JP2704460B2 - Silver halide photographic light-sensitive material and its development processing method - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material and a method for developing the same, particularly having excellent rapid processing suitability, that is, high sensitivity in a short time development processing and drying in a shorter time. The present invention relates to a technique for reducing roller marks generated during processing of a film, and particularly to an ultra-rapid processing film for X-ray.

(Prior art)

In recent years, high-temperature rapid processing has rapidly become widespread in the development process of photographic light-sensitive materials, and the processing time has been greatly reduced even in the processing of automatic processing machines for various photosensitive materials. In order to achieve high-speed rapid processing, a developer for realizing sufficient sensitivity in a short time, a photosensitive material which is excellent in progress and does not leave a residual color even in short-time processing, and is dried in a short time after washing with water Sensitive materials are required. Many automatic processors have a built-in drying zone, and if the dryness of the photosensitive material is poor, the automatic processor must have a higher drying capacity. I have to help. Further, as a result of generating a large amount of heat, adverse effects such as an increase in the temperature of a room in which the automatic developing machine is installed occur.

Efforts are made to increase the drying speed of the photosensitive material as much as possible to prevent such a phenomenon. A commonly used method is to add a sufficient amount of a hardening agent in advance in the photosensitive material coating step to reduce the amount of swelling of the emulsion layer and the surface protective layer in the development-fixing-washing step. Is a method for reducing the water content in the photosensitive material before the start of drying. In this method, if a large amount of hardener is used, the drying speed can be accelerated accordingly.However, by strengthening the hardener, development is delayed and sensitivity is reduced, and even if high aspect ratio tabular grains are covered, There is a drawback that the power is lowered and various adverse effects are caused, such as a delay in fixing speed of undeveloped silver halide grains, deterioration of residual color, and an increase in residual hypo in the processed photographic material. On the other hand, reducing the water content in the light-sensitive material before the start of drying can also reduce the amount of a hydrophilic substance applied to the light-sensitive material, that is, gelatin, a synthetic polymer, a hydrophilic low-molecular substance, and the like. The hydrophilic low-molecular substance is generally added for the purpose of preventing dry fogging of silver halide grains in a coating step, and if this is removed, fogging occurs in the light-sensitive material. On the other hand, if gelatin or a synthetic high molecular substance used as a binder for silver halide grains is removed, the amount of binder relative to silver halide grains will decrease, and the Ag / Binder ratio will increase. If the amount of the binder is reduced, there are disadvantages that the graininess is deteriorated in photographic performance and that roller marks are easily generated during processing. Even if an attempt is made to improve the drying property by reducing the amount of the binder, it is difficult to reduce the amount of the binder due to these adverse effects.

(Object of the present invention)

An object of the present invention is to solve the above-mentioned problems of the prior art,
An object of the present invention is to provide a photographic light-sensitive material which is less sensitive to roller marks during processing, has a sufficiently high drying speed, is short-time processing, and has high sensitivity, and a developing method using the same.

[Disclosure of the Invention]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having two or more photosensitive silver halide emulsion layers comprising a tabular silver halide emulsion on at least one side of the support. The emulsion layer is composed of a pure silver bromide emulsion, and the silver halide emulsion layer farther from the emulsion layer when viewed from the support is achieved by a silver halide photographic light-sensitive material comprising a plurality of emulsion layers composed of a silver iodobromide emulsion. I found something. Generally, tabular silver iodobromide emulsions are characterized by having less fogging than tabular pure silver bromide emulsions and are widely used, but have the disadvantage that roller marks are easily generated. This is thought to be due to the infectious development effect of iodine ions released during development, but the detailed mechanism is not yet clear.

The present invention relates to a silver halide photographic light-sensitive material in which the occurrence of roller marks is reduced as much as possible while maintaining the characteristic of low fog by bringing an emulsion layer comprising a tabular pure silver bromide emulsion closest to a support.

Although the reason why the layer constitution of the present invention can prevent the occurrence of roller marks is not clear, it may be related to the fact that the roller marks are likely to be generated in a portion of the emulsion layer close to the support.

