JPH02127638A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To decrease after-colors even after an ultra-rapid processing is carried out by incorporating specific dyes and anionic surfactants into at least one layer in the silver halide photographic sensitive material and processing the material within 40 seconds of the processing time up to developing fixing, washing and/or stabilizing processing by using an automatic developing machine of >=1,500mm/min line speed. CONSTITUTION:The silver halide photographic sensitive material contains at least one kind of the dyes and anionic surfactants expressed by the formulas Ia, Ib, Ic in at least one layer thereof and is processed within 40 seconds processing time up to the developing, fixing, washing and/or stabilizing processing by using the automatic developing machine of >=1,500mm/min line speed. In the formulas, R1 to R6 respectively denote an alkyl group; Y1 and Y2 denote a nonmetallic atom group necessary for forming a pyrrolopyridine ring; L denotes a methyne group; X<-> denotes anion; m denotes 4 to 5 integer; n denotes 1 or 2: and n is 1 when the dye forms an intramolecular salt. The generation of the after-colors, etc., is decreased in this way even if the photosensitive material is subjected to the ultra-rapid processing.

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 method for processing printed photosensitive materials having rapid developability.

[Conventional technology]

In recent years, the consumption of silver halide photographic materials has continued to increase. For this reason, the number of 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 platemaking field.

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

However, shortening the processing time causes deterioration of residual color and unevenness of residual color, which is not preferable.

[Purpose of the invention]

In order to solve the above-mentioned problems, it is an object of the present invention to provide a method for processing silver halide photographic materials that causes less residual color even when subjected to ultra-rapid processing.

[Structure of the invention]

The above object of the present invention is to provide a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support and a back layer on the opposite side of the support. At least one layer has the following general formula 1:Ia
), (Ib), (Ic) and at least one anionic surfactant, and is developed and fixed using an automatic developing machine with a line speed of 1500 mm/min or more. This is achieved by a processing method characterized in that the processing time up to water washing and/or stabilization processing is within 40 seconds.

General formula CI a) General formula % formula %) In the formula, R□, Rx, R3, R4, RS and R6 each represent an alkyl group, and Y and Y2 are nonmetallic atoms necessary to form a pyrrolopyridine ring. represents a group and includes a Yl bond.

R l+RZ+R3, RI+R in general formula (Ia)
s, Ra.

Y , , Y 2 , R , , R in general formula (Ib)
,R,,R4+Rs,Ra,Y+,Yz
and R1゜R2, R3, R4, in general formula (Ic),
RS, Ra+Y +, Y! are each a group that allows the dye molecule to have at least two acid groups or -CH
, C) +201i' represents a group that allows at least two substituents having II or more groups.

R represents a hydrogen atom or an alkyl group. L represents a methine group; e represents an anion; m represents an integer of 4 to 5; n represents an integer of 1 or 2; when the dye forms an inner salt, n is 1;

The present invention will be explained in detail below.

Examples of the acid group in the general formulas CI a), [I b) and (Ic) include a sulfonic acid group, a carboxylic acid group, a phosphonic acid group, and each of these acid groups includes its salt. Examples of the salt include alkali metal salts such as sodium and potassium salts, and organic ammonium salts such as ammonium, triethylamine, and pyridine.

The alkyl groups represented by R, , R2, R, , R4, R, and R6 are preferably lower alkyl groups having 1 to 8 carbon atoms (
For example, -CI (, CH
, may have a substituent other than the OR group.

The alkyl group represented by R is preferably a lower alkyl group having 4 or less carbon atoms.

-C8□CH20R group-containing substituents include, for example, bitroxyethyl group, hydroxyethoxyethyl group, methoxyethyneethyl group, hydroxyethylcarbamoylmethylthylcarbamoylmethyl group, N,N-dihydroxyethylmethylcarbamoylmethyl group, and hydroxyethylcarbamoylmethyl group. Examples include an ethylsulfamoylethyl group and a methoxyethoxyethoxyethquincarbonylmethyl group.

Y. Other substituents that Y2 may have include sulfo groups (including salts), carboxyl groups (including salts)
, hydroxyl group, anano group, halogen atom (e.g.
fluorine, chlorine, bromine atoms, etc.).

