JPS5945975B2 - Gazo Keiseihou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a method for forming dye images, and more particularly to a method for rapidly obtaining silver and dye images.

In photographic materials, especially radiographic recording materials, it is required that the recorded information can be reviewed as quickly as possible, so exposed photographic materials must be processed quickly.

For this purpose, automatic processing machines are already known, for example, in which the photographic material is automatically guided at a constant speed from one processing unit to another (for example, U.S. Pat.
025, No. 779). A method is known in which an exposed black-and-white radiographic light-sensitive material is processed within three and a half minutes using such an automatic processing machine to obtain an image (for example, U.S. Pat. No. 3,
545, 971 angle). On the other hand, it is also known to create color images by irradiating color photographic materials with radiation. (For example, U.S. Pat. No. 3,114,83
No. 3, No. 2, 644, 096, No. 2, 931, 904
No. 3,493,748, No. 3,695,882, U.S. Pat. No. 2,994,610, etc.). According to this method, a color image can be formed by coupling with an oxidized product of an aromatic primary amine developer.A color radiographic image is produced together with a silver image on a radiographic light-sensitive material containing at least one color coupler. .

When the radiographic light-sensitive material does not contain a coupler, a color image is similarly produced together with a silver image by developing it with a color developing solution containing a coupler. These color radiographic light-sensitive materials are disclosed in Japanese Patent Application Laid-Open No. 47-37539,
As described in U.S. Pat. No. 3,734,735, etc., it has a high degree of discrimination, a large exposure latitude, a large amount of information due to good graininess, and a low silver halide content. It is advantageous because it has advantages over black-and-white radiographic materials, such as the ability to move quickly. In the above-mentioned color radiographic light-sensitive materials, phenol type or a-naphthol type couplers are usually used as color couplers.

However, in general, quinoneimine dye images produced by coupling an oxidized aromatic primary amino developer with a conventional phenol type or a-naphthol type color former have a reduced dye density in an acidic fixer. Since a partially brown dye image recovers its color when oxidized, it does not pose much of a problem when a desilvering bleaching step is involved, as in the processing of general color sensitive materials. However, in the case of a color radiographic image forming method in which a color radiographic image is obtained together with a silver image through rapid color development, fixing, washing, and drying steps, there is no need for desilvering, and it is desirable to obtain an image in as short a time as possible. There is no bleaching and desilvering process. Therefore, the decrease in dye density during the above-mentioned fixing step was a major drawback. The first object of the present invention is to provide an image forming method suitable for rapid processing. A second object of the present invention is to provide an image forming method for rapidly obtaining an image in a color radiographic light-sensitive material capable of obtaining both a color radiation image and a silver image. A third object of the present invention is to provide an image forming method capable of rapidly obtaining a dye image with little loss of density in a fixing solution.

The inventors have already studied the above objectives. Japanese Patent Application No. 50-24796 (Japanese Unexamined Patent Publication No. 51-99522)
disclosed a method employing high PH fixing, the present invention relates to another method for achieving the above object.

However, of course, the method disclosed in Japanese Patent Application No. 50-24796 is also effective in the present invention. That is, the present invention is an image forming method characterized in that a silver halide photographic light-sensitive material containing a coupler of the general formula shown below is subjected to imagewise exposure, followed by color development and fixing, without going through a desilvering step.

general formula Here, R1 is a monovalent group having 9 or more carbon atoms. R2 is a divalent group having 2 to 6 carbon atoms X is a hydrogen atom or uncoupling basis are shown respectively.

Each element used in the present invention will be sequentially explained below.

The silver halide emulsion used in the present invention is usually prepared by mixing a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halide salt (for example, potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. It will be done.

As the silver halide, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide and silver iodomonobromide can be used. Desirable silver iodide content is 10 mol%.
The following silver iomonobromide. The shape of these silver halide grains may be cubic, octahedral, or a mixed crystal form thereof. The particle size does not need to be particularly uniform. Furthermore, two or more types of silver halide photographic emulsions formed separately may be mixed.

Furthermore, even if the crystal structure of silver halide grains is uniform throughout the interior, there are also those with a layered structure with different interior and exterior structures, as well as British Patent No. 635,841 and U.S. Patent No. 3,622,3.
It may be of a so-called conversion type as described in No. 18.

