JPH0470652A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the degradation in image density and the generation of fogging at the time of ultra-rapid processing and to obtain the higher sensitivity by processing, after exposing, the specific photosensitive material within the prescribed time of the total processing up to developing, fixing, washing and/or stabilizing by using an automatic developing machine of a specific line speed. CONSTITUTION:The photosensitive material formed by incorporating a developing agent into at least one of the photograph constituting layers on the side provided with silver halide emulsion layers and allowing silver halide particles to be flocculated and settled by modified gelatin is exposed and is then processed by using the automatic developing machine of >=1500mm/min line speed in such a manner that the total processing up to the developing, fixing, washing and/or stabilizing is within 40 seconds. More preferably, 1-phenyl-3- pyrazolidones are used as the developing agent. The modified gelatin is the gelatin in which at least >=50% of the amino groups of the gelatin molecules are substd. With respective groups of carbamoyl and/or aryl. The degradation in the image density and the generation of the fogging at the time of the ultra- rapid processing are prevented in this way and the higher sensitivity is obtd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for processing silver halide photographic materials,
More specifically, the present invention relates to a highly sensitive processing method for photosensitive materials that does not cause a decrease in image density even when ultra-rapid processing is performed and causes less fog.

[Conventional technology]

In recent years, processing processes for photosensitive materials have been moving toward speeding up and at the same time toward simplifying process control. This is to reduce the labor and expense required for maintenance and management of the processing process, reduce replenishment of processing liquids, extend the period for updating processing liquids, and process photosensitive materials that were conventionally processed under different conditions under the same conditions. This is a movement such as doing something.

With the speeding up and simplification of such processing steps, measures have been taken for photosensitive materials to reduce the dependence of photographic properties on development processing.

For example, addition of hydroquinones as described in JP-A-50-39928, JP-A-57-1973θ
Addition of l-phenyl-3-pyrazolidones as described in No. These are all compounds that are used as developing agents in ordinary photographic developing solutions. That's what it's like.

As already mentioned, recently there has been an increasing movement to process photosensitive materials, which were conventionally processed under different conditions, under the same conditions.For example, computerized phototypesetting film and computerized phototypesetting paper,
There is an example in which plate-making film and computerized phototypesetting paper are processed under the same conditions.

In general, film has a higher amount of coated silver than paper, so it tends to be developed at higher temperatures or for a longer time. Therefore, paper that is developed at the same time has harsher development conditions than the original. As a result, performance such as fogging will be adversely affected.

On the other hand, however, when processing is performed using computer-generated typesetting paper alone, lower temperature and faster processing are desired. Therefore, in the case of computer-generated phototypesetting paper, it is strongly desired to reduce the dependence of photographic characteristics on development processing.

Not limited to the example of computer phototypesetting paper, it is required for all light-sensitive materials to reduce the dependence of photographic properties on development processing.

In order to reduce the dependence on development processing, silver chlorobromide (Ag
(containing 50 mol% or more of 14) may be considered, but this has the drawback that a highly sensitive photosensitive material cannot be obtained. For this reason, a highly sensitive sensitive material can be obtained, and silver bromide-rich chlorobromide @
(Containing 50 mol % or more of AgBr) may be considered, but this has the disadvantage that it is extremely difficult to reduce the dependence on development processing because the developability of the silver halide grains themselves is poor.

On the other hand, the consumption of silver halide photographic materials has been increasing steadily in recent years. For this reason, the number of silver halide photographic materials to be processed 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. This trend can also be seen in the printing and plate making field. In other words, as the immediacy of information and the number of times information is rapidly increasing, it has become necessary to shorten delivery times and handle more processes in printing plate-making operations. 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 photosensitive materials for printing plate making more quickly.

However, when a conventional silver bromide-rich light-sensitive material is used and subjected to ultra-rapid processing, there is a drawback that image density decreases. For this reason, it may be considered to increase the concentration of the developing agent contained in the photosensitive material, but this has the drawback that fog increases and is not practical.

[Problem to be solved by the invention]

SUMMARY OF THE INVENTION An object of the present invention is to provide a highly sensitive method for processing photosensitive materials that does not reduce image density even during ultra-rapid processing and causes less fog.

[Means to solve the problem]

The above object of the present invention is to contain 60 mol% or more of silver bromide on at least one side of the support, and have an average particle size of 0.3 mol.
In the processing method for a silver halide photosensitive material having at least one silver halide emulsion layer containing silver halide grains as described above, in at least one of the photographic constituent layers on the side where the silver halide emulsion layer is provided. contains a developing agent, and is obtained by coagulating and precipitating the silver halide particles with modified gelatin, and after exposing the light-sensitive material, using an automatic developing machine with a line speed of 1500+ am/sin or more, This is achieved by a method for processing a silver halide photographic material, which is characterized in that the entire process from development, fixing, washing and/or stabilizing solution is performed within 40 seconds.

The present invention will be explained in detail below.

The silver halide developing agent used in the present invention includes a silver halide developing agent and a developing agent precursor.

