JPH0395544A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To allow short-time processing and to improve a fixing drop-out property and the preservable property of the photosensitive material after processing by subjecting one layer of silver halide emulsion layers to the color sensitization by sensitizing dyestuffs expressed by specific general formulas and confining the gelatin deposition of photographic constituting layers to <=3.0g/m<2>. CONSTITUTION:This invention relates to the process for processing the silver halide photographic sensitive material having the photographic constituting layers having at least one layer of the silver halide emulsion layers on at least one side of a base. At least one of any layers of this silver halide photographic sensitive material are color-sensitized by at least one kind of the arbitrary sensitizing dyestuffs selected from the group consisting of the sensitizing dyestuffs expressed by formula I and the sensitizing dyestuff expressed by formula II. The gelatin deposition of the photographic constituting layers is <=3.0g/cm<2> and at least one of any layers of the silver halide emulsion layers contain the silver halide particles having >=5 (100)/(111) face ratio and <=0.4mum average grain size.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for processing silver halide photographic materials. In particular, the present invention relates to a method for processing silver halide photographic abrasive materials that enables shortening of processing time.

[Conventional technology]

Conventionally, in the field of silver halide photographic materials, there has been a demand for shortening processing time to enable rapid processing.

For example, in the field of printing plate making, there is a need for increased efficiency and rationalization of operations, and in addition, there is a need to shorten the processing time of photosensitive materials for printing. In order to meet such demands, shortening of processing time is being considered.

However, if the processing length is shortened or the processing line speed (transport speed during processing of the photosensitive material to be processed) is increased in order to shorten the processing time, a number of problems arise. In particular, there are problems such as poor fixing (silver that should be removed remains during the fixing process) and poor storage stability of processed photosensitive abrasives, as well as decreased sensitivity, residual color, and soft tones. There is a problem in that the performance of the photosensitive material deteriorates.

[Purpose of the invention]

The present invention solves the above-mentioned problems of the prior art, enables short-time processing, has good fixing and peeling properties, has good storage stability of photosensitive materials after processing, has high sensitivity, and has no residual color. It is an object of the present invention to provide a method for processing a silver halide photographic material, which can produce images with good quality and high contrast.

[Means for solving the problem] As a result of intensive research, the present inventors have developed a silver halide photograph having a photographic constituent layer having at least one silver halide emulsion layer on at least one side of a support. In the method for processing a light-sensitive material, at least one silver halide emulsion layer of the silver halide photographic light-sensitive material contains a sensitizing dye represented by the general formula (I) described in detail later and a sensitizing dye represented by the general formula (I) described in detail below. (IJ)
sensitized with at least one arbitrary sensitizing dye selected from a certain group of sensitizing dyes represented by, the amount of gelatin applied to the photographic constituent layer is 3.0 g/rrY or less, and at least one of The silver halide emulsion layer of IN is (100
) face/(111) face ratio of 5 or more and contains silver halide grains with an average grain size of 0.4 um or less. After image exposure, the silver halide photographic material has a pH of 4. ．．
Line speed 1000mm using fixer 3 or higher
The present invention has been completed by discovering that the above objects can be achieved by a method for processing silver halide photographic materials, which is characterized by processing in an automatic processor at a processing speed of 1/min or more.

Although the effects of the present invention are not necessarily clear, it was unexpected and surprising for the present inventors that the various objects of the present invention were achieved by the above structure.

The present invention will be explained in more detail below.

The photosensitive material to be processed to which the processing method of the present invention is applied has a photographic constituent layer including at least one silver halide emulsion layer on at least one side of the support. Therefore, a structure may be adopted in which one side of the support has a photographic constituent layer including at least one silver halide emulsion layer, and the opposite side has, for example, a packing layer. It may have photographic constituent layers each having at least one silver halide emulsion layer on both sides.

The photographic constituent layer must have a silver halide emulsion layer, but may also have non-photosensitive layers such as a protective layer, an intermediate layer, and an antihalation layer. The silver halide emulsion layer may have two or more layers.

Next, in the photosensitive material to be processed, at least one of the silver halide emulsion layers has a sensitizing dye represented by the following general formula (I) and a sensitizing dye represented by the following general formula (n). Color sensitization is performed using at least one arbitrary sensitizing dye selected from a certain group of sensitizing dyes (hereinafter also referred to as "sensitizing dye of the present invention").

General formula (1) (U) is as follows.

General formula (1) General formula (It) They can also be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle.

Furthermore, Rll and RI5 and R23 and R25 can be linked to each other to form a 5-membered ring or a 6-membered ring.

χ. and X. each represents an anion. nII + n
l ■. n21 and n2■ do not each represent 0 or 1.

Next, specific examples of the sensitizing dye of the present invention will be shown, but the present invention is not limited thereto. In addition, ■-1 to 13 are compounds represented by the general formula (I), and ■-14 to 21 are compounds represented by the general formula (II)? Middle, Yz.
Yl2 + Yz+ and Y2■ each represent a nonmetallic atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle. Such nitrogen-containing heterocycles include, for example, a henzothiazole ring, a naphthothiazole ring, a henzoselenazole ring, a naph1-selenazole ring, a henzoxazole ring, a naphthoxazole ring, a quinoline ring, a 3,3-dialkylindolenine ring, and a benzylindolenine ring. Examples include a dazole ring and a pyridine ring.