Further, either a type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the particle may be used. These photographic emulsions were published in ``The Ory'' by Mess.
OfPhOtOgraphicPrOcess'2 (The Theory of Photographic Processes), M
Published by acMillan; P. Written by Grafkides゛゜ChimiePh0t0g-Ra
phique'' (Simiichi Photographique), Pau
It is also described in books such as IMOntel (1957) and can be prepared by various generally accepted methods such as the ammonia method, neutral method, and acid method. After forming such silver halide grains, they are washed with water to remove by-product water-soluble salts (for example, potassium nitrate when silver bromide is made using silver nitrate and potassium bromide) from the system, and then Heat treatment with chemical sensitizers, such as sodium thiosulfate, N
, N,N' monotrimethylthiourea, monovalent gold thiocyanate complex salt, thiosulfate complex salt, stannous chloride, hexamethylenetetramine, etc., to increase sensitivity without coarsening the particles. These general laws are set out above. Hydrophilic colloids used as vehicles for silver halide include, for example, gelatin, colloidal albumin,
Cellulose derivatives such as casein, carboxymethyl cellulose and hydroxyethyl cellulose, agar, sodium alginate, starch derivatives and other synthetic hydrophilic colloids, such as polyvinyl alcohol, polyN-vinylpyrrolidone, acrylic acid copolymers, polyacrylamide, or these Examples include derivatives and partial hydrolysates of.

If desired, compatible mixtures of two or more of these colloids are used. Among these, gelatin is the most commonly used, but gelatin can be partially or completely replaced with synthetic polymeric substances, and it can also be made into so-called gelatin derivatives, which include amino groups, imino groups, etc. as functional groups contained in the molecule. It may be used by replacing the hydroxyl group, carboxyl group with a reagent that has one group that can react with them, or with a graft polymer in which molecular chains of other polymeric substances are bonded. .

Reagents for making the above derivatives include, for example, isocyanates, acid chlorides, acid anhydrides as shown in U.S. Pat. No. 2,614,928, U.S. Pat.
Acid anhydrides such as those shown in , No. 766,
Bromoacetic acids shown in No. 5514, Special Publication No. 42-26
phenyl glycidyl ethers as shown in US Pat. No. 845, vinyl sulfone compounds as shown in US Pat. No. 3,132,945, N-allyl vinyl sulfonamides as shown in UK Patent No. 861,414, 18
Maleimide compounds as shown in No. 6,846,
Acrylonitrile as shown in U.S. Pat. No. 2,594,293, polyalkylene oxides as shown in U.S. Pat. No. 3,312,553, Japanese Patent Publication No. 42-2684
Epoxy compounds described in No. 5, U.S. Patent No. 2,7
63,639;
Examples include alkanesultones as shown in US Pat. No. 1,033,189.

In addition, branch polymers grafted onto gelatin are used in U.S. patents 2 and 7.
No. 63,625, No. 2,831,767, No. 2,95
No. 6,884 or POlymer Letters,
5,595 (1967), PhOt. Sci, Eng.
9, l48 (1965), J. POlymerSci,
A-1, 9, 3199 (1971), etc., there are many descriptions of acrylic acid, methacrylic acid, their esters, amides, nitriles, and other derivatives, or the polymers of what are generally called vinyl monomers such as styrene. A wide variety of polymers, copolymers, etc. can be used.

However, hydrophilic vinyl polymers having some degree of compatibility with gelatin, such as polymers or copolymers of acrylic acid acrylamide, methacrylamide, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, are particularly desirable. The above-mentioned silver halide emulsion can also be chemically modified by conventional methods.

Chemical sensitizers include, for example, U.S. Pat. No. 2,399,083.
Gold compounds such as chlorauric acid salts and gold trichloride as shown in U.S. Pat.
No. 2,549,086, No. 2,566,245,
Salts of noble metals such as platinum, palladium, iridium, rhodium, and ruthenium as shown in U.S. Pat. No. 2,598,079, U.S. Pat.
No. 0,689, No. 3,189,458, No. 3,50
Sulfur compounds that react with silver salts to form silver sulfide, such as those described in U.S. Pat. No. 2,487,
No. 850, No. 2,518,698, No. 2,521,9
No. 25, No. 2,521,926, No. 2,694,63
No. 7, No. 2,983,610, No. 3,201,254
Examples include stannous salts, amines, and other reducing substances as described in this issue. Stabilizers, antifoggants, surfactants, hardeners, and development accelerators can be added to the above photographic emulsions.