In the present invention, the ratio of pure silver bromide / silver iodobromide is from 2/1 to 1/1.
2. The total coated silver amount is preferably 2.5 g to 5 g / m ² . The silver / hydrophilic binder ratio of the emulsion layer is preferably 2.5 ≧ Ag / binder ≧ 0.7 by weight. In particular, it is preferably 1.0 or more and 2.4 or less.

Tabular silver halide emulsions are described in Cugnac and Chateau, "Evolution of the Morphology of Physically Ripened Silver Bromide Crystals (Evolution of the Morphology of Silver Promide Crystals Duar). Ring Physical Living) "Science and Industry Photography, Vol. 33, No.2 (19
62), pp. 121-125, Duffin, Photographic Emulsion Chemistry (Photographic e)
mulsion chemistry ”Focal pre
ss), New York, 1966, pp. 66-72, APH Trivclli, WF Smith (Smith) Photographic journal, 80, 285
Vol. (1940), etc.
1, it can be easily adjusted by referring to the methods described in JP-A-58-113,927, JP-A-58-113,928 and U.S. Pat. No. 4,439,520.

Further, in an atmosphere having a relatively low pBr value of pBr 1.3 or less, a seed crystal in which tabular grains are present at 40% or more by weight is formed, and silver and a halogen solution are added simultaneously while maintaining the same pBr value. Obtained by growing a seed crystal.

It is desirable to add a silver and halogen solution so that no new crystal nuclei are generated during the grain growth process.

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

Further, among the tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains.

The details of the structure and the production method of the monodisperse hexagonal tabular grains referred to in the present invention are described in JP-A-63-151618, but in brief, the emulsion is a silver halide comprising a dispersion medium and silver halide grains. An emulsion, wherein 70% or more of the total projected area of the silver halide grains has a ratio of the length of the side having the maximum length to the length of the side having the minimum length of 2 or less. Rectangular and occupied by tabular silver halide having two parallel surfaces as outer surfaces,
The coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains [the value obtained by dividing the variation (standard deviation) of the grain size represented by the circle-converted diameter of the projected area thereof by the average grain size] is 20% or less. It has dispersibility. The crystal structure may be uniform, but it is preferable that the inside and the outside are composed of different halogen compositions, and may have a layered structure. Further, it is preferable that the grains contain reduction sensitized silver nuclei. The aspect ratio of tabular grains is 3 or more and 30 or less,
Preferably it is 4.5 or more and 20 or less.

For the present invention, UK Patent 635,841, US Patent 3,62
So-called halogen conversion type (conversion type) particles as described in US Pat. No. 2,318 are particularly effective.

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 halogen conversion method, usually, an aqueous halogen solution having a smaller solubility product with silver than the halogen composition on the grain surface before the halogen conversion is added. For example, for a silver bromide or silver iodobromide plate, conversion is performed by adding an aqueous solution of potassium iodide. The concentration of the aqueous solution to be added is preferably as low as possible, preferably 30% or less, more preferably 10% or less. Further, it is preferable to add the converted halogen solution at a rate of 1 mol% or less per minute per mol of silver halide before halogen conversion. Further, a sensitizing dye may be present during the halogen conversion, and silver iodobromide or silver halide fine particles of silver iodide may be added instead of the converted halogen aqueous solution. The size of these fine particles is desirably 0.2 μm or less, preferably 0.1 μm or less, and particularly desirably 0.05 μm or less. The halogen conversion amount is 0.1% of the silver halide before conversion.
11 mol%, especially 0.1 to 0.6 mol% is preferred.

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

The iodine content contained in the entire tabular silver iodobromide grains of the present invention is preferably 0.1 to 5.0 mol%, particularly preferably 0.3 to 3.0 mol%. The tabular silver bromide grains of the present invention contain no iodine at all or, if at all, 0.1 mol% or less, particularly 0.05 mol% or less.

