to restore the pH lowered by carbon dioxide to a certain level.
It is preferable to charge. In the washing tank 14, it remains on the surface of the developed plate.
Remove the alkaline developer, and go to the gum tank 15 of the next process
Rinse the plate with water to reduce the amount of alkaline liquid
The Thus, in particular, photopolymerizable photosensitive lithographic printing plates and discarded plates
Without distinguishing the same amount so that the washing water will not deteriorate
Should be replenished. Note that the power of the automatic processor 1 is turned on.
When it is turned off or turned off, the water volatilizes naturally
Replenish the same amount of water as the volatilized amount
It is preferable to do. In the gum tank 15, gum is applied and alkali
The sensitive photosensitive resin is returned to acid and the image area is developed by development.
Suppresses damage and prevents dirt and scratches on non-image areas
To do. Gum is applied to the entire surface regardless of image and non-image areas
Therefore, separate photopolymerizable photosensitive lithographic printing plates and discarded plates
If you replenish the same amount of gum replenishment stock solution etc.
Good. If the automatic processor is turned on or
When FF is selected, water volatilizes naturally.
Volatile separately from the throughput of the photosensitive photosensitive lithographic printing plate and discarded plate
It is preferable to replenish the same amount of water as the water that has been removed. Next, the discarded version of the present invention will be described.
The undercoat layer of the discarded plate of the present invention will be described. Hydrophilic surface
Undercoat with water-soluble compounds shown below
You may give it. Water-soluble compounds used for undercoating
For example, carboxymethylcellulose, dex
Thrin, gum arabic, 2-aminoethylphosphonic acid
Any amino group-containing phosphonic acid or substituent
Good phenylphosphonic acid, naphthylphosphonic acid, alkyl
Ruphosphonic acid, glycerophosphonic acid, methylene diphospho
Organic phosphones such as acid and ethylene diphosphonic acid
Acid, phenylphosphoric acid optionally substituted, naphthyl
Organics such as acid, alkyl phosphate and glycerophosphate
Phosphoric acid, optionally substituted phenylphosphinic acid,
Naphthyl phosphinic acid, alkyl phosphinic acid and
Organic phosphinic acids, such as lysophosphinic acid, glycine
And amino acids such as β-alanine, and triethanol
Amines with hydroxyl groups such as hydrochloride of ruamine
And water-soluble polymers having sulfonic acid groups are preferred.
Water-soluble polymerization, especially with sulfonic acid groups
The body is particularly preferred. A water-soluble polymer having a sulfonic acid group is
Repeat at least one monomer unit having a sulfonic acid group.
A water-soluble polymer compound contained in the molecule as a repeating unit.
For example, Japanese Patent Publication No. 4-9296 (column 3, line 22 to
(4th column, 41st line). Sulfonic acid
As a monomer unit having a group, for example, p-styrene
Sulfonic acid, 2-acrylamido-2-methylpropane
Preferred are sulfonic acid, ethylene sulfonic acid, etc.
1 or 2 are appropriately selected and polymerized.
Or copolymerized with other monomers. Co-weight with other monomers
When combined, the partner monomer has a sulfonic acid group
Any monomer can be copolymerized with the monomer
Yes. Specific examples include, for example, methyl methacrylate / ether.
Tyl acrylate / 2-acrylamido-2-methyl group
Sodium lopansulfonate, methyl methacrylate /
Methyl acrylate / p-styrene sulfonate sodium
And sodium polystyrene sulfonate
The The molecular weight range of the water-soluble compound of the present invention is water-soluble.
There is no limit as long as there is, but if you give a general guide, weight average
A molecular weight range of about 1000 to 1000000 is appropriate.
Preferably 2000-100000, most preferably
Is in the range of 10,000 to 100,000. This subbing layer is composed of water, methanol, ethanol.
, Isopropyl alcohol, methyl ethyl ketone, etc.
Alternatively, the above compound is dissolved in a mixed solvent thereof,
It can be applied and dried on a support. Undercoat
The coating layer after drying is 10 to 500 mg / m²Is appropriate
Preferably 50 to 200 mg / m²It is. 1 undercoat
0mg / m²If it is less, the ability to prevent printing stains will be insufficient. under
Coating layer is 500mg / m²More, non-photosensitive applied later
The film strength of the conductive resin layer decreases and scratches are prevented by handling
Ability is reduced. A non-photosensitive resin layer is provided following the undercoat layer.
It is done. Preferred as the resin is an acid content of 0.1 to
3.0 meq / g, preferably 0.2 to 2.0 meq / g
Substantially water-insoluble (ie, neutral or acidic water
Organic polymer compound that is insoluble in the liquid and has film-forming properties
It can be dissolved or swelled in an alkaline aqueous solution.
What can be done is preferred. The acid content is less than 0.1 meq / g
Is difficult to dissolve, especially when it exceeds 3.0 meq / g
The strength of the film during storage at high temperature and high humidity is significantly weakened. Non-photosensitive
Resin molecular weight is dissolved in coating solvent and alkaline aqueous solution
There is no limit as long as it dissolves or swells, but the weight average molecule
1000 to 1000000 in quantity, preferably 10,000
~ 500,000. If the molecular weight is low, the film strength is weak,
High molecular weight degrades solubility. A particularly suitable non-photosensitive resin is acrylic.
Essential acid, methacrylic acid, crotonic acid or maleic acid
Copolymers contained as components, for example, JP-A-50-1188
2-Hydroxyethyl as described in No. 02
Acrylate or 2-hydroxyethyl methacrylate
, Acrylonitrile or methacrylonitrile,
Rilic acid or methacrylic acid and other co-polymers as required
Multicomponent copolymer with polymerizable monomers, JP-A-53-12
The terminal as described in No. 0903 is hydroxy.
A group containing a dicarboxylic acid ester residue
Stealted acrylic or methacrylic acid, acrylic
Luric acid or methacrylic acid and other copolymers as required
Multi-component copolymers with possible monomers, JP-A-54-986
Terminate an aromatic hydroxyl group as described in Japanese Patent No. 14
Monomer (for example, N- (4-hydroxypheny
E) Methacrylamide etc.), acrylic acid or methacrylate
With rilic acid and optionally other copolymerizable monomers
A multi-component copolymer described in JP-A-56-4144
Alkyl acrylate, acrylonitrile
Or from methacrylonitrile and unsaturated carboxylic acid
Can be mentioned. In addition, acidic
Polyvinyl alcohol derivatives and acidic cellulose derivatives
Useful. Polyvinyl acetal and polyurethane
Japanese Patent Publication No. 54-19773, which has been solubilized with alkali,
JP-A-57-94747, JP-A-60-182437,
Of 62-58242 and 62-123453
Binders are also useful, solubilizing polyurethane with alkali
Resin having high film strength is particularly preferable. The non-photosensitive resin layer composition has various known coatings.
