GB2069164A - Lithographic Printing Plate Making Process - Google Patents
Lithographic Printing Plate Making Process Download PDFInfo
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- GB2069164A GB2069164A GB8101826A GB8101826A GB2069164A GB 2069164 A GB2069164 A GB 2069164A GB 8101826 A GB8101826 A GB 8101826A GB 8101826 A GB8101826 A GB 8101826A GB 2069164 A GB2069164 A GB 2069164A
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- printing plate
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- silver halide
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
- G03F7/0952—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer comprising silver halide or silver salt based image forming systems, e.g. for camera speed exposure
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- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
A printing plate precursor is used which comprises, on a hydrophilic support, (a) a non-silver light- sensitive, e.g. diazo resin, layer for forming an oleophilic image and (b) a light-sensitive silver halide photographic emulsion layer with AgX grains of a mean grain size 0.7 micron optionally containing oleophilic resin particles. This precursor is imagewise exposed, treated in a silver halide developer and the developed silver image is fixed. Then the plate is exposed to light to which layer (a) is sensitive, at least part of layer (b) is removed with warm water, and layer (a) is appropriately developed to remove exposed or unexposed areas to give a lithographic printing plate. The silver halide developer is an aqueous solution of pH 9 to 13 containing, per litre, (a) 0.45 to 1.2 mols of sulfite (b) 0.09 to 0.45 mol of hydroquinone and (c) 0.005 to 0.03 mol of a substituted 1-aryl-3- pyrazolidone of specified formula, and optionally (d) a glycol, which allows good formation of the silver image.
Description
SPECIFICATION
Lithographic Printing Plate Making Process
This invention relates to a process of making a printing plate from a light-sensitive lithographic printing plate, and more particularly to a process of making a printing plate from a light-sensitive lithographic printing plate precursor having a non-silver light-sensitive layer and a light-sensitive silver halide emulsion layer using an improved silver halide developer.
A light-sensitive lithographic printing plate precursor comprising a support having a hydrophilic surface, such as an aluminum sheet having formed thereon successively a non-silver light-sensitive layer as the light-sensitive layer comprising an o-quinonediazido compound and a gelatino silver halide light-sensitive emulsion layer is described in British Patent 1,227,603.A process of making a printing plate from such a light-sensitive lithographic printing plate precursor fundamentally comprises the steps of (1) imagewise exposing the light-sensitive printing plate precursor, (2) developing the imagewise exposed plate with a silver halide developer (hereinafter referred to as the "first development"), (3) fixing the developed image to form a silver image, (4) exposing the non-silver lightsensitive layer existing under the silver image to actinic light using the silver image as a mask, (5) removing at least part of the layer containing the silver image (that is, the silver halide emulsion layer imagewise exposed and developed), and (6) developing the non-silver light-sensitive layer to remove either the exposed or unexposed area to the actinic light.
The first development in such a printing plate-making process must meet the following various requirements:
(1) The silver-image obtained by the first development has a maximum optical density of 1.6 or more and 2.5 or more of a gradation (or edge contrast) of half-tone dots constituting the density from "base density plus 0.3" to shadow, and further such a silver image is stably obtained in a stable manner in a development time of less than about 60 seconds, preferably less than 30 seconds.
(2) The above-described silver image is obtained regardless of the variation in processing time (e.g., a variation of 10-60 seconds).
(3) The silver image obtained by the exposure to actinic light in the above-described printing platemaking process does not have spots and image distortion.
(4) The silver halide developer used for the first development shows less degradation in properties due to air oxidation and can be stored in a stable manner for a long period of time.
(5) The removal of the silver halide emulsion layer in the above-described printing plate-making process is not hindered. In particular, removing the silver halide emulsion layer using a proteolytic enzyme as described in British Patent Application No. 8025459, it is important to not hinder the action of the enzyme.
However, it is very difficult to find a silver halide developer satisfying the above-described requirements from conventional developers.
As the result of various investigations on light-sensitive lithographic printing plate precursors and procedures for making printing plates using light-sensitive printing plate precursors under those circumstances, a printing plate-making process satisfying the above-described various characteristics has now been discovered.