The methine group represented by groups), halogen atoms (e.g.
Examples include fluorine, chlorine, bromine atoms, etc.), aryl groups (eg, phenyl groups), and alkoxy groups (eg, methoxy, ethoxy groups, etc.). The substituents of the methine group are bonded to each other to form a 6-membered ring containing three methine groups (for example, 4.4
-dimethyl/lylohexene ring).

The anion represented by Xo is not particularly limited, but specific examples include halogen ions, p-toluenesulfonic acid ions, and ethyl sulfate ions.

Specific examples of the dyes represented by the general formulas (Ia), [:Ib) and (Ic) (hereinafter referred to as dyes of the present invention) used in the present invention are shown below. It is not limited to.

Specific Compounds The dyes of the present invention are described in Journal of the Chemical Society ((J, Chem, Soc,) p. 189 (19
1933), U.S. Patent No. 2,895,955 and Japanese Unexamined Patent Publication No. 6
It can be synthesized with reference to No. 2-123454 and the like.

Examples of the mother nucleus of the dye of the present invention include the following compounds.

Compound (A) is described in J, Chem, Soc, 3202 (1
959) and the method described in British Patent No. 870,753, bo compound (B) can be synthesized by the method described in J. Chem.
It can be synthesized by the method described in (1961).

Compound (C) can be synthesized by the method described in British Patent No. 841.588.

Using these cores, quaternization, sulfonation, etc. can be performed as necessary. Or J, Chem.

Soc, , 3202 (1959) and J. Che+
++, Soc, 584 (1961) to synthesize N-alkyl-N-pyridylhydrazine, perform a cyclization reaction via hydrazone, and optionally treat with acid to obtain l-alkyl-substituted - It is also possible to obtain a 3H-pyrrolopyridine derivative and use this as a starting material.

The above-mentioned dyes can be used in a suitable solvent (e.g. water, alcohol (e.g. methanol, ethanol, etc.), methyl cellosolve, etc.).
or a mixed solvent thereof) and added to the coating solution for a hydrophilic colloid layer of the present invention.

Two or more of these dyes can also be used in combination.

The specific amount of dye used varies depending on the purpose and is difficult to set uniformly, but generally 10 bows/m"-1.0 g/m",
Particularly preferred amounts can be found in the range from 10''g/m'' to 0.5g/m''.

The dye represented by the general formula [1] of the present invention is particularly effective for the purpose of preventing irradiation, and when used for this purpose, it is mainly added to the emulsion layer.

The dyes of this invention are also particularly useful for antihalation purposes, where they are added to the backside of the support or to a layer between the support and the emulsion layer.

The dyes of this invention are also useful as dyes to impart safelight safety, in which case they are added to layers above the emulsion layers.

Further, the anionic surfactant used in the present invention is not particularly limited as long as it has a hydrophobic part and a hydrophilic part in its molecule and exhibits a decrease in surface tension at least in its solution. do not have.

The anionic surfactants particularly preferably used in the present invention include the following general formulas [1[A], (nB), [
Examples include compounds represented by [C] and [IID].

General formula ([IA) R, -0CO-CH2 Rz-OCO-CHF? s General formula (nB) R, -0CO-CH.

book R, -0CO-CH R, -0CO-CH-R.

General formula ([) General formula (I[D) In the above formula, Rl+Rt, R4+Rs, Ra, Rg, Rs
and R1° may be the same or different, and each represents a halogen atom, such as chlorine or bromine, or an alkyl group such as methyl, ethyl, butyl, isobutyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, octadecyl group, etc. It may be linear or branched, and preferably has 1 to 32 carbon atoms. These alkyl groups may be substituted with any substituent such as a halogen atom, such as a chlorine atom or a bromine atom, or an aryl group, such as a phenyl group or a heptyl group. Also, R1 and R
7 represents an alkali metal salt of a carpoquine group, a sulfo group, and a phosphonic acid group. n and n represent an integer of 1 to 3.

Specific compounds represented by the general formulas [:IIA) to CIID) are illustrated below, but the compounds of the present invention are not limited thereto.

