JPH03114040A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To ensure high sensitivity and superior pressure resistance and to enable processing not including hardening by specifying the diameter and thickness of silver halide particles in an emulsion layer, the amt. of a binder in coating layers on one side of a support, the rate of swelling of the layers with water and the total processing time. CONSTITUTION:Flat platy silver halide particles having 3- <8 ratio of diameter to thickness, 0.3-10mum diameter and <=0.4mum thickness are used in an emulsion layer. The amt. of a binder in the emulsion layer, a protective surface layer and other layer on one side of a support is regulated to 2.0-4.5g/m<2> in total and the rate of swelling of the coating layers with water is regulated to <=200%. A gelatin hardening agent is added to neither a developing soln. nor a fixing soln. and all of developing, fixing, washing and drying stages are finished in 30-90sec. High sensitivity, superior pressure resistance and suitability to processing not including hardening can be ensured.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material, particularly a silver halide photographic material that has high sensitivity and excellent pressure resistance, and is suitable for non-hardening processing. It relates to photosensitive materials.

(Prior Art) In recent years, silver halide photographic materials have become increasingly sensitive. In order to increase the sensitivity, the size of the silver halide grains may be increased, but since this reduces the covering power, it is necessary to increase the amount of coated silver, making rapid processing difficult.

Furthermore, in general, higher sensitivity results in better pressure resistance (especially pressure burr).
becomes worse. If the amount of binder is reduced in order to enable rapid drying, the pressure resistance will further deteriorate. On the other hand, another method for increasing sensitivity is to set the iodine content of silver halide grains to a relatively high level, but this results in residual color and poor fixability, making rapid processing difficult. .

Recently, the use of tabular emulsions with high covering power has made it unnecessary to increase the amount of coated silver, but conventional tabular emulsions with a wide size distribution have As a result, the pressure fluctuation becomes even worse.

Conventionally, processing hardeners that function in the developer and fixer (e.g., glutaraldehyde (in the developer), water-soluble aluminum salt (in the fixer), etc.) have been used to improve drying properties in rapid processing. However, from the viewpoint of the stability of the processing solution and the odor, there was a desire for a photographic material that could be processed without hardening.

(Object of the invention) The object of the invention is to provide a silver halide photographic light-sensitive material,
The object of the present invention is to provide a processing method using a silver halide photographic material that has particularly high sensitivity, excellent pressure resistance, and is suitable for non-hardening processing.

(Structure of the Invention) The above object of the present invention is to provide a method for developing a photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, in which silver halide grains in the emulsion layer have an aspect ratio. Consisting of monodisperse tabular grains (dispersion coefficient of 20% or less) with a ratio of 3 or more and less than 8, and a binder for one side of the coating film (including the silver halide emulsion layer, surface protection layer, and other layers) on the support. The coating amount is in the range of 2.0 to 4.5 g/m2, the water swelling rate of the coating film is 200% or less, and the total processing time is 30 to 90 seconds without hardening. This was achieved using silver halide photographic materials.

The tabular silver halide grains of the present invention have a diameter/thickness ratio (aspect ratio) of 3 or more and less than 8.

The diameter of a silver halide grain herein refers to the diameter of a circle having an area equal to the projected area of the grain. In the present invention, the diameter of the tabular silver halide grains is preferably 063 to 10μ, more preferably 0.3 to 5.0μ, particularly preferably 0.5 to 1Oμ.
It is 2.5μ.

In general, tabular silver halide grains are tabular with two parallel surfaces, and therefore "thickness" in the present invention refers to the distance between the two parallel surfaces constituting the tabular silver halide grains. expressed.

The thickness for which the present invention is effective is 0.4 μm or less, preferably 0.3 μm or less, and 0.05 μm or less.

An aspect ratio of 8 or more is not preferable because pressure blur becomes extremely aggravated.

In the present invention, monodisperse tabular grains are defined as having a value (coefficient of variation) obtained by dividing the variation (standard deviation) of the grain size expressed by the circular diameter of the projected area of the grain by the average grain size.
96 or less.

The coefficient of variation is particularly preferably 15% or less.

As the halogen composition of the tabular silver halide grains, any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver iodochlorobromide may be used, but silver chloride is preferable from the viewpoint of high sensitivity. Silver oxide or silver iodobromide is used. Here, the silver iodide content is preferably 8 mol% or less, particularly preferably 4 mol% or less. The distribution of iodine may be uniform or may be different inside and on the surface.

