JPS63250652A - Method for processing color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the generation of a stain, even in case of processing the titled material with a saved washing water by incorporating a specified magenta coupler in a green photosensitive emulsion layer, and by processing the obtd. titled material with a processing solution contg. an epoxy compd. etc., after developing the titled material. CONSTITUTION:The magenta coupler shown by the formula is incorporated in the green sensitive photosensitive emulsion layer. In the formula, R<1> is hydrogen atom. or a substituent group, X is hydrogen atom. or a releasing group capable of releasing by reacting with the oxidant of an aromatic primary amine developing agent, Za-Zc are each methine group, =N- or -NH group, etc. and together with each other may form an aromatic ring. And, the photosensitive material is developed, followed by effecting stabilization processing. The processing solution for the stabilization contains an epoxy compd., an aziridine compd., a triazine compd., an acryloyl compd. or a vinylsulfonyl compd., etc. Accordingly, as the titled material is effected the stabilization processing, even in the case that said material is processed with the saved washing water or the washing of said material is omitted, the generation of the stain of the titled material can be suppressed.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for processing color photographic materials, and in particular to methods for producing magentastin in color photographic materials (hereinafter referred to as color materials). The present invention relates to a method of making protected and stable color dyes.

(Prior Art) Generally, when processing a color sensitive material, a color dye image is obtained by desilvering, water washing and/or stabilizing treatment after color development. However, various color development methods can be considered depending on the purpose.

For example, the present color processing method also includes so-called reversal color processing in which black and white development is performed in advance before color development and color development is performed by fogging exposure or fogging bath treatment. Further, as the desilvering treatment, bleaching treatment, bleach neutralization bath treatment if necessary, fixing treatment, bleach-fixing treatment, etc. are included in this color treatment method. However, JP-A-3.2-/333! ,same! 2-73
3! A.

The present invention also includes a color processing method in which there is substantially less residual silver and no desilvering treatment is performed, using a development intensification method as described in JJ-20737.

Furthermore, as the water washing or stabilization treatment, water saving water washing or stabilization only, the treatment solution described in Japanese Patent Application Shoj Goichi//7li No. 74 and J4-/32li No. 07, or a stabilizing bath after water washing may be used. This color processing method includes processing methods that add processing.

Conventionally, color photosensitive materials after processing, especially color print photosensitive materials, are displayed in a frame or attached to an album for a long period of time to observe and appreciate the color dye image, which causes the print to change color and fade. In particular, staining on white backgrounds was a big problem. At one time, due to storage conditions (constant exposure to light, exposure to high humidity, high temperature), there was a problem in which staining occurred on the white background, significantly reducing the saturation of the color pigment image. . For example, if a processed color print is pasted in an album and exposed to high temperature and humidity, the white background will take on a magenta tinge, making it look like a dirty color print.

Furthermore, in recent years, in urban areas, the cost of supplying washing water for photographic processing has become high, and discharging washing wastewater also costs an enormous amount of money, so there is a demand for water conservation. Moreover, heating the washing water requires a great deal of expense, and there is a tendency to save on washing, and these conditions are said to be particularly related to the occurrence of stains on white backgrounds. For example, published by the Japan Wedding Photography Association, a study on setting standards for processing to prevent discoloration and fading of color photographs, ``Tokyo Polytechnic University Research Group Report Sponsored by Toshio Miyayo,'' Nisshashi.
<t2,5r2 (/ri2ri), diary 4t4t.

It is written in gu/♂(/ri//), etc.

In order to prevent such staining, a stabilizing bath is provided between washing and drying to keep the pH of the processed sensitive material film as low as 3 to 3 and prevent staining from occurring. It has been known. However, this method of providing a stabilizing bath is not satisfactory for processing methods that save washing water or do not perform washing at all.

In addition, after color development and stopping, only bleach-fixing is used (
That is, a method (West German Patent No. 1,772,995) is known in which images are stabilized (by omitting the water washing process), but this method causes a significant number of stains and is not practically satisfactory.