When the halogen conversion is carried out by the above method, a method in which a silver halide material is present is particularly effective. Preferred solvents include thioether compounds, thiocyanates, and 4-substituted thioureas. Of these, thioether compounds and thiocyanates are particularly effective, and thiocyanate is used in an amount of 0.5 g to 5 g per mole of silver halide,
The use of 0.2 g to 3 g is preferred.

The projected area diameter of the tabular emulsion of the present invention is 0.3 to 2.0 μm,
In particular, it is preferably from 0.5 to 1.6 μm. The distance between the parallel planes (particle thickness) is preferably 0.05 μm to 0.3 μm, particularly preferably 0.1 to 0.25 μm, and the aspect ratio is preferably 3 or more and less than 20, particularly preferably 4 or more and less than 8. In the tabular silver halide emulsion of the present invention, silver halide grains having an aspect ratio of 3 or more are present in 50% (projected area) or more, particularly 70% or more of all grains, and the average susceptibility of the tabular grains is 4 to 4. 8 is preferable.

The chemical sensitization of the silver halide emulsion is preferably carried out using one or more of noble metal sensitization, sulfur sensitization and reduction sensitization.

Chemical sensitization is THJames, The Theory of the Photographic Process, 4th Edition, Macramin, 197
7, pp. 67-76, and can be performed using active gelatin, and is also described in Research Disclosure 120, April 1974, Item 12008, Research Disclosure, 134, June 1975. , Item 13452,
U.S. Patent Nos. 1,623,499, 1,673,522, and 2,399,
No. 083, No. 2,642,361, No. 3,297,447, No. 3,29
No. 7,446, No. 3,772,031, No. 3,761,267, No. 3,8
57,711, 3,565,633, 3,901,714 and 3,904,415 and British Patents 1,315,755 and
As described in U.S. Pat. No. 1,396,696, it can be carried out with sulfur, selenium, tellurium, gold, platinum, palladium and multiple combinations of these sensitizers at pAp 5-10, pH 5-8 and temperature 30-80 ° C. it can.

Chemical sensitization is optimally carried out in the presence of a thiocyanate compound as described in U.S. Pat.No. 2,642,361 and in U.S. Pat.Nos. 2,521,926, 3,021,215 and 4,052.
It is carried out in the presence of a sulfur-containing compound of the type described in US Pat.

Further, it can be chemically sensitized in the presence of a finish (chemical sensitization) modifier. Finish modifiers used include azaindene, azapyridazine, azapyrimidine,
Compounds known to suppress fog and increase sensitivity during chemical sensitization, such as benzothiazolium salts and sensitizers having one or more ring nuclei, are used.

Examples of finish modifiers are described in U.S. Pat.
3,411,914, 3,554,757, 3,565,631 and 3,901,714, Canadian Patent 778,723 and Duffin, Photographic Emulsion
Chemistry Focal Press (1966), New York, PP. 138-143.

Further, it is also useful to carry out chemical sensitization in the presence of a commonly used sensitizing dye to obtain an emulsion having high sensitivity and good development progress.

Also, as described in U.S. Pat. Nos. 3,891,446 and 3,984,249, reduction sensitization can be performed using, for example, hydrogen, and U.S. Pat. No. 2,983,609, oftedarl et al., Research Disclosure ,
Volume 136, August 1975, Item 13654, U.S. Patent No. 2,518,
No. 698, No. 2,739,060, No. 2,743,182, No. 2,74
Using reducing agents such as stannous chloride, thiourea dioxide, polyamines and amine boranes as described in US Pat. Nos. 3,183, 3,026,203 and 3,361,564, or with low pAg (eg, less than 5) and / or high pAg. Reduction sensitization can be achieved by pH treatment (for example, greater than 8).

