JPH0269740A - Image forming method - Google Patents

Abstract

PURPOSE:To obtain an image which has less unequal densities and degraded densities and has excellent halftone quality in case of executing a rapid processing by processing a specific silver halide photographic sensitive material by using an automatic developing machine of >=1,500nm/min line speed. CONSTITUTION:The silver halide photographic sensitive material having >=4 gamma value regulated by 0.15 to 1.5 density of the characteristic curve ob served when the silver halide photographic sensitive material having at least one layer of photosensitive silver halide emulsion layers on a base is processed for <20 second development processing time is processed by using the automatic developing machine of >=1,500nm/min line speed. Arbitrary silver halides such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide which are used for ordinary silver halide emulsions are usable as the silver halide of the silver halide emulsions used for the photo sensitive material. The photosensitive particles obtd. by any of an acidic method, neutral method and ammonia method are satisfactory. The degradation in the density is lessened and the images having the excellent halftone quality is obtd. in this way even the ultra-rapid processing is executed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for forming an image on a silver halide photographic light-sensitive material, and more particularly to a method for forming an image on a printed light-sensitive material having rapid developability.

[Conventional technology]

In recent years, the consumption of silver halide photographic materials has continued to increase. For this reason, the number of sheets of silver norogenide photographic light-sensitive materials to be developed has increased, and there is a demand for speeding up the development process, that is, increasing the amount of processing within the same amount of time.

The above trend can also be seen in the printing plate making field.

In other words, as the immediacy and number of times information is rapidly increasing, it has become necessary to perform printing plate-making work in a short delivery time and in larger quantities. In order to meet such demands of the printing plate making industry, it is necessary to promote the simplification of the printing process and to process printing plate making films more quickly.

One way to shorten the development processing time is to shorten the length of the processing line. However, when developing with a roller conveyance type automatic processor, if you try to shorten the length of the processing line to shorten the processing time, a) a decrease in density b)
Problems such as a) deterioration in halftone dot quality, C) occurrence of uneven development, and d) occurrence of uneven fixing occur. These problems tend to occur in silver halide photographic materials whose characteristic curve has a gamma of 4 or more, defined as a density of 0.3 to 1.5, when processed for less than 20 seconds. An effective way to solve these problems is to reduce the amount of gelatin in the silver halide photographic light-sensitive material, but reducing the amount of gelatin tends to deteriorate the graininess of the photographic image and drags the low-density areas. will occur. Another method is to improve the agitation in the processing tank, but since the processing tank is made smaller depending on the length of the processing line, improving the agitation will cause waves on the processing liquid surface, which will actually cause unevenness. A problem arises that causes deterioration.

[Purpose of the invention]

In order to solve the above-mentioned problems, the object of the present invention is to develop a silver halide photographic light-sensitive material that exhibits little loss of density and excellent halftone dot quality even when ultra-rapid processing is performed in which the development processing time is less than 20 seconds. The purpose of the present invention is to provide an image forming method. Another object of the present invention is to provide an image forming method in which processing unevenness and the like are less likely to occur.

[Structure of the Invention] The above-mentioned object of the present invention is to process a /10 silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support in a development processing time of less than 20 seconds. A silver halide photographic light-sensitive material with a gamma value of 4 or more, which is defined by a characteristic curve density of 0.15 to 1.5,
This was achieved by an image forming method characterized by processing using an automatic developing machine with WinSpy 11,500 mm/ff1 inch or higher.

As mentioned above, the problem with the conventional method is that when the processing time is less than 20 seconds, the density of the characteristic curve is 0.3 to 1.5.
This is likely to occur in silver halide photographic materials with a gamma value of 4 or more, but as a method of shortening the development time, increasing the processing line speed without shortening the length of the processing line is recommended. It has been found that the object of the present invention can be achieved without causing such problems.

The silver halide emulsion used in the light-sensitive material of the present invention includes conventional silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Any commonly used silver halide grains can be used, and the silver halide grains may be those obtained by any of the acid method, neutral method, and ammonia method.

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and the surface layer of the grain, and the latent image may be The particles may be formed mainly on the surface or may be formed mainly inside the particles.

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having the flo01 plane as a crystal surface.

Also, U.S. Patent Nos. 4.183.756 and 4,225.6
No. 66, JP-A-55-26589, JP-A-55-42
737, etc., and The Journal of Photographic Science (J, Photgr, S
Particles having shapes such as octahedrons, tetradecahedrons, dodecahedrons, etc. can be prepared by the method described in literatures such as Ci), 21.39 (1973), and used.

Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention may have a single shape, or may be a mixture of grains of various shapes.
;It could be something.

Also, any grain size distribution may be used, and emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (referred to as monodisperse emulsions) may be used. They may be used alone or in combination. or,
A polydisperse emulsion and a monodisperse emulsion may be mixed and used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

In the present invention, monodisperse emulsions are preferred. As monodisperse silver halide grains in a monodisperse emulsion, the weight of silver halide contained within a grain size range of ±20% around the average grain size r is 60% or more of the weight of all silver halide grains. A certain amount is preferable, particularly preferably 70% or more, and still more preferably 80% or more.

Here, the average particle size 7 is the frequency ni of particles having particle size ri
Define the grain size ri when the product niX ri3 of and r13 is maximum.

(3 significant digits, round off the smallest digit.) The grain size here refers to the diameter in the case of spherical silver halide grains, and the projected image in the case of grains with shapes other than spherical. This is the diameter when the circumferential area is converted into a circular image.

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on the print.

(The number of grains to be measured shall be 1000 or more indiscriminately.) Particularly preferred highly monodisperse emulsions of the present invention have a degree of monodispersity of 20 or less, more preferably 15 or less. be.

Here, the average particle size and particle size standard deviation shall be determined from ri defined above. Monodisperse emulsion is disclosed in Japanese Patent Application Laid-Open No. 54-4852.
No. 1, No. 58-49938 and No. 60-122935
This information can be obtained by referring to the Publication No.

Although the photosensitive silver halide emulsion can be used as a so-called Pri+mltive emulsion without chemical sensitization, it is usually chemically sensitized.

For chemical sensitization, the Glafkides or Z
The book by Elikman et al. or the book by H. Frleser,
Die
Grundlagen der Photography
ischen Prozesse mit Silbe
rhalogenidenSAkademichche
Verlagsgesellschaft11968)
The method described in can be used.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, and gold or other noble metal compounds can be used.

As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, specific examples of which are described in U.S. Pat. No. 1,574.944.
No. 2,410,689, No. 2,278.947, No. 2,728,668, and No. 3,656.955. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidisulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in U.S. Pat. Nos. 2,487,850 and 2,419. ,97
No. 4, No. 2,518,698, No. 2,983.609
No. 2,983,610, and No. 2,694,637. For noble metal sensitization, in addition to total complex salts, complex salts of metals in group II of the periodic table, such as platinum, iridium, and palladium, can be used.
, No. 399,083, No. 2,448.060, British Patent No. 618.061, etc.

Further, there are no particular restrictions on the conditions such as pHSpAg and temperature during chemical sensitization, but the pH value is preferably 4 to 9, particularly 5 to 8, and the pAg value is 5 to 11. In particular, it is preferable to keep it between 7 and 9. Also, the temperature is 40 to 90°C, especially 4
5-75°C is preferred.

In addition to the aforementioned sulfur sensitization and gold/sulfur sensitization, the photographic emulsion used in the present invention can also be subjected to reduction sensitization using a reducing substance, noble metal sensitization using a noble metal compound, or the like.

As the photosensitive emulsion, the above emulsion may be used alone,
Two or more emulsions may be mixed.

When carrying out the present invention, for example, 4-hydroxy 6-methyl-1,3,
Various stabilizers can also be used, including 3a,7-titrazaindene, 5-mercaptotophenyltetrazole, 2-mercaptobenzothiazole, and the like.

Furthermore, if necessary, a silver halide solvent such as thioether,
Alternatively, a crystal habit control agent such as a mercapto group-containing compound or a sensitizing dye may be used.

The silver halide grains used in the emulsion of the present invention are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. Alternatively, metal ions can be added using complex salts and included inside the particles and/or on the particle surfaces.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

In the silver halide photographic material according to the present invention, a sensitizing dye may be further added and used in combination.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxanol dyes, and the like. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus,
Tetrazole nucleus, pyridine nucleus, etc. Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei, and nuclei in which an aromatic hydrocarbon ring is fused to these nuclei, Sochi, indolenine nucleus, benzindolenine nucleus, indole A benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbital acid group, etc. can be applied.

The sensitizing dye used in the present invention is used at a concentration equivalent to that used for ordinary negative-working silver halide.

In particular, it is advantageous to use the dye at a concentration that does not substantially reduce the inherent sensitivity of the silver halide emulsion.

Approximately 1.0% of sensitizing dye per mole of silver halide. OX 10-
' to about 5 X 10-' moles of sensitizing dye are preferred, especially about 4 X 10-' to 2 X moles of sensitizing dye per mole of silver halide.
Preferably, a concentration of 10-' molar is used.