In order to prevent staining, it is known to increase washing efficiency by thoroughly washing with water or by using air bubbles during washing, but it is also possible to conserve the washing water or do not wash with water at all. Even in the case of treatment, there is currently no method that can effectively prevent staining.

On the other hand, research on magenta couplers is progressing toward two-equivalence formation by introducing an anion leaving group in order to save silver. The hope of developing magenta taco-equivalent couplers was to overcome the following technical drawbacks of hiroequivalent pyrazolone couplers:

■ The dye formation yield is low (~0%), and coupler and silver are wasted.

■ Couplers are easily oxidized, making it difficult to prevent yellowing during storage of photographs.

■ It easily reacts with formalin gas, etc., and tends to disrupt the balance of the three colors in the photo.

■ Dye formation rate is relatively low, making it difficult to adjust the coupling rate.

In order to overcome these drawbacks, a magenta dye-forming turnip 2- represented by the general formula N) was proposed. However, since this magenta coupler has a fast dye formation speed, it has the disadvantage that it reacts with the main ingredient remaining after processing, causing coloration and staining, making it difficult to put it into practical use.

(Objective of the Invention) The object of the present invention is to obtain the general formula (
An object of the present invention is to provide a new processing method that suppresses the occurrence of stain (especially magenta stain) after processing a color sensitive material containing a magenta dye-forming coupler represented by 1).

Another object of the present invention is to provide a treatment method that suppresses the occurrence of post-treatment stains even in treatments where washing water or the like is saved or where the temperature of the washing water is low.

(Structure of the Invention) As a result of various studies, the present inventor found that the above object can be achieved by the following method for processing color photographic materials.

A color photographic light-sensitive material containing a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support is used as a color photographic light-sensitive material containing an aromatic primary amine compound. In the method of desilvering treatment after development, the green-sensitive/% silver halide emulsion layer is prepared by the following general formula (I
), and after color development, epoxy compounds, aziridine compounds, acryloyl compounds, vinylsulfonyl compounds, triazine compounds, isoxazolium compounds, sulfonic acid ester compounds, carbodiimide compounds, maleimide compounds, and 1. A method for processing a color photographic material, comprising processing it with a processing solution containing at least seven compounds selected from the group consisting of incyanate compounds.

General formula (1) (wherein, R1 represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. Za , Zb and Zc are methine, substituted methine, =N-4 or -NH-
represents l, one of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. Zb-Zc
An aromatic ring may be fused there. R1 or X
This also includes the case where a dimer or more multimer is formed. Also, Z
When a%zb or Zc is a substituted methine, it also includes the case where the substituted methine forms a multimer of λ-mer or more. ) The compounds used in the present invention are 1. Water soluble, pH
Preferably, the compound is stable in an aqueous solution of 7 to ♂. Compounds with seven water-soluble groups (e.g., sulfonic acid groups, amino groups, carboxylic acid groups, hydroxyl groups, etc.) should have a molecular weight of 300 or less, and compounds with λ water-soluble groups should have a molecular weight of aOO or less. is preferred.

The epoxy compound used in the present invention includes the following compounds.

A-/, 2.2'-Bis(p-glyci
doxy)-benzene A-λ i, 2-Bia(ko', 3'-epoxy
propoxy) ethaneA-J prop
ylene oxideA-/I Tri-(
, z , J-epOXy propyl)phosp
hate A-z Tri(epoxy propylet
hyl)phosphate A-4Tri(epoxy propylbutyl
) phosphate A-7hexandiol-/, t-bis(di-
(epoxypropyl)phoshate)A-/
hexandiol −/ , t-big(d
i-(epoxybutyl)phosphate)
A-9hexandiol-/, t-bis(di
-(epoxyethyl)phosphate)A
-/ o butadiene monoxi
deA-//propadiene mon
oxide The allydine compounds used in the present invention include the following compounds.