Aluminum that dissolves in a solvent and has a hydrophilic surface and subbing layer
The dry coating weight on the um support is 0.2 to 3.0 g / m.²When
Preferably, 0.3 to 1.5 g / m²To be
Can be applied and dried to obtain a lithographic waste plate
The Application amount is 0.2g / m²If it is less, scratches will be prevented
Insufficient capacity, conversely 3.0g / m²The above is the ability to prevent scratches
It is sufficient as a force, and the dissolution speed at the time of dissolution removal decreases.
In addition, the processing capacity of the solution is reduced. When applying
The solid content concentration of the resin layer composition is suitably 1.0 to 50% by weight.
Preferably, 2.0 to 30% by weight is appropriate.
The As a method of applying the resin layer composition on the support,
Known methods such as roll coating, bar coating
Coating, spray coating, curtain coating
A method such as coating or spin coating can be used. Applied
The resin layer composition solution should be dried at 50 to 150 ° C.
preferable. The drying method is to pre-dry by lowering the temperature at the beginning.
After drying, it may be dried at a high temperature or directly at a high temperature.
May be allowed. For the non-photosensitive resin layer, various additives such as
For example, pigments for distinguishing coating layers,
Coating with plasticizer, low molecular acid compound, fluorine surfactant, etc.
A cloth surface quality improving agent can be added. In particular, Zippi
Choline acid, malic acid, sulfosalicylic acid, sulfophthalate
Carboxylic acid group such as acid, tricarballylic acid or sulfone
Low-molecular acid compounds containing acid groups have a
Furthermore, it has an effect of preventing printing stains during long-term storage, which is preferable. Ma
Fluorosurfactants can only be applied to improve the coating surface quality.
Therefore, there is an effect of improving resistance to scratches, which is preferable. Low molecular acid
The compound is contained in an amount of 1 to 20 wt%, non-photosensitive resin layer.
The fluorine-based surfactant is added in an amount of 0.1 to 5 wt%. Hydrophilic
The aluminum support having a surface is photopolymerizable as described later.
The same photosensitive lithographic printing plate can be used. Next, the photopolymerizable photosensitive lithographic printing plate of the present invention.
Will be described. Photopolymerizable lithographic printing plate used in the present invention
The photopolymerization type photosensitive composition constituting the photosensitive layer is addition polymerization.
Possible ethylenically unsaturated compounds, photopolymerization initiators, polymers
A binder is an essential component, and if necessary, colorants, plasticizers,
Various compounds such as thermal polymerization inhibitors can be used in combination.
The The ethylenically unsaturated compound is a photopolymerization type feeling.
When the photocomposition is irradiated with actinic rays, a photopolymerization initiator
Ethylene that undergoes addition polymerization, crosslinking, and curing by the action of
A compound having an unsaturated bond. Addition polymerization possible
Compounds containing ethylenic double bonds are
Have at least one, preferably two or more saturated bonds
Any one of the compounds can be selected. For example
Nomers, prepolymers, ie dimers, trimers and
Oligomers or mixtures thereof as well as
It has a chemical form such as a polymer. As examples of monomers and copolymers thereof
Unsaturated carboxylic acids (e.g. acrylic acid, methacrylate)
Formic acid, itaconic acid, crotonic acid, isocrotonic acid, male
Esthetic acid etc. and aliphatic polyhydric alcohol compounds
Of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound
And the like. Non-aliphatic polyhydric alcohol compounds
Specific examples of ester monomers with saturated carboxylic acids
As the acrylic ester, ethylene glycol di-
Acrylate, triethylene glycol diacryl
1,3-butanediol diacrylate, tetrameth
Tylene glycol diacrylate, propylene glycol
Rudiacrylate, neopentyl glycol diacrylate
, Trimethylol propane triacrylate, tri
Methylolpropane tri (acryloyloxypropiyl
E) Ether, Trimethylolethane Triacrean
Hexanediol diacrylate, 1,4-cyclo
Hexanediol diacrylate, tetraethylene glycol
Cold diacrylate, pentaerythritol diacryl
Rate, pentaerythritol triacrylate, pen
Taerythritol tetraacrylate, dipentaeryth
Ritol diacrylate, dipentaerythritol pen
Acrylate, dipentaerythritol hexaacrylate
Rate, sorbitol triacrylate, sorbitol
Tetraacrylate, sorbitol pentaacrylate
, Sorbitol hexaacrylate, tri (acrylo
Yloxyethyl) isocyanurate, polyester
Examples include acrylate oligomers. Methacrylic acid esters include tetrameth
Tylene glycol dimethacrylate, triethylene glycol
Cold dimethacrylate, neopentyl glycol dimethyl
Tacrylate, trimethylolpropane trimethacrylate
, Trimethylolethane trimethacrylate, ethyl
Lenglycol dimethacrylate, 1,3-butanedio
Dimethacrylate, hexanediol dimethacrylate
, Pentaerythritol dimethacrylate, penta
Erythritol trimethacrylate, pentaerythritol
Tetramethacrylate, dipentaerythritol di
Methacrylate, dipentaerythritol hexametac
Relate, dipentaerythritol pentamethacrylate
Sorbitol trimethacrylate, sorbitol
Tetramethacrylate, bis [p- (3-methacrylo
Xyl-2-hydroxypropoxy) phenyl] dimethyl
Methane, bis- [p- (methacryloxyethoxy) phenyl
Nenyl] dimethylmethane and the like. Itaconic acid esters include ethylene glycol
Recall Diitaconate, Propylene Glycol Diita
Conate, 1,3-butanediol diitaconate,
1,4-butanediol diitaconate, tetramethyle
Glycol diitaconate, pentaerythritol di
Itaconate, sorbitol tetritaconate, etc.