That is, this invention provides a process of making a lithographic printing plate from a lightsensitive lithographic printing plate precursors including the steps of
imagewise exposing a light-sensitive lithographic printing plate precursor comprising a support having a hydrophilic surface and having successively thereon a non-silver light-sensitive layer capable of forming oleophilic images and a light-sensitive silver halide emulsion layer containing silver halide grains having a mean grain size of 0.7 micron or below,
developing the silver halide emulsion layer with a silver halide developer,
fixing the image formed,
exposing the non-silver light-sensitive layer to actinic light to which the non-silver light-sensitive layer is sensitive,
removing at least a part of the silver halide emulsion layer, and,
thereafter, developing the non-silver light-sensitive layer to remove either the exposed or unexposed area to the actinic light thereby to reveal the hydrophilic surface,
wherein the silver halide developer is an aqueous solution containing
(a) from 0.45 to 1.2 mols/liter of sulfite,
(b) from 0.09 to 0.45 mol/liter of hydroquinone and
(c) from 0.005 to 0.03 mol/liter of a compound represented by the following formula (I)
wherein A represents an aromatic group; R1, R2 and R3, which may be the same or different, each represents a hydrogen atom, an aliphatic group, or an aromatic group; and Z represents a hydrogen atom, an aminoalkyl group, or a hydroxyalkyl group; with the proviso that R1, R2, R3 and Z are not simultaneously hydrogen atoms, and having a pH of 9 to 13.
The fundamental structure of the light-sensitive lithographic printing plate precursor used in the printing plate making process of this invention comprises a support having a hydrophilic surface and having successively thereon a non-silver light-sensitive layer capable of forming oleophilic images and a light-sensitive silver halide emulsion layer, and the silver halide grains of the silver halide emulsion layer have a mean grain size of 0.7 micron or below.
As the support having a hydrophilic surface, various materials can be used but a particularly preferred support is an aluminum sheet. It is preferred that the surface of the aluminum sheet be subjected to a surface treatment such as a graining treatment, a chemical treatment, for example, with an aqueous solution of sodium silicate, potassium fluorozirconate or a phosphate or an anodic oxidation treatment.
Exemplary non-silver light-sensitive layers capable of forming oleophilic images formed on such a support include a light-sensitive layer suitable for pre-sensitized lithographic printing plates (called a "PS plate"). The term "oleophilic" as used herein means that the material is repellant to dampening water used in printing and is receptive to greasy ink. Representative compositions for such a non-silver light-sensitive layer include that comprising a diazo resin, that comprising an o-quinonediazido compound, that comprising a light-sensitive azido compound, that comprising a high molecular weight (polymeric) compound having the group of the formula
in the main chain or side chain of the compound, and a photopolymerizable composition comprising an addition polymerizable unsaturated compound and a photoinitiator.The non-silver light-sensitive layer is disclosed in detail in U.S. Patent 4,238,560. These compositions are well known in the art. Such a composition is coated on a support as a solution in an appropriate solvent at a dry coverage of about 0.1 g/m2 to about 5 g/m2 of the support.
The light-sensitive silver halide emulsion formed on the non-silver light-sensitive layer is a conventional negative type or direct-positive type and can be an emulsion of silver chloride, silver bromide, silver iodide or a mixed silver halide thereof usually used for silver halide photographic materials but the mean grain size thereof must be 0.7 micron or less. If the mean grain size is larger than 0.7 micron, for example, if a silver iodobromide emulsion used for X-ray film is used, the characteristics (1) and (2) described above cannot be satisfied. Furthermore, in such a case it becomes difficult to finish the fix process in a short period of time and a silver image having a low covering power to actinic light to which the non-silver light-sensitive layer is exposed is obtained.Consequently, the preferred mean grain size of the silver halide used in this invention is 0.01 to 0.5 micron. The lightsensitive silver halide emulsion used in this invention can be subjected to a chemical sensitization such as sulfur sensitization, reductive sensitization or noble metal sensitization or a spectral sensitization with sensitizing dyes as well as may contain various additives usually used in the art.
A silver halide emulsion layer particularly preferably used in this invention is an emulsion of silver halide containing at least 20 mol% silver chloride, at most 80 mol% silver bromide, and from 0 to at most 2 mol% silver iodide.
It is also preferred that a substantially water-insoluble oleophilic resin be dispersed as fine particles (preferably particle sizes of 0.01 to 10 microns) in the silver halide emulsion layer and the amount thereof is preferably 1 to 10 parts by weight per 1 0 parts by weight of the hydrophilic colloid (e.g., gelatin) present in the silver halide emulsion layer. Exemplary oleophilic resins include shellac, polyamide resins, phenol resins, polyvinyl acetal resins, linear polyurethane resins, polyester resins, etc.
