JPH03223843A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the photographic sensitive material which decreases after- colors, obviates the adhesion of the photosensitive materials to each other by grazing and preserving and has an excellent preservable property with lapse of time by incorporating a specific dye and anionic surfactant into the layers of the photographic sensitive material and hardening the layers with a specific sensitive material and hardening the layers with a specific hardener. CONSTITUTION:The layers in the photographic sensitive material contain the dye expressed by formula I and the anionic surfactant and are hardened with the hardener expressed by formula II. In the formula I, R1 and R2 respectively denote the group selected from a carboxyl group, alkyl group, aryl group, etc.; R3 and R4 respectively denote the group selected from an alkyl group substd. with a sulfonic acid group or carboxyl group or an aryl group substd. with a sulfonic acid group or carboxyl group. In the formula II, L denotes a vibalent org. group; m, n denote positive integers; p denotes 0 or 1. The photographic sensitive material which decreases the after-colors in site of rapid processing and has the excellent resistance to grazing, adhesiveness and preservable property with lapse of time is obtd. in this way.

Description

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

[Background of the invention]

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

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

In other words, as the immediacy and number of times information is rapidly increasing, it has become necessary to handle a larger volume of printing plate-making work even with shorter delivery times. In order to meet the demands of the printing plate making industry, it is necessary to facilitate the simplification of the printing process and to process the printing plate making film more quickly.

However, in order to achieve rapid processing, a photosensitive material is required that has excellent GL image properties, leaves no residual color even in a short processing time, and dries in a short time.

A common method for obtaining photosensitive materials that dry in a short time is to add a sufficient amount of hardening agent to reduce the amount of swelling. problems such as decreased sensitivity, increased residual silver, and increased residual hypo. Other problems include deterioration of residual color and deterioration of storage stability of the photosensitive material.

[Purpose of the invention]

In order to solve the above-mentioned problems, the purpose of the present invention is to provide a halogenated material that has excellent storage stability over time, with little residual color even during ultra-rapid processing, and without causing scratches or adhesion between photosensitive materials during storage. An object of the present invention is to provide a silver photographic material.

[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, in which at least one layer in the silver halide photographic material has the following formula - CI ) and at least one anionic surfactant, and is characterized by being cured with a hardener represented by the following formula [] This can be achieved using silver halide photographic materials.

General formula CI) [In the formula, R1 and R2 each represent a group selected from a carboxyl group, an alkyl group, an aryl group, an alkoxycarbonyl group, or an aryloquinyl group, and R1
and R4 each represent a group selected from an alkyl group substituted with a sulfonic acid group or a carboxyl group, or an aryl group substituted with a sulfonic acid group or a carboxyl group. ] General formula II) Cllz=C)ISOz(C)lx)IIIO(L 0
)p(CHz)nsOzcH=cHz [In the formula, L represents a divalent organic group, m and n represent a positive integer, and p represents 0 or l. ] Hereinafter, the details of the present invention will be specifically explained.

First, regarding formula CI), in the formula, R+ and R2 are each a carboxyl group, an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms), or a substituted alkyl group (preferably an alkyl group having 1 to 3 carbon atoms). Preferred substituents are halogen atoms, hydroxyl groups, etc.), aryl groups (preferably phenyl groups), alkoxycarbonyl groups (the alkyl moiety preferably has 1 to 3 carbon atoms), and aryloquine carbonyl groups (preferably phenyloxy groups). R1 and R1 each represent an alkyl group (carbonyl group) substituted with a sulfonic acid group or a carboxyl group (
Preferably an alkyl group having 1 to 3 carbon atoms) and a sulfonic acid group≠, 1. (1-sun Rokuru+: represents a group selected from aryl groups (preferably phenyl groups) substituted with Bankuru-myo.) Specific examples of the dye represented by the general formula [I] are listed below. The invention is not limited to this.

-1 The content of the dye of the present invention in the silver halide photographic light-sensitive material is preferably from l tag to 2 g per m'', more preferably from 5 mg to 1 g.

Further, the above dye is used by dissolving it in a suitable solvent, for example, water, alcohol such as haemethanol or ethanol, al, or a mixed solvent thereof and adding it to the coating solution for the hydrophilic colloid layer.

Further, these dyes may be mordanted with a cationic polymer or the like.

Next, general formula [II] will be explained.

In the formula, L represents a divalent organic group. m and n represent positive integers, and p represents 0 or l.

A more detailed explanation of the hardening agent used in the present invention is as follows:
- The divalent group represented by L in formula [II] is preferably an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, -o-, -s--5o-SO, - , -C-, or a divalent group made by combining two or more of these divalent groups are preferred. Both ends of the divalent group shown as (the part bonded to the different atom) are carbon atoms, and L may be substituted. n and m are preferably integers of 1 to 6, and ■ is particularly preferred.