The As crotonic acid ester, ethylene glycol
Dicrotonate, tetramethylene glycol dicrotone
, Pentaerythritol dicrotonate, sorbite
And tetratetracrotonate. Isocrotonic acid
As stealth, ethylene glycol diisocrotonate
, Pentaerythritol diisocrotonate, sorbi
Examples include tall tetraisocrotonate. Maleic acid esters include ethylene glycol
Recall dimaleate, triethylene glycol dimale
, Pentaerythritol dimaleate, sorbitol te
There are trauma rates. In addition, the ester monomers described above
-Can also be mentioned. In addition, aliphatic polyvalent polymers
Of amide monomer of amine compound and unsaturated carboxylic acid
Specific examples include methylene bis-acrylamide, methyl.
Renbis-methacrylamide, 1,6-hexamethylene
Bis-acrylamide, 1,6-hexamethylene bis-
Methacrylamide, diethylenetriamine trisacryl
Luamide, xylylene bisacrylamide, xylylene
Examples include bismethacrylamide. Other examples include Japanese Patent Publication No. 48-417.
Two or more a) molecules per molecule described in No. 08
To the polyisocyanate compound having a socyanate group,
Vinyl containing a hydroxyl group represented by the following general formula (A)
Two or more polymerizable polymers in one molecule with added monomers
And vinyl urethane compounds containing nyl groups.
The [0026]   CH₂= C (R^Five) COOCH₂CH (R⁶) OH (A) (However, R^FiveAnd R⁶Is H or CH
_ThreeIndicates. ) Japanese Patent Laid-Open No. 51-37193, Japanese Patent
Urethane action as described in No. 2-32293
Relates, JP-A-48-64183, JP-B-49-
No. 43191 and Japanese Patent Publication No. 52-30490
Polyester acrylates, such as epoxies
Epoxy actives made by reacting a resin with (meth) acrylic acid
Polyfunctional acrylates and methacrylates such as relates
Can be mentioned. Furthermore, Vol. 2
0, No. 7, light on pages 300-308 (1984)
Introduced as curable monomers and oligomers
Things can also be used. In addition, these ethylenic
The amount of unsaturated compound used is from 5 to 80% by weight of the total components of the photosensitive layer.
%, Preferably in the range of 30 to 70% by weight. The photosensitive layer of the photopolymerizable lithographic printing plate of the present invention
The photopolymerization initiator contained in the
Depending on the length, various photoinitiators known in patents, literature etc.,
Or use a combination system (photoinitiation system) of two or more photoinitiators.
It can be selected and used appropriately. Specific examples are listed below.
However, it is not limited to these. 400nm or more
Visible light, Ar laser, second harmonic of semiconductor laser
When using a wave or SHG-YAG laser as the light source,
Various photoinitiator systems have been proposed, for example, U.S. Pat.
Certain photoreducible dyes described in US Pat. No. 2,850,445;
For example, Rose Bengal, Eosin, Erythrosine,
Or a system with a combination of dye and initiator, eg
For example, a complex starting system of dye and amine (Japanese Examined Patent Publication No. 44-2018)
9), hexaarylbiimidazole and radical generation
Combined use of dye and dye (Japanese Examined Patent Publication No. 45-37377), f
Oxaarylbiimidazole and p-dialkylaminobenzene
Nylidene ketone system (Japanese Patent Publication No. 47-2528, JP
Sho 54-155292), cyclic cis-α-dicarbonyl
Compound and dye system (Japanese Patent Laid-Open No. 48-84183), ring
Triazine and Merocyanine Dye System (JP 54-1)
51024), 3-ketocoumarin and activator system
JP 52-112681, JP 58-15503
No.), biimidazole, styrene derivatives, thiol systems
(JP 59-140203 A), organic peroxides and dyes
(Japanese Patent Laid-Open Nos. 59-1504, 59-1402)
03, JP 59-189340, JP 62-1
74203, Japanese Examined Patent Publication No. 62-1641, US Patent No. 4
766055), dyes and active halogen compounds (special
No. 63-258903, JP-A-2-63054
A dye / borate compound system (Japanese Patent Laid-Open No. 62-1430)
44, JP-A-62-154042, JP-A-64-1
3140, JP-A 64-13141, JP-A 64-
13142, JP-A 64-13143, JP-A 64
No. 13144, JP-A 64-17048, JP-A 1
-229003, JP-A-1-298348, JP-A-1
1-138204, etc.) a dye having a rhodanine ring;
Radical generator system (JP-A-2-179634, JP-A-2
Hei 2-244050), titanocene and 3-ketokumari
Dye systems (Japanese Patent Laid-Open No. 63-221110), titanose
And xanthene dyes, amino groups or urethane groups
Combination of addition-polymerizable ethylenically unsaturated compounds containing
System (JP-A-4-221958, JP-A-4-21)
9756), of titanocene and certain merocyanine dyes
System (Japanese Patent Laid-Open No. 6-295061), titanocene and benzo
A dye system having a pyran ring (JP-A-8-334897)
No.). Recently, a wavelength of 400 to 410 nm has been recorded.
The laser (violet laser) was developed and felt
A photoinitiating system that exhibits high sensitivity at wavelengths below 450 nm
These photoinitiating systems are also used. example
For example, a cationic dye / borate system (Japanese Patent Laid-Open No. 11-8464).
7), merocyanine dye / titanocene system (Japanese Patent Laid-Open No. 2000)
-147763), carbazole type dye / titanocene system
(Japanese Patent Application No. 11-212480)
The Especially in the present invention, a system using a titanocene compound
However, it is preferable in terms of sensitivity. Various titanocene compounds are available.
For example, Japanese Patent Laid-Open No. 59-1523 can be used.
96, and JP-A 61-151197.
Select from various titanocene compounds
Can do. More specifically, di-cyclopentadieni
Ru-Ti-di-chloride, di-cyclopentadienyl
-Ti-bis-phenyl, di-cyclopentadienyl-
Ti-bis-2,3,4,5,6-pentafluorofe
Ni-1-yl, di-cyclopentadienyl-Ti-bis
-2,3,5,6-tetrafluorophen-1-yl,
Di-cyclopentadienyl-Ti-bis-2,4,6-
Trifluorophen-1-yl, di-cyclopentadie
Nyl-Ti-bis-2,6-di-fluorophen-1-
Yl, di-cyclopentadienyl-Ti-bis-2,4
-Di-fluorophen-1-yl, di-methylcyclope
Tantadienyl-Ti-bis-2,3,4,5,6-teto
Rafluorophen-1-yl, di-methylcyclopenta
Dienyl-Ti-bis-2,6-difluorophen-1
-Yl, di-cyclopentadienyl-Ti-bis-2,
6-Difluoro-3- (pyr-1-yl) -pheni-1
-Yl etc. can be mentioned. Further, 2-mer may be added to the photoinitiator as required.