Various compounds are added to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage, or processing of photosensitive materials. Those compounds are 4-hydroxy-6methyl-1,3,3
a,7-tetrazaindene, 3-methyl-benzothiazole, 1-phenyl-5-mercaptotetrazole, dihydroxy benzene, dihydroxy naphthol, and many other heterocyclic compounds, mercury-containing compounds, mercapto compounds, metal salts, phenols, etc. A large number of compounds have been known for a long time. An example of a compound that can be used is K.
Written by Mees “TheOryOfthePhOtO
In addition to citing the original document in graphic PrOcess (3rd edition, 1966), it is also described in the following patents.

U.S. Patent No. 1,758,576, U.S. Patent No. 2,110,178
No. 2,131,038, No. 2,173,628, No. 2,697,040, No. 2,304,962,
No. 2,324,123, No. 2,394,198, No. 2
, 444,605-8, 2,566,245, 2,694,716, 2,697,099, 2
, No. 708,162, No. 2,728,663-5, No. 2,476,536, No. 2,824,001, No. 2
, No. 843,491, No. 2,886,437, No. 3,
No. 052,544, No. 3,137,577, No. 3,2
No. 20,839, No. 3,226,231, No. 3,23
No. 6,652, No. 3,251,691, No. 3,252
, No. 799, No. 3,281,135, No. 3,326,
No. 681, No. 3,420.668, No. 3,622,3
No. 39, British Patent No. 893,428, British Patent No. 403,789
No. 1,173,609, No. 1,200,188. Surfactants may be added alone or in combination.

They are coating aids, emulsification dispersion, sensitization, improvement of photographic properties,
Applied for anti-static, anti-adhesion, etc. These surfactants include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkylamines, quaternary ammonium salts, pyridine and other heterocycles, phosphonium or Cationic surfactants such as sulfoniums, carboxylic acids, sulfonic acids, phosphoric acids, sulfuric acid ester groups, anionic surfactants containing acidic groups such as phosphoric ester groups, amino acids, aminosulfonic acids, sulfuric acid or phosphoric acid esters of amino alcohols It is divided into amphoteric active agents such as

Some examples of surfactant compounds that can be used include U.S. Pat. No. 2,271,623, U.S. Pat.
, No. 068, 101, No. 3,158,484, No. 3,
No. 201,253, No. 3,210,191, No. 3,2
No. 94,540, No. 3,415,649, No. 3,44
No. 1,413, No. 3,442,654, No. 3,475
, No. 174, No. 3,545,974, West German Patent Application (0LS) No. 1,942,665, British Patent No. 1,07
No. 7,317, No. 1,198,450, Ryohei Oda et al. [Synthesis of surfactants and their applications] (Maki Shoten 19)
1964 edition) and A. W. Perry, "Surf S Active Agents" (Interscience Publication, Inc. 1958 edition), J.
P. It is described in books such as ``Encyclopedia of Surf S Active Agents, Volume 2'' (Chemical Publishing Company, 1964 edition) by Sisli.

Pyrazolidone compounds, quaternary ammonium salts, and polyethylene glycols are used as development accelerators, and quaternary ammonium salts and polyethylene glycols are particularly effective when processing with a fixer having a pH of 6 or higher.

Hardening of the emulsion can be carried out according to conventional methods.

Examples of curing agents include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, and bis(2-
chloroethyl urea), 2-hydroxy-4,6-dichloro-1,3,5 triazine, and other U.S. patents 3,28
No. 8,775, No. 2,732,303, British Patent No. 974
, 723 and 1,167,207, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahythro-1,3,5-triazine, In addition, 3 US patents,
635,718, 3,232,763, compounds with reactive olefins such as those shown in British Patent No. 994,869, N-hydroxymethylphthalimide, and other U.S. Patent No. 2,732,316 No. 2,
N-methylol compounds as shown in US Pat. No. 586,168, isocyanates as shown in US Pat. No. 3,103,437, US Pat. No. 3,017,
Aziridine compounds such as those shown in US Pat. No. 280, US Pat. No. 2,983,611, etc., US Pat.
No. 2,725,295, etc.; carbodiimide compounds as shown in U.S. Pat. No. 3,100,704; U.S. Pat.
, 091,537, etc., U.S. Pat. Nos. 3,321,313 and 3,5
43,292, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and ditalolodioxane, or chromium alum as an inorganic hardening agent. Examples include zirconium sulfate.