Examples of hardeners used in the present invention are listed below, but the present invention is not limited thereto.

■ COx −Cl1SO*CHtOCHxSO2CB =
CHz■ 2 C11□-C)ISOzCH2CHiOC1lzCH2
SO2CH=CHz ■ CI , = CH30F (CH Raiba CHiηSO,C
H=CH.

■ CI, = CI! 502C820C) 12CH, 0C
H2SO, CH-CI.

■ CIl□= C11SO, CI (20CH2CI, CI
, QC) I, 5oICH= CH2■ 6 CI□” Cll5OzCHzOCHzCH20CH2
CH20CHZSO□CH=CH2■ CH2” CH30zCH2CH20CH2CHzOc
lI 2CH1s (hcH= CI□■ 1-9 The synthesis method of these hardening agents is described in Japanese Patent Publication No. 44-29622,
It is described in publications such as No. 47-24259 and No. 47-25373.

The amount of hardening agent used in the present invention can be selected arbitrarily depending on the purpose. Usually 0 for dry gelatin
．． It can be used in proportions ranging from 0.01 to 20 weight percent. Particular preference is given to using proportions ranging from 0.05 to 15 percent by weight.

The hardener of the present invention can be used in all black and white photographic materials that use gelatin. Examples include black-and-white photosensitive materials such as black-and-white photographic film, X-ray film, plate-making film, black-and-white photographic paper, aviation film, microfilm, facsimile film, and graph film.

In this case, there is no particular limitation on the photographic layer using the hardener of the present invention, including silver halide emulsion layers as well as non-photosensitive layers such as undercoat layers, back layers, filter layers, intermediate layers,
It can be used in gelatin-containing photographic layers such as overcoat layers.

The hardener of the present invention may be used alone, or two or more kinds of hardeners of the present invention may be used in combination. It may also be used in combination with other hardening agents known so far. Known hardeners include, for example, aldehyde compounds such as formaldehyde and glutaraldehyde;
bis(2-chloroethyljlWX), 2-hydroquine-
4,6-dichloro-1,3°5-triazine, etc. U.S. Pat. No. 3,288.775, U.S. Pat. No. 2,732.303
No. 974,723, British Patent No. 1.167207
Compounds containing reactive halogens, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-) riazine,
Other U.S. Patent Nos. 3,635.718 and 3.23
No. 2.763, compounds containing reactive olefins such as those described in British Patent No. 994,869, N-hydroxymethylphthalimide, and other U.S. Patent No. 2.7
N-methylol compounds described in US Pat. No. 32,316, US Pat. No. 2,586,168, etc., US Pat.
Examples include isocyanates and halogencarboxaldehydes such as mucochloric acid, which are described in , No. 437 and the like. Alternatively, there are chrome light pans and the like as hardeners made of inorganic compounds. In addition, compounds in the form of precursors instead of the above compounds, such as alkali metal bisulfite aldehyde adducts, methylol derivatives of hydantoin, primary aliphatic ditroalcohols, methyloxyethylsulfonyl compounds, chloroethylsulfonyl It may be used in combination with other compounds.

A compound that accelerates the hardening of gelatin can also be used together with the hardening agent of the present invention. For example, a polymer containing a sulfinic acid group described in JP-A-56-4141 may be used as a hardening agent in combination with the hardening agent of the present invention.

The gelatin to which the hardening agent of the present invention is applied is produced in the following manner: before gelatin extraction, so-called alkali-treated (lime-treated) gelatin is immersed in an alkaline bath, acid-treated gelatin is immersed in an acid bath, or both treatments. Any of double-soaked gelatin, hydrogen peroxide-treated gelatin, and carbon-treated gelatin may be used. Furthermore, the present hardening agent can also be applied to low molecular weight gelatin which has been partially hydrolyzed by heating the gelatin in a water bath or by treating it with a proteolytic enzyme.

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.

As the anionic surfactant particularly preferably used in the present invention, the following formula (nlA), (IIIB
], f:I[Ic) and ([I[D:l).

General formula (■A) J OCOCHi R, -〇〇〇-CIl-R General formula [1 [IB) R, -0CO-CI+□ R, -0CO-CH R, -0CO CIl Ry General formula (IIIC) General formula (ID) SOl In the above formula, Rl+Rz, R<, Ra, R6+Rh, R!
and R1° may be the same or different, and each represents a halogen atom, such as chlorine, bromine, or an alkyl group, such as methyl, ethyl, butyl, isobutyl, pentyl, hexyl, octyl, nonyl, denyl, dodenyl, 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, a bromine atom, etc., or an IJ-yl group, such as a phenyl group or a heptyl group. Further, R3 and R7 represent an alkali metal salt of a carboxyl group, a sulfo group, or a phosphonic acid group. nl and n2 represent integers of 1 to 3.