The sensitizing dyes of the present invention can be used alone or in combination of two or more. More specific examples of the sensitizing dyes advantageously used in the present invention include the following.

That is, examples of sensitizing dyes used in the blue-sensitive silver halide emulsion layer include West German Patent No. 929.080, US Pat. No. 2,231,658, US Pat. No. 2,519,001, No. 2
, No. 912.329, No. 3,656゜956, No. 3,
No. 672,897, No. 3,694.217, No. 4.0
No. 25゜349, No. 4,046,572, British Patent 1
, No. 242.588, Special Publication No. 44-14030, No. 5
No. 2-24844, JP-A-48-73137, JP-A No. 61
-172140 etc. can be mentioned. In addition, as sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat.
, No. 072,908, No. 2,739.149, No. 2,
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 945.763, British Patent No. 505,979, and Japanese Patent Publication No. 4G-42172. Further, as sensitizing dyes used in red-sensitive and infrared-sensitive silver halide emulsions, for example, U.S. Pat.
270.378, 2,442.710, 2,4
No. 54.629, No. 2,776.280, Special Publication No. 1977
-17725, JP-A No. 50-62425, JP-A No. 61-
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in No. 29836 and No. 60-80841.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization. Typical examples are U.S. Patent Nos. 2,688,545, 2,977.229, and 3
, No. 397.060, No. 3,522.052, No. 3,
No. 527,641, No. 3,617.293, No. 3,6
No. 28.964, No. 3,666.480, No. 3,67
No. 2,898, No. 3,679.428, No. 3,703
゜377, 3,769.3 old number, 3,814,6
No. 09, No. 3,837゜862, No. 4,026,70
No. 7, British Patent No. 1,344,281, British Patent No. 1,507.
No. 803, Special Publication No. 43-4936, No. 53-1237
No. 5, JP-A-52-110618, JP-A No. 52-1099
It is described in No. 25, etc.

The silver halide photographic material according to the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation and halation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like. Among them, oxanol dyes; hemioxanol dyes and merocyanine dyes are useful.

In the silver halide photographic material according to the present invention, when dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

Various compounds can be added to the above (1) photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage, or processing of the silver halide photographic light-sensitive material.

That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted), peterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazoles (especially l-7enyl-5-mercaptotetrazole), mercaptopyridines, the above-mentioned heterocycles and mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group,
Thioketo compounds such as oxazolinthione, azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes), benzenethiosulfonic acids, benzenesulfinic acids, etc. are known as stabilizers. Many compounds can be added.

An example of a compound that can be used is K. Mees, The Theory of the Photographic Process.
Theory of the Photography
ic Process, 3rd edition, 1966), citing the original literature.

For more detailed examples and other methods of use, see, for example, U.S. Pat.
No. 82.947, No. 4,021,248 or Tokuko Sho 5
The description in No. 2-28660 can be referred to.

Further, the silver halide photographic light-sensitive material of the present invention has U.S. Pat.
12, Japanese Patent Publication No. 45-5331, etc., may be included.

The silver halide photographic material of the present invention may contain the following various additives. As thickeners or plasticizers, for example, U.S. Pat.
No. 15, Belgian Patent No. 762.833, US Patent No. 3
, No. 767.410 and Belgian Patent No. 588.143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardeners include aldehyde-based, epoxy-based, Examples of various hardeners and ultraviolet absorbers such as ethyleneimine, active halogen, vinyl sulfone, incyanate, sulfonic acid ester, carbodiimide, mucochloric acid, and acyloyl-based hardeners include those described in US Pat. No. 3,253. 92
No. 1, British Patent No. 1,309,349, etc., particularly 2-(2'-hydroxy-5
-tertiary butylphenyl)benzotriazole, 2-(2
'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2.hydroxy-3
'-tertiary butyl-5'-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',
Examples include 5'-di-tertiary butylphenyl)-5-chlorobenzotriazole. Furthermore, coating aids,
British Patent No. 548.53 describes emulsifiers, permeability improvers for processing solutions, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials.
No. 2, No. 1,216,389, U.S. Patent No. 2,026.
No. 202, No. 3,514,293, Special Publication No. 1977-26
No. 580, No. 43-17922, No. 43-17926
No. 43-3166, No. 48-20785, French Painting Patent No. 202.588, Belgian Patent No. 773.459
Anionic, cationic, nonionic or amphoteric compounds described in JP-A-48-101118 and the like can be used, and among these, anionic surfactants having a sulfone group, e.g. Preferred are succinic acid ester sulfonates, alkylbenzene sulfonates, and the like. In addition, as an antistatic agent, Japanese Patent Publication No. 46-2415
No. 9, JP-A-48-89979, U.S. Patent No. 2,882
．． No. 157, No. 2,972.535, JP-A No. 1972-2
No. 0785, No. 48-43130, No. 48-9039
No. 1, Special Publication No. 46-24159, No. 46-39312
There are compounds described in the following publications: No. 48-43809 and JP-A No. 47-33627.