Captobenzthiazole, 2-mercaptobenzimid
Thio such as sol, 2-mercaptobenzoxazole
Compounds, N-phenylglycine, N, N-dialkyl
Water such as amine compounds such as amino aromatic alkyl esters
Higher photoinitiating ability by adding elemental donor compound
It is known that The amount of these photopolymerization initiators (systems) used is
0.05 to 100 parts by weight of 100 parts by weight of the tyrenic unsaturated compound
100 parts by weight, preferably 0.1 to 70 parts by weight, more preferably
Preferably, it is used in the range of 0.2 to 50 parts by weight. Used for the photosensitive layer of the photopolymerizable lithographic printing plate of the present invention
The polymer binder that can be used includes a film-forming agent of the composition
As well as need to dissolve in alkaline developer
Therefore, organic high solubility or swellable in alkaline water
Molecular polymers are used. The organic polymer is, for example,
For example, water development is possible with water-soluble organic polymer
become. As such an organic polymer, the side chain has a cap
Addition polymers having rubonic acid groups, for example, JP-A-59-4
4615, Shoko 54-34327, Shoko 58-
12577, JP-B 54-25957, JP-A 54
-92723, JP-A-59-53836, JP-A-5
No. 9-71048, that is,
Tacrylic acid copolymer, acrylic acid copolymer, itaconic acid
Copolymer, crotonic acid copolymer, maleic acid copolymer,
Examples include partially esterified maleic acid copolymers. Similarly, an acid having a carboxylic acid group in the side chain
There are functional cellulose derivatives. In addition to this
A product obtained by adding a cyclic acid anhydride to a polymer is useful.
is there. Especially among these [benzyl (meth) acrylate
G / (meth) acrylic acid / other additional weight as required
Compatible vinyl monomer] copolymer and [allyl (meth) a]
Acrylate (meth) acrylic acid / other as required
Addition-polymerizable vinyl monomer] is preferable. This
In addition to water-soluble organic polymers, polyvinylpyrrolidone
And polyethylene oxide are useful. Also hardened skin
To increase the strength of the membrane, alcohol-soluble polyamides and
2,2-bis- (4-hydroxyphenyl) -propane
And a polyether of epichlorohydrin are also useful.
Also, Japanese Patent Publication No. 7-120040 and Japanese Patent Publication No. 7-12004
No. 1, No. 7-120042, No. 8-1224
No. 4, JP-A 63-287944, JP-A 63-28
7947, JP-A-1-271741, JP-A-11-
The polyurethane resin described in 352691 is also used in the present invention.
Is useful. These high molecular polymers have radical reactions on the side chains.
Improves the strength of the cured film by introducing a functional group
be able to. Ethylene as a functional group capable of addition polymerization reaction
Unsaturated unsaturated groups, amino groups, epoxy groups, etc.
Mercapto is a functional group that can be converted to radicals by irradiation.
Group, thiol group, halogen atom, triazine structure, oni
Um salt structure, etc.
And the like. A functional group capable of undergoing an addition polymerization reaction;
For example, acrylic group, methacryl group, allyl group,
Particularly preferred is an ethylenically unsaturated bond group such as
Amino group, hydroxy group, phosphonic acid group, phosphoric acid group, cal
Vamoyl group, isocyanate group, ureido group, ureire
Functional group selected from an amine group, a sulfonic acid group, and an ammonio group
Groups are also useful. In order to maintain the developability of the composition, the present invention is used.
The bright polymer binder should have an appropriate molecular weight and acid value.
Preferably, the weight average molecular weight is 5,000 to 300,000, the acid value is 2
0 to 200 high molecular weight polymers are effectively used. these
The organic polymer of this is mixed in any amount in the whole composition
be able to. However, if it exceeds 90% by weight, it is formed
Does not give a favorable result in terms of image strength and the like. Like
10 to 90%, more preferably 30 to 80%
The Also, photopolymerizable ethylenically unsaturated compounds and organic
The molecular polymer should be in the range of 1/9 to 9/1 by weight.
Is preferred. A more preferable range is 2/8 to 8/2
More preferably, it is 3/7 to 7/3. In the present invention, the above basic components
Other polymerization during production or storage of the photosensitive composition
Prevent unnecessary thermal polymerization of possible ethylenically unsaturated compounds
To add a small amount of thermal polymerization inhibitor
Yes. Suitable thermal polymerization inhibitors include haloid quinone, p-
Methoxyphenol, di-t-butyl-p-creso
, Pyrogallol, t-butylcatechol, benzoquino
4,4'-thiobis (3-methyl-6-t-butyl
Phenol), 2,2'-methylenebis (4-methyl-
6-t-butylphenol), N-nitrosophenyl
Droxylamine primary cerium salt, N-nitrosofeni
And the like.
The addition amount of the thermal polymerization inhibitor is approximately about the total composition weight.
0.01% to about 5% is preferred. If necessary, acid
Behenic acid and behenic acid to prevent polymerization inhibition by silicon
After coating with higher fatty acid derivatives such as amide
In the course of drying, it may be unevenly distributed on the surface of the photosensitive layer. Luxury
The amount of fatty acid derivative added is about 0.5% to about 1% of the total composition.
0% is preferable. Further, for the purpose of coloring the photosensitive layer, a colorant is added.
It may be added. As a colorant, for example, phthalocyan
Nin-based pigment (CI Pigment Blue 1
5: 3, 15: 4, 15: 6, etc.), azo pigments, car
Bon black, pigments such as titanium oxide, ethyl violet
, Crystal violet, azo dye, anthraki
Non dyes and cyanine dyes are available. Of dyes and pigments
The amount added is preferably from about 0.5% to about 20% of the total composition.
In addition, in order to improve the physical properties of the cured film, inorganic fillers
And dioctyl phthalate, dimethyl phthalate, tric
Additives such as plasticizers such as resin phosphate may be added
Yes. These additions are preferably 10% or less of the total composition.