These heterocycles include lower alkyl groups, alkoxy groups, hydroxyl groups, aryl groups, alkoxy carbonyl groups,
It may be substituted with a halogen atom.

Rz, R+■, R2, and R2■ each represent a substituted or unsubstituted alkyl group, aryl group, or aralkyl group.

R+:+. RIa. R+s. R23.
R24. Rzs and R26 are each a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a phenyl group, a benzyl group, I-1 1-2 I-3 ■e 10 ■ 4 ■ 5 ■ 6 CzHs 1 ■ ■ 10 ■ 11 ■ 12 1 3 He C211,, 10 IO IO ■ 7 ■ 8 ■ 9 C2H, 1 2 ■ 13 ■ 14 ■ 15 14 IO C2115 Ie IU ■Il:l ■ 16 ■ 19 ■ 17 Il-1 H-20 ■ 18 ■-21 Calls ■0 E5 1G The sensitizing dye of the present invention may be contained in at least one of the silver halide emulsion layers of the light-sensitive material of the present invention; When two or more layers are present, it may be appropriately contained in at least one necessary layer depending on the desired configuration.

The sensitizing dye of the present invention may use one or more compounds represented by the general formula (1), or may use one or more compounds represented by the general formula (H). Both of the compounds represented by ``2'' may be used alone or in combination. Even when two or more halogenated emulsion layers are used, any combination thereof may be used.

The amount of the sensitizing dye of the present invention to be used may be appropriately determined so as to bring about the desired effect, and is not limited, but in general, it is preferably 1 mg to Ig per mole of silver halide, more preferably 5 mg to Ig. It is preferable to include it in the silver halide photographic emulsion in an amount of 0.5 g.

The sensitizing dye of the present invention can be directly dispersed and contained in the emulsion. Alternatively, the sensitizing dye is first dissolved in a suitable solvent, such as methyl alcohol, ethyl alcohol, methyl cellosolp, acetone, water, pyridine, or a solvent containing these, and added to the emulsion in the form of a solution. You can also do it like this.

The sensitizing dye of the present invention may be used alone as described above,
Although two or more types may be used in combination, it is also possible to use a combination of sensitizing dyes other than those of the present invention. When a sensitizing dye is used in combination, it is preferable that the total amount is the above content.

The sensitizing dye of the present invention is disclosed in U.S. Pat. No. 2,503,77.
No. 6, British Patent No. 742,112, French Patent No. 2,06
It can be easily synthesized with reference to No. 5,662 and Japanese Patent Publication No. 40-2346.

Next, in the photographic material to be processed in the present invention, the amount of geladine applied to the photographic constituent layer on the side having the silver halide emulsion layer is 3.
．． 0 g/m or less, and at least one silver halide emulsion layer has a (100) plane/(111) plane ratio of 5.
2, containing silver halide grains with an average grain size of 0.4 μm or less.

In the present invention, the amount of gelatin attached to the photographic structural layer is the amount for one side of the support. Preferably,
The amount of gelatin applied to the photographic constituent layer on the side having the silver halide emulsion layer is preferably 2.8 g or less, more preferably 2.5 g or less.

Further, the amount of coated silver is preferably 3.0 g/nT or more, more preferably 3.5 g/rd or more.

In the present invention, the silver halide grains having a (100) plane/(111) plane ratio of 5 or more may have 100% (100) planes.

The (100) plane/(111) plane ratio of the particle is
, which can be measured by the dye adsorption method of . In this method, a dye is preferentially adsorbed to either the (100) plane or the (111) plane, and the association state of the dye on the (100) plane and the association state of the dye on the (111) plane are spectrally different. Select and use. The (100) plane/(111) plane ratio can be determined by adding such a dye to an emulsion and examining the spectra in detail with respect to the amount of the dye added.

The detailed ratio of (100) planes on the silver halide grain surface is as follows:
Tadaaki Tani, “Identification of crystal phase of silver halide fine grains in photographic emulsions using dye adsorption phenomenon,” Journal of the Chemical Society of Japan 6, 942
~9/16 (1984).

Silver halide grains having a (100) plane/(111) plane ratio of 5 or more can be prepared by various methods. Generally, the pAg value of the particles is maintained at a constant value of 8.10 or less, and a silver nitrate aqueous solution and an alkali halide aqueous solution are simultaneously added at a rate that is faster than the dissolution rate of the particles and at which re-nucleation is large. It can be preferably prepared by the control double jet method. More preferably, the PAg value is 7.80 or less, and even more preferably the pAg value is 7.60 or less. When the silver halide grain shape is divided into two processes: nuclear shape and its length, there is no restriction on the PAg value at the time of the nucleus shape, and the PAg value at the time of the length is preferably 8.10 or less.
More preferably 7.80 or less, still more preferably 7.60
It is best to set it to the following. Although the soluble root salt and the soluble halogen salt may be reacted by a one-sided mixing method, the simultaneous mixing method is better in order to obtain good monodispersity.

