JPH096004A - Film unit by silver salt diffusion transfer method and planographic printing plate - Google Patents

Abstract

PURPOSE: To provide a film unit or planographic printing plate which is safe and has excellent dimensional accuracy by using substantially the water alone without using a processing liquid. CONSTITUTION: A photosensitive material having at least a) an image receiving layer contg. a silver precipitant, b) a release layer, c) a halation preventive layer having a light shielding function and d) a photosensitive silver halide emulsion layer on a base is subjected to imagewise exposing and is thereafter, its film surface is brought into tight contact with a processing sheet having a hydrophilic colloidal layer contg. a silver halide solvent on a base, by which the photosensitive material is subjected to silver salt diffusion transfer development in the presence of water, a developing agent, base and/or base precursor. The photosensitive material is peeled at its release layer at the time of peeling afterward and the layers upper than the release layer are stripped in tight contact with the processing sheet, by which the positive image is obtd. on the photosensitive material. The base of such film unit is a styrene polymer having a syndiotactic structure.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film unit used for a monochrome image by a silver complex salt diffusion transfer method, such as a film for printing plate making and a lithographic printing plate.

[0002]

2. Description of the Related Art An image forming method by a diffusion transfer method using a silver salt such as silver halide is well known. Explaining the method in detail, for example, an imagewise exposed light-sensitive silver halide emulsion is treated with an alkaline aqueous solution containing a developer, a silver halide solvent and a film-forming agent (thickener) to obtain an exposed halogen. The silver halide grains are reduced to silver by a developer, while the remaining unexposed silver halide grains are made into a transferable silver complex salt by a silver halide solvent, and the silver complex salt is superposed on the emulsion layer to form a silver precipitate. It consists of diffusing and transferring to the agent-containing layer (image receiving layer) by permeation, where the silver complex salt is reduced with a developer with the aid of a silver precipitating agent to obtain development. In carrying out this method, for example, a light-sensitive element having a light-sensitive silver halide emulsion layer usually provided on a support, an image-receiving element and a developer having an image-receiving layer containing a silver precipitating agent on a support, a halogenated compound are used. A film unit is used which is combined with a processing element consisting of an active alkali aqueous solution containing a silver solvent and a film forming agent. First, the emulsion layer of the light-sensitive element is imagewise exposed, and then the light-sensitive element is superposed so that the emulsion layer and the image-receiving layer of the image-receiving element face each other, while a pair of viscous aqueous alkali solutions of the processing element is developed therebetween. Pass between the rollers. Then, after leaving the image receiving element for a predetermined period of time and peeling the image receiving element from the photosensitive element, a print having a desired image formed on the image receiving layer can be obtained.

Further, in the light-sensitive material using this silver salt diffusion transfer method, a film unit having a peeling layer provided between the image receiving layer and the emulsion layer for the purpose of peeling and removing the emulsion layer containing the processing composition. Are described in JP-A-2-205845. However, in JP-A-2-205845, since a viscous and highly alkaline liquid is used as the treatment liquid, the handling risk is high. Further, as a release layer having a similar release layer, there is a release layer between the image receiving layer and the photosensitive layer, hydrophilic layers are provided on both sides of the release layer, and one layer contains a granular substance (US Patent 4499174), having a light opaque layer between the image receiving layer and the photosensitive layer (US Pat. No. 373).
0718), two release layers (a layer containing gelatin and a layer containing a hydrophilic polymer not containing gelatin) are provided between the image-receiving layer and the photosensitive layer, and at least the two layers adjacent to the release layer are provided. One layer contains no pigment (JP-A-60-
No. 42755), etc., but all of them use a viscous and highly alkaline treatment liquid, and thus have problems in handling.

Further, a printing plate has been already put into practical use in which a silver complex diffusion transfer method is applied to make the formed surface metallic silver pattern lipophilic and to be used as an ink receiving property. For example, as described in JP-B-48-16725 and JP-A-48-30562, a "physical development nucleus" composed of a heavy metal or a sulfide thereof is used alone or in a specific proportion of a polymer compound as a binder. A printing plate composed of an image-receiving layer and a silver halide emulsion layer contained therein, and a novel material having improved printing characteristics and photographic characteristics has also been proposed. However, many of these lithographic printing plates use a highly alkaline activator as a processing liquid, which poses a problem in handling the processing liquid and waste liquid. Further, it is required that the dimensional stability is good for use as a photomechanical material. A polyester-based polymer typified by polyester terephthalate (hereinafter referred to as PET) is generally used as a plastic support of a light-sensitive material used in photoengraving. But P
In ET, there are dimensional changes before and after development and dimensional changes due to expansion and contraction due to temperature and humidity changes, and there was a problem in registering a plurality of plates in multicolor printing. This is an important item for dimensional stability not only in intermediate materials such as films for photolithography but also in printing plates such as lithographic printing plates, and there has been a strong demand for photosensitive materials that do not undergo dimensional changes during development processing.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel film unit which is safe by using substantially only water without using a developing solution and has a small dimensional change due to changes in temperature and humidity. , To provide a new lithographic printing plate.

[0006]

The object of the present invention is to provide, on a support, at least a) an image-receiving layer containing a silver precipitating agent, b) a peeling layer, c) an antihalation layer having a light-shielding function, and d).
After imagewise exposure of a light-sensitive material having a light-sensitive silver halide emulsion layer, a treatment sheet having a hydrophilic colloid layer containing a silver halide solvent on the support is brought into close contact with the film surface,
After performing silver salt diffusion transfer development in the presence of water and a developing agent, a base and / or a base precursor, the peeling layer of the photosensitive material peels when peeling, and the layer above the peeling layer adheres to the processing sheet. And a film unit capable of being stripped off to obtain a positive image on a light-sensitive material, wherein the support is a styrene polymer having a syndiotactic structure, and a silver salt diffusion transfer film unit and a support. A light-sensitive material having at least a) a hydrophilic undercoat layer, b) an image-receiving layer containing a silver precipitating agent, c) a peeling layer, d) an antihalation layer having a light-shielding function, and e) a light-sensitive silver halide emulsion layer. After imagewise exposure to the above, the treatment sheet having a hydrophilic colloid layer containing a silver halide solvent on the support is brought into close contact with the film surface, and in the presence of water, a developing agent, a base and / or a base precursor. After peeling after silver salt diffusion transfer development, the layer above the release layer of the light-sensitive material is intimately adhered to the processing sheet and peeled off, and the positive image remaining on the light-sensitive material is used as the ink receiving property. A lithographic printing plate was achieved by a silver salt diffusion transfer lithographic printing plate characterized in that the support was a styrene polymer having a syndiotactic structure.

A preferred embodiment of the film unit of the present invention will be described. Photosensitive material Protective layer: containing at least gelatin Silver halide emulsion layer: containing at least one silver halide emulsion Antihalation layer: containing at least one pigment having absorption at the wavelength of exposure light source Release layer: at least one release Receptor layer containing agent: At least one silver precipitant Support: Film or paper Treatment sheet Treatment layer: At least one silver halide solvent,
A base precursor and a developing agent are included, and at least gelatin is used as a binder. Support: film or paper processing solution No development processing component is contained, and it is substantially water. However,
A small amount of antibacterial agent for the purpose of preventing water stain may be contained.