B-/N-ethyl-N'-ethylene
ureaB-2p-phenylene bis(
di-(/-aziridinyl)phosph
onate) B-J N-pentadecyl −
N-ethylenerea B-y N-pentadecyl -N-ethy
lenerea B-s N-methyl -N'-ethylen
e ureaB-4/, /4-Hexadecam
ethylene -N, N'-bisethylene
e ureaB-70xal bis(β-ethy
lene -1m1n.

ethyl amide) The acryloyl compound used in the present invention is one in which CH2=CH-Co-NH- or CH2=CH-C
It is a compound containing 0-0-. Specifically, the following can be mentioned.

C-/ mucochloric amide C-2
Hydroxy mucochloric acid
C-33-bromo-2-phenoxy-male
aldehydic acid The vinylsulfonyl compound used in the present invention contains CH2=C
It is a compound containing H-8O2-. Among these, compounds represented by the following general formula are preferred.

General formula D-1 Here, m is an integer from 7 to 2, and Z is 7 heteroatomic groups (
For example, triazine, diazine, monoazine, etc.), R
each represents a hydrogen atom or an alkyl group (eg, methyl group, ethyl group, isopropyl group, etc.).

General formula D-11 [CH2=CXsO2(NHCo)m-8-Y)nZ, where X is a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom, etc.), Y is 10-1-S- or -NH-
1m is/or , n is 2~. The integer 2 represents an n-valent aliphatic group, an n-valent aromatic group, or an n-valent heterocyclic group (eg, benzene, toluene, ethylene, propylene, butylene, diazine, triazine, morpholine, etc.).

General formula D-1[I (CH2=C)i-8O2-CH2-CHCONHjR
□Here, R represents a hydrogen atom or a methyl group, and Ro represents an alkylene group with carbon number/~.

General formula D-IV (H2C=HC02SH4C2COHNjZ+NHCO
C2H4SO4CH=CH2)2+CHz)n (n
ttl 2-j (D integers are shown) General formula D-V ■ CH2 C=0 Here, V represents a vinyl group.

General formula D-■ Here, a and d represent / or co, b and c represent 01/ or -, and R111 represents an alkylene group having a carbon number of / to 1.

Specific examples of vinylsulfonyl compounds include the following.

D-/CH2=CH-802-CH2-8O2-CH=
CH2D-J CH2=CH-8O2-C3H6-8
O2-CH=CH2~ Toad
4′+(111! Ro Ro Ro
(b) Examples of the triazine compound used in the present invention include halogen triazine compounds and hydroxytriazine compounds.

These compounds are preferably compounds represented by the following general formula.

General formula E-1 Here, (e.g., methyl group, ethyl group, isopropyl group, etc.) or alkoxyalkyl group (preferably carbon number -~!)
For example, methoxymethyl group, ethoxymethyl group, etc.)
represents.

X)=NXoeMe Here, X is a halogen atom (e.g., chlorine atom, bromine atom, etc.), M is a cation (e.g., Na, K, etc.)
represents.

Here, X represents a halogen atom (e.g., chlorine atom, bromine atom, or iodine atom, with chlorine atom being particularly preferred), n represents an integer of - to 10, and R represents an n-valent organic acid residue (e.g., Acetic acid, phthalic acid, oxalic acid, carboxypyrimidine,
adipic acid, etc.).

Specific compounds represented by these general formulas include the following.

E − / , 2 , 4t-dichloro-t-h
ydroxy −/ , J , j-triazin
e aodiumaltE-2J, 4t-di
chloro-a-carboxymethoxy-/
, ! , , t-triazinesodium
5alt E-j hexahydro-/ , j , r-t
ria(chloroacetyl)-8-triaz
There is an inoxacillium compound used in the present invention.

The following can be mentioned.

Specifically, F-/2-methyl-isoxazolium
p -toluenesultonateThe carbodiimide compound used in the present invention is a compound in which -N=C
=N--containing compound.

