JPH01183652A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the decoloring property, the color-reproducibility and the safe-light stability of the title material by incorporating a specified dyestuff in the sensitive material. CONSTITUTION:The dyestuff shown by formula I is incorporated in the emulsion layer or the another colloid layer of the sensitive material. In formula I, R1-R4 are each alkyl, aryl or a heterocyclic ring residual group, L1-L3 are each a methine group, (n) is 1-3, any one of the groups R1-R4 is a group having two or more of carboxylic or sulfo groups. The dyestuff may be incorporated in the sensitive material directly or in a dissolved state or in a dispersed state. The dyestuff can be localized in a prescribed layer by coexisting the dyestuff with a hydrophilic polymer having an electric charge opposite to that of an dyestuff ion, as a mordant. And the dyestuff is exemplified by the compd. shown by formula II, etc.

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-rhodanide photographic light-sensitive 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, the entire photographic emulsion layer 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 is reflected at the interface between the emulsion and the support, or at the surface of the light-sensitive material opposite to the emulsion layer, and enters the photographic emulsion layer again. In order to prevent blurring of the original image, that is, halation, a colored layer is provided between the photographic emulsion layer and the support, or on the side of the support opposite to the photographic emulsion layer. Such a colored layer is called an antihalation layer. In the case of a multilayer color photosensitive material, an antihalation layer may be placed between each layer.

Deterioration of image sharpness due to light scattering in the photographic emulsion layer (this phenomenon is generally called irradiation)
In order to prevent this, the photographic emulsion layer is also colored.

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. In other words, it has an adverse effect on the performance of the silver halide photographic emulsion layer in a chemical sense.
For example, avoid reducing sensitivity, latent image regression, or shading.

(3) Although it is decolored during the photographic processing process, it is dissolved and removed and does not leave any harmful coloring on the photographic material after processing.

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, British patent @s o t.

Jlj issue, same/, /77, μkota issue, same/, J//,
Itl No. 1, Ibid./, No. 331,799, Ibid./.

JI! , No. 37/, No. 44j7.21II, No. 1
,≠33,10th issue, same/, 1! ! ,! It issue, JP-A Show IAt-rs, TSO issue, same + tar//4 (.

4t20, same! No. 2-20,130, 1j-/l/
,J,! J issue, Pl! ? -/ / /, A 4A
No. 0, U.S. Patent No. 3.2 H.7.127, U.S. Pat. ≠6
2゜ri tx, 3.7 Hirot, 33ri, Dohiro, 0
oxonol dyes containing all pyrazolone nuclei or barbylic acid nuclei described in US Patent No. 7g, No. 233, etc.;
j33. ≠No. 72, No. 3.37, No. 533, British Patent No. 1. λ71,62/No., West German Patent No. 2. Ri it
, other oxonol dyes described in British Patent Nos. j7j, t9/, tro, tsi, etc.
Same j Tata, No. 623, No. 7♂t, No. 207, No. 07,
No. 12g, same l.

O Hirosu, tori issue, US Patent No. ≠, 2! r! , Jco 2, Tokukai Sho! Azo dyes described in Tar2//, 0≠3, etc., published by JP-A-Sho! 0. -/00. / / No. 4, Pl! Hiro-//I, No. 2177, British Patent %2,0/≠, J Riwo No. 7! θ, azomethine dye described in oJi, etc., US Patent @ λ, 161.7! Anthraquinone dye described in U.S. Pat. No. 2,331,002, r
, try, zai issue, same 2. ! No. 31,001, British Patent No. JR TX.

No. 60, same/, 210, 2, No. 2, JP-A No. 1 O-4c
O, 4, 2j, same! /-J, No. 623, same! /-10
．． '? No. 27, same jp-7lr,! No. 447, Special Publication Showa 4
J'-3,216, Tatar No. 37,303, etc. A IJ IJ Den dye, Tokko Sho λ1-, J, 0
No. 12, No. 4444-74.1944, No. 5y-2t
, the steryl dye described in the RRI issue, etc., British Patent No. ≠
lit, jlJ issue, i, 33z.

Reference λλ issue, Tokukaisho! Triarylmethane dyes described in Turcoco L', No. 2!0, etc., British Patent No. 1゜071.
No. 633, same /, /! ! , Jμ) issue, same/, 21
No. 11.730, same/, 1771.221, same/, 5
4tu, merocyanine dyes described in Ir07, etc.
US Patent No. 2. Examples include cyanine dyes described in IIItJ, Kot No. 6, 3.2 Rihiro, No. 532, and the like.

Among these, oxonol dyes, which have two pyrazolone nuclei, have the property of being decolorized in developing solutions containing sulfites, and are used as dyes for photosensitive materials as useful dyes that rarely have any adverse effects on photographic emulsions. I've been exposed to it.

However, although some dyes belonging to this family have little effect on the photographic emulsion itself, they have a negative effect on the spectrally sensitized emulsion.
It has the disadvantage of causing a decrease in sensitivity, which may be caused by spectral sensitization in unnecessary areas or by desorption of the sensitizing dye.

Furthermore, due to the speeding up of development processing that has become popular in recent years, some residual particles may remain 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 decrease over time. It has the disadvantage that the desired photographic effect cannot be obtained.

In addition, in order to improve color reproducibility and safelight safety in color photosensitive materials,
No. 30, U.S. Patent No. J, 74tJ.

The use of specific oxonol dyes has been proposed in the West German patent 'WJ Co, Tacor, irI/-'. However, in addition to the above-mentioned drawbacks, these methods also have the drawback that, because the spectral absorption of the dye is not appropriate, if a large amount is added to obtain a sufficient effect, the photographic sensitivity may be reduced.

(Problems to be Solved by the Invention) The object of the present invention is, firstly, to obtain a silver halide emulsion layer dyed with a hydrophilic colloid layer by 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 photographic materials.

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 novel water-soluble dye that exhibits excellent decolorization properties upon processing.

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

A fourth object of the present invention is to provide a color photographic material with improved color reproducibility.

A fifth object of the present invention is to provide a silver halide photographic material with improved safelight safety.

(Means for Solving the Problems) These objects of the present invention are achieved by containing at least one dye represented by the general formula [I].

General formula [■] In the formula, R1, R2, R3, and R4 each represent an alkyl group, an aryl group, or a heterocyclic residue;
3 each represents a methine group. n represents /, -2 or 3. However, any one of R1, R2, R3, and R4 has a carboxyl group or a sulfo group, and the total number is at least two or more.