In place of the above compounds, compounds in the form of precursors, such as alkali metal bisulfite aldehyde adducts, methylol derivatives of hydantoin, primary aliphatic ditroalcohols, etc. may be used.

The above-mentioned hardeners are also used for fixing at high pH.

Especially when processing with an automatic processing machine, scratches caused by rollers and dryness of the finish are closely related to the degree of hardness.
If there is no hardener in the fixer, it is necessary to increase the hardness of the sensitive material. As for the degree of hardening, it is preferable that the film thickness at the end of the water washing step is within 8 times the thickness of the dry film before treatment.

The hardener described above may be added to the silver halide emulsion before being mixed with the coupler solution described below, or may be added to the silver halide emulsion immediately before coating after mixing with the coupler solution.

A solution containing the following coupler is added to the silver halide emulsion thus prepared.

The coupler used in the present invention is represented by the following general formula. Here, R1 represents a monovalent aliphatic or aromatic group having a total carbon number of 9 or more, preferably 13 to 25. Preferably an alkyl group (nonyl group, dodecyl group, 3-octylbutyl group,
octadecyl group, pentacosal group, etc.), alkenyl group (3-nonanyl group, oleyl group, etc.), aryl group, etc. These groups may be substituted with an alkyl group, an alkoxy group, an aryloxy group, or the like. A particularly preferred example is -Cl3H27.

R2 represents a divalent aliphatic group or aromatic group having a total of 2 to 6 carbon atoms.

The aliphatic group is a saturated or unsaturated, linear, branched or cyclic group, preferably C2H4-, -C3H6-, -
C4H8-, -C6Hl2-, C2H2- -C6Hl
There are O--C6H8- and so on. Examples of aromatic groups include phenylene groups.

Among these, -C2}{4- is particularly preferred. X is a hydrogen atom or a substituent capable of coupling with and leaving a developing agent, such as a halogen atom; other examples include JP-A No. 472,328;
7-3480, a development inhibitor releasing group or azomethine, indoaniline, indophenol,
Represents a dye group such as anthraquinone.

Another possible method for improving this drawback is to improve the color forming agent used in the color radiographic light-sensitive material.

Couplers used in color radiographic materials are required to have the following properties.

(1) A large amount of high-density dye can be produced in a short time of development, (2) High color development efficiency per unit silver amount, (3) Small volume, etc. In other words, it is constant. It can be said that a coupler that can form a photographic image of high density in as short a time as possible using a fixed amount of silver and a fixed amount of color forming agent is preferable.

The coupler used in the present invention provides a high density color radiographic image together with a silver image through rapid color development, fixing, washing and drying steps.

Moreover, when the above couplers are used, there is an advantage that the color development speed is significantly high. Therefore, the method of the present invention is particularly suitable for rapid color development. Moreover, a photographic image with even higher density can be obtained by carrying out an acid bath treatment for 5 seconds to 10 minutes between rapid color development and fixing. The acid bath is defined as a mineral acid or an organic acid as long as the pH is substantially 6 or less. There are the following methods for dispersing the couplers described below. The above coupler is dissolved in a solution of an alkali metal hydroxide in water or a mixture of water and alcohol, such as sodium hydroxide, alcoholic potassium hydroxide, etc., and this solution is directly mixed into a photographic emulsion, or a monovalent hydrophilic colloid is used. There is a method of mixing the colloid into the composition and adding the colloid solution to the photographic emulsion.

At that time, the amount of neutralizing agent necessary to neutralize the alkaline solution containing the above coupler is added in advance to the photographic emulsion or hydrophilic colloid composition, or the neutralizing agent is added after mixing the alkaline solution. It is commonly done. The neutralizing agent may be substantially any of the above-mentioned neutralizable acids, such as general mineral acids and organic acids. Although it is most advantageous to use gelatin as the hydrophilic colloid used to disperse the coupler, the aforementioned hydrophilic colloids as vehicles for silver halide can also be used, and water-soluble colloids with carboxylic acid groups can be used. materials or mixtures thereof can also be used. The photographic emulsion is applied to a planar material that does not undergo significant dimensional changes during processing, such as a hard or flexible support such as glass, metal, or ceramic, depending on the purpose.

Typical flexible supports include ordinary photographic supports. Materials used include cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, cellulose acetate propionate film, polystyrene film, polyethylene terephthalate film, polycarbonate film, and other laminates thereof, thin glass film, There are paper etc.