Specifically, the following can be mentioned.

G-/propyl arylcarbodiim
ideG-J hydroxyethyl alyl
carbodiimideG-J/, j-di-i
sopropyl-carbodi 1mlde The sulfonic acid ester compound used in the present invention is a compound having a sulfonic acid ester moiety.

Specifically, the following can be mentioned.

H-//-methyl 5ulfoxy-,2,,
? -epoxypropane H-2glycidyl allylsulfona
teThe maleimide compound used in the present invention is a compound having a maleimide bond.

Specifically, the following can be mentioned.

I-/N, N'-trimethylenebts
maleimide H-,23,q-divinyl-2,4t,t,10
=tetra oxaspiro(j, r]unde
The isocyanate compound used in the present invention is a compound having an incyanate group.

Specifically, the following can be mentioned.

J-/copoly(acryloyl morp
holine/vinyl 1socyanete
bisulfitadduct] J-2polyisopropenyl 1socy
anatebisulfit adduct J-j ethylene 1 socyanet
e Among these compounds used in the present invention, preferred are halogen triazine compounds, hydroxytriazine compounds, vinyl sulfone compounds, and epoxy compounds, and even more preferred are halogen triazine compounds, hydroxytriazine compounds, Vinyl sulfone compounds are preferred, and halogen triazine compounds are particularly preferred.

Other specific examples and synthetic methods of these compounds include, for example, T,
H. James' The Theory of
thePhotographic Process
' (9th edition), pages 27-2.

By the processing method of the present invention, the stability of color dye images, particularly the occurrence of magenta staining, can be significantly suppressed.

Furthermore, in the conventional processing method, at least 1073 water was consumed per m2 of sensitive material, and the treatment was carried out for 3 to 10 minutes with water at a high temperature of 24 A to 34 t'C, but with this method, the sensitive material/ m2 per 1) 0. It is also possible to wash with water of /j-206C of /l to /l for about /min. Furthermore, it is also possible to perform the above-mentioned stabilization treatment using a low replenishment amount without washing with water.

The amount of the compound of the present invention added is θ, 7g/l-10g/l
It is preferably θ, rg/l - θg/l.

The treatment temperature is usually chosen between /10C and 10C, but temperatures lower than /10C or above 10C may also be used.

As a special form of development processing, a developing agent is added to the light-sensitive material.
For example, a method may be used in which the photosensitive material is included in the emulsion layer and the photosensitive material is processed in an alkaline aqueous solution to perform development.

The color developer used in the present invention generally consists of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known secondary aromatic amine developer, such as phenylenediamines (eg, q-amino-N).

N-diethylaniline, 3-methyl-Q-7 minnow N,
N-diethylaniline, teramino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-teramino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-quaamino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-teramino-N −
ethyl-N-β-methanesulfamide ethylaniline,
9-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition to this, Photogr by F. A. Mason
aphicProcessing Chemistry
(Published by Focal Press, /? 1966) Here≦
' ~ 229 pages, U.S. Pat. -J4tri33
You may use those listed in the No.

The color developer may also contain a pH buffer, a development inhibitor or an anti-capri agent, and the like.

In addition, water softeners, preservatives, organic solvents, development accelerators, dye-forming couplers, competitive couplers, fogging agents, auxiliary developers, viscosity-imparting agents, polycarboxylic acid chelating agents, and antioxidants are added as necessary. , an alkaline agent, a solubilizing agent, a surfactant, an antifoaming agent, and the like.

Specific examples of these additives are listed in Research Disclosure (RD-i2t3) as well as in U.S. Patent Nos. <<, 0jr
J, No. 723, OLS, 2°12.2
, rij0 issue, etc.

Furthermore, the smaller the amount of benzyl alcohol, the lower the stay/rate when the coupler of the present invention is used.

From this point of view, benzyl alcohol is preferably /rr/l/l or less, and 0. Iml/l or less is more preferable.