Emulsions of the present invention include nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotoluazoles, aminotriazoles, etc .; mercapto compounds {eg, mercaptothiazoles, mercapto Benzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazole, mercaptopyrimidines, mercaptotriazines and the like; thioketo compounds such as oxadrinethione; azaindenes such as triazaindenes and tetraazaindenes (Especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes and the like｝; benzenethiosulfonic acid, benzenesulfinic acid, benzenes Known as antifoggants or stabilizers, such as acid amides, it can be added a number of compounds.

In particular, nitrones and their derivatives described in JP-A-60-76743 and JP-A-60-87322, mercapto compounds described in JP-A-60-80839, and heterocyclic compounds described in JP-A-57-164735. Compounds and complex salts of silver with a heterocyclic compound (for example, silver 1-phenyl-5-mercaptotetrazole) can be preferably used.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may have coating aids, antistatic, improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties (eg, development acceleration, hardening For various purposes such as sensitization and sensitization).

For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene oxide adducts of silicone), alkyl esters of sugars Nonionic surfactants such as alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, N-acyl-N-alkyltaurines, sulfosuccinates, sulfoalkyl Anionic surfactants such as polyoxyethylene alkyl phenyl ethers; amphoteric surfactants such as alkyl betaines and alkyl sulfobetaines; Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, pyridinium salts, and imidazolium salts can be used.

As antistatic agents, perfluorooctanesulfonic acid K salt, N-propyl-N-perfluorooctanesulfonylglycine Na salt, N-propyl-N-perfluorooctanesulfonylaminoethyloxypoly (n-3) oxyethylenebutanesulfone Acid Na salt, N-perfluorooctanesulfonyl-N, N ', N'-trimethylammoniodiaminopropane chloride, N-perfluorodecanoylaminopropyl-N', N'-dimethyl-N'-carboxybetaine Fluorine-containing surfactant, JP 60
-80848, 61-112144, 62-172343, 62-1
No. 7,3459, etc., a nonionic surfactant, a nitrate of an alkali metal, conductive tin oxide, zinc oxide, vanadium pentoxide, or a composite oxide doped with antimony or the like can be preferably used.

In the present invention, U.S. Pat.
No. 2701245, No. 4142894, Polymethyl methacrylate homopolymer or copolymer of methyl methacrylate and methacrylic acid as described in No. 4396706, Organic compounds such as starch, silica, titanium dioxide, sulfuric acid,
Fine particles of an inorganic compound such as strontium barium can be used.

The particle size is preferably from 1.0 to 10 μm, particularly preferably from 2 to 5 μm.

In the surface layer of the photographic light-sensitive material of the present invention, in addition to a silicone compound described in U.S. Pat. Nos. 3,489,576 and 4,047,958 as a slipping agent, colloidal silica described in JP-A-56-23139, paraffin wax , Higher fatty acid esters, starch powder derivatives and the like.

In the hydrophilic colloid layer of the photographic light-sensitive material of the present invention, polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be used as a plasticizer.

As the binder or protective colloid that can be used in the emulsion layer or surface protective layer of the light-sensitive material of the present invention, it is advantageous to use gelatin and a water-soluble polyester, but other hydrophilic colloids may also be used. it can.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose 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, polyvinylimidazole, polyvinylimidazole, etc. Can be used.

As the gelatin, besides lime-processed gelatin, acid-processed gelatin or enzyme-processed gelatin may be used, and hydrolyzate or enzyme-decomposed product of gelatin can also be used.

Among these, the average molecular weight is 5,000 or more together with gelatin.
It is preferable to use 100,000 or less dextran or polyacrylamide in combination. JP-A-63-68837, JP-A-63-149641
The method described in the above item is also effective in the present invention.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glital aldehyde, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N,
N'-methylenebis- [β- (vinylsulfonyl) propionamide], an active halogen compound (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalic acids (mucochloric acid, etc.) alone or It can be used in combination. Above all, JP-A-53-4122
Preferred are the active vinyl compounds described in 1, 53-57257, 59-162546 and 60-80846 and the active halides described in U.S. Pat. No. 3,325,287.

