JPS63244034A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having the excellent secular stability and less exposure dependence by incorporating a specified dyestuff which does not adversely affect to the photographic characteristics, especially the spectral sensitizing property of a photographic emulsion, in the titled material. CONSTITUTION:The titled material contains at least one kind of the dyestuff shown by formula I, in the titled material. In formula I, R1 and R2 are each alkyl group, etc., R3-R6 are each hydrogen atom., etc., Q1 and Q2 are each aryl group, X1 and X2 are each a single bond or a divalent bonding group, Y1 and Y2 are each sulfo group, etc., L1-L3 are each methine group, (n) is 0, 1 or 2, (m1) and (m2) are each 1 or 2, (p1) and (p2) are each 0, 1, 2, 3 or 4, (q1) and (q2) are each 1 or 2. Thus, the hydrophilic colloidal layer is colored by a water soluble dyestuff which does not harmfully affect to the photographic characteristics of a silver halide emulsion layer, and the stable titled material is obtd. even if after lapse of time of the hydrophilic colloidal layer.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer, which is photochemically inactive and easily decolorized during photographic processing. The present invention relates to a silver halide photographic material having a hydrophilic colloid layer containing a dye to be eluted and/or a hydrophilic colloid layer.

(Prior Art) In silver halide photographic materials, photographic emulsion layers or other layers are often colored for the purpose of absorbing light in a specific wavelength range.

When it is necessary to completely control the spectral composition of light incident on the photographic emulsion layer, a colored layer is provided on the photographic light-sensitive material on the side farther from the support than the photographic emulsion layer.

Such a colored layer is called a filter layer. When there are a plurality of photographic emulsion layers, such as in a multilayer color light-sensitive material, a filter layer may be located between them.

Light scattered during or after passing through the photographic emulsion layer may be reflected at the interface between the emulsion layer and the support, or at the surface of the light-sensitive material opposite to the emulsion layer, and enter the photographic emulsion layer again. Between the photographic emulsion layer and the support, in order to prevent blurring of images, that is, halation,
Alternatively, a colored layer may be provided on the opposite side of the support from the photographic emulsion layer. Such a colored layer is called an anti-nollage layer. In the case of a zero-layer color photosensitive material, an anti-nolage layer may be placed between each layer.

Deterioration of image sharpness due to scattering of light in the photographic emulsion layer (this phenomenon is generally called irradiation)
Coloring of the photographic emulsion layer is also used to prevent t-rounding.

These layers to be colored are often composed of hydrophilic colloids, and therefore, for coloring them, a water-soluble dye is usually incorporated into the layer. This dye must satisfy the following conditions.

(1) Must have appropriate spectral absorption according to the purpose of use.

(2) Photochemically inert. tb Do not adversely affect the performance of the silver halide photographic emulsion layer in a chemical sense, such as a decrease in sensitivity, latent image regression, or capri.

(3) No harmful coloring will remain on the photographic material after processing by being bleached or dissolved away during the photographic processing process.

Many efforts have been made by those skilled in the art to find dyes that meet these conditions, and the dyes listed below are known, for example from British Patent No. RORT.

No. 313, same/, /77.442? No., same/, 31i,
era issue, same/, 331. No. m, same l.

Jr., No. 371, same/, 4Abu 7. Kol≠No., samel,
Reference JJ, / OJ issue, same /, 11! , j14, JP-A No. 4 At-rJ, No. 130, 4cy-its.

μco No. 0, same! J-/l/, Ko J3 No., Same jW-iit
, t4co, U.S. Patent No. J, co 117. /No. 27, 3. Hiroty, Ri No. 11, same≠, 07t.

No. 933, etc., which have a pyrazolone nucleus or a barbylic acid group, are medium sonol dyes, U.S. Patent No. λ, JJJ,
No. 4A7, J, 37f, JJJ, British Patent No. 7.
Other medium sonol dyes described in Core No. 1,127, etc., British Patent No.! 7J.

1ri1 issue, same tIO, 4J/issue, same! Tade, Bu23,
Same 7ft! No. 07, 907. /2! r, i, o
uj, to2, U.S. Patent No. 1, cojj.

Azo dyes described in JP-A No. 3 Kobu No. 3, JP-A No. 3 Jl/, 0≠3, etc., JP-A No. 3 JO-100, No. 3, zu-
tit, co≠7, British patent no. 1゜oia, zft,
7!0.03/, etc., U.S. Patent No. 7, t≦j.

7! Anthraquinone dyes described in U.S. Patent Nos. A, ZSR, OAT, U.S. Pat. See, No. 102, Same I, Koio,, xs Ko, Tokukai Sho J0-3, 4 Ko! No., J/-J, J/-10,927, J/-10,927, J/-ITR, XA7, Special Public Shosan T-J, Cort No.,
same! Azomethine dyes described in 37゜301, etc., Tokko Shoko t-J, Or-, Kokoda IT, sr≠, JP-21. Styryl dye described in Iff etc., British License No. φ dub, No. 113, same l, 33! , No. 1■, JP-A-Sho JW-Cocor, λJθ, etc., triarylmethane dyes described in British Patent No. 1.071, ≦j3, Ibid./, /! J, No. 341, same/, 2114.730
No., same/, 4471.22r, same/, Jug, 107
Mexyanine dye described in US Patent No. 2, etc.
1443, No. 4 & 14, No. 3,2P≠, No. j32, etc., and nine cyanine dyes.

Among these, oxonol dyes, which have a number of pyrazolone nuclei, have the property of being decolorized in the liquid solution containing sulfites, and are used as useful dyes for dyeing photographic materials as they have little negative effect on photographic emulsions. I've been exposed to it.

However, some of the dyes belonging to this family have little effect on the photographic emulsion itself, but on the spectrally sensitized emulsion,
There is a drawback that a decrease in sensitivity is caused by spectral sensitization in unnecessary areas or by desorption of the sensitizing dye.

Furthermore, due to the speeding up of current processing that has become popular in recent years, some residual substances remain in photographic materials after processing. In order to solve this problem, it has been proposed to use dyes that are highly reactive with sulfite ions, but in this case, the stability in the photographic film is insufficient, and the concentration may change over time. Disadvantages of low cost and failure to obtain the desired photographic effect t-V
are doing.

(Problems to be Solved by the Invention) The object of the present invention is, firstly, to prepare a hydrophilic colloid layer dyed with 7% halogen by dyeing a hydrophilic colloid layer with a novel water-soluble dye that does not have a detrimental effect on the photographic properties of the silver halide emulsion layer. An object of the present invention is to provide a silver oxide photographic material.

A second object of the present invention is to provide a silver halide photographic material in which a hydrophilic colloid layer is dyed with a conventional water-soluble dye having excellent decolorizing properties upon processing.

A third object of the present invention is to provide a silver halide photographic material in which the dyed hydrophilic colloid layer contains a novel water-soluble dye that is stable over time.

(Means for Solving the Problems) These objects of the present invention are achieved by containing at least -a't- of the dye represented by general formula (1).