Yes. Photosensitive layer composition of the photopolymerizable lithographic printing plate of the present invention
When applying the product on the support described later, various organic solvents are used.
Dissolved and used. As a solvent used here
Is acetone, methyl ethyl ketone, cyclohexane,
Ethyl acetate, ethylene dichloride, tetrahydrofuran
, Toluene, ethylene glycol monomethyl ether
, Ethylene glycol monoethyl ether, ethylene
Glycol dimethyl ether, propylene glycol
Nomethyl ether, propylene glycol monoethyl ester
Ether, acetylacetone, cyclohexanone, diace
Ton alcohol, ethylene glycol monomethyl ether
Ruacetate, ethylene glycol ethyl ether acetate
Tate, ethylene glycol monoisopropyl ether
, Ethylene glycol monobutyl ether acetate
G, 3-methoxypropanol, methoxymethoxyethane
Nord, diethylene glycol monomethyl ether, di
Ethylene glycol monoethyl ether, diethylene glycol
Recall dimethyl ether, diethylene glycol die
Till ether, propylene glycol monomethyl ether
Ruacetate, propylene glycol monoethyl ether
Ruacetate-3-methoxypropyl acetate, N,
N-dimethylformamide, dimethyl sulfoxide, γ
-Butyrolactone, methyl lactate, ethyl lactate, etc.
The These solvents can be used alone or in combination.
You can. And the concentration of the solid content in the coating solution is 1 to
50% by weight is suitable. In the photosensitive layer of the photopolymerizable lithographic printing plate of the present invention,
In order to improve the coating surface quality,
A surfactant can be added. The coating amount is after drying
Weight of 0.3g / m²~ 5.0 g / m²The range is suitable
is there. Preferably 0.5-3 g / m²It is. Further, the polymerization of oxygen is prohibited on the photosensitive layer.
An oxygen barrier protective layer is necessary to prevent the stopping effect
The A water-soluble vinyl polymer contained in the oxygen barrier protective layer;
The polyvinyl alcohol and its partial esthetics
, Ether, and acetal, or required for them
A substantial amount of unsubstituted vinyl alcohol that is highly water soluble.
Mention may be made of copolymers thereof containing alcohol units. Po
71 to 100% hydrolysis as rivinyl alcohol
And those having a degree of polymerization in the range of 300-2400.
It is. Specifically, Kuraray Co., Ltd. PVA-105, P
VA-110, PVA-117, PVA-117H, P
VA-120, PVA-124, PVA-124H, P
VA-CS, PVA-CST, PVA-HC, PVA-
203, PVA-204, PVA-205, PVA-2
10, PVA-217, PVA-220, PVA-22
4, PVA-217EE, PVA-220, PVA-2
24, PVA-217EE, PVA-217E, PVA
-220E, PVA-224E, PVA-405, PV
A-420, PVA-613, L-8, etc. are mentioned.
As said copolymer, it is hydrolyzed 88-100%
Polyvinyl acetate chloroacetate or propylene
Honate, polyvinyl formal and polyvinyl acetate
Tar and their copolymers. Other existence
Useful polymers include polyvinylpyrrolidone, gelatin and
And gum arabic, which can be used alone or in combination.
May be used. In the photopolymerizable lithographic printing plate of the present invention, an acid is used.
As a solvent used when applying an elemental protective layer, pure water is used.
It is preferable to use alcohol such as methanol or ethanol.
And ketones such as acetone, methyl ethyl ketone
It may be mixed with pure water. And the concentration of solids in the coating solution
The degree is suitably from 1 to 20% by weight. The oxygen barrier of the present invention.
In the protective layer, the interfacial activity for further improving the coatability
Water-soluble plasticizers to improve the physical properties of coating agents and films
Known additives may be added. As a water-soluble plasticizer
For example, propionamide, cyclohexanedio
And glycerin and sorbitol. Also water soluble
(Meth) acrylic polymer or the like may be added.
The coating amount is 0.5 g / m in weight after drying.²-10g /
m²The range of is appropriate. More preferably 1.0 g / m²
~ 5.0 g / m²It is. Next, support of the photopolymerizable lithographic printing plate of the present invention
Explain the body. Obtaining the photopolymerizable lithographic printing plate of the present invention
The photosensitive layer is provided on a support having a hydrophilic surface.
The As a hydrophilic support, a conventionally known lithographic printing plate
Can be used without limitation on the hydrophilic support used in
Yes. The support used is a dimensionally stable plate.
Preferably, for example, paper, plastic (for example,
Polyethylene, polypropylene, polystyrene, etc.)
Minated paper, metal plates (eg, aluminum,
Lead, copper, etc.), plastic film (eg, diacetic acid
Roulose, cellulose triacetate, cellulose propionate
, Cellulose butyrate, cellulose acetate butyrate, cellulose nitrate
, Polyethylene terephthalate, polyethylene, polyethylene
Restyrene, polypropylene, polycarbonate, poly
Vinyl acetal, etc.) and the above metals are laminated
Or vapor-deposited paper or plastic film, etc.
If necessary, attach hydrophilicity to these surfaces.
Well-known physical and chemicals suitable for the purpose of increasing the strength, etc.
May be subjected to manual processing. In particular, preferred supports include paper, poly
Examples include ester film or aluminum plate.
Among them, it has good dimensional stability, is relatively inexpensive, and is necessary
Providing a surface with excellent hydrophilicity and strength by appropriate surface treatment
An aluminum plate that can be provided is particularly preferred. In addition, Shoko
Polyethylene as described in 48-18327
An aluminum sheet is bound on the terephthalate film.
Combined composite sheets are also preferred. The preferred aluminum plate is pure aluminum
Mainly composed of plate and aluminum, and contains trace amounts of foreign elements.
Alloy plate, and also aluminum laminated or
May be a deposited plastic film. Armini
The different elements contained in the aluminum alloy include silicon, iron, and manga.
Copper, magnesium, chromium, zinc, bismuth, nickel
There are Kell and Titanium. The content of foreign elements in the alloy is at most
10% by weight or less. Particularly suitable for the present invention
Minium is pure aluminum, but it is completely pure aluminum.
Since ruminium is difficult to manufacture due to refining technology,
It may contain foreign elements. Thus, it is suitable for the present invention.