- substituents R1, R2, R of the dye represented by the formation [■]
3. 4 is an alkyl group (e.g., methyl, ethyl, butyl, octyl, dodecyl, etc. with carbon number /-/2)
, a substituted alkyl group (an alkyl group having a carbon number of up to 12, and as a substituent, a sulfo group (flJ, t, sulfomethyl, sulfoethyl, sulfobutyl), a carboxyl group (
For example, carboxymethyl, carboxyethyl), hydroxy groups (e.g. hydroxyethyl, hydroxypropyl), alkoxy groups (e.g. methoxyethyl, ethoxyethyl), halogen atoms [fluoro atom, chlorine atom,
Bromine atom (e.g. 2-chloroethyl, 2,J,2-trifluoroethyl)], cyano group (FJeva, λ-cyanoethyl), sulfonyl group (e.g. Ha, methanesulfonylethyl), nitro group (9Ql Ha, - 2-nitrobutyl)
, amino group (e.g. dimethylaminoethyl, diethylaminopropyl), aryl group [further for aryl group]
・Contains substituents such as rhodan atoms, sulfo groups, carboxyl groups, alkyl groups, alkoxy groups, cyano groups, nitro groups, amine groups, sulfonyl groups, alkoxycarbonyl groups, acyl groups, carbamoyl groups, sulfamoyl groups, and acylamino groups. (eg, benzyl, p-chlorobenzyl, 0-sulfobenzyl, o-, p-disulfobenzyl, p-hydroxybenzyl, p-methoxybenzyl, p-dimethylaminobenzyl, p-sulfophenylethyl) ]), aryl groups (e.g. phenyl, naphthyl), substituted aryl groups [substituents include slyt4(
For example, p-sulfophenyl, 2.1-disulfophenyl, μm sulfonaphthyl), carboxyl group (e.g., t-carboxyphenyl, m-carboxyphenyl)
, hydroxy group (e.g. p-hydroxyphenyl),
Alkoxy group IJ, tb, p-methoxyphenyl, m-
ethoxy7enyl), halogen (flLt, p-
Chlorophenyl% p'romophenyl, p-fluorophenyl), cyanogen (e.g. p-cyanophenyl,
0-cyanophenyl), nitro group (fFllttf, p
-nitrophenyl), amine groups (e.g. p-dimethylaminophenyl), alkyl groups (e.g. p-methylphenyl, O-methylphenyl), acylamino groups (e.g. p-acetylaminophenyl, p-methanesulfonylaminophenyl) ), carbamoyl groups (e.g., carbamoyl, dimethylaminocarbamoyl), sulfamoyl groups (e.g., dimethylaminosulfamoyl, piperidinosulfamoyl)], heterocyclic residues [the petero ring contains a nitrogen atom, an oxygen atom, a sulfur atom ! ~ is a membered ring, which may be further fused with a benzene ring (e.g., λ-pyridyl, goupyridyl, copyrimidyl, 2-triazinyl, kochizazolyl, copenzothiazolyl, kochizazolyl, cobenzimidazolyl), etc. .

L1, L2, and L3 represent methine groups, and these methine groups may be independently substituted with methyl, ethyl, phenyl, chlorine, sulfoethyl, carboxyethyl, or the like.

n represents 1%, 3t.

However, any one of R1, R2, R3, and R4 has at least one carboxyl group or sulfo group. Further, these carboxyl groups and sulfo groups may form not only free acids but also salts (eg, Na salt, K salt, ammonium salt, ≠ grade ammonium salt).

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

SO3 to λ O3K S03 to -! OsS Na03S -Formation (I) Compound Vis can be synthesized by the synthesis method shown in (I). For example, as shown in the reaction formula below, 1. Koji substitution-3,! -pyrazolidinedione (I [
) and (■a ), (II[b ), (■C), (I[I
It can be synthesized by condensing the compound represented by d) or (]IIe) in the presence of a gold base.

(In) (IIIa) (IIIb) HC(0CzHs)3 (I[[d) In the formula ・R1% R2, R3・R4・Lls L2・L3
．． n has the same meaning as above, and Z represents a hydrogen atom, a nitro group, or a rhodane atom (eg, chloro, bromo). R5 represents a hydrogen atom, an alkyl group (eg, methyl, ethyl, etc.), or a phenyl group. X represents an anion (eg chloride, bromide, iodide, perchlorate, methylsulfate, ethylsulfate, p-toluenesulfonate, etc.).

The compound represented by the general formula (TI) is listed in "Chemical Abstracts"! As described in Volume O, r7u3e (/9!6) 1. It can be easily synthesized by condensing Kodi-substituted hydrazine and a malonic acid derivative.

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

Synthesis example 1 (synthesis of the present invention/) /, 2-diphenyl-3,j-pyrazolidinedione/l
, 7f gold concentrated sulfuric acid 4 tlytl and oleum sulfuric acid J 4gJ
Add it inside and heat it in a steam melter for a long time. After cooling, it is added to water and further neutralized with potassium hydroxide solution. When the precipitated crystal yfr:F was removed and washed with methanol, a sulfonated product of 7,2-diphenyl-3,5-pyrazolidinedione was obtained. can get.

1,-2-diphenyl-3,! - Sulfonated product of pyrazolidinedione, 72; ethyl orthoformate/, J'f
, triethylamine λ? Then, acetic acid Itd was added to methanol (20ml), heated under reflux for 1 hour, and the precipitated crystals tF were collected. Melting point JOO'C or higher, λH20,, cm, g
7.0/ - Sulfonated product of pyrazolidinedione, 71, tetramethoxypro/ξ/, 3? , mix methanol 2 and IItl,
Further, triethylamine λ1 and acetic acid LD were added and the mixture was heated under reflux for 6 hours. When all the precipitated crystals were washed with hot methanol and dried, the compound 6. I was able to get more. Melting point J
OO0C or higher, λH20 Hiro Jnm, t/,! /X/
(75ax Synthesis Example 3 (Compound 3 of the Present Invention) /, 2-diphenyl-3,j-pyrazolidinedione sulfonated product 10,71, /-anilino- obtained in Synthesis Example 1
j-phenylimino-/, J-ntadiene hydrochloride,
ry, triethylamine≠d? Methanol λ! - and acetic anhydride≠, jdk was added dropwise under stirring at room temperature. After further reaction for 2 hours, nine crystals were separated and collected. When the crude crystals were added to methanol jO-, heated and washed, and the dried crystals were dried, compound 3 was obtained. / can be obtained. Melting point 3
00°C or higher, λH20, ri(1) nm.

