JPH03223746A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve adhesiveness and preservable property with lapse of time by incorporating specific dyes and anionic surfactants into at least one layer and hardening the photosensitive material by a specific hardener. CONSTITUTION:At least one kind of the dyes expressed by formula I and at least one kind of the anionic surfactants are incorporated into at least one layer of the silver halide photographic sensitive material and the material is hardened by the hardener expressed by formula II. In the formula I, R1 and R2 denote an alkyl group, aralkyl group, etc.; R2, R4 denote an alkyl group, -COOR6, -SO2NR6R7, etc.; L1, L2, L3 respectively denote a methine group; M denotes hydrogen or other cation. In the formula II, L denotes a bivalent org. group; (m), (n) denote positive integer; (p) denotes 0 or 1. The after-color and the resistance to flawing by rubbing are improved in this way; in addition, the adhesiveness and the preservable property with lapse of age are improved as well.

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 and 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 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.

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

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

However, in order to achieve rapid processing, a photosensitive material is required that has excellent developability, 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 leaves little residual color even when ultra-quick processing is performed, does not cause scratches or adhesion between photosensitive materials due to storage, and has excellent storage stability over time. 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 general formula CI ) and at least one anionic surfactant, and is cured with a hardening agent represented by the following general formula [II]. In the formula CI), R8 and R1 each represent an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group having at least one sulfonic acid group or carboxylic acid group; The acid group may be bonded to an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group via a divalent linking group. R
1, R4- is each an alkyl group, COORa, C
0NRsRy, -NRsRy.

NRmCORs, NR5C0NRaRy, -CN,
ORs, C0R5゜SO! Representing R1,5ORi or -5OxNRaRy, R is an alkyl group,
It represents an aralkyl group or an aryl group, and Ri and Rt each represent a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and R and RT may be connected to form a 5- or 6-membered ring. ), L t, L t, and L x each represent a methine group, and M is the water general formula (n) CHz=CH3O*(C)It)110'(L 0
)p(CHz)nso, CB-CH! In the formula, L represents a divalent organic group, m and n represent positive integers, and p represents 0 or l.

The present invention will be specifically explained below.

First, the compound represented by general formula (1) will be explained in detail.

The carposi acid group or sulfonic acid group having an aryl group, aralkyl group, alkyl group, or heterocyclic group in R9 and R3 not only directly bonds to the aryl group, aralkyl group, alkyl group, or heterocyclic group, but also forms a divalent linkage. groups (e.g. alkylene amino groups (e.g. 2-sulfoethylamino,
3-sulfoethylamino, 2-carboxyethylamino), alkyleneoxy groups (e.g. 2-carboxyethoxy, 4-sulfobutoxy), alkyleneacylamino groups (e.g. β-carboxypropionylamino), phenylene groups (e.g. 0-flufophenyl) etc.).

The aryl group, aralkyl group, alkyl group, or heterocyclic group in R2 and R1 is a substituent other than carboxylic acid or sulfonic acid (for example, a halogen atom such as fluorine, chlorine, or bromine,
Hydroxyl group, cyano group, nitro group, alkyl group having 1 to 4 carbon atoms (e.g. methyl, ethyl, isopropyl, n-butyl), aryl group (e.g. phenyl, naphthyl), alkoxy group having 1 to 6 carbon atoms (e.g. methoxy, Ethoxy, n-
butoxy, 2-methoxyethoxy, 2-hytomoxyethoxy), an aryloxy group (eg, phenoxy), an amino group (eg, dimethylamino, diethylamino), an acylamino group (eg, acetylamino), etc.).

The aryl group in R1 and R3 is a phenyl group having at least one carboxylic acid group or sulfonic acid group (e.g. 4-sulfophenyl, 4-carboxyphenyl, 2.
Methyl-4-sulfophenyl, 3-sulfophenyl, 2
14-disulfophenyl, 3.5-disulfophenyl,
2-chloro-4-sulfophenyl, 2-methoxy-4-
Sulfophenyl, 4-chloro-3-sulfophenyl, 2
-methoxy-5-sulfophenyl, 2-hydroxy, 4
-sulfophenyl, 2,5-dichloro-4-sulfophenyl, 4-phenoxy-3-sulfophenyl, 4-(3
-sulfopropyloxy)phenyl, 4-(N-methyl-N-sulfoethylamino)phenyl, 3-carboxy-2-hydroxy-5-sulfophenyl, 2,6-diethyl4-sulfophenyl) or naphthyl group ( For example, 3,6-disulfo-α-naphthyl, 8-hydroxy 3°6-disulfo-α-7tyl, 5-human axy-7-sulfo-β-naphthyl, 6,8-disulfo-β-naphthyl) is preferred.

The aralkyl group in R1 and R1 has at least one carboxylic acid group or sulfonic acid group and has 7 to 15 carbon atoms.
aralkyl groups (e.g., 4-sulfobenzyl, 2-sulfobenzyl, 2,4-disulfobenzyl, 2-(4
-sulfobutyloxy)benzyl, 4-methyl-2-sulfobenzyl, 4-sulfophenethyl, 4-carpoxybenzyl, 2,4-di(3-sulfopropyloxy)
benzyl, 2-human axy-4-(2-sulfoethoxy)benzyl) is preferred.