Paper made of baryta or a-olefin polymer coated or laminated with an a-olefin polymer having 2 to 10 carbon atoms, such as polyethylene, polypropylene, or ethylene-butene copolymer, with a roughened surface as shown in Japanese Patent Publication No. 19068/1983. Supports such as plastic films, which have improved adhesion to other polymeric substances and printability by being modified, also give good results. These supports are selected to be transparent or opaque depending on the purpose of the photosensitive material.

In addition, when it is transparent, it is not only colorless and transparent, but also dyes and
It is also possible to add pigments to make it transparent. This has been done in the past with X-Ray films, and also with J. SMPTE6! ．． 296 (1958), etc. For example, it can be colored yellow or blue to improve image quality. For example, in the case of polyester, which is the most common, blue coloring agents include anthraquinone dyes, indanthrone dyes, indigoid dyes, phthalocyanine dyes, and azo dyes, particularly anthraquinone dyes.

For example, anthraquinone dyes include 1,4-dimedicinoanthraquinone 1,4-bis(2',6-diethylanilinolianthraquinone 1,4-bis(2',4',6'-triethylanilino) ) Anthraquinone 1-(2',6'-dimethylanilino)-4,5,8-trihydroxyanthraquinone 1-(2',4',6'-trimethylanilino)-4,
5,8-trihydroxyanthraquinone 1-(2',6
'-diethylanilino)-4,5,8-trihydroxyanthraquinone 1-(2'-methyl-6'monoethylanilino)-4,5,8-trihydroxyanthraquinone 1
-amino-4benzoylaminoanthraquinone 1,4,
5,8-tetra-(0-carboxyanilino)anthraquinone 1-methylamino-4-(ocarboxyanilino)anthraquinone 1,5-bis(0-carboxyphenylthio)anthraquinone 1,4-di 1-p-Butylanilino-5',8-dihydroxyanthraquinone 1,4,5
, 8-tetrahydroxyanthraquinone, etc.

Regarding these, U.S. Patent Nos. 2,571,319 and 3
, No. 372,138, No. 3,488,195, No. 3,
No. 359,230, No. 3,413,257, No. 3,5
No. 30,132, No. 3,487,041, British Patent 1
, No. 196, 707, etc.

In addition, other indanthrone dyes include C (Color Index) 68420, and indigoid dyes include C.
I7335, CI7336O Phthalocyanine dyes include CI7435O, azo dyes include Clll2l5,
There are CI26O8O, CI26lO5, etc.

Opaque supports include those that are inherently opaque such as paper, transparent films with pigments such as dyes and titanium oxide added, or plastics that have been surface-treated by the method described in Japanese Patent Publication No. 19068/1983. It also includes films, as well as paper and plastic films that have been made completely light-shielding by adding carbon black, dyes, etc.

When the adhesive strength between the support and the photographic emulsion layer is insufficient, a layer having adhesive properties to both is provided as an undercoat layer. Further, in order to further improve the adhesion, the surface of the support may be subjected to preliminary treatment such as corona discharge, ultraviolet irradiation, flame treatment, etc. Each layer of the photographic material may be applied by a variety of coating methods including dip coating, air knife coating, curtain coating, or extrusion coating using a hopper as described in U.S. Pat. No. 2,681,294. can.

U.S. Pat. No. 2,761,791, U.S. Pat. No. 3, U.S. Pat.
No. 508,947 and No. 2,941,898, No. 3,
It is also possible to apply two or more layers simultaneously by methods such as those described in US Pat. No. 526,528. For medical purposes, intensifying fluorescent screens used with radiographic materials mostly contain calcium tungstate, lead/barium sulfate or calcium tungstate/barium sulfate as the phosphor.

Furthermore, intensifying screens containing phosphors having more than half of their spectral emission above 410 nm and having a predominant fluorescence emission maximum in the green range of the spectrum are also advantageously used. The green light-emitting intensifying screen is made of a rare earth element having an atomic number of 39 or 57 to 71, as described in JP-A-48-55730, JP-A-49-52,990, and JP-A-49-63,424. , yttrium, gadolinium, lanthanum, cerium, and other fluorescent substances are preferred. 480-60
In combination with an emulsion for radiographic light-sensitive materials or a green light-emitting intensifying screen, which is characterized by being spectrally sensitized to a wavelength range between 0 nm and 0 nm, radiographers can receive a substantially lower X-ray dose. It can be made possible to use it.