ax t /, IO×105 Synthetic gal (compound of the present invention 10) l-phenyl-λ-(cosulfonyl)-3,5-
Pyrazolinedione sodium salt (Intermediate C) Phenylhydrazine IO≠2 is dissolved in 100 ml of methanol, and sodium O-formylbenzenesulfonate dissolved in 200 ml of methanol is added dropwise to this solution at room temperature. Further, this mixture was heated under reflux for 2 hours while stirring, and after cooling, crystals 'tF were collected and washed with methanol to obtain sodium λ-phenylhydrazonobenzenesulfonate (intermediate A) f:A 1. Intermediate As
oy2 water λ! A palladium carbon catalyst dissolved in Oyd was added and hydrogenated in an autoclave. When Improper Tool 2IOalt- is added after all the catalysts have been separated, colorless crystals are precipitated. After several washes with isopronominol and drying, sodium λ-phenylhydrazinobenzenesulfonate (intermediate B) is obtained μ3. Next, intermediate B
4LOf, diethyl malonate/trit1 sodium methylate (λr methanol solution) 2j1, and n-butanol 100tdk were mixed and heated under reflux for 10 hours. Condense n-butanol and add 00 txlf of water to the residue. Next, the aqueous layer is acidified with concentrated hydrochloric acid to precipitate crystals. After several washes with a small amount of methanol, 322 of Intermediate C is obtained.

/-phenyl-2-(2-sulfobenzyl)-3,j-
Pyrazolidinedione sodium salt7. Hiroshi 1 was added to methanol, followed by triethylamine≠, malonaldehyde cyanyl hydrochloride-2, and heated to form a homogeneous solution. After cooling to room temperature, acetic anhydride ≠, jd!
? ! - Drip. After reacting for 2 hours, imprononol λjlttl'i was added to precipitate light-colored crystals.

This crystal 'tF was collected, washed with isoprozenol, and dried to obtain compound io. Melting point 300°C or higher,
λH20≠rpax nm, ε/, 3x105 Synthesis example! (Compound of the present invention//) /-phenyluco-(cosulfo-kunjil)-3,j
-Pyrazolidinedione sodium salt7. Compound // was prepared by the same procedure as in Synthesis Example 3 using Hirot. ! ? can get. Melting point: 3000C or higher, -formation (When the dyes shown in 2) are used as filter dyes, anti-irradiation dyes or antinorcidin dyes, any effective amount can be used, but the optical density is between 0.05 and 0.05.
It is preferable to use it in a range of 3.0, and it can be added at any step before coating.

The dyes according to the invention can be incorporated into emulsion layers and other hydrophilic colloid layers (interlayers, 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, using a suitable solvent, e.g. , methyl alcohol, ethyl alcohol, propyl alcohol, methyl cellosolve, JP-A-48-9715, U.S. Patent 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, etc., and a molecular weight of 5,000 or more, particularly preferably 10,000 or more. .

For example, vinyl pyridine polymers and vinyl pyridinium cationic polymers disclosed in U.S. Pat. No. 2,548.564, etc.; vinylimidazolium cationic polymers disclosed in U.S. Pat. 3゜625.694, etc., a polymer mordant capable of crosslinking with gelatin, etc.; an aqueous sol type mordant disclosed in U.S. Patent No. 3,958.995, JP-A-54-115228, etc. : A water-insoluble mordant disclosed in U.S. Patent No. 3,898,088; A reactive mordant capable of forming a covalent bond with a dye disclosed in U.S. Patent No. 4,168.976, etc.; British Patent No. 685 , 475; polymers derived from ethylenically unsaturated compounds having dialkylaminoalkyl ester residues as described in British Patent No. 850.281.
products obtained by the reaction of polyvinyl alkyl ketones with aminoguanidine as described in US Pat. No. 3,445,231;
Mention may be made, for example, of polymers contaminated with methyl-1-vinylimidazole.

■ A method of dissolving a compound using a surfactant.

Useful surfactants may be oligomers or polymers.

For details of this polymer, please refer to JP-A-60-15843.
No. 7 (filed by Fuji Photo Film on January 26, 1980), section 4, pages 19 to 27 of the specification.

Further, in the hydrophilic colloid dispersion obtained above, for example, hydrosyl, a lipophilic polymer described in Japanese Patent Publication No. 51-39835, 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 emulsions used in the present invention are preferably silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride.

The silver halide grains used in the present invention may have regular crystal shapes such as cubic or octahedral, or irregular crystal shapes such as spherical or plate-like.
ular) or a composite of these four crystal forms. It is also possible to use a mixture of particles of various crystal forms, but it is preferable to use regular crystal 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.
For example, it may be a negative-tone emulsion), or it may be a grain that is mainly formed inside the grain (for example, an internal latent image type emulsion, a pre-fogged direct reversal type emulsion), and preferably,
These are particles on which a latent image is formed primarily on the surface.

The silver halide emulsion used in the present invention has a thickness of 0.5
Particles having a diameter of 0.6 microns or less, preferably 0.3 microns or less, and an average aspect ratio of 5 or more occupy the entire projected area of the 5'JA3 sea [
At 1td, a-ξ/y, = 11b/(1) or 'tLIA
Preferably, emulsions with a weight of 11 are mr, and tabular grain emulsions and monodisperse emulsions are Hff! The above may be mixed.

The photographic emulsion used in the present invention is P.
, Glafkides), Chimie er Phys Photographic (Chimie er Phys Photography)
iquePhoLographeque) (Paul Montell, 1967), G.F. Duffin (
G, F. Duffin), Photographic Emulsion Chemistry
E+mulsion Chemistry) (Focal Press, 1966), V, L, Zelikman et al., Making and Coating Photographic Emulsion (Making and Coating Ph
otographic Emulsion) (Focal Press, 1964).

In addition, during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, thioether compounds (e.g., U.S. Pat. No. 3,271,157, U.S. Pat. No. 3,574, U.S. Pat. No. 628, No. 3,704,130, No. 4,297.439, No. 4,276.374, etc.), thione compounds (e.g., JP-A No. 144319/1983)
No. 53-82408, No. 55-77737, etc.), amine compounds (for example, JP-A-54-100717, 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, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example, H, Friesel (11°F
rieser) km, Die Grundlagen der Fotografisien Brozesse Mint Zilberhalogenden
rPhotographischen Prozes
se wit Silberhalogenide
n) (Academische Verlags Gesellschacht 1
96B) The method described on pages 675-734 can be used.

That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts); , amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g. gold prices,
Pt.