The light-sensitive silver halide emulsion layer is formed on the non-silver light-sensitive layer directly or, if necessary, through an interlayer and the dry coverage thereof is from 1 g/m2 to 10 g/m2, preferably from 2 g/m2 to 6 g/m2. Also, in using the above-described silver halide emulsion having the preferred halogen composition, the silver coverage thereof may be from 1.0 g/m2 to 2.5 g/m2, which corresponds to 1/3 to 1/1 O of the silver coverage in an X-ray film.
On the light-sensitive silver halide emulsion layer may be formed a protective layer. The protective layer used in this case may be one uesd in general sliver halide photographic materials or may be a protective layer as described in U.S. Patent 4,233,393.
A printing plate precursor is produced and processed as follows using the above-described PS plate. The PS plate is first imagewise exposed form a latent image on the silver halide in the gelatino silver halide light-sensitive emulsion layer. Then, the development (the first development) of the silver halide is performed and, after processing with a Fix solution, the non-silver light-sensitive layer is exposed to actinic light.Then, the PS plate is processed to wash off at least a part, preferably all, of the gelatino silver halide light-sensitive emulsion layer, for example, by treating the PS plate with warm water at a temperature of 300 to about 60 C, and then a second development process for obtaining a lithographic printing plate is performed for dissolving off either the exposed portion or the unexposed portion of the non-silver light-sensitive layer to uncover the hydrophilic surface of the support. In this case, a processing solution selectively dissolving only the exposed portion or the unexposed portion of the non-silver light-sensitive layer is used for the second development and various kinds of processing solutions suitable for various kinds of non-silver light-sensitive layers can be used.For example, when the non-silver light-sensitive layer comprises an o-quinonediazido compound, an aqueous solution of sodium silicate or the developer as described in U.S. Patent 4,141,733 may be used.
Preferably in the first development in the above-described printing plate-making process a silver halide developer is used comprising an aqueous solution containing (a) from 0.45 to 1.2 mols/liter of sulfite, (b) from 0.09 to 0.45 mol/liter of hydroquinone and (c) from 0.005 to 0.03 mol/liter of a compound represented by the formula (I)
wherein A represents an aromatic group; Ra, R2 and R3, which may be the same or different, each represents a hydrogen atom, an aliphatic group, or an aromatic group; and Z represents a hydrogen atom, an aminoalkyl group, or a hydroxyalkyl group; with the proviso that R,, R2, R3 and Z are not simultaneously a hydrogen atom, and having a pH of 9 to 13.
The developing agents in the developer used in this invention are hydroquinone and a 1-aryl-3pyrazolidone derivative represented by the formula (I). By using hydroquinone in comparatively high concentration, i.e., in a concentration of 0.09 to 0.45 mol/liter and the 1 -aryl-3-pyrazolidone derivative represented by the formula (I), a developer satisfying the above-described characteristics (1) and (2) can be obtained. Furthermore, by using sulfite at a concentration higher than that ordinarily used, i.e., at a concentration of from 0.45 mol/liter to 1.2 mols/liter together with the above-described components, a developer satisfying other characteristics than the above-described characteristics (1) and (2) can be obtained. The sulfite can be an alkali metal sulfite or ammonium sulfite.By using more than 0.45 mol/liter of sulfite, the stability and solubility of the developing agent are improved, the developing activity of silver halide is increased, the tolerance of the optimum processing time is enlarged, facility of processing is increased, the fatigue of the fix solution used in the subsequent processing is reduced, and further the above-described characteristic (3) is attained. Moreover, hardening of the silver halide emulsion layer in the steps of development, fixing the exposure is suppressed and also an advantageous wash-off characteristic can be obtained.