Among tabular silver halide grains, monodisperse hexagonal tabular grains are one of useful grains.

The structure and manufacturing method of the monodispersed hexagonal tabular grains used in the present invention are as described in JP-A-63-151618, but briefly, the emulsion consists of a dispersion medium and silver halide grains. A silver emulsion, in which 70% or more of the total projected area of the silver halide grains has a ratio of the length of the side with the maximum length to the length of the side with the minimum length of 2 or less. It is occupied by tabular silver halide grains having a certain hexagonal shape and two parallel surfaces as outer surfaces, and furthermore, the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains [of its projected area] It has a monodispersity of 20% or less (value obtained by dividing the variation (standard deviation) in particle size expressed by the diameter in terms of a circle by the average particle size). Although the crystal structure may be similar to -, it is preferable that the inside and outside have different halogen compositions, and may have a layered structure. Further, it is preferable that the particles contain reduction-sensitized silver nuclei.

For the present invention, so-called halogen conversion type particles, such as those described in British Patent No. 635,841 and US Pat. No. 3,622,318, can be particularly effectively utilized.

The amount of halogen conversion is 0.0% relative to the amount of silver. 2mo42%~2m
a1% especially 0. 2moI is preferably 1% to 0.6mof%.

For silver iodobromide, grains having a structure having a high iodine layer inside and/or on the surface are particularly preferred.

By converting the surface of the tabular silver halide grains of the present invention, a silver halide emulsion with higher sensitivity can be obtained.

As a method for halogen conversion, an aqueous halogen solution having a solubility product with silver that has a smaller solubility product with silver than the halogen composition on the particle surface before halogen conversion is usually added. For example, for silver chloride and silver chloroiodobromide tabular grains, an aqueous solution of potassium iodide with a bromide power of 10 is added, and for silver bromide and silver iodobromide tabular grains, an aqueous solution of potassium iodide is added. The concentration of the aqueous solution to be added is preferably 30% or less, more preferably 10% or less. Furthermore, the conversion rate is 1 mol% or less per minute per 1 mol of silver halide before halogen conversion. It is preferable to add a conversion halogen solution.Furthermore, a sensitizing dye may be present during halogen conversion.
Instead of converted halogen aqueous solution, silver bromide, silver iodobromide,
Silver halide fine grains of silver iodide may be added. The size of these fine particles is 0.2 μm or less, preferably 0.1 μm or less.
It is desirable that the thickness be .mu.m or less, particularly 0.05 .mu.m or less. The amount of halogen converted is from 0.1 to that of silver halide before conversion.
1moI! %, particularly preferably 0.2 to O16 mo1%.

The halogen conversion method of the present invention is not limited to any one of the above methods, but may be used in combination depending on the purpose. The silver halide composition on the grain surface before halogen conversion is preferably 1 mol % or less. In particular, it is preferably 0.3 moA% or less.

When performing halogen conversion using the above method, a method in which a silver halide solvent is present is particularly effective.

Preferred solvents include thioether compounds, thiocyanates, and 4-substituted thioureas. Among them, thioether compounds and thiocyanates are particularly effective, and thiocyanates are used in amounts of 0.5 g to 5
The amount of g1 thioether is preferably in the range of 0.2 g to 3 g.

Monodisperse tabular silver halide grains can be produced by appropriately combining methods known in the art.

For example, in an atmosphere with a relatively high pAg value of pBrl, 3 or less, a crystal in which tabular grains are present in an amount of 40% or more by weight is formed, and while maintaining the pBr value at the same level, silver and halogen solutions are simultaneously added and seed crystals are formed. Obtained by growing .

During this grain growth process, it is desirable to add a silver and halogen solution to prevent the generation of new crystal nuclei.

The size of tabular silver halide grains can be adjusted by controlling temperature adjustment, selection of the type and amount of solvent, silver salt used during grain growth, rate of addition of halide, etc.

When producing the tabular silver halide grains of the present invention, grain size and shape (diameter/thickness ratio, etc.), grain size distribution, and grain growth rate can be controlled by using a silver halide solvent as necessary. . The amount of solvent used is 10-3 to 1.0% by weight of the reaction solution, especially lO-! ~1O
-1% by weight is preferred.

For example, as the amount of solvent used increases, the particle size distribution can be made monodisperse and the growth rate can be accelerated. On the other hand, there is also a tendency for the thickness of the particles to increase with the amount of solvent used.