A noble metal aggravation method using complex salts of metals of group 1 of the periodic table such as Ir, Pd, etc. 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 fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. can. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted);
Heterocyclic mercapto compounds such as mercaptothiazole Zhao, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; The above-mentioned heterocyclic mercapto compounds having a water-soluble group; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindene (particularly 4-hydroxy substituted (1°3.3a
, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid: a number of antifoggant or stabilizer compounds 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 color by oxidative coupling with an aromatic primary amine developer (e.g., phenylene diamine derivative, amine phenol derivative, etc.) in color development treatment. For example, as a Mazenk coupler, 5-pyrazolone Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides), etc. ,
Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule.

The coupler may be either 4-equivalent or 2-equivalent to the i-ion, 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 coupler). good.

In addition to the DIR 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, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, and urethane derivatives. , urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

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, hemioxonol dyes, and merocyanine dyes) as filter dyes or for various purposes such as preventing irradiation. In addition, as a spectral sensitizer, it may be used in combination with known cyanine dyes, merocyanine dyes, and hemicyanine dyes other than the dyes shown in the present invention.

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.

In addition, the photosensitive material of the present invention contains anti-fading agents, hardening agents, anti-color fogging agents, ultraviolet absorbers, protective colloids such as gelatin, and various additives, as detailed in Research Disclosure Vol. 1.176 ( 197B, XI[)R
D-17643 etc.

The finished emulsion is coated onto a suitable support such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, other plastic bases or glass plates.

The silver halide photographic light-sensitive materials of the present invention include color positive films, color papers, color negative films, color reversals (which may or may not contain couplers), and photographic materials for platemaking (for example, lithium film, lithography), and color reversal films (which may or may not contain couplers). eup 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 (Silver 5alt diffusion)
transfer process) photosensitive materials, color diffusion transfer process photosensitive materials, die transfer process (imbibition trans)
fer process), photosensitive materials used in silver dye bleaching, photosensitive materials for recording printout images, photo-developable printouts, Direct Pr1nt ima
ge) Photosensitive materials, photosensitive materials for thermal development, photosensitive materials for physical development, etc.

Exposure to obtain photographic images may be carried out using conventional methods: natural light (sunlight), tungsten lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots. Any of a wide variety of known light sources can be used. The n light time is usually an exposure time of 1/1000 second to 30 seconds, but an exposure shorter than 1/1000 second, for example, an exposure of 1/10' to 1/10' second using a xenon flash lamp or cathode ray tube is used. or exposures longer than 30 seconds can be used. The spectral composition of the light used for exposure with color filters if necessary. Can be adjusted. Laser light may be used for exposure, or exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, gamma rays, alpha rays, or the like.

Photographic processing of light-sensitive materials made using the present invention includes, for example, Research Disclosure (Research Disclosure).
Disclosure) No. 176, pages 28-30 (RD-17643), any of the known methods and known processing solutions may be used, or photographic processing for forming dye images (color photographic processing) may be used. The processing temperature, which may be any, is usually chosen between 18 and 50°C, but may also be below 18°C or above 50°C.

There are no particular restrictions on the color photographic processing method, and any method can be applied.For example, a typical method is to perform color development, bleach-fixing processing after exposure, and further washing with water and stabilization processing as necessary. , After exposure, color development, bleaching and fixing are performed separately, and 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 agent to give -like exposure. After that, color development and bleach-fixing are carried out, and if necessary, washing with water and stabilization are carried out, or after exposure, development is carried out with a developer containing a black and white developing agent, and then a fogging agent (
For example, there is a method 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 further washing with water and stabilization treatment as required.

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 agents include aminophenol type and p-phenylenediamine type m8 type. Preferred examples are p-phenylenediamine derivatives, and representative examples are shown below, but the invention is not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotolu-32
-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl~N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N -(β-hydroxyethyl)aminocoaniline D-6N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline D-7N-(2-amino-5-diethylaminophenylethyl) Methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl-N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N- β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-butoxyethylaniline These p-phenylenediamine derivatives may also be salts such as sulfate, hydrochloride, sulfite, p-1-luenesulfonate, etc. The above compounds are described in U.S. Pat.
No. 3,015, 2. 552゜241, same 2,56
No. 6.271, No. 2,592.364, No. 3,656
, No. 950, No. 3゜698.525, etc. The amount of the aromatic primary amine color developing agent used is in a concentration of about 0.1 g to about 20 g, more preferably about 0.5 g to about Log per 11 of the developer solution.

As is well known, the color developer used in the present invention may contain hydroxylamines.

Although hydroxylamines can be used in the form of free amines in color developers, it is more convenient to use them in the form of water-soluble acid salts. Common examples of such salts are sulfates, oxalates, chlorides, phosphates, carbonates, acetates, and others. The hydroxylamines may be substituted or unsubstituted, and the nitrogen atom of the hydroxylamine may be substituted with an alkyl group.

The amount of hydroxylamine added is Og per 11 parts of color developer.
~Log is preferred, and more preferably 0 to 5 g.As long as the stability of the color developing solution is maintained, it is preferable that the amount added be small.

In addition, as preservatives, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, etc.
It is preferable to contain carbonyl sulfite adducts, and the amount of these added is Og ~ 20g/j! is preferably Og to 5 g/i, and as long as the stability of the color developing solution is maintained, the smaller the amount, the more preferable.

Other preservatives include JP-A Nos. 52-49828, 56-47038, 56-32140, and 59-
Aromatic polyhydroxy compounds described in US Pat. No. 1,601,42 and US Pat. No. 3,746,544; US Pat. No. 3,615,5
03 and British Patent No. 1,306,176; α-aminocarbonyl compounds described in JP-A-52-143020 and JP-A-53-89425; JP-A-57-44148 and JP-A-57- 5374
Various metals described in No. 9 etc.; JP-A-52-102727
Hydroxamic acids described in No. 52-27638; α, α'-dicarbonyl compounds described in No. 59-160141; salicylic acids described in No. 59-180588; alkanols described in No. 54-3532. Amines; poly(alkyleneimine)s described in No. 56-94349; gluconic acid derivatives described in No. 56-75647; and the like. Two or more of these preservatives may be used in combination if necessary, and addition of 4,5-dihydroxy-m-benzenedisulfonic acid, poly(ethyleneimine), triethanolamine, etc. is particularly preferred.