Now, British Patent 1,227,603 discloses, in the Examples thereof, addition of a trace of phenidone, i.e., 1-phenyl-3-pyrazolidone (unsubstituted) to a developer. However, if 1-phenyl-3pyrazolidone is used in place of the 1 -aryl-3-pyrazolidone derivative used in this invention, not only the above-described characteristics (2) and (4) are not sufficiently attained but also the developing activity of the developer is lost on continuous processing of 2 to 3 days with fog occurring. On the other hand, when the 1 -aryl-3-pyrazolidone derivative represented by formula (I) is used in a definite amount, the fatigue of hydroquinone is reduced as well as the fatigue of the 1 -aryl-3-pyrazolidone derivative is astonishingly reduced greatly.In the developer having the composition used in this invention, the development of silver halide proceeds with consumption of almost the theoretical amount of hydroquinone and the theoretical amount of sulfohydroquinone formed during the development process and also it is considered the development proceeds without consuming too much of the 1-aryl3-pyrazolidone derivative.
The compound represented by the formula (I) is described in greater detail below. A in the formula (I) represents an aromatic group which includes unsubstituted aryl groups and substituted aryl groups. Examples of unsubstituted aryl groups include a phenyl group and examples of substituted aryl groups include tolyl, p-methoxyphenyl, p-ethoxyphenyl, p-hydroxymethylphenyl, hydroxyphenyl, o chlorophenyl and carboxyphenyl groups. RX, R2 and R3 in the formula (I) each represents a hydrogen atom, an aliphatic group or an aromatic group. Exemplary aliphatic groups include unsubstituted alkyl groups and substituted alkyl groups and exemplary aromatic groups include unsubstituted aryl groups and substituted aryl groups.Specific examples of preferred unsubstituted alkyl groups are alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and isopropyl groups and examples of preferred substituted alkyl groups are hydroxymethyl, methoxymethyl, aminoethyl, chloromethyl, carboxymethyl, vinylmethyl, benzyl and o-chlorobenzyl groups. Also, an example of an unsubstituted aryl group is a phenyl group, and examples of substituted aryl groups are p-hydroxyphenyl, omethoxyphenyl, m-aminophenyl, and o-carboxyphenyl groups. Furthermore, Z in the formula (I) represents a hydrogen atom, an aminoalkyl group such as an aminoethyl group or a hydroxyalkyl group such as a hydroxyethyl group.
Compounds represented by the formula (I) wherein R3 and Z are each a hydrogen atom are particularly preferred in this invention. Specific examples of preferred compounds represented by the formula (I) are as follows:
(1-1) 4-Methyi-1-phenyl-3-pyrazolidone (1-2) 4,4-Dimethyl-1 -phenyl-3-pyrazolidone (1-3) 4-Hydroxymethyl-1-phenyl-3-pyrazolidone (1-4) 4,4-Di(hydroxymethyl)-1-phenyl-3-pyrazolidone
(1-5) 4-Methyl- 1 -p-tolyl-3-pyrazol idone
(1-6) 4-Dimethylaminomethyl- 1 -p-chlorophenyi-3-pyrazolidone
The compounds represented by formula (I) are described in British Patent 1 093,281, French
Patents 1,454,109,1,454,177 and 1,573,593, and U.S.Patents 3,241 967,3.453,109 and 3,740,221 and other compounds than those described in the above patent specifications can be easily obtained using the production processes described in these patents.
The compounds represented by the formula (I) can be used alone or as a combination of two or more thereof and the amount thereof must be in the range of from 0.005 mol/liter to 0.03 mol/liter, preferably from 0.006 mol/liter to 0.015 moVliter.
Preferred examples of sulfites present in the silver halide developer are an alkali metal sulfite such as sodium sulfite and potassium sulfite and ammonium sulfite and the amount thereof must be in the range of from 0.45 moi/liter to 1.2 mols/liter, preferably from 0.55 mol/liter to 1.2 mols/liter.
Also, the preferred amount of hydroquinone is in the range of from 0.18 mol/liter to 0.40 mol/liter.
The pH of the silver halide developer used in this invention is 9 to 13 and hence an alkali is added to the developer. Alkalis which can be used for this purpose are alkali metal hydroxides, alkali metal carbonates, alkali metal phosphates, alkali metal borates, and aqueous ammonia and they are used together with an appropriate buffer, for example, the inorganic acid corresponding to the abovedescribed salt and an organic acid, a silicate, and an organic amine (e.g., pyridine, triethanolamine or diethanolamine).
By further incorporating a glycol in the silver halide developer used in this invention, the abovedescribed characteristics (3) and (5) can be easily attained. Preferred glycols which can be used in this invention have a boiling point of 1 800C or higher, have a solubility in water of 10% by weight or more, are good solvents for the developing agent, in particular, the 1 -aryl-3-pyrazolidone represented by the formula (I), and are selected from compounds represented by the formula (Il)
wherein R4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms: R5 represents a hydrogen atom, a methyl group or an ethyl group: and n is an integer of 1 to 5.