The alkyl group in R1 and R1 is an alkyl group having 1 to 6 carbon atoms and having at least one carboxylic acid group or sulfonic acid group (e.g., sulfomethyl, carboxymethyl, 2-sulfoethyl, 2-carboxyethyl, 3-sulfopropyl). , 3-sulfo-2-methylglobil, 3-sulfo-2,2-dimethylpropyl, 4-sulfoptyl,
4-carboxybutyl, 5-sulfopentyl, 6-sulfohexyl, 5-carboxypentyl, 6-carboxyhexyl The heterocyclic group in R1 and R has at least one carboxylic acid group or sulfonic acid group, and at least 1
5- or 6-membered nitrogen-containing heterocyclic group having 5 nitrogen atoms (e.g. 5-sulfopyridin-2-yl, 5-carboxypyridin-2-yl, 6-sulfoquinolin-2-yl, 6
-Sulfoquinolin-4-yl, 5-sulfobenzothiazol-2-yl, 5-carboxybenzothiazol-2
-yl, 6-sulfobenzoxazol-2-yl, 6
-Carboxybenzoxazol-2-yl, 6-sulfomethylpyridin-2-yl, 5-sulfopyrimidine-
2.il) is preferred.

The alkyl group in R or R is a substituent (for example, a halogen atom such as fluorine or chlorine, a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an alkoxy group having 1 to 6 carbon atoms (for example, methoxy, ethoxy, n-butoxy), cyano group, amino group (e.g. dimethylamino, diethylamino)), and an alkyl group having 1 to 8 carbon atoms (e.g. methyl, ethyl, n-propyl, inpropyl, -butyl,
SeG-butyl, t-butyl, isobutyl, n-pentyl, sec-pentyl, isoamyl, n-hexyl,
n-heptyl, n-octyl, 2-ethylhexyl, 2
-ethylbutyl, trifluoromethyl, 2-chloroethyl, 2-hydroxyethyl, 4-hydroxybutyl, 5
-Hydroxypentyl, 6-hydroxyhexyl, 7-
Hydroxypentyl, 2-sulfoethyl, 2-carboxyethyl, 4-sulfobutyl, 2-cyanoethyl, 4-
Dimethylaminobutyl, ) or alicyclic alkyl groups having 5 to 7 carbon atoms (eg, cyclopentyl, cyclohexyl) are preferred.

R-R. Or the alkyl group in R7 is a substituent (for example, a halogen atom such as fluorine or chlorine, a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an alkoxy group having 1 to 6 carbon atoms (for example, methoxy, ethoxy, n-butoxy), a cyan group, amino group (e.g. dimethylamino, diethylamino)), and an alkyl group having 1 to 8 carbon atoms (e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, [-butyl, Isobutyl, n-
Pentyl, 5eC-pentyl, inamyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, 2-ethylbutyl, trifluoromethyl, 2-chloroethyl, 2-hydroxyethyl, 4-hydroxybutyl, 5-hydroxypentyl , 6-hydroxyhexyl, 7-hydroxypentyl, 2-sulfoethyl, 2-carboxyethyl, 4-sulfobutyl, 2-cyanoethyl, 4-dimethylaminobutyl, ) or aliphatic alkyl groups having 5 to 7 carbon atoms (e.g. cyclopentyl, cyclohexyl) is preferred.

The aralkyl group in R, R, or R7 is a substituent (e.g., a halogen atom such as fluorine or chlorine, a hydroxyl group, a sulfonic acid group, a carboxylic acid group, an alkyl group having 1 to 4 carbon atoms (e.g., methyl, ethyl, n-propyl), , lobutyl), alkoxy groups having 1 to 6 carbon atoms (e.g. methoxy, ethoxy,
n-butoxy), cyano group, nitro group, alkoxycarbonyl group (e.g. carbetoxy, methoxy, carbonyl), amino group (e.g. dimethylamino), diethylamino)), and has 7 to 15 carbon atoms. Aralkyl groups (eg evahensyl, phenethyl, 4-methylbenzyl, 2-chlorobenzyl, 4-methoxybenzyl) are preferred.

The aryl group in R6 or R7 is a substituent (e.g., a halogen atom such as fluorine or chlorine, a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an alkyl group having 1 to 4 carbon atoms (e.g., methyl, ethyl, isopropyl, n-propyl) , n-butyl), alkoxy groups having 1 to 6 carbon atoms (e.g. methoxy,
ethoxy, n-butoxy), cyano group, nitro group, alkoxycarbonyl group (e.g. carbetoxy, methoxycarboxyl), amino group (e.g. dimethylamino), diethylamino)), phenyl group (e.g. unsubstituted phenyl group, 3-sulfophenyl, 4-sulfophenylxyphenyl, 2-hydroxyphenyl, 2-sulfophenyl, 4-cyanophenyl, 3.4-dichlorophenyl, 4-methoxyphenyl, 4-(3-sulfophenyl) propoxy)phenyl, 4-nitrophenyl, 4-carbetoxyphenyl, 4-methylphenyl, 2-methylphenyl,
4-fluorophenyl) or naphthyl group are preferred.