The pH of the color developer used in the present invention is preferably 9.
-12, more preferably 9-11, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffering agents. Examples of the buffering agent include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt,
N,N dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3゜4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1゜3-propanediol salt, valine salt, Proline salts, trishydroxyaminomethane salts, lysine salts, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates have excellent solubility and buffering ability in the high i)H region of pH 9.0 or higher, and even when added to color developers, they do not affect photographic performance. It is particularly preferable to use these buffering agents because they have the advantages of not causing any negative effects (fogging, etc.) and being inexpensive.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, and boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate)% Potassium O-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) ), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developing solution is preferably 0.1 mol/1 or more, particularly 0.1 mol/1 to 0.4 mol/1.
Particular preference is given to mol/l.

In addition, various chelating agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or to improve the stability of the color developer.

As the chelating agent, peroxide acid compounds are preferred, such as aminopolycarboxylic acids described in Japanese Patent Publication Nos. 48-030496 and 44-30232, and JP-A-56-9734.
No. 7, Special Publication No. 56-39359 and West German Patent No. 2,2
Organic phosphonic acids described in No. 27,639, JP-A-52-
No. 102726, No. 53-42730, No. 54-12
No. 1127, No. 55-126241 and No. 55-6
Examples include phosphonocarboxylic acids described in JP-A-58-195845, JP-A-5B-203440, and JP-B-Sho 53-40900. Specific examples are shown below, but the invention is not limited to these.

・Nitrilotriacetic acid ・Diethyleneaminopentaacetic acid ・Ethylenediaminetetraacetic acid ・Triethylenetetraminehexaacetic acid ・N,N,N-)rimethylenephosphonic acid ・Ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid ・1 .3-diamino-2-propano-tetraacetic acid, transcyclohedondiaminetetraacetic acid, nitrilotripropionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, hydroxyethylene diamine Triacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-)licarboxylic acid, 1-hydroxyethane-1,1-diphosphonic acid, N,
N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid Two or more of these chelating agents may be used in combination if necessary.The amount of these chelating agents added depends on the amount of the color developer. The amount may be sufficient as long as it is sufficient to sequester metal ions, for example, about 0.18 to Log per 1β.

Any development accelerator can be added to the color developing solution if necessary.

As a development accelerator, in addition to benzyl alcohol, Japanese Patent Publications No. 37-16088, No. 37-5987, and No. 38-7
826, No. 44-12380, No. 45-9019, and U.S. Pat. No. 3,813,247, etc.;
p-phenylenediamine compounds described in No. 15554, JP-A-50-137726, JP-B-Sho 44-3007
No. 4, JP-A-56-156826 and JP-A No. 52-43
Quaternary ammonium salts described in No. 429, etc.; US Patent 2
, 610,122 and 4,119°462; U.S. Pat. No. 2,494,9
No. 03, No. 3,128.182, No. 4,230,79
No. 6, No. 3.253゜919, Special Publication No. 41-1143
No. 1, U.S. Patent No. 2,482,546, U.S. Patent No. 2,596,
Amine compounds described in Japanese Patent Publication No. 37-16088 and Japanese Patent Publication No. 42-25
No. 201, U.S. Patent No. 3,128.183, Special Publication No. 1973
-11431, No. 42-23883, and U.S. Pat. No. 3,532,501, etc., polyalkylene oxides, 1-phenyl-3-pyrazolidones, hydrazines, meso ion type compounds, thione type compounds, imidazoles , etc. can be added as necessary. Particularly preferred are thioether compounds and 1-phenyl-3-pyrazolidones.

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 halides such as sodium chloride, potassium iodide and organic anti-capri agents can be used. Examples of organic anti-capri agents include benzotriazole, 6-nitropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, Nitrogen-containing heterocyclic compounds such as 2-thiazolylmethylbenzimidazole, mercapto-substituted heterocyclic compounds such as 2-mercaptobenzimidazole and 2-mercaptobenzothiazole, adenine, and even mercapto-substituted aromatics such as thiosalicylic acid. Group compounds can be used. These antifoggants 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 emissions, it is preferable that the amount of these accumulated is small. .

The color developing solution of the present invention preferably contains a fluorescent whitening agent. Examples of the fluorescent whitening agent include 4,4-diamino-2,
A 2'-disulfostilbene compound is preferred, and the amount added is O~5gz! Preferably it is 0.1 g to 2 g/l.

Furthermore, various surfactants such as alkylphosphonic acids, arylphosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color developing solution in the present invention is 30 to 50°C.
is preferable, and more preferably 33 to 42°C. The amount of replenishment is from 30 to 2000 d, preferably from 30 to 1500 d, per 1 rrr of photosensitive material. From the viewpoint of reducing the amount of waste liquid, it is preferable that the amount of these replenishments be 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. Aminopolycarboxylic acid salts or aminopolyphosphonic acid salts are salts of aminopolycarboxylic acids or aminopolyphosphonic acids with alkali metals, ammonium, or water-soluble amines. Examples of alkali metals include sodium, potassium, lithium, etc., and examples of water-soluble amines include alkyl amines such as methylamine, diethylamine, triethylamine, butylamine, ring amines such as cyclohexylamine, aniline, m-
) alkylamines such as luidine and heterocyclic amines such as pyridine, morpholine, piperidine.

Typical examples of chelating 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 Ethylenediaminetetraacetic acid tetrasodium salt Ethylenediaminetetraacetic acid trisodium salt Diethylenetriamine Bencacetic acid Diethylenetriaminepentaacetic acid Pentasodium salt Ethylenediamine-N-(β-oxyethyl)-N,N
',N''-1-Ethylenediamine lyacetate-N-(β-oxyethyl)-N,N
',N'-Triacetic acid trisodium salt ethylenediamine-N-(β-oxyethyl)-N,N
”, N'-triammonium salt propylene diamine tetraacetate propylene diamine tetraacetate disodium salt nitrilotriacetate nitrilotriacetate trisodium salt cyclohexanediamine tetraacetate cyclohexanediamine tetraacetate disodium salt iminodiacetate dihydroxyethylglycine ethyl ether diamine tetraacetic acid glycol Etherdiaminetetraacetic acidethylenediaminetetrapropionic acidphenylenediaminetetraacetic acid 1,3-diaminopropanol-N,N,N'.

N'-tetramethylenephosphonic acid ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid 1,3-propylenediamine-N,N,N'.

Examples include N'-tetramethylenephosphonic acid, but the compound is not limited to these exemplified compounds.

The ferric ion complex salt may be used in the form of a complex salt, or as a ferric ion complex salt.
Iron salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc. and chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, phosphonocarboxylic acids, etc. A ferric ion complex salt may be formed in a solution using On the other hand, when forming a complex salt in a solution using a ferric salt and a chelating agent, one or more types of ferric salts may be used, and one or more types of chelating agent may be used. You may.