Examples include hydroquinone, 2-methylhydroquinone, 2
, 5-dimethylhydroquinone, trimethylhydroquinone, 2-chloro-hydroquinone, 2phenyl-hydroquinone, 2-tert-butylhydroquinone, catechol, 4-tert-butyl-catechol, substituted or unsubstituted dihydroxybenzene compounds such as nibilocalol, etc. phenol compound = 1-phenyl-3
-virasoliton (phenidone), l-(m-tolyl)
-3-pyrazolidone, 1-phenyl-2-acetyl-3
-Pyrazolidone, I-phenyl-4-methyl-3-pyrazolidone, 1-phenyl4.4-dimethyl-3-vilanlidone, l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-p-chlorophenyl -4
-Methyl-4hydroxy-3-villanridone, 1-(p-
3-pyrazolidone compounds such as tolyl)-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-4=hydroxymethyl-3-pyrazolidone: p-aminophenol, 2-amino-4-methyl-phenol, metol, Amino-phenolic compounds such as 4-hydroxyphenylaminoacetic acid: p-phenylenediamine, 4-
(N,N-diethyl)aminoaniline, 4- (N-ethyl-N-hydroxyethyl)aminoaniline, 4-
(N-ethyl-N-βmethylsulfonaminoethyl)
Amino-2-methyl-aniline, 4-(N-ethyl-
4-aminoaniline compounds such as N-hydroxyethyl)amino-2-methylaniline and their hydrochlorides, sulfates, p-trienesulfonates, and tetraphenylpolone salts, amine hequine reductone compounds, naphthalene diols , aminonaphthalene diol, hydrazine, etc.

Further, as specific examples of the developing agent precursor substance, for example,
4-chloroacetyloxy-hydroquinone, hydroquinone monoacetate, 1,4-dichloroacetyloxy-hydroquinone, catechol monobenzoate, 2
Examples include, but are not limited to, -methylhydroquinone monoacetate, hydroquinone monoacetate, 2-methoxyhydroquinone monobenzoate, and the like.

In the present invention, the above developing agents may be contained alone or in combination.

Among these developing agents, l-phenyl-3-pyrazolidones are preferably used in the present invention.

Next, we will discuss 1-phenyl-3-pyrazolidones preferably used in the present invention. As the 1-phenyl-3-pyrasolitons, those represented by the following formula (A) can be preferably used.

- Killing (A) [wherein R1 is a hydrogen atom or an acetyl group R2, R3,
R4 represents a hydrogen atom or a substituted or S-substituted alkyl group.1 Typical examples of compounds of general formula (A) are listed below.

(A-1) (A-2) (A-3) 1-phenyl-3-pyrazolidone 1-phenyl-4-methyl-3-pyrazolidone 1-phenyl-4,4-dimethyl-3-pyrazolidone (A-4 ) l-phenyl-5-methyl-3-pyrazolidone (A-5) l-phenyl-4-methyl-4'-hydroxymethyl-3-virasoliton (A-6) I-phenyl-4,4-dihydroxymethyl- 3-pyrazolidone (A-7) l-7,nyl-4,4-di-n=propyl 3-pyrazolidone (A-8) l-phenyl-2-acetyl-4,4-
Dimethyl-3-pyrazolidone The amount of 1-phenyl-3-pyrazolidones added is preferably in the range of 0.2 g to 5 g per mole of silver halide.
If it is less than 0.2 g, the effect may be small, and if it exceeds 5 g, the stability over time may be poor.

The 1-phenyl-3-pyrazolidones can be added to any photographic constituent layer on the emulsion layer side, but it is particularly effective to add them to the emulsion layer.

In the present invention, modified gelatin is seratin in which at least 50% or more of the amino groups of the gelatin molecule are acyl, carbamoyl, and substituted with a polygroup of sulfonyl, naorubamoyl alkyl, and/or aryl.

Examples of substituents for the amine group of seratin are given in U.S. Patent 2.
[No. i91,582, No. 2,814,928, No. 2,
It is described in No. 525.753.

Useful substituents include (+) acyl groups such as alkylacyl, arylacyl, acetyl, and substituted or unsubstituted hennyl; (2) carbamoyl groups such as alkylcarbamoyl and arylcarbamoyl; (3) alkylsulfonyl, arylsulfonyl, etc. Sulfonyl group, (4) Thiocarbamoyl group such as alkylthiocarbamoyl, arylthiocarbamoyl, etc. (5) Straight chain mono-branched alkyl group having 1 to 18 carbon atoms (6)
Examples include substituted and unsubstituted aryl groups such as aromatic heterocycles such as fecol, naphthyl, pyridyl, and furyl.

Among them, preferred modified gelatin has an acyl group (-COR
;) or Cal\moylX (-CONRl).

Said R1 is the substitution 1'M! It is a substituted aliphatic group (for example, an alkyl group having 1 to 18 carbon atoms, an allyl group), an aryl group, or an aralkyl group (for example, a phenethyl group), and R2 is a hydrogen atom, an aliphatic group, an aryl group, or an aralkyl group.

Particularly preferred is the case where R+ is an aryl group and R] is a hydrogen atom.

Specific examples of modified seratin that can be used in the present invention are illustrated below using amine substituents, but the present invention is not limited thereto.