[Compound example]

C,H,,0OCCH2CHz Cr,H1100ccH2cHSOsNaCH3(CH
2) II OOCCH2'' CI, (CH2), -00C-CI-5O, NaCs
H+ +OOCC112 CIOH2100CCH5O3Na CH3(CH2)3 00CCH2 CH, (CH2)! -00C-CH-SO3NaCH3
(CI?-0CO-CH2 CH3(CH2)7 0COCH 薯CH3CCH2)? -0CO-CH-5o3N
a The silver halide emulsion used in the light-sensitive material of the present invention includes conventional silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Any silver halide grains used in
It may be obtained by any of the acidic method, neutral method and ammonia method.

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

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having a (100) plane as a crystal surface.

Also, U.S. Patent Nos. 4,183,756 and 4,225.6
No. 66, JP-A-55-26589, JP-A-55-42
Specifications such as No. 737, The Journal of Photographic Science (J, Photogr, 5ci
), 21.39 (1973), etc., particles having shapes such as octahedrons, tetradecahedrons, dodecahedrons, etc. can be prepared and used. Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention 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 emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (referred to as monodisperse emulsions) may be used. They may be used alone or in combination. or,
A polydisperse emulsion and a monodisperse emulsion may be mixed and used.

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

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

Here, the average particle size r is the particle size when the product ni
Define l.

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

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

(The number of grains to be measured is indiscriminately 1,000 or more.) Particularly preferred highly monodisperse emulsions of the present invention are those with a monodisperse degree defined by 20 or less, more preferably 15 or less. It is.

Here, the average grain size and grain size standard deviation shall be determined from ``1'' in the above definition.
No. 1, No. 58-49938 and No. 60-122935
This information can be obtained by referring to the Publication No.

Although the photosensitive silver halide emulsion can be used as a so-called primit 1ve emulsion without chemical sensitization, it is usually chemically sensitized.

For chemical sensitization, Glafkides or Ze
l il<mHHl et al.'s book, or H, Fr1ese
r ljide Grundlagen 7'Jshi Photography en Prozesse Mid Zilberhalogenideen ([)i6 (:rundlagender P
photographischen Prozesse
mit 5ilberhal.

Geniden, Akademicche Verl
agsgesellschaft, 1968) can be used.

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

As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof are described in U.S. Patent No. 1.574.944.
No. 2,410.689, No. 2,278.947, No. 2,728,668, and No. 3,656,955.

As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidisulfinic acid, Nran compounds, etc. can be used, and specific examples thereof are described in U.S. Pat.
No. 87.850, No. 2,419.974, No. 2.51
No. 8,698, No. 2,983,609, No. 2,983
．． No. 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. 2,448.060, British Patent No. 618,061
It is stated in the number etc.

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

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

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

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

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

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

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

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

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxanol dyes, and the like. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes, such as basic standard ring nuclei, can be applied to these dyes.

That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, detrazole nucleus, pyridine nucleus, etc., and nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei, and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms.

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

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

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

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

The sensitizing dyes of the present invention can be used alone or in combination of two or more.

More specific examples of the sensitizing dyes advantageously used in the present invention include the following.

That is, examples of sensitizing dyes used in the blue-sensitive silver halide emulsion layer include West German Patent No. 929.080, US Pat. No. 2,231.658, US Pat. No. 2,519.0 Old No. 2,
No. 912,329, No. 3,656゜956, No. 3,6
No. 72,897, No. 3,694,217, No. 4,02
No. 5゜349, No. 4,046,572, British Patent No. 1,
No. 242,588, Special Publication No. 44-14030, No. 52
-24844, JP-A-48-73137, JP-A-61-
Examples include those described in No. 172140 and the like.

Further, as sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat.
No. 2.908, No. 2,739.149, No. 2,945
, No. 763, British Patent No. 505.979, Special Publication No. 1976-
Typical examples include cyanine dyes, melonanine dyes, and composite cyanine dyes as described in 42i72 and the like.