In the formula, R11 and R are each an alkyl group 1, where the alkyl group includes those having a substituent t-, such as a methyl group, an ethyl group, a t-methyl group, an isopropyl group, an n-butyl group,
n- as a substituent, such as a methyl group, heptyl group, octyl group, dodecyl group, k-ntadecyl group, heptadecyl group, etc.
Halogen atoms such as fluorine, chlorine, and bromine atoms (
For example, trifluoromethyl group, Coke C! loether group,
difluoromethyl group s't'sco, 2-tetrafluoroethyl group s't'sλ, λ, 3,3-hexafluoroofa pyl group, coop a moedel group, etc.), phenyl group (e.g. benzyl group, phenethyl group) , glucosbenzyl group, dibenzyl group in termet, dibenzyl group in sulfo-sulfoglobyl, etc.), hydroxy group (e.g., co-hydroxyethyl group, 3-hydroxyethyl group, etc.), or cyano group (e.g., λ-cyanoethyl group, etc.). can include 1
, aryl group (here, aryl group includes those having a substituent, such as phenyl group, naph, thyl group, etc.), sulfonic acid group (for example, cosulfophenyl group, !-
Sulfophenyl group! ,! -disulfophenyl group, etc.),
power, rubonic acid group (e.g. cocalmexiphenyl group, etc.)
, alkoxy groups (e.g. diphenyl group in l-meth, ref.
sulfodithyloxyphenyl group, etc.), a halogen atom (e.g., 3-chlorophenylene group, R6 is a hydrogen atom, an alkyl group (e.g., methyl group, ethyl group, isopropyl group, butyl group, etc.), a sulfo group (e.g., sulfomethyl group), , sulfoether group, etc.), carboxylic group (e.g., carboxymethyl group, carboxymethyl group, etc.), hydroxy group (e.g., μ-droquiethyl group, 'e codihyde a-xyglobyl group, etc.), alkoxy group (e.g., methoxyethyl group, methoxyethyl group) ), halogen atoms (
7 Tsuso atoms, chlorine atoms, A atoms (e.g. - chromityl, copromoether, co, co, cotrifluoroethyl groups, etc.), cyano groups (e.g. cyanoethyl groups, etc.), sulfonyl it (e.g. methanesulfonyl ethyl) group), nitro group (e.g. -m; trobutyl group, λ-nitromethylbrobyl group, etc.), amino group (e.g. dimethylamine ethyl group, diethylaminotukpyr group, etc.), nitro group (e.g. benzyl group) , p-chlorobenzyl group), phenyl group, or substituted phenyl group (substituents include sulfo group (e.g., p-sulfophenyl group, co-,!-disulfophenyl group, etc.), carboxyl group (e.g., p-carboxyphenyl group, m-carboxyphenyl group, etc.), human group (e.g., p-hydroxyphenyl group, m-hydroxyethyl group, etc.), alkoxy group (e.g., p-methoxyphenyl group, m-hydroxyphenyl group, etc.)
-+diphenyl group), halogen atom (e.g. p-chlorophenyl i, p-'romophenyl group, p-fluorophenyl group, etc.), cyano group (e.g. p-cyanophenyl group, O-7 anophenyl group, etc.) , nitro group (e.g. p-nido aphenyl group, m-nitrophenyl Jl, etc.),
Amino groups (e.g. p-dimethylaminophenyl Ji,
p-diethylaminophenyl group, etc.), alkyl group (1
1F'lJ, f-hap-methylphenyl, 0-methylphenyl group, etc.) 1, or -SO□
R7 represents an alkyl group (eg, methyl group, ethyl group, etc.), an aryl group (eg, phenyl group, p-methylphenyl, p-chlorophenyl group, etc.). Also R1. ,R,de! Alternatively, a Δ-membered ring (for example, a piperidino group, a morpholino group, etc.) may be formed. l(+3,
R4 each represents a hydrogen atom or an alkyl group (eg, methyl group, ethyl group, globyl group, etc.). Q, R2 is an aryl group [here, the aryl group includes all those having substituents,
For example, a 7-enyl group, a naphthyl group, an alkyl group having 7 to ≠ carbon atoms, an alkoxy group having 7 to μ carbon atoms, 80! ')'' 7 K groups (chloro, furo, fluoro), carbamoyl groups (e.g. ethylcarbamoyl), sulfamoyl groups (e.g. ethylsulfamoyl), cyanogen groups, nitro groups, alkylsulfonyl groups (e.g. methanesulfonyl) group), arylsulfonyl group (e.g. benzenesulfonyl group, etc.), amino group (e.g. dimethylamino group, etc.), acylamino group (e.g.
(e.g., acetylamino group, etc.), sulfonamide group (e.g., methanesulfonamide group, etc.); X□ and X2 each represent a bond or a divalent linking group, and 几 is a hydrogen atom,
Carbon number! The following alkyl groups and carbon numbers! The following substituted alkyl groups (substituents include alkoxy groups with 3 or less carbon atoms, sulfo groups (e.g. sulfoether group, sulfopropyl group, etc.), carboxyl groups (e.g. carboxyethyl group, etc.)
, cyano group, hydroxy group, amine group (such as hydroxyethyl group), sulfonamide group (such as methanesulfonamide group), carbonamide group (such as acedelamino group), carbamoyl group (such as ethylaminocarbonyl group), sulfamoyl group (e.g. ethylaminosulfonyl group, etc.), Yl, Y.

represent a sulfo group and a carboxyl group, respectively, and these may form not only a free acid but also a salt (eg, NJI salt, K salt, ammonium salt, primary ammonium salt, etc.). L□, +2, +3 are methine groups (here, methine groups include all those with substituents, substituents include methyl groups,
Examples include ethyl group and phenyl group) 1? represent.

"1" and "2" are respectively l or 2, n is 0.11 or 2, p□, R2 are respectively o, i, ko, 3 or #i≠,
qo and R2 each represent or.

Among the substituents represented by general formula (I), R3 is 几.

Water, XyK, and methyl groups are preferred, and R5%.

is a hydrogen atom, an alkyl group with a carbon number of μ or less, a substituted alkyl group with a carbon number of 4 or less (substituents include a sulfo group, a carboxyl group, a hydroxy group, an alkoxy group with a carbon number of less than or equal to 1),
A chlorine atom, a cyano group, an amino group, and an alkylamino group having 3 or less carbon atoms are preferred. 1. Phenyl group, substituted phenyl group (substituents include sulfo group, carboxyl group, alkoxy group with carbon number of μ or less, chlorine atom, cyan group, carbon number 3)
The following alkyl groups and alkylamino groups having a carbon number of μ or less are preferred. ) Also in R3 and R6! It is preferable to form a membered ring or a membered ring (for example, a morpholino ring, a pyrrolidine ring, or a lysine ring).

Q, Q2 is a phenyl group, a substituted phenyl group (substituents include an alkyl group with a carbon number of μ or less, an alkoxy group with a carbon number of less than 1, a halogen atom (aa, etc.).

(bromo, fluoro), dialkylamino group having carbon number≠ or less, and the like are preferable. 1 is preferred.

For Xl and X2, 10-1 elementary atoms, alkyl groups with 3 or less carbon atoms, and carbon numbers! The following substituted alkyl groups (as the fil substituent, an alkoxy group having 3 or less carbon atoms, a cyano group, a cyano group, an alkylamino group having 3 or less carbon atoms, etc.) are preferable.

Furthermore, among the dyes represented by the general formula (1), m□=m 2
=/ is preferable.

Next, specific examples of dyes used in the present invention will be shown, but the present invention is not limited thereto.

S (J a N a b s, IN
mct α7+
2 80sNa F3C), Na/J / 三0(CH,)4803Na 0(CH2人SO,Nal!/r so3ic asu, 5/P 803Na 803Nako O! Self 12: Koko J3 u(CH2)4803Na 0 (OH2), S(J,
Nako ≠ 80, Nu 803Na J 80 s Na SOx Na
Kobuko 7 803 N a 8 (J a N
ako r-? 803K B (J, Ni α α J Ko J J 蓼 j SO, Na 503Na 80, K S (J, Ni r J Risen 〇 AI 80 s Na 8 () s
N m≠ko1 J (J(CH,)2C(JIJK (J(C)i,
), C(j(JK Sansanhiro! at SO□CH20H280,Na 802CH2C
M, 803N aL 7 at at P! Q! l! The compound represented by the general formula (1) can be synthesized by various synthetic methods, but for example, as shown in the reaction formula below, pyrazolone (n) and (lna ), (lllb), (11
C), (IIId)-! or a compound represented by <■e> in the presence of a base.

Q engineering +
) In the formula, 几い 几3, Q□, Xl, Yl, L,.

L2, L3, ml, ns pl, (1□ represents the same meaning as above, Z represents a hydrogen atom, nitro group, halogen atom (e.g. chloro, bromo). 几9 represents a hydrogen atom,
In alkyl groups (eg methyl, ethyl, etc.), phenyl groups. X is an anion (e.g. chloride, bromide, iodide, perchlorate, methyl sulfate, ethyl sulfate, p-toluenesulfo*-
Tona! ') t-represent.

Synthesis examples of compounds according to the present invention are described below, but the present invention is not limited thereto.

Synthesis Example 1 (Compound 2) 3-phenyl-/-(4A-sulfobenzyl)cerazoline-! -one 7, JP%N,N/-diphenylformamidine hydrochloride, JP,) rietheramine d1 methanol 70g mixed and heated under reflux for 3 hours to form a homogeneous solution. To this solution, sodium acetate-t methanol 4A
When the OIL1 solution is added, dark brown crystals are precipitated. When this crystal t-F is taken and washed with ethanol, the compound 3 is
．． 2? Obtained nine.

Melting point JOO"C or higher λmax" nm (g=2..2/X/17)
Synthesis example 2 (compound 3)! -1f Ru/-(cosulfobenzylumvirazoline-!-on!0.rif, malonaldehyde cyanyl 2.2
? , ) ethylamine l , Ads methanol! 0n11 - Mix and heat under reflux for 3 hours to form a homogeneous solution. After cooling this solution to room temperature, potassium acetate
．． Addition of 2t of methanol/4% solution precipitates dark red crystals. When this crystal t-F is taken and washed with ethanol, compound 3 is obtained! ? Obtained.

