JPH0798507A - Planographic printing material - Google Patents

Abstract

PURPOSE:To prevent the elongation of a plate, to ensure superior dimensional stability and to prevent color blurring in the case of color printing by using a plastic film contg. fibers as a substrate. CONSTITUTION:In a planographic printing material having at least a silver halide emulsion layer and a physical developing nucleus layer on the substrate and utilizing a silver salt diffusion transfer process, a plastic film contg. fibers is used as the substrate. This plastic film is formed by drawing a polyethylene terephthalate polymer contg. fibers such as glass fibers or whiskers. The pref. fiber content is 0.5-30wt.% and the thickness of the plastic film substrate is 50-500mum. When a hydrophilic colloidal layer using gelatin as the principal binder is tightly stuck on the plastic film substrate, a photographic emulsion is applied after surface activation treatment so as to obtain adhesive strength.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver salt offset printing material, which has a support excellent in dimensional stability without plate elongation, and has excellent characteristics not only for camera exposure but also for laser light. It relates to a lithographic printing material for laser having.

[0002]

2. Description of the Related Art Hitherto, many methods have been known as a lithographic printing material by a silver salt diffusion transfer method, in which a photosensitive element and a printed image element are integrated, and a physical development nucleus-containing layer is used. Japanese Patent Publication No. 48-30, which is present in the upper layer of the emulsion layer
562, JP-A-53-21602, 54-103.
No. 104, No. 56-9750, etc., and US Pat. No. 5,21.5, in which a layer containing physical development nuclei exists under the emulsion layer.
No. 3,943, No. 5,196,260 and the like are well known. The support used for the lithographic printing material by the silver salt diffusion transfer method is a cellulose acetate film, a cellulose acetate butyrate film, a polystyrene film, a polyethylene phthalate film, a polycarbonate film, a polyimide film or a laminate thereof, a paper. and so on. Furthermore, paper coated or laminated with a baryta or an α-olefin polymer, in particular an ethylene, polypropylene, ethylene butylene copolymer or the like, an α-olefin polymer having 2 to 10 carbon atoms is mentioned. Further, a support in which a metal foil, for example, an aluminum foil is laminated on paper or the above-mentioned film in order to reduce plate elongation is described.

However, with these supports, even if a metal foil is used and printed on a printing machine,
There is a problem that the plate gradually expands, and in particular, when performing color printing, there is a problem that color misregistration easily occurs due to overprinting.

In recent years, a direct plate-making technique using a laser beam has been developed, but in consideration of plate elongation, a metal plate (for example, an Al plate) must be used as a support, and therefore, an exposure system such as an image setter is used. However, there is a problem that it is limited to flat exposure as in the flat bed type, and there is a demand for a support that has flexibility to adapt to a drum type exposure system and that is difficult to plate extension.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a lithographic printing material having a silver image produced by a silver salt diffusion transfer method as an ink receptive material, which does not stretch and has excellent dimensional stability and color printing. The purpose of the present invention is to provide a lithographic printing material that is free from color misregistration even when used for printing.

[0006]

The above-mentioned object of the present invention is as follows.
A lithographic printing material utilizing a silver salt diffusion transfer method having at least a silver halide emulsion layer and a physical development nucleus layer on a support, wherein the support is a plastic film containing fibers. Achieved by the material. The fibers contained in the polyethylene terephthalate are glass fibers, carbon fibers, boron fibers, Usker, etc., which can be contained in the polyethylene terephthalate polymer and stretched to form a film. The film can be formed by the methods described in JP-B-48-40414, JP-A-50-81325 and JP-A-50-109715. The fiber content is preferably 0.5% by weight to 30% by weight, more preferably 1% by weight to 20% by weight. The plastic film support of the present invention has a thickness of 50 μm to 500 μm, preferably 80 to 300 μm, and more preferably 150 to 500 μm.
It is 300 μm.

