JPH01179148A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To dye a hydrophilic colloidal layer with a water soluble dye having no adverse effect on photographic characteristics by incorporating a specified dye. CONSTITUTION:A hydrophilic colloidal layer can be dyed with a water soluble dye having no adverse effect on photographic characteristics, especially spectral sensitizability by incorporating at least one kind of dye represented by formula I. The water soluble dye has superior decolorability and the dyed hydrophilic colloidal layer has aging stability. In the formula I, each of R1 and R2 is aliphat., alicyclic or arom. acryl, each of R3 and R4 is H, alkyl, alkoxy, halogen or hydroxyl, each of L1-L5 is methine, L1-L5 may be different from one another, M is H or a cation, each of (m) and (n) is 0 or 1 and Q is a bonding radical or a bivalent connection group.

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 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 antihalation layer. In the case of multilayer color photosensitive materials,
An antihalation 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)
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.

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

(2) being photochemically inert, that is, having an adverse chemical effect on the performance of the silver halide photographic emulsion layer;
For example, it should not cause a decrease in sensitivity, latent image regression, or fog.

(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 following dyes are known.For example, British Patent No. 506°385;
No. 7.429, No. 1,311', No. 884, No. 1.33
No. 8.799, No. 1゜385.371, No. 1,467
．． No. 214, No. 1.433.102, No. 1,553,
No. 516, JP-A-48-85.130, JP-A No. 49-11
4゜420, 55-161.233, 59-1
No. 11.640, No. 62-273527, U.S. Patent No. 3.247.127, U.S. Pat.
．． Oxonol dyes having a pyrazolone nucleus or a barbylic acid nucleus described in US Patent No. 078.933 etc., US Pat.
．． 533.472, 3,379.533, British Patent No. 1,278.621, and other oxonol dyes.

Among these, oxonol dyes, which have two pyrazolone nuclei, have the property of being decolorized in developing solutions containing sulfites, and are used as useful dyes for dyeing photographic materials as they have little negative effect on photographic emulsions. It's here.

However, some dyes belonging to this family have little effect on the photographic emulsion itself, but 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 been carried out in recent years, some residual particles may remain after processing. 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). However, it has the disadvantage that the desired photographic effect cannot be obtained.

(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 through 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 one dye represented by the general formula (R).

In the formula, R1 and R are each an aliphatic, alicyclic or aromatic acyl group, such as an acetyl group, a propanoyl group, a dodecanoyl group, an isobutyroyl group, a cyclohexylcarbonyl group, a benzoyl group, etc. each represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, or an alkoxy group. Here, the alkyl group preferably has 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a butyl group, an octyl group, or a dodecyl group. On the other hand, the alkoxy group preferably has 1 to 8 carbon atoms, such as a methoxy group, an ethoxy group, an amyloxy group, or an octyloxy group.
Ll, Lx, Ls, L4, Ls are each a methine group,
or a substituted methine group (for example, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group substituted with a carboxy group, a sulfo group, a sulfato group, a thiosulfato group, etc., a phenyl group, a benzyl group, etc.)
0M, which may form a ring between any of the methine carbons from L to LS, represents a hydrogen atom or a cation, and m and n each represent 0 or l.

Q is a bond or a divalent linking group (e.g. alkylene amino group (e.g. 2-sulfoethylamino, 3-sulfopropylamino, 2-carboxyethylamino), alkyleneoxy group (e.g. 2-carboxyethoxy, 4-sulfo) butoxy), alkyleneacylamino groups (e.g. β-
(carboxypropionylamino), phenylene group (e.g. 〇-flufophenyl), etc.).

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

a03S a03S NaO, S a03S a03S H3 SO3Na
5OsNa20. 5υ3'
5ILII member 5OsK
5O
The compound shown in the slt general formula (summer) can be synthesized by various synthetic methods, but for example, as shown in the reaction formula below, pyrazolone (Il), (Illa), (I11b
), (Illc), (Illd) or (IIIs) in the presence of a base.