Melting point soo@c or higher 2m, x J/2nm (lst, rhiro
! -on/0, 79. Glutaconaldehyde cyanyl salt J, 2? , triethylamine l≠4, methanol! 0 tdf and stirred at room temperature for 3 hours. When a methanol/4% potassium acetate solution is added to this solution, dark green crystals are precipitated. When this crystal was taken out and washed with methanol, compound r was found to be 10. JP was obtained.

Melting point: 5oooc or higher H2O λmax t07nm (s=7.I×10') Synthesis example 4 (compound 10) J-trifluoromethyl-7-(λ-sulfobenzyl)
Pyrazoline! -one7,/f, glutaconaldehyde cyanyl hydrochloride co, rf, triethylamine t,
7rd and 30 di of dimethylformamide were mixed and stirred at room temperature for 3 hours. Add sodium vinegar to this solution! When a methanol JQd solution of 1 is added, blackish brown crystals are precipitated. When P was removed from this crystal and washed with methanol, compound IO was found.

rf obtained.

Melting point 3oo0C or higherzO λmax 64A3nm (t=xxri, r4Axio
) Synthesis Example 5 (Compound Hiro 0) J-cyano-/-(J-sulfobenzyl)pyrazoline-
! -onj,/t, glutaconaldehyde cyanyl hydrochloride co, rf,) rietheramine t.

7txl, dimethylformamide dog 0tdf mixed,
The mixture was stirred at room temperature for 3 hours. Add sodium acetate to this solution! ,
2F methanol! When Oxl solution is added, blackish brown crystals are precipitated. This crystal t-F was collected and washed with methanol to obtain 3.22 of compound 4to.

Melting point: 3oo"c or higher (M=r, P5FX10) When using the dye represented by the general formula (1) as a filter dye, anti-irradiation dye, or antihalation dye, use an arbitrary amount that achieves the desired effect. However, it is preferable to use it so that the optical density is in the range of 0.02 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, a/tech layers, filter layers, etc.) by various known methods.

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 an aqueous solution is used in an emulsion layer or a hydrophilic colloid layer after being dissolved or dispersed in a solvent. Suitable solvents, e.g., methyl alcohol, methyl alcohol, zorobyl alsul, methyl cellosolve, JP-A-Sho μt-P7/! No., U.S. Patent J, 7!
t, rJO, halogenated alcohol, acetate/
It can also be added to the emulsion in the form of a solution dissolved in water, pyridine, etc., or a mixed solvent thereof.

■ A hydrophilic polymer having a charge 11tt- opposite to that of the dye ion is made to coexist in the layer as a mordant, and by interaction with this rtt-dye molecule, the dye 'f! I: Method of localization 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 primary cadeon group, etc., and preferably has a molecular weight of 10,000 or more. .

For example, vinyl pyridine polymers and vinyl pyridinium cationic polymers are described in US Pat.

Vinylimidazolicum cateion polymers disclosed in US Pat.

Polymer mordant crosslinkable with gelatin etc. disclosed in US Pat. No. 421, JP No. 421, etc.;
Aqueous sol-type mordant disclosed in JP-A No. 144-111221, etc.; U.S. Patent No. 3. ryr, or
Water-insoluble mordants disclosed in US Pat. No. 41. Reactive mordant capable of forming a covalent bond with a dye disclosed in Patent No. 61,5'74, etc.; British patent trj
Polymers derived from ethylenically unsaturated compounds having a sialic aminoalkyl ester residue t-V as described in the British patent rzo, cor/r/; Products obtained by reaction of aminoguanidine; U.S. Pat. J.
Examples include polymers derived from comethyl-/-vinyl ξdazole as described in No. 444, No. 231.

■ Compound 1 - Method of dissolving using a surfactant.

Useful surfactants may be oligomers or polymers.

For details of this polymer, please refer to JP-A-10-13114
No. 37 (filed by Fuji Photo Film, filed in January 1920), from page 1 to core page of the specification.

In addition, during the dispersion of the hydrophilic colloid obtained above, for example, Tokukai Akira! Hydrosyl, a lipophilic polymer described in No. 1-3-231, may be added.

Gelatin is a typical hydrophilic colloid, but any other conventionally known hydrophilic colloids that can be used for photography can be used.

The silver halide emulsion used in the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride. Silver particles have regular crystal shapes such as cubes and octahedrons, and irregular crystal shapes such as spherical and plate shapes.
ular) crystal form, or a composite form of these crystal forms.

It is also possible to use mixtures of particles of various crystalline forms, but it is preferred to use regular crystalline forms.

The silver halide grains used in the present invention may have different phases inside and on the surface, or may consist of a uniform phase. Also, particles whose latent image is mainly formed on the surface (
For example, it may be a negative type emulsion), or it may be a grain mainly formed inside the grain (for example, an internal latent image type emulsion, a pre-fogged direct reversal type emulsion), and preferably,
The particles are such that the latent image is mainly formed on the surface.

The silver halide emulsion used in the present invention has a thickness of 0.03 mm.
A tabular grain emulsion in which grains having a diameter of 0.3 microns or less, preferably 0.3 microns or less, and an average aspect ratio of 1 or more occupy JO- or more of the total projected area. , statistical coefficient of variation (standard difference S when the projected area is approximated as a circle divided by the diameter d, ratio value 8/d)
A monodisperse emulsion in which the emulsion is less than or equal to 0. Further, one or more amounts of a tabular grain emulsion and a monodispersed emulsion may be mixed.

The photographic emulsion used in the present invention is P graphide x (P
, Glafkides), Chjmie or Physique Photography (Chjmie or Physique Photography)
(Photographeque) (published by Ballmontel, /P 47), Photographic Emulsion Chemistry, written by G. F. Duffin)! J-(Photo-g
raphfc Emulsion Chemistry
) (7O published by Legres, /lit tl, written by V, L, Zellkman et al.
Making and Coating Photographic e-emulsion (Maklng and Coati)
ngPhotographic Emulslon) (
It can be prepared using the method described in Focal Press, Vol. 4).

In addition, during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, and thioether compounds (e.g., U.S. Pat. .tJr No. 3,704I, No. 130, same cylinder part, 2 f 7゜≠3ri No., same No. DA, core 1.
3 reference), thione compounds (e.g. JP-A-Sho JJ゛-
/4'4'j/P issue, same J3 Lee 4Lor issue, same! ! −
No. 77737, etc.), amine compounds (e.g., JP-A No. 77737, etc.), amine compounds (e.g.,
-100777, etc.) can be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, an adium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example H, Friesel (H.

Die Grundlagende Fr1eser), Die Grundlagende
r Photography Proze
ssemit Silberhalogeniden)
(Akademissier Fuerlagus Gesellschacht/P4
r) The method described in pages A7J-73≠ can be used.

Namely, sulfur sensitization using active gelate/compounds containing sulfur that can react with silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts); , amines, hydrazine derivatives, formamidine sulfinic acid, sila/compounds); noble metal compounds (e.g., total complex salts,
Pt.

Complex salts of metals from group ■ of the periodic table such as IrS Pd)? The noble metal sensitization methods used can be used alone or in combination.

The silver halide photographic emulsion used in the present invention may contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of light-sensitive materials, or for stabilizing photographic performance. can. That is, azole analogs such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (CWK Etro or No. 10 gene substitution products)
; Heterocyclic mercazoto compounds such as mercaptodeazoles, mercaptobenzothiazoles, mercaptobe/zimidazoles, mercaptothiadiazoles,
Mercaptotetrazoles (especially /-phenyl-!-mercaptotetrazole), mercazotopyrimidines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as carxyl group or sulfone group; thioketo compounds such as oxazolinthione; azaindenes For example, tetraazaindenes (particularly μm hydroxysubstituted ('+J, j
a, 7) Tetraazaindefs): benzenethiosulfonic acids; benzene/insulfinic acids; and many other compounds known as anti-capri agents or stabilizers can be added.

The silver halide photographic emulsion of the present invention can contain color pigments such as cyan coupler, magenta coupler, yellow coupler, etc.
It can include a coupler and a compound that disperses the coupler.

That is, it may contain a compound that can develop a color by oxidative coupling with an aromatic/grade amine coloring agent (for example, a phenine/diamine derivative, an aminophenol, a derivative, etc.) in a color development process. For example, as a magenta coupler! - Virazolone cazolers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, pyrazolotriazole couplers, open chain acylacetonitrile couplers, etc., as yellow couplers,
Examples of cyan couplers include acylacetamide couplers (eg, benzoylacetanilides and piparoylacetanilides), and naphthol couplers and phenol couplers. These couplers are preferably non-diffusive and have a hydrophobic group called a /ζ last group in the molecule.