On the plastic film (preferably polyethylene terephthalate) support of the present invention, a hydrophilic colloid layer using gelatin as a main binder (eg, silver halide emulsion layer, antihalation layer, intermediate layer, backing layer, etc.) The following method known in the related art can be used for firmly adhering). (1) Surface activation treatment such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, harmonic treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc. After that, a method of directly applying a photographic emulsion to obtain an adhesive force, and (2) a method of forming a subbing layer and then coating a photographic emulsion layer on the surface after these surface treatments or without surface treatment. There are two methods (for example, US Pat. Nos. 2,698,241 and 2,764,
No. 520, No. 2,864,755, No. 3,462,3
No. 35, No. 3,475, 193, No. 3, 143, 42
No. 1, No. 3,501,301, No. 3,460,944
No. 3,974,531, British Patent No. 788,3
No. 65, No. 804,005, No. 891,469, Japanese Patent Publication No. 48-43122, No. 51-446, etc.).

All of these surface treatments are thought to be caused by the formation of polar groups on the surface of the support, which was originally hydrophobic, and the increase of the crosslink density on the surface. It is considered that the affinity of the component contained in the undercoat liquid with the polar group is increased, or the fastness of the adhesive surface is increased. In addition, various arrangements have been made for the composition of the undercoat layer. A layer that adheres well to the support (hereinafter referred to as the first undercoat layer) is provided as the first layer, and a second layer is used as a photograph. A so-called multi-layer method of applying a hydrophilic resin layer (hereinafter, abbreviated as the second undercoat layer) that adheres well to a layer, and a single layer of applying a single resin layer containing both a hydrophobic group and a hydrophilic group There is a law.

Among the surface treatments of (1), corona discharge treatment is the most well known method, and any of the conventionally known methods, for example, Japanese Patent Publication Nos. 48-5043 and 47-5.
1905, JP-A-47-28067 and JP-A-49-83.
No. 767, No. 51-41770, No. 51-13157.
This can be achieved by the method disclosed in No. 6 or the like.
Discharge frequency is 50 Hz to 5000 KHz, preferably 5
KHz to several hundred KHz is suitable. If the discharge frequency is too low, stable discharge cannot be obtained and pinholes are generated in the object to be treated, which is not preferable. If the frequency is too high,
A special device for impedance matching is required, which increases the cost of the device, which is not preferable. Regarding the treatment strength of the object to be treated, in order to improve the wettability of ordinary polyester, polyolefin and other plastic films, 0.001 KV · A · min / m ^{2 to 5} KV · A · min /
m ² , preferably 0.01 KV · A · min / m ^{2 to 1} KV · A
・ Minute / m ² is appropriate. The gap clearance between the electrode and the dielectric roll is 0.5 to 2.5 mm, preferably 1.0 to
2.0 mm is suitable.

In many cases, the glow discharge treatment, which is the most effective surface treatment, is performed by any conventionally known method, for example, Japanese Patent Publication Nos. 35-7578 and 36-1033.
No. 6, No. 45-22004, No. 45-22005,
45-2440, 46-43480, U.S. Pat. Nos. 3,057,792, 3,057,795, 3,179,482, 3,288,638 and 3,309. No. 299, No. 3,424,735, No. 3,462,335, No. 3,475,307, No. 3,761,299, British Patent 997,093, JP-A No. 53-129262, etc. Can be used.

The glow discharge treatment conditions are generally pressure of 0.
005-20 Torr, preferably 0.02-2 Torr
r is suitable. If the pressure is too low, the surface treatment effect will be reduced, and if the pressure is too high, an excessive current will flow and sparks will easily occur, which is dangerous and may damage the object to be treated. The electric discharge is generated by applying a high voltage between metal plates or metal rods arranged in a vacuum tank with one or more pairs of spaces. This voltage is the composition of the atmosphere gas,
Although various values can be obtained depending on the pressure, normally, a stable steady glow discharge occurs between 500 and 5000 V within the above pressure range. A particularly suitable voltage range for improving the adhesion is 2000 to 4000V. Further, as seen in the prior art, a suitable discharge frequency is from direct current to several 1000 MHz, preferably 50 Hz to 20 MHz. Regarding the discharge treatment strength, 0.01KV · A · min / m ^{2 to} 5KV ·
A · min / m ² , preferably 0.15 KV · A · min / m ² -1
KV · A · min / m ² is suitable.

[0012] Next, regarding the undercoating method (2), all of these methods have been well studied, and for example, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid are used for the first undercoating layer in the multilayer method. , Itaconic acid, maleic anhydride, etc., starting with copolymers selected from monomers, polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and many other polymers The properties of the two layers have been investigated mainly for gelatin.