R. , R, are linked to form a 5- or 6-membered ring such as a pyrrolidine ring, a piperidine ring, or a morpholine ring.

The methine group in Ll, Ll, LSs is a substituent (e.g. methyl, ethyl, sulfoethyl, chlorine atom, cyano, etc.)
It may have.

As cations other than hydrogen in M@, metal ions (eg Na'', K2 or inorganic or organic ammonium ions (eg NH.'', (C*Hi)xNH''pyridinium) are preferred.

In the above general formula [1], the carboxylic acid group or sulfonic acid group may be a free acid or a salt (for example, Na salt, K salt, (C2H
4) 3N) I salt, pyridinium salt, ammonium salt, etc.)
may be formed.

In the above general formula CI), preferred are R, and R
, is a phenyl group having at least one sulfonic acid group,
It represents an alkyl group having 1 to 4 carbon atoms having at least one sulfonic acid group, or a benzyl group or phenethyl group having at least one sulfonic acid group.

The method for producing the oxonol dye of the present invention is disclosed in Japanese Patent Publication No. 43
-3504, JP-A-49-99620, JP-A-49-Sho.
-5125, U.S. Pat.
5-on is disclosed in Japanese Patent Application Laid-open No. 62-273527 or Heterocyclic
Hunbound: Pyrazolone, Pyrazolidone and Privatib (HeterocyclicCotspou)
nds: Pyrazolones, Pyraza
lidenes and DerivativesX Interscience Paprisi! It can be synthesized by the method described by John Wiley and Thump, New York, 1964).

When using the dye represented by general formula [I] as a filter dye, anti-irradiation dye or antihalation dye, any effective amount can be used;
It is preferable to use it so that the optical density is in the range of O.OS to 3.0. The addition time may be any step before coating.

The dyes according to the invention can be dispersed in emulsion layers and other hydrophilic colloid layers (interlayers, protective layers, antihalation layers, filter layers, etc.) by various known methods.

(2) A method in which the dye of the present invention is directly dissolved or dispersed in an emulsion layer or a hydrophilic colloid layer, or a method in which the dye of the present invention is dissolved or dispersed in an aqueous solution or solvent and then used in an emulsion layer or a hydrophilic colloid layer. Suitable solvents, such as methyl alcohol, ethyl alcohol, propyl alcohol, methylcellosolve, JP-A-48-9715, U.S. Pat. No. 3,75
It can also be added to the emulsion in the form of a solution dissolved in a halogenated alcohol, acetone, water, pyridine, etc., or a mixed solvent thereof, as described in No. 6,830.

■ A method in which a hydrophilic polymer with a charge opposite to that of the dye ions is made to coexist in the layer as a mordant, and this interacts with the dye molecules to localize the dye in a specific layer.

The polymer mordant is a polymer containing a secondary and tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing a quaternary cation group, and a molecular weight of 5,000 or more, particularly preferably 1,000 or more. be.

For example, vinyl pyridine polymers and vinyl pyridinium cationic polymers disclosed in US Pat. No. 2,548.564; vinyl imidazolium cationic polymers disclosed in US Pat. No. 4,124.386; US Pat. , 625.694, etc.; aqueous sol mordant type disclosed in U.S. Pat. No. 3,958,995, JP-A No. 115228/1983, etc.; US patent 3
, 898.088; reactive mordants capable of covalently bonding with dyes as disclosed in U.S. Pat. No. 4,168,976; British Patent No. 685,475; Polymers derived from ethylenically unsaturated compounds having dialkylaminoalkyl ester residues as described; products obtained by reaction of polyvinyl alkyl ketones with aminoguanidine as described in British Patent No. 850,281: Mention may be made, for example, of polymers derived from 2-methyl-1-vinylimidazole as described in US Pat. No. 3,445,231.

■ A method of dissolving a compound using a surfactant.

Useful surfactants include oligomers.Next, general formula (If) 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 formula [II] is preferably a carbon ax-io alkylene group, an arylene group having 6 to 10 carbon atoms, ~o--s-, -5o--SO ,-,-C-
A divalent group represented by or a divalent group made by combining two or more of these divalent groups is preferred. Both ends of the divalent group shown as (the part bonding to the oxygen atom) are carbon atoms, and L may be substituted. n and m are preferably integers of 1 to 6, and 1 is particularly preferred.

Compound 1 C) 11 = CH5OzCHzOcH*5OzCH-C Examples of hardening agents used in the present invention are given below.
Hz Compound 2 CH2”CHSO2CH*CH20CHICH*5Ot
CH-C)! z Compound 3 CHz -CI(SOB[CHRaibaCHRai5O1CH-
CHx compound 4 CH2-CHSO, CH, OCR, CI, 0CR1So
, CH-CI! Compound 5 CHx -CH5OtCHzOCHzCHzCHzOC
HJOzC1'1-C)It Compound 6 CH2'' CI(S02CH!QC)l ICI'1z
OcHzcH! OCH! 5ozcH-C)I! Compound 7 CH2= CH30, co, co! oco, co! QC
) I, co, so, ct+ = CH! Compound 8 Compound 9 The synthesis method of these hardeners 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 10% to 20% by weight. 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 any gelatin-containing photographic layer, such as an overcoat layer.