N-carbamoylpyridinium salts (for example, (1-morpholinocarbonyl-3-pyridinio) methanesulfonate and the like), haloamidinium salts (for example, 1- (1-
Chloro-1-pyridinomethylene) pyrrolidinium 2-naphthalenesulfonate and the like are also useful.

As the hardener of the present invention, a polymer hardener can also be effectively used.

As the high hardening agent used in the present invention, for example,
56-142524, U.S. Pat.No. 4,161,407, JP-A-54-6503
3. Polymers having an active vinyl group described in Research Disclosure Magazine 16725 (1978) or the like or a group which is a precursor thereof.

In the present invention, the photographic emulsion layer or other layers may be colored with a dye for the purpose of preventing halation or irradiation, or providing a filter layer to control the spectral composition of light to be incident on the photographic emulsion layer. Good. In a double-sided film such as a direct medical X-ray film, a layer intended for crossover cutting may be provided below the emulsion layer. Examples of such dyes include oxonol dyes having a pyrazolone nucleus or barbituric acid nucleus, azo dyes, azomethine dyes, anthraquinone dyes, arylidene dyes, styryl dyes, triarylmethane dyes, merocyanine dyes, cyanine dyes, and the like.

When using these dyes, it is an effective technique to mordant an anionic dye to a specific layer in a light-sensitive material using a polymer having a cation site. In this case, it is preferable to use a dye which irreversibly decolorizes during the development-fixing-washing step. The layer that mordantes the dye using a polymer having a cation site, even in the emulsion layer, even in the surface protective layer, may be on the side opposite to the emulsion layer and the support, preferably between the emulsion layer and the support, Particularly for the purpose of crossover cutting of medical X-ray double-sided film, it is ideal to mordant into the undercoat layer.

As a method for immobilizing a dye, JP-A-55-155350 and WO88 / 047
94, and the solid dispersion method described in Japanese Patent Application No. 2-118042 is also effective.

As a coating aid for the undercoat layer, a polyethylene oxide-based nonionic surfactant can be preferably used in combination with a polymer having a cation site.

As the polymer providing the cation site, an anion conversion polymer is preferable.

Various known quaternary ammonium salt (or phosphonium salt) polymers can be used as the anion conversion polymer.
Quaternary ammonium salt (or phosphonium salt) polymers are widely known as mordant polymers and antistatic polymers in the publications listed below.

JP-A-59-166,940, U.S. Patent 3,958,995, JP-A-55-166,940
142339, JP-A-54-126,027, JP-A-54-155,835, JP-A-53-30328, JP-A-54-92274; U.S. Patents 2,548,564, 3,148,061, 3,757
Polyvinylviridinium salts described in 6,814; US Patent 3,7
And water-insoluble quaternary ammonium salt polymers described in U.S. Pat. No. 3,898,088.

Furthermore, since the compound moves from the desired layer to another layer or into the processing solution and does not have a photographically unfavorable effect, at least 2 or more (preferably 2 to 2) ethylenically unsaturated groups are contained.
4) It is particularly preferable to use the resulting monomer as a crosslinked aqueous polymer latex by copolymerizing the monomer.

In the present invention, the method of coating an emulsion layer, a surface protective layer, and the like on a support is not particularly limited, and is described in, for example, U.S. Patent Nos. 2,761,418, 3,508,947, and 2,761,791. A multilayer simultaneous coating method can be preferably used.

The developer used in the present invention can contain a known developing agent. As the developing agent, dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol) may be used alone or in combination. The developing solution generally contains other known preservatives, alkali agents, pH buffers, antifoggants, etc., and if necessary, a solubilizing agent, a color tone agent, a development accelerator (for example, quaternary salt,
It may contain a hydrazine, benzyl alcohol), a surfactant, an antifoaming agent, a water softener, a hardening agent (for example, glutaraldehyde), a viscosity imparting agent, and the like.

As the fixing solution, those having a commonly used composition can be used. As the fixing agent, in addition to thiosulfate and thiocyanate, an organic sulfur compound known to have an effect as a fixing agent can be used. The fixer may contain a water-soluble aluminum salt as a hardener.