(Ins) (Illb) HC(OCt Hs) 5 (Ic) Su(file) In the formula, R+ SRs , M, Lt , Lx , Ls, L
a, Ls, rnsn represent the same meanings as above, and X is an anion such as chloride, bromide, iodide, perchlorate, methylsulfate, ethylsulfate, p-toluenesulfonate, etc.)
represents.

Z represents a hydrogen atom, a nitro group, or a halogen atom (eg, chloro, bromo).

Rs, R&, Rt, Re are hydrogen atoms, alkyl groups (e.g. methyl group, ethyl group, etc.), alkyl groups substituted with woody groups such as carboxy groups, sulfo groups, sulfato groups, thiosulfato groups, phenyl groups, It represents a benzyl group, etc., and may be fused between R2 and R1.

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

Synthesis Example 1 (I) 3-acetyl-1-(4-sulfophenyl)pyrazoline-5 oz Sodium sulfanilate (I 9.6 g
, 0.10+5 mol) was cooled on ice, and sodium nitrite (6.9 g, 0.10 mol) was added. 2N hydrochloric acid (I00d) was added dropwise to this solution over a period of 10 minutes, and after the addition was completed, stirring was continued for an additional 30 minutes while cooling with water.

To the solution thus obtained was added an aqueous solution of ethyl 3-acetyl-4-oxopencunate (20.4 g, 0.11 mol) and pyridine (Loom) dissolved in water (I00d). Thereafter, the mixture was heated and stirred in a hot water bath for 1 hour. After cooling to room temperature, the reaction solution was adjusted to pH 10 with 10% NaOH water, and the oil-soluble components in the reaction solution were removed by chloroform extraction. Obtained as a precipitate.

After standing still, the supernatant liquid was removed by decantation, and the precipitate was extracted with methanol. The methanol extract was concentrated and dried under reduced pressure to obtain 9.1 g of the desired product as a brown powder.

Melting point 300℃ or higher.

(2) Bis[3-acetyl-1-(4-sulfophenyl)-pyrazolin-5-one-(4)]-pentamethine oxonol trisodium salt ■3-acetyl- prepared with NaO,5 (I) 1-(4sulfophenyl)-pyrazolin-5-one (3.5 g), glutaconaldehyde cyanyl hydrochloride (2.8 g), triethylamine (6.7 m) in dimethylformamide (40M1)
and stirred at room temperature for 10 hours. A solution of 5.2 g of sodium acetate in 50 methanol was added to this solution, and the precipitate precipitated was collected by filtration to obtain 2.1 g of the title compound.

Melting point over 300°C.

Synthesis Example 2 Bis[3-benzoyl-1-(4-sulfophenyl)-
Pyrazolin-5-one-(4)-pentamethine oxonol trisodium salt ■ a03S 3-benzoyl-1-(4sulfophenyl)-pyrazolin-5-one (4.4 g), glutaconaldehyde cyanyl hydrochloride ( 2.8g), triethylamine (6.7m
) was dissolved in dimethylformamide (40-) and stirred at room temperature for 10 hours. Add 5.2 ml of sodium acetate to this solution.
g of methanol 50+d solution was added, and the deposited precipitate was collected by filtration to obtain 2.2 g of the title compound.

Melting point 300℃ or higher.

Synthesis Example 3 Bis[3-acetyl-1-(4-sulfophenyl)-pyrazolin-5-one-(4)]-trimethine oxonol trisodium salt■ 3-acetyl-1-(4-sulfophenyl)-pyrazoline- 5-one (3.5g), malonaldehyde cyanyl hydrochloride (2.6g), and triethylamine (6.7m) were dissolved in dimethylformamide (40d) and stirred at 60°C for 3 hours. After cooling to room temperature, a solution of 5.2 g of sodium acetate in 50 methanol was added to the solution, and the precipitate precipitated was collected by filtration to obtain 2.8 g of the title compound.

Melting point 300℃ or higher.

Synthesis Example 4 Bis[3-acetyl-1-(4-sulfophenyl)-pyrazolin-5-one-(4)]-monomethyloxonol trisodium salt ■ Na0sS ■ 3-acetyl-1-(4-sulfophenyl)-pyrazoline- 5-one (3.5 g), trimethyl orthoformate (I, 1 g), ) ethylamine (6.7 m) were dissolved in methanol (40 ad) and heated under reflux for 3 hours. After cooling to room temperature, a methanol 20-solution of 5.2 g of sodium acetate was added to this solution, and the precipitate precipitated was collected by filtration to obtain 2.2 g of the title compound.