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. I; It may be used in combination with other hardening agents known so far. Known hardening agents include, for example, aldehyde compounds such as formaldehyde and glutaraldehyde;
bis(2-chloroethylurea), 2-human ax-4,
6-dichloro-1,3,5-triazine, and others U.S. Patent Nos. 3,288,775 and 2.732,303,
Compounds containing reactive halogens, such as those described in British Patent Nos. 974.723 and 1,167.207, divinylsulfone, 5-acetyl-1°3-diacryloylhexahydro-1,3, 5-triazine, and other U.S. Pat. Nos. 3,635,718 and 3,232.
No. 763, compounds with reactive olefins described in British Patent No. 994.869, N-hydroxymethylphthalimide, and other US patents @ 2.732
．． N-methylol compounds described in US Pat. No. 316, No. 2.586,168, etc., U.S. Pat.
Examples include incyanates described in No. 37, etc., and halogen carboxaldehydes such as mucochloric acid. Alternatively, there are chrome light pans and the like as hardeners made of inorganic compounds. In place of the above compounds, compounds in the form of breaker, such as alkali metal bisulfite aldehyde adducts, methylol derivatives of hydantoin, primary aliphatic di-alcohols, methyloxyethylsulfonyl compounds , chloroethylsulfonyl compounds, etc. may be used in combination.

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, this 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.

The anionic surfactants particularly preferably used in the present invention include the following general formulas (IA) and (1[IB)
, (IIIC) and (IIID).

General formula (I[IA) R, -0CO-CH.

R, -0CO-CI(-R3 General formula CDI B) R4-OCO-CH.

L -0CO-C1 R, -0CO-CI-R7 General formula (I[[C) General formula (IIID) SO, - In the above formula, R,, R1+Ra, Rs, Ra, R*, 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, decyl, dodecyl, octadecyl group, etc. represents a straight chain or a branched chain, 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 naphthyl group. Also, R8 and R
6 represents an alkali metal salt of a carboxyl group, a sulfo group, and a phosphonic acid group. nl and N2 represent integers of 1 to 3.

Specific compounds represented by the general formulas [A) to (I[[D)] are illustrated below, and the compounds of the present invention [compound examples] ■ ■ ShiN3 ■ CH+ ShiN3 -3 11-4 1l-5 CH.

CI, -CH-CHx ■-6 m-7 +11-9 ■ -10 C, l (+ 100CCHxCHt C, H1+0OCCH, CH-SO, Nall-11 CI, (ni) l, no, l-υυshi-L ;tl->IJ,
Na[0-12 CbHoOOCCH2 SeeCIIIH! 1OOCCH5O3Na ■ 3 CH3(CHz)s OOCCL CH3(CHri3-00C-CH-5O3Na1[1-
14 C1l s (C)Io)s CH(CtHJCHz
-■) C-CH.

C1(, (CI, -CHCC!th)CH, -(X)
C-CH-SO3Na■ 5 ■ -16 -17 ll-18 C)l, (CH,), -0CO-CH.

■-19 ■-20 ll-21 -22 The silver halide emulsion used in the light-sensitive material of the present invention contains silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and chloroiodromide as silver halide. Any grains commonly used in silver halide emulsions such as silver halide may be used, and the silver halide grains may be those obtained by any of the strict 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 inside 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, US Patent 4
Specifications such as No. 183.756, No. 4,225.666, JP-A-55-285-J39, and JP-A-55-42737, The Journal of Photographic Science (J, Photogr., s. ci) -
Particles having shapes such as octahedron, tetradecahedron, dodecahedron, etc. can be prepared by the method described in literature such as 21, 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.

Furthermore, emulsions having any grain size distribution may be used, and emulsions with a wide grain size distribution (referred to as polydisperse emulsions) or emulsions with a narrow grain size distribution (referred to as monodisperse emulsions) may be used. It may be used alone or in combination of several types.Also,
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 rt.
The particle size r when the product n1Xri'' of and ci3 is maximum
Define i.

(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 constant grains is indiscriminately 1000 or more.) Particularly preferred highly monodisperse emulsions of the present invention have a monodispersity defined by 20 or less, and more preferably 15 These are as follows.

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

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

For chemical sensitization, the Glafkides or Z
elikman et al. or H. Fr1eserl.
If Day Grundlagen der Fotografisien Prozesse Mid Zilbel Halogennieden (
Die Grundlagen der Photo
graphischen Prosasse sl
itSjJberhaloganjden, Akad
e*jsche Verlagsgesellscha
ft., 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. 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. 2,51L698, 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 I of the periodic table, such as platinum, iridium, and palladium, can be used, and specific examples thereof include U.S. Pat.
No. 399.083, No. 2.44LOfiO, British Patent No. 618.061, etc.

Further, there are no particular restrictions on the conditions such as pH, spAgq temperature, etc. during chemical sensitization, but the pH value is preferably 4 to 9, particularly 5 to 8, and the I) Ag value is 5 to 11. In particular, it is preferable to keep it between 7 and 9. Further, the temperature is preferably 40 to 90°C, particularly 45 to 75°C.