The coupler may be either 4c-equivalent or mono-equivalent to silver ions, and may be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR cazoler). It's okay.

In addition to the DI coupler, the coupling reaction product may include a colorless DIR coupling compound which is colorless and releases a development inhibitor.

For the purpose of increasing sensitivity, increasing contrast, or accelerating development, the photographic emulsion of the present invention may contain, for example, polyols, derivatives thereof such as ethers, esters, and amines, thioether compounds, thiomorpholinos, quaternary ammonium salt compounds, Urethane derivatives, urea derivatives, imidazole derivatives, J-pyrazolidones, etc. may contain gold.

The silver halide photographic emulsion of the present invention may contain known water-soluble dyes other than the dyes disclosed in the present invention (for example, oxonol dyes; It may also be used in combination with and merocyanine dyes.Also, it may be used in combination with known cyanine dyes, merocyanine dyes, and hemicyania dyes other than the dyes shown in the present invention as spectral sensitizers.

The photographic emulsion of the present invention may contain various surfactants for various purposes such as coating aids, antistatic properties, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, and sensitizing). But that's fine.

Please note that the photosensitive material of the present invention contains additives such as anti-fading agents, hardening agents, anti-color capri agents, ultraviolet absorbers, gelate/etc. Disclosure vol.1. /74(/97r%XM)R
D'-/7t4AJ etc.

The finished emulsion can be prepared on a suitable support, such as ephemeral paper, resin-coated paper, synthetic paper, triacetate film, polyniterate/terephthalate film,
Applied on other plastic bases or glass plates.

The silver halide photographic light-sensitive materials of the present invention include color positive films, color vanes, color negative films, color reversals (which may or may not contain couplers), photographic materials for plate making (for example, lithium film, lithium Dugue film, etc.), photosensitive materials for cathode ray tube displays (e.g. photosensitive materials for emulsion X-ray recording, materials for direct and indirect photography using screens), silver salt diffusion transfer process (851ver 5alt diffusion)
photosensitive material for color diffusion transfer process, photosensitive material for color diffusion transfer process, gui transfer process (1mb1bition transfer)
Direct Pr1nt
image) W! Examples include photosensitive materials for thermal development, photosensitive materials for physical development, and photosensitive materials for physical development.

The ninth exposure to obtain the photographic image may be carried out using conventional methods: natural light (sunlight), tungsten lamps, fluorescent lamps, mercury lamps, Φ mono/arc lamps, carbon arc lamps, xenon flash lamps, cathode rays. Any known multiple light source can be used, such as a tube flying spot. Exposure times are typically 771,000 seconds to 30 seconds, but exposures shorter than 1/1000 seconds, such as xenon flash lamps or cathode ray tubes, can be used. It was//10'~///0
Exposures of seconds can be used, or exposures longer than 30 seconds can be used. If necessary, the spectral composition of the light used for exposure can be completely adjusted using color filters. Laser light can also be used for exposure. Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, r-rays, α-rays, or the like.

For photographic processing of light-sensitive materials made using the present invention, for example, Search Disclosure (Re5earch Disclosure)
Dlsclosure) / No. 74, No. t~30
Any of the known methods and known treatment liquids as described in Sada (RD-/7 Buhiro J) can be applied. Depending on the purpose, this photographic processing may be either a photographic processing that forms a silver image (black and white photographic processing) or a photographic processing that forms a dye image and sound (force 2-photographic processing). The processing temperature is usually chosen between it and to''c,
The temperature may be lower than ir"c or higher than !0@C.

There are no particular restrictions on the color photo processing method, and any method can be applied. For example, representative methods include a method in which after exposure, color development and bleach-fixing are performed, and if necessary, further washing with water and stabilization treatment; after exposure, color development, bleaching and fixing are completely separated; If necessary, further washing with water and stabilization treatment are performed. After exposure, development is performed with a developer containing a black and white developing herbal medicine. After uniform exposure, color development and bleach-fixing treatment are performed, followed by further washing with water if necessary. , after stabilization treatment or after exposure, development is done with a developer containing all black and white developing agents, and then a captivity agent (
For example, a method is used in which the image is developed with a color developing solution containing (for example, sodium borohydride) and then subjected to bleach-fixing treatment, followed by washing with water and stabilization treatment if necessary.

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developing crude drugs include aminophenol and p-phenylenediamine derivatives. Preferred examples include p-phenylenediamine derivatives. Representative examples are shown below, but the invention is not limited thereto.

D-/N, N-diethyl-p-phenylenediamine D-j Coramino-! -Jiedelua ζnotorue D-
J co-amino-z-(N-ethyl-N-laurylamino)toluene D-44t-(N-ethyl-N-(β-hydroxyethyl)annocoaniline D-J co-methyl-a-(N-ethyl-N-(β) −
hydroxyethyl)aminocoaniline D-B N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-≠-aminoaniline D-7N-(coamino!-diethylaminophenylethyl)methanesulfonamide D-IN , N-zmedel-p-phenylenecyamine D-2≠-annor-3-methyl-N-ethyl-N-methoxyethylaniline D-104cm A〉No-no-methyl-N-ethyl-N-
β-Ethoxyethylaniline D-//4! -Amino-3-methyl-N-ethyl-N-
β-Ctoxyetheraniline These p-phenyl diamide y derivatives may also be salts such as sulfate, hydrochloride, sulfite, and p-toluenesulfonate. The above compounds are described in US Pat. Otj issue, same co! ! Ko.

Ko4L1, same Ko! ≦t, core No. 1, same, j ter,
No. 34, same J, tJ&, ri No. 30, same 3゜t r, j
Ko! It is stated in the number etc. The amount of the aromatic primary amine color developing agent to be used is about 0.1 ml of developer solution/l. /f ~ approx. 1
Of1 is more preferably a concentration of about 0, If to about ioy.

As is well known, the color developing solution used in the present invention may contain hydroimythylamines.

Although hydrodylamines can be used in the free amine form in color developers, it is more common to use them in the form of water-soluble acid salts. Common examples of such salts are sulfates, shellates, chlorides, phosphates, carbonates, acetates, and the like. The hydrozylamines may be substituted or unsubstituted, and the nitrogen atom of the hydroxyl amines may be substituted with an alkyl group.

The amount of hydroxylamine added is 0f- per color developer H.
10f is preferred, and 0-79 is more preferred.

If the stability of the color developing solution is to be maintained, it is preferable that the amount added be small.

In addition, as a preservative, it is preferable to contain sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts. -10 t/l is preferred, and more preferably 0f-jf/l, and the smaller the number, the more preferred, as long as the stability of the color developing solution is maintained.

Other preservatives include JP-A No. 14-4470 Jr. Bu-3114cO, same J
P-/40/4L and U.S. Patent 37μ J4tμ
Aromatic polyhydroxy compounds described in US Pat. No. 3. t
it, to3 and British patent/, 304. Human Kuki Diacet Class 7 84I) Kaisho J, 2-/1 No. 3020 and J3-19442! α of symbol 11t
-A-ζ-nocarmenylated compound; t% of various metals described in JP-A No. 7-≠Reference/≠R and JP-A No. J7-JJ712, etc.
Kaisho! 2-10 Various sugars described in Kokukoa issue;
Human a medial sum rfRs described in No. 7tJr;
α,αI-dicarbonyl compound 1 described in issue 0/41/! Salicylic acids described in data trozrt issue; same j1-J
Alkanolamines described in jrJa issue; It-2≠
Poly(alkylene imine)s described in J4C number; gluconic acid derivatives described in JBU-73T Duff, etc. can be mentioned. These preservatives should be added as needed.
May be used together. Especially Hiro! -Dihydroxy-m-benzenedisulfonic acid, poly(ethyleneimine), triethanolamine, and the like are preferably added.

The pH of the color developing solution used in the present invention is preferably about -1, more preferably about - //, and the color developer may contain other known developer component compounds. can.

In order to maintain the above pHt, it is preferable to use various buffers. As buffering agents, carbonate, phosphate, borate, tetraborate, hydroxybenzoate 1. Glycine salt, N,N dimethylglycine salt, aisine salt, norleucine salt, guanine [, J.

μm dihydro c1 diphenylalanine salt alanine salt,
Aminobutyrate, -monoamino-λ-methyl-/.

3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates have high solubility, pH, and high p)1
It has nine advantages that it has a buffering capacity in the area, has no adverse effect on photographic performance (such as fogging) when added to color developer, and is inexpensive, and it is recommended to use these buffer tubes.
preferable.