Further, as sensitizing dyes used in red-sensitive and infrared-sensitive silver halide emulsions, for example, those described in US Pat. No. 2,269.
No. 234, No. 2,270.378, No. 2,442.7
No. 10, No. 2,454.629, No. 2.776.28
No. 0, Special Publication No. 49-17725, Japanese Patent Publication No. 50-624
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 25, No. 61-29836, No. 60-80841, and the like.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization. Typical examples are U.S. Pat. Nos. 2,688,545 and 2,977.229,
3,397.060, 3,522.052, 3,527,641, 3,617,293, 3
, No. 628,964, No. 3,666.480, No. 3,
No. 672.898, No. 3,679,428, No. 3,7
03゜377, 3,769.301, 3,81
No. 4,609, No. 3,837゜862, No. 4,026
, No. 707, British Patent No. 1,344,281, No. 1,5
No. 07.803, Special Publication No. 43-4936, No. 53-1
No. 2375, JP-A-52-110618, JP-A No. 52-1
No. 09925, etc.

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

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

Various compounds can be added to the above photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles,
Benzimidazoles (especially nitro- or halogen-substituted), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzimidazoles, mercaptothiazoles (especially l-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 tetraazaindenes (especially 4-hydroxy substituted (1,3 Many compounds known as stabilizers can be added, such as .3a, 7) tetraazaindenes), benzenethiosulfonic acids, benzenesulfinic acids, etc.

An example of a compound that can be used is The Theory of the Photo Process, by K-Mees.
Graphic Process, 3rd edition, 1966
(2013), with the original literature cited.

For more detailed examples and other methods of use, see, for example, US Pat. No. 3,954.474, 3.

982, 947, 4.021,248, or Japanese Patent Publication No. 52-28660 can be referred to.

Further, the silver halide photographic light-sensitive material of the present invention contains U.S. Pat. No. 3,411,911 and U.S. Pat.
12, Japanese Patent Publication No. 45-5331, etc., may be included.

The silver halide photographic material of the present invention may contain the following various additives. As thickeners or plasticizers, for example, US Pat.
No. 15, Belgian Patent No. 762,833, US Patent No. 3
, 767, 410 and Belgian Patent No. 588.143, such as styrene.
Sodium maleate copolymer itself, dextran sulfate, etc. Hardening agents include aldehyde, epoxy, ethyleneimine, active halogen, vinyl sulfone, isocyanate, sulfonic acid ester, carbodiimide, mucochloric acid, Various hardening agents such as acyloyl type,
As the ultraviolet absorber, for example, U.S. Patent No. 3,253,9
No. 21, British Patent No. 1,309,349, etc., particularly 2-(2'-hydroxy-5-tertiary butylphenyl)benzotriazole, 2-
(2'-Hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3'-tert-butyl-5'-butylphenyl)-5-chlorobenzotriazole, 2-( Examples include 2'-hydroxy-3'.5'-di-tert-butylphenyl)-5-chlorobenzotriazole.

Further, as coating aids, emulsifiers, permeability improvers for processing liquids, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials, British Patent No. 548.532, 1,216.389, U.S. Patent No. 2,026.202, U.S. Patent No. 3,514.293,
Special Publication No. 44-26580, No. 43-17922, No. 43-17926, No. 43-3166, No. 48-2
Use of anionic, cationic, nonionic or amphoteric compounds described in No. 0785, Buddhist Patent No. 202,588, Belgian Patent No. 773,459, JP-A-48-1.01118, etc. Among these, anionic surfactants having a sulfone group, such as succinic acid ester sulfonates, alkylbenzene sulfonates, and the like are particularly preferred. In addition, as antistatic agents, Japanese Patent Publication No. 46-24159, Japanese Patent Application Laid-Open No. 48-89979,
U.S. Patent No. 2,882.157, U.S. Patent No. 2,972, 53
No. 5, JP-A-48-20785, JP-A No. 48-43130
There are compounds described in Japanese Patent Publication No. 48-90391, Japanese Patent Publication No. 46-24159, Japanese Patent Publication No. 46-39312, Japanese Patent Publication No. 48-43809, and Japanese Patent Publication No. 47-33627.

In the manufacturing method of the present invention, the pI (pI) of the coating liquid is 5.3 to
A range of 7.5 is preferred. In the case of multilayer coating, it is preferable that the pH of the coating solution, which is a mixture of the coating solutions 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 is undesirable, and if the pH is greater than 7.5, it is undesirable because it adversely affects photographic performance.