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 may also be used, including 3a,7-titrazaindene, 5-mercapto-1-phenyltetrazole, 2-mercaptobenzothiazole, and the like.

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

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

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

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

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxanol dyes, and the like. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the basic basic ring nuclei commonly used for cyanine dyes can be applied to these dyes. That is, viroline nucleus, oxazoline nucleus, thiazoline nucleus, virol 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 complex 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. 2,493.748,
2,503゜776, 2,519.0 old number, 2
, No. 912.329, No. 3,656゜956, No. 3,
No. 672.897, No. 3,694,217, No. 4.0
No. 25゜349, No. 4,046.572, British Patent 1
, No. 242,588, Special Publication No. 44-14030, No. 5
No. 2-24844, JP-A-48-73137, JP-A No. 61
-172140 etc. can be mentioned. In addition, as sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat.
, No. 072,908, No. 2,739.149, No. 2,
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 945.763, British Patent No. 505,979, and Japanese Patent Publication No. 48-42172. Further, as sensitizing dyes used in red-sensitive and infrared-sensitive silver halide emulsions, for example, U.S. Pat.
270.378, 2,442.710, 2,4
No. 54.629, No. 2,776.28D, Special Publication No. 1977
-17725, JP-A No. 50-62425, JP-A No. 61-
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in No. 29836 and No. 60-180841.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization. Typical examples are U.S. Patent Nos. 2,688.545, 2,977.229, and 3
, No. 397.060, No. 3,522.052, No. 3,
No. 527.641, No. 3,617.293, No. 3,6
No. 28,964, No. 3,666.480, No. 3,67
No. 2.898, No. 3,679.428, No. 3,703
No. 377, No. 3,769,301, No. 3,814.
No. 609, No. 3,837゜862, No. 4,026,7
07, British Patent No. 1,344.281, British Patent No. 1,507
．． No. 803, Special Publication No. 43-4936, No. 53-123
No. 75, JP-A-52-110618, JP-A No. 52-109
No. 925, 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 radial condensation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like. Among them, oxal 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-mentioned 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, mercaptotetrazoles (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 Many compounds known as stabilizers can be added, such as 4-hydroxy substituted (1,3,3a,7)tetrazaindenes), benzenethiosulfonic acids, benzenesulfinic acids, etc.

An example of a compound that can be used is in The Theory of the Photographic Process, by K. Mees.
Theory or 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 Special Publication No. 5
You can refer to the description in No. 2-28660.

Further, the silver halide photographic light-sensitive material of the present invention is
In the H1t layer, U.S. Patent No. 3,411.911, No. 3,4
11.912, Japanese Patent Publication No. 45-5331, and the like.

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. Hardening agents include aldehyde-based, epoxy-based, Ethylene: Various hardeners such as 7-based, active halogen-based, vinyl sulfone-based, incyanate-based, sulfonic acid ester-based, carbodiimide-based, mucochloric acid-based, acyloyl-based, etc.
As the ultraviolet absorber, for example, U.S. Patent No. 3,253,9
No. 21, British Patent No. 1,309,349, etc., especially 2.(2'-hydroxy-
5-tertiary butylphenyl)benzotriazole, 2-(
2'-hydroxy-3', 5'-di-tertiary butylphenyl)benzotriazole, 2-(2'-hydroxy-3
1-tertiary butyl-5'-butylphenyl)5-chlorobenzotriazole, 2-(2'-hydroxy-3',5
Examples include '-di-tertiary butylphenyl)-5-chlorobenzotriazole. Furthermore, British Patent No. 548.532 describes coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials.
No. 1,216,389, U.S. Patent No. 2,026.2
No. 02, No. 3,514.293, Special Publication No. 44-265
No. 80, No. 43-17922, No. 43-17926, No. 43-3166, No. 48-20785, Buddhist Patent No. 202.588, Belgian Patent No. 773,459, JP-A-48-101118, etc. It is possible to use anionic, cationic, nonionic or amphoteric compounds described in , among which anionic surfactants having a sulfone group, such as succinic acid ester sulfonates, alkylbenzene sulfonates, etc. is preferred. In addition, as an antistatic agent, Japanese Patent Publication No. 46-24159
No. 48-89979, U.S. Patent No. 2,882.
No. 157, No. 2,972.535, Japanese Unexamined Patent Publication No. 1972-20
No. 785, No. 48-43130, No. 48-90391
There are compounds described in Japanese Patent Publication Nos. 46-24159, 46-39312, 4g-43809, and 47-33627.

In the manufacturing method of the present invention, the pi-t of the coating liquid is 5.3
It is preferable that it is in the range of ~7.5. In the case of multilayer coating, it is preferable that the PL (of the coating liquid obtained by mixing the coating liquids of each layer in the ratio of coating amounts is in the above range of 5.3 to 7.5. The pH is less than 5.3. This is undesirable because the hardening process is slow, and a pH higher than 7.5 is undesirable because it adversely affects photographic performance.