A preferred embodiment of the planographic printing plate of the invention will be described. Photosensitive material Protective layer: containing at least gelatin Silver halide emulsion layer: containing at least one silver halide emulsion Antihalation layer: containing at least one pigment having absorption at the wavelength of exposure light source Release layer: at least one release Receptor layer containing agent: Undercoat layer containing at least one silver precipitating agent: Containing at least gelatin Support: Film or paper The treatment sheet and the treatment liquid are the same as those in the preferred embodiment of the film unit described above. As a layer structure, an undercoat layer and an image receiving layer are provided in this order on a support. A release layer is provided adjacent to the image receiving layer, but a protective layer containing gelatin may be provided between the image receiving layer and the release layer for the purpose of improving the scratch resistance of the image after processing. On the release layer,
An antihalation layer, a silver halide emulsion layer and a protective layer are provided in this order. Gelatin is preferable as the binder contained in the undercoat layer, and the coating amount is 0.3 to 3.0 g.
/ M ² is preferred. In the undercoat layer, colloidal silica is added to the binder in an amount of 20 to 200% by weight, and silica mat having an average particle diameter of 0.1 to 5 μ is added to the binder in an amount of 5 to 5.
It is also preferable to add -30% by weight.

Next, a film (SPS film) made of a styrene polymer having a syndiotactic structure used as a support in the present invention will be described. The styrene-based polymer having a syndiotactic structure used in the present invention is a steric structure in which a phenyl group which is a side chain and its derivative are alternately located in opposite directions with respect to the main chain formed from carbon-carbon bonds. And its stereoregularity (tacticity) is based on the nuclear magnetic resonance method ( ¹³ C) using isotope carbon.
-NMR method) is general and excellent in accuracy. The stereoregularity measured by this ¹³ C-NMR method is the existence ratio of a plurality of continuous structural units, for example, 2
The number can be indicated by a diad, the number of three by a triad, and the number of five by a pentad. The styrene-based polymer having a syndiotactic structure as referred to in the present invention is usually a racemic dyad of 75% or more, preferably 85% or more, or a racemic pentad of 30% or more, preferably 50% or more of stereoregularity. It has a sex. Specifically, stereoregular polystyrene, poly (alkyl styrene), poly (halogenated styrene), poly (halogenated alkyl styrene), poly (alkoxy styrene), poly (vinyl benzoic acid ester), hydrogenated compounds of these It refers to a coalesced product, a mixture thereof, or a copolymer containing these structural units.

As the poly (alkylstyrene), poly (methylstyrene), poly (ethylstyrene), poly (propylstyrene), poly (butylstyrene), poly (phenylstyrene), poly (vinylnaphthalene). , Poly (vinylstyrene), poly (acenaphthylene), and the like, and poly (halogenated styrene) includes poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene), and the like. Examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene). Further, as the comonomer component of the copolymer containing these structural units, in addition to the monomer of the styrene-based polymer as described above,
Examples thereof include olefin monomers such as ethylene, propylene, butene, hexene and octene, diene monomers such as butadiene and isoprene, cyclic olefin monomers, cyclic diene monomers and polar vinyl monomers such as methyl methacrylate, maleic anhydride and acrylonitrile. . Among these, particularly preferable styrene polymers include polystyrene, poly (alkylstyrene), hydrogenated polystyrene, and copolymers containing these structural units.

The molecular weight of the styrene polymer is not particularly limited, but the weight average molecular weight is 10,000 or more and 3,000 or more.
It is preferably 0,000 or less, particularly preferably 50,000 or more and 1,500,000 or less. Further, the molecular weight distribution is not limited in its breadth and width, and various materials can be applied, but the weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 1.5 or more and 8 or less. The styrene-based polymer having the syndiotactic structure is remarkably excellent in heat resistance as compared with the conventional styrene-based polymer having the atactic structure.

The styrene-based polymer having such a syndiotactic structure can be obtained, for example, by using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst in an inert hydrocarbon solvent or in the absence of a solvent. It can be produced by polymerizing a weight-based product (monomer corresponding to the styrene-based polymer) (JP-A-62-62).
187708). Alternatively, it can be produced by polymerizing with a compound comprising a titanium compound and a cation and an anion in which a plurality of groups are bound to an element as a catalyst (JP-A-4-249504).

In the present invention, the styrene-based polymer is used as a material for the film, but other resin components may be contained within the range not impairing the object of the present invention. For example,
Styrene polymers with atactic or isotactic structures, polyphenylene ether, etc., polyolefins such as polyethylene, polypropylene, polybutene, polypentene, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, nylon-6 and nylon-6, Polyamides such as 6 and polythioethers such as polyphenylene sulfide,
Polycarbonate, polyarylate, polysulfone, polyetheretherketone, polyethersulfone, polyimide, halogenated vinyl polymers such as Teflon, acrylic polymers such as polymethylmethacrylate, polyvinyl alcohol, crosslinked resins containing the above resins, Can be mentioned.

Further, inorganic fine particles, antioxidants, antistatic agents, dyes and the like can be blended within the range not impairing the object of the present invention. The inorganic fine particles that can be used here include IA group, IIA group, IVA group, VIA group, VIIA group, VIII group.
Group, IB, IIB, IIIB, IVB group oxides,
Hydroxides, sulfides, nitrides, halides, carbonates,
Examples thereof include acetates, phosphates, phosphites, organic carboxylates, silicates, titanates, borates and hydrous compounds thereof, complex compounds centering on them, and natural mineral particles. Specifically, group IA element compounds such as lithium fluoride, borax (sodium borate hydrate), magnesium carbonate,
Magnesium phosphate, magnesium oxide (magnesia),
Magnesium chloride, magnesium acetate, magnesium fluoride, magnesium titanate, magnesium silicate, magnesium silicate hydrous salt (talc), calcium carbonate, calcium phosphate, calcium phosphite, calcium sulfate (gypsum), calcium acetate, calcium terephthalate, hydroxylation Calcium, calcium silicate, calcium fluoride, calcium titanate, strontium titanate,

Group IIA element compounds such as barium carbonate, barium phosphate, barium sulfate and barium phosphite, titanium dioxide (titania), titanium monoxide, titanium nitride, zirconium dioxide (zirconia), zirconium monoxide, etc.IVA
Group element compounds, molybdenum dioxide, molybdenum trioxide,
Group VIA element compounds such as molybdenum sulfide, manganese chloride,
Group VIIA element compounds such as manganese acetate, cobalt chloride,
Group VIII element compounds such as cobalt acetate, I such as cuprous iodide
Group B element compounds, IIB group element compounds such as zinc oxide and zinc acetate, IIIB group element compounds such as aluminum oxide (alumina), aluminum oxide, aluminum fluoride, aluminosilicate (alumina silicate, kaolin, kaolinite), oxidation Examples thereof include particles of IVB group elements such as silicon (silica, silica gel), graphite, carbon, graphite, and glass, and natural mineral particles such as carnal stone, kainite, mica (mica, quinnemo), and birose ore.