Melting point 300℃ or higher.

Synthesis Example 5 Bis[3-acetyl-1-(3-sulfophenyl)-pyrazolin-5-one-(4))-pentamethine oxonol trisodium salt■ 3-acetyl-1-(3-sulfophenyl)-pyrazoline- 5-one (3,5g), gluconaldehyde cyanyl hydrochloride (2,8g), triethylamine (6,7d)
was dissolved in dimethylformamide (40m) and dissolved at room temperature for 1
Stirred for 0 hours. Add 5.2 g of sodium acetate to this solution.
A 50-methanol solution of was added, and the precipitate precipitated was collected by filtration to obtain 1.8 g of the title compound.

Melting point over 300°C.

Synthesis Example 6 1.5-bis[3-acetyl-1-(4-sulfophenyl)-pyrazolin-5-one-(4))-3-(2-sulfoethyl)pentamethine oxonol trisodium salt ■ Na03S ■ 3-acetyl-1-(4sulfophenyl)-pyrazolin-5-one (
3,3g), 3-(2-sulfoethyl)-glitaconaldehyde dianyl hydrochloride (2,8g), pyridine (
6.5m) was dissolved in dimethylformamide (40m) and stirred at room temperature for 10 hours. A solution of 5.2 g of sodium acetate and 50 methanol + dt8 was added to this solution, and the precipitate precipitated was collected by filtration to obtain 1.4 g of the title compound.

Melting point 300℃ or higher.

When using the dye represented by general formula (I) as a filter dye, anti-irradiation dye or antihalation dye, any effective amount can be used;
It is preferable to use it so that the optical density is in the range of 0.05 to 3.0, and it may be added at any step before coating.

The dye according to the invention can be used as a hydrophilic colloid J in emulsion layers and other areas.
It can be dispersed in the li (interlayer, protective layer, antihalation layer, filter layer, etc.) by various known methods.

■ A method of directly dissolving or dispersing the dye of the present invention in an emulsion layer or a hydrophilic colloid layer, or a method of dissolving or dispersing it in an aqueous solution or solvent and then using it in an emulsion layer or a hydrophilic colloid layer, an appropriate solvent, etc. x Li s Methyl alcohol, ethyl alcohol/propyl alcohol, methyl cellosolve, JP-A-48-9715, U.S. Patent 3
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. 756.830.

■ 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. ; Water-insoluble mordant disclosed in U.S. Pat. No. 3,898.088; Reactive mordant capable of covalent bonding with dyes disclosed in U.S. Pat. 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;
Examples include polymers derived from 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), 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) crystal form, or a composite form of these gold 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
For particles with a diameter of 0.6 microns or less, preferably 0.3 microns or less, and an average aspect ratio of 5 or more, the value (S/1) of the total projected area of 5 deviations S divided by the diameter 1) A monodisperse emulsion in which the emulsion is 20% or less is preferred, and two or more types of tabular grain emulsions and monodisperse emulsions may be mixed.

The photographic emulsion used in the present invention is B. gelafchides (P
, Glafkides), Chimie er Phys Photographic (Chimie er Phys Photography)
iquePhotographeque) (Paul Montell, 1967), G.F. Duffin (
G., F. Duffin), Photography Inc.
Emulsion Chemistry (Photography)
c Emulsion Chemistry) (Focal Press, 1966), V. L. Zelikman et al., Making and Coating Photographic Emulsions (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. 14431/1983)
No. 9, No. 53-82408, No. 55-77737, etc.), amine compounds (e.g., 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 (I1°F
r1eser) W, Day-Grundlagen der.
Fotographiegen Prozesse Mint Zirbel/'to Genden (Die Grundlagen d
erPhotographischen Prozes
se ＋＊it Silberhalogeniden
) (Akademifsche Verlags Geserschacht 19
68) The method described on pages 675 to 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 G5, formamidine sulfinic acid, silane compounds); noble metal compounds (for example, total complex salts,
A noble metal sensitization method using complex salts of metals of Group 1 of the Periodic Table, such as PT, 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 capri during the manufacturing process, storage, or photographic processing of light-sensitive materials, or for stabilizing photographic performance. can. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles 1! (especially nitro- or halogen-substituted products)
; Heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, frequently -mercaptothiadiazoles, mercaptotetrazoles (especially l-phenyl-5-
mercaptotetrazole), mercaptopyrimidines;
The above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindenes (especially 4-hydroxy substituted (I゜3.
3a,? Antifoggants or stabilizers such as tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; and the like 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, aminophenol derivative, etc.) in color development treatment. For example, as a magenta 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 too.