In the light-sensitive material of the present invention, the constituent layers include 77 tonerizing agents, such as silica described in Swiss Patent No. 330 and No. 158, glass powder described in Buddhist Patent No. 1,296,995, and glass powder described in British Patent No. 1,173.181. Inorganic particles such as alkaline earth metals or carbonates such as cadmium, zinc, etc.; starch as described in US Pat. No. 2,322.037; Belgian Patent No. 6;
Starch derivatives described in No. 25.451 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 U.S. Pat. , 079.257, and polycarbonate described in U.S. Pat. No. 3,022.169.

In the photosensitive material of the present invention, the constituent layers may contain slipping agents, such as those described in U.S. Pat.
higher alcohol esters of higher aliphatics as described in 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, No. 3,489, and No. 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, 1 ter.
s17643 (December 1978) and Volume 187 I
te+518716 (November 1979), and in carrying out the silver halide photographic light-sensitive material of the present invention, for example, the emulsion layer and other layers are formed on one side of a flexible support commonly used in photographic light-sensitive materials. Alternatively, it can be configured by coating on both sides. Useful flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or α-olefin polymers. (For example, paper coated or laminated with 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. Undercoat treatment is JP-A-52-1049
The treatments described in Japanese Patent No. 13, No. 59-18949, No. 59-19940, and 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 black and white developer I used in the present invention is a developing agent that has dihydroxybenzene chains and monomers because it is easy to obtain good performance.
Most preferred is the combination of -phenyl-3-pyrazolidones. Of course, a p-aminophenol type developing agent may also be included.

The dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, inpropylhydroquinone, methylhydroquinone, 2.3-dichlorohydroquinone, and 2.5-dihydroxybenzene developing agents.
- Dichlorohydroquinone, 2,3-diglomehydroquinone, 2,5-dimethylhydroquinone, etc., but hydroquinone is particularly preferred as the developing agent for l-phenyl-3-pyrazolidone or its derivatives used in the present invention, l-phenyl-4 , 4-dimethyl-3-pyrazolidone, l-phenyl-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-ruaminophenol N-(β-hydroxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl)cridine. ,
Examples include 2-methyl-p-aminephenol and p-benzylaminophenol, among which N-methyl-p-ruaminophenol is preferred.

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

Preservatives for i4E salts used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium oxide, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. Wits salt is 0.2 mol/a or more mt/nA mol/θ
2.5 mol/
It is preferable to set it to a.

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, methyl cellosolve, hexylene glycol, nitinol, methanol; l-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, etc. It may contain an antifoggant such as a mercapto compound, an indazole compound such as 5-nitroindazole, or a pentztriazole compound such as 5-methylbenztriazole, and may further contain a color toning agent, a surfactant, and an antifoaming agent as necessary. , hard water softener, JP-A-1987-
The amine compound described in No. 106244 may also be included.

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

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

In addition, 7 Otographic Processing Chemistry by F. A. Meson, published by Focal Press (L.F.
, A MASON, Photographic Pro
cessing Chewistory, Focal
Press, London) (1966), 22
pp. 6-229, U.S. Patent No. 2.193.015, No. 2
, No. 592.364, JP-A-48-64933, etc. may be used.

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

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

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

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 pH of 3.8 or higher, preferably 4.2 to 5.5.

Sodium thiosulfate and ammonium thiosulfate are available as fixing agents, but they contain thiosulfate ions and ammonium ions as essential components, and from the viewpoint of fixing speed, thiosulfate is preferred.
Particularly preferred is ljtl ammonium. 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 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 solution 1a, particularly 0.01 mol/6 to 0.03 mol/1.

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), pH
It can contain a conditioning agent (for example, sulfuric acid), a chelating agent with water softening ability, and a compound described in Japanese Patent Application No. 60-213562.

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

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

The fixer solution can exist stably as a l agent 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 thioits salt 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,
In a range of 5 or more, less sulfur dioxide gas is generated and the working environment is improved. The upper limit of pn is not so strict, but if it is fixed at too high a pH, the pH of the membrane will be high even after subsequent washing with water, and the membrane will swell, increasing the drying load, so the upper limit is around pH 7. 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: θ ~ 8. The total amount of each of the developer and fixer is preferably from 50 ml to 1,500 ml per 18 of the light-sensitive material.

In the present invention, the photosensitive material is developed, fixed, and then 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 312 or less 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.

If anti-mildew water is used in combination with washing water or stabilizing liquid, the formation of lime scale can be effectively prevented, so photosensitive materials I
Water saving treatment of 0 to 3 g, preferably θ to IQ1 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 countercurrent method is applied to the present invention, the photosensitive material in the fixer will be processed in a progressively cleaner direction, that is, in order to contact the processing solution that is not contaminated with the fixer, resulting in even more efficient processing. Washing is done. According to this, unstable thiosulfates and the like are removed to an appropriate extent, 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.

In addition, the washing or stabilizing bath may be replenished with water treated with anti-mold measures depending on the treatment, and part or all of the resulting over-70 liquid from the washing or stabilizing bath may be used in JP-A-60
As described in Japanese Patent Application No. 235133, it can also be used in a processing liquid having a fixing ability, which is a processing step before that. By doing this, you can save the above-mentioned stock water,
Moreover, it is more preferable because the amount of waste liquid is 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 the antibacterial agent described in No. 3030 and No. 61-51396 can be used.