Also, U.S. Patent Nos. 4,183,756 and 4,225
, 666ji, JP-A-55-26589, JP-A-55-
42737, and The Journal of Photographic Science (J.Photogr.
Sci). 21. Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literatures such as No. 39 (1973) and used. Furthermore, particles having double-sided surfaces may be used.

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

The silver halide grains having a (100) face/(111) face ratio of 5 or more used in the present invention have an average grain size of 0.4 μm or less. More preferably, the thickness is 0.1 μm to 0435 μm.

The average grain size of silver halide grains is generally the average grain size of an emulsion containing the grains, and the grain size follows the definition and measurement method described below.

The emulsion containing halogenated root particles may have any grain size distribution, and may be an emulsion with a wide grain size distribution (referred to as a polydisperse emulsion), or an emulsion with a narrow grain size distribution. Emulsion (referred to as monodispersed emulsion).

) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

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

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 r is the frequency ni of particles having particle size rt.
Define the particle size ri when the product n iXr i' of In the case of silver oxide grains, the diameter is required, and in the case of grains with shapes other than spherical, the diameter when the projected image is converted into a circular image of the circumferential 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 pudding 1. (The number of particles to be measured shall be 1000 or more indiscriminately.) A particularly preferred highly monodisperse emulsion of the present invention is preferably:
It is preferable to use a silver halide emulsion having a silver chloride content of 50 mol % or more.

The silver halide grains may have a uniform distribution of silver halide &I1 within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain, and the latent image is Even if the particles are mainly formed on the surface, the monodispersity defined by
It is 0 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-, No. 19938 and No. 60-12293
It can be obtained by referring to Publication No. 5 and the like.

The silver halide contained in the silver halide emulsion layer of the photosensitive material to be processed in the present invention is a conventional halogen such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. Any material used in silver oxide emulsions can be used.

23 24 Photosensitive silver halide emulsions can be used as so-called primitive emulsions without chemical sensitization;
mann et al. or H. Die Gru
ndlagender Photography
en Prozesse mit Silberhal
ogeniden, eight kademicche
Verlagsgesellschaft, 19
68) 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, a noble metal sensitization method using gold or other noble metals, etc. can be used. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof include U.S. Pat. , same 2,
No. 278,947, No. 2,728, 668, No. 3,
No. 656.955.

As the reduction sensitizer, stannous salts, apolins, hydrazine derivatives, formamidisulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in U.S. Pat.
No. 487,850, No. 2,419,974, No. 2,5
No. 18,698, No. 2, 983, 609, No. 2,
No. 983,610 and No. 2,694,637. For noble metal sensitization, in addition to gold complex salts, complex salts of metals in group I of the periodic table, such as platinum, iridium, and palladium, can be used.
．． No. 083, No. 2,448,060, British Patent No. 61
．． No. 8,061.

In addition, there are no particular restrictions on the conditions such as pH, pAg, temperature, etc. during chemical sensitization, but the pI-[value is 4 to 9, especially 5 to
8 is preferable, and the pAg value is 5 to 11, especially 7 to 9.
It is preferable to keep it at Also, the temperature is 40-90℃
, particularly preferably 45 to 75°C. In addition to the sulfur sensitization and gold/sulfur sensitization described above, the silver halide emulsion used can also be subjected to a reduction sensitization method using a reducing substance, a noble metal sensitization method using a noble metal compound, or the like.

In carrying out the present invention, for example, 4-hydroxy-6-methy25 26 Ru 1,3.3a. 7-te1・razaindene, 5-mercap-1・-1-phenyltetrazole, 2-mercapl・
Various stabilizers can also be used, including henzothiazole and the like. Furthermore, if necessary, a halogenated root solvent such as a thioether, or a crystal habit controlling agent such as a compound containing a mercabutic group or a sensitizing dye may be used.

The silver halide grains used in the emulsion are treated with cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, orthodium salt or complex salt, during the process of shaping and/or elongating the grains. Metal ions can be added using iron salts or complex salts and included within the particles and/or on the particle surface.

Unnecessary soluble salts may be removed from the emulsion after the aging of the silver halide grains, or they may be left in the emulsion. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The grain of the silver halide photosensitive material to which the present invention is applied 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, hexaxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like.

Among them, oxanol dyes; hemioxanol dyes and merocyanine dyes are useful.

When dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer of the silver halide photographic light-sensitive material, they may be mordanted with a cationic polymer or the like.

Various compounds can be added to the above 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. Namely, azoles such as penzothiazolium salts, 21-loindazoles, 1-lyazoles, penzotriazoles, penzimidazoles (particularly nitro- or halogen-substituted), heterocyclic mercapto compounds such as mercaptothi27 azole. mercaptohenzudandazoles, mercaptothiazoles, mercaptotetrazoles (especially 1
-phenyl-5-mercaptotetrazole), mercaptoviridines, the above-mentioned heterocycles having water-soluble groups such as carboxyl groups and sulfone groups, mercap} compounds, thioketo compounds such as oxazolinthione, azaindenes such as tetraazaindenes Many compounds known as stabilizers can be added, such as (especially 4-hydroxy-substituted (1,3.3a,7)tetraazaindenes), henzenethiosulfonic acids, henzenesulfinic acids, etc. .