Examples of frequently used silver halide solvents include ammonia, thioethers, and thioureas, with ammonia and thioethers being particularly preferred. For thioethers, U.S. Pat. No. 3,271,157;
Same 3rd. 790. No. 387, same No. 3,574,62
You can refer to No. 8 etc.

When producing the tabular silver halide grains of the present invention, a silver salt solution (for example, A g N
0! A method of increasing the addition rate, amount, and concentration of the aqueous solution) and the halide solution (for example, KBr aqueous solution) is preferably used.

These methods are described, for example, in British Patent No. 1°335.
No. 925, U.S. Patent No. 3. 672. 900, 3,650,757, 4,242.445, JP-A-55-142329, JP-A-55-158124, and the like.

In the process of grain formation or physical ripening of the monodisperse tabular silver halide emulsion of the present invention, cadmium salt, zinc salt,
A lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof, etc. may be present together.

The monodispersed tabular silver halide grains of the present invention can be chemically sensitized if necessary.

Chemical sensitization methods include so-called gold sensitization methods using gold compounds (for example, U.S. Pat. Nos. 2,448,060 and 3,32).
No. 0,069) or sensitization methods using metals such as iridium, platinum, rhodium, palladium (for example, U.S. Pat.
No. 48,060, No. 2.566.245, No. 2,56
6.263) or a sulfur sensitization method using a sulfur-containing compound (for example, U.S. Pat. No. 2,222,264), or a reduction sensitization method using tin salts, polyamines, etc. (for example, U.S. Pat. No. 2,487,850). , No. 2,518,698, No. 2,521,925), or a combination of two or more of these can be used.

Particularly from the viewpoint of saving silver, the tabular silver halide grains of the present invention are preferably gold-sensitized, sulfur-sensitized, or a combination thereof.

The monodisperse tabular silver halide grain emulsion of the present invention may be used as a mixture of two or more emulsions having different sizes (sensitivities), or may be coated in separate layers.

In the layer containing the tabular silver halide grains of the present invention,
It is preferable that the tabular grains are present in an amount of 40% or more, particularly 60% or more by weight of all the silver halide grains in the multilayer.

The thickness of the layer containing tabular silver halide grains is from 0.3 to
5.0μ, especially 0. It is preferably 5 to 360μ.

Also, the coating amount of tabular silver halide grains (for one side)
is preferably 0.5 to 6 g/i, particularly 0.5 to 4 g/i.

The emulsion layer of the silver halide photographic light-sensitive material of the present invention may contain ordinary silver halide grains in addition to tabular silver halide grains. These are P, Glaf
Chimie et Physique by kids
Photographique (Paul Mon
te1 Publishing, 1967), by G. F. Duffin.
Photographic Emulsion Che
Mistry (The Focal Press
Published in 1969, published in 1966 by L, Zelikman e.
Making and Coati by t et
ngPotographic Emulsion (
The Focal Press, 1964)
It can be prepared using the method described in et al.

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

The silver halide may be any one such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. Further, if necessary, chemical sensitization can be carried out in the same manner as tabular silver halide grains.

The photographic emulsion used in the present invention includes steps in the manufacturing process of light-sensitive materials,
Various compounds can be included for the purpose of preventing fog during storage or photographic processing or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-
mercaptopyrimidines: mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a, 7) Tetraazaindenes), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. . For example, U.S. Patent Nos. 3,954,474 and 3,982,9
47, and those described in Japanese Patent Publication No. 52-28,660 can be used.

The photographic emulsions used in this invention may be spectrally sensitized with methine dyes and others.

Useful sensitizing dyes include, for example, German Patent No. 929.080;
U.S. Pat. No. 2,493,748, 2°503.77
No. 6, No. 2,519,001, No. 2.912,329
No. 3,656,959, No. 3,672,897, No. 3,694,217, No. 4,025,349,
Same 4. 046. No. 572, British Patent No. 1,242,5
No. 88, Special Publication No. 14030/1973, No. 52-2484
This is what is described in No. 4.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. A typical example is US Patent 2
, No. 688,545, No. 2゜977.229, No. 3,
No. 397,060, No. 3.522,052, No. 3,5
No. 27,641, No. 3,617,293, No. 3,62
No. 8,964, No. 3,666.480, No. 3.672
．． No. 898, No. 3,679,428, No. 3,703゜377, No. 3,814,609, No. 3,837.8
No. 62, No. 4,026,707, British Patent No. 1,344
, No. 281, No. 1,507,803, Special Publication No. 43-4
No. 936, No. 53-12375, JP-A-52-110
No. 618 and No. 52-109925.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. For example, aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat. Nos. 2.933.390 and 3,63
5,721), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like. U.S. Patent Nos. 3,615°613, 3,615,641, 3,617.295, 3
, 635,721 are particularly useful.