Specific examples of these laxatives include carbonic acid, IJ cum, potassium carbonate, sodium bicarbonate, potassium bicarbonate,
Trisodium phosphate, dipotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate [salicylic acid] Sodium], O-human adP potassium cybenzoate,
! - Sodium sulfocohyde a-oxybenzoate (j-
Sodium sulfosalicylate! -Potassium sulfohydroxybenzoate (!-Potassium sulfosalicylate) and the like can be mentioned. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developing solution is preferably Q, 7 mol/1 or more, particularly 0.1 mol/lN0.4
Particularly preferred is A mol/l.

In addition, various chelating agents can be used in the color developing solution as an anti-settling agent for calcium or magnesium, or to improve the stability of the color developing solution.

As the chelating agent, organic acid compounds are preferable, such as the aminopolycarboxylic acids described in JP-B Sho μl-0 JO4 No. 24 and Gu-JO Co-J No. 7;
Organic phosphonic acids described in J Gua, Japanese Patent Publication No. 14-39312 and West German Patent Co., Cocoa, No. 43P, Japanese Patent Publication No. 14-39312.
Coal lO core No. 24, same j3-≠2730, same j4t
-/Co//Core issue, same! ! -/- Bucog No. 1 and the same!
! - Phosphonocarboxylic acids described in 1J RiJbu issue, etc., and others! I-/ri! See! Same issue! t-203μ≠
The compound t-S described in No. 0 and Japanese Patent Publication No. 13-440900 can be obtained. Specific examples are shown below, but the invention is not limited to these.

・Nitrilotriacetic acid ・Diethyleneaminopentaacetic acid ・Ethylenediaminetetraacetic acid eTriethylenetetraminehexaacetic acid, N, N, N-) riftele/phosphonic acid ・Ethylenediamine-N, N, N/, N/-tetramethylenephosphonic acid mono/ , J-DiaminoCorp c! /4nol-≠acetic acid e
trans cyclohexanediaminetetraacetic acid/nitri-atripropionic acid/l,-monodiaminoglopanetetraacetic acid-hydroxyetheriminoniacetic acid/glycol ethercyaminetetraacetic acid/hydroxyethylenecyaminetriacetic acid/ethylenediane orthohydride a4 diphenylacetic acid +12-phosphonobutane-7,co, ≠-tricarmenic acid/-hydroxyethane-/, l-diphosphonic acid, N,
N/-bis(cohydroxybenzyl)ethylenediamiy-N,N'-diacetic acid One or more of these intermediate chelating agents may be used in combination as necessary. The amount may be sufficient as long as it is sufficient to sequester metal ions. For example, /(l is 0./1-1091 degrees.

If necessary, any development accelerator can be added to the color developing solution.

As the development accelerator, in addition to benzyl alcohol, Japanese Patent Publication No. 7-Itart, No. 37-J, No. 31-7,
No. 126, No. 4A4A-/2JrO, No. 7-40/
Thioether compounds described in No. P and US Pat. No. 3,113,247; JP-A-Sho! Ko≠rirλrigo and the same!
p-phenylenediamine compounds described in No. 10-/11114;
JOO744, Tokukai Sho, tj-/! ≦μ class ammonium salts described in US Pat. No. 410,122 and US Pat.

p-aminophenols described in No. 11; US Pat.
4c ri 4A, PO2, same! , /λr, /r2 issue, Dohiro, -30.7fla issue, same 3. Ko33゜ri/P No., Special Public Sho≠/-//≠J1 No., U.S. Patent Ko, μt Ko, O No. 6,
Same co, j de 4. Akin-based compounds described in Tako No. 1 and No. J, No. 11, No. 34 C, etc.
-ii* Dako No. 2!201, U.S. Patent 3. ix
r, its issue, special public show 4t/-//gei J1 issue, same≠--
KoJrtJ issue and US patent! ,! 12. ! 0/, etc., as well as l-phenyl-3-pyrazolidones, hydrazines, menion type compounds, thion type compounds, imidazoles, etc. *I
It can be added depending on the IC. Particularly preferred are thioether compounds and l-phenyl-3-virazolidones.

If necessary, any anti-capri agent can be added to the color developing solution of the present invention. Anti-capri agents include potassium bromide,
Alkali metal agnides such as sodium chloride and potassium iodide and organic anti-capri agents can be used. Organic anti-capri agents include, for example, benzotriazole, bu-nido abe/zimidazole,! - Nitroinindazole! -Methylbenztriazole,! -Nido abenztriazole,! -Oa benzotriazole, cochiazolylbenzimidazole, cochiazolylmethyl bene/
Nitrogen-containing heterocyclic compounds such as zimiguzole, mercapto-substituted heterocyclic compounds such as λ-mercaptobenzimidazole and comelcabutobenzotheazole, abino, and even mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. . These anti-capri agents may be eluted from the silver halide color photographic light-sensitive material during processing and may accumulate in the color developing solution, but from the viewpoint of reducing the amount of discharge, it is preferable that the amount of these accumulated amounts is small. .

It is preferable that the color developing solution of the present invention contains a fluorescent whitening agent. As the fluorescent whitening agent, μ,4L-diamino-1-2/-disulfostilbene-based compounds are preferable, and the amount added is Q~! f/! Preferably it is o, 1t-2f/l.

Furthermore, various surfactants such as phosphonic acid in alcohol, arylphosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary.

The processing temperature of the color developer in the present invention is! Q～to”
c is preferred, and more preferably 33~≠0C. The amount of replenishment is approximately JO to 000 per m'' of photosensitive material, preferably 30 to I!00. From the viewpoint of reducing the amount of waste liquid, it is preferable that the amount of replenishment is small.

Ferric ion complex salts are generally used as the bleaching agent in the bleach solution or bleach-fix solution used in the present invention.

A ferric ion complex salt is a complex of ferric ion and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or a salt thereof. Aminopolycarboxylate or aminopolyphospho/acid is aminopolycarbo/f
lI or a salt of aminopolyphosphonic acid with an alkali metal, ammonium, or water-soluble amine. Examples of alkali metals include sodium, potassium, lithium, etc.; examples of water-soluble amino acids include alkylamines such as methylamine, diethylamine, triethylamine, and butylamine;
Cyclic amino such as cyclohedylamine, aniline,
m-) arylamines such as luidine and pyridine;
Heterocyclic amino acids such as morpholine and biridine.

Typical examples of intermediate rate agents such as these aminopolycarboxylic acids and aminopolyphosphonic acids or their salts include: ethylenediaminetetraacetic acid ethylenediaminetetraacetic acid disodium salt ethylenediaminetetraacetic acid diammonium salt ethylenediaminetetraacetic acid tetra(trimethylammonium) salt Ethylenediamine/tetraacetic acid tetrapotassium salt ethylenediamine tetraacetic acid tetrasodium salt ethylenediamine tetraacetic acid trisodium salt diethylenetriamine pentaacetic acid diethylenetriamine pentaacetic acid pentanatricum salt ethylenediamine-N-(β-oxyethyl)-N,N
', N'-) ethylenediamine acetate-N-(β-oxyethyl)-N,N
',N/-)acetic acid trisodium salt ethylenediamine-N-(β-oxyethyl)-N,N
', N'-1 Dorianmonicum acetate salt Propylene diamine Tetraacetate Propylenethia Z Tetraacetic acid disodium salt Nitrilotriacetic acid Nitrilotriacetic acid trisodium salt Cyclohexanediamine Tetraacetic acid Cyclohexanediamine Tetraacetic acid disodium salt Iminodiacetic acid dihydroxyethylglycine ethyl ether diamine Tetraacetic acid glycol ether diamine tetraacetic acid nitre/diaminetetraglopionic acid phenylenediaminetetraacetic acid/,! -Diaminopropanol N, N, N/.

N'-tetramethylenephosphonic acid/acid ethylenediamine-N,N,N/,N/-tetramethylenephosphonic acid/,J-propylenediamine-N,N,N/.

Examples include N/-tetramethylene phospho/acid, but are not limited to these exemplified compounds.

Ferric ion complex salts may be used in the form of complex salts, and ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferrous phosphorus 1112, etc. A ferric ion complex salt may be formed in solution by mixing with a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarmenic acid. When used in the form of a complex salt, seven types of Any complex salt may be used, or two or more types of complex salts may be used. On the other hand, when a complex salt is formed in a solution using a ferrous salt and a gold chelating agent, one or more types of ferrous salts may be used. Furthermore, the chelating agent t-
One type or two or more types may be used.

Moreover, in any case, the chelating agent may be used in excess of the amount required to form the t-ferric ion complex salt.

Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.0/~/, Omo 1/l,
Preferably 0,0j~0,! Omo 1 /l.

