JPS63158545A - Color photography and its production - Google Patents

Abstract

PURPOSE:To prevent the deterioration of image quality caused by the lapse of time, and the generation of a stain in the color photography by incorporating a compd. which is chemically inactive and is substantially colorless by chemically binding with a residual color developer contg. an aromatic amine, after color development, to a photosensitive material. CONSTITUTION:The photographic sensitive material contains a color image forming coupler capable of forming a color matter by effecting the oxidative coupling reaction of a silver halide emulsion layer provided on a substrate body by applying it, and the color developer contg. the aromatic amine. Said photographic sensitive material is image-wisely exposed, followed by processing the color development and a bleach- fixing treatment to form the color photography. In the color photographic processing, the compd. which is capable of improving a preservable property and is chemically inactive and substantially colorless by chemically binding with the color developer composed of the aromatic amine, is incorporated optionally to the photosensitive material at the time of the processing step such as at the time of producing the photosensitive material, during or after processing it. Thus, the generation of discoloration in a white ground of the color photography is prevented, even in case of storaging or displaying it for long period.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a color photograph and a method for producing the same, and more specifically to color development using an aromatic amine present in a silver halide photosensitive material after color development processing. This invention relates to a method for producing color photographs that improves the shelf life of color photographs by making drugs chemically inert.

(Prior art and its problems) A silver halide color photographic light-sensitive material is imagewise exposed and developed with an aromatic amine color developer, and the resulting oxidized product of the developer and a dye image-forming coupler (hereinafter referred to as A dye image is formed by reaction with a dye (referred to as a coupler). In color photographic photosensitive materials, a combination of yellow coupler, cyan coupler and magenta coupler is usually used.

Since Fischer et al. discovered the basis of this color development method in 7972, improvements in this method have been made dramatically.

Particularly recently, we have been conducting improvement research on, for example, shortening development processing time, simplifying processing steps, reusing processing waste liquid, reducing the amount of replenisher, waterless washing processing, and removing benzyl alcohol in consideration of environmental conservation. is being actively carried out.

However, there are still many problems; for example, in the development process, it is not necessary to prepare a new processing solution each time the development process is performed.
In reality, problems arise because the developer is replenished according to the amount of development to be processed.

That is, the processing solution usually consists of a color developing solution, a stop solution, a bleach solution, a fixing solution, a bleach-fix solution (Blix), etc., but in order to maintain the processing temperature at a high temperature such as 370 to 4t3 °C, it takes a long time. During this process, developing agents may decompose or become oxidized due to contact with air, eluates from the photosensitive material may accumulate during processing, and processing solutions may adhere to the photosensitive material and cause problems in the next process. The composition of the processing liquid changes due to factors such as being brought into the bath, resulting in a so-called run-end liquid. For this reason, efforts are being made to replenish by adding additional chemicals that are in short supply and to regenerate by removing unnecessary items, but this is not perfect. Furthermore, in the washing process, due to economic reasons such as lack of water resources, rising water charges, and environmental conservation reasons, the amount of washing water is reduced or waterless washing is performed, which reduces the amount of thiosulfate, sulfite, and other components of the processing liquid. Inorganic components such as metabisulfite and organic components such as developing agents are contained in or attached to the photosensitive material.

Even if we look at examples such as deterioration of the processing liquid composition, reduction in the amount of water washing in the washing step, or waterless washing, it can be seen how the amount of processing liquid components carried into the light-sensitive material tends to increase.

On the other hand, in order to obtain good color reproducibility, we are developing couplers that provide bright cyan, magenta, and yellow dyes with little side absorption, and at the same time, we are developing highly active couplers that can complete color development in a short time. It is being done.

Furthermore, new additives and the like are being developed to bring out the excellent performance of these couplers. However, conversely, these new features interact with the processing solution components remaining in the light-sensitive material after processing, resulting in a decrease in the shelf life of color photographs.

Among the processing solution components remaining in the photosensitive material after development, especially the aromatic primary amine compound as the developing agent and the compounds derived therefrom are exposed to light, heat, humidity, oxygen, etc. during long-term storage. It is known that the solidity of the image is deteriorated due to the effects of oxidation, and that it itself changes into a colored substance due to self-coupling or interaction with coexisting substances, resulting in so-called "stain". This is a drawback that can be said to be fatal for color photography.

On the other hand, apart from this, many studies have been conducted to prevent image deterioration and stain prevention. For example, proposals have been made to select and use couplers with low fading properties, to use anti-fading agents to prevent fading due to light, and to use ultraviolet absorbers to prevent image deterioration due to ultraviolet rays.

Among them, the anti-fading agent has a great effect in preventing image deterioration.
For example, idokuquinones, hindered phenols,
Tocopherols, chromans, coumarans, and compounds obtained by etherifying the phenolic hydroxyl groups of these compounds (U.S. Patent No. 3゜J!, 0/O, No. 3,9
30. No. 266, No. 3, 700, Gu! ! No. 3
, 76g, 332, No. J, No. 4132.300, No. J, 373°θ! O issue, same issue G, 2! Gu, 2/6, British Patent No. 2,01 O, Wa 2! No. 7. ! 26.
II issue, Tokko Akira! /-301 etc.) are known.

(Problems to be Solved by the Invention) Although these compounds are recognized to be effective as agents for preventing fading and discoloration of dye images, they are insufficient to meet the demands of customers who are increasingly demanding high image quality. Until it is sufficient and exhibits an overall excellent effect for color photography due to changes in hue, generation of capri, poor dispersion, or formation of microcrystals after emulsion coating. has not yet been achieved.

More recently, U.S. Pat. 3゜9// issue,
Tokukai Akira! Tar2/r, 4t4tj, same! Tar 22
9. j! The effectiveness of certain amine compounds has been proposed in No. 2 and others. However, none of these conventional compounds were sufficient to achieve this objective.

On the other hand, it is known to add /-aryl-3-pyrazolidone derivatives, especially their precursors, into the sensitive material layer, for example in US Patent No. 3, 3! ♂.

! 2yo issue, same gu, 4t4j, 762 issue, same gu,! λ
λ, ri No. 77, JP-A-Sho jt'! --! t2Ojj No., jj-6330, j2-da θ2g! Same issue! 2-1
0416g/No. 0416, No. 0416/J"9-/2/32♂, etc.However, these compounds have the drawback that their addition deteriorates photobleaching properties. This is to a large extent for pyrazoline derivatives.

Therefore, the object of the present invention is to provide a method for producing color photographs in which the white background of color photographs is prevented from discoloring even after long-term storage and display after color development, bleaching, and fixing of silver halide color light-sensitive materials. It is about providing.

Another object is to provide a color photograph in which deterioration of dye images due to residual color developing agent carried into the light-sensitive material after color development, bleaching and fixing processes is prevented.

Another purpose is to process liquids in a running state, processing liquids with a small amount of water washing or non-water washing processing liquids, color developing liquids that do not substantially contain benzyl alcohol, and other processing liquids in which processing liquid components are carried into the photosensitive material. Or, color image formation of a color photosensitive material that prevents side effects such as image deterioration and staining caused by residual aromatic amine color developer even after processing with a processing solution that places a burden on background color development. It is about providing law.

(Means for Solving the Problems) As a result of various studies, the present inventors have found that the above-mentioned solution is based on a silver halide emulsion layer coated on a support and an aromatic amine color developing agent. After imagewise exposure of a photographic light-sensitive material containing a color image-forming coupler that forms a dye through an oxidative coupling reaction with the aromatic amine, the aromatic amine is Preservation-improving compound 1 that chemically bonds with a color developer to produce a chemically inert and substantially colorless compound! ＃、、
``Karihe far'' η, end of viewing l `` [Nine new end k・J! (l!
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The present invention has been made based on this knowledge.

That is, the present invention chemically bonds with the aromatic amine color developer remaining after color development (preferably under conditions of pH ♂ or lower) to produce a chemically inert and substantially colorless compound. This is a color photograph characterized in that at least one photographic layer on a support contains a preservability-improving compound.

The aromatic amine color developing agent as used in the present invention includes aromatic primary, secondary and tertiary amine compounds, and more specifically includes phenylene diamine compounds and amine phenol compounds. A typical example is 3-methyl-
Guamino-N,N-diethylanili/, 3-methyl-kuamino-N-ethyl-N-β-hydrogynelethylaniline, 3-methyl-der-amino-N-ethyl-N-
β-meta/sulfonamidoethylaniline, 3-methyl-guamino-N-ethyl-N-β-methoxyethylaniline, goomethyl-co-amino-N, N-diethylaniline, goomethyl-no-amino-N-ethyl-N-β
-Methanesulfonamide ethylaniline, no amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-goomethylamino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-gudimethylamino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-goobutylamino-N, N-diethylaniline, 3-methyl-guacetylamino-N
-ethyl-N-β-hydroxy/ethylaniline, 3-methyl-gumethanesulfonamide-N-ethyl-N-β
-methanesulfonamidoethylaniline, 3-methyl-
Cubenzylamino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-gucyclohexylamino-N-ethyl-N-methylamino/and their sulfates, hydrochlorides, phosphates or p- +-luenesulfonate, tetraphenylborate, p-(t
-octyl)benzenesulfonate, 0-aminephenol, p-aminephenol, guamino-λ-methylphenol, no-amino-3-methylphenol, 2-
Oxy-3-amino-/, kudimethylbenzene, etc. are included.

In addition, "Photographic Ink Processing Chemistry" by F. A. Menon, published by Focal Press (
7966) (L, F, A, Mason.

”Photographic ProcessingC
hemistry”, Focal Press)
pp. 2-26-22, U.S. Patent 2. No. X93.01j, same λ.

Examples include those described in Japanese Patent Application Laid-open No.

Preferred compounds that form a substantially colorless compound by chemically bonding with an aromatic amine developer after color development treatment can be represented by the following general formula (1) or (II).

General formula (1) % formula % (General formula (■) R2-C=Y Of the methods that chemically bond with the residual aromatic amine developer,
Typical examples are substitution reactions and addition reactions.