An example of a compound that can be used is K. Mees, The Theory of the Photographic Ink 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.
, 982, 947, 4,021.248, or Japanese Patent Publication No. 5228-28660.

In addition, silver halide photographic light-sensitive materials include U.S. Pat. No. 3,411,911 and U.S. Pat.
The alkyl acrylate latex described in Japanese Patent Publication No. 45-5331 and the like can be included.

The silver halide photographic material may contain various additives as described below. As thickeners or plasticizers, for example, U.S. Pat.
- No. 63715, Belgian Patent No. 762,833
No. 3,767,410, Belgian Patent No. 588,143,
For example, styrene-sodium maleate copolymer, dextran sulfate, etc. As a hardening agent, aldehyde-based,
Various hardeners and ultraviolet absorbers such as epoxy, ethylene, active halogen, vinyl sulfone, isocyanate, sulfonic acid ester, carboxylic acid, mucochloric acid, and acyloyl are used, for example, in the United States. Patent No. 3,253,921, British Patent No. 1,309,3
Compounds described in the specifications of No. 49, especially 2-(2'-hydroxy-53-butylphenyl)henzotriazole, 2(2'-hydroxy-3'.5'-di-tertiary butylphenyl) Penzotriazole, 2-(2-hydroxy-3'-tertiary butyl-5'-butylphenyl)-5-chlorohenzo I riazole, 2(2'-hydroxy-3',5-di-tertiary butylphenyl) Examples include 1-5-chlorhenzo-1-liazole. Furthermore, coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials are described in British Patent No. 548,532, L216.389, U.S. Patent No. 2. No. 026202, No. 3,514,293, Tokukosho, 14-265
No. 80, No. 43-17922, No. 43-17926
No. 43-31.66, No. 48-20785, French Patent No. 202,588, Belgian Patent No. 773
, No. 459, JP-A-48-101118, etc., anionic, cationic, nonionic or amphoteric compounds can be used, among which anionic surfactants having a sulfone group are particularly suitable. For example, succinic acid ester sulfonates, alkyl hanzene sulfonates, and the like are preferred. In addition, as an antistatic agent,
No. 6-24159, Japanese Patent Application Publication No. 1989-89979, U.S. Pat.
No. 5, JP-A-48-20785, JP-A No. 484313
No. 0, No. 48-90391, Special Publication No. 46-241
There are compounds described in the following publications: No. 59, No. 46-39312, No. 48-43809, and JP-A-4733627.

When manufacturing photosensitive materials, the pH of the coating solution 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 blending 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 pH is less than 5.3, the progress of hardening will be slow, which is undesirable, and if the pH is greater than 7.5, the photographic performance may not be adversely affected, which is not preferred.

The photographic constituent layer of the light-sensitive material may contain a capping agent such as silica described in Swiss Patent No. 330,158, glass powder described in Immuno Patent No. L296,995, British Patent No. 31 32 L1.73,181. Inorganic particles such as alkaline earth metals or carbonates of cadmium, zinc, etc.; US Pat. No. 2,322. 037, Hergie Patent No. 625,451 or British Patent No. 981,
Starch derivatives described in No. 198, Special Publication No. 1973-3
Polyvinyl alcohol as described in US Pat. No. 643, polystyrene or polymethyl methacrylate as described in Swiss Patent No. 330,158, US Pat. No. 3,079,2
No. 57, polyacrylonyl I-lyl, U.S. Pat.
．． 022. Organic particles such as the polycarbonate described in No. 169 may be included.

In the photographic structure layer of a light-sensitive material, shearing agents such as higher aliphatic alcohol esters described in U.S. Pat. No. 2,588,756 and U.S. Pat. No. 3,121,060, U.S. Pat. Casein described in British Patent No. L
Higher aliphatic calcium salts as described in No. 263,722, British Patent No. 1.313.38/I, U.S. Patent No. 3,04
2,522 and 3,489,567, etc. may be included. Dispersions of liquid paraffin and the like can also be used for this purpose.

The photosensitive material to which the present invention is applied may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure 176S I
ten 17643 (December 1978) and 187
Vol. Useful flexible supports include semi-synthetic materials such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, and polycarbonate. Alternatively, it may be a film made of a polymer, a baryta layer, or a paper coated with or laminated with an α-olefin polymer (eg, 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 may generally be primed to improve adhesion with the emulsion layer. The undercoating treatment is as per JP-A-52-104913 and JP-A-52-104913.
No. 9-18949, No. 59-19940, No. 5!
The treatments described in each publication No. 1-119.11 are preferred.

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

35 36 In silver halide photographic materials, 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 force coating method, an extrusion coating method, etc. can be used.

Next, the processing when processing the photosensitive material to be processed according to the present invention will be further explained. In the present invention, pH
Line speed LOO using a fixer with a value of 4.3 or higher
Process using an automatic processor with a speed of 0 mm/min or more. The structure of other steps is arbitrary. Preferred processing steps include development, fixing, washing, and drying steps.

The line speed of the photosensitive material to be processed in the processing method of the present invention is preferably 1500 mm/min or more, more preferably 1800 mm/min or more.