The aluminum plate used has a specific composition
Rather than using a publicly known aluminum plate
It can be used as appropriate. Al used in the present invention
The thickness of the minium plate is suitably 0.1 mm to 0.6 mm,
Preferably 0.15 mm to 0.4 mm, particularly preferably 0.
2 mm to 0.3 mm. It also has a metal, especially aluminum surface.
In the case of a support, a roughening (graining) treatment,
Aqueous solution of potassium, hydrofluoric zirconate, phosphate, etc.
It is preferable that surface treatment such as immersion in
That's right. Anodizing treatment is used to prevent scratches on non-image areas after development.
Necessary, preferably 0.5 to 5.0 g / m²,
More preferably, 1.0 to 4.0 g / m²Anodized film
Apply. The roughening treatment of the surface of the aluminum plate
For example, the surface is mechanically roughened.
A method for electrochemically dissolving and roughening the surface and
It is carried out by a method of selectively dissolving the surface chemically. Machine
Mechanical methods include ball polishing, brush polishing, and bra
Use known methods such as strike polishing, buffing, and polishing.
it can. Electrochemical roughening methods include hydrochloric acid and glass.
There are methods that use alternating current or direct current in electrolytes such as acids.
The Moreover, it is disclosed by Unexamined-Japanese-Patent No. 54-63902.
You can also use a method that combines both
The Also, prior to roughening the aluminum plate, desired
For example, to remove rolling oil on the surface, the interface
Degreasing with activator, organic solvent or alkaline aqueous solution
Processing is performed. Further, after roughening, the sodium silicate
Aluminum plate immersed in aqueous solution is preferably used
it can. As described in Japanese Patent Publication No. 47-5125
After anodizing the aluminum plate,
What is immersed in an aqueous solution of metal silicate is preferably used.
It is. Anodizing treatment is, for example, phosphoric acid, chromic acid, sulfur
Inorganic acids such as acid and boric acid, or oxalic acid and sulfamic acid
An aqueous or non-aqueous solution of an organic acid or a salt thereof
Aluminum in a single or a combination of two or more electrolytes
This is carried out by passing an electric current using a metal plate as an anode. Also described in US Pat. No. 3,658,662.
Silicate electrodeposition is also effective. More
JP-B-46-27481, JP-A-52-5860
2 and as disclosed in JP-A 52-30503
And a support with an appropriate electrolytic grain and the above-mentioned anodizing treatment
A surface treatment in combination with sodium silicate treatment is also useful.
Further, as disclosed in JP-A-56-28893
Mechanical roughening, chemical etching, electrolytic grain, positive
Preference is also given to polar oxidation treatment and sodium silicate treatment in order.
Is suitable. Furthermore, after these treatments,
Resin such as polyvinylphosphonic acid, sulfonic acid group
Polymers and copolymers having a pendant in the side chain, polyacryl
Acid, water-soluble metal salt (for example, zinc borate) or yellow dyeing
Also preferred is a primer or amine salt. further
Radiation as disclosed in JP-A-7-159983
A functional group capable of undergoing an addition reaction by cal is covalently bonded.
A sol-gel treated substrate is also preferably used. As another preferred example, on an arbitrary support.
In addition, the surface layer may be provided with a water-resistant hydrophilic layer.
be able to. As such a surface layer, for example, US3
No. 055295 or JP-A-56-13168
Layer comprising machine pigment and binder, JP-A-9-80744
The hydrophilic swelling layer described in JP-A-8-507727
Zo consisting of titanium oxide, polyvinyl alcohol and silicic acids
A Lugel membrane can be used. These hydrophilic treatments
Is applied to make the surface of the support hydrophilic.
In addition, the harmful reaction of the photopolymerizable composition provided thereon
To prevent and improve the adhesion of the photosensitive layer
Is. On the above support, the photopolymerizable composition
By forming a photosensitive layer made of a product, the photopolymerizability of the present invention
Produces a lithographic printing plate, but is required before coating the photosensitive layer
Depending on the situation, an organic or inorganic subbing layer may be provided.
Yes. In the photopolymerizable lithographic printing plate of the present invention,
The photosensitive layer can be, for example, helium cadmium laser,
Lugon ion laser, FD / YAG laser, helicopter
Mneon laser, semiconductor laser (350nm-60
0 nm), etc., after image exposure with conventionally known actinic rays
By developing with the dynamic developing machine 1, an image is formed on the surface of the support.
An image can be formed. After laser exposure, the degree of polymerization of the photopolymerizable photosensitive layer
Plate for the purpose of improving printing durability and improving printing durability.
You may heat with the heating part 11. FIG. On the photosensitive layer of the photopolymerizable lithographic printing plate of the present invention
As described above, an oxygen barrier protective layer is provided on the
In the pre-washing tank 12 of the automatic processor 1,
Remove the protective layer first, and then remove the unexposed photosensitive layer.
The developer is removed by the developer in the developing tank 13 of the automatic developing machine 1. In the present invention, as described above, automatic development is performed.
In the pre-washing tank 12 of the machine 1, a photopolymerizable photosensitive lithographic printing plate and
Discarded plates are transported and processed, but each process
Change the replenishment amount of water, preservative aqueous solution, etc. according to the amount
Can maintain the pre-water tank 12 in an appropriate state.
Yes. Development used in the developing tank 13 of the automatic developing machine 1
The liquid is not particularly limited, but preferably,
Examples include developers as described in US Pat. No. 57-7427.
Sodium silicate, potassium silicate, sodium hydroxide
Lithium, potassium hydroxide, lithium hydroxide, tertiary phosphate
Sodium, dibasic sodium phosphate, tribasic ammonium phosphate
Ni, dibasic ammonium phosphate, sodium metasilicate
Inorganic, such as sodium bicarbonate, sodium bicarbonate, aqueous ammonia
Alkaline agent, monoethanolamine or diethanol
An aqueous solution of an organic alkaline agent such as amine is suitable.
The The concentration of such an alkaline solution is 0.1 to 10 weight
%, Preferably 0.5 to 5% by weight
The In addition, such an alkaline aqueous solution includes
Surfactant, benzyl alcohol, 2-ph as necessary
Like enoxyethanol, 2-butoxyethanol
A small amount of organic solvent can be included. For example, US Patent No.
Described in US Pat. Nos. 3,375,171 and 3,615,480.
Can be mentioned. Furthermore, JP-A-5
0-26601, 58-54341, Shoko 56
-39464, 56-42860 described in each publication
The developer that is used is also excellent. The development in the developing tank 13 follows a conventional method.