In the single layer method, good adhesion is often achieved by swelling many supports and interfacially mixing with the hydrophilic undercoat polymer. Examples of the hydrophilic undercoating polymer used in the present invention include water-soluble polymers, cellulose esters, latex polymers and water-soluble polyesters. As the water-soluble polymer, gelatin, gelatin derivative, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, maleic anhydride copolymer, etc.,
Examples of the cellulose ester include carboxymethyl cellulose and hydroxyethyl cellulose. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers and butadiene-containing copolymers. Of these, gelatin is the most preferable.

As the compound for swelling the support used in the present invention, resorcin, chlorresorcin, methylresorcin, o-gresol, m-cresol, p-gresol, phenol, o-chlorophenol, p-chlorophenol, dichloro. Examples include phenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, and chloral hydrate. Of these, resorcin and p-chlorophenol are preferred. Various gelatin hardeners can be used in the subbing layer of the present invention. As gelatin hardening agents, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), epichlorohydrin resin And so on.

The subbing layer of the present invention comprises SiO ₂ , Ti
O ₂ and inorganic fine particles such as a matting agent or polymethylmethacrylate copolymer fine particles (1 to 10 μm) can be contained as a matting agent. In addition to this, the undercoat liquid may contain various additives as required. For example, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants and the like. In the present invention, when the undercoat liquid for the first undercoat layer is used, it is not necessary to include an etching agent such as resorcin, chloral hydrate, chlorophenol, etc. in the undercoat liquid. However, if desired, an etching agent as described above may be contained in the base coat.

The undercoating liquid according to the present invention is generally well-known coating method such as dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, or US Pat. It can be applied by the extrusion coating method using the hopper described in the specification of 2,681,294. If desired, US Pat. No. 2,761,791
Issue No. 3,508,947 Issue 2,941,898
, And 3,526,528, Yuji Harasaki,
Two or more layers can be simultaneously coated by the method described in "Coating Engineering", page 253 (page 1973, published by Asakura Shoten). Hereinafter, the present invention will be described in more detail. The lithographic printing material (preferably laser light printing material) of the present invention is a layer in which an antihalation layer, a photosensitive silver halide emulsion layer and a physical development nucleus layer are provided on the support as described above. Although basically based on the configuration, an intermediate layer can be provided between the above layers. The sensitizing dye used in the present invention is preferably a compound represented by the following general formula (I).

[0017]

[Chemical 1]

(Wherein A is a lower alkyl group having 1 to 4 carbon atoms, R ¹ and R ² are the same or different lower alkyl groups, hydroxyalkyl groups, sulfoalkyl groups,
Represents a carboxyalkyl group. Y ¹ and Y ² are an oxygen atom, a sulfur atom and a selenium atom, respectively, and are Z ¹ and Z ^2.
Represents a condensed product of a benzene ring or a naphthalene ring which may have a substituent. X represents an alkali metal atom, an ammonium group, and n represents 0 or 1. ) Next, specific examples of the compound represented by the above general formula are shown.

[0019]

[Chemical 2]

[0020]

[Chemical 3]

[0021]

[Chemical 4]

The above compound can be prepared by a known method such as FMHam.
er "The Cyanine Dyes and Related Compounds"
(The Cyanine Soybean and Relied Compounds) 1964. The method described in the publication of Inter-Science Publishers, or British Patent No. 742,112,
It can be synthesized according to the method described in US Pat. No. 2,213,238. To add the compound to a silver halide emulsion by the method of the present invention, it is dissolved in water or a hydrophilic solvent such as methanol or ethanol and used. The addition time may be arbitrary, but preferably before or after the chemical aging. The amount of addition is sufficient in the range of 10 to 500 mg per mol of silver halide. The thus-obtained printing material of the present invention has compatibility with various laser beams as described above, and among these, application to helium-neon and argon lasers is preferable. Further, it can be applied to a semiconductor laser or a light emitting diode [LED].
In addition, JP-A-60-179744 and JP-A-59-7
No. 1055, Japanese Patent Publication No. 2-38941, Japanese Patent Publication No. 1-27
416, JP-A-62-105148, JP-A-62-
105149, JP-A-62-105150, JP-A-62-139555, JP-A-62-103649,
JP-A-62-105147, JP-A-63-24394
3, JP-A-2-251,853, and JP-A-53-21.
The sensitizing dyes described in the scope of claims such as No. 601 can also be used depending on the wavelength of laser light.