Examples of modified gelatin (amino group substituents) -IG-2 - coc, ++, (t) -COC11°COO1+ m6 Seratin derivatives, graft polymers of Shichikitin and Ike's polymer, proteins such as aldimine and casein; 1 type of cellulose such as hydroquine ethyl cellulose, calhoki methyl cellulose, etc.; agar, alkino acid sorta,
Sugars such as starch derivatives, J4 forms; Synthesis of various types such as mono- or copolymerization of polyhydric alcohol, poly-N-onylpyrrolitone, polyacrylic acid, polyacrylamide, polyvinylimigsol, polyhinylpyrasol, etc. Hydrophilic polymeric substances can be used.

G~12 There is no particular limit to the amount of modified gelatin used in the desalting process, but it should be 5 to 70% of the total gelatin amount in the emulsion layer.
, preferably 10 to 50%.

In the method for producing the silver halide photographic emulsion of the present invention, gelatin is usually used as the binder or protective colloid, but other than gelatin may also be used. Examples include silver halides such as silver chlorobromide and silver chloroiodobromide containing 60% mole or more of silver bromide, and silver halide grains can be prepared by any of the acid method, neutral method, and ammonia method. It can be whatever you have obtained.

Silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains with different internal and surface layers, with latent images forming primarily on the surface or primarily within the grain. It may be a particle that is

Any shape of silver halide grains can be used. One preferred example is a cube having the (1001 plane) as a crystal surface.
．． No. 75f1, No. 4,225,1368, Japanese Unexamined Patent Publication No. 1975
Specifications such as No. 5-26588 and Special Publication No. 55-42737, The Journal on Meeting Photographic Science (J, Photogr, 5ci), 21.39
(lf173) etc., particles having shapes such as octahedrons, tetradecahedrons, dodecahedrons, etc. can be made and used.Furthermore, particles having twin planes can also be used. good.

The silver halide grains may be of a single shape or may be a mixture of grains of various shapes.

Also, any grain size distribution may be used, and it may be an emulsion with a wide grain size distribution (polydisperse emulsion), or an emulsion with a narrow grain size distribution (monodisperse emulsion) alone or in combination. Alternatively, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

In the present invention, it is preferable to use a monodispersed emulsion.

The silver halide grains in the monodisperse emulsion have an average grain size r
It is preferable that the weight of silver halide contained within a grain size range of ±20% around , is 60% or more of the total weight of silver halide grains, particularly preferably 70% or more, and still more preferably 80% or more. .

Here, the average particle size r is the frequency n of particles having particle size r1.
It means the particle size when the product n1Xr- of 1 and ri3 becomes maximum.

(3 significant digits, round off the smallest digit) The grain size referred to here means the diameter in the case of spherical silver halide grains, and the projected image in the case of grains with shapes other than cubic or spherical. Represents the diameter when converted to a circular image with the same area.

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 particles to be measured is assumed to be 1000 or more indiscriminately.

) In the present invention, a highly monodisperse emulsion is preferred, with a coefficient of variation (monodispersity) defined by the following formula preferably 20 or less, more preferably 15 or less.

Here, the average particle diameter and particle diameter 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
You can obtain it by referring to the number etc.

The average grain size of the silver halide grains used in the present invention is 0.
3. Shoes must be at least 3 feet long.

Silver halide emulsions can be chemically sensitized by conventional methods. In other words, sulfur sensitization using compounds containing sulfur that can react with silver ions or active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Sensing methods and the like can be used alone or in combination.

After completion of chemical sensitization as described above, a stabilizer such as 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene can be used. Furthermore, if necessary, a silver halide solvent such as thioether may be used. Further, compounds such as mercapto group-containing compounds, nitrogen-containing heterocyclic compounds, or sensitizing dyes may be added during the formation of silver halide grains or after the completion of grain formation.

In the present invention, the silver halide grains used in the emulsion are cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, in the process of grain formation and/or grain growth. Metal ions can be added to the interior of the particles and/or on the surface of the particles using iron salts or complex salts thereof, and metal ions can be added to the interior of the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. Can provide sensitizing nuclei.

Emulsions containing silver halide grains may have unnecessary soluble salts removed after the growth of silver halide grains has finished, or may be left in the emulsion. This can be carried out based on the method described in Disclosure No. 17843.

Silver halide emulsions are used during chemical ripening, at the end of chemical ripening, and/or to prevent fog during storage during the manufacturing process of light-sensitive materials or during photographic processing, or to maintain stable photographic performance. After completion of the process and before coating the silver halide emulsion, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazole necks (particularly nitro- or halogen-substituted), heterocyclic mercapto Compounds such as mercaptothiazoles, mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole),
Mercaptopyridines, the above-mentioned heterocycles having a water-soluble group such as a carboxyl group or a sulfone group, mercapto compounds, thioketo compounds such as oxazolinthione, azaindenes such as tetrazaindenes (specially di-4-Hyl:roxy-substituted) Antifoggants or stabilizers such as 1,3,3a, ?) tetrazaindenes) henzene thiosulfonic acids, henzene sulfinic acids, etc. can be added.

An example of a compound that can be used is KMaes
), The Theory on the Photography / The Theor7 of the P
Photographic Process, 3rd edition, 1
966), citing the original document.

For more detailed examples and other methods of use, see, for example, U.S. Pat.
No. 82,947, No. 4,021,248 or Special Publication No. 5
2-28 [The description in No. i60 can be referred to.

Further, the photographic constituent layer may contain an alkyl acrylate latex as described in U.S. Pat. No. 3,411,911, U.S. Pat.