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

Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01" 1.0 mol/l,
Preferably it is 0.05 to 0.50 mol/1.

Further, a bleach accelerator can be used in the bleaching solution or the bleach-fixing solution, if necessary. Specific examples of useful bleach accelerators include U.S. Pat. No. 3,893.858, West German Pat. No. 57831, same 3
No. 7418, No. 53-65732, No. 53-7262
No. 3, No. 53-95630, No. 53-95631,
Compounds having a mercapto group or a disulfide group as described in No. 53-104232, No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure & No. 17129 (July 1978), etc.; Thiazolidine derivatives described in Japanese Patent Publication No. 140129/1982;
No. 20832, No. 53-32735, U.S. Patent No. 3,
Thiourea derivatives described in No. 706゜561; iodides described in West German Patent No. 1゜127.715 and JP-A-58-16235; West German Patent No. 966.410, No. 2.74
Polyethylene oxide compounds described in Japanese Patent Publication No. 8,430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and others such as JP-A-49-42434, 49-59644, 53-94927, 54-35727, Same 55-
Examples include the compounds described in No. 26506 and No. 58-163940, as well as iodine and bromide ions. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as disclosed in U.S. Pat.
The compounds described in JP-A-53-95630 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) rehalogenating agents. If necessary, add boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. One or more inorganic acids, organic acids, and alkali metal or ammonium salts thereof having the following properties may be added, as well as corrosion inhibitors such as ammonium nitrate, guanidine, and the like.

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, 3,6-cythia-1,8-octanediol, etc. These are water-soluble silver halide dissolving agents such as thioether compounds and thioureas, and these can be used alone or in combination of two or more. In addition, a special bleach-fixing solution consisting of a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used.In the present invention, thiosulfate, especially Preference is given to using ammonium thiosulfate salts.

1! The amount of fixing agent per mol is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol.

The pH range of the bleach-fix solution or fix solution in the present invention is:
eP is preferably 3 to 10, and particularly preferably 4 to 9.
If H is lower than this, the desilvering property will be improved, but the deterioration of the solution and the leucoization of the cyan dye will be promoted. On the other hand, if pi is higher than this, desilvering is delayed and staining is likely to occur.

To adjust the pH to 11, 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.

The bleach-fix solution may also contain various other fluorescent brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, methanol, and other ja'fJ media.

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. , metabisulfites (e.g. potassium metabisulfite)
, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds have a concentration of approximately 0.02 to 0.02 in terms of sulfite ion.
The content is preferably 50 mol/l, more preferably 0.04 to 0.40 mol/l.

Sulfites are commonly added as preservatives, but 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 process of the present invention will be explained.In the present invention, instead of the usual "water washing process", a convenient processing method is used, such as not providing a substantial water washing process and only performing a so-called "stabilization process". You can also do that. As described above, the term "water washing treatment" as used in the present invention is used in the broad meaning described above.

The amount of washing water in 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 less than lXl0-'0 For example, in the case of 3 tank countercurrent water washing, about 100 per 1 d of photosensitive material
It is preferable to use 01n1 or more, more preferably 5
000- or more. In addition, in the case of water saving treatment, it is preferable to use 100 to 1000 d per photosensitive material.

The water washing temperature is 15°C to 45°C, more preferably 20°C to 3°C.
The temperature is 5°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 anti-spiking agents that prevent the growth of various bacteria, algae, and molds (e.g. , "Journal of Antibacterial and Antifungal Agents" CJ, ^antibact, Antifung,
Agents) Vol. 11, Arashi compounds, metal salts such as magnesium salts and aluminum salts, alkali metal and ammonium salts, or surfactants to prevent dry load and unevenness may be added as necessary. Can be done. Or by West [Photographic Science and Engineering Magazine (Photo,
Sci.

Eng.), Volume 6, pp. 344-359 (196
The compounds described in 5) etc. may be added.

Further, 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 significantly reduced by multistage countercurrent washing using two or more tanks. Also, instead of the usual water washing process, a multi-stage countercurrent stabilization process (so-called stabilization process) as described in JP-A No. 57-8543
It is also particularly effective when implementing. In these cases,
The bleach-fix component of the R final bath is preferably 5×10-” or less.
It is sufficient if Xl0- is below.

In this stabilizing bath, various compounds are added for the purpose of stabilizing the image.For example, a membrane p)l is prepared.

Various buffering agents (e.g., borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, ammonia water,
Typical examples include monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and aldehydes such as formalin. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericidal agents (
Various additives such as thiazole type, isothiazole type, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, fluorescent brighteners, and hardening agents may be used, and they can be used for the same or different purposes. Two or more kinds of 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.

When the amount of washing water is significantly reduced as described above, it is preferable for the purpose of reducing the amount of waste water to flow some or all of the overflow liquid of the washing water into the bleach-fixing bath or stabilizing bath, which is a pre-bath.

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. Replenishment ■ can be reduced to half or less than the standard replenishment amount to reduce costs.

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

Color photographic processing is a process that uses a color developing solution.
It can be applied to any processing process, such as color paper-2 color reversal paper, 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/A photosensitive material for color printing was prepared by applying photosensitive layers consisting of the first layer to the seventh layer on a paper support laminated on both sides with polyethylene.

The polyethylene on the side coated with the first layer contains titanium dioxide and traces of ultramarine blue.

(Structure of Photosensitive Layer) The numbers corresponding to each component are shown in Coating 1 expressed in units of 17 m2, and for the silver halide emulsion, the coating weight is shown in terms of silver.

1st layer (FF sensitive layer) Silver chlorobromide emulsion [see Table 1]... Silver 0.
30 yellow coupler (+/)・・・・・・・・・・・・
...0.70 Same as above solvent (TNP) ...
・・・・・・・・・・・・・・・・・・0. /j Gelatin ・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・／、20th λ layer (middle layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
......
BP)・・・・・・・・・・・・・・・・・・・・・
...θ, i.