The SPS film of the present invention is a film made of the above materials and has a thickness of 20 to 500 μm.
And haze is 3% or less. In order to obtain a film having a thickness and haze within this range, a film having a relatively low crystallization rate is suitable. Among the above styrene-based polymers, those having a slow crystallization rate are random copolymers having a content of 30 mol% or less, for example, styrene-alkylstyrene copolymers. Here, the content of the alkylstyrene unit is 1 to 30 mol%, preferably 1 to 20 mol%, more preferably 1 to 15 mol%.
It is.

Further, in order to obtain a film having the above-mentioned properties in the present invention, the residual styrene monomer content in the styrene polymer or its composition is preferably 7,000 ppm or less. In order to obtain such a styrene polymer or composition, the following method may be used. (1) A method of drying under reduced pressure the styrene-based polymer after polymerization or after further treatment. When drying under reduced pressure here,
Efficiency is good when the drying temperature is set to a temperature not lower than the glass transition temperature of the polymer. (2) Further, deaerate with an extruder to obtain a molding material (pellet) at the same time. Here, the extruder preferably has a vent,
Either a single-screw or twin-screw extruder may be used. If the residual monomer volatile content exceeds 7,000 ppm, the haze may exceed 3% because of foaming during extrusion formation or roughening of the surface during stretching, which is not preferable.

A film is produced by using the styrene polymer of the present invention or the composition containing the polymer as a raw material. The method for producing the film is not particularly limited as long as it can be carried out under the condition that the above object can be achieved. Specifically, it is manufactured by heating, melting, extruding, cooling and solidifying.
The extruder used here may be a single-screw extruder or a twin-screw extruder, and may be a vented or non-vented one. It is preferable to use an appropriate mesh filter in the extruder for pulverizing and removing secondary aggregated particles or removing dust and foreign matter. The extrusion conditions are not particularly limited and may be appropriately selected depending on various circumstances, but are preferably selected in the range of the melting point of the temperature forming material to a temperature 50 ° C. higher than the decomposition temperature, such as T-die. Using.

After the extrusion formation, the obtained preform (raw sheet) is cooled and solidified. Various refrigerants such as a gas, a liquid, and a metal roll can be used at this time.
When a metal roll or the like is used, a method such as an air knife, an air chamber, a touch roll, and electrostatic imprinting is effective in preventing thickness unevenness and waving. The temperature for cooling and solidification is usually in the range of 0 ° C. to a temperature 30 ° C. higher than the glass transition temperature of the original sheet, preferably 50 ° C. lower than the glass transition temperature to a glass transition temperature. The cooling rate is 20
It is appropriately selected within the range of 0 to 3 ° C / sec. The raw sheet obtained in this manner has a thickness in the range of 100 to 5,000 μm.

Next, the cooled and solidified raw sheet is uniaxially or biaxially stretched. In the case of biaxial stretching, it may be simultaneously stretched in the machine direction and the transverse direction, but may be sequentially stretched in any order. The stretching may be performed in one stage or in multiple stages. Here, as the stretching method, there are various methods such as a tenter method, a method of stretching between rolls, a method of bubbling using gas pressure, and a method of rolling, and these may be appropriately selected or combined and applied. Generally, the stretching temperature may be set between the glass transition temperature and the melting point of the original sheet. However, in the case of successive stretching or multi-stage stretching, it is preferable that the first stage is performed in the range of glass transition temperature and cold crystallization temperature, and the latter stage is performed in the range of glass transition temperature and melting point. The stretching speed is usually 1 × 10
~ 1 x 10 ⁷ % / min, preferably 1 x 10 ³ to 1 x 10
⁷ % / min. Here, the area stretching ratio is 8 times or more, preferably 10 times or more, and if it is less than 8 times, it is difficult to obtain a film which is transparent and has smoothness, heat absorption dimensional stability, and thermal dimensional stability.

The stretched film obtained by stretching under the above conditions
Dimensional stability at high temperature, heat resistance, fill
In order to improve the strength balance of the in-plane
And are preferred. Heat setting is done by the usual method
This stretched film can be tensioned or relaxed.
The glass of the film under
Transfer temperature to melting point, preferably the upper limit of operating environment temperature to melting point
By holding for 0.5 to 1880 seconds.
Just do it. In addition, this heat setting changes the conditions within the above range.
It is also possible to do it more than once. Also this heat fixing
Under an inert gas atmosphere such as argon gas or nitrogen gas
You can go. Here, to obtain a film with a small heat shrinkage
Therefore, either of the steps of heat setting should be performed in the restricted shrinking state.
Is preferable, and the rate of limited shrinkage is in the longitudinal direction and / or
Or 20% or less, preferably 15% or less. further
The absolute value of the birefringence of the film under the conditions of stretching and heat setting | △ n
Is 40 × 10 ^-3By adjusting so that
The film is excellent in physical properties such as transparency and is preferable.
Yes.

Production Example 1 (1) Preparation of contact product of trimethylaluminum and water
Acid copper pentahydrate (CuSO _Four・ 5H₂O) 17.8 g (71
Mmol), toluene 200 ml and trimethylaluminium
Add 24 ml (250 mmol) of um and at 40 ° C for 8 hours
Reacted. After that, the solution obtained by removing the solid part
Further, toluene was distilled off under reduced pressure at room temperature to obtain a contact product.
6.7 g was obtained. Decrease the freezing point of the molecular weight of this contact product
It was 610 when measured by the method.

(2) Production of styrene polymer In a reaction vessel having an internal volume of 2 liters, 950 ml of purified styrene was added.
And 50 ml of p-methylstyrene, 5 mmol of the contact product obtained in the above (1) as an aluminum atom, 5 mmol of triisobutylaluminum, and 0.025 mmol of pentamethylcyclopentadienyl titanium trimethoxide. A polymerization reaction was carried out at 5 ° C for 5 hours. After completion of the reaction, the product was decomposed with sodium hydroxide in methanol to decompose the catalyst component, repeatedly washed with methanol, and dried to obtain 308 g of a polymer. The resulting copolymer had a co-syndiotactic structure and 9.5 p-methylstyrene units.
It was confirmed by ¹³ C-NMR that it contained mol%. The weight average molecular weight was 438,000, and the weight average molecular weight / number average molecular weight was 2.51.

Production Example 2 Production of Styrenic Polymer (JP-A-1-316246 Reference Example 2) 6 liters of toluene and 5 mmol of tetraethoxytitanium as a reaction solvent and 500 mmol of methylaluminoxane as an aluminum atom were placed in a reaction vessel,
At 50 ° C., 48.75 mol of styrene and 1.25 mol of p-methylstyrene were added and a polymerization reaction was carried out for 2 hours. After completion of the reaction, the product was washed with a mixed solution of hydrochloric acid and methanol to decompose and remove the catalyst component. Then, it was dried to obtain 640 g of a copolymer. This copolymer had a weight average molecular weight of 440,000, a number average molecular weight of 240,000 and a melting point of 255 ° C. The content ratio of the p-methylstyrene unit in this copolymer was 5 mol%. Further, this copolymer was analyzed by ¹³ C-NMR to find that it was 145.11 ppm, 145.22 ppm, 14
Absorption was observed at 2.09 ppm, and the syndiotacticity of the styrene unit in the racemic pentad calculated from the peak area was 72%.