In a radiographic combination of an X-ray, intensifying screen and a radiographic light-sensitive material, the screen may be provided separately from the radiation-sensitive silver halide material, or the screen and silver halide emulsion layer may be on the same support. It is also possible to provide one. The silver halide emulsion can be provided on only one side of the support or on both sides. The screen and the silver halide emulsion can be placed on the same support, but in such a case an intermediate layer or release layer can also be placed between the silver halide emulsion and the screen or on top of the emulsion.

When a green light-emitting intensifying screen is used, the silver halide emulsion for radiographic light-sensitive materials has a wavelength of 480 nm to 600 nm.
It is spectrally sensitized to the nm wavelength range. The spectral sensitization maximum is preferably between 520 and 560 nm. The emulsion can be spectral sensitized or superchromically sensitized by using cyanine dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or in combination with styryl dyes and the like.

These color sensitization techniques have been known for a long time. Such dyes are used in amounts ranging from 10 to 3,000 mg, preferably from 20 to 1,000 mg per mole of silver halide. Appropriate spectral sensitizing dyes for silver halide to be used in combination with a screen that emits light in the wavelength range of 480 to 570 nm are disclosed in Japanese Patent Publication No. 4414030, Japanese Patent Application Publication No. 47-33626, and Japanese Patent Application Publication No. 48-59828. It is described in.

If the emulsion is processed under normal darkroom red safety light conditions, the spectral sensitization of the silver halide emulsion should be such that the sensitivity to darkroom illumination is kept as low as possible.

It is also preferable to add a selectively acting sensitivity dye to the emulsion in order to reduce the sensitivity to dark room illumination, if necessary. The color developer used in the present invention develops the exposed silver halide and produces a silver image pattern in the exposed area through a coupling reaction between the oxidation product of the developing agent and the coupler, which forms an image in the exposed area. An alkaline aqueous solution containing a color developing agent that produces a dye image according to the following.

This developer generally contains components such as a developing agent, a preservative, an antifoggant, an alkaline buffer, a metal ion suppressant, an accelerator, and an auxiliary agent.

As color developing agents, known aromatic primary amines,
For example, aminophenols, phenylenediamines,
and so on. As aminophenols, p-aminophenol, 2,6cyclo-4-aminophenol,
2-Bromo-4-aminophenol, 2-phenyl-4-
Aminophenol, 2-methyl-4-aminophenol 2
, 6-dimethoxy-4-aminophenol and the like. Examples of phenylene diamines include unsubstituted p-phenylene diamine and o-phenylene diamine, as well as those in which one or two amino groups are substituted, such as alkyl, hydroxyalkyl, carboxyalkyl, and acyloxyalkyl. , alkoxycarbonyl, alkyloxoalkyl, alkanesulfonamidoalkyl, cycloalkyl, halogenoalkyl, etc., and may be substituted with a group having a bond such as an ether bond, an ester bond, or an amide bond. Alternatively, this amino group
It may form part of a 5- to 6-membered saturated or unsaturated ring. Such rings include piperidine, piperazine, pyrrolidine, morpholine, dihydroindole,
Examples include tetrahydroquinoline and tetrahydroisoquinoline. Specifically, N,N-dimethylparaphenylenediamine, N,N-diethylparaphenylenediamine,
4-(N-ethyl-N-β-hydroxyethyl)aminoaniline, 4-(N-ethyl-N-β-hydroxyethino(c)-2-methylaniline, 4-(N-ethyl-N
-β-methylsulfamidoethyl)amino-2-methylaniline, 4-(N,N-diethyl)amino-2-methylaniline, N,N-diethylamino-2-ethoxyaniline, 2,3-dihythro-5-amino -N methylsulfamide ethyl indole and the like. Alkali metal sulfites as preservatives, U.S. Pat. No. 2,286
, 662; as antifoggants, alkali bromide and alkali monoxide; and nitrobenzimidazoles described in U.S. Pat. Nos. 2,496,940 and 2,656,271. First, mercaptobenzimidazole, 5-methylbenztriazole, 1
-Phenyl-5-mercaptotetrazole, etc., as an alkaline buffer for pH adjustment, such as alkali metal or ammonium hydroxides, carbonates, phosphates, borates, etc.
Other additives include EDTA, sodium hexametaphosphate as a metal ion detergent, and L. F
．． A. MasOn゛TheJournaIOfPhOt
Ographic Science Volume Pl36-13
9 (1963), G. F. van Veelen''Th
eJournalOfPhOtOgraphicSci
Auxiliary developing agents such as pyrazolidones, pyrazolines, aminophenols, substituted phenylene diamines, substituted hydroquinones, Weitz radicals, redox indicators, etc. As a development accelerator, for example, U.S. Pat. Nos. 2,648,604 and 3,671,247
Various pyridinium compounds and cationic compounds, potassium nitrate and sodium nitrate, U.S. Patent No. 2,533,990, U.S. Patent No. 2,577,127, etc.
2,950,970, etc., polyethylene glycol condensates and derivatives thereof, British Patent No. 1,
Nonionic compounds such as polythioethers as typified by the compounds described in US Patent No. 020,033 and US Pat. In addition, organic amines such as pyridine and ethanolamine, benzyl alcohol, and hydrazines may be included.