In the light-sensitive material of the present invention, the constituent layers include matting agents, such as silica described in Swiss Patent No. 330.158, glass powder described in French Painting Patent No. 1,296.995, and British Patent No. 1.
, 173,181; inorganic particles such as alkaline earth metals or carbonates of cadmium, zinc, etc.; starch as described in U.S. Pat. No. 2,322,037; Belgian Patent No. 62;
Starch derivatives described in No. 5.451 or British Patent No. 981,198, polyvinyl alcohol described in Japanese Patent Publication No. 44-3643, polystyrene or polymethyl methacrylate described in Swiss Patent Nos. 330 and 158.
1., polyacrylonitrile as described in US Pat. No. 3,07'l, 257, and polycarbonate as described in US Pat. No. 3,022,169.

In the photosensitive material of the present invention, the constituent layers include slipping agents, such as those described in U.S. Pat.
higher alcohol esters of higher aliphatics as described in US Pat. No. 3,295,979; higher aliphatic calcium salts as described in UK Patent No. 1,263.722; , U.S. Patent No. 3,042
, No. 522, and No. 3,489°567. Dispersions of liquid paraffin and the like can also be used for this purpose.

The photosensitive material of the present invention may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Vol. 176.
+17643 (December 1978) and Volume 187 I
tem18716 (November 1979), and the relevant parts are summarized in the table below.

In carrying out the silver halide photographic material of the present invention, for example, the emulsion layer and other layers can be constructed by coating on one or both sides of a flexible support commonly used in photographic materials. Useful 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 i, etc., baryta layers or α- Paper coated with or laminated with an olefin polymer (eg, polyethylene, polypropylene, ethylene/butene copolymer), etc. The support may be colored using dyes or pigments.

It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion with emulsion layers and the like. The undercoating treatment is as per JP-A-52-104913, JP-A-59-18949, JP-A-59-19940, and JP-A-5L1.
The treatments described in each publication of No. 1941 are preferred.

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

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

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

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

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

The developing agents for 1-phenyl-3-pyrazolidone or its derivatives used in the present invention include l-phenyl-4,4-dimethyl-3-pyrazolidone, l-7enyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, Examples include l-phenyl-4,4-dihydroxymethyl-3-pyrazolidone.

Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β- and droxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl)glycine. , 2-methyl-p-aminophenol, p-benzylaminophenol, etc. Among them, N-methyl-p-
Aminophenols are preferred.

The developing agent is usually 0. Preferably, it is used in an amount of O1 mol/Q-1,2 mol/Q.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. The amount of sulfite is preferably 0.2 mol/Q or more, particularly 0.4 mol/Q or more. Further, the upper limit is preferably 25 mol, / (1).

+11H of the developer used in the present invention is preferably 1. stomach. More preferably pH 10 to 1
The range is up to 2.

(2)) The alkaline agents used for setting 1 include pH adjusters such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate.

JP-A-61-28708 (borates), JP-A-60-
Buffers such as 93439'+ (eg, sucrose, acetoxime, 5-sulfosalcylic acid), phosphates, carbonates, etc. may also be used.

Additives other than those listed above include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, and nitinol. , methano′
Organic solvents such as l-phenyl-5-mercaptotetrazole, mercapto compounds such as 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole compounds such as 5-nitroindazole, 5-methylbenztriazole, etc. It may contain an antifoggant such as a penztriazole compound, and if necessary, a color toning agent, a surfactant, an antifoaming agent, a water softener, and JP-A-56
It may also contain the amino compound described in No.-106244.

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

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

In addition, L., F., A. Meson, "Photographic Processing Chemistry", published by Focal-kai Press (1966), pp. 226-229, American Press Department 2.
No. 193゜015, No. 2,592,364, JP-A-4
Those described in No. 8-64933 may also be used.

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

Further, "washing time" refers to the time during which the product is immersed in the washing tank liquid. Also, "drying time" is usually 35℃~100℃
A drying zone where hot air, preferably 40° C. to 80° C., is blown is installed in the automatic processing machine, or the period of time the machine is in that drying zone.