Specific examples of preferred glycols are ethylene glycol monomethyl ether, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, etc. The glycol is preferably used in the range of from 10 g to 80 g per liter of the silver halide developer. The use of the glycol facilitates not only the dissolution of the developing agent as an aqueous solution but also controls the rapid drying of the silver halide emulsion layer after development or fixing, thereby preventing the deposition of salts, preventing the formation of spots by light exposure and the occurrence of distortion and unevenness of the silver images, and also facilitates the wash-off for silver halide emulsion layer.
The silver halide developer used in this invention may further contain various additives generally used in the art, such as, for example, potassium bromide: potassium iodide; an antifoggant such as nitrobenzimidazole or 1-phenyl-5-mercaptotetrazole, described in U.S. Patents 2,496,940 and 2,656,271; and a sequestering agent such as an alkali metal alkylenepolyaminopolycarboxylate (e.g.,
E.D.T.A. di-sodium salty, an alkali metal polyphosphate, and an alkali metal phosphonate.
The development using such silver halide developer (first development) is generally carried out at a developer temperature of 200C to 500C, more preferably 240C to 400C, for a period of time of 10 to 120 seconds, more preferably 10 to 40 seconds.
According to the printing plate-making process of this invention, the first development can be finished in a short period of time. Therefore, in producing an automatic printing plate-making device, the capacity for the first development can be re gu-ed as an advantage of this invention. Also, since the silver halide developer used in this invenrion is air oxidized with difficulty, a spray system can be employed for applying the developer to the g r1t-sensitive silver halide emulsion layer of the PS plate in this invention and this is very advartageous far producing the automatic printing plate-making device.
Then, the invention is exp;a.ned in greater detail by the following examples wherein all percents (%) are by weight, unless otherwise indicatJ-.
Example 1
A 2S aluminum sheet mechanically grained by the method as described in Japanese Patent
Application (OPI) No. 33911/73 (the term "OPI" as used herein refers to a "published unexamined
Japanese patent application") was immersed in an aqueous 2% sodium hydroxide solution kept at 400C for one minute to etch a part of the surface. After washing the sheet with water, the aluminum sheet was immersed in a sulfuric acid-chromic acid solution for about one minute to uncover a pure aluminum surface. The aluminum sheet was then immersed in 20% sulfuric acid maintained at 3000 and after anodically oxidizing the aluminum sheet for 2 minutes under conditions of 1.5 volts and a direct current density of 3 amperes per square decimeter, the sheet was washed with water and dried.
Then, a light-sensitive coating solution having the composition shown below was continuously coated on the aluminum sheet using a roll coater at a dry coverage of 2 g/m2 to form a non-silver lightsensitive layer: Naphthoquinone-1 ,2-diazido(2)-5-sulfonic Acid Ester of Acetone
Pyrogallol Resin (prepared by the method described in Example 1 of
U.S. Patent 3,635,709) 2.5 g
Hitanol 3110 (trade name for a cresol-formaldehyde resin, made by
Hitachi Chemical Co., Ltd) 5.0 g
Methyl Ethyl Ketone 75 g
Cyclohexanone 60 g
Then, a light-sensitive coating solution having the composition shown below was continuously coated on the non-silver light-sensitive layer at a dry coverage of 4.5 g/m2 and dried with a hot air blast of 9000 as the final temperature. The sample thus prepared was denoted as Sample No. 1.