In the printing material of the present invention, it is preferable that a physical development nucleus layer is directly provided on the photosensitive silver halide emulsion layer in the above layer constitution. However, in the laminated support using Al foil, It is preferred to provide a light sensitive silver halide emulsion layer on top. In the present invention, the undercoat layer which is provided closest to the support and also serves as an antihalation layer is a hydrophilic colloid layer in which, for example, carbon black, a dye or a pigment is dispersed. Further, the silver halide composition of the photosensitive silver halide emulsion layer according to the present invention includes silver chlorobromide, silver chloride,
Silver chloroiodobromide is preferred, but silver bromide and silver iodobromide can also be used. A silver chlorobromide or silver chloroiodobromide emulsion containing a trace amount of silver iodide or silver bromide is particularly preferable. The method for preparing such a silver halide emulsion may be a method well known in the art, for example, a single jet method,
The double jet method or the control jet method can be used. The silver halide of the above silver halide emulsion has an average grain size of about 0.05 μ to 2.0 μm.
The range of μ is preferred. Further, in this silver halide emulsion, soluble salts are removed by a usual method after grain formation. After desalting, the above emulsion can be chemically sensitized with a sulfur sensitizer such as thiosulfate, allylthiocarbamide, thiourea and allylisothiocyanate. Further, US Pat. Nos. 2,399,083 and 2,597,856,
Gold compounds described in U.S. Pat. No. 2,597,915 and the like, U.S. Pat. Nos. 2,448,060 and 2,54
No. 0,086, No. 2,566,245, No. 2,5
The above emulsions can be ripened using noble metal salts such as platinum, palladium, iridium, rhodium and ruthenium described in Nos. 66,263 and 2,598,079.

As a hydrophilic binder which is advantageously used in the silver halide emulsion according to the present invention, there is gelatin, and a part or all of gelatin is a synthetic high molecular polymer such as polyvinyl alcohol or poly-N-vinyl. Pyrrolidone, a polyacrylic acid copolymer, a copolymer of methyl vinyl ether and maleic anhydride, or a compound substituted with a cellulose derivative, a gelatin derivative or the like can be used. Further, various compounds may be added to the above emulsion for the purpose of stabilizing the emulsion during the production process or storage or preventing the generation of fog during development. Further, in addition to the above compounds, for example, a sensitizer, a hardener, a surfactant and the like can be appropriately used. For specific compound examples, "Product Licensing Index" Vol. 92, No. 9232, 107- 110 pages, I-XI
II, XVI to XVII, XXIII, (December 1971). The photosensitive silver halide emulsion layer according to the present invention can be formed by coating the emulsion thus prepared as a layer on the antihalation layer by a known method.

Next, the development nuclei of the physical development nuclei layer according to the present invention will be described. For example, water-soluble noble metal salts such as gold, silver, platinum and palladium, or zinc, lead, cadmium, nickel, cobalt, iron, Metal colloids obtained by reducing heavy metals such as chromium, tin, antimony, and bismuth, or water-soluble metal salts of these, such as nitrates, acetates, borates, chlorides, and hydroxides are water-soluble. Development nuclei and the like obtained by mixing with sulfides such as sodium sulfide can be used. As the kind of the hydrophilic binder used in the physical development nucleus layer according to the present invention, the same kind of hydrophilic polymer substance as that used in the above-mentioned photosensitive silver halide emulsion layer is applied, but gelatin, carboxymethyl cellulose, Hydroxymethyl cellulose, albumin, starch, polyvinyl alcohol,
Gum arabic, polyvinylpyrrolidone, polyacrylamide, sodium alginate, a styrene-maleic anhydride copolymer, a copolymer of methyl vinyl ether and maleic anhydride, and the like are preferable, and they may be used in combination. The amount of these hydrophilic binders is not necessarily uniform depending on the type of precious metal or binder,
It is in the range of 30% to 100% by weight relative to the physical development nuclei. The physical development nucleus layer is preferably coated directly on the photosensitive silver halide emulsion layer.