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 contains 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 increasing Z). But that's fine.

In addition, the photosensitive material of the present invention contains anti-fading agents, hardening agents, anti-color capri agents, ultraviolet absorbers, protective colloids such as gelatin, and various additives, as detailed in Research Disclosure Vol. 1.176 ( I97B, X1l)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). transfer process (Silver 5 alt diffusion 11)
photosensitive material for color diffusion transfer process, photosensitive material for color diffusion transfer process, imbibition transfer process
photosensitive materials for use in the silver dye bleaching method, photosensitive materials for recording printout images, photosensitive materials for photodevelopment type printing (Direct Pr1nt image), photosensitive materials for heat development, photosensitive materials for physical development, etc. can be mentioned.

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 variety of known light sources can be used. The n light time is usually an exposure time of 171,000 seconds to 30 seconds, but exposures shorter than 1/100 seconds, such as exposures of 1/10' to 1/10' seconds using xenon flash lamps or cathode ray tubes, can also be used. Yes, exposures longer than 30 seconds can be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. Laser light can also be used for exposure. Another electron beam, X! i
Exposure may be performed by light emitted from a phosphor excited by T-rays, α-rays, etc.

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, further washing 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 caplacing 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 and p-phenylenediamine derivatives. 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-)luenesulfonate, etc. The above compounds are described in U.S. Pat.
, No. 015, No. 2,552゜241, No. 2,566.
No. 271, No. 2,592.364, No. 3,656,9
No. 50, No. 3゜698.525, etc.

The amount of the aromatic primary amine color developing agent used is about 0.1 g to about 20 g, more preferably about 0.1 g to about 20 g per liter of developer solution.
The concentration is from 5g to about 10g.

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

Although hydroxylamines 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 hydroxylamines may be substituted or unsubstituted, and the nitrogen atom of the hydroxylamines may be substituted with an alkyl group.

The amount of hydroxylamine added is 0g per 11 color developer.
-10 g is preferable, and 0 to 5 g is more preferable.If the stability of the color developing solution is maintained, it is preferable that the amount added is 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. It is preferably 20 g/l to 5 g/E, and the smaller the content, the more preferred it is, as long as the stability of the color developing solution is maintained.

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
Various saccharides described in No. 52-27638; hydroxamic acids described in No. 59-160141; α, α゛-
Dicarbonyl compounds; salicylic acids described in No. 59-180588; alkanolamines described in No. 54-3532; poly(alkyleneimines) described in No. 56-94349; gluconic acid derivatives described in No. 56-75647, etc. can be given. These preservatives can be used in combination with 21ffi or higher, especially 4.5ffi, if necessary.
-dihydroxy-m-benzenedisulfonic acid, poly(
Preferable additions include ethyleneimine) and triethanolamine.

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 buffering agents include carbonates, phosphates, borates, tetraborates, hydroxybenzoates, glycine salts,
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-pi region (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 buffers because they have the advantages of not having the negative effects of (such as capri) 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, ditrium borate, and boron. Potassium acid, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium O-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
etc. 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 0.1 mol/l or more, particularly 0.1 mol/l-0.4
Particular preference is given to mol/l.