The photosensitive material may contain the following various additives, namely:
As thickeners or thickeners, e.g. U.S. Pat.
No. 04, Special Publication No. 43-4939, West-German Application Publication 1,
904. [No. 104, JP-A-48-83715, Belgian Patent No. 782,833, U.S. Patent No. 3,787,4
No. 10, Peruvian Patent No. 588,143, such as styrene-maleic acid sorta copolymer, dextran sulfate, etc. Hardeners include aldehyde, epoxy, and ethyleneimine hardeners. , active halogen type, vinyl sulfone type, incyanate type, sulfonic acid ester type, carbodiimide type, mucochloric acid type, acyloyl type, etc.; as ultraviolet absorbers, for example, U.S. Pat. No. 3,253,921; Compounds described in the specifications, specifications, etc. of British Patent No. 1,309,349, especially 2-(2'-hydroxy-5-tertiary butylphenyl)pensotrianol, 2-(2'-hydroxy -3',5'-di-tertiary butylphenyl)benzotriazole, 2-(2-hydroxy-3'-tertiary butyl-5'-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tertiary butylphenyl)-5-chlorobenzotriazole and the like. Furthermore, coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials are disclosed in British Patent No. 548,532 and I?
? 11.21J389 No. 2,026,202, No. 3,514,293, Japanese Patent Publication No. 44-28580, No. 43-17922, No. 43-17921 (No. 43-3188, No. 49- No. 20785, Buddhist temple patent 2
Anionic, cationic, nonionic or amphoteric compounds described in No. 02.51118, Belgian Patent No. 773,459, JP-A-48-101118, etc. can be used, but among these, In particular, ion surfactants having a sulfonic group, such as succinic acid ester sulfonates, alkyl hanzene sulfonates, etc., are preferable.
No., JP-A-48-89!979, U.S. Patent No. 2.8B2
J57, No. 2,972,535, Japanese Patent Application Publication No. 1972-20
No. 785, No. 48-43130, No. 48-90391
There are compounds described in Japanese Patent Publication No. 46-24159, Japanese Patent Publication No. 4G-39312, Japanese Patent Publication No. 48-43809, and Japanese Patent Publication No. 47-33827.

The constituent layers of the photosensitive material include matting agents, such as Swiss Patent No. 33.
Silica is described in No. 0,158, Buddhist Patent No. 1,29 [i,
Crow powder as described in No. 995, British Patent No. 1,173,18
Inorganic particles such as alkaline earth metals or carbonates of cadmium, zinc, etc. as described in No. 1 7 U.S. Patent 2,322.0
Starch as described in No. 37, Starch as described in Pelpaud Patent No. 825,451 or British Patent No. 881,198, Polyvinyl alcohol as described in Japanese Patent Publication No. 1983-3843, Polystyrene as described in Swiss Patent No. 330,158 or polymethyl methacrylate, U.S. Patent 3,0
Polyacrylonitrile as described in US Pat. No. 79,257, U.S. Pat. No. 3,022. Organic particles such as polycarbonate described in I[i9] may be included. 77) The average particle size of the agent is preferably 2 to 8 μm.

A slippery agent 1 is added to the constituent layers of the photosensitive material, such as U.S. Patent 2,5.
Higher aliphatic higher alcohol esters described in No. 88,756 and No. 3,121,080, U.S. Patent No. 3.295
Casein described in No. 979, British Patent No. 1,283,72
Higher aliphatic calcium salts described in No. 2, British Patents 1 and 3
No. 13.384, U.S. Pat. No. 3,042,522, No. 3
, 489.5ft No. 7, etc. may also be included.

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

The photosensitive material may further contain various additives depending on the purpose. These additives, including those mentioned above, are described in more detail in Research Disclosure No. 176@I.
tem 17643 (December 1978) and 18
It is described in Volume 7 Ite+w 1871B (November 1979), and the relevant parts are summarized in the table below.

Additive type RD17843 1, chemical sensitizer 2, sensitivity enhancer 3, spectral sensitizer supersensitizer 4, brightener 5, antifoggant and stabilizer 8, light absorber filter dye, ultraviolet absorber 7. Anti-stinting agents 25 right column 8. Dye image stabilizers 25 pages 9. Hardeners 26 pages 10. Binder 26 pages 11. Plasticizers/lubricants 27 pages 12. Coating aids/26-27 pages Surfactants 13. Sudachi Fuku Inhibitor Page 27 Page 23 Page 23-24 Page 24 Page 24-25 Page 25-26 RD18718 Page 648 Right column Same as above Page 648 Right column ~ Page 648 Right column Page 649 Right column Page 649 Right column ~ Page 64 θ Left Column 650, left-right column, page 851, left column, same as above, page 850, right column, same as above, same as above. In the present invention, the amount of gelatin on the silver halide emulsion layer side of the light-sensitive material is preferably 10 g or less per lrn'.

Useful flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta paper, or α-olefins. Examples include paper coated or laminated with a polymer (eg, polyethylene, polypropylene, ethylene/butene copolymer), etc.

The support may be colored using a dye or pigment,
The surface of these supports, which may be colored blue for the purpose of blocking light, is generally subjected to an undercoat treatment to improve adhesion with silver halide emulsion layers and the like.