Next, although the processing method of the present invention uses an automatic developing machine, there are no limitations on the type or model of the automatic developing machine, and for example, a roller conveyance type automatic developing machine can be used. . Such an automatic processor is described in U.S. Pat.
, No. 025,779 and Specification No. 3,545.971 of the same. This type of automatic developing machine generally has
It consists of four steps of development, fixing, washing, and drying, and it is preferable that the method of the present invention also be carried out in these steps.

In the present invention, the fixing time is preferably 15 seconds or less, more preferably 10 seconds or less.

The pH of the fixer is 4.3 or more, but more preferably 5.5 or less, and even more preferably 4.5 to 5.5.
Good range.

In the present invention, preferably, the fixing time and the developing time are each 20 seconds or less, and more preferably 15 seconds or less. Further, it is preferable that the treatment time (so-called dry-to-dry time) is 60 seconds or less, and the water washing time is preferably 10 seconds or less.

In the present invention, when a black and white developer is used, a combination of dihydroxybenzenes and 1-phenyl-3-virazolitones is most preferable as the developing agent because it is easy to obtain good performance. Of course, in addition to this, a p-a-phenolic developing agent may also be included.

Examples of the dihydroxybenzene developing agent that can be used in the present invention include hydro[coquinone, chlorohydroquinone, promhydroquinone, isobrobylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 23-dibutylhydroquinone, Examples include comhytroquinone, 2,5-dimethylhydroquinone, and hydroquinone is particularly preferred.

The developing agent for 1-phenyl-3-vilazolidone or its derivative that can be used in the present invention includes 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-vilapridone. , 1-phenyl-4,4-dihydroxydimethyl-
Examples include 3-virazolidone.

Examples of the p-aminophenol developing agent that can be used in the present invention include N-methyl-p-aξnophenol,
p-aminophenol, N-(βhydroxyethyl)-
r)-aminophenol, N-(4-hydroxyphenyl)glycine, 2methyl-p-antanophenol, p-
Among them, N-methyl p-aminophenol is preferred.

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

Sulfite preservatives can be used in the present invention, such as sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde bisulfite, etc. including sodium. The amount of sulfite added is
0.2 mol/β or more 39 40 Particularly preferably 0.4 mol/l or more. Also, the upper limit is 2.
Preferably it is up to 5 mol/I2.

The pH of the developer used in the present invention is preferably in the range of 9 to 13. More preferably pH 10 to 12
The range is up to

The alkaline agent used for setting the pH is optional.
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Contains pH regulators such as potassium carbonate, sodium triphosphate, and potassium triphosphate.

JP-A-61-28708 (borates), JP-A-609
No. 3439 (e.g., saccharose, acetoxime,
Buffers such as sulfosalcylic acid), phosphates, and carbonates may also be used.

Additives used in addition to the above-mentioned ingredients include sodium bromide],
organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethyl formamide, methyl cellosolve, hexylene glycol, ethanol, methanol; 1-phenyl-5-mercap l-tetrazole, 2-mercaptohentsuiξdazole-5-
It may contain an antifoggant such as a mercapto compound such as sulfonic acid sodium salt, an indazole compound such as 52I-loindazole, or a benztriazole compound such as 5-methylbenz-1-lyazole. It may also contain color toning agents, surfactants, antifoaming agents, water softeners, amino compounds described in JP-A-56-106244, and the like.

In the present invention, a silver stain preventive agent, such as the compound described in JP-A-56-2434, can be used in the developer.

In the present invention, the developing solution includes JP-A-56-10624
No. 75 compounds such as alkanolamines described in No. 4 can be used.

Besides this, L. F. A. Messon, “Photograph Ink Processing Query”, 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, "developing time" and "fixing time" refer to the time from when the photosensitive material to be processed is immersed in the developing tank liquid of an automatic processor until it is immersed in the next fixing liquid; After immersion in the liquid, the next washing tank liquid (stabilizing liquid)
This refers to the time it takes to soak in the water.

In addition, "washing time" refers to the time spent immersed in the washing tank liquid.

In addition, "drying time" refers to the period in which the automatic processor is equipped with a drying zone in which hot air of 35°C to 100°C, preferably 40°C to 80°C, is blown. It means blasphemy.

Development/M1 degree and time t7rl are 25 degrees (~50 degrees Celsius)
It is preferable that the time is 15 seconds or less, more preferably 3 seconds or less.
The temperature is 0°C to 45°C for 5 seconds to 15 seconds.

The fixer is generally preferably an aqueous solution containing diosulfate, and has a pH of 4.3 or more, more preferably 4.5 to 5.
．． It is 5.

Examples of the fixing solution include sodium thiosulfate and ammonium thiosulfate, but it generally contains thiosulfate ions and ammonium ions, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of fixing agent used can be varied as appropriate, and is generally about 0.1 to 0.6 mol/l.

In the present invention, the fixing solution may contain a water-soluble aluminum compound that acts as a hardening agent, and such compounds include, for example, aluminum chloride, aluminum chloride, and potassium alum.

Further, tartaric acid, citric acid, or their derivatives may be used alone or in combination in the fixing solution. In general, it is effective to use 0.005 mol or more of these compounds per 1 p of fixer, especially 0.0 mol or more.
Particularly effective is 1 mol/E to 0.03 mol/C.