General formula (1), (n
), the compound represented by the general formula (1) is preferred, and more preferably the second-order reaction rate constant with p-'f dinonono is 2(♂00C)ka/, ol/mol.
sec ~/X/(7,1/mOl It is a compound that reacts in the range of SeC. Lips!?-)'-7-:, V>v
tv--'/! -, D-rbs kjIi-, No1
112, gx gr rto °e: > r+
x to-'l/;, 1.4. 8/X10-'l
/set, aec1)4'bf)z'J2t':r j
J'/Otsug Wt h-4L:d ty jj (
If the value of 1rit, tt-2 is larger than this range, the compound itself will become unstable and will react with gelatin/water and decompose. On the other hand, if k2 is smaller than this range, the reaction with the remaining aromatic amide/developing agent will be slow, and as a result, it will not be possible to prevent the side effects of the remaining aromatic amide/developing agent, which is the object of the present invention.

The method for measuring k2 is explained in the Examples below.

Each group of the compound represented by the general formula (11, ([1)] will be explained in more detail.

The aliphatic group referred to in R1, R2 and B represents an ffi in, branched or cyclic alkyl group, alkynyl group or alkynyl group, which may be further substituted with a substituent. The aromatic groups referred to in It, R2 and B include carbocyclic aromatic groups (e.g. phenyl group, naphthyl group, etc.) and heterocyclic aromatic groups (e.g. furyl group, chenyl group, etc.).
pyrazolyl group, pyridyl group, indolyl group, etc.), and may be a monocyclic system or a condensed ring system (eg, benzofuryl group, phenanthridinyl group, etc.). Furthermore, these aromatic rings may have a substituent.

The heterocyclic group referred to in Rls R2 and B is a carbon atom,
A group having a 3- to 10-membered ring structure composed of an oxygen atom, a nitrogen atom, a sulfur atom, or a hydrogen atom is preferable,
The heterocycle itself may be a saturated ring or an unsaturated ring, and may be further substituted with a substituent (for example, furanyl group, pyrrolidyl group, pyrrolinyl group, morpholinyl group, etc.)
.

X represents a group that reacts with an aromatic amine developer and leaves the group, and is a group that is bonded to A via an oxygen atom, sulfur atom, or nitrogen atom (e.g., 3-pyrazolyloxy group, 3H-/, x
, <t-oxadiazolin-j-oxy group, aryloxy group, alkoxy group, alkylthio group, arylthio group, substituted N-oxy group, etc.) A halogen atom is still preferred.

A represents a group that reacts with an aromatic amine developer to form a chemical bond, and contains a group containing a low electron density atom, R/ -L-8i-. R where X is an atom
// In this case, the symbol represents O. Here, L is a single bond, an alkylene group, -0-, -3-, -N-.

R'' I Y/ (e.g. carbonyl group, sulfonyl group, sulfinyl group, oxycarbonyl group, phosphonyl group, thiocarbonyl group, aminocarbonyl group, silyloxy group, etc.)
.

Y has the same meaning as Y in general formula (b), and Y' has the same meaning as Y.

R' and R'/ may be the same or different, and each -L
rrt Represents Ro.

Ro represents the same meaning as R. R″′ is a hydrogen atom, an aliphatic group (e.g., methyl group, inobutyl group, t-methyl group, vinyl group, befryl group, octadel/chromanyl group, etc.), aromatic group (e.g., phenyl group) , pyridyl group, naphthyl group, etc.), heterocycles (for example, pyridyl group, naphthyl group,
pyranyl group, furanyl group, chromanyl group, etc.), aryl group (eg, acetyl group, be/diyl group, etc.), and sulfonyl group (e.g., meta/sulfonyl group, penda/sulfonyl group, etc.).

L', L" and L"' are 10-, -S-, and -N
- represents.

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Among them, Aba-o-c-, -5-c- and monoalkylene/-
A divalent group represented by C- is preferred.

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Y in the general formula (If) is an oxygen atom, a sulfur atom,
Here, R4, R5 and R6 are hydrogen atoms, aliphatic groups (e.g. methyl group, isopropyl group, t-butyl group, vinyl group, benzyl group, octadecyl group, nclohexyl group, etc.), aromatic groups (e.g. phenyl group, pyridyl group, etc.). group, naphthyl group, etc.), petro-term group (e.g. lysyl group, pyranyl group, furanyl group, chromanyl group, etc.), acyl group (e.g. acetyl group, benzoyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, benzene group, etc.) sulfonyl a, etc.), and R5 and R6 may be bonded to each other to form a cyclic structure.

Representative examples of these compounds are shown below, but the compounds used in the present invention are not limited thereby.

N-, 2) (+-31 (1-g) (1-j) (1-ot) (1-10) (1-/ko) (I-/ni) (1-/, !1') (n) C18H37■ (+-/9) ”)01BH37Br (+--2(7) (+--21) White L, (0) (1--1,,?) (1-λ4t) (1 Zurike 2 no 0-phantom (1-1tri (1-!12) ``y′teU-sagino(L-5ranoΦdeλ (X(7) σ-6suσ-riσ- 62) σ-→ (1-6ζn(x-t7) σ-7?) 29. Sitl〆-11ノ (O bass chorus 1 (U bats tjla75- and 0iCJ) lj up χ , Now 1a h g, Iji6.46/
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--,-,----CI)2Jz-3-- (II-1) (If-2) (II-3) CH2=CH-8O2-C18H3□(n) (n-9) (Ill ) Synthesis examples of representative compounds of the present invention are shown below.

Synthesis Example/(Synthesis of 1-9) Synthesis of Gooddecylbenzenethiocarbonic acid λ-ethylhexyl ester (Exemplary Compound 1-9) Dartodecylbenzenethiol/! g(0,.

Add 9 ml (0,077 mol) of chloroform/rOml triethylamine to 61 mol) and dissolve! j
Stir at 0C. , 73.3 g (o, o, <r mol) of chlorocarbonate niethylhexyl ester was added dropwise thereto. After stirring for 30 minutes, cold hydrochloric acid solution was added to separate the layers, and the chloroform layer was washed three times with cold water and dried with sodium sulfate. After removing Glauber's salt, chloroform was distilled off and the product was purified by column chromatography. Oily substance.

Yield/7. ．． 2g Yield ratio, 2% Calculated value (%) 2 yen, 60 10. T? / Da, 2!
Synthesis Example 2 (Synthesis of 1-73) i) Synthesis of s-(3-hexadecylox7phenyl)-3-hydroxy-/-phenylpyrazole ix, r-dihydroxy-J--(J-hexadecylox/phenyl)-3 -Hydroxy-/-phenylpyrazole t, 3 g (o, o/3 mol) in toluene, Oml;
Manganese dioxide log (o, 72 mol) was added and heated and stirred in a steam bath for 2 hours. After removing the inorganic substances, the residue was concentrated to dryness and crystallized with 20 ml of ethyl acetate. Melting point 10r~10
9°C0 yield j, dog yield w2. ! H1i) j-(,z-ethylhexyloxycarbonyloxy)-s-(3-hexadecyloxy/phenyl)-/
Synthesis of -phenyl-hyrasole (exemplified compound!-/J) -(3-hexadecylox7phenyl)-3-hydroxy-/-phenylpyrazole 5.3 g (0,0i1
9 ml (0,0i 14 mol) of 1% triethylamine 7/l/l/l/mole was added and dissolved, and the mixture was stirred at 2!0C. To this, chlorocarbonic acid 2-
2.3 g (0°0i 2 mol) of ethylhexyl ester was added dropwise. After stirring for 30 minutes, cold water was added to separate the layers, and the chloroform layer was washed twice with JOml of cold water and dried with sodium sulfate. After filtering out the Glauber's salt, chloroform was distilled off and the product was purified by column chromatography.

Oily substance. yield! , 7g Yield/2CH Elemental analysis result (C40H6ON204) CHN Actual value (CH) 2t, i3 TA, 4t7 GU, // Calculated value (CH) 2! , Wa/Wa, St 4t, G3 Synthesis Example J' (Synthesis of 1-2g) Synthesis of Guhebutyloxycarbonyloxy-pyridine (Exemplary Compound!-Co4t) Derhydroxypyridine/Hydrate <t ,sg(o.

0 mol) to chloroform/o o ml -, F
') Ethylamine 7.3ml (0,032mol)
was added, dissolved, and stirred at 2!0C. To this was added dropwise 9 g (0,010 mol) of hebutyl chlorocarbonate. After stirring for 30 minutes, add cold hydrochloric acid water and separate the liquid.
The chloroform layer was washed twice with cold water and dried over Glauber's salt.

After separating 2"I of Glauber's salt, chloroform was distilled off, purified by column chromatography, and crystallized with ethanol.9. Melting point: 1~!0°C
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lJ solution, □, 2. ? If the compound of the present invention has a low molecular weight or is easily soluble in water, it may be added to the processing solution and incorporated into the photosensitive material during the development process. Preferably, it is added to the photosensitive material at the stage of manufacturing the photosensitive material. The latter method typically uses a boiling point of 770 at atmospheric pressure.
It is prepared by dissolving it in a high boiling point solvent (oil) of 0C or more, a low boiling point solvent alone, or a mixed solvent of the oil and a low boiling point solvent, and emulsifying and dispersing this solution in an aqueous solution of a hydrophilic colloid such as gelatin. . Preferably, the compounds of the invention are soluble in high boiling organic solvents.

There is no particular restriction on the particle size of the emulsified dispersion particles, but o:o
sμ~O9! μ is preferred, especially 0. /μ to 0.3μ is preferable. In particular, from the viewpoint of the effects of the present invention, it is preferred that the compound of the present invention is co-emulsified with a coupler. In this case, the oil/coupler ratio is preferably 0.00 to λ, O in terms of weight ratio.

Further, the proportion of the compound of the present invention is 1 x 10 -2 to 70 mol, preferably 3 x 10 mol, per 1 mol of coupler.
-2 or so! It is a mole.

Specific examples of the oil include phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, diindecyl phthalate, dimethoxyethyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, trinoenyl phosphate, tricresyl phosphate, etc.). dioctyl butyl phosphate, monophenyl-p-t-butylphenyl phosphate), citric acid esters (e.g. acetyl tributyl citrate)
, benzoic acid esters (e.g., octyl benzoate), alkylamides (e.g., diethyl laurylamide, dibutyl laurylamide), fatty acid esters (e.g., dimethoxyethyl phthalate, diethyl azelate), trimesic acid esters (e.g., tributyl trimesate), ), compounds containing epoxy rings (e.g. 0.4
37), phenols (e.g. ethers (e.g. phenoxyethanonyl, diethylene glycol monophenyl ether)), and low boiling point solvents used as replenishing solvents include Organic solvents at 30°C to /!0°C, such as etinoacetate, isopropyl acetate, lower argyl acetates such as butyl acetate, etinopropionate, methanol, ethanol, butyl alcohol, cyclohexanol, fluorinated alcohol, methyl isopropionate. Butyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate acetone, methyl acetone, acetonitrile,
Dioxane, dimethylformamide, dimethylsulfoxide, chloroform, cyclohexane and the like can be mentioned.