In the manufacturing method of the present invention, the pH of the coating liquid is 5.3 to 7.
．． It is preferable that it is in the range of 5. For multi-layer coating,
It is preferable that the pH of the coating liquid obtained by mixing the coating liquids for each layer in the ratio of coating amounts is within the above range of 5.3 to 7.5. If the pI is less than 5.3, the progress of dura mater will be slow, which is undesirable, and if the pH is more than 7.5, it will be undesirable because it will adversely affect photographic performance.

In the light-sensitive material of the present invention, the constituent layers include matting agents, such as silica described in Swiss Patent No. 330,158, glass powder described in French Painting Patent No. 1,296,995, and British Patent No. 1.
, 173,181; inorganic particles such as alkaline earth metals or carbonates of cadmium, zinc, etc.; starch as described in U.S. Pat. No. 2,322,037; Belgian Patent No. 62;
Starch derivatives described in No. 5.451 or British Patent No. 981,198, polyvinyl alcohol described in Japanese Patent Publication No. 44-3643, polystyrene or polymethyl methacrylate described in Swiss Patent No. 330.158, and US Pat. No. 330.158. , 079.257, and polycarbonate described in U.S. Pat. No. 3,022.169.

In the photosensitive material of the present invention, the constituent layers may contain slipping agents, such as those described in U.S. Pat.
higher alcohol esters of higher aliphatics as described in U.S. Pat. No. 3,295.979, casein as described in U.S. Pat. , U.S. Patent No. 3,042
．． No. 522 and No. 3,489.567, etc. may also be included.

Dispersions of liquid paraffin and the like can also be used for this purpose.

The photosensitive material of the present invention may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Vol. 176, 1 tem.
17643 (December 1978) and Volume 187 It
em18716 (November 1979), and the relevant parts are summarized in the table below.

In carrying out the silver halide photographic material of the present invention, for example, the emulsion layer and other layers can be constructed by coating on one or both sides of a flexible support commonly used in photographic materials. Useful as visibility supports are films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate mtmm, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or α-olefin polymers ( Examples include paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer, or the like. 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 emulsion layers and the like. The undercoating treatment is performed in accordance with Japanese Patent Application Publication Nos. 52-104913, 59-18949, 59-19940, and 59-
The treatments described in the 1994 publications are preferred.

The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

In the silver halide photographic light-sensitive material according to the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used.

The development time in the present invention is within 20 seconds, preferably 15 seconds.
Describe the development, fixing, washing, and drying processes that take less than seconds.

The developing agent used in the black and white developer used in the present invention has a dihydroxybenzene chain and 1-
Most preferred is a combination of phenyl-3-pyrazolidones. Of course, a p-aminophenol type developing agent may also be included.

The dihydroxybenzene developing agent used in the present invention includes hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-
Examples include dichlorohydroquinone, 2,3-diglomehydroquinone, and 2,5-dimethylhydroquinone, with hydroquinone being particularly preferred.

As the developing agent for l-phenyl-3-pyrazolidone or its derivative used in the present invention, l-7enyl-4.4dimethyl-3-pyrazolidone, ■-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, l-7 Examples include enyl-4,4-dihydroxymethyl-3-pyrazolidone.

Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl)cridine. ,
There are 2-methyl-p-aminophenol, p-benzylaminophenol, etc., among which N-methyl-p-aminophenol is preferred.

The developing agent is usually 0. Preferably, it is used in an amount of O1 mol#-1.2 mol/Q.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. The amount of sulfite is preferably 0.2 mol/a or more, particularly 0.4 mol/Q or more. Further, the upper limit is preferably 2.5 mol/Q.

The pH of the developer used in the present invention is preferably in the range of 9 to 13. More preferably, the pH range is from 1O to 12.

Alkaline agents used to set pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
Contains H regulator.

JP-A-61-28708 (borates), JP-A-60-
Buffers such as No. 93439 (eg, sucrose, acetoxime, 5-sulfosalcylic acid), phosphates, carbonates, etc. may also be used.

Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide:
Organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, nitinol, methanol, at-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, etc. It may contain antifoggants such as mercapto compounds, indazole compounds such as 5-nitroindazole, and benztriazole compounds such as 5-methylbenztriazole, and may further contain color toning agents, surfactants, and antifoaming agents as necessary. , hard water softener, JP-A-1987-
The amine compound described in No. 106244 may also be included.

In the present invention, silver stain preventive agents such as the compounds described in JP-A-56-24347 can be used in the developer.

In the developer of the present invention, amino compounds such as alkanolamines described in JP-A-56-106244 can be used.

In addition, "Photographic Processing Chemistry" by F. A. Messon, published by Focal Press (1
966), pages 226-229, U.S. Patent No. 2゜193
．． No. 015, No. 2,592.364, Japanese Unexamined Patent Publication No. 1973-6
Those described in No. 4933 may also be used.

In the present invention, "development time" and "fixing time" respectively mean
The time from when the photosensitive material to be processed is immersed in the developing tank solution of the automatic processing machine until it is immersed in the next fixing solution, and the time from when it is immersed in the fixing tank solution until it is immersed in the next washing tank solution (stabilizing solution). say the time

Further, "washing time" refers to the time during which the product is immersed in the washing tank liquid.

Furthermore, "drying time" refers to a drying zone where the automatic processing machine is equipped with a drying zone where hot air is blown at a temperature of usually 35°C to 100°C, preferably 40°C to 80°C. refers to time.

The development temperature and time are about 25 DEG C. to 50 DEG C. for 15 seconds or less, but preferably 30 DEG C. to 40 DEG C. for 6 seconds to 15 seconds.

The fixer is an aqueous solution containing thiosulfate and has a pH of 3.8 or higher, preferably 4.2 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, which contain thiosulfate ions and ammonium ions as essential components, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of the fixing agent used can be changed as appropriate, and is generally about 0.1 to about 6 mol/Q.

The fixer may also contain water-soluble aluminum salts that act as hardeners, such as aluminum chloride, ammonium sulfate, potassium alum, and the like.

The fixer can be prepared by using tartaric acid, citric acid, or conductors thereof alone or in combination of two or more thereof.

Those containing 0.005 mol or more of these compounds per fixer N2 are effective, especially 0.01 mono/β to 0.03
Mol/a is particularly useful.

Specific examples include tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, citric acid, sodium citrate, potassium citrate, lithium citrate 1, and ammonium citrate.

The fixing solution optionally contains a preservative (e.g. sulfite, bisulfite), p) I buffer (e.g. acetic acid, nitric acid),
It can contain a pFI adjuster (for example, sulfuric acid), a chelating agent with water softening ability, and a compound described in Japanese Patent Application No. 60-213562.

The fixing temperature and time are preferably 6 seconds to 1 minute at about 0°C to about 50°C, more preferably 6 seconds to 30 seconds at 30°C to 40°C, even more preferably 6 seconds to 30°C to 40°C. seconds ~ 15
Seconds.

Where the fixer concentrate is replenished into the automatic processor in the method of the invention with water to dilute it as the light-sensitive material is processed, it is most preferred that the fixer concentrate is comprised of an I agent. is the same as for the developer.

Fixer agglomeration can stably exist as a l agent at pH 4,
5 or more, more preferably pi (4.65 or more). If the pH is less than 4.5, especially if the fixer is left for a long period of time before it is actually used, thiosulfate will decompose and eventually This is because it becomes sulfurized.

Therefore, when the pH is in the range of 4 to 5 or higher, less sulfur dioxide gas is generated, which improves the working environment. The upper limit of pn is not so strict, but if it is fixed at too high a pH, the pH of the membrane will be high even after subsequent washing with water, and the membrane will swell, increasing the drying load, so the upper limit is around pH 7. Fixing solutions that use aluminum salts to harden films have a pH limit of 5.5 to prevent precipitation of aluminum salts.

In the present invention, either the developing solution or the fixing solution may be a so-called working solution that does not require dilution water as described above (that is, it is replenished as an undiluted solution).

The amount of each concentrate supplied to the processing tank liquid and the mixing ratio with dilution water can be varied depending on the composition of the concentrate, but generally the ratio of concentrate to dilution water is 1:0 to 8. The total amount of each of the developer and fixer is preferably from 50mQ to 1500a+ff with respect to the photosensitive material li.

In the present invention, the photosensitive material is subjected to water washing or stabilization treatment after being agglomerated and fixed.