Specific compounds represented by formulas (III A) to (III D) are illustrated below, but the compounds of the present invention [
Compound Examples] ■-1 ShitIs ■ CHl ShiN1 ■ 11-4 +1l-5 CH.

1[+-6 -7- 1[1-9 ■ 0 CJ+ 100CCH2CHx csl(llooccl12cu SOsNa1[[
-11 III-12 Cs)l++oOc CHl CIIIH! I OOC (JI S03N&
-13 C)1. (CH2)3-00C-CI.

CH3(C)liri3 00C CI SOsNa
1 4 - 15 nl-16 m-17 ■ 8 C) I, (CH,), -0CO-CFI.

CI+3(C11,), -〇C0-Cl+CI+3(
C)12)7 0COC1I 5O1Nall-19 ■ -20 I[1-21 ■-22 2os C2+(.

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

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

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having the 0001 plane as the crystal surface. Also, U.S. Patent 4,
No. 183,756, No. 4,225,666, Japanese Unexamined Patent Publication No. 5
Specifications such as No. 5-26589 and Japanese Patent Publication No. 55-42737, The Journal on Photographic Science (J, Photogr, Sci), 2
Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literature such as 1.39 (1973) 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. A certain amount is preferable, particularly preferably 70% or more, and still more preferably 80% or more.

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

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

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

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

Here, the average particle diameter and particle diameter standard deviation shall be determined from ri defined above. The monodispersed emulsion is disclosed in Japanese Patent Application Laid-Open No. 5448521.
No. 58-49938 and No. 60-122935.

Although the photosensitive silver halide emulsion can be used as a so-called unripened (P-tive) emulsion without chemical sensitization, it is usually chemically sensitized.

For chemical sensitization, the Glafkides or Z
eltkman et al. or H., Fr1eser, ed.
eGrundlagen der Photograp
hischen Prozesse IIitSilb
Erhalogeniden, Akademich
e VerlagsgesellschafL, 196
The method described in 8) can be used.

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

As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, specific examples of which are described in U.S. Pat. No. 1,574.944.
No. 2,410,689, No. 2,278.947, No. 2,728,668, and No. 3,656.955. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidisulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in U.S. Pat. .97
No. 4, No. 2,518,698, No. 2,983.609
No. 2,983.610 and No. 2,694.637. For noble metal sensitization, in addition to total complex salts, complex salts of metals in group II of the periodic table, such as platinum, iridium, and palladium, can be used.
, No. 399,083, No. 2,448.060, British Patent No. 618.061, etc.

In addition, there are no particular restrictions on the conditions such as pH1pAg and temperature during chemical sensitization, but the pH value is preferably kept at 4 to 9, especially 5 to 8, and the pAg value is preferably kept at 5 to 11, especially 7 to 9. is preferred. 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 metal compound, and 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, and the like.

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

The 7% silver halide grains used in the emulsion of the present invention are formed by forming cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, Metal ions can be added using iron salts or complex salts to be included inside the particles and/or on the particle surface.

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 cyanine dyes, melonanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus,
Nuclei in which alicyclic hydrocarbon rings are fused to these nuclei, such as tetrazole nuclei and pyridine nuclei, and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, such as indolenine nuclei, benzindolenine nuclei, and indole nuclei. , benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

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

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

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 Patent No. 2.231.658, US Pat. No. 2,519,001, No. 2
, No. 912.329, No. 3,656゜956, No. 3,
No. 672,897, No. 3,694,217, No. 4.0
No. 25349, No. 4,046,572, British Patent 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. In addition, as sensitizing dyes used in green-sensitive silver halide emulsions, for example, US Pat.
No. 72,908, No. 2,739.149, No. 2,94
No. 5.763, British Patent No. 505.979, Special Publication No. 1973
Cyanine dyes such as those described in -42172, etc.
Representative examples include melonanine dyes and complex cyanine dyes. Further, as sensitizing dyes used in red-sensitive and infrared-sensitive silver halide emulsions, for example, U.S. Pat.
No. 0,378, No. 2,442,710, No. 2,454
, No. 629, No. 2,776.280, Special Publication No. 1977-1
No. 7725, JP-A-50-62425, JP-A No. 61-29
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in No. 836 and No. 60-80841.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are used particularly for the purpose of supersensitization. Typical examples are U.S. Patent Nos. 2,688,545, 2.977.229, and 3
, No. 397,060, No. 3, No. 522, No. 052, No. 3,527,641, No. 3,617,293, No. 3
, No. 628,964, No. 3,666.480, No. 3.
672.898, 3.679,428, 3.7
03゜377, 3.769,301, 3.81
No. 4.609, No. 3,837゜862, No. 4.026
．． 707, British Patent No. 1,344.281, 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, cyanine dyes, azo dyes, and the like. Among them, oxanol dyes; hemioxanol dyes and melonanine dyes are useful.