Emulsion (prepared by dissolving 45 g of a phenol-formaldehyde resin, MP
120 HH (trade name, made by Gunei Kagaku Kogyo K.K.) in a mixture
of 330 g of ethyl acetate and 120 g of methyl ethyl ketone and
dispersing the solution in a solution formed by adding 60 ml of a 10%
solution of sodium nonylbenzenesulfonate and 150 ml of a 10%
methanol solution of Turkey red oil to 600 ml of a 10% aqueous
solution of gelatin) 1,300 g
Gelatino Silver Chlorobromide Emulsion (silver chlorobromide with 70
mol% or and 30 mol% Bur~, mean grain size of 0.28 , and containing
55 g of gelatin and 0.85 mol of silver halide per kg of the emulsion) 2,000 g 0.1% Methanol Solution of 1,3-Diethyl-5-{2- [ 3-(3-sulfopropyl)- benzoxazole-2-ylidene ] ethylidene}-thiohydantoin Sodium Salt 100 ml 0.5% Alkali Aqueous Solution of 4-Hydroxy-6-methyl-1 ,3,3a,7- tetraazaindene 200 ml 2% Aqueous Solution of 2,4-Dichloro-6-hydroxy-2-triazine 70 ml
For comparison, Sample A was prepared by following the same procedure as in preparing Sample
No. 1 except that 2,000 g of a silver halide emulsion for an X-ray film, i.e., a silver iodobromide emulsion (silver iodobromide with 98 mol% Br and 2 mol% I-, mean grain size of 1.0 Xu, and containing 55 g of gelatin and 0.85 mol of silver halide per kg of the emulsion) in place of 2,000 g of the gelatino silver chlorobromide emulsion used in Sample A.
After allowing each sample to stand for 4 days at room temperature (about 20--300C), the sample was imagewise exposed to an original, i.e., a transparent micro negative film obtained by photographing characters reduced to about 1/6 of the original size in an enlargement of 6 times using an enlarger for microfilm having a light source of 300 lux for 5 seconds. In this case, Sample A was imagewise exposed through a gray filter having an optical density of 1.34.
Then, the following processing was employed using an automatic printing plate-making device.
Each sample was passed through the base liquid composition for the silver halide developer having the composition shown in Table 1 diluted 1:1 by volume with water or as it was at 3200 for 20 seconds and passed through fix solution (I) described below at 2000 for 10 seconds. Then, each sample was passed through an ultraviolet exposure section composed of three reflector type mercury lamps for 15 seconds, passed through wash-off solution (II) having the composition described below at 40 to 45 CC, rubbed with a brush, passed through squeeze rollers, passed through developer (II) having the composition shown below at 3000 for 30 seconds, and coated with a gum arabic solution to produce a printing plate.
Table 1
Silver Halide Developer Base Liquid Composition
I 11 Ill IV V A B C
Water 700 700 700 700 700 700 700 700
Sodium Sulfite 140 140 140 140 140 45 140 55
Hydroquinone 40 40 40 40 40 12 40 35
Metol - - - - - 3 - - 1-Phenyl-3-pyrazolidone - - - - - - 2.5
Compound (1-1) ) 2.5 - - 1.3 2.5 - -
Compound (1-2) - 2.5 - 1.2 - - - -
Compound (I-3) - - 1.2 - - - - 1.5
Compound (I-5) - - 1.3 - - - -
Sodium Carbonate - - - - - 80 -
Potassium Carbonate 40 40 40 40 40 - 40 40
Sodium Hydroxide 7 7 7 7 7 - 7 4
Diethylene Glycol 55 60 55 - - - - 40
Propylene glycol - - - 40 - - -
Potassium Bromide 15 15 15 15 15 2 15 10
Water to make 1l 1l 1l 1l 1l 1l 1l 1l
Fix Solution (I) Water 700 ml
Ammonium Thiosulfate 224 g
Sodium Sulfite 20 g Water to make 11 Wash-Off Solution (I)
Bioplase PN-4 (trade name of enzyme, made by Nagase Seikagaku
Kogyo K.K.) 10 g
Water to make 1 1
Developer (II)
Sodium Silicate (JIS #1) 100 g
Sodium Metasilicate 50 g
Pure Water 1,800 ml
The properties of each of Sample No. 1 and Sample A as a printing plate were evaluated by treating each sample in 5 m2/liter over a period of 4 days by the above-described printing plate-making process and by treating each sample in 10 m2/liter over a period of 8 days.The printing test was performed on each printing plate thus prepared using a Heidel Printing Machine and the results shown in Table 2 below were obtained.