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

The fixing solution may optionally contain preservatives (e.g., sulfites, bisulfites), pIl buffers (e.g., acetic acid, 43 nitric acid), pH adjusters (e.g., sulfuric acid), chelating agents with water softening ability, and patent applications. The compound described in No. 1-213562 (Sho 6) may be included.

The fixing temperature and time are preferably about 20° C. to about 50° C. and 15 seconds or less, more preferably 30° C. to 40° C. and 5 seconds to 15 seconds.

When a fixer concentrate is used and dilution water is used, the fixer concentrate is usually composed of two agents, but it may be composed of one agent.

Usually, it is preferable that the fixer stock solution can exist stably as one agent in P H 4 . 5 or more, more preferably p
H4.65 or higher. If the pH is less than 4.5, the thiosulfate may decompose and eventually become sulfided, especially if the fixer is left for a long period of time before it is actually used. pH 4.3 or higher in the present invention, preferably p
In the range of H4.5 or higher, less sulfur dioxide gas is generated, which improves the working environment. The upper limit of pH is not so strict, but if it is fixed at too high a pH, the pH of the membrane will change even after washing with water.
pH of up to 7 is desirable because the membrane swelling becomes large and the drying load becomes large44. When an aluminum salt is used as an acidic hardener in the fixing solution to harden the film, the pH is generally adjusted to 5.5 or less in order to prevent precipitation of the aluminum salt.

In the present invention, it goes without saying that the developer and/or fixer may be a so-called working solution that does not require dilution water (that is, is replenished as an undiluted solution).

When using concentrates, add {J
(The amount of feed and the mixing ratio with dilution water can be varied depending on the composition of the concentrate, respectively, but in general, the ratio of concentrate to dilution water is preferably 1:0 to 8, and these The total amount of each of the developer and fixer is preferably from 50 mf to 1500 ml per photosensitive material 1.

In a preferred embodiment of the present invention, the photosensitive material is developed and fixed, and then washed with water or subjected to stabilization treatment.

For the washing or stabilization treatment, any method known in the art 45 46 can be applied, and water containing various additives known in the art can also be used as the washing water or stabilizing liquid. . For example, washing or stabilizing water that has been treated with fat mold methods? By using it in &, not only is it possible to save water by reducing the replenishment amount to 3 liters or less per 1 m of photosensitive material, but it also eliminates the need for piping for installing an automatic developing machine, and furthermore, it is possible to reduce the number of tanks. In other words, washing water (and diluting water for developer and fixer if necessary) and fixing solution can be supplied from one common bath tank, and the automatic processing machine. It becomes possible to make it even more compact.

When water treated with anti-mold measures is used in conjunction with washing or stabilizing liquid, the formation of limescale can be effectively prevented, so 1% photosensitive abrasive
For example, 0 to 37! , preferably 0-17! Water-saving treatment can be carried out.

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 "reservation 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 present invention, the photosensitive material in the fixer will be processed in a progressively cleaner direction, that is, in order to contact the processing solution that is not contaminated with the fixer, resulting in even more efficient processing. Good 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 washing water, the patent application 1.72/1980
It is more preferable to provide a squeeze roller cleaning tank as described in No. 968.

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, is treated as disclosed in Japanese Patent Application Laid-open No. 6
As described in Japanese Patent No. 0-235133, 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 above-mentioned stock water can be saved and the amount of waste liquid can be further reduced.

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 method using ion exchange resin described in JP-A No. 61-131632. How to make pure water, patent application 1976
No. 0253807, No. 60-295894, No. 61-
The method using the antibacterial agent described in No. 63030 and No. 61-51396 can be used.

Furthermore, L. E. West Water Quali
ty Criteria” Photo Sci & E
ng. Vol. 9 No. 6 (1965), M.
W. Beach Microbiological
Growths in Motion-PicLure
Processing″SMPTE .Iourna
l Vo1.85, (1976), R. O. Decga
n, Photo Processing Wash
Water Biocides”J.Imaging
Tech. Vol 10, No. 6 (1984) and JP-A-57-8542, JP-A No. 57-5814.
No. 3, No. 58-105145, No. 57-1321
46, No. 58-18631, No. 5797531, No. 57-157244, etc., antibacterial agents, thickening agents, surfactants, etc. can also be used in combination.

Furthermore, in the washing bath, R. T. Kreiman, J. Im
age. Isothiapurine compounds described in Tech48 10, (6) 242 (1984), Research Disclosure Vol. 205, inthiazoline compounds described in I tem 20526 (May 1981 issue), Research Disclosure Vol.
Vol., Item 22845 (April issue, 1983) Patent Application for Isothiazoline Compounds 1986-5
The compounds described in No. 1396, etc. are used as antibacterial agents (Mic
It can also be used in combination as (robiocide).

Furthermore, specific examples of anti-piping agents include phenol, 4-chlorophenol, pentac phenol, cresol,
O-phenylphenol, chlorophene, dichlorophene, formaldehyde, glutaraldehyde, chloracetate, p-hydroxybenzoic acid ester, 2-
(4-thiarizone)-benzimidazole, penduisothiazolin-3-one, dodecylbenzyl-dimethylammonium chloride, If-(fluorodichloromethylthio)-phthalimide, 2, 4. 41・
Examples include lichloro-2°-hydrooxydiphenyl ether.