And a temperature of about 0 to 60 ° C., preferably about 15 to 40 ° C.
For example, an exposed photopolymerizable lithographic printing plate
It is performed by immersing in a brush and rubbing with a brush. In the present invention, as described above, automatic development is performed.
Dispose of photopolymerizable photosensitive lithographic printing plate in developer tank 13 of machine 1
The plate is transported and development processing is performed.
Change the replenishment amount of water, development replenishment stock solution, etc. according to the amount
By adjusting the pH of the developer in the developing tank 13 to an appropriate state
Can be maintained in a state. The photopolymerizable plain developed in this way is used.
Plate printing plates are disclosed in JP-A Nos. 54-8002 and 55-1150.
45, 59-58431, etc.
As in the washing tank 14, washing water, surfactant, etc.
In the gum layer 15, treated with a rinse solution containing
Post-treatment with a desensitizing solution containing gum arabic or starch derivatives
And dried in the heating unit 16. Development processing
Later, the entire surface was exposed to UV light for the purpose of improving printing durability.
May be. In the post-treatment of the photopolymerizable lithographic printing plate of the present invention,
Various combinations of these processes can be used. [0062] The present invention will be described more specifically with reference to the following examples.
Of course, the scope of the present invention is of course limited by these.
Is not something [Preparation of photopolymerizable photosensitive lithographic printing plate] Thickness 0.30 mm
1S aluminum plate with 8 nylon brush and 8
The surface of a 00 mesh Pamiston water suspension
After being grained, it was thoroughly washed with water. 10% sodium hydroxide
Etching by immersing in thorium at 70 ° C for 60 seconds
After washing with running water, 20% HNO_ThreeWith neutralization washing, water washing
It was. This is V_A= 1 Sine wave alternating wave under the condition of 12.7V
300 coulomb / d in 1% aqueous nitric acid solution using a galvanic current
m²Electrolytic 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 0.45 μm (Ra indication).
It was. Continuously 30% H₂SO_FourImmersion in aqueous solution
And desmutted at 55 ° C for 2 minutes, then 33 ° C, 20%
H₂SO_FourPlace the cathode on a grained surface in an aqueous solution.
Current density 5A / dm²Anodized for 50 seconds at
As a result, the thickness is 2.7 g / m.²Met. On the aluminum plate thus treated
The undercoat layer was provided by the following procedure. The following undercoat liquid
The composition was mixed and stirred at 30 ° C. I saw a fever after about 5 minutes
After reacting for 60 minutes, transfer the contents to another container.
And liquid application by adding 30,000 parts by mass of methanol.
A liquid was prepared. [0064] (Liquid composition for undercoat)   The following compound [Chemical Formula 1] 50 parts by mass   130 parts by mass of methanol   20 parts by weight of water   5 parts by mass of paratoluenesulfonic acid   50 parts by mass of tetraethoxysilane   3-Methacryloxypropyltrimethoxysilane 50 parts by mass [0065] [Chemical 1] This liquid coating solution is treated with the above-mentioned treated alkane.
0.1 g / m on the minium plate²Apply so that
Dry at 100 ° C. for 1 minute. On the undercoat layer thus obtained,
The photopolymerizable composition 1 having the above composition has a dry coating weight of 1.48 g.
/ M²Apply and dry at 100 ° C for 1 minute
A photosensitive layer was formed. [0068] (Photopolymerizable composition 1)   Ethylenically unsaturated bond-containing compound (A1) 2.2 parts by weight   Linear organic polymer (B1) 2.0 parts by weight   Sensitizer (C1) 0.15 parts by weight   Photopolymerization initiator (D1) 0.25 parts by weight   Sensitization aid (E1) 0.3 parts by weight   ε-phthalocyanine (F1) dispersion 0.02 parts by weight   0.03 parts by weight of fluorine-based nonionic surfactant Megafac F176     (Dainippon Ink Chemical Co., Ltd.)   Methyl ethyl ketone 15.0 parts by weight   Propylene glycol monomethyl ether acetate 15.0 parts by weight [0069] [Chemical 2]On this photosensitive layer, 6% water composed of the following materials:
The solution was used as an oxygen barrier layer and the dry coating weight was 2.5 g / m.²
It is applied so that it becomes
A sex lithographic printing plate was obtained. Polyvinyl alcohol (PVA-105, manufactured by Kuraray Co., Ltd.,   Saponification degree 98 mol%, polymerization degree 500) 2.2 parts by weight Polyvinylpyrrolidone (K30, manufactured by Wako Pure Chemical Industries, Ltd.) 0.12 parts by weight Piionin D625 (Takemoto Yushi Co., Ltd.) 0.073 parts by weight EMALEX 710 (Nihon Emulsion Co., Ltd., surfactant) 0.043 parts by weight [Preparation of Discarded Plate] 99.5 wt% Aluminum
Um, 0.01 wt% copper and 0.03 wt% titanium
%, Iron 0.3% by weight, silicon 0.1% by weight
JIS A1050 aluminum material thickness 0.30mm pressure
The plate is made of 400 mesh Pamiston (manufactured by Kyoritsu Ceramics)
20 wt% aqueous suspension and rotating nylon brush (6,1
0-nylon)
Washed well with water. This was mixed with a 15% by weight aqueous sodium hydroxide solution.
Soaked in aluminum (contains 4.5 wt% aluminum)
The dissolution amount of um is 5 g / m²Etched to be
Then, it was washed with running water. Furthermore, neutralize with 1 wt% nitric acid,
Next, a 0.7 wt% nitric acid aqueous solution (aluminum 0.5 wt.
%)), Anode voltage 10.5 volts, cathode voltage
9.3 volt square wave alternating waveform voltage (current ratio r = 0.9)
0, described in the example of Japanese Patent Publication No. 58-5796
160 coulomb / dm using current waveform)²Anode anode
The electrolytic surface-roughening treatment was performed with the volume. 10 minutes at 35 ° C after washing with water
Immerse in an aqueous solution of sodium hydroxide by weight
The dissolution amount of um is 1 g / m²After etching to become
Washed with water. Next, it is immersed in a 30% by weight sulfuric acid aqueous solution at 50 ° C
After pickling and desmutting, it was washed with water. Furthermore, a 20% by weight aqueous solution of sulfuric acid at 35 ° C.