In addition, instead of high boiling point organic solvents, not only oil-based solvents (including those that are solid at room temperature such as wax) for additives such as couplers, but also latex polymers can be used, or couplers, color mixing inhibitors, and ultraviolet rays can be used. The additive itself, such as an absorbent, may also serve as an oily solvent.

Latex polymers include acrylic acid, methacrylic acid and its esters (e.g. methyl acrylate, ethyl acrylate, butyl methacrylate, etc.), acrylamide, methacrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate, etc.), acrylonitrile, styrene, divinyl Benzene, vinyl alkyl ether (e.g. t is vinyl ethyl ether), maleic acid ester (e.g. maleic acid methyl ester)
, N-vinyl-2=pyrrolidone, N-vinylpyridi/,
- A latex polymer produced using monomers such as vinylpyridine or two or more monomers is used.

Examples of surfactants used when dispersing a solution of the compound of the present invention alone or together with a coupler in an aqueous protective colloid solution include savonine, sodium alkylsulfosuccinate, sodium alkylbenzenesulfonate, etc. It can be mentioned.

The compounds of this invention can be used in combination with yellow, magenta, or cyan couplers. Among these, it is particularly preferable to use it in combination with a magenta coupler in terms of the effects of the present invention.

The couplers used in combination may have 1 or 2 equivalents with respect to silver ions, and may be in the form of polymers or oligomers. Further, the couplers used in combination may be used alone or in a mixture of two or more types.

The general formulas of preferred couplers for use in the present invention are shown below.

General formula (III) l General formula (IV) General formula (V) General formula (■) General formula (■) H3 (wherein, R1, R4 and R5 are each an aliphatic group,
represents an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group, R2 represents an aliphatic group, R3 and R6
each represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group, R5/ has the same meaning as a hydrogen atom or 1dRs, R7 and R9 represent a substituted or unsubstituted phenyl group, R8 represents a hydrogen atom, an aliphatic or aromatic anru group, an aliphatic or aromatic sulfonyl group, RIO represents a hydrogen atom or a substituent, Qt [represents a substituted or unsubstituted N-phenylcarbamoyl group, Za and zb represents methine, substituted methine, or =N-, and Y1%Y2, Y3, Y4, and Y5 are hydrogen atoms or groups that can be separated during the coupling reaction with the oxidized product of the developing agent (hereinafter referred to as (abbreviated as ``base'').

In general formula (III) and general formula (IV), R2 and R3 and R5 and R6 are respectively! , Otsu or a 7-membered ring.

Furthermore, R1, R2, R3 or YISR4, R5, R6 or Y2; R7, R8, R9 or Y3: R10, Za, Z
b or Y4: Q or Y5 may form a comer or higher polymer.

The aliphatic group mentioned here refers to a linear, branched or cyclic alkyl, alkenyl or alkynyl group.

Preferred specific examples of couplers represented by general formulas (III) and (1'1) are shown below.

(C-1) (C-4t) α (C-r) α (C-g) 1' (C-7) (C-, 1) α (C-q) e (C-10) (C- /J) H (C-/3) α (C-/, t) (C-/+) (C-77) (C-ro) (C-22) (C-, 2g) (C-2s ) (C-,2 ota) (C-ko+bl (C--27) (C-ko♂) (C-30) (C-3,2) (C-33) (C-jjl (C- 3+) (C-3z) x/y/z=toylo/3° (C-J9> (C-4to) (Wt
ratio) (C-<t/1 x/y = !θ/!0 (w t b, 1 (C-da, 2) e (ratio of w) (C-g3) (C-tada) (wt ratio) (C-da!) r1 x/y=4tt/rr (.-96) ("1 ratio)
(C-g2) α (M-t) α (M-ni) α (M-7) α α (M-, r) α (M-ta) l (M-10) Cp α (M-/ +2) r/ (M-76) (M-/1) and BH17(t) (M-/9) (M-,23) (M-2ri(M-26) (M-,!ri(M -30) (M-J3) (M-j Otsu) (M-3♂) (M-39) H3 (M-da0) (M-xz) H3 ■ α (M-Goo) H3 (Wt ratio) (M-4t3) CH3 (M-gugu) x/y=gu S/Sj (w L ratio) CM-dari x/y/z=j0/gu S/S (wt ratio) (M-da 6) CH3 (M-da 7) x/y/z=4t!/!0/j (ratio of w) (M-g1) x/y=jO/jO (wt ratio) (M-4tq) x/y =sθ/!0 (wt ratio) (M-to) (wj ratio) Preferred specific examples of the coupler represented by the general formula (■) are shown below.

(Y-/1 (Y-1) (Y-J) (y-4t) (Y-r) H3 (Y-6) (Y-7) (Y-, r) (Y-2) Ni″i O2CH3 (Y-10) OH (Y-/1) H3 (Y-/J) (Y-73) (Y-/4t) (Y-/j) (Y-/, 4;) (Y-/7 ) (Y-/1) and 12'25 (Y-/ri) (Y-, 2o) (Y-x1) (Y-ko 1) (Y-, 2,?) tt (Y-ko 4t) CH3 -C-NH CH2CH2QC2H5 (Y-2r) (Y-2≦) H3 (Y-,27) (Y-,21) UtJH (Y-29) (Y-30) (Z (Y-37) (Y -32) (Y-33) -CI ■ (Y-Jl) (Y-Jj) (Y-3g) (Y-37) H (Y-JJ') (Y-39) (Y-da0) ( Y-4tt) x/y=jθ15θ (ratio of w) (Y-daλ) H3 ■ (ratio of w) (Y-g3) H3 ■ Couplers expressed by the general formulas from (III) to (■) References describing other exemplary compounds or synthetic methods are listed below.

Cyan couplers represented by general formula (III) and general formula (■) can be synthesized by known methods. For example, general formula [
■] The cyan coupler represented by
3.730, 3,772°002, etc. The cyan coupler represented by the general formula CII1) is synthesized by the method described in U.S. Pat. Ru.

The magenta coupler represented by the general formula [■] is disclosed in JP-A-9-2-027, Sho-da 9-2, θ2! No. 27930, No. 63-33776, and U.S. Patent No. 3. ! /9. It is synthesized by the method described in '729, etc. The magenta coupler represented by the general formula ('4] is disclosed in Japanese Patent Application Laid-open No. 1987-19-1, U.S. Pat. No. Otsu and JP-A No. 60-33,662.

The yellow coupler represented by the general formula [■] is made by Tokukai Sho!
Derg/jgu/issue, special public Akira! ! -10239, US Patent No. 324.0241, Research Disclosure (R,D,)/♂0j3, and the like.

These couplers are generally added in an amount of λ x 10 -3 mol to x 10 -1 mol, preferably / x 10 -2 mol to Ex 10 -1 mol, per 7 mol of silver in the emulsion layer.

The compound of the present invention may be used in combination with a known anti-fading agent, and particularly preferred anti-fading agents include (i) general formula [
Aromatic compound represented by (11) general formula [■]
An amine compound represented by (iii) or a metal complex having a central metal of copper, cobalt, nickel, radium, or platinum, and at least one organic ligand having a conformation of λ or higher. .

General formula [■] R4 In the formula, R1 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, and R9 may be the same or different from each other, and each represents an alkyl group, an alkenyl group, an aryl group, or an alkoxy group. group, alkenoxy group, or aryloxy group. R2, R3, R4, R5 and R6 may be the same or different from each other, and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acylamino group, an alkylamino group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, or an aryloxy group. Represents a carbonyl group, a halogen group, or -0-R1'.

Here, R1' represents the group represented by R1. R1 and R combine with each other! They may form a membered ring, a membered ring, or a spiro ring.

R2 and R3 or R3 and R4 are bonded to each other! member ring,
A 6-membered ring or a spiro ring may be formed.

IO In the formula, Rlo is a hydrogen atom, an alkyl group, an alkenyl group,
It represents an alkynyl group, an acyl group, a sulfonyl group, a sulfinyl group, an oxy radical group, or a hydroxyl group.

R11, R12, R13 and R14 may be the same or different and each represents a hydrogen atom or an alkyl group. A
teeth! Represents a group of nonmetallic atoms necessary to form a 6-membered, 6-membered, or 2-membered ring.

Among the groups in general formula [■] and general formula [■], alkyl,
A group containing even a partial aryl or heterocycle may be further substituted with a substituent.

Representative examples of these specific compounds include the patent application 1986-
Compounds A-/-60 described on pages 419 to 63 of Specification No. 233♂69 and other compounds listed below can be mentioned.

A-Go 3 A-B Gu A-Otsu A-Otori CH2=CH20CJ4H29(n) The compound represented by the general formula (■) or (■) is preferably 10 to θθmolti with respect to the coupler. is 30-3
00 molti is added. On the other hand, the metal complex is added to the coupler by /~10 θmolt, preferably from 3 to aOmolt.

In the photosensitive material produced using the present invention, when the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc.
They may be mordanted, such as by cationic polymers.

The light-sensitive material produced using the present invention may contain a no-hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbyl/acid derivative, etc. as a color antifoggant.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (eg, those described in US Pat. No. 3,133,7941), tertiazolidone compounds (eg, US Pat.

Benzophenone compounds (e.g. those described in JP-A-6-27F41), cinnamic acid ester compounds (e.g. U.S. Patent No. 3,2θ!f, tO
No. #, J, 7θ7, 37T), butadiene compounds (for example, those described in US Patent No.

θ'13,229) or benzoxidol compounds (e.g., those described in US Pat. No. 3.7θ0,4#
! ) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, melonanine dyes, cyanine dyes and azo dyes. Among them, okidinol dyes; hemioxonol dyes and merocyanine dyes are useful.

As the binder and protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by Arthur Vuis (Academic Press, published in 2009).

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention.