In addition, various caloric acid 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, organic acid compounds are preferable, such as aminopolycarboxylic acids described in Japanese Patent Publication Nos. 4B-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-trimethylenephosphonic acid ・Ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid ・1. 3-diamino-2-propanol-tetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, hydroxyethylenediamine triacetic acid, ethylenediamine Orthohydroxyphenylacetic acid/2-phosphonobutane-1,2,4-)licarboxylic acid/1-hydroxyethane-1,l-diphosphonic acid/N,
N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid Two or more of these 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, 0.1 g to Log per 11 L.

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: US Pat. No. 2,494,9
No. 03, same 3. 128. No. 182, 4,230,
No. 796, 3. No. 253゜919, Special Publication No. 41-1
No. 1431, U.S. Pat. No. 2,482,546, U.S. Pat.
Amine compounds described in Japanese Patent Publications No. 37-16088 and No. 42
1-phenyl-3- Pyrazolidones, hydrazines, mesoion type compounds, thione type compounds, imidazoles, etc. can be added as necessary. Especially thioether compounds and 1-phenyl-
3-pyrazolidones are preferred.

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 antifoggants may be used. Examples of organic anti-capri agents include benzotriazole, 6-nidrobenzimitasole, 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 heterocyclic compounds such as thiosalicylic acid. Aromatic compounds 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. .

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 0 to 5 g/J, preferably 0.1 g to 2 g/J! It is.

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 replenishment amount is 30 to 2,000 m, preferably 30 to 1,500 m per ffr of the 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 toluidine and heterocyclic amines such as pyridine, morpholine and 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 Diethylenetriaminepentaacetic acid Diethylenetriaminepentaacetic acid pentasodium salt Ethylenediamine-N-(β-oxyethyl)-N,N
', N'-) ethylenediamine acetate-N-(β-oxyethyl)-N,N
',N'-)trisodium acetate ethylenediamine-N-(β-oxyethyl)-N,N
',N'-triammonium triacetate propylene diamine tetraacetic acid propylene diamine tetraacetic acid disodium salt nitrilotriacetic acid nitrilotriacetic acid trisodium salt cyclohexanediamine tetraacetic acid cyclohexane diamine tetraacetic acid disodium salt iminodiacetic acid dihydroxyethylglycine ethyl ether diamine tetraacetic acid glycol Etherdiaminetetraacetic acidethylenediaminetetrabrobionic 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 with On the other hand, when forming a complex salt in a solution using a ferric salt and a chelating agent, one or two types of ferric salts are used.
More than one type of chelating agent may be used, and one or more chelating agents may be used.

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

Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0. O1-1.0 mol/l, preferably 0.05-0.50 mol/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. 3,893.858, 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. 140129/1983;
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 oxides described in Japanese Patent Publication No. 8.430; polyamine compounds described in Japanese Patent Publication No. 45-8836; others, Japanese Patent Publication Nos. 49-42434, 49-59644, 53-94927, 54-35727, Same 55-
Examples thereof include the compounds described in No. 26506 and No. 5B-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 US Pat. No. 3.893.858 and West German Patent No. 1.
The compounds described in JP-A-53-95630 are preferred.

Additionally, the bleach or bleach-fix solutions of the present 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. iodine). (ammonium chloride) rehalogenating agents.

Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, as required
Phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. pH 1! E Street Noh 1
More than one type of inorganic acid, organic acid, alkali metal or ammonium salt thereof, and W11 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, 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.

The amount of fixing agent per 11 is preferably in the range of 0.3 to 2 moles, more preferably in the range of 0.5 to 1.0 moles.

The pHtl range of the bleach-fixing solution or fixing solution in the present invention is 3.
-10 is preferable, and 4-9 is especially preferable, pH
If it 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 the pH is higher than this, desilvering is delayed and staining is likely to occur.

To adjust pi (hydrochloric acid, sulfuric acid,
Nitric acid, acetic acid (glacial acetic acid), bicarbonate, ammonia, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, etc. can be added.

The bleach-fix solution may also 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. , 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.
It is preferable to contain 50 mol/l, more preferably 0.04 to 0.40 mol/l! It is.