These sensitizing dyes may be added at any time from the time of emulsion grain formation to coating, but it is particularly preferable to add them before chemical sensitization.

As a binder that can be used in the emulsion layer, intermediate layer and surface protective layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, 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, dextran, and starch derivatives; Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyvinylimidazole, polyvinylpyrazole, and the like.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used (also, gelatin hydrolysates or enzymatically decomposed products can also be used).

Among these, it is preferable to use dextran or polyacrylamide with an average molecular weight of 50,000 or less together with gelatin. Patent application No. 61-213503, No. 61-2984
The method described in No. 05 is also effective in the present invention.

The total amount of binder in the emulsion layer, surface protective layer and other layers of the photographic material of the present invention on one side of the support is 2.0 to 4.
It is necessary that it be in the range of 5 g/rrr. Especially 2.
A range of 0 to 3.5 g/nr is preferred. 2.0g/m2
If it is less than 4.5 g/rrr, the pressure resistance will deteriorate, and if it is more than 4.5 g/rrr, drying properties, residual color, etc. will deteriorate, making it unsuitable for rapid processing.

Other constituents of the layer containing the tabular silver halide grains of the present invention, such as hardeners, antifoggants, silver halide stabilizers, surfactants, spectral sensitizing dyes, dyes, ultraviolet absorbers, chemicals, etc. There are no particular restrictions on sensitizers, thickeners, coating aids, preservatives, etc. For example, Re5earh Dis
Closurel vol. 76, pages 22-28 (December 1978) can be referred to.

The photographic material of the present invention has a synthetic or natural polymeric material such as gelatin, a water-soluble polyvinyl compound, or an acrylamide polymer on its surface (for example, US Pat.
, No. 142,568, No. 3゜193.386, No. 3,
062,674) as a main component.

In addition to gelatin or other polymeric substances, the surface protective layer may include:
It can contain a surfactant, an antistatic agent, a matting agent, a slipping agent, a hardening agent, a thickener, and the like.

In addition, the photographic material of the present invention may optionally include an intermediate layer,
It can have a filter layer, an antihalation layer, etc.

Water swelling rate of the coating film of the photographic light-sensitive material of the present invention (38°C, 5
A photographic material aged for 3 days at 0% relative humidity was
It is necessary that the amount of change in the thickness of the coated film when immersed in distilled water at ℃ for 3 minutes compared to the thickness before immersion (percentage) is 200% or less.

In particular, 150% or less is preferable. If it exceeds 200%, drying properties and roller marks during processing deteriorate, making it unsuitable for non-hardening processing.

The water swelling rate can be controlled to be 200% or less by adjusting the gelatin hardener.

As the gelatin hardener, triazine compounds and vinyl sulfone compounds can be preferably used.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as a plastic film or paper that is commonly used in photographic materials. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (e.g. polyethylene,
Paper coated or laminated with polypropylene, ethylene/butene copolymer, etc.

The support may be colored using dyes or pigments.

It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion with photographic emulsion layers and the like. The undercoat layer may be colored using dyes or pigments. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

In the present invention, a layer containing tabular grains, an emulsion layer,
There are no particular limitations on the method for applying the surface protective layer, but for example, U.S. Pat.
The multilayer simultaneous coating method described in Japanese Patent No. 08,947 and Japanese Patent No. 2761.791 can be preferably used.

Specifically, the silver halide photographic light-sensitive material of the present invention includes
- Ray-sensitive materials (for indirect X-ray, direct X-ray),
It includes black-and-white photographic materials such as lithographic materials, black-and-white photographic paper, and black-and-white negative film.

For photographic processing of the light-sensitive material of the present invention, for example, Research Disclo
sure) No. 176, pages 28-30 (RD-17643
), any of the known methods and known base liquids can be applied. The processing temperature is usually chosen between 18°C and 50°C, but between 30°C and 45°C.
Preferably, the temperature is between ℃.