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

The fixer is an aqueous solution containing thiosulfate, [)H3,8
Above, preferably 4.2 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and these include thiosulfate 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 can be varied as appropriate, and is generally about 0.1 to about 67 l/Q.

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

The fixing solution can be made by using tartaric acid, citric acid, or conductors thereof alone or in combination of two or more thereof.

It is effective to use these compounds in an amount of 0.005 mol or more per fixer IQ, particularly 0.01 mol/Q to 0.03 mol/a.

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), pH buffering agents (e.g., acetic acid, nitric acid), p.
All of the compounds described in Japanese Patent Application No. 60-213562, such as o-regulating agents (for example, sulfuric acid), chelating agents capable of softening water, and the like can be used.

Fixing temperature and time are approximately 20°C to approximately 50°C for 6 seconds to 1
It is preferably 6 seconds to 30 seconds at 30°C to 40°C, still more preferably 6 seconds to 30°C at 30°C to 40°C.
It is 15 seconds.

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

It is pi (4
, 5 or more, more preferably p 1.14 , 65
That's all. This is because if the pH is less than 4.5, the thiosulfate will decompose and eventually become sulfided, especially if the fixer is left for a long period of time before it is actually used.

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

In the present invention, either the developing solution or the fixing solution may be a so-called working solution that does not require dilution water as described above (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 to 8. The total amount of each of the developing solution and fixing solution is 50 m (preferably from i to 1500 mQ) per 1 m2 of the photosensitive material.

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

Any method known in the art can be applied to the washing or stabilization treatment, and water containing various additives known in the art can also be used as the washing water or stabilizing liquid. By using anti-mold water for washing water or stabilizing liquid, not only is it possible to save water by replenishing less than 3Q per 1m2 of photosensitive material, but it also eliminates the need for piping for installing an automatic processing machine. It is possible to reduce the number of stock tanks. That is, the solution dilution water and washing water or stabilizing solution for the developer and fixer can be supplied from a common single layer stock tank, making it possible to further downsize the automatic developing machine.

If anti-mildew water is used in combination with washing water or stabilizing liquid, the formation of lime scale can be effectively prevented.
0-3Q per 2, preferably O-IQ.

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 "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 present invention, the photosensitive material in the fixer will be processed by contacting the uncontaminated processing solution in a progressively cleaner direction, that is, at a constant nWi, 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 water, patent application 1729/1986
It is more preferable to provide a squeeze roller cleaning tank as described in No. 68.

Further, the washing or stabilizing bath is treated with anti-mold means; some or all of the over-70 solution from the washing or stabilizing bath, which is generated by replenishing water depending on the treatment, is used in JP-A-60-2.
As described in Japanese Patent No. 35133, it can also be used in a processing liquid having a fixing ability, which is a processing step before that.

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

Anti-mildew methods include the ultraviolet irradiation method described in JP-A No. 60-263939, the method using a magnetic field described in JP-A No. 60-263940, and the use of ion exchange resin described in JP-A No. 61-131632. How to make pure water, patent application 1986-
No. 253807, No. 60-295894, No. 61-6
The method using a fungicide described in No. 3030 and No. 61-51396 can be used.

In history, L, E, West ``Water Qual
ity Cr1teriaPhoro Sci &
Eng, Vol. 9 No. 6 (1965), M.
, W, Be-ach +'Microbiology
cal Growths in Motion-
Picture Processing'' SMPT
E Journal Vol, 85. (1976)
-R, O, Deegan, “Photo Proce
ssing Wash Water Bio-c
ides” J, Imaging Tech, Vol.
10. No. 6 (1984) and JP-A-57-85
No. 42, No. 57-58143, No. 58-105145
No. 57-132146, No. 58-18631,
Antibacterial agents, anti-inflammatory agents, surfactants, etc. described in Japanese Patent Nos. 57-97530 and 57-157244 can also be used in combination.

Furthermore, for the washing bath, R.T. Kreiman, J.I.
mage, Techlo, (6) 242 (1
Isothiazoline compounds described in 984), RES
EiCHDISCLO3IJRE Volume 205, ILem
20526 (May issue, 198), inthiazoline compounds, Volume 228, Item 228
45 (April issue, 1983), compounds described in Japanese Patent Application No. 61-51396, etc. can also be used together as microbiocides.