In the silver halide photographic light-sensitive 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. Namely, azoles such as penzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted), heterocyclic mercaguto compounds such as mercaptothiazoles, mercaptobenzimidazoles. , mercaptodeazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetracil), mercaptopyridines, the above-mentioned heterocycles containing a water-soluble group such as a carboxyl group or a sulfone group, mercapto compounds, thioketo Compounds known as stabilizers such as oxazolinthione, azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7)tetrazaindenes), benzenethiosulfonic acids, benzenesulfinic acids, etc. Many other compounds can be added.

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

For more detailed examples and other methods of use, see, for example, U.S. Pat.
No. 82.947, No. 4,021.248 or Tokuko Sho 5
The description in No. 2-28660 can be referred to.

Further, the silver halide photographic light-sensitive material of the present invention has U.S. Pat. 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, U.S. Pat.
No. 15, Belgian Patent No. 762.833, US Patent No. 3
, No. 767.410 and Belgian Patent No. 588,143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardeners include aldehyde-based, epoxy-based, Various hardeners and ultraviolet absorbers such as ethyleneimine, active halogen, vinyl sulfone, isonanate, sulfonic acid ester, carbodiimide, mucochloric acid, and acyloyl include, for example, U.S. Pat. No. 3,253,92.
No. 1, British Patent No. 1,309,349, etc., particularly 2-(2'-hydroxy-5
-tertiary butylphenyl)benzotriazole, 2-(2
'-Hydroxy/-3',5'-di-tert-butyl7enyl)benzotriazole, 2-(2'-hydroxy-3'
-3kJltphthyl-5'-butylphenyl)-5-chlorobenzo] lyazole, 2-(2'-hydroxy/-
Examples include 3',5'-di-tertiary butylphenyl 15-chlorobenzotriazole. Further, coating aids, emulsifiers, permeability improvers for liquid liquids, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials are described in British Patent No. 548.
No. 532, No. 1,216,389, U.S. Patent No. 2,02
No. 6,202, No. 3,514,293, Special Publication No. 1977-
No. 26580, No. 43-17922, No. 43-179
No. 26, No. 43-3166, No. 48-20785,
French Painting Patent No. 202,588, Belgian Patent No. 773,4
Anionic, cationic, nonionic or amphoteric compounds described in No. 59, JP-A No. 48101118, etc. can be used, and among these, anionic surfactants having a sulfone group, e.g. Preferred are succinic acid ester sulfonates, alkylbenzene sulfonates, and the like. In addition, as an antistatic agent, Japanese Patent Publication No. 46-241
No. 59, JP-A-48-89979, U.S. Patent No. 2,88
No. 2.157, No. 2,972.535, Japanese Unexamined Patent Publication No. 1972-
No. 20785, No. 48-43130, No. 48-903
No. 91, Special Publication No. 46-24159, No. 46-3931
No. 2, No. 48-43809, JP-A-47-33627
There are compounds described in each publication.

In the manufacturing method of the present invention, the pH of the coating liquid is 5.3 to 7.
．． It is preferable that it is in the range of 5. For multi-layer coating,
It is preferable that the pH of the coating liquid obtained by mixing the coating liquids for each layer in the ratio of coating amounts is within the above range of 5.3 to 7.5. If the 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.
．． Inorganic particles such as alkaline earth metals or carbonates such as cadmium, zinc, etc. as described in US Pat. No. 173.181; starch as described in US Pat. No. 2,322,037;
Starch derivatives described in No. 5,451 or British Patent No. 981.198, polyvinyl alcohol described in Japanese Patent Publication No. 3643/1983, polystyrene or polymethyl methacrylate described in Swiss Patent No. 330.158, and US Pat. , 079,257, and polycarbonate described in US Pat. No. 3,022,169.

In the photosensitive material of the present invention, the constituent layers may contain slipping agents, such as those described in U.S. Pat.
higher alcohol esters of higher aliphatics as described in 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 Volume 176 r tem
17643 (December 1978) and volume 187■t
ea+18716 (November 1979), and in carrying out the silver halide photographic photosensitive material of the present invention, for example, the emulsion layer and other layers are formed on a flexible support commonly used in photographic photosensitive materials. Useful flexible supports include cellulose nitrate, cellulose acetate, cellulose acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc. These include films made of synthetic or synthetic polymers, papers coated with or laminated with baryta layers, or σ-olefin polymers (e.g., polyethylene, polypropylene, ethylene/butene copolymers), etc. The support is coated with or laminated with dyes or pigments. It may be colored.It may be made black for the purpose of blocking light.The surface of these supports is generally subjected to an undercoating treatment to improve adhesion with an emulsion layer, etc.The undercoating treatment is described in Japanese Patent Application Laid-Open No. 1983-1999. 1049
], No. 3, No. 59-18949, No. 59-19940
No. 59-18949 are preferred.