Specific examples of the silver precipitating agent contained in the image-receiving layer include heavy metals such as iron, lead, zinc, nickel, cadmium, tin, chromium, copper and cobalt, particularly noble metals such as gold, silver, platinum and palladium. There is. Other useful silver precipitants are sulfides and selenides of heavy and noble metals, especially mercury, copper, aluminum, zinc, cadmium, cobalt, nickel, silver, lead, antimony, bismuth, cerium, magnesium, gold, platinum and palladium. And the selenides of lead, zinc, antimony and nickel. Particularly, gold, platinum, palladium or their sulfides are preferable. The addition amount of physical development nuclei cannot be specified because the effect depends greatly on the kind and size of nuclei, but it is not more than 1 g / m ² , especially 0.1 g / m ²
The following is desirable.

The peeling layer must have a function of keeping the image-receiving element and the light-sensitive element in close contact with each other when untreated and peeling off cleanly after the treatment. Preferred examples of such a release agent include those disclosed in JP-A-47-8237 and JP-A-56-6.
5133, ibid. 59-220727, ibid. 59-22955
5, JP-B-49-4334, 49-4653, 45
-24075, U.S. Patents 3,220,835 and 43,595.
18, the same 3227550, the same 2759825, the same 440
1746 and 4366227. Specific examples include water-soluble (or alkali-soluble) cellulose derivatives. Examples include hydroxy cellulose, cellulose acetate phthalate, plasticized cellulose, carboxymethyl cellulose and the like. Also,
There are various natural polymers such as alginic acid, pectin, and gum arabic. Also, various modified gelatins, for example, acetylated gelatin, phthalated gelatin and the like can be used. Furthermore, water-soluble synthetic polymers can also be used. For example, polyvinyl alcohol, polyacrylate, polymethacrylate, butyl methacrylate, or a copolymer thereof may be used. The release layer may be a single layer or may be composed of a plurality of layers. Examples thereof are disclosed in JP-A-59-220727 and JP-A-60-60642.
Etc.

The antihalation layer may be formed using a known dye or pigment. Further, it is advantageous to use an infrared absorber or carbon black for providing the antihalation layer on the infrared photosensitive layer. It is particularly advantageous to use carbon black for preventing halation. As a specific embodiment, those described in Japanese Patent Application No. 61-18963 can be used. In the present invention, as a base precursor in the image forming reaction system, a compound that can undergo a complex formation reaction in water as a medium, with respect to a water-insoluble basic metal compound and a metal ion constituting the basic metal compound (hereinafter, Complexing compound) and the reaction between these two compounds in the presence of water elevates the pH of the reaction system. The image forming reaction system in the present invention means a region where an image forming reaction occurs. Specifically, for example, it refers to a layer belonging to both the photosensitive material and the processing sheet.

In the present invention, water used as a medium is
Water can be supplied by a method of supplying water from the outside, a method of preliminarily including a capsule containing water in the image forming reaction system, and destroying the capsule by heating to supply water. Examples of the water-insoluble basic metal compound used in the present invention include 2
Carbonates, phosphates, silicates, borates, aluminates, hydroxides, oxides having a solubility in water at 0 ° C. (the number of grams of a substance soluble in 100 g of water) of 0.5 or less, And double salts of these compounds such as basic salts. And what is represented by Formula TmXn is preferable. Here, T represents a transition metal, for example, Zn, Ni, Co, Fe, Mn, or the like, or an alkaline earth metal, for example, Ca, Mg, Ba, or the like, and X represents a complex forming compound described later in water. M coming out
Capable of being a counter ion of and exhibiting alkalinity, for example, carbonate ion, phosphate ion, silicate ion,
Borate ion, aluminate ion, hydroxy ion,
Represents an oxygen atom. m and n each represent an integer such that the valences of T and X are balanced.

Preferred specific examples are listed below. Calcium carbonate, barium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, magnesium calcium carbonate (CaMg (Co ₃ ) ₂ ), magnesium oxide, zinc oxide, tin oxide, cobalt oxide, zinc hydroxide, aluminum hydroxide,
Magnesium hydroxide, calcium hydroxide, antimony hydroxide, tin hydroxide, iron hydroxide, bismuth hydroxide, manganese hydroxide, calcium phosphate, magnesium phosphate, magnesium borate, calcium silicate, magnesium silicate, zinc aluminate, Calcium aluminate, basic zinc carbonate (2ZnCO ₃・ 3Zn (OH) ₂・ H ₂ O), basic magnesium carbonate (3MgCO ₃・ Mg (OH) ₂・ 3H ₂ O), basic nickel carbonate (NiCO ₃・2Ni (OH) ₂ ), basic bismuth carbonate (Bi ₂ (CO
₃ ) O ₂ · H ₂ O), basic cobalt carbonate, (2CoCO ₃ 3Co (O
H) ₂ ) and magnesium aluminum oxide Among these compounds, those not colored are particularly preferable.

The complex-forming compound used in the present invention forms a complex salt having a stability constant of 1 or more in log K with the metal ion constituting the poorly water-soluble basic metal compound. Examples of these complex-forming compounds include AE Martel and AE Martel.
l. RM Smith) Co-authored “Critical Stability Constants, 1st
~ 5 ", Plenum Press. Specifically, aminocarboxylic acids, iminodiacetic acid and its derivatives, anilinecarboxylic acids, pyridinecarboxylic acids, aminophosphoric acids, carboxylic acids (mono,
Di, tri, tetracarboxylic acids and compounds having substituents such as phosphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio and phosphino), alkali metals such as hydroxamic acids, polyacrylates, polyphosphoric acids, guanidine And salts such as amidines and quaternary ammonium salts.

As a preferred specific example, picolinic acid,
2,6-Pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 4-dimethylaminopyridine-2,6-dicarboxylic acid, quinoline-2-carboxylic acid, 2-pyridylacetic acid, oxalic acid, citric acid, tartaric acid, isocene Alkali metal salts of acids, malic acid, gluconic acid, EDTA, NTA, CyDTA, hexametaphosphoric acid, tripolyphosphoric acid, tetraphosphoric acid, polyacrylic acid, salts of guanidines,
Examples thereof include salts of amidines and quaternary ammonium salts. Of these, an aromatic heterocyclic compound having at least one —CO ₂ M and one nitrogen atom in the ring is preferable. The ring may be a single ring or a condensed ring, and examples thereof include a pyridine ring and a quinoline ring. And -C
The position at which O ₂ M is bonded to the ring is particularly preferably the α position with respect to the N atom. M is any of alkali metal, guanidine, amidine and quaternary ammonium ions. As the poorly soluble basic metal compound and complex forming compound, those described in JP-A-64-13546 can be used.

In the present invention, the basic metal compound which is poorly soluble in water and the complex-forming compound must be added to at least another layer in order to prevent the reaction from occurring before the development processing.
A more preferred form is a form in which a basic metal compound and a complex-forming compound that are hardly soluble in water are contained in at least one layer on separate supports. For example, it is preferable that a basic metal compound which is poorly soluble in water is contained in a light-sensitive material and a complex-forming compound is contained in a processing sheet. When a basic metal compound which is hardly soluble in water is added to the light-sensitive material, the layer to be added may be any of an emulsion layer, an antihalation layer and a protective layer. Further, it may be added dividedly in multiple layers, or may be added concentratedly in one layer. Basic metal compounds are described in JP-A-59-174830,
It is desirably contained as a fine particle dispersion prepared by the method described in JP-A-53-102733 and the like, and the average particle size is preferably 50 μm or less, particularly preferably 5 μm or less.