As the developing method by the automatic developing machine in the present invention, US Pat. Nos. 3,025,779, 3,515,556, and 3,357,391
No. 4,367,459 and British Patent No. 1,269,268 are preferably used.

The developing temperature is preferably from 18 ° C to 50 ° C, particularly from 30 ° C to 45 ° C, and the developing time is preferably from 6 seconds to 25 seconds.

The entire development process from the start of development to the completion of fixing, washing and drying is preferably 25 seconds to 100 seconds.

There are no particular restrictions on the various additives, development methods, exposure methods, etc., of the light-sensitive material of the present invention. Research Disclosure, 176, Item 17643 (December 1978) and 18
Volume 4, Item 18431 (August 1979) and JP-A-2-68539
The description on pages 8 to 9 of the issue can be referred to.

(Example) Next, the present invention will be specifically described.

Example 1 Preparation of Emulsion-a In water 1, 5 g of potassium bromide, 0.05 g of potassium iodide, 30 gelatin
g, 5 of the thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH
2.533 g of an aqueous solution of silver sulfate, 5.94 g of potassium bromide, and 5.94 g of potassium iodide
An aqueous solution containing 0.726 g was added in 45 seconds by the double jet method. Subsequently, after adding 2.5 g of potassium bromide, an aqueous solution containing 8.33 g of silver nitrate was added over 26 minutes so that the flow rate at the end of the addition was twice that at the start of the addition. After this 25
20% ammonia solution, 10% 50% NH ₄ NO ₃
After physical aging for 2 minutes, 240 cc of 1N sulfuric acid was added for neutralization. Subsequently, an aqueous solution of 153.34 g of silver nitrate and an aqueous solution of potassium bromide were added over 40 minutes by a control double jet method while maintaining the potential at pAg8.2. The flow rate at this time was accelerated so that the flow rate at the end of the addition was 9 times the flow rate at the start of the addition. 15 cc of 2N potassium thiocyanate solution at the end of addition
And 55 cc of a 1% aqueous solution of potassium iodide was added over 30 seconds. After that, the temperature was lowered to 35 ° C, and soluble salts were removed by a sedimentation method.
And 2 g of phenol, added with soda and potassium bromide
The pH was adjusted to 6.40 and pAg to 8.10.

After raising the temperature to 56 ° C, the sensitized color dye
0 mg and 150 mg of stabilizer were added. Ten minutes later, 2.4 mg of sodium thiosulfate pentahydrate, 140 mg of potassium thiocyanate, and 2.1 mg of chloroauric acid were added to each emulsion, and after 80 minutes, the emulsion was solidified by rapid cooling. In the emulsion thus obtained, 98% of the total projected area of all grains consisted of grains having an aspect ratio of 3 or more. The average projected area diameter of all grains having an aspect ratio of 2 or more was 1.4 μm, the standard deviation was 15%, and the thickness was Average is 0.187μm
And the aspect ratio was 7.5.

Preparation of Emulsion-b In water 1, 7 g of potassium bromide, 30 g of gelatin, thioether H
Add _2.5 cc of a 5% aqueous solution of O (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH and, while stirring, 8.33
g and an aqueous solution containing potassium bromide 6.5 were added by the double jet method over 45 seconds. Subsequently, after adding 2.5 g of potassium bromide, an aqueous solution containing 8.33 g of silver nitrate was added over 26 minutes so that the flow rate at the end of the addition was twice that at the start of the addition. After this, 13cc of 25% ammonia solution, 50% NH
₄ Add 10cc of NO ₃ and physically ripen for 20 minutes, then add 1N sulfuric acid 16
0 cc was added to neutralize. Subsequently, an aqueous solution of 153.34 g of silver nitrate and an aqueous solution of potassium bromide were added over 40 minutes by a control double jet method while maintaining the potential at pAg8.2. The flow rate at this time was accelerated so that the flow rate at the end of the addition was 9 times the flow rate at the start of the addition. At the end of the addition, 5 cc of a 2N potassium thiocyanate solution was added. Thereafter, the temperature was lowered to 35 ° C., and after removing soluble salts by a sedimentation method, the temperature was raised to 40 ° C., 30 g of gelatin and 2 g of phenol were added, and pH was adjusted to pH 6.40 and pAg 8.10 with soda and potassium bromide. It was adjusted.