3rd layer (green sensitive layer) Silver chlorobromide emulsion (see Table 1)...Silver O1
Hirota magenta coupler (bitter 2)・・・・・・・・・・・・
...0.3! Same as above solvent (TOP)・・・・・・・・・
・・・・・・・・・・・・・・・O0≠≠Fading inhibitor (Axe 3/Minohiro)...0.0j10. IO gelatin
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・／、OO 1st layer (ultraviolet absorbing intermediate layer) Ultraviolet absorber (screen r/+A/glue 7) ・・・・・・・・・0.0610. Ko! 10. Same as above solvent (TNP)・・・・・・・・・・・・・・・・・・
・・・・・・0.20 gelatin ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・1. Jth! Layer (red-sensitive layer) Silver chlorobromide emulsion (see Table 1)...Silver 0.
20 cyan coupler (*♂/Kaoru 5P)...0.210
．． λ coupler solvent ('I'NP/DBP)...
...0. /,! Same as above solvent (TNP) ・・・・・・・・・
・・・・・・0.1010.20 Gelatin・・・－・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...Oori 6th layer (ultraviolet absorbing intermediate layer) Ultraviolet absorber (Kettle!/Kettle A/*7) ......0. Itlo, Koj10. Same as above solvent (DBP)・・・・・・・・・・・・・・・・・・
・・・・・・・・・Ol-〇Gelatin ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・／、j7th layer (retention layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・18! Here, D.B.
P represents dibutyl phthalate)'t, TOP represents tri(n-octyl) phosphate, and TNP represents tri(n-nonyl) phosphate'.

(Outside l) (Kaoru 2) (Arrow) (Kaoru) (Yo 7) H C4H9(t) (Tatami?) (★ri) α Also, as a hardening agent, Cohydroxy-Hiro, 6-dichloro-S -) containing sodium lyazate, each emulsion layer contains μm hydroxy-+-methyl-(/.

J, 33.7)-Tetraazaindene was added.

The emulsions used in each emulsion layer are shown below.

DYE-i DYE-co DYE-J To the red-sensitive emulsion layer, the following compound was added in an amount of λ,t×10-3 mol per mol of silver halogenide.

Comparative compound a Comparative compound Comparative compound C Comparative compound d Comparative compound e For the color photographic papers of Samples A-J thus prepared, 16 Color reproducibility in prints from test negatives (Group 1 A-E) λ, safe A test was conducted on the lambda item of light safety (first group A and second group F-J).

1. All test negatives were created as follows.

Using Fuji Photo Film Company's color negative film Fujicolor 5UPERHRtoo (ISO sensitivity 10O),
Standard light source C color temperature for photography! ! Macbeth color checker (The Macbeth) under the illumination by OQ'K)
Co1or Checker) was photographed at an appropriate exposure level. The photographed film was developed using Fujicolor negative film genuine processing agent CN-/Otsu under standard conditions to obtain a color negative for testing.

Test color negatives photographed by the Macbeth color checker described above were printed on samples A to E of the first group shown above. At this time, the degree of print and color tone were adjusted so that the uJ tier (Neutralzray optical density 0.70) of the Macbeth color checker was most faithfully reproduced on the print.

The color photographic paper was developed using the following steps and processing solution.

Processing type Temperature Time Color development 33°0 3 minutes 30 seconds Bleach constant N
JJoC 7 minutes 30 seconds water washing KO4t~3≠'CJ external rotation drying ♂θ'C/The components of the dispensing treatment liquid are as follows.

Color developer water ♂θ
Oxl diethylenetriaminepentaacetic acid j, 0? Benzyl alcohol /jyttl diethylene glycol 10ml Sodium sulfite λ,oy Potassium bromide
0. j1 potassium carbonate
J17,0fN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-μmaminoaerin sulfate r,of hydroxylamine sulfate μ,01fluorescent brightener (≠
, ≠'-distilbene system) /, Of water gold whole egg 1ooo, 1pH (koj'
C) io,t.

Bleach-fix water 4'
00m ammonium thiosulfate (70ml solution) l! θ屓l Sodium sulfite ethylenediaminetetraacetate iron (I [I ) ammonium
! ! 2ethylenediaminetetraacetic acid 2Na acetate! ? add water
1000tdpH (J-t'c)
A. 7° per print obtained, l1
1st row (YellowGreen) and 16th row (Y
The B and G densities of yellow) were measured and CDG (G density)/DB (B@degree)] was determined, which was used as a guideline for the magenta density to the yellow coloring area. These values are summarized in Table 2 as relative values with the value t-100 determined from the original measurement values.

Also, at this time, the white background of the sample after processing! Fully measured once,
The degree of residual color was investigated and summarized in Table 2.

As is clear from the results, by using the dye of the present invention, it is possible to reduce the magenta color mixture in the yellow coloring area.

At the same time, the white background density after treatment was almost the same as that of sample A in which no dye was used, indicating that the decolorization property was significantly superior to that of the comparative dye.

26 Safelight safety was tested as follows.

An ioow light bulb was equipped with a color filter safelight filter 10JAk manufactured by Fuji Photo Film ■, and the emulsion layer coated side of the sample was irradiated from a distance of 1 m. Thereafter, normal sensitometric exposure was carried out using an optical wedge and red filter, and after the above-mentioned development process, the density was measured.

At this time, the time fO minutes for irradiating the safelight light is -
Changes in photo quality were investigated by changing the length of the session to 10 minutes. Overlapping part of sample not fully irradiated with safelight light, color density 0.2
The color density of each sample at the sensitometric exposure amount corresponding to each portion of 0.6 and 0.6 was determined, expressed as the amount of change, and summarized in Table 3.

In addition, the white background density of samples that were not irradiated with safelight after treatment was also measured and summarized in the table.

As is clear from the results, by using the dye of the present invention, it is possible to significantly improve safelight safety without damaging the white background after treatment.

Example A similar test was conducted using the coating sample prepared in Example 1 containing the anti-irradiation dye shown below.

The results were similar to those in Example/1, and it was found that the effects of the present invention were not impaired even if dyes for other purposes were co-present.

Green-sensitive emulsion layer = (maximum absorption in the light-sensitive material)
) 80 a K S Oa K red-sensitive emulsion layer: (Maximum absorption JArinm in the light-sensitive material) Example 3 On the same paper support as in Example 1, it consists of the following layers from the first layer to the seventh layer. A color photosensitive material was prepared by applying a photosensitive layer.

(Structure of Photosensitive Layer) The numbers corresponding to each component indicate the coating amount expressed in units of f//m2, and for silver halide, the coating amount is expressed in terms of silver.

1st layer (blue sensitive layer) Silver chlorobromide emulsion (see Table 1)...Silver O1
λ yellow coupler (+io)・・・・・・・・・・・・
・・0.7≠Color image stabilizer (appetizer//)・・・・・・・・・
...old and old...0. /7 Same as above solvent (DBP)...
・・・・・・－・・・・・・・・・・・・θ, 3/gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・／, It second layer (middle layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0. Di-t-octylhydroquinone...o, or the same solvent (
DBP)・・・・・・・・・・・・・・・・・・・・・
... o, i.