Further, a bleach accelerator can be used in the bleaching solution or the bleach-fixing solution, if necessary. Specific examples of useful bleaching accelerators include U.S. Pat. No. 3, 13-! 713/No. 5
7air, 33-6173λ, JJ-72t2
J issue, same! J-ta! ! No. 30, same! ! -41buJ/remaining
7J-104c2J2, same! ! -/J444J4C
No. 7J-104c2J2, No. 13-2r4Aλ, Research Disclosure/I6/7/λP (/
Compounds having a mercapto group or disulfide group described in JP-A No. 1989-10-0/2, etc.;
Tokukai Shoj Co. 2013.2 issue, same! j-Jλ731,
Thiourea derivatives described in U.S. Pat.
23! Iodide described in No. West German patent @Pjbu, lA10
Same issue! , 74Lr, polyethylene ogicides described in No. 4c317; polyamine compounds described in Japanese Patent Publication No. 4ct-r♂3; and others published in Japanese Patent Application Publication No. 4CT-R♂3; −≠2≠3 Hirogo, same≠2−! No. 211, 1l-P4Af No. 27, j≠-
3J727, 77-JJjOj and 3JjOj
43? Examples include compounds described in μO, iodine, bromine ions, and the like. Among these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and are particularly preferred as described in US Pat.
The compounds described in No. 1 are preferred.

Additionally, the bleach or bleach-fix solutions of the invention may contain bromides (e.g. potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodides (e.g. iodide). ammonium) rehalogenation/rehalogenation agent. If necessary, use pH buffering agents such as boric acid, starch sand, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Seven or more types of inorganic acids, organic acids, and their alkali metal or ammonium salts, as well as corrosion inhibitors such as ammonium nitrate and guanidine, can be added.

The fixing agent used in the bleach-fixing solution or fixing solution of the present invention is:
Known fixing agents, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid, J,4-dithia-/, If-octanediol, etc. These t-
Seven types or a mixture of two or more types can be used.

In addition, a special bleach-fixing solution consisting of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in Japanese Patent Application Laid-Open No. 1996-0103 can also be used.
In the present invention, it is preferred to use thiosulfates, particularly ammonium thiosulfates, in an amount of 1/l of fixing agent.
．． 3-comole is preferred, more preferably O0! ~i,
o mole range.

The pH range of the bleach-fix solution or fix solution in the present invention is 3 to 3.
A value of 10 is preferred, and a value of 10 to 10% is particularly preferred. If the pH is lower than this, the desilvering performance is improved, but the deterioration of the solution and the leucoization of the cyan dye are accelerated. On the other hand, if the pH is too high, desilvering will be delayed and staining will occur more easily.

To adjust the pH'kt4, add hydrochloric acid, sulfuric acid, nitric acid, acetic acid (glacial acetic acid), bicarbonate, ammonia, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, etc. as necessary. Can be done.

11fcfl! The 4-white fixer may contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fix solution and fixer of the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives. , metabisulfite (e.g. potassium metabisulfite,
Sodium metabisulfite, ammonium metabisulfite,
Contains a sulfite ion-releasing compound Wt such as Naton. These compounds have approximately 0.0-~0,j in terms of sulfite ion.
The content is preferably 0 mole/E, more preferably 0.0 to 0 mole/l.

As preservatives, sulfites are commonly added, and other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

Furthermore, buffering agents, fluorescent whitening agents, chelating agents, antifungal agents, etc. may be added as necessary.

Next, the water washing step of the present invention will be explained. In the present invention, instead of the usual "water washing process", there is no substantial water washing process, and only a so-called "stabilization process" is performed. You can also use kumquats for convenient processing. As described above, the term "water washing treatment" as used in the present invention is used in the broad meaning described above.

The washing water 't of the present invention is difficult to specify because it varies depending on the number of baths in multistage countercurrent washing and the amount of pre-bath components of the photosensitive material brought in. However, in the present invention, the bleach-fix solution in the final washing bath is It is sufficient if the component is /x10-' or less. For example, in the case of 3-tank countercurrent water washing, approximately 1 m2 of photosensitive material
It is preferable to use 000rd or more, more preferably,
1000J or more. In the case of water treatment, it is preferable to use a photosensitive material/m'' of 10100N1000.

The water washing temperature is iz＠c−μj ”C, more preferably 20
°C~3z@c.

In the washing process, for the purpose of preventing sedimentation and stabilizing the washing water,
Various known compounds may be added. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid; bactericidal agents and antibacterial agents that prevent the growth of bacteria, algae, and mold in each glaze (for example, Antifung,
Agents)Mo1. //, AJ%pco07~CocoJ(/frJ) Compounds described in K and compounds described in "Chemistry of Antibacterial and Antifungal" by Hiroshi Horiguchi, metal salts represented by magnesium salts and aluminum salts, Alkali metal and ammonium salts, surfactants for preventing drying load and unevenness, etc. can be added as necessary. Or "Photo, Sci, Eng" by West.
), Volume 3, 3μ4c to JJf Easy (/Ribu!), etc. may be added.

Furthermore, the present invention is particularly effective in cases where a chelating agent, a bactericide, or an anti-piping agent is added to the washing water, and the amount of washing water is greatly reduced by multi-stage countercurrent washing in multiple tanks or more. In addition, in addition to the usual water washing process, a multi-stage countercurrent stabilization treatment S (so-called stabilization treatment) as described in JP-A No. 7-1183 is applied.
1- It is also particularly effective when implemented. In these cases, the bleach-fixing component of the final bath may be Jxlo or less, preferably lx10 or less.

Various compounds are added to this stabilizing bath for the purpose of stabilizing images. e.g. membrane pH 1-adjust (e.g. p)I
various buffering agents (e.g. borate,
Representative examples include aldehydes such as metaborate, starch sand, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin. This can be cited as an example. In addition, chelating agents (inorganic phosphoric acid, aminopolycarbo/acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarmenic acid, etc.), fungicides (thiazole type, isothiazole type) - rognated phenol, sulfanilamide, benzotriazole, etc.), surfactants, fluorescent whitening agents, hardeners, etc., and two or more compound golds for the same or different purposes may be used in combination.

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

・If you want to significantly reduce the amount of washing water as described above, why not use some or all of the O/9-flow solution in the washing water as a pre-bath, such as a bleach-fix bath or a fixing bath? It is preferable to introduce St, for the purpose of reducing the amount of drained liquid.

In this treatment step, during continuous treatment, a constant finish can be obtained by using a replenisher for each treatment solution to prevent fluctuations in the liquid composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

Each treatment bath may be equipped with a heater, a temperature sensor, a liquid level sensor, a circulating bong filter, various types of floating pigs, various types of squeegees, nitrogen stirring, air stirring, etc., as necessary.

For color photographic processing, if a color developing solution is used,
It can be applied to any processing step. For example, it can be applied to processing color paper, color reversal eater, color positive film, color negative film, color reversal film, etc.

(Example) Next, the present invention will be explained in more detail based on examples.

Example 1 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support which was laminated on both sides with polyethylene and then toned. The coating solution was prepared as follows.

First layer coating liquid! ! I4 made Ixa coupler (Ex Y 1) / t,
j f O and color image stabilizer (Cpd-1) a, AP with acetic acid ether core, 2cc and solvent (8o1v-1) 7
．． 7CC' and dissolve this solution t-/ 0% sodium dodecylbenzein sulfonate j cc f i
It was emulsified and dispersed in an aqueous solution of oszeyten/rzcc. On the other hand, the average particle size is 0. Monodisperse cubic silver chlorobromide emulsion (silver bromide 10.0 mol%, Ag7
11 were prepared by adding 0 f/icy and 7 moles of blue-sensitive sensitizing dye shown below per 7 moles of gold and silver. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below.

Coating solutions for the second to seventh layers were also prepared vI4 in the same manner as the first layer coating solution.

As a gelatin hardening agent for each layer, CJ,! −
Dichloro-a-)riazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer (per mole of silver halide!, O x 10-4 mol) Green-sensitive emulsion layer (0 x 10-' mole per mole of silver halide) and (Schiff per mole of silver halide, 0x10-' mole) Red-sensitive emulsion layer (0x10" mole per mole of silver halide) For the red-sensitive emulsion layer, the following compound 1 - 9 λ per mole of silver halide, 6X10 “””””moles were added.

Also, for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, /-(j-methylureidophenyl)-! - mercaptotetrazole at 41.0% per 7 moles of silver nologonide, respectively. Next, add O x 10 mol, 3°17X/o-'' mol, O x 10' mol.

In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, H-hydroxy-bu-methyl-/, J, Ja, and 7-chitrazaindene were added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer, respectively.
Mol, 1. ! ×10 mol was added.