The developer used in black-and-white photographic processing can contain known developing agents. As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-
Pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p
-Aminophenol and the like can be used alone or in combination. The developer generally contains other known preservatives,
Contains alkaline agents, pH buffering agents, anti-fogging agents, etc., as well as solubilizing agents, color toning agents, development accelerators (e.g. quaternary salts, hydrazine, benzyl alcohol), surfactants, antifoaming agents, water softeners, etc. It may also contain agents, viscosity-imparting agents, and the like.

As a special form of development processing, a developing agent is added to the light-sensitive material.
For example, a method may be used in which the photosensitive material is included in the emulsion layer and the photosensitive material is processed in an alkaline aqueous solution to perform development. Research Disclosure 1 for hydrophobic developing agents
No. 69 (RD-16928) U.S. Patent No. 2,739,8
They can be incorporated into the emulsion layer in a variety of ways, such as those described in US Pat. No. 90, UK Pat. Such development treatment may be combined with silver salt stabilization treatment with thiocyanate.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfate and thiocyanate, organic sulfur compounds known to be effective as stabilizers can be used.

A feature of the present invention is that neither the developer nor the fixer contains a gelatin hardener.

Furthermore, it is characterized in that the total processing time for development, fixing, washing, and drying is 30 to 90 seconds.

Next, the present invention will be specifically explained with reference to Examples.

Example 1 A biaxially stretched polyethylene terephthalate film having a thickness of 175 μm and dyed blue was subjected to a corona discharge treatment, and a first undercoating liquid having the following composition was applied in an amount of 5.5 μm. 1c
It was coated with a wire bar coater so that the coating was e/rrr and dried at 175° C. for 1 minute. Next, a first undercoat layer was provided on the opposite side in the same manner.

Butadiene-styrene copolymer latex solution 79 cc (solid content 40%, butadiene/Ste9F weight ratio = 31/69) 2.4-dichloro-6-hydroxy-s-triazine sodium trilam salt 4% solution 20.5 cc distilled water
900.5ccIn addition, in the latex solution, there is an emulsifying dispersant that is added to the solid content of the latex.
Contains 0.4wt%.

Prepare the following two liquids as the second undercoat layer coating liquid,
After each solution became uniform, the two liquids were mixed.

[Present] Liquid - Gelatin 8g - Polymer latex 1cc with a solid content of 15% - 3cc as a 3% dye solution 0cc as a 1% solution - Methyl cellulose 0°g (Shin-Etsu Chemical Co., Ltd.: Metrose SMI 5) [F] Liquid - H2O・Gelatin matting agent Polymethyl methacrylate with an average particle size of 2.5 μm 67cc g 0゜g ・H2O308CC A mixed solution of liquid [with] and liquid [F] was applied in an amount of 8. 5cc/
An undercoat layer film was prepared by applying the above-mentioned double-sided first undercoat layer to one side at a time and drying it on both sides so as to obtain rrr.

(Preparation of emulsion layer coating solution) Kyokukokunin Ω tone 1 5 g of potassium bromide, 0.05 g of potassium iodide, 35 g of gelatin, 1 thioether HO (CH2), 5 (CH 2 S (CHt) 20 H) in 11 water
% aqueous solution was added into the solution kept at 75°C,
While stirring, add an aqueous solution of 8.33 g of silver nitrate and 5 g of potassium bromide.
．． 94 g of potassium iodide and an aqueous solution containing 0.726 g of potassium iodide were added in 45 seconds using a double jet method. Subsequently, 2.5 g of potassium bromide was added, and then an aqueous solution containing 8.33 g of silver nitrate was added over 7 minutes and 30 seconds so that the flow rate at the end of addition was twice that at the start of addition. followed by silver nitrate 15
3.34 g of an aqueous solution and an aqueous solution of potassium bromide, the potential is set to pA.
It was added in 25 minutes using a controlled double jet method while maintaining the g content at 8.2. The flow rate at this time was accelerated so that the flow rate at the end of addition was eight times the flow rate at the start of addition. After the addition was completed, 15 cc of 2N potassium thiocyanate solution was added, and then 50 cc of 1% aqueous potassium iodide solution was added over 30 seconds. After that, the temperature was lowered to 35°C and soluble salts were removed by the sedimentation method, and then the temperature was raised to 40°C, 68g of gelatin, 1g of phenol and 7.5g of trimethylolpropane were added, and the pH was adjusted to 6 with sodium chloride and potassium bromide.
, 40, pAg was adjusted to 8.45.