As the support of the printing material according to the present invention, Japanese Patent Publication No. 47-19068 and Japanese Patent Publication No. 55-1975.
No. 6, a method for enhancing the adhesiveness to other polymer substances by roughening the surface, or JP-B-56
The surface roughening methods described in JP-B-135840, JP-B-62-50320, and JP-B-62-41480 can also be used. In order to reduce the plate elongation, a metal foil such as an aluminum foil can be used as a support laminated with paper.

Hardening treatment of the silver halide emulsion and / or other constituent layers can be carried out by a conventional method. Examples of the curing agent include aldehyde compounds such as formaldehyde and aldehydes such as glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), and 2-hydroxy-4,6-.
Dichloro-1,3,5-triazine, other U.S. Pat. Nos. 3,288,775 and 2,732,303,
British patents 974,723 and 1,167,207
Compounds having a reactive halogen as shown in each specification, divinyl sulfone, 5-acetyl-1,3
-Diacryloylhexahydro-1,3,5-triazine and other U.S. Pat. Nos. 3,635,718, 3,232,763, 3,490,911, and 3,642,486. , British Patent No. 994,869, etc., compounds having a reactive olefin, N-hydroxymethylphthalimide,
Other US Pat. Nos. 2,732,316 and 2,58
No. 6,168, N-methylol compounds as shown in each specification, isocyanates as shown in US Pat. No. 3,103,437, US Pat.
017,280, 2,983,611 and the like, aziridine compounds as shown in the respective specifications, US Pat. Nos. 2,725,294, and 2,725,295 and the like. Acid derivatives as shown in US Pat. No. 3,100,704, carbodiimide compounds as shown in US Pat. No. 3,100,704, and US Pat. No. 3,091,5.
Epoxy compounds as shown in US Pat. No. 37, U.S. Pat. Nos. 3,321,313 and 3,54
No. 3,292, isoxazole compounds as shown in each specification, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, or chromium as an inorganic hardener. There are vans and zirconium sulfate. Instead of the above compounds, precursors may be used, for example, alkali metal bisulfite aldehyde adducts, hydantoin methylol derivatives, primary aliphatic nitroalcohols and the like.

A known surfactant may be added to the printing material constituting layer of the present invention, if necessary, alone or in combination. These may be used as coating aids, but in some cases, they are also applied for other purposes such as emulsion dispersion, development acceleration, other improvement of photographic characteristics, charge series adjustment, and antistatic. These surfactants include natural products such as saponins, alkylene oxide-based, glycerin-based, glycidol-based, and fluorine-based anionic or nonionic surfactants, higher alkylamines, quaternary ammonium salts, pyridine and other heterocycles. , Cationic surfactants such as phosphonium or sulfonium, carboxylic acids,
Anionic surfactants having amino groups such as sulfonic acid, phosphoric acid, sulfuric acid ester, and phosphoric acid ester, amino acids,
Included are amphoteric activators such as amino sulfonic acids, sulfuric acid or phosphoric acid esters of amino alcohols. Some examples of these surfactant compounds that can be used are described in US Pat. Nos. 2,271,623 and 2,240,472.
No. 2, ibid. 2,288,226, ibid. 2,739,89
No. 1, No. 3,068, 101, No. 3, 158, 4
No. 84, No. 3,201,253, No. 3,210,
No. 191, No. 3,294,540, No. 3,41
No. 5,649, No. 3,441,413, No. 3,4
42,654, 3,475,774, 3,
545,574, British Patent 1,077,317,
No. 1,198,450, Ryohei Oda et al. “Synthesis of surfactants and their applications” (Maki Shoten, 1
964) and A. W. Perry, "Surf Active Agent" (Interscience Publications Incorporated, 1958), J. P. Sisley "Encyclopedia of Active Agents Vol. 2" (Chemical Publish Company, 1
964) and the like.

The printing material of the present invention contains US Pat. Nos. 2,274,782, 2,527,583, 2,956,879 and 2,956,879 as filter dyes or anti-irradiation dyes. No. 3,177,078,
No. 3,252,921 and Japanese Patent Publication No. 39-39
It may contain the compounds described in 22069.
These dyes are optionally incorporated into US Pat.
It may be mordanted by the method described in 699 specification.
Further, as the antihalation layer, a colored layer such as a pigment (for example, lamp black, carbon black, fast black, ultramarine, malachite green, crystal violet) can be used. As a method for applying the constituent layers of the printing material according to the present invention to the above-mentioned support, a coating method well known in the art can be used. For example, there are a dip method, an air knife method, an extrusion doctor method and the like, and the bead coating method described in US Pat. No. 2,761,791 is particularly preferable.