The undercoating treatment is as per JP-A-52-104913 and JP-A-59-I.
Preferred are the treatments described in Publications No. n49, No. 59-19940, and No. 59-1994.

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

In light-sensitive materials, the photographic emulsion layer and the colloid layer can be coated on the support or other surface by various coating methods. Application methods include day coating method, roller coating method,
A curtain coating method, an extrusion coating method, etc. can be used.

Next, a method for processing a photosensitive material according to the present invention will be explained.

The present invention is characterized in that it uses an automatic developing machine with a line speed of 1500 mm/1 lin or more and performs rapid processing in which the developing, fixing, washing and/or stabilizing processing time is within 40 seconds.

A combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidone is preferred as a developing agent used in a developer, especially a black and white developer, since it is easy to obtain good performance. It may also contain the main drug.

Examples of the dihydroxybenzene developing agent include hydroquinone, chlorohydroquinone, bromohydroquinone,
Isopropylhydroquinone Methylhydroquinone,
2,3-dichlorohydro1:roA-/n, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
Examples include 2,5-dimethylhydroquinone, and hydroquinone is particularly preferred.

As a developing agent for the above 1-phenyl-3-pyranlidone or its derivative, 1-phenyl-4,4-dimethyl 3-
Viraturiton, 1-7 Eko-4-methyl-4-hydroxymethyl-3-Viraturiton, 1-phenyl 4,4-
Examples include dihydroxymethyl-3-pyranlidone.

As the above p-aminephenol developing agent, 1±N methyl-P~aminephenol, P-aminephenol, N
-(β-hydroxyethyl)-p-7 minophenol,
(4-hydroxyphenyl)glycine 2-methyl-p
-Aminophenol, p-benzylaminophenol and the like, among which N-methyl-p-aminophenol is preferred.

The developing agent is preferably used in an amount of usually 0.01 mol/day to 1.2 mol/day.

Sulfites are used as preservatives in developing solutions, and examples of such sulfites include sodium sulfite, potassium sulfite, lithium sulfite, ammonium nitrogenite, sodium bisulfite, potassium metasulfite, and formaldehyde. Examples include sodium sulfite. The amount of ionic acid salt is preferably 0.2 mol/I1 or more, particularly 0.4 mol/I1 or more, and the upper limit is preferably 25 mol/I1 or more.

The pl+ of the developer is preferably in the range of 9 to 13, more preferably in the range of pH 1o to 12. pH0
Alkaline agents used for first adjustment include sodium hydroxide,
Containing pH adjusters such as potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, tribasic potassium phosphate, etc., No. 81-28708 (borate), JP-A No. 10-93439 (e.g. saccharose, acetoxime, 5-sulfosarcyl lS), phosphates,
Buffers such as carbonates 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, ethanol, methanol: l-phenyl-5-mercaptothiranol, 2-mercap), henzimitazole-5-sulfone alcohol It may contain an antifoggant such as a mercapto compound such as a sodium salt, an intertool compound such as 5-nitrointazole, or a henttriazole compound such as 5-methylbenztrianol, and may further contain a color toning agent if necessary. , surfactant, antifoaming agent, water softener, JP-A-56-
The amine compound described in No. 10 [1244] may also be included.

In the present invention, a silver stain preventive agent, for example, a compound described in JP-A No. 58-24347, a compound described in JP-A No. 56-1
Amine compounds such as flukanolamine described in No. 06244 can be used.

In addition, "Photographic ◆ Brocecin Chemistry" by F. A. Menn, published by Focal Press (19
81 (year), pages 226-229, U.S. Patent No. 2,193.
, No. 015, No. 2,592,384, JP-A-4844
Those described in No. 933 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 viewing machine until it is immersed in the next fixer solution, and the time from when it is immersed in the fixer tank solution until it is immersed in the next washing tank solution (stable tank solution). "Washing time" refers to the time spent immersed in the water washing tank liquid, and "drying time" is usually 35°C - +00°C, preferably 40°C to 80°C.
The processing machine is equipped with a drying scene in which hot air is blown.

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

Next, the fixing solution is an aqueous solution containing thiosulfate and has a pH of 3.8.
The above is preferable, and the pH is more preferably 4.2 to 5.5.

Fixing agents include sodium thiosulfate and ammonium thiosulfate, but they contain periosulfate ions and ammonium ions as essential components, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed.The amount of fixing agent used may be changed as appropriate. and generally from about 0.1 to about 6 moles/mole.

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

In the fixing solution, tartaric acid, citric acid, or their salts can be used alone or in combination of two or more. Those containing 0.005 mol or more of these compounds per fixer 141 are effective, especially 0.005 mol or more per fixer 141. O1 mol/liter ~ 0.03 mol/
dan is valid. Specifically, tartaric acid, potassium tartrate,
These include sodium tartrate, potassium sodium tartrate, citric acid, sodium citrate, potassium citrate, lithium citrate, and ammonium citrate.

The fixing solution optionally contains a preservative (for example, sulfite monobisulfite), a pH buffer (for example, acetic acid, nitric acid),
A p)l regulator (for example, sulfuric acid), a chelating agent having water softening ability, and a compound described in Japanese Patent Application No. 60-213582 may be included.