After raising the temperature to 56°C, a sensitizing dye (X
-1) was added for 735 μ. After 10 minutes, 8.2 µm of sodium thiosulfate hydrate, 163 µm of potassium thiocyanate, and 5.4 µm of chloroauric acid were added, and after 5 minutes, it was rapidly cooled and solidified. In the resulting emulsion, 93% of the total projected area of all grains consists of grains with an aspect ratio of 3 or more, and the average projected area diameter of all grains with an aspect ratio of 2 or more is 0.95μ.
m1 standard deviation 18.5%, average thickness 0.161μm
The aspect ratio was 5.9.

(X-1) Water 1j! 5 g of potassium bromide, 0.05 g of potassium iodide, 35 g of gelatin, 2.5 cc of a 5% aqueous solution of thioether HO (CHS(CH2)2S(C,H2)20H) were added to the solution kept at 75°C. While stirring, an aqueous solution of 5.55 g of silver nitrate, an aqueous solution containing 3.96 g of potassium bromide, and 0.484 g of potassium iodide were added in 45 seconds by a double jet method. Subsequently, 2.5 g of potassium bromide was added. Afterwards, an aqueous solution containing 8.33 g of silver nitrate was added over 7 minutes and 30 seconds so that the flow rate at the end of addition was twice that at the beginning of addition. After the end of addition, 25 wt.
After adding 20 cc of % ammonia solution and performing physical ripening for 20 minutes, the pH was adjusted to 5.5 with IN sulfuric acid. Subsequently, an aqueous solution of 153.34 g of silver nitrate and an aqueous solution of potassium bromide were added over 25 minutes by a controlled double jet method while maintaining the potential at pAg 8.3. The flow rate at this time was accelerated so that the flow rate at the end of addition was eight times the flow rate at the start of addition. After completion, 15 cc of 2N potassium thiocyanate solution was added, and further 50 cc of 1% aqueous potassium iodide solution was added over 30 seconds. Thereafter, desalting and chemical ripening were carried out in the same manner as in the case of Emulsion A. In the resulting emulsion, 96% of the total projected area of all grains consists of grains with an aspect ratio of 3 or more, and the average projected area diameter of all grains with an aspect ratio of 2 or more is 0.97μ.
m, standard deviation was 14%, average thickness was 0.165 μm, and aspect ratio was 5.9.

Manufactured by Yu Yudan Ruiyu (comparative emulsion) Add 35 g of gelatin and 6 g of potassium bromide to water 11, and add a silver nitrate aqueous solution (4 g as silver nitrate) and 0.15 g of potassium iodide while stirring in a container kept at 60°C. An aqueous potassium bromide solution was added over 1 minute using a double jet method. After raising the temperature to 70°C, add a silver nitrate aqueous solution (145 g as silver nitrate)
) and an aqueous potassium bromide solution containing 4.2 g of potassium iodide were added by a double jet method. At this time, the addition flow rate was accelerated so that the flow rate at the end of addition was five times that at the start of addition.

After the addition, soluble salts were removed at 35°C by the sedimentation method, the temperature was raised to 40°C, and 58 g of gelatin was added.
H was adjusted to 6.7. The obtained emulsion has a projected area diameter of 0.95 μm, a standard deviation of 27.5%, and an average thickness of 0.16.
The tabular grains were 3 μm and the aspect ratio was 5.8. This emulsion was chemically sensitized using gold and sulfur sensitization.

After chemical sensitization, the antifoggant 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene was added, and the sensitizing dye (X-1) having the above structural formula was added at a concentration of 600% per mole of silver halide grains. ■ Added ortho sensitization.