Any method known in the art can be applied to the washing or stabilization treatment, and water containing various additives known in the art can also be used as the washing water or stabilizing liquid. By using anti-mold water as washing water or stabilizing liquid, not only is it possible to save water by reducing the amount of replenishment to less than 3A per 1lffi of photosensitive material, but it also eliminates the need for piping for installing an automatic processor. It is possible to reduce the number of stock tanks. That is, the solution dilution water and washing water or stabilizing solution for the developer and fixer can be supplied from a common single layer stock tank.
It is possible to make the automatic developing machine even more compact.

If anti-mildew water is used in combination with the washing water or stabilizing liquid, the formation of limescale etc. can be effectively prevented.
11! Water saving treatment of O to 3Q1, preferably O to IQ1, can be performed per unit.

Here, when the replenishment amount is O, there is no replenishment at all except for appropriately replenishing the amount of washing water in the washing tank that has decreased due to natural evaporation, etc. In other words, the so-called "reservoir water" is essentially not refilled. This refers to the case of performing the geographical method.

As a method of reducing the amount of replenishment, a multistage countercurrent system (for example, two stages, three stages, etc.) has been known for a long time. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material in the fixer will be processed in a progressively cleaner direction, that is, in sequential contact with the processing solution that is not contaminated with the fixer, resulting in even more efficient processing. Washing is done. According to this, unstable thiosulfates and the like are appropriately removed, the possibility of discoloration and fading is further reduced, and an even more significant stabilizing effect can be obtained. The amount of water used for washing is also much smaller compared to conventional methods.

When washing with a small amount of water, patent application 1729/1986
It is more preferable to provide a squeeze roller cleaning tank as described in No. 68.

Further, part or all of the overflow liquid from the washing or stabilizing bath, which is generated by replenishing the washing or stabilizing bath with anti-mold water depending on the treatment, is disclosed in Japanese Patent Application Laid-Open No. 60-23
As described in No. 5133, it can also be used in a processing liquid having a fixing ability, which is a processing step before that.

This is more preferable because the stock water can be saved and the amount of waste liquid can be reduced.

The anti-mildew methods include the ultraviolet irradiation method described in JP-A No. 60-263939, the method using a magnetic field described in JP-A No. 60-263940, and the use of ion exchange resin described in JP-A No. 61-131632. How to make pure water, patent application 1986
-253807, 60-295894, 61-
63030 and 6I-51396 can be used.

Furthermore, L, E, West “Water Qual
ity Cr1teria” Photo Sci &
Eng, Vol. 9 No. 6 (1965), M.
W, Be-ach “Microbiological
Growths in Motion-Pic-tur
eProcessing”SMPTE Journal
l Vol, 85. (1976).

R.O. Deegan, “Photo Proce
ssing Wash Water Biocides”
J, Imaging Tech, Vol 10. No
, 6 (1984) and JP-A No. 57-8542, 57
-58143, 58-105145, 57-1
No. 32146, No. 58-18631, No. 57-975
30, No. 57-157244, etc., antibacterial agents, anti-inflammatory agents, surfactants, etc. can also be used in combination.

Furthermore, for the washing bath, R.T. Kreiman J.Ima
RESEARCH, an inthiazoline compound described in GE, Techlo, (6) 242 (1984)
DISCLOSURE Volume 205, I tea2052
6 (May 1981), isothiazoline compounds described in Volume 228, Item 22845 (
Inthiazoline compounds described in Japanese Patent Application No. 1983-51396 (April issue, 1983), compounds described in Japanese Patent Application No. 61-51396, etc. can also be used in combination as microbiocides.

Furthermore, specific examples of anti-piping agents include phenol, 4-chlorophenol, pentachlorophenol, cresol,
0-phenylphenol, chlorophene, dichloro7ene, formaldehyde, geltaraldehyde, chloracetamide, p-hydroxybenzoic acid ester, 2-
(4-Thiazoline)-benzimidazole, benzisothiazoline-3one, dodecyl-benzyl-dimethylammonium chloride, N-(fluorodichloromethylthio)-7talimide, 2,4.4'-)dichloro-2
Such as fluorohydroxydiphenyl ether.

The water treated with antifungal measures and stored in the water stock tank is diluted with water for diluting the stock solution of the processing solution such as the developer fixer, and the amount thereof added is preferably 0.01 to LOg/Q, more preferably 0.1.
~5g/Q.

Furthermore, in addition to the silver image stabilizer, various surfactants can be added to the washing water for the purpose of preventing uneven water droplets. As the surfactant, any of cationic, anionic, nonionic, and amphoteric types may be used. Specific examples of surfactants include compounds described in "Surfactant Handbook" published by Kogaku Tosho Co., Ltd.

Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, adjusting the membrane pu (e.g. pH 3
~8) various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid) Typical examples include aldehydes such as (used in combination) and formalin. In addition, various additives such as chelating agents, bactericidal agents (thiazole-based, inthiazole-based, halogenated phenols, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, and hardening agents are used. Alternatively, two or more of the same or different target compounds may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve image storage stability.

The water washing or stabilization bath temperature and time using the above method is θ℃
~50°C for 6 seconds to 1 minute is preferred, but 15°C to 40°
C for 6 to 30 seconds, more preferably 15 to 4
6 to 15 seconds at 0°C is preferred.

According to the method of the present invention, the developed, fixed and washed photographic material is dried by squeezing out the washing water, that is, by using a squeeze roller method. Drying is carried out at about 0°C to about 100°C, and the drying time can be changed as appropriate depending on the surrounding conditions, but usually it is about 5 seconds to 1 minute, but preferably at 40°C.
~80°C for about 5 seconds to 30 seconds.

In the present invention, an even more excellent effect is exhibited in that the lower the swelling percentage of the photosensitive material, the shorter the drying time thereof.

According to the method of the present invention, the so-called dry-to-dry processing time from development, fixing, washing, and drying is 1
Within 00 seconds, preferably within 60 seconds, more preferably within 50 seconds
It should be processed within seconds.

Here, ``'dry to dry'' refers to the time from the moment the leading edge of the photosensitive material to be processed enters the film insertion area of the processor to the moment the leading edge emerges from the processor after being processed. .

[Examples] Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not limited thereto.

Example 1 (Preparation of coating solution for emulsion layer) Solution A Sodium chloride gelatin solution B 9.70 Water 3.8a Sodium chloride 80g Gelatin potassium bromide 420g Hexachloroiridium, 0.01% aqueous solution of acid potassium salt 28mQ
0.01% aqueous solution of potassium hexabromorodate salt 5.0mm
solution water
3.8Q nitrate M silver
1, p in the above solution A kept warm at 700938℃
While maintaining H3,5, pAg 8.0, the above solution B and solution C were added functionally at the same time over 60 minutes, and after continued stirring for an additional 10 minutes, the pH was adjusted with an aqueous sodium carbonate solution.
was adjusted to 5.8, and 20% magnesium sulfate aqueous solution 1
．． 5% aqueous solution of 7Q and polynaphthalene sulfonic acid2.
Add 55Q and curate the emulsion at 35°C for 70 minutes.
Decant and wash with water to remove excess salt from the aqueous solution. Next, water of 3,7a is added thereto to disperse it, and 0.912% of a 20% aqueous magnesium sulfate solution is added again to remove the excess salt in the aqueous solution. And 3.
Add 7Q water and 1419 gelatin and heat at 55°C.
Disperse for 0 minutes. This yields particles of 38 mol % silver bromide, 65 mol % silver chloride, and an average of 0.22 μm 1 semidispersity 9. This emulsion is designated as E+nA. Further, EmC was obtained by removing Em B s from EmA with potassium hexabromorodate at 1.0 ma. Add 12 mQ of 1% citric acid aqueous solution (2, 120 mQ of 5% sodium chloride aqueous solution to pH 5.5, p
After adjusting the Ag to 7, 120a+Q was added to an aqueous solution of 0.1% sodium thiosulfate, and 80ml of 0.2% chloroauric acid was added, and the mixture was aged at 60°C to obtain the highest sensitivity.

The above emulsion was divided into 10 equal parts, and 0.5% of l-phenyl-5-mercaptotetrazole was added to each as an antifoggant.
% solution to 25ml12. 4-hydroxy-6 as a stabilizer
-1% of methyl-1,3,3a,7-chitrazaindene
Liquid 180a+ff, 400m of 10% gelatin aqueous solution
(15ml) each of 0.1% methanol solutions of the following sensitizing dyes (a) and (b) were added, and 15ml of each of hydroxin as an antifoggant was added.
50ml of 0% solution + 50ml of 5% solution of potassium bromide
ff and 20% saponin aqueous solution as a spreading agent.
4 of styrene-maleic acid polymer as a 9mff thickener
% aqueous solution, 50mQ1 ethyl acrylate polymer latex, 30g1 hardening agent, formalin and 1-
Hydroxy-3,5-dechlorotriazine sodium salt was added and the emulsion was coated on a subbed polyethylene terephthalate support with 5 g/m of silver and 2 gelatin.
．． Furthermore, as a protective film, 100 mQ of an aqueous solution of bromide and potassium IO% was added to an aqueous solution of 500 g of gelatin, and as a spreading agent, 1-decyl-2-(
400 tons (l) of a 1% aqueous solution of sodium 5-isopentyl)succinate-2-sulfonate was added, and the average particle size was 3.
An emulsion layer and a protective layer were simultaneously coated by adding and dispersing too much amorphous phosphoric acid having a diameter of 5 μm and applying gelatin to a concentration of 1.0 g/m 2 .