The average grain size of silver halide grains in photographic emulsions (the grain size is the grain diameter in the case of spherical or approximately spherical grains, and the average length in the case of cubic grains, expressed as an average based on the projected area) is particularly important. 8 The grain size may be narrow or wide, but it is preferable to use a monodispersed emulsion with a variation rate of 75% or less.

The silver halide grains in the photographic emulsion layer may have a regular crystalline structure such as a cube or hexagonal, or may have an irregular crystalline structure such as a ring or a plate. It may be a composite form of the crystal form. It may also consist of a mixture of particles of various crystalline forms. Among these, it is preferable to use a normal crystal emulsion.

Further, an emulsion may be used in which tabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area.

The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which a latent image is mainly formed on the surface, or may be particles in which a latent image is mainly formed inside the particles.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a thallium salt, a lead 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.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chloropene imitazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, Aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially /-phenyl-j-mercaptotetrazole, etc.), mercaptopyrimidines, mercaptotriazines, etc.: thioketo compounds such as oxadorinthion; Azaindenes, such as triazaindenes, tetraazaindenes (particularly hydroxy B-converted (/, 3.3a).

2) Tetraazaindene), haftaazai/dene; benzenethiosulfonic acid, benzenesulfinic acid,
In addition to anti-capri agents, many compounds known as stabilizers can be added, such as benzenesulfonic acid amides and the like.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a green-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The supports used in the present invention are usually cellulose nitrate films, cellulose acetate films, cellulose acetate butyrate films, cellulose acetate propionenite films, polystyrene films, polyethylene terephthalate films, polycarbonate films, which are used in photographic materials. In addition, there are laminates of these materials, thin glass films, paper, etc. Baryta or α-olefin polymers, especially polyethylene,
Paper coated with a polymer of α-olefin having ~10 carbon atoms, such as polypylene, ethylene butene copolymer, etc., but still laminated. A support such as a plastic film, which has an 11-sided surface and has improved adhesion to other polymeric substances, as shown in the above publication, also gives good results. Further, an ultraviolet curable resin can also be used.

These supports are selected to be transparent or opaque depending on the purpose of the photosensitive material. It is also possible to add dyes or pigments to make it colored and transparent.

Opaque supports include those that are inherently opaque, such as paper, and
Transparent film with pigments such as dyes and titanium oxide added, or Tokkosho & 7-/9θ6! It also includes plastic films whose surface has been treated by the method shown in No. 1, as well as paper or plastic films that have been made completely light-shielding by adding carbon black, dyes, etc. The support is usually provided with an undercoat layer. In order to further improve adhesion, the surface of the support may be subjected to preliminary treatment such as corona discharge, ultraviolet irradiation, flame treatment, etc.

The color photosensitive material that can be used to create the color photograph of the present invention is preferably a normal color photosensitive material, especially a color photosensitive material for printing, but US Pat.
27. jjo issue, same 3. -227゜ssi number, same j,
No. 227.662 and U.S. Preliminary Publication 'FjrFUS, II
J j /, No. 673, etc., may be applied to a non-color photographic method, or in particular, a color diffusion transfer photographic method. In order to obtain dye images by conventional photographic methods, post-exposure color photographic processing is necessary. Color photographic processing basically includes color development, bleaching, and fixing steps. The two steps of bleaching and fixing may be completed in one treatment. Alternatively, a combination of color development, first fixing, and bleach-fixing is also possible. In the development processing step, various steps such as a pre-hardening bath, a neutralization tower, first development (black and white development), an image stabilizing bath, and water washing are combined as necessary. The processing temperature is often 7106 or higher. Particularly often used are 2o0C~6θQC1 and recently 3o'c
-to'c range.

The color developing solution contains a p-containing aromatic/class amine color developing agent.
H! Above, preferably it is an alkaline aqueous solution of 9 to /-.

After the fixing or bleach-fixing process, there is usually a washing process.
However, instead of the water washing treatment, a simple treatment method may be used, such as performing only the so-called 6-stabilization treatment without providing a substantial water washing step.

A preferred example of the aromatic primary amine developer is a p-phenylenediamine derivative, and representative examples are shown below, but the developer is not limited thereto.

D-/N,N-diethyl-p-722-diamine D-22-amino-yo-diethylamine toluene D-3-mono-amino-5-(N-ethyl-N-laurylamino)toluene D-Gu Gu [N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-s, 2-methyl-gu[N-ethyl-N-(β-hydroxyethyl)aminecoaniline D-tN-ethyl-N-( β-methanesulfonamidoethyl)-3-methyl-quaaminoaniline D-7N-(s-amino-!-diethylaminophenylethyl)methanesulfonamide D-♂ N,N-,)) If loop p-phenylenediamine D -2 Guamino-3-methyl-N-ethyl-N-methoxyethylaniline D-10<t-amino-3-methyl-N-ethyl-N-
β-Ethoxyethylaniline D-// Guamino-3-methyl-N-ethyl-N-
These p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-toluenesulfonate. The above compound is disclosed in US Pat.
．． θ/Yu issue, same co, ! ! 2.

λ Gutu issue, 2.666.27/issue, same co,! Octopus, 3
No. 641, same! ,t! 6. the law of nature! θ No. 3゜49J'
, No. 3.26, etc. The amount of the aromatic-grade amine developing agent used is about 0.00% per liter of developer solution. /g to about 20g, more preferably about 0. ! g to about 10 g.

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

The processing temperature of the color developer in the present invention is 3o'C-
to'c is preferred, more preferably 33°C-g2°
It is C. The replenishment amount is 30ml to 20ml per m2 of photosensitive material.
00m1 preferably 30m1~/! ;00m1.

From the viewpoint of reducing the amount of waste liquid, it is preferable that the amount of these replenishments be small.

Further, when benzyl alcohol is contained in the color developing solution, it is preferably 2.0 ml/ll or less, and θ.

More preferably, it is 5 ml/l or less. Preferably, no benzyl alcohol is added. Color development time is 2
The time is preferably within 30 seconds, more preferably from 70 seconds to 30 seconds. The most preferable case is between ys seconds and 2 minutes.

Example/ A dye (hereinafter referred to as ( C-1) It is abbreviated as dye.The other dye symbols after Sunda have the same meaning.)! g was dissolved in tricresyl phosphate λOml and 20ml of ethyl acetate, and this solution was emulsified and dispersed in a gelatin solution tag containing ♂ml of an aqueous solution of /tide/sodium rubenzenesulfonate.

Next, sodium dodenlebenzene sulfonate was added to this emulsified dispersion as a coating aid, and the mixture was coated on a double-sided laminated paper support with polyethylene.

The amount of applied dye was set so as to obtain a density value of 7.0 using a Macbeth densitometer RD-SLTT type (Status AA filter).

A gelatin protective layer (gelatin/g/m2) was applied on top of this layer to create sample A.

Samples A-/-/3 were also prepared using the combinations shown in Table 1 in preparing the emulsified dispersions described above in a similar manner.

Each sample thus prepared was stored at room temperature in the dark for two months. To test the light resistance, attach a Fuji Photo Film ultraviolet absorption filter that cuts out light below 00 nm, and use a xenon tester C (100,000 lux)! θ
A θ time fading test was conducted to determine the dye residual rate (percentage). The results are shown in Table 1.

(Comparative compound A) British Patent Nos. 1 and 3-B.

(Comparative Compound B) (Comparative Compound C) As is clear from Table 1, the fastness is improved by adding Compound 1 of the present invention against the deterioration of fastness caused by the developing agent remaining in the photosensitive material. Improved. The extent of this effect could not be expected from known antifading agents.

Example 2 Dye (C-1) of sample A in Example/ was combined with magenta coupler (M-1) and guamino-3-methyl-N-ethyl-
Sample B was prepared in the same manner as in Example except that the dye obtained by oxidative coupling reaction with N-β-(methanesulfonamido)ethylaniline was used. In addition, combined samples (B-/~, 2O) as shown in Table 2 were also prepared.

It was stored in the dark at room temperature for λ months in the same manner as in Example. A 200 hour fading test was conducted using a xenon tester to determine the dye residual rate (percentage). The results are shown in Table 1.

(Comparative Compound D) (Comparative Compound E) (Comparative Compound F) As is clear from Table 2, the fastness deteriorates due to the developing agent remaining in the photosensitive material, but the compounds of the present invention have a high image quality due to the developing agent. It can be seen that the effect of preventing deterioration is remarkable. This effect was unexpected from known compounds.

Example 3 The dye (C-1) of sample A in Example 1 was combined with a yellow coupler (Y-3t) and a cup of guamino-3-methyl-N-ethyl-N-β-(methanesulfonamido)ethylaniline. Sample C was prepared in the same manner as in Example except that the dye obtained by the ring reaction was used. Sample combinations C-/-/2 were prepared as shown in Table 3.

It was stored in the dark at room temperature for 2 months in the same manner as in Example. In order to examine the light resistance, a 100 hour fading test was conducted using a xenon tester in the same manner as in Example.

In addition, to examine heat resistance, SOO time at 1006C,
Stored in the dark. Table 3 shows the results expressed in 6 fractions of dye remaining 1.

As is clear from Table 3, the addition of the compound of the present invention significantly improves the fastness to light and heat, and prevents deterioration of color fading caused by the developing agent.

Example: p-Aningin and the compound represented by the general formula (1) of the present invention were mixed into trinonyl phosphate at a concentration of 0.03.
It was dissolved to a concentration of mol/l.

10ml of this mixed solution was heated in a ♂o 'C constant temperature bath,
The reaction was followed by high-performance liquid chromatography and a second-order reaction rate constant was obtained.

The second-order reaction rate constants of representative compounds thus obtained are shown in Table 9 below.

Table 9 Example j On a paper support laminated on both sides with polyethylene, the first
A color photographic material was prepared by sequentially applying the first layer (lowest layer) to the second layer (top layer) according to the structure shown in the table.

The spectral sensitizing dyes used in each emulsion layer are as follows.

Sweat-sensitive emulsion layer: (Addition of uXlo-4 mol per mol of silver halide.) Green-sensitive emulsion layer: (Addition of x, 5x10-4 mol per mol of silver halide.) Red-sensitive emulsion layer: (Addition of x, 5x10-4 mol per mol of silver halide.) 2.3 x 10-4 mol added per mol.) (a) Solvent (iso CgH1gO4yP=0) (b) Color mixing inhibitor (C) Solvent mixture (weight ratio) (d) Ultraviolet absorber ([) Color Image Stabilizer (/:3:3 Mixture C Molar Ratio) A-/J'-3O A-G 3 The following dyes were used as anti-irradiation dyes in each emulsion layer.