3rd layer (green sensitive layer) Silver chlorobromide emulsion (see Table V)...
0. /A magenta coupler (+/2)...
・・・・o、tit color image stabilizer (supper≠)・・・・・・
・・・・・・Old・・・・・・・・・0.20 Same as above solvent (
TOP/TCP) ・・・・・・・・・・・・ 0.3010. /yo gelatin ・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・／, 10th Hiro layer (ultraviolet absorbing intermediate layer) Ultraviolet absorber (axe j/axe 2/ku 7) ・・・・・・・・・0. 0410.2!10.2 Yoji-
t-octylhydroquinone...0.0! Same as above solvent (TNP)・・・・・・・・・・・・・・・・・・・・・
...0-20 gelatin ......
・・・・・・・・・・・・・・・・・・・・・・・・／
,! O-th layer (red-sensitive layer) Silver chlorobromide emulsion (see Table V) 00-
2 Ko Cyan Coupler (Kan/J) ,,,,,,,,,
, , , , , 0 , j r color correction stabilizer (+/4'
)・・・・・・・・・・・・・・・・・・・・・0. /
7 Same as above solvent (DBP)・・・・・・・・・・・・・・・
・・・・・・・・・00.23 Gelatin ・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...O6 Ri6 6th layer (ultraviolet absorbing intermediate layer) Ultraviolet absorber (Kanj/Kaoru6/Ao7) ......0.0610.2!10. ．． 2j Same as above solvent (DBP) , , , , , , , , , , , ,
1. , -0-0, λO gelatin ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・／、! O 7th layer (protective layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・／、! The structural formula of the compound such as a coupler used on the main side is as shown below.

(Meal lO) Yellow coupler (Blue//) Color image stabilizer (Ch/2) Magenta coupler (Kan/J) Cyan coupler (秀l≠) Color image stabilizer and and The emulsions used in each layer are shown below.

For the red-sensitive emulsion layer, the following compound was added in an amount of 2.6 x 10-3 mol per mol of silver halide.

DYE-g DYE, t DYE-J The thus prepared sample ■ (for the color photographic paper up to Safelight safety (Group 1 K and Group 2 P-T) was tested. The results are shown in Tables J and 6.

However, the development process was performed using the following steps and processing solution.

Processing process Temperature Time Color development J j 'C≠! Bleach and fix for seconds 30~j j 'C≠j seconds rinse■ 30~330 (: λO seconds rinse■
30~3!0C-θ seconds■ 30~3j0C+20 seconds 1Jyx■
30~3!0CJO seconds drying 70~IO'
c60 seconds (3-tank countercurrent flow method from rinsing ■ to ■).

) The composition of each treatment liquid is as follows.

color developer water l
00yJ ethylenediamine-N, N, N'.

N'-tetramethylenephosphonic acid /,! rf triethylenediamine (/, l-diazahicyclo(2,2,2) octane)! , 0 sodium chloride 1. ≠2 potassium carbonate
21f? N-ethyl-N-(β
-methanesulfonamidoethyl)-3-methyl-guaminoaniline sulfate r,oyN
, N-diethylhydroxylamine ≠, 21 Add whitening agent (UVITEX CK) 1 to 1 oooILlpH
(koj'c) 10,10 bleach-fix solution water ≠0
0yJ ammonium thiosulfate C7o4) loo
,z Sodium sulfite / If ethylenediaminetetraacetic acid iron acetate II) Ammonium tjyEthylenediaminetetraacetic acid iron sodium 3 Ammonium bromide ≠oy Glacial acetic acid
If add water
1ooolypH (23'C)
r, z Rinse liquid ion exchange water (calcium, magnesium each
pm or less) Example 3 A similar test was conducted using the coating sample prepared in Example 3 containing all of the anti-irradiation dyes shown below.

The results were similar to those in Example 3, and it was found that the effects of the present invention were not impaired even when dyes for other purposes were co-present.

Green-sensitive emulsion layer; (maximum absorption in light-sensitive material!≠nm) Red-sensitive emulsion layer; (maximum absorption tt in the light-sensitive material.

(nm) A similar test was conducted except that the coating sample used in Example ≠ was treated with the following treatment steps and treatment liquid. The results were similar to those in Example 3, confirming the effects of the present invention.

Processing process Temperature Time Color development J j 0 (' μ! seconds σ White fixing Stable for 30-36°C 4Ls seconds■ Stable for 20 seconds at 30-37°C■ Stable for 20 seconds at 3θ-37°C■ Stable for 20 seconds at 30-37°C■ 3Q~37°C 30 seconds dry 70-J'J"C 40 seconds (rinse)
→■ A tank countercurrent system was adopted. ) The composition of each treatment liquid is as follows.

color developer water
♂00 Ethylenediaminetetraacetic acid resistance J, Of
Triethanolamine ♂, O2 sodium chloride 1. ≠ Potassium dicarbonate 23tN-ethyl-N-(
β-methanesulfonamidoethyl)-3-methyl≠-aminoaniline sulfate r, oyN, N
-diethylhydroxylamine
Hiro, Ko 2! , 6-
Hydroxybenzene/.

Co, 4t-) Lysulfonic acid 0.32 Fluorescent brightener (Hiroshi, ≠-diaminostyl) Co, Of water'r: Addi o o o, Hl p H (coj'(T) 10,10 bleach-fix solution water ≠0
0rptl ammonium thiosulfate (70 units) 1
00ml Sodium sulfite l♂1
Ethylenediaminetetraacetic acid iron acetate II) Ammonium rsyEthylenediaminetetraacetic acid iron sodium trilam 32 Add water to 1000tdpH (Jj 'C
)', evening stabilizer formalin (37%) 0. /f formalin-sulfite adduct 0.71-chloro-2-methyl-hiro-ifthiazolin-3-one 0.027 co-methyl-hiro-isothiazolin-3-one o, oiy sulfate
o, add oozy water
1ooogopH(-t'c)
Hiroshi, O (Circulation Effect) According to the present invention, it is possible to achieve faithful reproduction of original colors when printing from a color negative without damaging the white background after processing, and to eliminate the adverse effects of safelight light. It becomes possible to eliminate it.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment

Claims (1)

[Scope of Claims] A silver halide photographic material containing at least one dye represented by the general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1, R_2, R_3, and R_4 each represent an alkyl group, an aryl group, or a heterocyclic residue, and L_1
, L_2 and L_3 each represent a methine group. n is 1, 2
Or represents 3. However, R_1, R_2, R_3, R_
4 has a carboxyl group or a sulfo group,
The total is at least two or more.