The fixing temperature and time are preferably 3 seconds to 30 seconds 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 40°C. seconds ~ 1
It is 5 seconds.

When the fixer concentrate is replenished with water to dilute it as the photosensitive material is processed in the automatic processor in the method of the present invention, it is most preferred that the fixer concentrate is comprised of an I agent. The same is true for developer.

■The fixer stock solution can stably exist as an agent at pH 4,
5 or more, more preferably pH 4.85 or more. This is because if p) I is less than 4.5, the thiosulfate will decompose and eventually become sulfurized, especially if the fixer is left for a long period of time before it is actually used. Therefore pH 4
, 5 or more, less sulfur dioxide gas is generated and the working environment is improved. The upper limit of the pH is not so strict, but if the fixing is done at too high a pH, the MpH will be high even after washing with water, the swelling will be large, and the drying load will be large, so the upper limit is around pH 7. Fixing solutions that use aluminum salts to harden the film prevent precipitation of aluminum salts.
The limit is up to H5.5.

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 50+a to 1500mM per m' of photosensitive material.

In the present invention, the photosensitive material is subjected to water washing or stabilization treatment after being developed 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 water treated with anti-corrosion measures for washing water or stabilizing liquid, not only is it possible to save water by reducing the amount of replenishment to 3 or less per rn' of photosensitive material, but there is no need for piping for installing an automatic processing machine. This makes it possible to further reduce the amount of stock.

That is, the preparation water for the developing solution and the fixing solution, the washing water, or the stabilizing solution can be supplied from a common one-layer stock tank, making it possible to further downsize the automatic developing machine.

If anti-mildew water is used in conjunction with the washing water or stabilizing liquid, the formation of limescale etc. can be effectively prevented.
A water saving treatment of 0 to 31, preferably O to li, can be performed per n'.

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. Refers to cases in which a processing method is used.

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 great invention, the photosensitive material in the fixer will be processed and processed in a progressively cleaner direction, that is, in the direction of the processing solution that is not contaminated by the fixer, and will be processed more efficiently. A good washing with water is done. According to this, unstable thio-i acid crucibles and the like are appropriately removed, the possibility of discoloration and fading is further reduced, and a more significant stabilizing effect can be obtained. The amount of washing water is also much smaller compared to conventional methods.

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

Furthermore, part or all of the overflow liquid from the washing or stabilizing bath, which is generated by replenishing the washing or stabilizing bath with water treated with anti-mold means, according to the treatment, is used in Japanese Patent Application Laid-Open No. Sho H-235.
As described in No. 133, 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 it saves the stock water and also reduces waste liquid.

Anti-mildew methods include the ultraviolet irradiation method described in JP-A No. 283939, the method using a magnetic field described in JP-A No. 60-263840, and the use of ion exchange resin described in IWI 61-131832. Method for making pure water, Japanese Patent Application No. 60253807, Japanese Patent Application No. 295884, Japanese Patent Application No. 61
The method using the antibacterial agent described in No. 63030 and No. 6151396 can be used.

Furthermore, L, E, West “Water Quali
t7 Cr1teria Photo Sci & En
g, νo1. SNo. 8 (1!485), M, W, Be
ach”Microbiological Growt
hs in ) lotion-PictureProc
essing” SMPTE Journal Vol.
, 85. (197G).

R.O. Deegan, “Photo Proce
ssing Wash Water Biocidas''
J, Imaging Tech, Vol, lθ, No.
8 (1984) and JP-A No. 57-8542, No. 57-
No. 58143, No. 58-105145, No. 57-13
No. 21413, No. 58-18631, No. 57-875
No. 30, same! Antibacterial agents, anti-inflammatory agents, surfactants, etc. described in No. 1i7-157244 and the like can also be used in combination.

Furthermore, for the washing bath, R.T. Kreiman J.Ima
ge, Techlo, ([1) 242 (1984) inthiazoline compounds, RESEARC)
I DISCLO9URE Volume 205, I te+52
Isothiazoline described in 052B (May 1981 issue).

System Compounds, Vol. 228, Item 22845 (1!
Inthiazoline compounds described in Japanese Patent Application No. 81-51398 (April 183 issue), compounds described in Japanese Patent Application No. 81-51398, etc. can also be used in combination as antibacterial agents.

Furthermore, specific examples of anti-inflammatory agents include phenol, 4-chlorophenol, pentachlorophenol, kleinol, and 0-chlorophenol.
Phenylphenol, chlorophene dichlorophene, formaldehyde, geltaraldehyde, chloracetamide 1. Rest in p-hydroxy! Acid ester, 2-(
4-thiazoline)-benzimidazole, benzisothiazoline-3-ondodecyl-benzyl-dimethylammonium chloride, N-(fluorodichloromethylthio)-phthalimide, 2,4.4'-)dichloro-2
'-Hydroxydiphenyl ether, etc.

The water treated with antifungal measures and stored in the water stock tank is diluted with water for diluting the stock solution of the developer, fixer, etc., and the amount thereof added is preferably 0.01 to 10 g/liter, more preferably 0.1 to 5 g/liter.
g/fL.

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. Any of cationic, anionic, nonionic, and amphoteric surfactants may be used as the surfactant. Specific examples of surfactants are listed in the "Surfactant Handbook" published by Kogaku Tosho ■. There are compounds listed.