The composition of each layer is shown below, the numbers are coating amount Cf/, 2
) represents. ...Silver rognide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [white pigment (TiC) 2 on the polyethylene on the first layer side
) and a bluish dye (ulmarine)] First layer (blue-sensitive layer) Average grain size o, yλμm1 Coefficient of variation r, second monodisperse chamber cubic silver chlorobromide emulsion (Br:r 0%) O , at gelatin /, rJ yellow coupler (ExY□) Q, 74 color image stabilizer (Cpd
-/ ) o, t trisolvent (Solv-/)
0.3! 2nd layer (color mixing prevention layer) Gelatin Q-Tade color mixing prevention agent (CPCT-2) o, or 3rd layer (green sensitive layer) Monodisperse cubic chlorbromide with average particle size 0.30μm1 coefficient of variation 70.3 Silver emulsion (Br: rO%) 0. / Bugelatin 7.7 Tamase 7 Takagura (EXMl) 0.32 Color image stabilizer (Cp
d-j) 0.20 color image stabilizer (C: pd-
4t) 0,0/solvent (8o1v-ri
0.4! Fourth layer (ultraviolet absorption layer) Gelatin /,! r Ultraviolet absorber (UV-/) o, Buko color mixing inhibitor (C
pd-7) 0.0! Solvent (Solv-J)
0.2μ fifth increase (red sensitive layer) Average grain size o, atμm1 Coefficient of variation p, tr% monodisperse cubic silver chlorobromide emulsion (Br near 0) 0.23 gelatin /, J4t cyan coupler ( ExCl) 0- j 0 color stabilizer (
Cpd-b) a, /7 polymer (Cpd-
y) 0. Related O solvent (Solv-see)
0.23 Sixth layer (ultraviolet absorption layer) Gelatin 0.1! Ultraviolet absorber (UV-i) O, Solvent (Sol)
v-j) 0.01 Seventh layer (protection/I) Gelatin 7.33 Acrylic modified polyvinyl alcohol 11 [8 bodies (degree of modification 17%) 0.17 Liquid paraffin 0.03 (ExYx)
Yellow coupler C) i3 (ExM engineering) Magenta coupler (ExC) Cyan coupler α (epa-/) Color image stabilizer (Cpd-2) Color mixture prevention agent (Cpd-J) Color image stabilizer (epa-Hiro) Color image stabilizer H (cpct-v) Color mixture prevention agent R (Cpd-4) Color image stabilizer C4H3(t) C4)4. (t) Konij:l mixture (weight ratio) (Cpd-7) Polymer (UV-/) Ultraviolet absorber C, Hll (t) e, H, (t) l:Hiroshi:3 mixture (weight ratio ) (8o1v-/) solvent (8o1v-2) -:l mixture of solvent ($1 ratio) (Solv-3) solvent (Solv-≠n solvent) Addition of dye of the invention and comparative dye to the above fourth layer Samples (1) to <r) were prepared. The dye added to each sample is shown in Table 1. Addition amount of each dye is A×10
Mol/m2.

For samples (1) to Cr), the stability of the dye in the film and the exposure humidity dependence were investigated. Regarding stability, raw sample t-3
! 'C-10% was evaluated based on the residual rate of dye after being left for one week, -! The exposure humidity dependence was 21'C-47
Attack! and Jj ”C-11% (After exposure under D conditions, the following treatment was performed, and the relative sensitivity at optical density = 80 was 1.
We evaluated the twilight layer, which exhibits large changes. The evaluation result is the second
Shown in the table.

Color development JJ'CJ minutes 30 seconds bleach fixing
JJ"C/min JO second water wash λμ~J@"c J revolution
Drying 7ONlθ℃ 7 The composition of the published treatment solution is as follows.

Color developer water r00
m diethylene triagine pentaacetic acid @ /, Of nitrilotriacetic acid /, if benzyl alcohol l! -Diethylene glycol 10w1 sodium sulfite
Of potassium bromide
0. jf potassium carbonate
JOfN-ethyl-N-(β-methanesulfonamidoethyl)-J-methyl-≠-aminoanili/sulfate! , Of and Doro Middle Siluaone Sulfate Hiroshi, o? Fluorescent tllll whitening agent (
W)iITEX*B.

Add water to iooowtpH (
aj”C) lo, a.

Bleach-fix water 4'0
0dAmmonicum thiosulfate (70%) / !
Owl Sodium sulfite lk/IP Ethylenecyaminetetraacetic acid iron <m) Ammonium Jjf Ethylenediaminetetraacetic acid disodium It Add water to 1000dpH (Koj@c)
4. As is clear from the 70th λ I,
Samples (1) to (7) using the dye of the present invention have excellent stability in the film and a high relative sensitivity of λj@c-it%,
There is also little decrease in sensitivity at z″c-rzs.

Example 2 The exposure humidity dependence of samples (1) to (r) in Example 7 was evaluated in the same manner as in Example 7, except that the processing was performed in the following steps. The evaluation results are shown in the third light.

Color Gen II 3r”c/min 4cO Bleach Constant 7iIF 30~3 〇CI minutes oo seconds rinse■
30-3 Hiro 0C 20 seconds! 77s @ 30 Nj! 'C20 second rinse 0
7ONJ≠11C Q seconds drying 70~rO'C! 0 seconds (rinse■
→ 3 tanks countercurrent method to [F] Next. ) The composition of each treatment liquid is as follows.

Color developer water r00
xddiethylenetriaminepentaacetic acid /, Of/-
Human adP Schechiriden-l.

l-Diphosphonic acid C40S)
Triacetate fR2, Of triethylenediami/(l, μ one diazabicyclo[ko, λ.

λ] octane) t,oy potassium bromide. ,! ? potassium carbonate
JOfN-ethyl-N-(β-
Methanesulfonamide ether)-3 Monomethyl≠-aminoaniline sulfate! @! f diethylhydroxylamine μ, of fluorescent 4 whitening agent (UVI
TEX-CK manufactured by Tepa Geigi) 1. jy Add water to 1 pH (,27
'C) 10.2! Bleach layer liquid water ≠0
0m ammonium thiosulfate (70%) 200y
dSodium sulfite Of ethylenediaminetetraacetate iron (1) Ammonium toy edelendia i/Tetraacetic acid ninato water added to 1000g pH (2
j @C) 7.00 Rinse liquid ion exchange water (calcium, magnesium each jpp
m or less) Table 3 As is clear from Table 3, samples using the dye of the present invention (
1) to (7) are 2! There is little decrease in sensitivity at @C-11%.

Example 3 A multilayer color photographic paper having the following J-configuration was prepared on a paper support laminated on both sides with polyethylene. The coating solution y4 was prepared as follows.

First layer coating solution preparation Yellow coupler (ExYz)/F-/f and color image stabilizer (Cpd-/)≠, ≠2 with ethyl acetate 4
7. Add and dissolve 7.7cc of Jcc and solvent (8o1v-/), and add this solution to the 10th gelate/aqueous solution/containing 1cct-of 10''S dodecylbenze/sodium sulfonate/
It was emulsified and dispersed in r j CC. On the other hand, the average particle size is 0. P4μm1 coefficient of variation2. Monodisperse cubic silver chlorobromide emulsion rumored to be λ (contains more than i, o mole of silver A, 7ot/14 Ag)
7 moles of back-sensitizing dye shown below! ,0X
10 moles were added. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below.

The spraying solutions for layers 2 to 71 were applied to the chest in the same manner as the #1 coating solution.

As a gelatin hardening agent for each layer, /- God Sea J,! -dichloro-5-) riazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Stomach-sensitive emulsion layer 03H C ag:/ka@/mohto-hl)j, oxto 4
(mole) Green-sensitive emulsion layer (7 moles of silver halide, 0 x 10"'-' moles) Red-sensitive emulsion layer (7.0 x 10-' moles per 1 mole of silver halide) Red-sensitive emulsion layer 2H5 C2 )16x+ (7 moles of silver halide, oxio-' moles) For red-sensitive emulsion layers, the following compound is added to /ScJ silver halide, 19 moles of silver monoxide, 0-3 Mol added.

For the light-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, /-(j-methylureidophenyl)-j-mercaptotetrazole was added (9F) per mol of silver halide, respectively.
T,! X10 moles, 7°7X/0-' moles, co, z×io moles were added and then.

The composition of each layer is shown below. The number is the coating amount (1/m2)'
R represents the total coating amount in terms of silver for the silver halide emulsion.