A silver halide developing agent may be incorporated in the constituent layers of the printing material according to the present invention. In this case, the development after exposure can be activated by an aqueous alkaline solution. The developing agent can be contained in the halogenated emulsion layer or its adjacent layer (undercoat layer, intermediate layer or antihalation layer). The developer may of course be included in the developer. As a specific compound of the developer,
Examples of polyhydroxybenzenes include hydroquinone, catechol, chlorohydroquinone, pyrogallol,
Bromohydroquinone, isopropylhydroquinone, tolhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, 2,3
-Dibromohydroquinone, 1,4-dihydroxy-2-
Acetophenone, 2,5-dimethylhydroquinone, 4-
Phenylcatechol, 4-t-butylcatechol, 4-
n-butylpyrogallol, 4,5-dibromocatechol, 2,5-diethylhydroquinone, 2,5-benzoylaminohydroquinone, 4-benzyloxycatechol,
4-n-butoxycatechol and the like are included. Among these, hydroquinone and methylhydroquinone are particularly preferably used.

As other developing agents, 3-pyrazolidone compounds such as 1-phenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1- Phenyl-
4,4-Dimethyl-3-pyrazolidone, 1-p-chlorophenyl-3-pyrazolidone, 1-p-methoxyphenyl-3-pyrazolidone, 1-phenyl-2-acetyl-
3-pyrazolidone, 1-phenyl-5,5-dimethyl-
3-pyrazolidone, 1-o-chlorophenyl-4-methyl-4-ethyl-3-pyrazolidone, 1-m-acetamidophenyl-4,4-diethyl-3-pyrazolidone,
1,5-diphenyl-3-pyrazolidone, 1- (m-tolyl) -5-phenyl-3-pyrazolidone, 4,4-dihydroxymethyl-1-phenyl-3-pyrazolidone,
4,4-dihydroxymethyl-1-tolyl-3-pyrazolidone, 4-hydroxymethyl-1-phenyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-
(P-chlorophenyl) -3-pyrazolidone and the like are included. Further, as aminophenols, for example, p-
(Methylamino) phenol, p-aminophenol,
2,4-diaminophenol, p- (benzylamino)
Examples thereof include phenol and 2-methyl-4-aminophenol.

The above developing agents can be used alone or in combination. Particularly, a combination of a polyhydroxybenzene compound and a 3-pyrazolidone compound is preferable. Although the amount of the developing agent used in the constituent layers is not uniform,
It may be in the range of 0.001 g to 1 g per 1 m ^{2, and in} the case of a silver halide emulsion layer 0.01 g to 3 g / g of silver halide.
Used in the range of. Further, if necessary, the constituent layers may contain a compound, which is referred to as a complexing agent, which easily forms a soluble silver complex salt with the unexposed portion of the silver halide, whereby physical development can be advantageously promoted. Examples of the complexing agent include thiosulfates, thiocyanates, and US Pat. No. 3,16.
Amine thiosulfates as described in JP-A-9,962, or cyclic imides described in JP-A-2,857,276, mercapto compounds described in JP-B-46-11957, and Europe. Patent Publication 535678A
The mesoionic compound described in 1 may be contained. The developing agents are dissolved in water or a hydrophilic solvent such as methanol, and then added to the coating solution, or
Alternatively, it may be dissolved in a high boiling organic solvent or a low boiling organic solvent and added. High boiling organic solvents generally have a boiling point of about 1
Alkyl esters of phthalic acid such as ethyl phthalate and n-butyl phthalate at 80 ° C. or higher,
Alternatively, there are phosphoric acid esters such as tricresyl phosphate. The low boiling point organic solvent is generally about 30 ° C to 1 ° C.
It has a boiling point of 50 ° C., and examples thereof include lower alkyl acetates such as ethyl acetate and butyl acetate.