In the present invention, when the basic metal compound or the complex-forming compound which is poorly soluble in water is contained in the layer on the support, the addition amount is the compound species, the particle size of the poorly soluble metal compound, and the complex formation reaction rate. It is suitable to use the coating film in an amount of 50% by weight or less in terms of weight, more preferably 0.01% by weight to 40% by weight, depending on factors such as the above. Further, in the present invention, the content of the complex-forming compound in the reaction system is 1/100 to 100 times, particularly 1/10 to 2 times by mole relative to the content of the hardly soluble metal compound.
0 times is preferred. In the present invention, a light-sensitive silver halide emulsion layer is provided on the peeling layer, and a protective layer is provided thereon. As the silver halide, any of silver iodobromide, silver iodochlorobromide, silver iodide, silver bromide, silver chloroiodide, and silver chloride may be used. General additives can be used in the silver halide emulsion. For example, chemical sensitizers such as gold compounds and sulfur compounds,
Reciprocity law failure property improving agents such as platinum group compounds, post-ripening stoppers such as tetrazaindenes, antifoggants such as heavy metal compounds and organic compounds, and sensitizing dyes. The average size of silver halide grains (particle diameter in the case of spherical particles or particles close to spheres, grain size in the case of cubic grains is represented by the average based on the projected area) is not particularly limited, but is preferably 3 μm or less. Further, 2 μm or less is preferable, and 0.1 to 1.0 μm is particularly preferable. The particle size distribution may be narrow or wide.

The silver halide grains in the silver halide emulsion may have an equiaxed crystal form such as a cube or octahedron, or a heteromorphic crystal form such as a sphere or a plate. Alternatively, it may have a composite form of these crystal forms. The silver halide emulsion may be one kind or a mixture of a plurality of kinds. The silver halide emulsion layer may be a single layer or a multilayer of two or more layers. The silver halide grains may be composed of different phases in the inside and the surface layer, or may be composed of a uniform phase. Further, the particles may be such that the latent image is mainly formed on the surface, or the particles may be mainly formed inside the particles, and the latent image may not be localized on any of them. . In particular, particles in which the latent image is formed as a seed on the surface are more preferable. The thickness of the silver halide emulsion layer is 0.5 to 8.0 μm, particularly 0.6 to 6.0 μm, and the coating amount of silver halide grains is 0.1 to 3 as silver.
g / m ^2, preferably from 0.2 to 2.0 g / m ^2.

Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloids, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl. Alcohol, polyvinyl alcohol partial acetal,
A wide variety of synthetic hydrophilic polymeric substances such as poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, and other single or copolymers can be used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Britenso Society of the Scientific Photography of Japan (Bu
ll. Soc. Sci. Phot. Japan), No. 16, No. 16, P (P) 30 (1966) may be used, and a hydrolyzate or enzyme of gelatin may be used. Degradation products can also be used. As the photographic gelatin, lime-processed bone gelatin is preferably used.
For general information on photographic gelatin and the content of impurities, see “Basics of photographic engineering-Silver salt photography”, January 3, 1979.
It is described in detail at 0-day issue Corona Company 116-150 pages.

The photographic emulsion used in the present invention is preferably chemically sensitized. For chemical sensitization, for example, H.Frieser Die Grundlagen der Photo (Die Grundlagen der Photo)
graphishen Prozesse mit Silderhalogeniden) (Akademische
Verlagsgesellschaft), 1968] 675-734
The sulfur sensitizing method, reduction sensitizing method, selenium sensitizing method, noble metal sensitizing method and the like described on the page can be used alone or in combination. For example, in sulfur sensitization, sulfur sensitizers, that is, compounds containing sulfur obtained by reacting with active gelatin or silver include, for example, thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine,
p-Toluenethiosulfonate, rhodan, mercapto compounds and the like are used. Others, US Pat. No. 1,57
4,944, 2,410,689, 2,2
78, 947, 2, 728, 668, and 3,
Those described in, for example, No. 656,955 can also be used. The addition amount of these sulfur sensitizers varies over a considerable range under various conditions, but is usually preferably about 10 ^-7 to 10 ^-2 mol per mol of silver.

In gold sensitization, the gold sensitizer may have an oxidation number of gold of +1 or +3. Specifically, chloroauric acid, potassium chloroaurate, auric trichloride, potassium auric thiocyanate. , Potassium iodoaurate, tetracyanoauric acid and the like are used. The addition amount of these gold sensitizers varies over a considerable range under various conditions, but is usually preferably about 10 ^-9 to 10 ^-2 mol per mol of silver. It is particularly preferred that 80% or more of the gold sensitizer be present in the silver halide grain phase as described in Japanese Patent Application No. 61-79687. In the present invention, selenium sensitization can also be used, but selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylic acids, and esters. , Selenophosphates, selenides such as diethyl selenide, diethyl diselenide, and the like, and specific examples thereof are described in U.S. Patent Nos. 1,574,944 and 1,60.
2, 592 and 1,623, 499. The addition amount of the selenium sensitizer is selected from a wide range, but normally, it is preferably 10 ^-7 to 10 ^-2 mol per mol of silver.

In addition to the above-mentioned sulfur sensitization, gold sensitization and selenium sensitization, a reduction sensitization method using a reducing substance (eg, primary tin salt, amines, hydrazine derivative, formamidinesulfinic acid, silane compound) A noble metal sensitizing method using a noble metal compound (for example, a complex salt of a metal of Group VIII of the Periodic Table such as Pt, Ir, Pd in addition to a gold complex salt) may be used in combination. Regarding the reduction sensitization method, US Pat. No. 2,983,
No. 609, No. 2,419,974, No. 4,05
Nos. 4,458 and the like, and the noble metal sensitizing method are described in US Pat. Nos. 2,399,083, 2,448,060 and US 618,061. As a combination of sensitizers, gold / sulfur sensitization, gold / sulfur sensitization
Selenium sensitization is typical, but other combinations are possible. In the gold / sulfur sensitization, the usage ratio of both sensitizers varies depending on the aging conditions, etc.
The sulfur sensitizer is used in an amount of about 1 to 1000 mol per mol. In gold / selenium sensitization, it is usually preferable to use about 1 to 1000 mol of the selenium sensitizer per mol of the gold sensitizer. In the gold / sulfur sensitization or the gold / selenium sensitization, the gold sensitizer may be added at the same time as the sulfur sensitizer or the selenium sensitizer, or during the sulfur or selenium sensitization.