Danri Pear (comparative emulsion) 5 g of potassium bromide, 0.05 g of potassium iodide, 35 g of gelatin, 1 thioether) 10(CH2)2S(CH2)2S(CH2)20H in water Il
2.5 cc of a 5% aqueous solution of was added and kept at 65°C, and while stirring, an aqueous solution of 8.33 g of silver nitrate and an aqueous solution containing 5.94 g of potassium bromide and 0.726 g of potassium iodide were double jetted. It was added in 45 seconds according to the method. Subsequently, 2.5 g of potassium bromide was added, and then an aqueous solution containing 4.17 g of silver nitrate was added over 7 minutes and 30 seconds so that the flow rate at the end of addition was twice that at the start of addition. After raising the temperature to 75° C., an aqueous solution of 153.34 g of silver nitrate and an aqueous solution of potassium bromide were added over 25 minutes by a controlled double jet method while maintaining the potential at pAg 8.5. At this time, flow I was accelerated so that flow I at the end of addition was eight times the flow rate at the start of addition. After the addition was completed, 15 cc of 2N potassium thiocyanate solution was added, followed by 50 cc of 1% potassium iodide aqueous solution.
c was added over 30 seconds. Thereafter, desalting and chemical ripening were carried out in the same manner as in the case of Emulsion A. In the obtained emulsion, 90% of the total projected area of all grains consists of grains with an aspect ratio of 3 or more, and the average projected area diameter of all grains with an aspect ratio of 2 or more is 1.03 μm 1 standard deviation 21.5%. , the average thickness is 0. The aspect ratio was 10.1 at 102 μm.

Preparation of emulsion E (comparative emulsion) Potato-shaped grains of silver iodobromide (3 mol % silver iodide) were formed in the presence of ammonia by the double jet method (average projected area diameter 0.91 μm), chlorauric acid salts. and chemical sensitization with sodium thiosulfate.

After chemical sensitization, an antifoggant 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene was added,
Ortho sensitization was carried out by adding 300 .mu.m of a sensitizing dye (X-2) having the following structural formula per mole of silver halide grains.

(X-2) The following chemicals were added to these emulsions per mole of silver halide to prepare a coating solution.

-4-hydroxy-6-methyl-1,3,3a.

7-chitrazaindene 1.94g・2,6-bis(hydroxyamino)-4-diethylamino-1,3
,5-1-riazine 80■ Sodium polyacrylate (average molecular weight 41,000) 4.0g 2,5
-Potassium dihydroxybenzenesulfonate
Copolymerized plasticizer with a composition ratio of 150mg/I ethyl acrylate/acrylic acid = 9515 20.0g gelatin
(Adjustment of Coated Gelatin Amount) The emulsion layer coating solution thus prepared and the surface protection layer solution were coated on both sides of the support in the same manner by coextrusion.

At this time, the amount of coating on one side of the surface protective layer was as follows.

Surface protective layer> Gelatin 0.81g/rrr Dextran (average molecular weight 390,000) 0.81g/m Matting agent (average particle size 3.5μm) Polymethyl methacrylate/methacrylic acid = 9 = 1 copolymer 0.06g/rriH 60mg/rrr 20■/Po2■/Bo CaF+ySOzN(CH2CHtO)sHt H 5■/d ・Sodium polyacrylate (average molecular weight 41,000) 70■/Bo 1,2-bis(sulfonylacetamido)ethane was used as a hardening agent, and samples ① to ＠ were prepared by adding it to the water swelling ratio shown in Table 1.

The following evaluations were performed on each of the samples obtained as described above.

(1) Water swelling rate After coating, each sample was aged for 3 days at 38° C. and 50% relative humidity. After the passage of time, the thickness a of the coating film of each sample was measured. Thereafter, the sample was immersed in distilled water at 21'C for 3 minutes, and the thickness b of the coating film at that time was measured. The water swelling rate was determined by the following formula.

(2) Evaluation of sensitivity and Dmax Each sample was exposed to green light through a continuous wedge.
/l After giving a 0 second exposure, use Fuji Photo Film (a horizontally split automatic developing machine "Fuji X-ray Processor FPM9000").
The entire process took 45 seconds at J.

A non-hardening processing solution having the following composition was used as the developer and fixer.

The density was expressed as the logarithm of the reciprocal of the exposure amount that gives a density of fog density + 0.5, and the relative sensitivity was evaluated based on the sensitivity of sample (1) as 100.

Developer solution> Potassium hydroxide 24g Sodium sulfite 40g Potassium sulfite
50g diethylenetriaminepentaacetic acid 2.4g boric acid
10g hydroquinone 3
5g diethylene glycol 11.2g4-
Hydroxymethyl-4-methyl- ■-phenyl-3-pyrazolidone 265g5-methylbenzotriazole 0.06g with water! (
(adjust to pH 10.65).

Before development, an aqueous solution IO- containing 2 g of potassium bromide and 1.8 g of acetic acid was added to adjust the pH to 10.5.

Fixer> Ammonium thiosulfate 140g Sodium sulfite 15g Ethylenediaminetetraacetic acid disodium dihydrate 0.025g Sodium hydroxide 6g Adjust to 11 with water (adjust to pH 4.8 with acetic acid.