These high and low boiling point solvents may be used in combination, and the dissolved developing agent may be dispersed in the hydrophilic colloid by any known method. When it is added to the constituent layers of the printing material according to the present invention, it is added directly to any layer or dissolved in gelatin or a synthetic polymer compound such as polyvinyl alcohol, polyvinylpyrrolidone, U.S. Pat. 3,488,708
Examples thereof include alkyl acrylates, sulfoalkyl acrylates, and acrylic acid copolymers described in the specification. When developing the printing material of the present invention,
Treatment liquids to which various substances are added can be used.

The main examples thereof are alkaline agents (eg, alkali metal or ammonium hydroxides, carbonates, phosphates), pH adjusting agents or buffers (eg, weak acids or weak bases such as acetic acid or sulfuric acid, or their bases). Salt), a development accelerator (for example, US Pat. Nos. 2,648,604 and 3,671,).
Various pyridinium compounds and cationic compounds described in US Pat. No. 247, etc., potassium nitrate and sodium nitrate, US Pat.
577,127, 2,950,970, etc., polyethylene glycol condensates and derivatives thereof, British Patent Nos. 1,020,033 and 1,020,032. Nonionic compounds such as polythioethers represented by the compounds described in the specification,
Polymer compounds having sulfite ester as represented by the compounds described in U.S. Pat. No. 3,068,097, other organic amines such as pyridine, ethanolamine, cyclic amine, benzyl alcohol, human azines, and JP-B-4. -44734 alkanolamine compounds), antifoggants (eg alkali chloride,
Alkali bromide, alkali iodide and US Pat. No. 2,49
No. 6,940 and No. 2,656,271, the nitrobenzimidazoles, mercaptobenzimidazole, 5-methylbenzotriazole, 1
-Phenyl-5-mercaptotetrazole, JP-A-56
Mercaptobenzoic acid described in -8145, cyclic imide compound, U.S. Pat. Nos. 3,113,864 and 3,34.
No. 2,596, No. 3,295,976, No. 3,6
Compounds for rapid processing solutions described in 15,522, 3,597,199 and the like, British Patent 972,2
No. 11, thiosulfonyl compounds, or phenazine-N-oxides as described in JP-B-46-41675 and other "Science Photographic Handbook", pages 29 to 47. Antifoggant), and other U.S. Pat. Nos. 3,161,513, 3,161,514, and British Patent 1,030,442.
No. 1, No. 1,144,481, No. 1,251,55
There are stain or anti-sludge agents described in No. 8 and preservatives (for example, sulfite salt, acidic sulfite salt, hydroxylamine hydrochloride salt, form sulfite, alkanolamine sulfite adjunct, etc.). Further, a sequestering agent such as sodium hexametaphosphate and ethylenediaminetetraacetic acid, a wetting agent such as saponin and ethylene glycol, and the like can be used.

Further, in the developer, as a silver halide solvent, sodium thiosulfate, sodium thiocyanate,
It can contain potassium thiocyanate, alkanolamines, cyclic imines, alkyl-substituted amino alcohols, thioureas, thiosalicylic acids, such as 5-methylcarbamoylthiosalicylic acid which can form thiosalicylic acid in alkaline solution. When it is necessary to stop development of the printing material according to the present invention after development, a neutralizing solution can be used. This neutralizing solution may be a normal acidic stop bath,
The pH may be adjusted to about 3.0 to 8.0.
The neutralizing solution may contain a water softening agent, a pH adjusting agent, a buffering agent, a film hardening agent and the like, and for the purpose of eliminating ink stains on the printing plate to be treated, colloidal silica,
Alternatively, polyols and the like may be added and contained, or the mercapto compound described in JP-B-56-3542 may be contained. After the printing material is processed as described above to obtain a plate, various post-treatments can be carried out for the purpose of improving and improving printability. For example, in order to improve ink receptivity, US Pat. Nos. 3,592,647 and 3,49
No. 0,906, No. 3,161,598, Japanese Patent Publication Nos. 46-10910, 48-29723, 51.
-15762 and 52-15762.