49 50 The water kept in the water stock tank after applying anti-mold means is used as dilution water for the stock solutions of processing solutions such as the developer and fixer, and the amount added is preferably 0.01 to Log,/j2, more preferably It is 0.1 to 5 g/ff.

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 ■.

Various compounds can be added to the stabilizing bath for the purpose of stabilizing the image. For example, adjusting membrane pH (e.g. pH
3 to 8) various buffering agents (e.g. borate, mekborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid) (used in combination with acids, etc.) and aldehydes such as polymarine are representative examples. In addition, various additives such as Kill-1 agents, fungicides (thiazole-based, isothiazole-based, halogenated phenols, sulfanilamide, benzo I-lyazole, etc.), surfactants, optical brighteners, and hardening agents are used. It may be used, or two or more of the same or different target compounds may be used in combination.

In addition, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a membrane pH adjusting agent for the processing solution in order to improve image storage stability.

The water washing or stabilization bath temperature and time according to the above method are 0.
℃~50℃ for 5 seconds to 30 seconds, but 15℃~40℃
℃ for 5 seconds to 20 seconds, more preferably 15℃ to 4℃
Preferably, the temperature is 5 seconds to 10 seconds at 0°C.

In the practice of the present invention, a method may be used in which 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 about 40
It can be carried out at a temperature of 51 52 °C to about 100 °C, and the drying time can be changed as appropriate depending on the surrounding conditions, but it is usually about 5 seconds to 1 minute, but it is more preferable to dry at a temperature of 40 °C to 80 °C. It is about 5 seconds to 30 seconds.

The present invention exhibits an even more excellent effect of shortening the drying time.

According to the method of the present invention, the so-called dry-to-dry processing time from development, fixing, washing, and drying is 1
The processing time is preferably within 0.00 seconds, and as described above, the processing time is more preferably within 60 seconds, and still more preferably within 50 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 section of the automatic processor to the moment the leading edge emerges from the automatic processor after being processed. .

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples. However, as a matter of course, the present invention is not limited to this.

Example 1 In the presence of water-soluble iridium 2XIO-6 moles/silver 1 mole and water-soluble rhodium 4X10-' moles/silver mol, p
While controlling i{ to 3.0, silver chlorobromide particles containing 30 mol% of silver bromide were obtained. At this time, 1) By controlling Ag, the silver chlorobromide particles are (100)/(11
1) The surface ratio was set to 95/5. The particles are cubic particles with an average particle size of 0.24 μm, and the width of the particle size distribution is 11
%Met. This is added to 0.6 g per mole of silver halide.
After gold sensitization and sulfur sensitization by adding potassium bromide of
The sensitizing dye shown in 1 is added, and 4-hydroxy-6-methyl-1 is added as a stabilizer per mole of silver halide.
3. Add 1 g of 3a,7-tetrazaindene, and add 700 mg of the following compound (■) as a tetrazolium compound, n-
Add 600 μl of sodium dodecylbenzenesulfonate, 2 g of tyrene-maleic acid copolymer, and 3 μg of cobolymer latex of ethyl acrylate and methacrylic acid.
g was added and coated on a polyethylene terephthalate film so that the amount of silver was 3.5 g/m and the amount of geladine was 1.5 g/m. This improved the shape of the silver halide emulsion layer. At that time, 1 decyl-2-(3-isobentyl)succinate 1-2-sodium sulfonate was added at 30 μ/n as a spreading agent so that the gelatin amount was 1.0 g/m.
, 1-hydroxy-3.5 dichlorotriazine sodium salt 3 9 mg/m2 formalin 25 μ/m2 as a hardening agent
A dura protective layer containing d was applied in multiple layers.

As a result, a sample having an emulsion layer and a surface protective layer (the total amount of gelatin for both was 2.5 g/m2) was obtained.

Cee The obtained test rice was passed through an optical wedge and a Kodasokurasoten filter No. 8 8 1 with xenon frassoille through A
After exposure to flash light for 0 to 5 seconds, processing was performed using a roller-type automatic developing machine using the following combination of developer and fixer under the conditions shown in Table 1, and the sensitivity was evaluated. Ta. In addition, halftone dot quality was evaluated using Contact 1 to Screen. Note that the sensitivity is the reciprocal of the amount of exposure necessary to give a density of 3.0, and is a relative value. The halftone dot quality was evaluated in 10 grades.

JO is level 1, 1 to 4 are unusable, and levels 5 and above are usable.

In addition, each data of fixability, preservability, sensitivity, and color retention was measured and evaluated as follows.

The fixability was determined by processing an unexposed film and visually evaluating the presence or absence of residual silver halide.

The storage stability of the processed film is as follows:
The samples were stored for 7 days under the conditions of 70% Rl+ and 70% Rl+, and the degree of coloration was measured using an optical densitometer to evaluate the difference from the untreated sample.

In addition, residual color was visually evaluated for samples obtained by processing unexposed films. A 5-level evaluation was performed, and a rating of “5” was given.
"1" indicated that it was colorless, and that there was a strong residual color. "3"
Residual color below this level is not suitable for general use.