Green-sensitive emulsion layer: Red-sensitive emulsion layer: Of these, the magenta coupler and cyan coupler were removed from the third and fifth layers, and a sample was prepared using (Y-3s) as the yellow coupler in the first layer. I made a sample.

First, other samples D-/-25 were prepared in the same manner as the sample sample except that the yellow coupler and the additive containing the compound of the present invention were changed as shown in the table.

Next, the sample thus prepared was exposed to light through an optical wedge, and then processed in the following manner to obtain a color image.

Using Fuji Color Roll Processor F'MPP1000 (partially modified) (manufactured by Fuji Photo Film ■), running development was carried out under the conditions shown below.

Color development Geta seconds 3yo'Cz♂l/! 0 bleach fixing
5 seconds 3t0c 3sl s.

Rinse■ 2θ seconds 3s0c i71 -Rinse■
2θ seconds 3s0C/7g - In the rinsing process, replenishment H is poured into the rinse tank ■, and the water that overflows the rinse tank ■ is led to the bottom of the rinse tank ■, and the water overflows the rinse tank ■. A three-tank countercurrent system was adopted in which water was led to the bottom of the rinse tank (■), and the overflow from the rinse tank (■) was discarded.

The amount brought in from the previous bath is 2 ml per e-im2.
Met.

The prescriptions for each tank fluid and each replenisher are shown below.

Color developer tank liquid Replenisher water 200ml ♂00m
1 Diethylenetriaminepentaacetic acid 3.0g 3.0g benzyl alcohol /jml 17ml diethylene glycol 10mI 10
m1 Sodium sulfite -, Qg 2.3g Potassium bromide 0.3g Sodium carbonate 30g J'! L
rN-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-guaminoaniline sulfate! , θg 7.0g Hydroxylamine sulfate g, θg g, tg Fluorescent brightener /, Og /, jg Add water
-1000ml 10θ0ml pH10,101
0,! 0 Bleach-fix tank liquid Replenisher water 'l00ml 1700ml
Ammonium thiosulfate (70% solution) 130ml 300ml Sodium sulfite 72g 26g Iron ethylenediaminetetraacetate ([1) Ammonium 66g / 10g Ethylenediaminetetraacetic acid 2 N a j g / O
g Add water 700θml 1000ml
00O,2j 'c) 6.70 t
,! 0 Rinse liquid ethylenediamine/N,N.

Add N',N'-tetramethylenephosphonic acid 0.3g benzotriazole 1.0g water
With 7000ml sodium hydroxide
pH2, Processing method B Color development Gu! Second Fe1l/! 0 bleach fixing ko'00 3! l 3!0 rinse■ /'θθ
/71 - Rinse ■ /'00 /71 - The same treatment liquid and replenisher as in treatment method A were used.

Next, for each of the photosensitive materials developed by the above method, the A-reflection density of the non-image area after processing/after time elapsed was measured. Below 0°C2o% (RH)! After leaving it for a day, the yellow reflection density of the non-image area was measured again.

The results are shown in Table 6.

Comparative compound (G) (n) C4I (9C4H9(n) \/ U.S. Patent No. DA, DA Comparative compound (H) Comparative compound CI) Comparative compound (J) JP-A-59-229 C121125N (CH2CH20H)2,2 As is clear from Table 3 of the compounds listed under the title, yellow stain after processing is not a problem in Process B, where the washing and bleach-fixing times are long and the amount of processing solution replenishment is sufficient.
In process A where the process time is short and the amount of replenishment is small, yellow stain occurs. By adding the compound of the present invention, this could be sufficiently prevented.

On the other hand, the comparative compound, which is a conventional known technique, was not found to have any preventive effect against yellow stain.

Example G In the same manner as in Example J, a color photographic light-sensitive material was prepared by sequentially coating the compositions shown in Table J on a paper support laminated on both sides with p-lyethylene.

Of these, the first and second layers! Sample E was obtained by removing the yellow coupler and cyan coupler from the layer and using the previously exemplified (M-, 23) as the magenta coupler in the third layer. Other samples E-/-2J were prepared in the same manner as sample E except for changing the magenta coupler of sample E and the additives containing the compound of the present invention as shown in Table 2.

These samples were passed through an optical wedge and exposed to light, followed by color development according to the processing method described below.

However, in order to clearly demonstrate the effects of the present invention, the processing method described below is formulated in such a way that the developing agent and other processing solution components tend to remain, and staining is likely to occur.

Color development 339C 3 minutes 30 seconds Bleach fixing 33°C 7 minutes 30 seconds Water wash 20~2! ;0C/min (no stirring) Dry, dry! 00~♂00C minute The components of each treatment liquid are as follows.

Color developer bleach-fix solution The above composition solution was used after being aerated for 1 hour.

Note) The above bleach-fix solution is a formulation that assumes the case where the color developer adheres to the photosensitive material during running and the solution composition changes due to a large amount being brought into the bleach-fix solution. be.

Next, for each of the developed samples, 7 hours after the development process, the magenta reflection density (stain) of the non-image area was measured using a Fuji self-recording densitometer under green light, and then ro
0c2o%R,H, when left for 17C3EI and at room temperature! For each case when left for θ days,
°The center reflection density (stin) of the non-image area was measured again in the same manner. Table 7 shows the above results, i.e. the increase in stain from post treatment/time.

M7 As is clear from Table 2, when the compound of the present invention is used, the effect of preventing staining over time is more remarkable than that of conventionally known comparative compounds.

Example 2 Same as Example 2! A color photographic material was prepared by sequentially coating the composition shown on the front on a paper support laminated on both sides with polyethylene.

Among these, the yellow coupler and the mita coupler were removed from the seventh and third layers, and a sample was designated as sample F in which (C-λ), which was exemplified earlier, was used as the cyan coupler in the fifth layer. As shown in Table 2, other samples F-/~,! 1 was created.

These samples were exposed and developed in the same manner as in Example 6. After processing each, measure the cyan reflection density of the non-image area using a Fuji type self-recording densitometer under red light, and then heat at 10°C.
Similarly, the 7mm reflection density of the non-image area was measured again for the case where the image was left at 70% R, H for 3 days and the case where it was left at 20°C dry (70~/j section R, H,) for s days. It was measured.

The results are shown in Table ♂.

As is clear from Table 1, the compound of the present invention has a remarkable effect of preventing staining over time, which is at a level that cannot be achieved by conventional techniques.

Example ♂ Example! Similarly, a color photographic material having the structure shown in Table 5 was prepared by coating the first to second layers on a paper support laminated on both sides with polyethylene.

Here, the first layer yellow coupler is shown as an example (
Y-3s), as a magenta coupler in the third layer (M-,
z3), a sample using a /:/ mixture (molar ratio) of (C-identification) and (C-/g) as a cyan coupler was designated as Sample G.

Sample G except for the change in the magenta coupler in the third layer of Sample G and the additive containing the compound of the present invention as shown in Table 2.
Other samples G-/~12 were prepared in the same manner as above.

After exposing these samples through an optical wedge,
Color development was carried out according to the following processing method.

Treatment process (33°C) [Color development 3 minutes 30 seconds The components of each treatment liquid are as follows.

Color developer benzyl alcohol /xml diethylene glycol j ml potassium carbonate
-2jig sodium chloride
0.7g sodium bromide
O, Sg anhydrous sodium sulfite
2g hydroxylamine sulfate 2
g Fluorescent brightener /g N-Ethyl-N-β-methanesulfonamidoethyl-3-mether-guar °C Noaniline sulfate <7g Add water to make /l and add NaOH to bring pH to 10°.

Bleach-fixing solution Ammonium thiosulfate, /241, 1g72 Sodium bisulfite /3.3g Anhydrous sodium sulfite λ, 2gE D'r A Ferric ammonium salt tsg Color developer
1oornlpH 6.7-6. Add water to the ♂ /l processing solution using a normal roller transport type processing machine.
The developing processing was performed while normal replenishment was being carried out, and the composition of the processing solution was almost at equilibrium.

Next, one hour after processing, the magenta reflection density (stain) of the non-image area was measured for each of the above-mentioned photosensitive materials that had been developed.
,Under,? The magenta reflection density (stain) of the non-image area was measured in the same manner again for the case where the sample was left for one day and the case when it was left for jθ days at room temperature. Table 1 shows the above results, i.e. the increase in stain from post-treatment/time.

As is clear from Table 9, the compounds of the present invention have a remarkable effect of preventing staining over time, and in particular, show a sufficient effect of preventing staining even when the composition of the developing treatment solution does not change.

Example 10 A color photographic material (Sample 1-I) was prepared as shown below.
)It was created.

A color photographic light-sensitive material was prepared by applying 77 layers from the first layer to a paper support double-sided laminated with polyethylene. The first layer coating side of the polyethylene contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye.

(Photosensitive layer composition) The components and coating amount in units of g/m2 are shown below. Regarding silver halide, the coating amount is shown in terms of silver.

m/W (antihalation layer) Black colloidal silver...0. θ/gelatin...0.2 Second layer (low sensitivity red sensitive layer) Silver iodobromide emulsion (silver iodide 3.j morti) spectrally sensitized with red sensitizing dyes (■! and , average particle size θ, 7
μ) ...Silver θ, /j gelatin
... /, 0 cyan coupler (bitter 3) ...
・θ, 30 anti-fading agent (Kaoruko) ...0.7
! Coupler solvent (-1f/j and bitterness 1)...θ, θ6 3rd layer (highly sensitive red-sensitive layer) Silver iodobromide emulsion (iodobromide emulsion) spectrally sensitized with a red sensitizing dye (-3+j and aroma) Silver oxide 2.0 molti, average grain size 0.2
μ) ...Silver θ, 10 gelatin
...O1!0 cyan coupler (bitter 3) ...
...0.10 Anti-fading agent (dinner) ...0
．． 0! Coupler solvent (bitter/! and aromatic 1)...0.02nd layer (intermediate layer) Yellow: ro()' silver ------o, os gelatin.../, θ0 color mixing inhibitor (
-pf/l, t)...θ, 0♂ Mixed color anti-mold solvent (-1+/J)...0.7 and polymer latex (-+6)...θ, g0 J-th layer (low-sensitivity green-sensitive layer) Silver iodobromide emulsion spectrally sensitized with a green sensitizing dye (Kaoru/2) (silver iodide λ, ! morch, average grain size o'ltμ
)...Silver 0.20 gelatin
...0.70 magenta coupler (-X-/1
)...o, tit.