Furthermore, specific examples of anti-piping agents include phenol, 4-chlorophenol, pentachlorophenol, cresol,
o-phenylphenol, chlorophene, dichlorophene, formaldehyde, geltaraldehyde, chloracetamide, p-hydroxybenzoic acid ester, 2-
(4-Deazoline)-benzimidazole, benzisothiazolin-3-one, dodecyl-pencyl-dimethylammonium chloride phthalimide, 2,4.4'-)sachloro-2'-hydroxydiphenyl ether, and the like.

The water stored in the water stock tank after being treated with anti-mold means is diluted with water for diluting the undiluted solution of the processing solution such as the developer-fixer, and the amount thereof added is preferably 0.01-log/Q, more preferably 0.1-log/Q. It is 5g/Q.

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

Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, adjusting the membrane pH (e.g. 83
~8) various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid) Typical examples include aldehydes such as (used in combination) and formalin.

In addition, various additives such as chelating agents, bactericidal agents (thiazole type, isothiazole type, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, hardening agents, 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 salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, 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°
Preferably 6 seconds to 1 minute at ~50°C, but to 15°C・4
More preferably 6 to 30 seconds at 0°C, more preferably 15°
C to 40°C for 6 seconds to 15 seconds, preferably.

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 a temperature of about 40° C. to about 100° C., and the drying time can be varied appropriately depending on the surrounding conditions, and is usually about 5 seconds to 1 minute, more preferably 4 minutes.
It is about 5 seconds to 30 seconds at 0°C to 80°C.

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

According to the method of the present invention, the so-called dry-to-dry processing time for development, fixing, washing, and drying is within 100 seconds, preferably within 60 seconds, and more preferably within 5 seconds.
It is to be processed within 0 seconds.

Here, 'dry to dry' refers to the time from the moment the tip of the photosensitive material to be processed enters the filler/insertion section of the processor to the moment the tip comes out of the processor after being processed. .

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 (Preparation of coating solution for back lower layer) After dissolving 500 g of gelatin in 8Q water, the dye of the present invention was added as shown in Table 1, and 20 g of saponin as a surfactant was added as shown in Table 1. Ig.

A polymer latex was prepared by adding 20 g of a copolymer of butyl acrylate and vinylidene chloride, 2.5 g of a styrene-maleic anhydride copolymer as a thickener, and 2 g of glyoxal as a hardening agent.

(Back upper layer coating liquid made by tfR) After dissolving 400 g of gelatin in 600 mQ of water, 20 g of polymethyl methacrylate with an average particle size of 4 μm was added as a matting agent, and 3 g of the surfactant shown in Table 1 was added. .

(Preparation of coating solution for emulsion layer) Gelatin, sodium chloride, and water are kept warm at 40°C. In the solution, there is an aqueous solution of silver nitrate and 1 2 A mixed aqueous solution of potassium bromide and sodium chloride to which a potassium chloroiridate salt and a hexabromolodium salt of 4 size 9%, cubic crystal, grain size 0
．． 25 μm) was prepared while maintaining the pH at 3.0 and the pAg at 7.7, and after returning the pH to 5.9, it was desalted by a conventional method.

This emulsion was sensitized with gold and sulfur, 60 mg of sensitizing dye (a) was added per mol of silver halide, and 1 mole of silver halide was added.
Per mole, 70 mg l-phenyl-5-mercaptotetrazole, 1.3.3 4-hydroxy-6-methyl
a. After adding 1.2 g of 7-titrazaindene and gelatin to stop the ripening, add 4 g of hydroquinone, 3 g of potassium bromide, 5 g of saponin, 2 g of styrene-maleic acid polymer as a thickener, and acrylic acid. A high molecular weight polymer latex of ethyl was prepared by adding Polmarine and 1-hydroxy-3,5-tic 1701.Ryazine sodium salt as a 3gs hardening agent.

Sensitizing dye (1) (Preparation of protective film for emulsion layer) Potassium bromide log was added to an aqueous solution of 500 g of gelatin, and l-decyl-2-(3-impentyl)sac/F-1-- was added as a spreading agent. 4 g of 1% aqueous solution of sodium 2-sulfonate was added, and 1 amorphous silica with an average particle size of 5 μm was added.
00g addition dispersion I7 was prepared.