[0036]

【Example】

Example 1 A polyethylene terephthalate support (thickness: 175 μm) subjected to a subbing treatment was provided with a matting layer containing silica particles having an average particle size of 5 μ on one side, and carbon black was added on the opposite side to a photographic gelatin. On the other hand, a halation-preventing undercoat layer containing 20% by weight of silica powder having an average particle size of 7 μm (adjusted to pH 4.0), and a silica powder having an average particle size of 7 μm after being chemically sensitized with a metal compound. Including
A high-sensitivity silver chlorobromide emulsion (AgCl ₉₉ Br ₁ ) layer containing 1 × 10 ⁻² mol / Ag mol of the sensitizing dye (15) was provided. The subbing layer gelatin is 3.0 g / m ² , and the emulsion layer gelatin is 1.0 g / m ² .
m ^2, and is applied at a rate of silver halide 1.8 g / m ² in terms of silver nitrate. This undercoat layer contains formalin as a hardening agent at 5.0 mg / g gelatin with respect to gelatin. After drying and heating at 40 ° C. for 14 days, the emulsion coating is coated with the core coating solution described in Example 2 of JP-A-53-21602 and dried to produce a lithographic printing plate. The silver halide emulsion is prepared by physically ripening it per mol of silver halide.
5 × 10 ^-7 mol of rhodium chloride and iridium ammonium chloride were added in an amount of 2 × 10 ^-8 mol, and the average particle size was 0.3 μ, and within the range of ± 30% of the average particle size, 9
It was a substantially cubic crystal in which 0% or more was distributed. This flat plate material is designated as A (comparative example). Planographic material A
On the other hand, as shown in Table 1, only the support was changed to polyethylene terephthalate containing glass fibers or carbon fibers to prepare planographic printing materials B to F.

[0037]

[Table 1]

Plate making method: Imagesetter (Linotronic 30
(0: He-Ne laser light source), a color image of 150 lines was output to each of Samples A and B in 4 plates.

Subsequently, the printing material was developed with the following processing solution. <Transfer developer> Water 700 ml Potassium hydroxide 20 g Anhydrous sodium sulfite 50 g Hydroquinone 20 g 2-Mercaptobenzoic acid 1.5 g 2-Methylaminoethanol 15 g Water to 1 liter After development, the original plate is placed between two squeezing rollers. The excess developing solution was removed by passing through, and immediately treated with a neutralizing solution having the following composition at 25 ° C. for 20 seconds, the excess solution was removed with a squeezing roller, and dried at room temperature.

<Neutralizing liquid> Water 600 ml Citric acid 10 g Sodium citrate 35 g Colloidal silica (20% liquid) 5 ml Ethylene glycol 5 ml Water is added to bring the total volume to 1 liter. Each lithographic printing plate was mounted on an offset printing machine, the following desensitizing liquid was applied all over the print, and printing was performed using the following dampening liquid.

<Desensitizing liquid> Water 600 ml Isopropyl alcohol 400 ml Ethylene glycol 50 g 3-Mercapto-4-acetamido-5-n-heptyl-1,2,4-triazole 1 g <Moisturizing liquid> O-phosphoric acid 10 g Nitric acid Nickel 5 g Sodium sulfite 5 g Ethylene glycol 100 g Colloidal silica (20% liquid) 28 g Water is added to make 2 liters.

As the printing machine, an AB Dick offset printing machine for multicolor printing was used, and the color misregistration of the printed matter was evaluated according to each number of printed sheets. The results are shown in Table 2.

[0043]

[Table 2]

It can be seen that the printing plate of the present invention is less likely to cause color shift, probably because of its high tensile strength.

[0045]

EFFECTS OF THE INVENTION With the constitution of the present invention, it has high sensitivity comparable to a scanner film (eg, LS4500 manufactured by Fuji Photo Film Co., Ltd.), and does not easily stretch like a PS plate (Al plate). In addition, it is possible to provide printing performance (for example, no color misregistration) compatible with color offset printing.

Claims (6)

[Claims] 1. A lithographic printing material utilizing a silver salt diffusion transfer method having at least a silver halide emulsion layer and a physical development nucleus layer on a support, wherein the support is a plastic film containing fibers. A lithographic printing material characterized by: 2. The lithographic printing material according to claim 1, wherein the fiber in claim 1 is a glass fiber. 3. The lithographic printing material according to claim 1, wherein the fiber in claim 1 is a carbon fiber. 4. The lithographic printing material according to claim 1, wherein the fiber in claim 1 is a boron fiber. 5. The lithographic printing material according to claim 1, wherein the fibers in claim 1 are whiskers. 6. The planographic printing material according to claim 1, wherein the plastic film according to claim 1 is polyethylene terephthalate.