After raising the temperature to 56 ° C, the sensitized color dye
0 mg and stabilizer 100 mg were added. Ten minutes later, 2.4 mg of sodium thiosulfate pentahydrate, 100 mg of potassium thiocyanate, and 2.1 mg of chloroauric acid were added to each emulsion, and after 80 minutes, it was rapidly cooled and solidified to form an emulsion. In the emulsion obtained, 95% of the total projected area of all grains consisted of grains having an aspect ratio of 3 or more. The average projected area diameter of all grains having an aspect ratio of 2 or more was 1.4 μm, the standard deviation was 13%, and the thickness was The average was 0.2 μm and the aspect ratio was 7.0.

Preparation of Emulsion-c In water 1, potassium bromide 5 g, potassium iodide 0.05 g, gelatin 30 g, thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ )
3.0 cc of a 5% aqueous solution of ₂ OH was added, and while stirring, an aqueous solution of 8.33 g of silver sulfate and 5.9 ml of potassium bromide were added to the solution kept at 73 ° C.
4 g and an aqueous solution containing 1.00 g of potassium iodide were added over 45 seconds by the double jet method. Subsequently, after adding 2.5 g of potassium bromide, an aqueous solution containing 8.33 g of silver nitrate was added over 26 minutes so that the flow rate at the end of the addition was twice that at the start of the addition. After this, 20cc of 25% ammonia solution, 50% NH ₄ NO ₃ 10
After cc was added and physically aged for 20 minutes, 240 cc of 1N sulfuric acid was added to neutralize. Subsequently, an aqueous solution of 153.34 g of silver nitrate and an aqueous solution of potassium bromide were added over 40 minutes by a control double jet method while maintaining the potential at pAg8.2. The flow rate at this time was accelerated so that the flow rate at the end of the addition was 9 times the flow rate at the start of the addition. At the end of the addition, 15 cc of a 2N potassium thiocyanate solution is added, and a 1% aqueous solution of potassium iodide 55 is added.
cc was added over 30 seconds. After this, lower the temperature to 35 ° C,
After the soluble salts were removed by the sedimentation method, the temperature was raised to 40 ° C., 30 g of gelatin and 2 g of phenol were added, and the pH was adjusted to 6.40 and pAg 8.10 with soda and potassium bromide.

After raising the temperature to 56 ° C., a sensitizing dye having the following structure was added to 60
0 mg and 150 mg of stabilizer were added. Ten minutes later, 2.4 mg of sodium thiosulfate pentahydrate, 140 mg of potassium thiocyanate, and 2.1 mg of chloroauric acid were added to each emulsion. After 80 minutes, the emulsion was rapidly cooled and solidified to form an emulsion. In the obtained emulsion, 98% of the total projected area of all grains consisted of grains having an aspect ratio of 3 or more. The average projected area diameter of all grains having an aspect ratio of 2 or more was 1.5 μm, the standard deviation was 18%, and the thickness was Average is 0.192μm
And the aspect ratio was 7.8.

§Preparation of emulsion coating solution ○ Emulsion layer 1st layer-A The following chemicals were added per 1 mol of silver halide to emulsion-a to prepare a coating solution.

Emulsion layer First layer A coating solution having exactly the same contents as the first layer B except that the Ag / gelatin ratio was 0.7 was prepared.

Emulsion layer First layer-c A coating solution having exactly the same contents as the first layer-a was prepared except that emulsion-b was used.

Emulsion layer First layer-d A coating solution having exactly the same contents as the first layer-b except that emulsion-b was used.

Emulsion layer Second layer-a A coating solution having exactly the same contents as the first layer-a was prepared except that emulsion-c was used.