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

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

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

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

The dihydroxybenzene developing agent used in the present invention includes hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-
Examples include dichlorohydroquinone, 2.3-dibromohydroquinone, and 2.5-dimethylhydroquinone, with hydroquinone being particularly preferred.

As the developing agent for 1-phenyl-3-pyrazolidone or haso(7) derivative used in the present invention, l-phenyl-4,
4-dimethyl-3-pyrazolidone, l-7enyl-4-
Methyl-4-hydroxymethyl-3-pyrazolidone, l
-phenyl-4,4-dihydroxymethyl-3-pyrazolidone and the like.

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

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

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. Ai
The acid salt is preferably 0.2 mol/Q or more, particularly 0.4 mol/a or more. Further, the upper limit is preferably 2.5 mol/α.

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

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

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

Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide:
Organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methylceasolve, hexylene glycol, nitinol, methanol = 1-phenyl-5-mercaptotetrazole, 2-j Irecabutobenzimidazole-5-
Mercagt compounds such as sulfonic acid sodium salt, 5-
It may also contain an antifoggant such as an indazole compound such as nito-a indazole, a pentztriazole compound such as 5-methylbenztriazole, and if necessary, a color toning agent, a surfactant, an antifoaming agent, and a water softener. , Japanese Patent Publication No. 5
The amino compound described in No. 6-106244 may also be included.

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

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

In addition, F. A. Meson, Photographic Brosesin Society Chemistry, published by Focal Press (L, F.
, A MASON, Photogral) hic Pr
ocessing Chemistry, Focal
Press, London) (1966) No. 2
Those described in pages 26 to 229, U.S. Pat.

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

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

In addition, "drying time" refers to a drying sheet that is usually blown with hot air at 35°C - 100°C, preferably 40°C to 80°C. This refers to the time you are in the 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, and has a pit of 3.8.
2, preferably 4.2 to 5.5.

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

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

The fixing solution may include 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 0.603 mol/Q.

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

The fixing solution may optionally contain preservatives (e.g. sulfites, bisulfites), pH balancers (e.g. acetic acid, nitric a), pH adjusters (e.g. sulfuric acid), chelating agents with hard water softening ability, and special agents. The compound described in Application No. 60-213562 may be included.

Fixing temperature and time are approximately 20°C to approximately 50°C for 6 seconds to 1
6 seconds to 30 seconds at 30°C to 40°C, more preferably 30'C! 6 at ~40°C
seconds to 15 seconds.

The fixer concentrate is exposed to light (
Most preferably, the fixer concentrate is one-part, as is the case with the developer, if it is replenished with water to dilute it as the image is processed.

The fixer lyophilic agent can stably exist at pH 4,
5 or more, more preferably pH 4.65 or more. This is because if the pH is less than 4.5, the thiosulfate will decompose and eventually become sulfurized, especially if the fixer is left for a long period of time before it is actually used. Therefore pH 4,5
In the above range, the generation of sulfur dioxide gas is reduced, and the environment for growing vegetables is also improved. The upper limit of 9H is not that strict or too high p
If the film is fixed with H, even if it is washed with water thereafter, the membrane pH will become high and the membrane will swell or become dry, thus increasing the drying load, so the pH is limited to about 7. In fixing solutions that use aluminum salts to harden the film, the pH level is low to prevent precipitation of aluminum salts.
The limit is up to 5.5.

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

The amount of each concentrate supplied to the processing tank liquid and the mixing ratio with dilution water can be varied depending on the composition of the concentrate, but generally the ratio of concentrate to dilution water is 1:0 to 8. The total amount of each of the developer and fixer is preferably 50+nQ to 1500 mc per 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 reducing the amount of replenishment to less than 3Q per 1 m2 of photosensitive material, but it also eliminates the need for piping for installing an automatic processing machine. Furthermore, the number of stock tanks can be reduced.

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.

When water treated with anti-mildew measures is used in combination with washing water or stabilizing liquid, the formation of lime scale can be effectively prevented.
Water saving treatment of 0 to 312, preferably 0-IQl per fi2 can be performed.

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 counter-current method is applied to the present invention, the photosensitive material in the fixer will gradually come into contact with the processing solution in a cleaner direction, that is, the processing solution that is not contaminated with the fixer, and will be more efficient. Washing is done. According to this, unstable thiosulfates and the like are appropriately removed, the possibility of discoloration and fading is further reduced, and an even more significant stabilizing effect can be obtained. The amount of water used for washing is also much smaller compared to conventional methods.