Anti-fading agent A (-X-10)...0.0! Anti-fade agent B (+9) ... o, os Anti-fade agent C (%, r) ...0.02 Coupler solvent (-Jf/1) ...0.60 No. 6 layer(
High-sensitivity green sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye (bitter/2) (silver iodide 3.! morch, average grain size O92μ)
...Silver 0.20 gelatin
...0.20 magenta coupler (-X-/i
)...0. Gu θ anti-fading agent A (-+10)...
... θ, θj anti-fading agent B (yellowing) ・・ O
, OS anti-fade agent C (winter)...0.0 cocoupler solvent (-1/J')...θ, 60 No. 7
Layer (yellow filter single layer) Yellow colloidal silver, -...-0,20 gelatin.../, 0θ.

Color mixing inhibitor (Kaoru/g)...0.06 Color mixing inhibitor solvent (+/j)...o,, z4 as the first layer (low sensitivity rr sensitive layer) Blue sensitizing dye (- %/+) spectrally sensitized silver iodobromide emulsion (silver iodide, !mo/l/%, average grain size O0!μ)
)...Silver 0.7j gelatin
...O,SO yellow coupler (bitter/l)・
...θ, -〇Coupler solvent (bitter/♂) ...O
, OS 9th layer (high sensitivity blue-sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye (+/4) (silver iodide, ! morch, average grain size/gμ)
...Silver θ, 2θ 2nd θ layer (ultraviolet absorption layer) Gelatin .../! 0 Ultraviolet absorber (-X-/9) ... /, 0 Ultraviolet absorber solvent (bitter/male) ...0.3C color mixture prevention agent (+/
7)...o, or 1st/layer (protective layer) Gelatin.../, 0 The compounds used here are as follows: Yellow/Dioctylphthalate 22-(2 -hydroxy-j-sec-f loop j
-t-butylphenyl)benzotriazole Kaoru 3 2~[α-(2,t-di-t-amylphenoxy)butanamide)-y,t-dichloro-yo-ethylphenol-X-4tj',j'-dichloro- 3.3'-di(3-
ethyl ammonium-3-[X-(
Co[3-(3-sulfopropyl)naphtho(/,2-d)thiazoline-λ-ylidenemethyl]-/-butenyl)-3-naphtho(
/, 2-d) Thiazolino] propane sulfonate polyethyl acrylate 2 Phosphoric acid trioctyl ester bitter male, Kuji t-hexyl hydroquino.

(2-Hydroxy-j-t-butyl-!-
methylphenyl) methane bitter 10 3,3.3',! '-Tetramethyl-! .

Otsu s / , , < /-tetrapropoxy-/.

/'-bisspiroindane+// 3-(2-chloro-j-tetradecanamide anilino)-/-(co, 4t, o-trichlorophenyl)-2-pyrazoline-! -one-kl-/2 j, j'-diphenylterethyl-3゜3'-disulfopropyloxacarbocyanine Na salt i3 +) phosphoric acid-〇-cresyl ester-1f/41
2. '! -G-t-octylhydroquinone roof/! α-pivaloyl-gu C (2,gu dioxo-
/-benzyl-j-ethoxyhydantoin-3-yl)-2-chloro-! -(α-2,4t-dioquine-t-amylphenoxy)butanamine]acetanilide yellow/Otriethylammonium 3-(J-(j-penzylrhodanine-!-i')f)-3-benzoxazolinyl]propane Sulfonate 1%/7 2. ¥-G5ee-oct/l/Hydroquinone"k/1 Phosphate trinonyl ester+!-/9
t-chloro-2-(2-hydroxy/-3-t-butyl-
5-tert-Octyl) Phenylbenztriazole As shown in Table 1O, other samples were prepared in the same manner as Sample I (and other Sample (-7~g) was prepared.

The sample thus obtained was exposed to light through an optical coating, and then subjected to color development according to the processing method described below.

[Processing process]

First development (black and white development) 3♂ 0C/min 7 minutes 75 seconds water washing 3♂ 0C/min 3o seconds reversal exposure /
00 Lux or more Color development for 7 minutes or more 3!
0C/! Second wash 3r 0
c 4tz seconds bleach fixing 3F0C,2
Wash for 00 seconds with water 3♂ 'Cx min/
j seconds [Processing solution composition] First developer Nitrilo-N, N, N-trinotylenephosphonic acid pentatrilam salt 06 g Diethylenetriaminepentaacetic acid pentasodium salt 9.0 g Potassium sulfite 30, 0 g Potassium thio7anate 7. 2g potassium carbonate
3 j, Og hydroquinone monosulfonate potassium 2! , 0g diethylene glycol/j, Oml/-phenyl-goohydroxymethyl-goomethyl-3-pyrazolidone 2.0g potassium bromide 0.6g potassium iodide
Add s, o mg water
7g (pH 2,70) Benzyl alcohol /3.0ml diethylene glycol /2.0ml13, di-dithia-
/,/-oftanediol 0.2g nitrilo-
N, N, N-trinotile/phosphonic acid pentatrilam salt o, sg diethylenetriaminepentaacetic acid 11, sodium salt λ, θg sodium sulfite 1 cum 2.0 g potassium carbonate -! , θg Hydroxylamine sulfate J, o gN-ethyl-N-(β-methanesulfo/amidoethyl)-3 monomethyl-guaminoaniline sulfate 1.0g Potassium bromide 0.6g Potassium iodide
/, add 0mg water
/l (pH10, gθ) Bleach-fix solution Komel Kabuto 7.3. Gate Sonozol /, θg Ethylenediaminetetraacetic acid, disodium, chlorine salt j, θg Ethylenediaminetetraacetic acid, Fe (Il+ > Ammonium hydrate ♂θ, Og Sodium sulfite, /j, 0g
Add sulfur and lithium thiosulfate (700 g / 1 liter solution) ito, oml glacial acetic acid, and Oml water to give 7 g (pHd, t
O) Next, after measuring the magenta reflection density (stin) of the non-image area on each J+ of each photosensitive dye of "Go C" which has been developed, the ratios θ0C7θ%R, I1. The magenta reflection density (stain) of the non-image area was measured in the same manner again for the case where the sample was left at room temperature for three days and the case where it was left at room temperature for several days. Table 7θ shows the increase in stain from post-treatment/time.

As is clear from Table 1O, the compound of the present invention has a remarkable effect of preventing stay/propagation over time, and the effect remains the same even when the structure of the photosensitive material and the development treatment recipe are different.

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．． 3g of 3,4-dimethyl-1,3-thiazoline-2-
They were simultaneously added to an aqueous gelatin solution containing thione at 75° C. for about 20 minutes without vigorous stirring to obtain a monodisperse silver bromide emulsion with an average grain size of about 0.401 Lm octahedron.

This emulsion contains 6B of sodium thiosulfate per mole of silver and 7B of sodium thiosulfate per mole of silver.
Chemical sensitization was carried out by adding -g of chloroauric acid (41 g of water) and heating at 75°C for 80 minutes.The silver bromide particles thus obtained were used as cores in the same precipitation environment as the first time. After further growth, a monodisperse octahedral core/shell silver bromide emulsion with an average grain size of 0.7 pm was finally obtained, and the coefficient of variation of the zero grain size was about 10%.

To this emulsion were added 1.5 g of sodium thiosulfate and 1.5 g of chloroauric acid (tetrahydrate) per mole of silver and heated at 60°C for 60 minutes to perform chemical sensitization treatment. A Wi image type halogenated emulsion was obtained.