Particularly preferred chemical sensitization for use in the present invention is sulfur sensitization or gold-sulfur sensitization. In the present invention, these chemical sensitizers are added to a silver halide photographic emulsion by a conventional method. That is, the water-soluble compound is added as an aqueous solution, and the compound soluble in an organic solvent is added as a solution of an organic solvent that is easily mixed with water, such as methanol or ethanol. In addition, conditions such as pH, pAg, and temperature during chemical sensitization are not particularly limited, but the pH value is 4 to
9, particularly 5 to 8 is preferable, and pAg value is 5 to 1
It is preferably maintained at 1, especially 7 to 10. Further, the temperature is preferably from 40 to 90C, particularly preferably from 45 to 75C.

The photosensitive emulsion layer includes a photographic material manufacturing process,
Various compounds can be contained for the purpose of preventing fogging during storage or photographic processing or stabilizing photographic performance. That is, azoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, Aminotriazoles, nitrobenzotriazoles, benzotriazoles and the like are preferable. For example, 1-phenyl-5-
Mercaptotetrazole is typical. Further, mercaptopyrimidines, mercaptotriazines, for example thioketo compounds such as oxadrine thione, azaindenes, for example triazaindenes, tetrazaindenes,
Pentaazaindenes are preferred. For example, 4-hydroxy-6-methyl and 1,3,3a, 7-tetrazaindene are typical. In addition, well-known antifoggants and stabilizers such as benzenesulfonic acids, benzenesulfinic acids, benzenesulfonic acid amides, α-lipoic acid, and a combination use of a tetrazaindene compound and an imidazole compound are used. For more specific examples and methods of using them, those described in, for example, U.S. Patents 3,954,474 and 3,982,947 and JP-B-52-28660 can be used. The light-sensitive material used in the present invention may contain a developer, for example, a hydrophobic compound such as a pyrazolidone compound or a hydroxylamine compound, and a silver halide solvent, for example, a uracil compound or a thiosulfate compound, for the purpose of increasing the developing speed.

The light-sensitive material used in the present invention can be spectrally sensitized with a methine dye or the like. The sensitizing dye used is preferably a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye, and a hemioxonol dye. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. JP-A-59-114533, 6
As described in 1-163334, a plurality of sensitizing dyes can be used in combination.

The light-sensitive material and the processing sheet of the present invention may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.) Aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), cioxane derivatives (2,3-dihydroxydioxane, etc.) , Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid, etc.) and the like can be used alone or in combination. A coating aid can be used in the hydrophilic colloid layer of the light-sensitive material and the processing sheet of the present invention. As a coating aid, Research Disclos
ure) Volume 176, 17643, p. 26 (1978.12
The compounds described in the section "coating aids" of the publication) and the compounds described in JP-A-61-20035 can be used.

The silver halide emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention have, for example, polyalkylene oxide or its ethers, esters, amines, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. Compounds such as derivatives of bisphenol, thioether compounds, thiomorpholines, quaternary ammonium compounds, urethane derivatives, urea derivatives, imidazole derivatives, and 3-pyrazolidones. Examples of such compounds are described in U.S. Pat.
6062, 3617280, 37702021, 3
Compounds described in 808003 and the like can be used. The hydrophilic colloid layer of the light-sensitive material and the processed sheet of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.
For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylamide, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or acryl with them. Acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate,
A polymer having a monomer component of a combination of styrene sulfonic acid and the like can be used.

A protective layer can be provided on the silver halide emulsion layer used in the light-sensitive material of the present invention. The protective layer is made of a hydrophilic polymer such as gelatin and is disclosed in JP-A-61-161.
Matting agents or sliding agents such as polymethyl methacrylate latex and silica as described in 47946 and 61-75338 can be included. In the light-sensitive material of the present invention, a light-sensitive silver halide emulsion layer and other hydrophilic colloid layers may contain a dye or an ultraviolet absorber as a filter dye or for the purpose of preventing irradiation. In addition, the light-sensitive material of the present invention may contain an antistatic agent, a plasticizer and an air fog preventing agent.

The developing agent may be present in the light-sensitive material and / or the processing sheet. As the developing agent, for example, hydroquinone, tert-butylhydroquinone, or a benzene or naphthalene-based organic compound having a hydroxy group at the para or ortho position is used. Further, reductic acid as described in U.S. Pat. No. 3,615,440 and U.S. Pat. No. 7,707.
Α, β-ene diols as described in 16 are preferably used. Further, a hydroxyamine developer as described in U.S. Pat. Nos. 3,287,125 and 3293034 is preferably used. Further, a 1-aryl-3-pyrazolidinone compound or an alkyl-substituted p-aminophenol described in JP-B-49-13580 as a developing agent may be used in combination with the hydroxylamine developer. The amount of the developing agent used is 0.5 mol to 3.0 mol, preferably 0.6 mol, per 1 mol of the coated silver amount.
It is from mol to 2.0 mol. More preferably, the developer is added to the processing sheet. Two or more developing agents can be used in combination. Particularly, a combination of a hydroquinone-based developing agent and another developing agent is preferable.

The silver halide solvent may be present in the light-sensitive material and / or the processing sheet. Among them, the processing sheet is most preferable. US Patents 2,857,274 and 2,857,727
The cyclic compounds described in Nos. 5 and 2857276 are suitable, and among them, uracil and 6-methyluracil are preferred examples. Further, alkali metal thiosulfates, particularly sodium or potassium salts, are preferred. U.S. Pat. Nos. 3,958,992, 3,976,647, and 40
09167, 4032538, 4046568, 4047954, 4047955, 41071176
And disulfonylmethane compounds disclosed in JP-A-47-330 and U.S. Patents 4,126,459, 4,150,228 and 42.
Dihydroxypyrimidine compounds having a thioether group described in US Pat.
51617, 4267254 and 4267256.
From aminothioethers.

As a method of applying water to a photographic material, for example, a roller coating method or a wire bar coating method as described in JP-A-59-181353 is described in JP-A-59-181354. Of applying water to a photographic material using a transparent water-absorbing member, JP-A-59-59
No. 181348, a method of forming a bead between a water-repellent roller and a photographic material to apply water.
In addition, various methods such as a dip method, an extrusion method, a method of ejecting as a jet from pores and applying, and a method of applying in a crushing manner of a pod can be used. The water as the solvent is not limited to so-called “pure water”, but includes water in a widely and conventionally used sense.

The amount of water used is at least 0.1 times, preferably 0.1 times or more the weight of the total coating film of the light-sensitive material and the processing sheet, and the solvent corresponding to the maximum swelling volume of the total coating film. Or less (particularly less than or equal to the weight of the solvent corresponding to the maximum swelling volume of the entire coated film minus the weight of the entire coated film). The state of the film at the time of swelling is unstable. Depending on the conditions, local bleeding may occur. Less than the amount is preferred.
Specifically, the range is preferably 1 g to 50 g, particularly 2 g to 35 g, and more preferably 3 g to 25 g per square meter of the total area of the photosensitive material and the processing sheet. The method described in JP-A-61-147244 can be applied to the pressure condition and the method of applying pressure when the light-sensitive material and the processing sheet are superposed and brought into close contact with each other.