Furthermore, if necessary, color couplers, competitive couplers, thickeners, anti-fading agents, etc. can be added to the P of O developer.
H is usually kept at an alkalinity of 9.0 to 13.0, depending on the dissociation constant of the coupler, the activity of the developing agent, and the like.

Regarding these, please refer to K. Mees″TheOry
OfThePhOtOgraphicPrOcessP
278-311 (Macmillan CompanyN
ewYOrk. 1966) 7.

Additives used in fixing solutions Examples of fixing agents include sodium thiosulfate, ammonium thiosulfate, potassium cyanide,
Among the many examples, such as ammonium sulfate cyanide, thiourea, and sodium sulfite, sodium thiosulfate and ammonium thiosulfate are preferred. It is also possible to use a mixture of both. The amount of the fixing agent added is appropriately selected based on fixing ability, fixing speed, solubility of the fixing agent, and stability of the fixing solution. Stabilizers for the fixer include sodium sulfite and isomeric potassium bisulfite, but sodium sulfite is generally preferred. The greater the amount added, the better the stability, but it is selected appropriately within a practically effective range. Various hardeners are usually added to the fixer.

As a hardening agent, trivalent aluminum ions are added as aluminum chloride, aluminum sulfate, potassium alum, etc., or trivalent chromium ions are added as chromium alum, etc. When these ions are added, it is more effective if the pH of the liquid is lower. When using thiosulfate, it is desirable to use an acidic sulfite in combination to prevent decomposition of the thiosulfate.

In order to prevent the developing solution adhering to the film from being carried into the fixing solution and increasing the pH value, acetic acid or the like may be added. Further, aluminum ions cause aluminum hydroxide to precipitate when the pH value becomes higher than 4.2. For this reason, it is convenient to add boric acid and use it at a pH of 6.5 or less. However, in the case of high pH (pH 6 or higher) fixing, which is more effective in increasing image density in the present invention, there is an advantage that organic hardeners such as aldehyde-based and triazine-based hardeners can be sufficiently effective. In addition, in the case of high pH fixing,
Various organic acids such as tartaric acid, citric acid, lactic acid, glacial acetic acid, and boric acid are used as stabilizers, and among the organic acids, boric acid and glacial acetic acid are particularly preferred. Any variety of salts can be used as the pH buffer, but in general, at low to neutral pH, acetate salts such as sodium acetate and sodium borate, borates, and high P
In the H region, carbonates such as sodium carbonate are used.
In addition, in order to promote the development stopping effect of the fixer having a pH of 6 or higher, various development inhibitors such as mercapto compounds, benzotriazole, 5-nitrobenzimidazole, 5-nitrointazoles, potassium bromide, or oxidation of the developing agent may be added. A substance capturing agent such as H acid, a preservative used in a color developing agent, etc. may be used in combination. Furthermore, it is also possible to add ammonium salts such as ammonium chloride as a fixing promoter. In the method of the present invention, the treatment temperature can be 20 to 60°C (preferably 30 to 4'C). Also, the development processing time is about 10 seconds to 9 seconds.
A time of about 0 seconds, especially about 15 to 60 seconds is convenient.

The effect obtained by the present invention is that the density of the image increases and a good color X-ray image can be obtained. Furthermore, since the effect of increasing density is large, the amount of silver halide used can be reduced. That is, the use of the coupler of the present invention has the advantage that a smaller amount of silver is required to obtain a constant image density than when other couplers are used. For example, the amount of silver per TrI is about 2 to 6.59, particularly about 3 to 69, which is sufficient.