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 more advanced treatment method is used, such as performing only a so-called "stabilization process" without providing a substantial water washing 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 amount of bleach-fix solution in the final washing bath is It is sufficient if it is less than lXl0-'0 For example, in the case of 3-tank countercurrent water washing, it is about 100 per photosensitive material.
It is preferable to use 0- or more, more preferably 500
0- or more. In addition, in the case of water-saving treatment, 1 liter of photosensitive material
It is preferable to use 100 to 1000 per d.

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 Antifung Agents” (J. Antibact, Antifung,
^gents) Vol, 11s Na compounds, metal salts such as magnesium salts and aluminum salts, alkali metal and ammonium salts, or surfactants to prevent drying load and unevenness are added as necessary. be able to. Or "Photograph Inc. Science and Engineering Lff" by West (
Photo, Sci.

Eng.), Volume 6, pp. 344-359 (I96
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 components of the final bath should be less than or equal to 5 x 10-'', preferably 1
It is sufficient if it is not more than ×10−2.

Various compounds are added to this stabilizing bath for the purpose of stabilizing the image.For example, the pH of the membrane is adjusted.

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. The replenishment amount 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 floats, various 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, 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 1 A multilayer color print sample ill having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene.

Layer structure The composition of each layer is shown below. The numbers represent coating weights (g/d), except for silver halide emulsions, which are coating weights in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiOi) and a bluish dye (ulmarine blue)] -th layer (blue-sensitive silver halide emulsion layer) Spectral sensitizer (Sen-1) Monodispersed silver chlorobromide emulsion (EM-1) containing 0.16 spectral sensitizer Se
Monodisperse silver chlorobromide emulsion (EM-2) added with n-1)
0.10 Capri inhibitor (Cpd-1)
0.004 gelatin 1.83
Yellow coupler (ExY) 0.83 Color image stabilizer (Cpd-2) 0.03 Polymer (Cp
d-3) 0.08 solvent (Solv-1 and 5
OIV-2 Volume ratio 121) 0.35 Hardener (
Hd) 0.02 Second layer (color mixing prevention layer) Gelatin 1.25 Color mixing prevention agent (Cpd-4) 0.04 Solvent (Solv-3
and 3o1v-4 volume ratio 1:1) 0.20 hardener (
Hd) 0.02 Third layer (green-sensitive silver halide emulsion layer) Monodispersed silver chlorobromide emulsion (EM-3) with added spectral sensitizer (Sea-2,3) 0.05 Spectral sensitizer (Son
-2,3> monodispersed silver chlorobromide emulsion (EM-4)
0.11 anti-capri agent (Cpd-5) o,
001 Gelatin 1.79 Magenta coupler (ExM) 0.32 Color image stabilizer (Cpd-6) 0.20 Color image stabilizer (Cp
d-7) 0.03 color image stabilizer (Cpd-8
) 0.03 solvent (Solv-3 and 5olv
-5 Volume ratio l:2) 0.65 Hardener (
Hd) 0.01 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1/2/3 molar ratio 1:4:4) 0.62 Color mixture prevention agent (Cpd-4) 0.05 Solvent
-6) 0.34 dye (Dy-1)
0.005 dye (Dy-2)
O,Ol 5 Hardener (Hd)
0.01 Fifth layer (red-sensitive silver halide emulsion layer) Monodisperse silver chlorobromide emulsion (EM-5) added with a spectral sensitizer (Sen-4, 5) 0.07 Spectral sensitizer (Sen-4, 5)
-4,5) Monodisperse silver chlorobromide emulsion (EM-6)
0.15 Anti-capri agent (Cpd~9) 0.0
002 Gelatin 1.34 Cyan coupler (ExC-1) 0.15 Cyan coupler (ExC-2) 0.18 Ultraviolet absorber (U
V-1/3/4 molar ratio 1:3=3) 0.17 Polymer (Cpd-3) 0.33 Solvent (Solv-
1) 0.23 hardener ()id)
0.01 Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1/2/3 molar ratio 1:4=43 0.21 Solvent (Sol
v-6) 0.08 Hardener (Hd)
0.01 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 Details of the silver halide emulsion used in the above sample Shown in the table.