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

Further, part or all of the overflow liquid from the washing or stabilizing bath, which is generated by replenishing the washing or stabilizing bath with anti-mold water depending on the treatment, is disclosed in Japanese Patent Application Laid-Open No. 60-23
As described in No. 5133, it can also be used in a processing solution having fixing ability in the previous geographical step. This is more preferable because the stock water can be saved and the amount of waste liquid can be reduced.

As anti-mildew methods, the ultraviolet irradiation method described in JP-A No. 60-263939, the method using a magnetic field described in JP-A No. 60-263,940, and the ion exchange resin described in JP-A No. 61-131632 are used. A method of purifying water by using
-253807, 60-295894, 61-
The method using the antibacterial agent described in No. 63030 and No. 61-51396 can be used.

Furthermore, L, Elest “Water Qualit”
y Cr1teriaPhoto Sci & Eng
, Vol. 9 No. 6 (1965), M.W.B.
each ”Microbiological Gro
wths in Motion-PieLure Pr
ocessing'''SMPTE Journal V
ol, 85. (1976)-R, O, Deegan,
”Photo Processing Wash Wa
terBiocides” J, 1maging Te
ch, Vol 10. No. 6 (1984) and Japanese Patent Application Publication Nos. 57-8542, 57-58143, and 58-
No. 105145, No. 57-132146, No. 58-1
No. 8631, No. 57-97530, No. 57-1572
Antibacterial agents, anti-inflammatory agents, surfactants, etc. described in No. 44 and the like can also be used in combination.

Furthermore, for the washing bath, R, T, Kreiman, J, 1 ma.
RESEARCH, an inthiazoline compound described in GE, Techlo, (6) 242 (1984)
DISCLO3URE Volume 205, Item 20526
(May issue, 1981), Volume 228, Ite+1122845 (
Isothiazoline compounds described in Japanese Patent Application No. 1983-51396 (April issue, 1983), compounds described in Japanese Patent Application No. 61-51396, etc. can also be used in combination as microbiocides.

Furthermore, specific examples of anti-piping agents include phenol, 4-chlorophenol, pentachlorophenol, cresol,
o-phenylphenol, chloro7ene, dichlorophene, formaldehyde, cultaraldehyde, chloracetamide, p-hydroxybenzoic acid ester, 2-
(4-Thiazoline)-benzimidazole, benzisothiazolin-3-one, dodenlupendyl-dimethylammonium chloride, N-(fluorodichloromethylthio)-phthalimide, 2,4.4'-)dichloro-2fuhydroxydif Al with enyl ether etc.

It is preferable that the water treated with anti-mildew means and stored in the water stock tank be used both as dilution water for the undiluted solutions of processing solutions such as the developer and fixer and as washing water, since this requires less space. However, dilution water and washing water that have been treated with anti-mildew measures (
(or stabilizing liquid) can be stored separately in separate tanks, or only one of them can be taken directly from the tap.

When stored separately in separate tanks, the washing water (or stabilization bath) can contain various additives in addition to applying anti-mildew measures such as those of the present invention.

For example, the chelate stability logK value with aluminum is 1
Zero or more chelate compounds may be included. These are effective in preventing scuttling in washing water when the fixing solution contains an aluminum compound as a hardening agent.

Specific examples of chelating agents include ethylenediaminetetraacetic acid (IogK16.l, the same applies hereinafter), cyclohexanediaminetetraacetic acid (17,6), diaminoglobanoltetraacetic acid (13,8), diethylenetriaminepentaacetic acid (18,4
) Triethylenetetraminehexaacetic acid (19,7), etc., and their sodium salts, potassium salts, and ammonium salts, and the amount added is preferably 0.01 to 1Og/Q1
More preferably 0.1 to 5 gIQ.

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. pH 3
~8) various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid) Typical examples include aldehydes such as (used in combination) and formalin.

In addition, various additives such as chelating agents, bactericidal agents (thiazole type, inthiazole 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 15°C to 40°C
6 seconds to 30 seconds at °C, more preferably 15 °C
6 to 15 seconds at ~40°C is preferred.

According to the method of the present invention, the developed, fixed and washed photographic material is dried by squeezing out the washing water, ie by using a squeeze roller method. Drying is approximately 40°C to approximately 100°C
The drying time may be changed as appropriate depending on the surrounding conditions, but is usually about 5 seconds to 1 minute, more preferably about 5 seconds to 30 seconds at 406°C to 80°C.

The present invention exhibits a further advantageous effect in that the drying time of the light-sensitive material can be shortened as the swelling percentage of the light-sensitive material is reduced.