That is, in that case, an image density of about 2.5 to 3.8 can be obtained. This value is sufficiently satisfactory for an image for X-ray. Considering that a typical X-ray film uses about 8 to 99 silver per d, it can be seen that the method of the present invention requires a significantly lower amount of silver. There are various other advantages in the process, such as rapid processing and fast drying speed. Example 1 Coupler 2.7f having the following structure! 4 (:!) to a mixture of 10 ml of sodium hydroxide solution and 43 ml of water.
Dissolved at °C.

(Tamashi R1 is a substituent shown in Table 1.

) On the other hand, 367n of a 2% citric acid solution was added to a 6.8% by weight aqueous gelatin solution 809 containing 0.037 mol of silver halide.
1 and then 2 ml of 5% chromium alum solution. Add the above coupler solution to this colloid solution and P
The temperature was adjusted to 6.5 to prepare a photographic colloid solution.

In addition, 4-hydroxy to 6-methyl-1 is added as a stabilizer.
,3,3a,7-tetrazaindene and as hardener dichlorohydroxytriazine sodium salt 0.14
9 was added and coated onto a 3 m2 polyethylene terephthalate support. In this case, the amount of silver is approximately 1 per TrI
．． It is 4g. After coating a gelatin layer of about 0.0015 mm on this gelatin silver halide emulsion layer and drying it,
A photographic material was obtained. This photographic light-sensitive material was cut into six strips, exposed through an optical wedge under the same conditions, and then treated with the following developer at 35° C. for 60 seconds.

developer Furthermore, use the following fixing solution at 35°C. Washed.

Fixer Water treated for 50 seconds ) A blue image was obtained by the above processing.

The image obtained by this process has a maximum absorption wavelength of about 55
The concentration was measured through a 0 mμ visual filter.
The results are shown in Table 1. Example 2 All processes were carried out in the same manner as in Example 1, except that fixing was carried out at 35° C. for 50 seconds using a fixing solution having the following composition.

The results are also listed in Table 1. As can be seen from the results in Fixer Table 1, the density of the image depends on the substituent R.
1, and when the number of carbon atoms is 9 or more, a particularly large value is given to 4.

Example 3 An example of using a sensitizing dye in combination is shown below.

In Example 1, before adding the stabilizer, the carbocyanine dye, (anhydro-5,6-dichloro-1-ethyl-5'phenyl-3!-(4-sulfobutyl)-3-(
3-Sulfopropyl)-benzimidazoleoxacarbocyanine hydroxide sodium salt) was added in an amount of 0.49 to 1 mol of silver halide, and then a photographic light-sensitive material was prepared in the same manner as in Example 1. Obtained. However, the amount of silver applied was 49 per square meter. A transparent original of a line drawing was superimposed on the photosensitive material thus obtained and exposed to light for about 1/20 second using white light as a light source through a filter having a transmission peak at 530 mμ.

The exposed photographic material thus obtained was developed and fixed in the same manner as in Example 1.

In this case, the density of the exposed area was approximately 3.0.

Example 41 The couplers shown in Table 1 above were coated in the same manner as in Example 1 and rapidly color developed.

Divide this film into two parts and add 15ml of glacial acetic acid to one part.
The remaining one was immersed in an acidic bath at a concentration of 11 with water for 1 minute, and the remaining one was fixed without being immersed in this solution. Example 1 The image density of the two types of films obtained in this way was measured.
Measured in the same manner.

The results are shown below. As can be seen from these results, processing with an acidic solution before fixing gives a higher density image.

Comparative Example A coupler having the following structural formula (hereinafter referred to as B) and a coupler used in Example 3 (hereinafter referred to as A) were used in Example 1.
Two types of photosensitive materials were obtained by coating in the same manner as above.

Then, the following developer and fixer were used at 35℃ and 60℃, respectively.
The image density was measured using a densitometer equipped with a visual filter.

Coupler A used in the present invention provides higher image density than the commonly used coupler B.

Claims (1)

[Scope of Claims] 1. An image forming method characterized in that a silver halide photographic light-sensitive material containing a coupler of the following general formula is subjected to imagewise exposure and then subjected to color development without undergoing a desilvering step. ▲There are mathematical formulas, chemical formulas, tables, etc.▼In the formula, R_1 is a monovalent group having 9 or more carbon atoms, R_2 is a divalent group having 2 to 6 carbon atoms, and X represents a hydrogen atom or a coupling-off group, respectively.