Using the above coating solution, the lower and upper layers of the back side were simultaneously coated on the undercoated polyethylene terephthalate base with the amount of gelatin shown in Table 1 2, and then on the side opposite to the back layer. The silver content is 3.8 g/m2, the gelatin emulsion layer is 1.8 g/m", the protective film layer 1 is Og/m"
The emulsion layer and the protective layer were coated at the same time in such a manner that the emulsion layer and the protective layer were coated at the same time.

The thus obtained sample was processed using a developing solution and a fixing solution having the following composition in a conventional roller type automatic developing machine at a line speed of 1800 mm/min, and residual color was evaluated. The residual color was evaluated in 10 grades.

10 is the best level, 1-4 is unusable, and 5 or higher is usable. The results are shown in Table 1. From Table 1, it can be seen that the products of the present invention have good residual color.

The lower layer and upper layer in Table 1 are back layers, respectively.

The surfactants used for comparison are shown below.

Developer composition (composition A) Pure water (ion exchange water) 150mf2
Ethylene ethylenediaminetetraacetic acid disodium salt Ren glycol 50g Potassium sulfite (55% W/V aqueous solution) 100m0° Potassium carbonate 50g Hydroquinone
15g 5-methylbenzotriazole 200mg 1-funyl-5-mercaptotetrazole 0mg Potassium hydroxide Amount to bring r+H to 11.5 after use Potassium bromide 3g (composition) Pure water (ion-exchanged water) 3m (1 diethylene glycol 50g diethylamino-
1,2-propanediol 5g Ethylenediaminetetraacetic acid disodium salt 5mg Acetic acid (90% aqueous solution) 0.3mQ5
-Nitroindazole 10 mg Tophenyl-3-pyrazolidone 500 mg When using a developer, the above compositions were dissolved in 500 mQ of water in the order of the above composition A1 and finished to Ic.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% w/v water filtration) 40mQ Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid
6g Sodium citrate trihydrate
8g acetic acid (90% W/V aqueous solution)
13.6mQ (composition) Pure water (ion exchange water) 17m (2 sulfuric acid (50% W/V aqueous solution) 4.7g aluminum sulfate (Aqueous solution with Al220. equivalent content of 8.1% v/v) 2
6.5g To use as a fixer, the above compositions A1 were dissolved in 500ml of water in the order of composition A1 and finished to 112ml. The pH of this fixer was about 4.3.

〔Effect of the invention〕

According to the present invention, it has been possible to provide a processing method that produces less residual color even when ultra-rapid processing is performed.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support and a back layer on the opposite side of the support. The following general formulas [I a], [I b], [I
c) Containing at least one dye represented by at least one type of anionic surfactant and developing using an automatic developing machine with a line speed of 1500 mm/min or more,
Processing time for fixing, washing and/or stabilization is 40
A processing method characterized in that it takes less than seconds. General formula [I a] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [I b] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [I c] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [Formula In the formula, R_1, R_2, R_3, R_4, R_5 and R_6 each represent an alkyl group, Y_1 and Y_2 represent a group of nonmetallic atoms necessary to form a pyrrolopyridine ring, and the ring of Y_1 has the formula ▲, There are chemical formulas, tables, etc.▼Includes bonds, and in the ring of Y_2 ▲There are mathematical formulas, chemical formulas, tables, etc.▼Assume that bonds are included. R_1, R_2, R_3, R in general formula [I a]
_4, R_5, R_6, Y_1, Y_2, general formula [I
R_1, R_2, R_3, R_4, R_5 in [b]
, R_6, Y_1, Y_2 and R_1, R_2, R_3, R_4, R_5, R_6 in general formula [I c],
Y_1, Y_2 are each a group that allows the dye molecule to have at least two acid groups or -CH_2CH_2
Represents a group capable of having at least two substituents having one or more OR groups. R represents a hydrogen atom or an alkyl group. L represents a methine group, and X^■ represents an anion. m represents an integer of 4 to 5, and n represents an integer of 1 or 2. When the dye forms an inner salt, n is 1. ]