Table 2
Silver Halide
Sample Developer Used 4 Days at 5 m2/liter 8 Days at 10 m2/liter
No. No. Dilution pH Treatment Treatment Coments
1 I 1:1 9.9 Good image quality Good image quality
1 II 1:1 9.9 Good image quality Good image quality
1 III 1:1 9.9 Good image quality Good image quality
1 IV 1:1 9.9 Good image quality Good image quality
1 V 1:1 9.9 Good image quality Image quality good
but some spots
A I 1:1 9.7 Poor sharpness of Poor sharpness of Poor development,
character edges, and character edges, and Insufficient
uneven image portions uneven image portions silver image
optical density
1 A 1:1 10.5 Insufficient image No image formation Insufficient
formation processing power
1 B 1:1 9.9 Good image quality Poor sharpness of Poor processing
character edges, and faculty, and poor
stain formed at non- preservative
image portions stability
1 C 1: :1 9.9 Poor sharpness of No image formed
character edges
1 C Base 10.0 Poor sharpness of Poor sharpness of
solution character edges character, developer
blackend, and roller
stained greatly From the results shown in Table 2 above, it can be seen that the lithographic printing plates obtained by the printing plate making process of this invention are excellent. In more detail, good results were obtained only when each of the amount of the sulfite, hydroquinone, and the 1-aryl-3pyrazolidone derivative was in a definite range. On the other hand, when 1 -phenyl-3-pyrazolidone which is not within the scope of the compounds, represented by the formula (I) was used, good results were not obtained even where the pyrazolidone was used in the above-described specific range (see the results for base liquid solution B for the silver halide developer shown in Table 2). Furthermore, even where the silver halide developer used in this invention was used, good results were not obtained when the mean grain size of the silver halide in the light-sensitive silver halide emulsion for the PS plate was larger than 0.7 micron (see Sample A shown in Table 2).
Claims (11)
1. A process of making a lithographic printing plate comprising
imagewise exposing a light-sensitive printing plate precursor comprising a support having a hydrophilic surface and having successively thereon a non-silver light-sensitive layer capable of forming an oleophilic image and a light-sensitive silver halide emulsion layer with silver halide grains having a mean grain size of 0.7 micron or below,
developing said silver halide emulsion layer with a silver halide developer,
fixing the developed layer,
exposing the light-sensitive printing plate to actinic light to which said non-silver light-sensitive layer is sensitive, and
after removing at least a part of said silver halide emulsion layer, developing said non-silver lightsensitive layer,
wherein said silver halide developer is an aqueous solution containing
(a) from 0.45 to 1.2 mols/liter of sulfite,
(b) from 0.09 to 0.45 mol/liter of hydroquinone and
(c) from 0.005 to 0.03 mol/liter of a compound represented by the formula (I)
wherein A represents an optionally substituted aromatic group; R,, R2 and R3, which may be the same or different, each represents a hydrogen atom or an optionally substituted aliphatic or aromatic group; and Z represents a hydrogen atom, an aminoalkyl group or a hydroxyalkyl group; with the proviso that
R1, R2, R3 and Z are not simultaneously hydrogen atoms,
and having a pH of 9 to 13.
2. A process of making a lithographic printing plate as claimed in Claim 1, wherein said non-silver light-sensitive layer comprises a layer of a diazo resin, an o-quinonediazido compound, a light-sensitive azido compound or a high molecular weight compound having a group of the formula
in the main chain or side chain thereof.
3. A process of making a lithographic printing plate as claimed in Claim 1 or 2, wherein R3 and Z of the compound represented by the formula (I) are hydrogen atoms.
4. A process of making a lithographic printing plate as claimed in Claim 3, wherein the compound is 4-methyl- 1 -phenyl-3-pyrazolidone, 4,4-dimethyl- 1 -phenyl-3-pyrazolidone, 4-hydroxymethyl-1 - phenyl-3-pyrazolidone, 4,4-d i(hydroxymethyl)- 1 phenyl-3-pyrazolidone, 4-methyl- 1 -p-tolyl-3pyrazolidone or 4-dimethylaminomethyl-1 -p-chlorophenyl-3-pyrazolidone.
5. A process of making a lithographic printing plate as claimed in any preceding claim, wherein said silver halide emulsion layer further contains fine particles of a substantially water-insoluble oleophilic resin dispersed therein.
6. A process of making a lithographic printing plate as claimed in Claim 5, wherein said olephilic resin is shellac, a polyamide resin, a phenol resin, a polyvinyl acetal resin, a linear polyurethane resin or a polyester resin.
7. A process of making a lithographic printing plate as described in any preceding claim, wherein said developer contains (a) from 0.55 to 1.2 mols/litre of sulfite, (b) from 0.18 to 0.40 mol/litre of hydroquinone and (c) from 0.006 to 0.01 5 mol/litre of the compound represented by the formula (I).