1st layer (antihalation layer) Black colloidal silver ...0.10 Gelatin °°°1.30 2nd layer (intermediate layer) Gelatin ...0.70 3rd layer (low sensitivity red sensitivity layer) Red enhancement Silver bromide spectrally sensitized with sensitive dyes (ExS-1, 2, 3) (average grain size 0.3 #L, size distribution 8%,
Octahedron) ・-0.0O red sensitizing dye (ExS-1
, 2, 3) spectrally sensitized with silver bromide (average grain size 0
．． 45 tiles, size distribution 10%, octahedral) 0.10 Gelatin 1.00 Cyan coupler (ExC-1) 0.14 Cyan coupler (ExC-2), -0,07 Anti-fading agent (Cpd
-2, 3, 4, 9'3 amount)...0.12 Coupler dispersion guy (Cpd-5)...0゜03 coupler 8 guys (Solv-1, 2, 3 equivalent amount)...-0 ,0
6 4th layer (high sensitivity red sensitive layer) Silver bromide spectrally sensitized with red sensitizing dyes (ExS-1, 2, 3) (average particle size 0.75 tiles, size distribution 10%
, octahedron)...0,15 Gelatin...1.00 cyan coupler (ExC-1) -0,20 cyan coupler (ExC-2) -0,10 antifading agent (Cpd-
2, 3, 4, 9 equivalents)...0.15 Coupler dispersion medium (Cpd-5)...0.03 Coupler solvent (So 1v-1, 2, 3 equivalents)...0. l
O 5th layer (intermediate layer) Gelatin °-1.00 Color mixing prevention agent (Cpd-7)...0.08k Color prevention agent solvent (Sol v-4,5)...0, 16 Polymer latex ( Cpd-8) ...0.10 6th layer (low sensitivity green sensitive layer) Green sensitized color; silver bromide spectrally sensitized with v (ExS-3,4) (average grain size 0.28 tiles) 1 particle size distribution 8%
, octahedron) ...0.04 green sensitizing dye (ExS-3
, 4) spectrally sensitized silver bromide (average grain size 0.4
514-, R child size distribution 10%, octahedron)...0
．． 06 gelatin...0.80
Magenta coupler (ExM-1)-0,10 Anti-fade agent (Cpd-9)...0.10 Anti-stain agent (Cpd-10)...0. Ol stain inhibitor (C
pd-11)...0.001 force puller dispersion medium (Cpd
-5)...0.05 coupler solvent (Solv-4
, 6 equivalents)...0.15 7th layer (high-sensitivity green-sensitive layer) Silver bromide (
Average particle size 0.9 tiles, particle size 1 (r l 0
%, octahedron) ...0. IO gelatin
...0.80 magenta coupler (ExM
-1) ・=0.10 anti-fading binding (Cpd-9)
...0. lO stain inhibitor (cpd-10)
...0.01 stain inhibitor (Cpd-11)...
0.001 force puller dispersion medium (Cp d -5)...
・0.05 coupler solvent (Solv-4,6 equivalent)・・
・0.15 8th layer (intermediate layer) Same as 5th layer 9th layer (yellow filter single layer) Yellow colloidal silver ...0.20 Gelatin ...1.00K color inhibitor (Cpd-7) -・0.06k Color protection 1F agent solvent (Solv-4, 5 etc.μ)...0.15 Bolimer Latinx (Cpd-8)...0. 10 10th layer 11th layer (low sensitivity blue sensitive layer) same as 5th layer Silver bromide (silver bromide) spectrally sensitized with blue sensitizing dye (ExS-5)
Average particle size 0.35. , particle size distribution 8%, 14
Face piece) ...0.07 blue sensitizing dye (ExS-5)
silver bromide (average grain size 0.45k,
Particle size distribution 10%, tetradecahedron) -0,10 gelatin...0.50 yellow coupler (ExY-1)...0.20 stain inhibitor (
Cpd-11)...o, ooi anti-fading agent (Cpd-
6) ...0. lO coupler dispersion medium (Cpd-
5) -・0.05 coupler solvent (Solv-2)
...-0,05 12th layer (high sensitivity blue sensitive layer) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5,6) (average grain size 1.2., grain size distribution 10%) ,
14-hedron) ...0.25 gelatin
...l, 00 yellow coupler (ExY
-1) -0,40 stain inhibitor (Cpd-11)...
・0.002 anti-fading agent (Cpd-6)...
0. lO coupler dispersion medium (Cp d -5)...
0.05 Coupler solvent (Solv-2)...0.
13th layer of lO (ultraviolet absorption layer) Gelatin...1.50 Ultraviolet absorber (Cpd-1, 3, 13 equivalent)...1.00 Color mixing prevention agent (Cpd-6, 14 equivalent)...・0.06 Dispersion medium (Cpd-5) Ultraviolet absorber solvent (Solv-1, 2 equivalent)...0.
15 Anti-irradiation dye (CPCT-TS, 16 equivalents) ...0.02 Anti-irradiation dye (Cpd-17, 18 equivalents) ...0.02 14th layer (protective layer) Fine particle chlorobromide Silver (11! Silver oxide 97 mol%, -P average size 0.2 hi)...0.15 Modified poval...0.02 Gelatin
...1.50 gelatin hardening agent (H-
1) ...0.17 Furthermore, in each photosensitive layer, (NI-9) was added as a nucleating agent at a ratio of I to the amount of silver halide coated.
O'wt%, 1% (ExZS-1) as a nucleation accelerator
0% by weight was used.

Each layer contains alkanol XC (D
succinate ester and Mage using sodium alkylbenzenesulfonate as a coating aid.
fac F-120 (manufactured by Dainippon Ink Co., Ltd.) was used. (Cpd-19, 20, 21) was used as a stabilizer in the silver halide or colloidal silver containing layer. This sample was designated as sample number (1) bb. The compounds used in the examples are shown below.

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Next, after measuring the magenta reflection density (stain) of the non-image area of each of the above-mentioned photosensitive materials that have been developed,
C2θ%R,H, when several lines are placed below for 3 days and at room temperature! The magenta reflection density (stain) of the non-image area was measured again in the same manner after each sample was left for θ days.

Table 1 ((shows the increment in stain from post-treatment/time).

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The compounds used in Examples 12 to 14 are shown below.

Sensitizing dye xS-1 xS-2 xS-3 xS-4 03HN (C2H5)3 ExS-5 ExS-6 ExS-7 ExS-8 ExS-9 ExS-10 ExS-11 ExS-12 xY-1 xY- 2 xM-1 C8H,7itl Cpd-4 Cpd-s Cpd-6 CH po -7 CH Cpd-8 CH CH Cpd-9 (C)h CH-)7 (n = 100 to 1000
) CONHC, Hgft1 Cpd-10 Polyethyl acrylate latenox Cpd-11 Cpd-12 (pd-13 Cpd-14 (pd-1,5 Cpd-16 Cpd-17 Cpd-19 H Cpd-20 Sui Cpd-21 H Solv-1 di(2-ethylhexyl) phthalate 5
olv-2: ) Linonyl phosphate 5olv-3
Ni(3-methylhexyl)phthalate 5olv-4:
Tricresine Rephosphate 5olv-5 Nidibutyl Phthalate 5olv-6: ) Lioctyl Phosphate Example 12 On a paper support laminated on both sides with polyethylene, a multilayer photographic paper having the layer structure shown below was packaged. ? @31 Fabric liquid was prepared as follows.

(First layer coating liquid made by FA) Yellow coupler (ExY-1) and (ExY-2)
to, 2g, 9.1g and color image stabilizer\C'βd, respectively.
-12,4,<z 27.2 cc of ethyl chloride; E
; and high boiling point solvent (Solv-5) 7.7CC (8:
Og) was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. This emulsion powder and emulsions EM1 and EM2 described below were mixed and dissolved, and the gelatin concentration was adjusted to have the following composition to prepare a first layer coating solution. Coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. The gelatin hardening agent for each layer is l-
Oxy-3,5-dichloro-5-tosoazine sodium salt was used.

(Layer structure LIj,) The composition of each layer is shown below, the number is the coating amount (g/rn')
The silver halide emulsion represents a silver-containing B coating.6 Support polyethylene laminate paper (the polyethylene on the first layer side contains a white pigment (T 10z ) and a bluish dye) First layer (blue-sensitive layer) ) Monodisperse silver chlorobromide emulsion (EMI) spectrally sensitized with sensitizing dye (ExS-1) - Monodisperse chlorobromide emulsion spectrally sensitized with -0,13 sensitizing dye (ExS-1) Silver emulsion (EM2) -0-13 gelatin -1,86 yellow coupler (ExY-1) -0,44 yellow coupler (
ExY-2) -0, 39 color image stabilizer (Cpd-
12) -0,19 solvent (Solv-5)
・-0, 35 second layer (color mixing prevention Il:
Layer) Gelatin...-0,99 Color mixing inhibitor (Cpd-7)...0.08 Third layer (green sensitive layer) Monodispersed salt spectrally sensitized with sensitizing dye (ExS-2,3) Silver bromide emulsion (EM3)/-0,05 sensitizing dye (EXS-
Monodisperse silver chlorobromide emulsion (EM4) spectrally sensitized with 2.
)・-0,11 gelatin...
1.80 magenta coupler (ExM-1) -
0,38 color image stabilizer (Cpd-11)...
・0.20 solvent (Solv-4)
-O, l 2 solvent (Solv-6)
-0, 25 Fourth layer (f: external ray absorption layer) Gelatin... 1.60 Ultraviolet absorber (CPd-1/Cpd-2/Cpd-3=3/
2/6 (weight ratio)) -0,7
0 Color mixing inhibitor (Cpd-6) --- 0
．． 05 solvent (Solv-2) -0,
27 Fifth layer (red h!!, layer) Monodisperse silver chlorobromide emulsion (EMS) spectrally sensitized with sensitizing dye (ExS-8,12)...-0,07 sensitizing dye (Ex
Monodisperse silver chlorobromide emulsion (S-8, 12) spectrally sensitized (
EM6)・-・0.16 gelatin
・-・ 0.92 cyan coupler (ExC-6)
・-・0, 32 color image stabilizer (Cpd-2/C
pd-3/Cpd-4=3/4/2 (weight ratio))--
・ 0.17 Polymer for dispersion ((:pd-9) -... 0
．． 28 solvent (SOIV-4) -0,
20 Sixth layer (ultraviolet absorption layer) Gelatin --- 0.54 ultraviolet absorber (Cpd~1/Cpd-3/Cpd-4-1/
S/:I (weight ratio)] ・−・
0.21 Solvent (Solv-4) −
= 0, 08 Seventh layer (protective layer) Gelatin... 1-33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%)... 0.17 Liquid paraffin °°° 0.03 Also. At this time, as dye 1 for irradiation prevention + l,
(Cpd-1, Cpd-1) was used.

Furthermore, it is used as an emulsifying dispersant and coating aid in each layer.

Alkanol XC (Dupon L), sodium alkylbenzenesulfonate, co-A phosphoric acid ester and Mag
cfacx F-120 (manufactured by Dairoki Ink Co., Ltd.)
Ta.

As a stabilizer for silver halide, (Cpd-+4.21
) was used. The silver halogen emulsion used in this example is shown below.

EMI cube 1.0 80 0.08
EM2 Cube 0.75 80 0.0
7EM3 Cube G, 5 8] 0.
09EM4 Cube 0.4 81 0.
10E 5 Cube 0.5 73 0.0
9EM6 Cube 0.4 73 0.1
0 Next, the sample Go 4-no C'h-' 3. Next, the sample prepared in this way is exposed to light through an optical wedge, and then processed by the method (1) shown below to obtain a color P.
A 3j image was obtained.

Processing method (I) Using Fuji Color Paper processing fiFPRP115,
Running development processing was performed under the conditions shown below.

Color development 37℃ 3 minutes 30 seconds 200n#
Somata bleach fixing 33°C 1 minute 30 seconds SSd
40 minutes water washing ■ 24-34°C 1 minute □ 20 fL water washing ■ 24-34:C 1 minute □ 20 Jl water washing ■ 24-34
℃ 1 minute 10rm 20JL drying 70-80℃
The composition of each processing solution was as follows: per rn' of photosensitive material (3 tank cascade from water washing to ■).