Coefficient of variation - standard deviation/average particle diameter (Son-1) 6X10-' mol/Ag mol (Se
n-2) 4x1o-' mol/Ag mol (Sen-
3) 8X10-' mo/Iz/Ag mole (Sen-
4) 1.8X10-' mol/Ag mol CsL+
T-CtHs (Sen-5) 3X10-3 mol/Ag mol (E
x Y) (ExM) (ExC-1) 0■ (ExC-2) (Hd) (Cpd-1) H (Cpd-2) (Cpd-3) +C1, -C1゜C0NICall*(t) Molecular weight Approx. 60000
(Cpd-4) OH 0■ (Cpd-5) (Cpd-6) (Cpd-7) Hot 0OCJs (Cpd-8) (Cpd-9) i! (UV-1) (UV-2) (UV-3) (UV-4) (Solv-1) υ (Solv-2) 0 = P+0CJI+w(iso))s(Solv-
3) (Solv-4) C neglect US op÷0CToCHCJ*)i (Solv-5) COOCHxCH(Calls)CeH*No.(CHg)e C00CBiCH(CtHs)CJ* (Dy-1) (Dy-2) Samples (2) to 4th layer with different dyes from the sample L
(7) was produced. The composition is shown in Table 2.

The stability of the dye in the film and the exposure humidity dependence were investigated for samples +11 to (8) in Table 2. The stability of the dye was evaluated by the residual rate of the dye after leaving the raw sample at 35° C.-80% for 2 weeks. In addition, the exposure 1 temperature dependence was determined by performing the following treatment after exposure under conditions of 25°C - 55% and 25°C - 85%, and the relative sensitivity at optical density = 1.0 was The silver emulsion layer was evaluated. The evaluation results are shown in Table 3.

Processing 1st base I skin Bright color development 33℃ 3 minutes 30 seconds bleach fixing
Wash at 33℃ for 1 minute and 30 seconds 24-34℃
Dry for 3 minutes at 70-80°C 1. The composition of the pollution treatment liquid is as follows.

Light negative anti-hair cinnabar water 800-
Diethylenetriaminepentaacetic acid 1.0g Nitrilotriacetic acid 1.5g Benzyl alcohol 15-diethylene glycol
10-Sodium sulfite 2.
0g potassium bromide 0.5g potassium carbonate 30g N-ethyl-N
-(β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0g Hydroxylamine sulfate 4.0g Optical brightener (WRITE)
X4B, made by Juju Chemical) Add 1.0g water to 1000dpH (25℃)
10.20 bleach-fix water 400i
dAmmonium thiosulfate (70%) 150dSodium sulfite 18gIron ethylenediaminetetraacetate (I[[)Ammonium 55gDisodium ethylenediaminetetraacetate 5゜・Add water to 1000+dpH (25℃)
6.70 Table 3 As is clear from Table 3, samples using the dye of the present invention (
2) to (8) have excellent stability in the membrane, and
The relative sensitivity of 5% is high, and there is little decrease in sensitivity at 25°C-8594.

Example 2 A sample (9) having the following N configuration was prepared in the same manner as in Example 1.

-th layer (blue-sensitive silver halide emulsion layer) Monodispersed silver chlorobromide emulsion (EM-7) with added spectral sensitizer (Sen-6) 0.27 gelatin
1.86 Yellow Cabler (ExY)
0.82 Solvent (Solv-4)
0.35 Hardener (Hd) 0
．． 02 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-4) 0.06 Solvent (Solv-3
and 5olv-4 volume ratio 1:1) 0.12-Hardening agent (
Hd) 0.02 Third layer (green-sensitive silver halide emulsion layer) Monodispersed silver chlorobromide emulsion (EM-8) with added spectral sensitizer (S en -7,3) 0.45 Gelatin
1.24 magenta coupler (Ex
M) 0.35 color image stabilizer (Cpd-6)
0.20 color image stabilizer (Cpd-7)
0.03 Color image stabilizer (Cpd-8) 0.0
3 solvent (Solv-3 and 3o1v-5 volume ratio 1:2) 0.65 Hardener (H
d) 0.01 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorber (UV-1/2/3 molar ratio 1:4=4) 0.62 Color mixing inhibitor (Cpd-4) 0.05 Solvent
-6) 0.34 dye (Dy-1)
0.005 dye (Dy-2)'
0.015 Hardener (Hd)
0.01 Fifth layer (red-sensitive silver halide emulsion layer) Monodispersed silver chlorobromide emulsion (EM-9) with added spectral sensitizer (Sen ~ 4.5) 0.20 Gelatin
0.92 cyan coupler (ExC-3)
0.15 cyan coupler (ExC-4)
0.18 Ultraviolet absorber (UV-1/3/4 molar ratio 1:3:3) 0.17 Solvent (S
olv-4) 0.20 Hardener (Hd)
0.01 6th layer (ultraviolet absorption N
) Gelatin 0.53 Ultraviolet absorber (UV-1/2/3 molar ratio 1:4:4) 0.21 Solvent (S
olv-6) 0.08 Hardener (Hd)
0.01 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 Details of the silver halide emulsion used in the above sample Shown in the table.