Using direct current in (containing 0.8% by weight of aluminum)
Then, a porous anodic oxide film forming treatment was performed. That is, electric
Flow density 13A / dm²Electrolysis is carried out by adjusting the electrolysis time.
Anodized film weight 2.7g / m ²It was. This support
After washing with water, add 3% by weight aqueous solution of sodium silicate at 70 ° C.
It was immersed for 30 seconds, washed with water and dried. The aluminum support obtained as described above.
The holder is a reflection measured with a Macbeth RD920 reflection densitometer.
The concentration was 0.30 and the centerline average roughness was 0.58 μm.
It was. Next, methyl methacrylate / ethyl acrylate
/ 2-acrylamido-2-methylpropanesulfonic acid
(Feed weight ratio 65/20/15) Natto part of the copolymer
What was made into a lithium salt to 1.0 wt% methanol / water
Apply as a 90/10 solution after drying with a bar coater
Amount 0.1g / m²It applied so that it might become. Further, the composition shown below is methanol / medium.
Tyl ethyl ketone / 1-methoxy-2-propanol /
Methyl methyl lactate = 30g / 30g / 25g / 12g
Dissolve in a mixed solvent and apply using a bar coater.
Dry at 0 ° C. for 45 seconds. Dry coating amount is 0.5g / m²
Met. [0076] ・ Alkali-soluble urethane binder 5.0 g     (Weight average molecular weight 85,000, acid content 1.64 meq / g, the following 4 types       Mer reaction product)     4,4-diphenylmethane diisocyanate 37.5 mol%     Hexamethylene diisocyanate 12.5 mol%     2,2-bis (hydroxymethyl) propionic acid 32.5 mol%     Tetraethylene glycol 17.5 mol% ・ Victoria Blue BOH 0.05g ・ Sulfophthalic acid 0.3 g ・ FC-430 (3M fluorine surfactant) 0.05g Beat the bleached kraft pulp to a concentration of 4%
0.4% by weight of a synthetic sizing agent is added to the stock diluted in
Aluminum sulfate was added until the pH was 5.0. This
3.0 weight of paper strength agent based on starch
% Coating, paper making, density 0.75g / cm^Three, Smoothness 5
0 second, moisture 6.0% 38g / m²I made a slip sheet. So
After that, process the normal PS plate while sandwiching this slip sheet
A discarded version was created on the line. 80 × 110 cm light obtained in this way
A polymerizable photosensitive lithographic printing plate, a discarded plate, FD-YAG
Lu made by Fuji Photo Film Co., Ltd.
xelPlate Setter P-9600 CTP NEWS
We set 90 sheets of photosensitive material and 30 sheets of discarded plates. From the upper computer system, newspaper
Instructions were given to process the paper. Discarded version is not exposed,
Photopolymerizable lithographic printing plate is 0.2 mJ / cm²909 dpi, 10
The image was exposed under the condition of 0 lpi. Then immediately each
Fuji Photo Film Co., Ltd. automatic processor FLP125NF
The plate surface temperature is transferred to S and the plate surface temperature is the center of the plate back surface in the heating unit 11.
After heating to 115 ° C. in the pre-washing tank 12
Then, the oxygen barrier layer was washed away with water at 40 ° C. That
After that, a developer manufactured by Fuji Photo Film Co., Ltd. in the developing tank 13
Developed at 25 ° C for 22 seconds using DV-2: water = 1: 4
It was. Then, it is washed with water in a water rinsing tank 14 and put into a gum tank 15.
In Fuji Photo Film Co., Ltd. Finishing Gum FP
-3W: water = 1: 1, standard treatment,
And dried with hot air of 50 ° C. At that time, the amount of gum applied
150 mg / m in dry weight²Met. The replenishment conditions shown in Table 1 for each tank are set in the automatic processor.
Enter 60 sheets of sensitive material in about 6 hours.
About 20 sheets were processed in about 6 hours. Turn on the power only during plate making
And others were turned off. When the power is turned on,
The replenishment shown in Table 1 was performed for the amount of time that had been turned OFF. This
For 28 days with occasional interruption of plate making
Total about 1970m²The plate material was processed. 28 days later
The solid content concentration of the oxygen barrier layer of the rinsing tank 12 is 2.0%, development
The pH of the tank 13 was 12.0, the same as the new solution. About waste liquid
It was 500 liters. [0081] [Table 1]Printing stains are caused by a printing machine manufactured by Tokyo Kikai Co., Ltd.
4-color tower type rotary press CT7000 (170,000), ink
Is Dainippon Ink Co., Ltd. newspaper ink.
News King Alky for newspaper made by Ki Co. pH = 10.
2. The paper is Oji Paper 44g / m ²Tomakomai, blanket is gold
Printed 100,000 copies using Yosha MP-75R, 2.07mm
And evaluated. Sense of performing the plate-making running process on the 28th day
Neither the material nor the discarded plate is soiled at all, and the printing durability is NG.
I did not remake the version. Throw away as a comparative example
When the plate is processed with the same replenishment as the photosensitive material, the waste liquid is about 6%.
The pH of the developer finally increased to 12.4.
Rose. As a result, 2% highlight when printing 100,000 copies
A flying jump occurred. [0084] The plate-making method according to the present invention is a separate development.
Economical without preparing a treatment line, reducing the replenishment amount
By reducing the waste liquid, we are dealing with environmental issues.
Stable current status for both photopolymerizable photosensitive lithographic printing plates and discarded plates
Image quality is obtained, printing stains do not occur, and sufficient printing durability
A lithographic printing plate can be obtained with
It can be suitably used for a printing plate.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an explanatory view showing an embodiment of an automatic processor used in the present invention. [Explanation of Symbols] 1 Automatic processor 11 Heating unit 12 Pre-washing tank 13 Developing tank 14 Washing tank 15 Gum tank 16 Drying unit

Claims (1)

What is claimed is: 1. A photopolymerizable photosensitive lithographic printing plate comprising a photopolymerizable photosensitive layer and an oxygen-blocking layer provided on an aluminum support having a hydrophilic surface, and a hydrophilic property. In a plate making method in which a waste plate having a non-photosensitive resin layer provided on an aluminum support having a surface is developed with the same automatic processor, a pre-water washing tank and a developing tank of the automatic processor depending on the plate material to be processed A plate-making method characterized by automatically changing the replenishment amount.