The sample thus obtained was subjected to image exposure using a semiconductor laser scanner having a wavelength of 780 nm,
Using a developing solution and a fixing solution with a rough composition, the samples were processed in an ordinary roller-type automatic processor under the conditions shown in Table 1, and the halftone dot quality and density were evaluated for gamma values of 0.15 to 1.5. went. Further, the film was exposed to light at a density of 1.0 to 1.3, processed in the same manner, and evaluated for development unevenness.

Note that the halftone dot quality and development unevenness were evaluated in 10 grades. IO is the best level, 1-4 is unusable, and 5 and above is usable. From Table 1, it can be seen that the samples of the present invention have good halftone dot quality and good development unevenness. When changing the developing time in the above automatic developing machine, the adjustment was made by changing the depth of the tank and the number of rollers.

Developer composition Pure water (ion exchange water) 800mff
Disodium ethylenediaminetetraacetate 2g diethylene glycol 25g potassium sulfite 609 potassium carbonate
15g hydroquinone
20g 5-methylbenzotriazole
300+1191-Phenyl-5-mercaptotetrazole 0mg Potassium bromide 3.59 Potassium hydroxide 10.591-Phenyl-4,4-dimethyl-3-pyrazolidone 300+11
9 Add pure water (ion-exchange liquid water) to 1,000 m (2
Finish it. Fixer formulation (composition A): pH was 1018 Ammonium thiosulfate (72.5% v/v aqueous solution) 2
40m12 Sodium sulfite 2
59 Sodium acetate trihydrate 6.5g
Boric acid 6g Sodium citrate dihydrate 2g Acetic acid (90
%v/v aqueous solution) 12.5mQ(
Composition) Pure water (ion exchange water) 17mQ Sulfuric acid (50% w/v aqueous solution) 4.0
9 Aluminum sulfate 26.5g (
When using a fixer (aqueous solution with an AI202 equivalent content of 8.1% w/v), it was dissolved in 500 ml of water in the order of the above composition A1 and finished to 1Q.

The pH of this fixer was about 4.6.

1zeg)\6 Example 2 In Example 1, the sodium chloride in solutions IA and B was replaced with sodium bromide and sodium iodide, and an appropriate amount of ammonia was added to solution C to adjust the pAg to 8.5. The pH was continuously changed from 10 to 8 while maintaining the average particle size of 0.
EmD of silver iodobromide (silver iodide 0.5 mol %) of 29 μm was obtained. The monodispersity was 12. In addition, EcnE and EmF were obtained in the same manner as in Example 1. Each of these emulsions is gold,
A sample was sensitized with sulfur and prepared in the same manner as in Example 1. However, the dye (C) was added.

(C) The obtained sample was heated with a He-Ne laser (wavelength: 632.8n).
+a) Image exposure was performed using a scanner, and evaluation was performed in the same manner as in Example 1 using the following developer.

The results are shown in Table 2, and it can be seen that the samples of the present invention have good halftone dot quality and good development unevenness. However, because of silver iodobromide, no halftone quality was obtained in Example 1.

Developer recipe Ethylenediaminetetraacetic acid, tetrasodium 1g Sodium sulfite 76g 5-methylbenzotriazole 0.4g Sodium bromide
3g sodium chloride
1.3 g 3-diethylamino-1,2-propanediol 5 g Hydroquinone 34 g 1 mol/a Phosphoric acid solution 400 tn (add amount of water necessary to adjust sodium dihydroxide pH to 11.4 to make 1Q).

Table 2 Procedural Amendment [Effects of the Invention] According to the present invention, it is possible to provide an image forming method for a silver halide photographic light-sensitive material that exhibits less density unevenness and density loss (and has excellent halftone dot quality) when rapidly processed. Ta.

1. Indication of the case Patent Application No. 223172 filed in 1988 2. Name of the invention Image forming method 3. Person making the amendment Relationship to the case Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Contact information 191 Konica Corporation, 1 Sakura-cho, Hino-shi, Tokyo (Tel: 0425-83-1521) Patent Department

Claims (1)

[Claims] When a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support is developed for less than 20 seconds, the density of the characteristic curve obtained is 0.15 to 1. A silver halide photographic material with a gamma value of 4 or more as defined by .5 is processed at a line speed of 1500 m.
An image forming method characterized by processing using an automatic developing machine with a speed of m/min or more.