Fourth layer variation coefficient = standard deviation/average particle diameter (Sen-6) P5OJ-N(CzHs)s (Sen-7) (EXC-3) I (ExC-4) H Samples OI~O with different dyes
e was produced. The composition is shown in Table 5.

The stability of the dye in the film and the exposure humidity dependence were investigated for samples (9) to OQ in Table 5. The stability of the dye was evaluated by the residual rate of the dye after leaving the raw sample at 35° C.-80% for 2 weeks. In addition, the exposure humidity dependence was determined by performing the following treatment after exposure under conditions of 25°C - 55% and 25°C - 85%, and the relative sensitivity at optical density = 1.0 was determined by The emulsion layer was evaluated. The evaluation results are shown in Table 6.

Processed Koo I Peel Dragon color development 35℃ 45 seconds bleach fix 30-35℃ 45 seconds rinse 0 30-35℃ 20 seconds rinse■ 30-35℃ 20 seconds rinse■ 30-35℃ 20 seconds rinse■ 30-35 ℃ 30 seconds drying 70-80℃ 60 seconds (3 tank countercurrent force type from rinsing ■ to ■) The composition of each treatment liquid is as follows.

Shusuri 1 healing water 800-
Ethylenediamine-N, N.

N',N'-tetramethidinephosphonic acid 1.5g triethylenediamine (I°4diazabicyclo(2,2°2)octane) 5.0g sodium chloride 1.4g potassium carbonate
25g N-ethyl-N-(β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0g N,N-diethylhydroxylamine 4.2g Fluorescent brightener (UVITEX CK Ciba Geigi) 2.0g Add water to 100 (ldp) I (25℃>
10.10 Wataru foot base Tatsumizu 400-
Ammonium thiosulfate (70%) 1G (ld Sodium sulfite 18g ethylenediaminetetraacetate iron (Ill) ammonium 55g disodium ethylenediaminetetraacetate 3g ammonium bromide 40g glacial acetic acid
Add 8g water
100 (ldpH (25℃) 5.5 Yue input sputum ion exchange water (calcium, magnesium 3pp each)
m or less) Table 6 As is clear from Table 6, sample 0 using the dye of the present invention
1-Ql has excellent stability in the film and is stable at 25℃-55℃.
% relative sensitivity is high, and there is little decrease in sensitivity at 25° C.-85%.

(Effects of the Invention) According to the present invention, a silver halide layer having a hydrophilic colloid layer containing a novel dye that is decolorized and eluted during photographic processing and does not adversely affect the photographic properties of the photographic emulsion, particularly the spectral sensitization. A photographic material can be obtained.

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

Patent Application University Fuji Photo Film Co., Ltd. Procedural Amendment

Claims (1)

[Scope of Claims] A silver halide photographic material comprising at least one dye represented by the following general formula (I). (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 and R_2 each represent an aliphatic, alicyclic, or aromatic acyl group, and R_3 and R_4 each represent a hydrogen atom, an alkyl group, an alkoxy group, represents a halogen atom or a hydroxyl group, L_1, L_2, L_3, L_4 and L_5 represent a methine group and each may be different; M represents a hydrogen atom or a cation; m and n represent 0 or 1; Q represents a Represents a bond or a divalent linking group.