[0049]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
The styrene-based polymer produced in Production Example 1 was depressurized at 150 ° C and dried, and then pelletized with a vented single-screw extruder, and the pellets were crystallized while stirring in hot air at 130 ° C. The content of styrene monomer in the crystallized pellets was 1,100 ppm. Next, the pellets were extruded by a device having a T-die attached to the tip of an extruder having a filter therein. The melting temperature at this time was 300 ° C. The sheet in the molten state was formed into a transparent sheet having a crystallinity of 9% and a thickness of 1400 μm by an electrostatic contact method. The obtained sheet is 3.5 times in the longitudinal direction at 110 ° C., 1
It was stretched 4 times in the transverse direction at 20 ° C., and heat-treated at 240 ° C. for 10 seconds in a fixed tension state for 20 seconds under 5% restricted shrinkage. The obtained film had a thickness of 100 μm and a haze of 1.0%.

Both sides of the obtained SPS support were subjected to glow discharge treatment under the following conditions. The cross section is 2 cm in diameter and 1 in length
Four 50 cm columnar rod-shaped electrodes having a hollow portion to serve as a coolant channel were fixed in an insulating plate shape at intervals of 10 cm. This electrode plate is fixed in the vacuum tank, 15 cm away from this electrode surface,
The biaxially stretched film is run so as to face the electrode surface,
The speed was controlled so that surface treatment was performed for 2 seconds. Immediately before the film passes through the electrode, the heating roll is arranged so that the film makes 3/4 round contact with the heating roll with a temperature control of 50 cm, and the thermocouple thermometer is placed on the film surface between the heating roll and the electrode zone. The film surface temperature was controlled at 115 ° C. The pressure in the vacuum chamber was 0.2 Torr, and the partial pressure of H ₂ O in the atmospheric gas was 75%. Discharge frequency is 30KHz,
The output was 2500 W and the treatment intensity was 0.5 KV · A · min / m ² . Before the support after the discharge treatment was wound up, the support was brought into contact with a cooling roll having a temperature controller having a diameter of 50 cm and wound up so that the surface temperature became 30 ° C.

Then, an undercoat layer having the following composition was applied on both sides. <Undercoat layer> Deionized alkali treated gelatin (isoelectric point 5.0) 10.0 parts by weight Water 24.0 〃 Methanol 961.0 〃 Salicylic acid 3.0 〃 JP-A-51-3619 0.5 〃 Synthesis Example 1 Polyamide-epichlorohydrin resin Described in Japanese Examined Patent Publication No. 3-27099 1.0 〃 Nonionic surfactant Compound I-13 This coating solution is applied at 10 ml / m ² using a wire bar,
It was dried at 115 ° C. for 2 minutes and wound up. The support of the present invention thus obtained and PET same as Comparative Example 10
A light-sensitive material was prepared using a support having a thickness of 0 μm.

Example-1 1. Preparation of Photosensitive Material A photosensitive material was prepared by sequentially providing the following layers on a support film. (1) Image Receptor Layer Preparation of Silver Precipitating Agent (Palladium Sulfide) Used for Image Receptor Layer Solution A; Palladium chloride 3.3 g Concentrated hydrochloric acid 20 ml Add 500 ml of water after dissolving the above solution Solution B; Na ₂ S.9H ₂ O 4.5 g Gelatin 140 g H ₂ O 2400 ml Solution B is heated to 70 ° C and solution A is added with stirring. After solution A is added, the temperature is lowered to 40 ° C and pH is adjusted to 5.0 with NaOH. Vinyl sulfone hardener CH ₂ = CHSO ₂ CH ₂ CONH (CH ₂ ) ₂ NHCOCH ₂ SO ₂ CH = CH ₂ 0.4g was added to make a coating solution, and the silver precipitant was applied at 2g / m ² . did.

(2) Image Protecting Layer For the purpose of protecting the processed image, gelatin was coated on the image receiving layer so that the coating amount was 0.3 g / m ² . (3) Release layer Hydroxyethyl cellulose (HEC SP-500
Daicel Co., Ltd.) was applied so as to be 0.15 g / m ² . (4) Antihalation layer Carbon black CB 10B (manufactured by Mitsubishi Kasei Co., Ltd.)
The gelatin dispersion of was prepared and coated so that the carbon solid content was 0.15 g / m ² and the gelatin was 0.3 g / m ² .

(5) Silver Halide Emulsion Layer 1.0 M silver nitrate aqueous solution and 3 × 10 ⁻⁷ per mol of silver
An aqueous solution of a halogen salt containing 0.3 M potassium bromide and 0.74 M sodium chloride, containing 1 mol of (NH ₄ ) ₃ RhCl _6, was added to sodium chloride and 1,3-dimethyl-2.
-Adding to an aqueous gelatin solution containing imidazoline thione by stirring with a double jet method at 45 ° C for 30 minutes, the average grain size is 0.28 µm, and the silver chloride content is 70.
Molar% silver chlorobromide particles were obtained. After that, it was washed with water according to the usual method by flocculation, 40 g of gelatin was added to adjust pH to 6.5 and pAg to 7.5, and further 5 mg of sodium thiosulfate and 8 mg of chloroauric acid were added per 1 mol of silver, and the mixture was kept at 60 ° C for 60 minutes 4-hydroxy-6-methyl-1,3,3a, which was heated and chemically sensitized to serve as a stabilizer,
150 mg of 7-tetrazaindene was added. The obtained grains have an average grain size of 0.28 μm and a silver chloride content of 70 mol%.
Silver chlorobromide cubic grains. (Variation coefficient 10%) The following sensitizing dye was added to this emulsion in an amount of 80 mg per mol Ag, and then 4,4'-bis (4,6-dinaphthoxy-pyrimidin-2-ylamino) was used as a supersensitizer and a stabilizer. ) -Stilbene disulfonic acid disodium salt and 2,
5-dimethyl-3-allyl-benzothiazole iodo salt was added at 300 mg and 450 mg per 1 mol of Ag, respectively.
Infrared sensitized. Sensitizing dye

[0055]

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The above emulsion was coated so that the coating amount of silver was 1.0 g / m ² and the coating amount of gelatin was 0.8 g / m ² . (6) Protective layer 1.4 g of gelatin / protective layer on top of the light-sensitive material
It was coated so as to become a m ^2. In this protective layer, 1.3 g / m ² of Zn (OH) ₂ was used as a base precursor, and a polymethylmethacrylate particle of 0.1 g / m ^{2 was} used as a matting agent.
It was contained at 1 g / m ² . 2. Preparation of a treatment sheet A treatment sheet was prepared by coating the following on a support PET film. Gelatin 7.6 g / m ² Guanidium picolinate 2.3 g / m ² Sodium picolinate 2.1 g / m ² Hypo 0.5 g / m ² Hydroquinone 0.4 g / m ² 4-Hydroxymethyl-4 -Methyl-1-phenyl-3-pyrazolidone 0.1 g / m ² vinyl sulfone type hardener 0.15 g / m ² vinyl sulfone type hardener is the same as that used in the light-sensitive material.