Furthermore, L, E, 1fest"Water Quali
ty Cr1teria” Photo Sci & E
ng, Vol. 9 No. 6 (1965), M.l.
F, Beach “Microbiological
Growths in Motion-Pic-tur
e Processing” SMPTE Journal
al Vol, 85. (1976)-R, O, Deeg
ao, ”Photo Processing Was
h Water Biocides” J, I+magi
ng Tech, Vol 10. No. 6 (1984)
and JP-A-57-8542, JP-A No. 57-58143,
No. 58-105145, No. 57-132146, No. 58-18631, No. 57-97530, No. 57-
Antibacterial agents, anti-inflammatory agents, surfactants, etc. described in No. 157244 and the like can also be used in combination.

In addition, for the washing bath, R, T, ) [Reiman J, Im
age, Techlo, (6) 242 (1984)
RESEARC, an inthiazoline compound described in
HDISCLOSURE Volume 205, Item 2052
6 (May issue, 1981), volume 228 of the same, Hem 22845 (1
Inthiazoline compounds described in Japanese Patent Application No. 1983-51396 (April issue, 1983), compounds described in Japanese Patent Application No. 61-51396, etc. can also be used in combination as microbiocides.

Furthermore, specific examples of anti-piping agents include phenol, 4-chlorophenol, pentachlorophenol, cresol,
o-phenylphenol, chloro7ene, dichloro7ene, formaldehyde, cultaraldehyde, chloracetamide, p-hydroxybenzoic acid ester, 2
-(4-thiazoline)-benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-dimethylammonium-chloride, N-(fluorodichloromethylthio)-7talimide, 2.4.4'-trichloro-2'-hydro Such as oxin diphenyl ether.

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 in separate tanks, in addition to applying anti-mold measures as in the present invention, the washing water (or stabilizing bath) can contain various additives.

For example, the chelate stability with aluminum is 1og [value of 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 (1ogK16.l, the same applies hereinafter), cyclohexanediaminetetraacetic acid* (17,6), diaminopropanoltetraacetic acid* (13,8), diethylenetriaminepentaacetic acid (18
, 4) triethylenetetraminehexaacetic acid (19,7), etc. These include sodium salts, potassium salts, and ammonium salts, and the amount added is preferably 0.01 to log/
Q1 is 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 "Surfactants/Tsuta Book" 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, 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.

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

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

According to the eighth aspect of the present invention, an even more excellent effect is exhibited in that the drying time of the photosensitive material can be shortened as the swelling percentage of the photosensitive material is reduced.

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

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

〔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 8C water, 801 g/m2 of the dye of the present invention was added as shown in Table 1, and 20 g/m2 of saponin was added as a surfactant per table. What is shown in 1 is I
g, 20 g of a copolymer of butyl acrylate and vinylidene chloride as a polymer latex, 2.5 g of a styrene-maleic anhydride copolymer as a thickener, and a compound of the general formula (11) shown in Table 1 as a hardening agent. It was prepared by adding

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

(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.
A 35μ intestine) was prepared while maintaining the pH at 3.0 and 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 sensitizing dye was added per mol of silver halide, and 1 mol of silver halide was added.
70-g14-hydroxy-6-methyl1.3.3 l-phenyl-5-mercaptotetrazole per mole
a, 1-2 g of 7-chitrazaindene 5 After adding gelatin to stop the ripening, add 4 g of hydroquinone, 2 g of phenidone, 3 g of potassium bromide, and 5 g of saponin.
2g of styrene-maleic acid polymer as thickener, 38g of ethyl acrylate polymer latex, formalin and 2-hydroxy-4,6-dichloro-1,3,5-5-triazine as hardener. Prepared by adding sodium salt.

Sensitizing dye (preparation of protective film for emulsion layer) 10g of potassium bromide was added to an aqueous solution of 500g of gelatin, and l-decyl-2-(3) was added as an anionic surfactant.
~4g of sodium succinate-2-sulfonate (inpentyl) was added, and 1 amorphous silica with an average particle size of 5μ was added.
0 (Ig added and dispersed and prepared.

2. Coat the back lower layer on a 100 μl thick polyethylene terephthalate base that has been undercoated using the above coating solution.
0 g/m", the top layer was coated simultaneously with a gelatin loading of 1.0 g/m", followed by the back layer on the opposite side with a silver loading of 3.0 g/m''.
The emulsion layer and the protective layer were coated at the same time in such a manner that 8 g/1 serving of gelatin, 1.4 g/8 of gelatin for the emulsion layer, and 0.6 g/2 of a protective film layer.

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 were evaluated on a 10 scale basis. lO is the best and l
~4 is an unusable level, and 5 or higher is a usable level.

In order to check the stability of the above sample over time, we tested it at 23℃ relative humidity 4.
After conditioning the humidity to 8%, it is polyvinyl acetate with a thickness of 100 μm. It was sealed and packaged with a laminated moisture-proofing agent and heat-treated in a constant temperature bath at 40°C for 10 days. This sample and the frozen sample were exposed to 1.0XIO for 6 seconds with a xenon flash through an optical wedge and a 670n interference filter, and then treated in the same manner under the following conditions and evaluated in terms of relative sensitivity.