Various compounds are added to the above stabilizing bath for the purpose of stabilizing the image.For example, the film pl+ is adjusted (for example, pi
43-8) various buffering agents (e.g. borate, metaborate, boric acid, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid,
Typical examples include aldehydes such as dicarboxylic acid, polycarboxylic acid, etc.) and formalin. In addition, various additives such as chelating agents, bactericidal agents (thiatool type, isothiazole type, halogenated phenol, sulfanilamide, hensitriacil, etc.), surfactants, optical brighteners, hardeners, etc. may be used. , two or more of the same or different desired compounds may be used in combination.

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

Water washing or stabilization bath temperature and time by the above method is 0℃
~50°C for 3 seconds to 30 seconds is preferred, but 15°C to 40°C
more preferably from 6 seconds to 30 seconds, and more preferably from 15°C to 4°C.
Preferably, the temperature is 6 to 15 seconds at 0°C.

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 (1) 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 processing time of the so-called lary-to-drama from development, fixing, washing and drying is within 100 seconds, preferably within 80 seconds, and more preferably within 50 seconds. be.

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 section of the automatic processing machine to the moment the leading edge emerges from the viewing machine after being processed.

〔Example〕

The present invention will be explained below with reference to Examples, but it goes without saying that the present invention is not limited to the Examples.

Example 1 Emulsions A and H below were prepared.

Emulsion prescription solution Egelatin 20g water
400+s
Mixing solution 1 AgN03 60g water
25G
Mixture solution m NaC 18gKB
r 21g water
150+s
u solution■ KBr 22gKI
0.8g water
200+
``Aqueous ammonia (28%) 4 o 1 solution V 1% to 3RhBr b 1 m
M25% KBr liquid 999m
M solution ■ 0 solution form Ih[Ir(rV El 6]
0.75tJ1 water
36.75m solution■ Modified gelatin listed in Table 1 5g water
2+fL (halogenated #1
per mole f-'J K3RhBr6 is s, oX 10
After 2 minutes, solutions n and m were simultaneously injected over 5 minutes, and after aging for 10 minutes, solution
was injected over a period of 1 minute, and 1 minute after the injection of solution (1) was completed, 0.25% of the mixture of solution (2) was added (rr (1'V) per mole of silver halide [4b is 8.0X 10-7% )
was collected and added. After addition of solution (2) and aging for 60 minutes, vinegar # (20%) was added to adjust the pH to 5.7. Then, divide the emulsion into two, add solution ■ to one emulsion, stir for 5 minutes,
Adjust the pH to 4.2 with 56% dilute acid. After 30 minutes of coagulation, the supernatant is drained and excess aqueous salt is removed. Next, 500mM pure water at 40°C was added and dispersed, and 4%
Adjust the pH to 5.3 with NaOH. After stirring for 5 minutes, 5
Coagulate again with 6% acetic acid to pH 4.2 and remove excess salt in the same way. Add 50111 parts of water to it and 1
After adjusting the pH to 5.9 with 4% NaOH and dispersing at 40°C for 30 minutes, 100ml of a 1% aqueous phenol solution was added to obtain emulsion A. During this time, the liquid temperature was maintained at 40°C. Emulsion A contains 90 mol% silver bromide, 9 mol% silver chloride, 1 mol% silver iodide.
The particle size was 0.8 pL, and the standard deviation of the particle size distribution was 0.1 μm.

In the other emulsion, 20% magnesium sulfate aqueous solution 2
5ml and 5% aqueous solution of polynaphthalenesulfonic acid lo
After coagulation, drain the supernatant liquid. Then add 500+sfl of pure water at 40°C and disperse again.
Excess water-soluble salts are similarly removed by adding 705M of 0% magnesium sulfate aqueous solution. Then, 50 m of ice was added and the mixture was dispersed at 55°C for 30 minutes, and then 10 m of a 1% aqueous phenol solution was added to obtain emulsion B. The silver halide composition of emulsion B, the grain size, and the standard deviation of grain size distribution are those of emulsion A.
were the same.

For emulsions A and B thus prepared, the sensitizing dye (
80 mg of 1 mol Ag of a) was added, and further optimal chemical sensitization was performed using ammonium thousocyanate, chloroauric acid, and sodium thiosulfate. Furthermore, 1.7 g 1 mol Ag of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added as a stabilizer, and l-
60-g 1 mol Ag of phenyl-5-mercaptotetrazole, 1 mol Ag of sodium triisopropylnaphthalene sulfonate as a fabric aid, and 60 g 1 mol of polyethyl acrylate latex as a film property improver.
Mol Ag, 20 g of diethylene gelcol, 1 mol Ag, and 0.4 g/m'' of compound (b) as an antifungal agent were added, and further an emulsified dispersion of optical brightener (C) prepared by the method shown below was added. , styrene-maleic anhydride copolymer as a thickener, and tetrakis(vinylsulfonylmethyl)methano and tauri〉' potassium salt as a hardening agent: 0.
A coating solution for an emulsion layer was prepared by adding 30 mg of the 25 mol reaction product per 1 g of gelatin and adjusting the pH to 5.5 with citric acid.

Sensitizing dye (a) Antifungal agent (b) r +10cH, -C-CIl, 01l No.