Emulsion layer Second layer-b A coating solution having exactly the same contents as the first layer-b except that emulsion-c was used.

§Preparation of base with mordant layer A base having a mordant layer having the following coating amount on both surfaces of a blue-colored polyethylene terephthalate base having a thickness of 175 μm was prepared.

The emulsion coating solution was coated on both sides of a PET base having a mordant layer in the same manner as the surface protective layer coating solution such that the coated silver amount per side was 1.8 g / m ² .

§Contents of surface protective layer §Evaluation of roller mark and drying property (i) Result of processing for 90 seconds The sample was exposed with a sensitometer and processed for 90 seconds with a Fuji X-Ray automatic developing machine RN. In this, the sample is developed with a developer having the following composition at 38 ° C. for 20 seconds.

Developer processing method Potassium hydroxide 29 g Glacial acetic acid 11 g Potassium sulfite 44 g Sodium bicarbonate 7.5 g Boric acid 1 g Diethylene glycol 29 g Ethylenediaminetetraacetic acid 1.7 g 5-Methylbenzotriazole 0.06 g 5-Nitroindazole 0.25 g Hydroquinone 30 g 1-phenyl-3- Pyrazolidone 1.5 g Sodium metabisulfite 12.6 g Glutaraldehyde 1 g Potassium bromide 6 g Finished to 1.0 by adding water (pH = 10.25) After treatment, the roller marks formed on each sample were visually evaluated. Given values of A to E for each sample, A
Indicates that there is no roller mark, and E indicates that roller marks occur frequently.

(Ii) Results after 38 seconds treatment Developer composition Potassium hydroxide 17 g Sodium sulfite 29 g Potassium sulfite 39 g Triethylenetetramine hexaacetic acid 2 g Boric acid 3 g Hydroquinone 28 g 1-Phenyl-3-pyrazolidone 1.7 g 5-Nitroindazole 0.2 g 5-methylbenzotriazole 0.02 g glutaraldehyde 5 g potassium bromide 2 g Adjust to 1 with water (adjust to pH 10.25) Composition of fixing solution Ammonium thiosulfate (70% wt / vol) 250 ml Sodium sulfite 15 g Boric acid 8 g Ethylenediamine tetra Acetic acid, disodium, dihydrate 0.025 g Sodium hydroxide 6 g Aluminum sulfate 15 g Adjust to 1 with water (adjust to pH 4.65 with acetic acid). Transfer this developing solution and fixing solution to the developing tank and fixing tank of the automatic developing machine. Each of them was developed under the following conditions.

Modified FPM-9000 manufactured by Fuji Photo Film Co., Ltd. and processed for 38 seconds with Dry to Dry.

Developing tank 22 35 ° C × 11.1 seconds Fixing tank 15.5 35 ° C × 8.6 seconds Rinse tank 14 20 ° C × 5.1 seconds Drying 55 ° C No difference was observed in Dmin between photosensitive materials -1 to -4.

From the results of the processing for 90 seconds and 38 seconds, it can be seen that the photosensitive material of the present invention has a small number of roller marks and has a rapid processing suitability.

Claims (3)

(57) [Claims] 1. Two or more layers of photosensitive silver halide comprising a silver halide emulsion in which at least one side of a support has tabular grains having an aspect ratio of 3 or more in which 70% or more of the total projected area of all grains is a tabular grain. In a silver halide photographic light-sensitive material having an emulsion layer, the emulsion layer closer to the support comprises a pure silver bromide emulsion, and the emulsion layer farther from the emulsion layer as viewed from the support comprises a silver iodobromide emulsion. Silver halide photographic material. 2. The silver halide photographic material according to claim 1, wherein the weight ratio of silver / hydrophilic binder in the emulsion layer is 1.0 or more. 3. A developing method comprising processing the silver halide photographic light-sensitive material according to claim 2 in a roller transport type automatic developing machine for a total processing time of 20 to 60 seconds.