According to the method of the present invention, development, fixing, washing and drying can be carried out.
The so-called Dry to Dry processing time is within 100 seconds, preferably within 60 seconds, and more preferably within 45 seconds.
It is to be processed within 0 seconds.

Dry to dry means that from the moment the tip of the photosensitive material to be processed enters the film insertion section of the processor,
This refers to the time from when the tip is processed until the moment when the tip comes out of the processor.

〔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, 80 mg/+o'' of the dye of the present invention was added as shown in Table 1, and 2 ( Ig, 1 g of those shown in Table 1, 20 g of a copolymer of butyl acrylate and vinylidene chloride as a polymeric latex, 2.5 g of a styrene-maleic anhydride copolymer as a thickener, and 2.5 g of a copolymer of styrene-maleic anhydride as a hardening agent. It was prepared by adding the compound of the general formula [■] shown in 1.

(Preparation of back upper layer coating solution) After dissolving 400 g of gelatin in 600 mC of water, 20 g of polymethyl methacrylate with an average particle size of 4 μm was added as a capping agent, and 3 g of the anionic surfactant shown in Table 1 was added. It was prepared by

(Preparation of coating solution for emulsion layer) In a solution containing gelatin, sodium chloride, and water kept at 40°C, an aqueous silver nitrate solution and 2 x 10-' mol of potassium hexachloroiridate per mol of silver halide are added. and a mixed aqueous solution of potassium bromide and sodium chloride to which 4 x 10-' hexabromorodium salt was added using a double jet method to obtain 35 mol% silver bromide.
Containing silver chlorobromide particles (width of distribution 9%, cubic crystal, grain size 0.
35 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, 150 mg of the following ortho-sensitizing dye was added per mole of silver halide, and further 70 mg of 1-phenyl-5-mercaptotetrazole and 4-hydroquine-6 were added per mole of silver halide. Methyl-1
．． 3.3a, 1.2 g of 7-chitrazaindene and gelatin were added to stop the ripening, and then 4 g of hydroquinone was added.
g, 2 g of phenidone, 3 g of potassium bromide, 5 g of saponin, 2 g of styrene-maleic acid polymer as a thickener.
g, high molecular weight polymer latex of ethyl acrylate 3
Formalin and 2-hydroxy-4,6 as g1 hardening agents
-Dichloro-1,3,5-3-triazine sodium salt was added.

Sensitizing dye (preparation of protective film for emulsion layer) 10 g of potassium bromide was added to an aqueous solution of 500 g of gelatin, and 1-decyl-2-(3
-Isopentyl) succinate-2-sulfonate (4g) was added, and 1 amorphous silica with an average particle size of 5μm was added.
00g was added and dispersed to prepare.

2. Apply the bottom layer on the back side onto a 100 μm thick polyethylene terephthalate base that has been undercoated using the above coating solution.
6 g/I11", the top layer was coated simultaneously with a gelatin loading of 1.3 g/m", and then on the side opposite to the back layer, the silver amount was 3.8 g10+2, and the gelatin emulsion layer was coated with a gelatin loading of 1.4 g/m". Interest 2
The emulsion layer and the protective layer were simultaneously coated in such a manner that the protective film layer OJg/w''.

The samples thus obtained were processed using a developing solution and a fixing solution having the following compositions in an ordinary roller type automatic developing machine under the following conditions, and evaluation of residual color and scratches was performed. Residual color and scratches are evaluated in 10 stages. IO is the best,
Levels 1 to 4 are unusable, and levels 5 and above are usable.

In order to examine the stability of the above sample over time, it was made of polyvinyl acetate with a thickness of 100 μm after being conditioned at 23° C. and relative humidity of 48%. Sealed packaging with laminated moisture proofing agent, 40°C
Heat treatment was performed for 10 days in a constant temperature bath. This sample and the frozen sample were passed through an optical wedge and a 670 nm interference filter, and then treated with 7 mL of xenon. After exposure to flash light for OX 10-' seconds, the samples were processed in the same manner under the following conditions and evaluated in terms of relative sensitivity.

To check the adhesion, after adjusting the humidity at 23°C and 80% relative humidity, 10 sheets of the same sample were stacked and sealed, a pressure of 100g per lctn2 was applied, and the temperature was left at 40°C for 24 hours. ) was evaluated on a five-point scale. 5 is the best,
Levels 1 to 2 were considered unusable, and levels 3 and above were usable.

The surfactant (a) and hardener (b) used for comparison are shown below.

(a) (b) 1-+2C=CH5O□CJbCHC1+2SOzCH
=CH2H Development processing was performed under the following conditions.