Fluorescent brightener (C) (Preparation of optical brightener emulsion) 0.8 g of oil-soluble optical brightener (c) was mixed with glecil phenyl phosphate 1.25 2 and 1-butanol 12 mJ1.
A 5% gelatin aqueous solution containing 0.5 g of triisopropylnaphthalene sulfonic acid sodium salt dissolved in 26
An emulsified dispersion was prepared by mixing with 0.0 ml and ultrasonic dispersion.

Next, in a gelatin painter, 70 mg/m' of polymethyl methacrylate with an average particle size of 4 cm was added as a matting agent.
, 2-sulfonate succinic acid bis(2-
ethylhexyl) ester sodium salt 8mg/m'
, the following compound (d) as a fluorine-containing surfactant 14
+sg/rn', 14 mg/rn' of the following compound (e) as an irradiation inhibitor, and 25 mg/rn' of formalin as a hardening agent per 1 g of Seratin.

Further, 1+uB/m'' of 1-phenyl-5-mercaptotetrazole was added as an antifoggant, and the pH was adjusted to 5.5 with citric acid to prepare a coating solution for a protective layer.

The thus prepared emulsion layer coating solution and protective layer coating solution were coated in multiple layers on a 110 μl thick polyethylene neat paper having a wood-philic colloid banking layer and an undercoat layer. Also, immediately before application (within 10 seconds), add the developing agent to Table 1.
According to the contents of the description, 5 g of the following compound (f) 1 mol Ag
A sample was prepared by adding the mixed solution with the emulsion layer coating solution.

(d) CHC00CII t f-cF 2 ) h Il
l.

NaO,S CI C00CI(z +CFz)a
11(e) (f) HOCH2SO3Na coated silver amount is 1
．． 4g/m', gelatin coating amount is 1 for emulsion layer, 5g/m'
rrl', the protective layer was 0.8 g/m''.

The sample thus obtained was passed through an optical wedge and a 680n interference filter for 10-10 minutes with a xenon flash.
After exposure to flash light for 5 seconds, the film was processed using the following developing solution and fixing solution in a conventional roller type automatic processor under the following conditions, and the sensitivity, Dmax, and Jt value of fog were determined.

(Sensitivity) Sensitivity is measured using a reflective densitometer, fog density (unexposed area) +
The value of the reciprocal of the exposure amount when giving a density of 1.6 is the sample No.
, l is expressed as a relative value with the sensitivity of 100.

(Dmax) The reflection density at the highest density part was measured by a conventional method.

Dmax of 1.5 or less is not practical.

(fog) A fog of 0.10 or more is not practical.

(Development processing conditions) (lower) (temperature) Development: 35℃ Fixation 34℃ Washing with water, normal temperature Drying 50℃ developer prescription Pure water (ion exchange water) potassium sulfite Ethylenediami potassium hydroxide 5-methylbenzotriazole diethylene glycol 1-phenyl-4,4-dimethyl-3 Pyrazolidone l-phenyl-5= potassium bromide Hydrokino potassium carbonate Add pure water (ion exchange water) Ru. The pH of the developer was about 10.8.

Approximately 800m 0g Tetraacetic acid disodium salt 2g 10.5g 300g 8 5g 300g Mercaptotetrazole 60mg 3.5g N2
0g5g Finished in one sentence Fixer prescription (composition A) Ammonium thiosulfate (72.5% sodium sulfite sodium acetate trihydrate boric acid W/V aqueous solution) 4Drm1 1? g 6.58 g 13.8g Sodium citrate dihydrate acetic acid (90%w/w aqueous solution) (Composition) Pure water (ion exchange water) 17ml acetic acid (50%w/w aqueous solution) 4.7゜Aluminum sulfate (AIL203 equivalent content: 8.1% w/w) aqueous solution) 2
8.5g When used, the above composition A was dissolved in 5QOm of water in the order of the composition, and the mixture was made into one sentence. The pH of this fixer is approximately 4.
．． It was 3.

Processing speed and processing time Processing speed: Listed in Table 1 Processing time: Within 40 seconds When changing the developing, fixing, and washing times at the same line speed, the depth of the tank and the number of rollers were adjusted.

The obtained evaluation results are shown in Table 1.

As is clear from Table 1, Samples 7 to 11 of the present invention have higher sensitivity, less fogging, and D
You can see that the saxophone is also expensive.

In sample No. 017 in Table 1, similar results were obtained even when the developing agent was changed from A-1 to A-2, 3, 4, 6, and 7. In addition, the developing agent A-1 was added to sample N007 in ul.
and modified gelatin from G-8 to G-4, G-5, G-
6. Similar results were obtained even when G-10 was substituted.

Claims (1)

[Claims] A silver halide photographic material having at least one silver halide emulsion layer containing 60 mol % or more of silver bromide and silver halide grains having an average grain size of 0.3 μm or more on at least one side of a support. In the processing method, at least one of the photographic constituent layers on the side where the silver halide emulsion layer is provided contains a developing agent, and the silver halide grains are coagulated and precipitated with modified gelatin. After exposing the photosensitive material, the line speed was 1500.
Developing, fixing,
1. A method for processing a silver halide photographic material, characterized in that the entire processing up to washing with water and/or a stabilizing solution is performed within 40 seconds.