3. Sensitometric processing and measurement of dimensional change The thus-obtained light-sensitive material was applied with 780 n from the emulsion film surface side.
Scanning exposure (irradiation light amount was 50 erg / cm ² ) was performed using a semiconductor laser emitting light at m. 30 ml / m ² of water was applied to the coated film surface of the processing sheet with a wire bar, and immediately thereafter, the exposed photosensitive material and the exposed photosensitive material were superposed so that the film surface was in contact with each other. Then, after keeping the temperature at 40 ° C. for 30 seconds and peeling off the processed sheet, it peeled from the peeling layer of the light-sensitive material and the antihalation layer, silver halide emulsion layer and the like were all transferred to the side of the processed sheet. A clear black positive image (Dmax = 3.0) was obtained on the light-sensitive material after peeling.
Thus, without using a processing solution such as a developing solution or a fixing solution, by simply applying a small amount of water, a highly concentrated image with good sharpness can be obtained in a short time, and no waste liquid is generated. A treatment system is obtained. Next, the dimensional change before and after the development process was examined. Before exposing the light-sensitive material, punch holes were made at intervals of 30 cm. Accurately measure the interval of these punch holes using a micro gauge, after development processing,
After peeling the processed sheet, the distance between the punch holes on the photosensitive material was measured again, and the difference was determined as a dimensional change. From the above results, it can be seen that the product using the SPS base of the present invention has a smaller elongation after treatment than PET and is excellent in dimensional change.

Example-2 1. Preparation of Photosensitive Material A photosensitive material was prepared by sequentially providing the following layers on a support film. (1) Undercoat layer 1.0 g / m ^{2 of} gelatin, 0.5 g / m ² of colloidal silica (Snowtex-C) having an average particle diameter of 0.02 μ, and a silica matting agent having an average particle diameter of 3.5 μ of 0. 1 g / m ^{2 of} the following vinyl sulfone type hardener was applied to 20 mg / m ² . _{CH 2 = CHSO 2 CH 2 CONH} (CH 2) 2 NHCOCH 2 SO 2 CH = CH 2 were also prepared even colloidal silica, samples silica matting agent was removed respectively as a comparative example. All of (2) the image receiving layer, (3) the peeling layer, and (4) the antihalation layer were applied in the same manner as in Example-1. (5) Silver Halide Emulsion Layer A silver halide emulsion was prepared in the same manner as in Example-1, and only the sensitizing dye was changed to the following and coated.

[0059]

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(6) The protective layer was applied in the same manner as in Example-1. 2. Preparation of treatment sheet A treatment sheet was prepared in the same manner as in Example-1. 3. Sensitometric processing and measurement of dimensional change The thus-obtained light-sensitive material was applied with 780 n from the emulsion film surface side.
Scanning exposure (irradiation light amount was 50 erg / cm ² ) was performed using a semiconductor laser emitting light at m. 30 ml / m ² of water was applied to the coated film surface of the processing sheet with a wire bar, and immediately thereafter, the exposed photosensitive material and the exposed photosensitive material were superposed so that the film surface was in contact with each other. Then, after keeping the temperature at 40 ° C. for 30 seconds and peeling off the processed sheet, it peeled from the peeling layer of the light-sensitive material and the antihalation layer, silver halide emulsion layer and the like were all transferred to the side of the processed sheet. A clear positive silver image like a silver mirror remained on the light-sensitive material after peeling. Since the anti-halation carbon black layer has also been peeled off,
The non-image area was white, and the visibility of the image was very good. Next, a printing test is carried out using the photosensitive material thus obtained.

The lithographic printing plate prepared by the above operation was mounted on an offset printing machine, the following desensitizing liquid was applied all over the plate surface, and printing was performed using the following dampening liquid. <Desensitizing liquid> Water 600 ml Isopropyl alcohol 400 ml Ethylene glycol 50 g 2-Mercapto-5-n-heptyl-1,3,4-oxadiazole 1 g <Moisturizing liquid> o-phosphoric acid 10 g Nickel nitrate 5 g Sodium sulfite 5 g Ethylene glycol 100 g Colloidal silica (20% liquid) 28 g Water is added to make 2 liters. The printing machine is AB
Dick 350CD (trademark of offset printing machine manufactured by AB Dick) was used, and F gloss black B manufactured by Dainippon Ink was used as the printing ink.

The printing results were good for both the SPS base of the present invention and the PET base of the comparative example. Next, the dimensional change was measured. In the same manner as in Example-1, before exposing the light-sensitive material, punch holes were made at intervals of 30 cm to determine the dimensional change before and after the processing. It can be seen that those using the SPS base of the present invention are excellent in dimensional change. As described above, according to the present invention, it can be seen that a printing plate excellent in dimensional change can be obtained without using any processing liquid, generating no waste liquid.

Claims (7)

[Claims] 1. A light-sensitive material having at least a) an image-receiving layer containing a silver precipitating agent, b) a peeling layer, c) an antihalation layer having a light-shielding function, and d) a photosensitive silver halide emulsion layer on a support. After imagewise exposure to the above, the treatment sheet having a hydrophilic colloid layer containing a silver halide solvent on the support is brought into close contact with the film surface, and in the presence of water, a developing agent, a base and / or a base precursor. After performing silver salt diffusion transfer development with, peeled off at the peeling layer of the light-sensitive material when peeling, the layer above the peeling layer adheres to the processing sheet and is peeled off, and a positive image is obtained on the light-sensitive material. In the film unit, the silver salt diffusion transfer method film unit, wherein the support is a styrene polymer having a syndiotactic structure. 2. A support having at least a) a hydrophilic undercoat layer, b) an image receiving layer containing a silver precipitating agent, c) a release layer, and
d) An image-wise exposure of a light-sensitive material having a light-sensitive silver halide emulsion layer, and e) a light-sensitive material having a light-sensitive silver halide emulsion layer, and then a treatment having a hydrophilic colloid layer containing a silver halide solvent on a support. After the sheet and the film surface are brought into close contact with each other, the silver salt diffusion transfer development is carried out in the presence of water, a developing agent, a base and / or a base precursor, and then the layer above the release layer of the light-sensitive material is treated when peeling. In a lithographic printing plate in which a positive image that is peeled off in close contact with a sheet and remains on a light-sensitive material is used as an ink receiving property, the support is a styrene-based polymer having a syndiotactic structure. The silver salt diffusion transfer method lithographic printing plate. 3. A developing agent is contained in a light-sensitive material, a processing sheet, or both, and water is supplied to a coating film of the light-sensitive material and / or the processing sheet during development processing before the both are brought into close contact with each other. The film unit according to claim 1, wherein 4. A developing agent is contained in a light-sensitive material, a processing sheet, or both, and water is supplied to a coating film of the light-sensitive material and / or the processing sheet during development processing before the both are brought into close contact with each other. The lithographic printing plate according to claim 2. 5. A combination of a basic metal precursor having a water-insoluble basic metal compound and a compound capable of complex-forming with a metal ion constituting the water-insoluble basic metal compound in water as a medium. The film unit according to claim 1, wherein the film unit is provided. 6. A base precursor is a combination of a water-insoluble basic metal compound and a compound capable of undergoing a complex formation reaction with water as a medium with respect to a metal ion constituting the water-insoluble basic metal compound. The planographic printing plate according to claim 2, wherein the planographic printing plate is present. 7. A light-sensitive material having on a support at least a) an image-receiving layer containing a silver precipitating agent, b) a peeling layer, c) an antihalation layer having a light-shielding function, and d) a photosensitive silver halide emulsion layer. 2. A light-sensitive material, wherein the support is a styrene polymer having a syndiotactic structure.