Color developer tank liquid m water
800 prints 800m1
Diethylenetriamine C1 Acetic acid 1. Qgl, og nitrilotriacetic acid 2.0g 2.0g benzyl alcohol 15 rubs 2 ml diethylene glycol 10 rubs 10 ml sodium sulfite 2.0 g 10 g potassium bromide
1.2g - potassium carbonate
]Og 25gN-ethyl-N-(β
-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0g 9.0g
Hydroxylamine sulfate 3-0g 4.5
g Fluorescent whitening agent (WlllTEX4B manufactured by Sumitomo Chemical) 1.0g '2.0
g Add water and rub 1000 times
0 pH (25℃) 10.20
10.801 Watadai Kaoru Tank liquid Minju Kaoru water 400
Field 400 Printed ammonium thiosulfate (70$)
150 d 300 m sodium sulfite
13g 26g Ethylenediaminetetraacetic acid iron (m) ammonium ssgIIOg Add ethylenediaminetetraacetic acid Niki T IQOOd 1o
00TnflPH (25℃)
6,70 6.30 Next, what is the magenta reflection in the non-image area of each of the above-mentioned photosensitive materials that have been developed? : After measuring i degree (stin), sedge t, l'lo%F2. The magenta reflection density (stin) of the non-image area was measured in the same way again for the case where the process was carried out in 1) and the case where it was left open for 0 days at room temperature. The increase in stain from Bi time is shown.

As is clear from Table 12, in the treatment method (I), 4,1et3^〈shibetsuana+j<乑くalso柤ninn Nakidome・Leopard 1L...be(←11,),i<82. 3゜12th book I7 O'p vine, Ira'j 13 q a <1"J 12 -r-xs & 1,4
-Law'4 ti i'ejll LL L Lless exposure 9t (≦To
Hi-chi 9 (1 reading, Lu Huanghui 1. - Concentrating on turning 1), late night pink λ1 pen M S< vo 6< W〆 5 Mine = r + ziq shi l # eG% A
<shi 'S'Q 'l-'R' -11t) wood, package, u1, 嘱°, L1 catty Peshimaku 'L T 'B
T! 7';15 yfF? ＼・τ；。

Processing method (11) 壓UNIGO kidney melon Kuixing color development Bleach fixation at 38°C for 40 seconds 30
～34°CI minute 00 seconds ■ 30～34℃
20 seconds dry ■ 30-34°C 20 seconds dry ■ 3.0-34°C 20 seconds dry
70 to 80°C for 50 seconds (3 tank countercurrent flow from Sonsu ■ to ■). The composition of each treatment liquid is as follows.

color developer water
800ml diethylenetosaminepentaacetic acid 1.0
g1-hydroxyethysoden-1,1-diphospho:zM(60ri2,0
g Nido Soro Tama l1lI Shochu 2.0g
1.3-diamino-2-propatol 4. Ogl, 4-diazabicyclo[2,2,2]octane 6.0g potassium bromide 0.5g potassium acetate
30gN=ethyl-N-(β-
Methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.5g8, Ro-5
゛Work 10 e,)'Q* z,, 1 mince beak i examination, 4
4. Ogfi light full'1ll (UVITEX-
Add wood to C and 1000dp
H (25℃) 10゜251a constant 1
Moon Wednesday 40
0m1thio1iIv7:z-f-=lam (7Gri
200nA&! L-acid natosium
20g ethylenediaminetetracholic acid ([111 ammonium) 60g ethylenediaminetetraacetic acid diPH (25°C) 7.00 rinse solution - ion exchange water (calcium, magnesium 3pp each
m or less) Processing method - (m) Color development 35°C 45 seconds 161d
17 Relationship self-establishment 30-36℃ 45 seconds 21
5d 17C stable ■ 0~37℃ 20 seconds □ 10Q stable ■ 30~37℃ 20 seconds □ 1
0 cycle stable ■ Co 0 ~ 3 bu (20 seconds □ 10 exchange stable ■ Co 0 - core °C 30 seconds 2
48i 10 sentences drying 70~85℃ 60
seconds per rn' of photosensitive material.

(A four-tank countercurrent system was used to ensure stability.) The composition of each treatment solution is as follows.

Color image liquid Tank liquid Replenishment water
800m1 80
0ml ethylenediaminetetrachoic acid 2. Og
2.0 (5,6-cyhydroxybenzene-1.2.4-trisulfonic acid 0.3g o, cog
Tosoethanolamine 8.0g8.0 Lt Shiyari/7IA Q, 6 pieces
- Potassium carbonate 25g
25g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoanisone sulfate S, Og 7.0g
Diethylhydroxylamine 4.2g 6.0g Optical brightener (4,4'- Add water +000d l [1
00ml pH (25℃) 10.05
10.4s bleach-fix solution (tank solution and replenisher are the same)
water 4
00d thio&tL ammonium acetate (702)
100d Asia&! Ll'it sodium
17g iron ethylenediaminetetraacetate ([[11ammonium 55g disodium ethylenediaminetetraacetate 5gpl+(25℃)
5.40 hours (tank liquid and replenisher are the same) Formalin (37 liters) 0.1 g formalin-sulfite adduct 0.7 g 5-chloro-2-methyl-4-inchanson-3-one (102 g 2-methyl-
4-Isothiazoso-3-one 0.01gpH (25℃
)4. .

Processing method ((V) Using PP100O (partially modified) (manufactured by Ushi Photo Film t1) in Fuji Color Roll Processor F, running development processing was performed under the conditions shown below.

Color development 45 sec. The overflow of the rinse tank ■ is led to the bottom of the rinse tank ■, and the overflow of the rinse tank ■ is led to the bottom of the rinse tank ■, and the overflow of the rinse tank ■ is drained. A tank countercurrent system was used. In addition, the amount of vapor brought in from the pre-bath is 9.
It was 25m1.

The prescriptions for each tank fluid and each replenisher are shown below.

L2 Niritoyo Tank Liquid Replenisher Wood 800 Suri 800
ml diethylene triamine l [acetic acid 3.0g 3.0g benzyl alcohol 15d 17 suri diethylene glycol IO suri 10 ml sodium sulfite
2.0g 2.5g Potassium Bromide 0
．． 5g) Sodium Tetraate 30g 35gN-
Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g Hydroxylamine sulfate 4.0 g 4.5 g Optical brightener 1. Add og 1.5g water
1000 dpi (10,1010,
50 Bleach-fix tank liquid Replenisher water 40014 4
00 functional ammonium thiosulfate (70% solution) 150 mfi 300 sodium sulfite 12 g 25 g ethylenediaminetetraacetic acid iron (m) 7 ammonium 55 g 110 g ethylenediaminetetraacetic acid mono2Na 5 g 10 g Add water and add tooo 100011 pH (25'
C) 6.70 6-50 Rinse liquid ethylenecyamine/N,N.

Add N',N'-tetramethylenephosphonic acid 0.3g benzotriazole 1.0g water
i ooo water resistant sodium hydroxide
pH7-5 processing method (v) Color development 45 seconds 88 times 150 Oi white fixing 2 minutes 00 seconds 35 times Cola 0 rinse ■
1 minute 00 seconds 17 cycles - Rinse ■ 1 minute 00 seconds 111 L - Note that the treatment solution and replenisher used were the same as in treatment method (IV).

Example 1 ni j da 葎, 4') 1)...Imine - 9 ki then ζ 雛mi (
1, L4 east general and 匍\Q in the evening forest 31,2 inches
Lmo (j-゛eg1-) ke-1-kanoran i, tp address 1~.
-Nt 藏、＼o１゛にとanti-customer))(ε已wawa ε
4 steam Vχ) and 1 and S east - 1, nryon 1 de) - 1 bi%C
, -1 ~ Shin c-bt ← 1 house ra tq otobun ε (
U']1λ and w4 *”H'Q<at'<1rr+b
5'o% Emulsion Name Shape Oko Diameter Clearance (U) (m.I Variation D Sensitized Color ＾EM
7 Cube 1. +99.0 0.1
(ExS-4)EXS Cube 0. t 9
9.0 0.1 (ExS-4)EM9 Cube 0.45 9+1.5 0.09 (E
xS-1,S)EMI2 Cubic 0.34 98
．． 4 0.10 (EXS-8, +2 lenses 11
? ψImpatient, 31) Waramotori, N)77) Iv
,4r dormitory second Qma(°futanufinnorib'1゛Ioε・
J → To・j Light 4′” Moya 5.

(Effect of the invention) By using a compound that chemically bonds with the aromatic amine color developer remaining after color development processing to produce a chemically inert and substantially colorless compound, the color change over time can be improved. It is possible to effectively prevent the deterioration of the image quality of photographs and the occurrence of stains. This effect is effective for processing liquids in which a large amount of processing liquid components are brought into the photosensitive material, such as processing liquids in running state, processing liquids with little or no water washing, and color developing liquids that do not substantially contain benzyl alcohol. Alternatively, good results can be achieved by processing with other processing solutions that place a burden on color development.

Patent applicant: Fuji Photo Film Co., Ltd.

Claims (1)

[Scope of Claims] 1) A support containing a preservability-improving compound that chemically bonds with an aromatic amine color developer remaining after color development processing to produce a chemically inert and substantially colorless compound. A color photograph characterized in that it is contained in at least one of the upper photographic layers. 2) The storage-improving compound has a second-order reaction rate constant k_2 (80°C) with p-anisidine of 1.0 l/mol·sec to
It is a compound in the range of 1 × 10^-^5 l/mol sec,
A color photograph according to claim (1). 3) The preservability improving compound chemically bonds with the aromatic amine color developer remaining after color development treatment under conditions of pH 8 or less to produce a chemically inert and substantially colorless compound. A color photograph according to claim (1). 4) After imagewise exposure of a photographic light-sensitive material containing a color image-forming coupler that forms a dye through an oxidative coupling reaction between a silver halide emulsion layer coated on a support and an aromatic amine color developer, , subjected to color development and bleach-fixing treatment, and the color development treatment, bleaching/fixing treatment, or other treatment is chemically combined with the aromatic amine color developer to produce a chemically inert and substantially colorless product. 1. A method for producing a color photograph, characterized in that the process is carried out in the presence of a preservation-improving compound that produces a compound. 5) In at least one of the photographic layers in the photographic light-sensitive material, chemically bonds with the aromatic amine color developer remaining after color development processing to form a chemically inert and substantially colorless compound. A method for producing a color photograph according to claim (4), characterized in that the method contains a preservability improving compound. 6) The method for producing a color photograph according to claim (5), wherein the preservability improving compound is contained in the photographic light-sensitive material in an amount of 1 x 10^-^2 to 10 mol per mol of the color image-forming coupler.