\156 57? Is that a lowly story? Lower white 1...■"・"■"ゝTable 1 shows that the processing method of the present invention has good halftone dot quality and high contrast, good fixing and clearing properties, good storage stability, high sensitivity and It can be seen that the color retention is also good.

In addition, when changing the line speed with the same development time,
Adjustments were made by changing the depth of the tank and the number of rollers.

<Developer prescription> (Guardian A) Pure water (ion exchange water) 150m/
Ethylenedianetetraacetic acid disodium salt 2g diethylene glycol 50g potassium sulfite (55% I1/ν aqueous solution) 100n+7 potassium carbonate
50g hydroquinone
15g 5-Methylbenz1.Reazol 200 mgl-Phenyl-5-mercapI.Tetrazole 30■ Potassium hydroxide Amount to adjust the pH of the working solution to 10.4 Potassium silver bromide 4.5g58-2 59 (Kumikai B) Pure water (ion-exchanged water) 3 ml diethylene glycol 50 g ethylene dianetetraacetic acid disodium salt 25, ■ acetic acid (90
% aqueous solution) 0.3ml 5-21 indazole 110■1-
Phenyl-3-pyrazolidone 700 ml When using a developing solution, the above group A and group B were dissolved in 500 ml of water in that order, and the solution was finished to 1 Il.

Fixer formulation> (Group A) Ammonium thiosulfate (72.5% W/ν aqueous solution) 24
0ae Sodium sulfite 1. Lium 17
g Sodium acetate trihydrate 6.5 g Boric acid 6 g Sodium citrate dihydrate 2 g Acetic acid (90% w/v aqueous solution) P11 adjustment required amount (m Wi B) Pure water (ion exchange water) 17 Monosulfuric acid (50 %w/v aqueous solution) 4.7g
26.5 g of aluminum sulfate (aqueous solution with AlzO2 equivalent content of 8.1% w/v) When using the fixer, add the above compositions A and B in 500ml of water.
The mixture was dissolved in the following order, adjusted to pH 4.5 with acetic acid, finished into an IC, and used as a fixer.

Each process of the automatic processor is as follows.

Development 38°C 12 seconds fixing 38°C 10 seconds washing 20"C 10 seconds drying 60°C 60 61 Example-2 In this example, a photosensitive material sample was prepared in the same manner as in Example-1. However, as the sensitizing dye, the above-mentioned exemplary sensitizing dye I-3 was used in an amount of 45 mg/Ag -2, and the line speed was 1800 mm/min.

From Table 2, excellent results can be obtained according to the present invention.
3 In this example, a light-sensitive material sample was prepared in the same manner as in Example-1, but the above-mentioned sensitizing dye ■-19 was used as the sensitizing dye in an amount of 60 mg/AgX 1 mol, and halogen The (100) plane/(111) plane ratio of the silver halide grains was 98/2, the amount of geladine was 2.5 g/n, and the average particle diameter of the silver halide grains and the amount of coated silver were as shown in Table 3. The line beat was set to 1800 mm/min.

From Table 3, excellent results can be obtained according to the present invention. [Effects of the Invention] As described above, according to the present invention, the fixing removal property is good even when processing is performed for a short time, and the photosensitive material after processing is It has good storage stability, high sensitivity, and good color retention.
In addition, it is possible to achieve processing that can obtain a high-contrast image.

Claims (1)

[Scope of Claims] 1. A method for processing a silver halide photographic material having a photographic constituent layer having at least one silver halide emulsion layer on at least one side of a support, comprising: At least one silver halide emulsion layer of the material may contain any sensitizing dye selected from the group consisting of a sensitizing dye represented by the following general formula (I) and a sensitizing dye represented by the following general formula (II). Color sensitized with at least one sensitizing dye, and the amount of gelatin applied to the photographic constituent layer is 3.
．． 0 g/m^2 or less, and at least one silver halide emulsion layer is (
100) plane/(111) plane ratio of 5 or more, average grain size 0.4
After imagewise exposing a silver halide photographic material containing silver halide grains of µm or less, a fixing solution with a pH of 4.3 or more is used to
1. A method for processing a silver halide photographic light-sensitive material, which comprises processing in an automatic developing machine with a line speed of 1000 mm/min or more. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Y_1_1, Y_1_2, Y_2_1 and Y_2
_2 each represents a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocycle. R_1_1, R_1_2, R_2_1 and R_2_2 each represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group. R_1_3, R_1_4, R_1_5, R_2_3, R
_2_4, R_2_5 and R_2_6 are each a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group,
Represents phenyl group, benzyl group, ▲numerical formula, chemical formula, table, etc.▼. Here, W_1 and W_2 each represent a substituted or unsubstituted alkyl group (the number of carbon atoms in the alkyl part is 1).
-18, preferably 1-4), represents an aryl group, W
_1 and W_2 can also be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle. Also, R_1_3 and R_1_5 and R_2_3 and R_2
_5 can be linked to each other to form a 5-membered ring or a 6-membered ring. X_1_1 and X_2_1 each represent an anion. n
_1_1, n_1_2, n_2_1 and n_2_2 are
Each represents 0 or 1.