(3) Evaluation of pressure resistance Exposure of each sample through a step wedge (285
The samples were scratched with a 0.5R sapphire needle with a load of 20 g to 200 g before or after exposure at 4° with 100 lux tungsten light for 1/10 seconds on both sides. After exposure, the sample was placed in a developer using Fuji Photo Film R.
D-7 was used at 35° C., and the fixer was Fuji F, manufactured by the same company, and processed using an automatic processor FPM-9000 manufactured by the same company. The degree of pressure sensitization and pressure fog in the scratched area was evaluated.

○: No practical problem.

△: There is a possibility of causing a problem in practice.

×: Not possible due to practical problems.

(4) Drying Each sample cut into a cut size (25.4an x 30.5cm) was subjected to the automatic developing machine and non-hardening treatment used in (1) above under a humidity condition of 28°C and 70% RH. Using coupling, 100 sheets were continuously processed and drying properties were evaluated.

○: No practical problems 82. There may be a problem depending on the conditions of use.

×: Impossible for practical use because it has not dried.
A rapid process was performed using M900 (developing solution RD-7, fixing solution Fuji F) for a total processing time of 45 seconds, and residual color was evaluated.

○: No practical problem.

△: There is a possibility of causing a problem in practice.

×: Impossible due to practical problems.

The results obtained as described above are summarized in Table-1.

Processing ■ to ■ and ■ to ■ of the present invention are sensitivity, Dmax
It has excellent pressure resistance, drying properties, and no residual color.
It can be clearly seen that it is suitable for rapid treatment without dura mater.

When the sample of the present invention was sandwiched between two fluorescent intensifying screens and subjected to practical X-ray photography, and the dura-free rapid treatment shown in evaluation method (2) was performed, very good images were obtained.

Example 2 Using the tabular emulsion of Example 1, an experiment was conducted on the stability of the coating solution over time. Each coating solution was divided into two parts, and one part was applied immediately. The other solution was left in a dissolved state at 40° C. for 7 hours and then applied. The support has a biaxially stretched thickness of 175 μm.
Samples @~@ and [phases]'~@' were prepared by using polyethylene terephthalate dyed blue and subjected to undercoating treatment and coating the compositions shown in Table 2 according to Example 1. Each sample was run through a continuous wedge and exposed to green light for 1 time.
After exposure for /lO seconds, the entire process was processed for 45 seconds using an automatic developing machine "Fuji X-Ray Processor FPM9000J" manufactured by Fuji Photo Film ■, and the sensitivity and Dmax were evaluated. R manufactured by Fuji Photo Film ■
D-7 and Fuji F were used. Sensitivity is fog density +0.
It is expressed as the logarithm of the reciprocal of the exposure amount that gives a density of 5, and the relative sensitivity was evaluated with the sensitivity of the sample @ as 100.

As is clear from Table 2, the sample [phase] of the present invention using a monodisperse tabular grain emulsion with an aspect ratio of 3 to 8 is good, with almost no decrease in Dmax or decrease in sensitivity as the coating liquid ages.

When the cross section of the sample in which Dmax decreased was observed under an electron microscope, it was found that the tabular grains were aggregated, which caused the covering power to decrease and Dmax to decrease. This problem did not occur with the configuration of the present invention.

Procedural amendment 1゜ Display of incidents 1999 Patent Application No. 2j3coj3 2゜ name of invention Processing method for silver halide photographic materials 3゜ person who makes corrections Relationship with the incident

Claims (1)

[Claims] In a method for developing a photographic material having at least one light-sensitive silver halide emulsion layer on a support, the silver halide grains in the emulsion layer have an aspect ratio of 3 or more,
Consisting of monodispersed tabular grains (dispersion coefficient of 20% or less) of less than 8%, and furthermore, the binder coating amount of one coating film (including the silver halide emulsion layer, surface protection layer, and other layers) on the support is 2%. The water swelling rate of this coating film is in the range of .0 to 4.5 g/m^2 (a photographic material aged for 3 days at 38°C and 50% relative humidity is immersed in distilled water at 21°C for 3 minutes). The percentage change in the thickness of the coated film when compared with the thickness before dipping is 200% or less, and the total processing time is 30%.
1. A method for processing a silver halide photographic material, which comprises performing a non-hardening process for ~90 seconds.