Support polyethylene laminate paper [white pigment (Ti (J2)
and bluish dye (#blue) t-] 1st/i1 (blue sensitive layer) Average particle size o, piμm1 Coefficient of variation? , Kohata's monodispersed cubic silver chlorobromide emulsion (Br 1 mol%) 0. JO gelatin
Hart IzO-Coupler (EX
Y2) 0-14 color image stabilizer (Cpd-/)
0.7? Solvent (Solv-/)
0. ! ! Second layer (color mixing prevention layer) Gelatin 0゜も2 color mixing prevention agent (cpci-2) o, or Third layer (green sensitive layer) Average particle size 0. ! Hiroμm1 Monodisperse cubic silver chlorobromide emulsion with coefficient of variation 10.0 (Br1 Moriho) θ, 3 gelatin
l-2″ magenta coupler (
E x M 2 ) 0.37 color image stabilizer (C
pd-3) 0.23 color image stabilizer (Cpd-
Jr) 0. /co-solvent (8o1v-2)
O-≠2 Fourth layer (ultraviolet absorption layer) Gelatin /, 11 Ultraviolet absorber (UV-t) o,≦K Color mixing prevention agent (
Cpd-1) 0.0! Solvent (8o1v-,
y) o, 2-Fifth layer (red sensitive layer) Average grain size 0.11 μm1 Coefficient of variation io, 3% monodispersed cubic silver chlorobromide emulsion (Br1 mol%) O, conogelatin
/, J Hiro cyan coupler (
E x Cz ) 0- J 4' Color stabilizer (cpa-4) 0./7 Polymer (Cpd
-7) 0. Solvent (8o1v-u)
0. KO3 6th layer (ultraviolet absorption #I) Gelatin Q,! 3 Ultraviolet absorber (UV-/) 0, 2/solvent (
Solv-J) 0. Or 7th layer (retaining layer) Gelatin / Acrylic modified copolymer of 13 polyvinyl alcohol (denaturation degree 17) 0. /7 Liquid paraffin 0.03 (E x Y
2) Yellow cutler (Ex M2) magenta coupler l (Ex C2) cyan coupler α (Cpd-#) color image stabilizer Sample (li) in which the dye of the present invention and comparative dye were added to the fourth layer. ~(/j)'t-Created. The dye added to each sample is shown in Table DA. The amount added is 1 for each dye.
It is 0 mol/m.

The exposure humidity dependence was investigated for samples (P) to (#).

The exposure humidity dependence is λz'c-zz% and λ! "C.
After exposure under the condition of -1j%, the following treatment was performed, and the relative sensitivity at optical density=1.0 was evaluated for the blue-sensitive layer with a large change of 1. The evaluation results are shown in Table 3.

Processing process Temperature Time Color appearance [
#! Jj"Cμ! seconds bleach fixing 30~JJ
@Cμ! 30-37°C of stable temperature ■
Stable at 30~37 °C for 20 seconds ■ 30~
Stable at 37°C for 0 seconds 0 30~J7'C, dry for 10 seconds 7ONrj'ctOsho (stable ■→
■To≠evening/reverse flow method and friend. ) The composition of each treatment liquid is as follows.

100t of water
dJ ethylenediaminetetraacetic acid 2.0f triethanolamine r, Of sodium chloride /, μ? potassium carbonate
CojfN-ether-N-(β-methanesulfo/amidoethyl)-3 monomethyl-≠-aminoaniline sulfate! , 09N, N-diethylhydroΦdylamine ≠, Co? J, t-dihydroxybenzene mono/, J, ≠-trisulfonic acid 0.32 Fluorescent brightener (≠, μ'-diamine water added to 1000xlpH (
λJ 'Cn 10.10 Bleach-fix solution *'00 xi Ammonium thiosulfate (70%) / 00rd
Sodium sulfite / If iron ethylenediaminetetraacetate cm) Ammonium 111 Disodium ethylenediaminetetraacetate Jj Add water 1000txlp) 1 (λi
``c) j, z stabilized formalin (37%) 0./l formalin-sulfite adduct 0.7fJ-chlorocomethyl-inteazolin-3-one 0.0 tcomethyl-Hiro-intheazolin-3-one on o, oit copper sulfate
o, oojt add water
1000tdpH(Jj'C)
44.0 As is clear from Table J, No. jfi, Samples (P) to (/) used on the dyes of the present invention have little decrease in sensitivity during high-humidity exposure;
This shows that it is an excellent dye.

Example 4 A silver halide emulsion consisting of silver chlorobromide (average grain size of silver bromide of 3 mol %: Q, Jμ) containing 1 xio-' mole of Ht-per 1 mole of silver. .

This emulsion 1! Near-split, each with cohydroΦcy μ, 6-dichloro-/,! as a hardening agent! ,! - Sodium triazine and potassium polystyrene sulfonate as a thickener were added and coated on a polyethylene terephthalate film so that the coated silver amount was 44 f7 m2.

On top of these seven emulsion layers, a gelatin solution with or without dye is added as a protective layer, and the gelatin amount is t, at/m.
It was applied so that The protective layer used p-dodecylbase/sodium insulfonate as a printing aid, and the same compound as the emulsion layer as a thickener.

The nine samples thus obtained were exposed to light using a P-6oy type printer manufactured by Dainippon Screen Co., Ltd., and then developed using a developer LD-r3J manufactured by Fuji Photo Film Co., Ltd.

The results are shown in Table 1.

Table 1 and Table 7 below are the nine performance test methods listed below.

l) Relative sensitivity; concentration 1. jt - Reciprocal of the exposure amount to be given.

The case where no dye is added is set as 100 in each case.

λ) Fog after safelight irradiation: Toshiba anti-fading fluorescent lamp (FLR≠08W-DL-XNu
/M) Fog at 9 o'clock when developing after 7 hours of irradiation under approximately J00 ru/x.

3) Residual color: As is clear from the table of absorbance values at λmax after development, the dyes of the present invention have less adverse effects on photographic emulsions, that is, lowering of sensitivity, and have significantly improved safelight properties than comparative dyes. It is folded.

Example-5 RbJ-containing silver chlorobromide (average diameter including silver bromide other than 1 mole; 0, coco μ) per mole of silver
) A silver halide emulsion was prepared.

This emulsion was divided into two parts, the same compounds as those in Example were added as hardeners and thickeners, and the amount of silver was 3.5 mm on a polyethylene terephthalate film. rt7m". Gelatin (an amount of 197m") was applied on top of this emulsion layer.
After dissolving the mordants shown below (in an amount of o, zf/m 2 ) and various dyes in water, they were applied as a protective layer. As the coating aid, the same compound as in Example ≠ was used.

Mordant The nine samples thus obtained were treated in the same manner as in the final example and tested for relative sensitivity, capri after safelight irradiation, and residual color.

The results are shown in Table 7.

As is clear from the results in Table 7, by using the dye in combination with a mordant, the effect on photographic sensitivity of the dye of the present invention can be greatly improved compared to that of the comparative dye, and the residual color after processing is also reduced. Few.

(Effects of the Invention) According to the present invention, a silver halide photograph having a hydrophilic colloid layer containing a novel dye that is decolorized in photographic processing and does not adversely affect the photographic properties and spectral sensitization of the photographic emulsion. It is possible to obtain photosensitive materials.

Further, according to the present invention, a silver halide photographic material having excellent stability over time and low exposure dependence can be obtained.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendments Showa G-Co! Mon > 1st Commissioner of the Patent Office, qJ
l.Indication of the incident 1937 patent application No. 7'? 44r
J No. 2, title of invention Silver halide photographic light-sensitive material 3
, Relationship with the case of the person making the amendment Patent applicant 4, Subject of the amendment The description in the "Detailed Description of the Invention" column 5 of the specification and the "Detailed Description of the Invention" section of the description of the contents of the amendment are as follows: Correct as shown.

1) Page 14? row Before “Kishukuke” VJ Insert all.

2) Third! Page dye specific example 3r and correct it.

Procedural amendment

Claims (1)

[Claims] A silver halide photographic material containing at least one dye represented by formula (I). (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 and R_2 are an alkyl group, an aryl group,
It represents a cyano group, ▲There are numerical formulas, chemical formulas, tables, etc.▼, R_5 and R_6 each represent a hydrogen atom, an alkyl group, an aryl group, -SO_2R_7, and R_7 represents an alkyl group or an aryl group. Further, R_5 and R_6 may form a 5- or 6-membered ring. R_3 and R_4 each represent a hydrogen atom or an alkyl group, Q_1 and Q_2 each represent an aryl group, X_1 and X_2 represent a bond or a divalent linking group, Y_1 and Y_2 represent a sulfo group and a carboxyl group, respectively, L_1, L_2, and L_3 each represent a methine group. n is 0, 1 or 2, m_1, m_2 is 1 or 2, p_1, p_2 is 0, 1, 2, 3 or 4, q_1
, q_2 represents 1 or 2.