(Development processing conditions) (Process) (Temperature) (Time) Development
38°0 12 seconds fixation 36°0
Wash with water for 10 seconds Regular @ Dry for 8 seconds 50°C 10 seconds Dry to Dry 45 seconds Developer composition (composition A) Pure water (ion-exchanged water) 150 mQ ethylenediaminetetraacetic acid disodium salt g Diethylene glycol 50 g Potassium sulfite (55% v/v aqueous solution) ) 100 m (potassium dicarbonate 50 g hydroquinone 15 g 5-methylbenzotriazole 200 mg 1-phenyl-5-mercaptotetrazole 0 ig p after using potassium hydroxide) (amount to make 11.5 Potassium bromide 3 g (composition) Pure water (ion Exchange water) 3mQ diethylene glycol 50g noethylamino-1,2-propanediol 5g ethylenediaminetetraacetic acid disodium salt 5mg acetic acid (90% aqueous solution) 0.3m
Q5-21-loindazole 110m
g1-phenyl-3-pyrazolidone 500
When using a mg developer, the above composition A was dissolved in water 5001 in that order, and the composition was finished to IQ.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) Sodium sulfite Sodium acetate, trihydrate Borate Sodium citrate, Trihydrate acetic acid (90% v/v aqueous solution) (Composition) Pure water (Ion exchange water) Sulfuric acid (50% w/v aqueous solution) Aluminum sulfate (AQ20. converted content 8.1% v/v aqueous solution) 40
m0 7g 6.58 g g 13.6a+ρ 17tr+Q 4.7g 26.5g For use as a fixer, the above composition A1 was dissolved in 500 mff of water in the order of composition and finished to IQ. p of this constant R solution
I-1 was about 4.3.

The results are shown in Table 1.

From the results in Table 1, compared to the comparative example, the sample of the present invention (remaining color,
Preservation Example 2 The following sample was prepared by changing one part of the additives from Example I.

(Preparation of coating solution for back lower layer) After dissolving 500g of gelatin in 8Q water, 150+ng/+a2 of the following dye was added, and 2g of saponin as a surfactant.
g.

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.

Dye (Preparation of back side upper layer coating solution) After dissolving 400 g of gelatin in 600 m of water, 20 g of polymethyl methacrylate with an average particle size of 4 μm as a capping agent, 1 l-decyl 2- as an anionic surfactant.
It was prepared by adding 4g of sodium (3-inpentyl)succinate-2-sulfonate.

(Preparation of coating solution for emulsion layer) In a solution containing gelatin, sodium chloride, and water kept at 40°C, an aqueous solution of silver nitrate and 1 mole of silver halide are added. A mixed aqueous solution of potassium bromide and sodium chloride to which potassium iridate salt and 4 x 10-' hexabromorodium salt had been added was added by a double jet method to obtain 28% silver bromide.
Silver chlorobromide particles containing mol% (width of distribution 12%, cubic crystal,
Particle size 0.25μ11) was prepared while maintaining pH 3.0 and pAg 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, and 150 mg of the same sensitizing dye as in Example 1 was added per mole of silver halide, and 70 mg of ■-phenyl-5-meJrecaptotetrazole was added per mole of silver halide. 1.2 g of 4-hydroxy-6methyl-1.3.3a,7-chitrazaindene,
After adding gelatin to stop ripening, add 4 g of hydroquinone, 3 g of potassium bromide, 5 g of saponin as a thickener, 2 g of styrene-malein strict polymer, 3 g of ethyl acrylate polymer latex as a hardening agent. It was prepared by adding the ingredients shown in Table 1.

Sensitizing dye (preparation of protective film for emulsion layer) 10 g of potassium bromide was added to an aqueous solution of 500 g of gelatin, and 100 mg/s of the dye of the present invention was added as shown in Table 1. What is shown in 4
100 g of amorphous Nrica with an average particle size of 5 μm.
g was added, dispersed, and prepared.

A support was coated using the above coating liquid in the same manner as in Example 1.

This sample was treated and evaluated in the same manner as in Example 1 using a 488 nm interference filter.

The results are shown in Table 2.

(Effects of the Invention) According to the present invention, it was possible to provide a silver halide photographic light-sensitive material that has excellent residual color and scratch resistance even when subjected to rapid drying, and also has good adhesiveness and storage stability over time.

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, at least one layer in the silver halide photographic material has the following general formula [I ] and at least one anionic surfactant, and is cured with a hardener represented by the following general formula [II]. Silver chemical photographic material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_2 are carboxyl groups,
Represents a group selected from an alkyl group, an aryl group, an alkoxycarbonyl group or an aryloxycarbonyl group,
R_3 and R_4 each represent a group selected from an alkyl group substituted with a sulfonic acid group or a carboxyl group, or an aryl group substituted with a sulfonic acid group or a carboxyl group. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, L represents a divalent organic group, m and n represent positive integers, and p represents 0 or 1. ]