To check the adhesion, 10 sheets of the same sample were stacked and sealed after conditioning at 23°C and 80% relative humidity, and 10 sheets per lam''
Apply a pressure of 0 g and wait at 40°C for 24 hours to determine the adhesive property (
Stickiness) was evaluated on a five-point scale. 5 is the best, 1~
A level of 2 is unusable, and a level of 3 or higher is usable.

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

(a) (b) H! c-CH5ChCHsCHCHzS (hCH-CH
*H Development processing was performed under the following conditions.

(Development processing conditions) (Process) (Temperature) (Time) Development
38℃ 12 seconds fixation 36℃
Wash with water for 10 seconds Dry for 8 seconds at room temperature 50℃ Dry for 10 seconds
Dry Developer composition 45 seconds (Composition A) Pure water (ion-exchanged water) 150sR engineered ethylenediaminetetraacetic acid disodium salt g Diethylene glycol 50g Potassium sulfite (55% sodium carbonate/V aqueous solution) 100mff Potassium carbonate 50g Hydroquinone 15g 5-methylbenzotriazole 200 ■gI-phenyl-5-mercaptotetrazole 30 g Amount to adjust pH to 11.5 after using potassium hydroxide Potassium bromide 3 g (composition) Pure water (ion-exchanged water) 3III2 Diethylene glycol 50 g Diethylamino-1,2-propane Diol 5g Ethylenediaminetetraacetic acid disodium salt 25g Acetic acid (90% aqueous solution) 0.3a 5-nitroindazole llomgl
-Phenyl-3-pyrazolidone 500mg
When using a developer, the above group J*A was dissolved in the order of composition in 500 sff of water, and the developer was finished to 112 and used.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 24
0■a Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid
6g sodium citrate
Trihydrate 8g acetic acid (90% w/v aqueous solution)
13.6mff (composition) Pure water (ion exchange water) 17■afI
L acid (50% v/v aqueous solution) 4.7
g Aluminum sulfate (Aff, aqueous solution with 03 equivalent content of L1% w/v) 2f
i, 5g To use as a constant tank solution, the above composition A was dissolved in 50OsQ of water in the order of the composition, finished to la, and used. This fixer's pi
-i was approximately 4.3.

The results are shown in Table 1.

From the results in Table 1, the samples of the present invention have excellent residual color, scratch resistance, and adhesion compared to the comparative examples.Storage Example 2The following samples were prepared by changing some of the additives in Example 1. did.

(Preparation of coating solution for back lower layer) After dissolving 500 g of gelatin in 8Q water, 150 g/ws of the following dye was added, and as a surfactant, 2 g of saponin and 1 g of dodecylbenzenesulfonic acid were added.

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 μm of water, 20 g of polymethyl methacrylate with an average particle size of 4 μm as a matting agent, 1 l-decyl 2-( as an anionic surfactant)
I: prepared by adding 4 g 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 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 28 mol% silver bromide.
Containing silver chlorobromide particles (width of distribution 12%, cubic crystal, particle size 0
．． A 25μ intestine) was prepared at pH 3.0 and pAg 7.7, and after returning the pi-t to 5.9, it was desalted by a conventional method.

This emulsion was sensitized with gold and sulfur, and 300 g of the following sensitizing dye was added per mole of silver halide, and 70 g of l-7enyl-5-mercagutotetrazole was added per mole of silver halide. -Hydroxy-6-methyl=1.3
．． After adding 1.2 gs of 3a,7-chitrazainden 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 3 g of high molecular weight polymer latex of ethyl acrylate.

A hardening agent shown in Table 1 was added to prepare the film.

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 of the dye of the present invention/Otori 1 was added as shown in Table 1. What is shown in 4
100 g of amorphous silica with an average particle size of 5 μl.
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 processed and evaluated in the same manner as in Example 1 using a 488 ns interference filter.

The results are shown in Table 2.

〔Effect of the invention〕

ADVANTAGE OF THE INVENTION According to the present invention, a silver halide photographic material is provided which has excellent residual color and scratch resistance even after rapid processing, and also has good adhesion 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] ▲ Numerical formulas, chemical formulas, tables, etc. , a sulfonic acid group or a carboxylic acid group is connected to an alkyl group via a divalent linking group,
It may be bonded to an aralkyl group, an aryl group or a heterocyclic group. R_2 and R_4- are each an alkyl group, -COOR_
6, -CONR_6R_7, -NR_6R_7, -NR
_6COR_6, -NR_6CONR_6R_7, -C
N, -OR_6, -COR_6, -SO_2R_5, -
SOR_6 or -SO_2NR_6R_7 (here, R_5 represents an alkyl group, an aralkyl group, or an aryl group, R_6 and R_7 each represent a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and R_6 and R_7 are connected to 5 or It may form a 6-membered ring.), L_1
, L_2 and L_3 each represent a methine group, and M^■ represents hydrogen or another cation. ] 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. ]