8. A process of making a lithographic printing plate as claimed in any preceding claim, wherein said developer further contains from 10 to 80 g/litre of a glycol represented by the formula (II)
wherein R4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R5 represents a hydrogen atom, a methyl group or an ethyl group; and n is an integer of 1 to 5.
9. A process of making a lithographic printing plate as claimed in Claim 8, wherein said glycol is ethylene glycol monomethyl ether, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol or butylene glycol.
10. A process of making a lithographic printing plate as claimed in any preceding claim, wherein the development with said developer is carried out at a temperature of 20 to 500C for a period of time of 10 to 120 seconds.
11. A process of making a lithographic printing plate, substantially as hereinbefore described with reference to any of the Samples used according to Claim 1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1462880A JPS56111852A (en) | 1980-02-08 | 1980-02-08 | Plate making method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2069164A true GB2069164A (en) | 1981-08-19 |
| GB2069164B GB2069164B (en) | 1983-07-06 |
Family
ID=11866454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8101826A Expired GB2069164B (en) | 1980-02-08 | 1981-01-21 | Lithographic printing plate making process |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS56111852A (en) |
| DE (1) | DE3104176A1 (en) |
| GB (1) | GB2069164B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6105500A (en) * | 1995-11-24 | 2000-08-22 | Kodak Polychrome Graphics Llc | Hydrophilized support for planographic printing plates and its preparation |
| US6138568A (en) * | 1997-02-07 | 2000-10-31 | Kodak Polcyhrome Graphics Llc | Planographic printing member and process for its manufacture |
| US6182571B1 (en) | 1996-11-21 | 2001-02-06 | Kodak Polcyhrome Graphics Llc | Planographic printing |
| US6293197B1 (en) | 1999-08-17 | 2001-09-25 | Kodak Polychrome Graphics | Hydrophilized substrate for planographic printing |
| US6357351B1 (en) | 1997-05-23 | 2002-03-19 | Kodak Polychrome Graphics Llc | Substrate for planographic printing |
| US6427596B1 (en) | 1997-05-23 | 2002-08-06 | Kodak Polychrome Graphics, Llc | Method for making corrections on planographic printing plates |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1093281A (en) * | 1963-03-22 | 1967-11-29 | Kodak Ltd | 3-pyrazolidones and their use as photographic developers |
| GB1227603A (en) * | 1968-02-29 | 1971-04-07 | ||
| JPS54152502A (en) * | 1978-05-19 | 1979-11-30 | Fuji Photo Film Co Ltd | Photosensitive printing plate material and method of making printing plate from said material |
-
1980
- 1980-02-08 JP JP1462880A patent/JPS56111852A/en active Granted
-
1981
- 1981-01-21 GB GB8101826A patent/GB2069164B/en not_active Expired
- 1981-02-06 DE DE19813104176 patent/DE3104176A1/en active Granted
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6105500A (en) * | 1995-11-24 | 2000-08-22 | Kodak Polychrome Graphics Llc | Hydrophilized support for planographic printing plates and its preparation |
| US6182571B1 (en) | 1996-11-21 | 2001-02-06 | Kodak Polcyhrome Graphics Llc | Planographic printing |
| US6138568A (en) * | 1997-02-07 | 2000-10-31 | Kodak Polcyhrome Graphics Llc | Planographic printing member and process for its manufacture |
| US6357351B1 (en) | 1997-05-23 | 2002-03-19 | Kodak Polychrome Graphics Llc | Substrate for planographic printing |
| US6427596B1 (en) | 1997-05-23 | 2002-08-06 | Kodak Polychrome Graphics, Llc | Method for making corrections on planographic printing plates |
| US6293197B1 (en) | 1999-08-17 | 2001-09-25 | Kodak Polychrome Graphics | Hydrophilized substrate for planographic printing |
| US6418850B2 (en) | 1999-08-17 | 2002-07-16 | Kodak Polychrome Graphics Llc | Hydrophilized substrate for planographic printing |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3104176C2 (en) | 1987-12-10 |
| GB2069164B (en) | 1983-07-06 |
| JPS56111852A (en) | 1981-09-03 |
| DE3104176A1 (en) | 1981-12-10 |
| JPS6119028B2 (en) | 1986-05-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19930121 |