The bleach-fix solution used in the present invention contains a polycarboxylic acid (specifically, the above-mentioned polycarboxylic acids are used as an oxidizing agent, and among them, ethylenediaminetetraacetic acid, diethylenetriamine ink acetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, and cyclohexanediamine). Ferrous salts of polyamine acetic acids such as tetraacetic acid are particularly preferred.

Further, as the fixing agent, commonly used fixing agents can be used. Specifically, thiosulfate, thiocyanate, potassium iodide, thiourea, etc. are used.

Bleach-fixing solutions include US Patent 3. θ4t, 2. jko θ,
3.24t/? Bleaching accelerators described in J Gogo, Tokko Shodayoichi/jOt No., Tokko Sho+1j-1136, etc.
Published in 1973! In addition to the thiol compound described in Item 3, various additives can also be added.

The silver bleaching solution used in the present invention is a processing solution containing ferrous salts, persulfates, etc. of inorganic or organic acids. For more information, see ``The Theory of the Pho.
tographic Process' ■edit
ion (/ri 72nd edition) P, 4t4t♂ The bleaching solutions listed in Table 4t♂ can be used.

The compound used in the present invention can be used in any known processing solution after color development. For example, it can be added to a silver bleaching solution, a bleaching solution, a bleach-fixing solution, a bleach-neutralizing solution, a fixing solution, a stabilizing solution, a washing water, a stabilizing solution, an intensifying solution, and the like. Furthermore, a liquid containing the compound of the present invention may be used as a new bath. Among these, it is preferable to use it as a stabilizing treatment liquid or a stabilizing liquid.

Further, the pH of the liquid to be added is preferably r or less, and particularly preferably pH a to 1.2.

The silver halide color photographic light-sensitive material used in the present invention is generally subjected to desilvering treatment such as fixing or bleach-fixing, followed by washing with water and/or stabilizing treatment.

The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the coating, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set to . Among these, the relationship between the number of flushing tanks and the amount of water in the multi-stage countercurrent method is Jour.
al of the Society of Moti
on Picture and Television
Engineers Volume 64, P, J4t! -, 2 evening 3 (/ri!j year! month issue) It can be obtained by the method described in K. Usually, the number of stages in the multistage countercurrent system is preferably 2-6, and particularly preferably -a.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced.
For example, it is possible to reduce the amount of water to 1) o, zL-/L or less per photosensitive material/m2, but due to the increased residence time of water in the tank, bacteria will propagate and the generated suspended matter will adhere to the photosensitive material. Problems such as this arise. As a solution to such problems in processing the color photosensitive material of the present invention, the patent application Sho t/-/
The method for reducing calcium and magnesium described in J//, No. 32 can be used very effectively. Also, Tokukai Showa J7-R! Inchiazoro/ as described in 4t No. 2
Compounds and thiabendazoles, 47-/20/4t
Chlorine-based disinfectants such as chlorinated sodium incyanurate described in No. J, benzotriazole, copper ions, etc. described in Patent Application Sho No. 0-101 G♂ No. 2, "Chemistry of Antibacterial and Antifungal Agents" by Hiroshi Horiguchi, You can also use the disinfectants listed in the Hygiene Techniques Complete Edition "Microbial Sterilization, Disinfection, and Antifungal Technology" and the Japanese Antibacterial and Antifungal Science Complete Edition "Encyclopedia of Antibacterial and Antifungal Agents J and K. Furthermore, the amount of water for washing should be adjusted according to the draining agent. as a surfactant and EDTA as a water softener.
A chelating agent represented by can be used.

The pH of the washing water in the processing of the photosensitive material of the present invention is preferably tartar! −It is a male. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but in general, /5-uroc = θ seconds - /θ minutes, preferably:
A range of 30 seconds to 5 minutes at −90° C. is selected.

The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. Compounds with an image stabilizing function are added to the stabilizing solution, such as aldehyde compounds such as formalin, buffering agents for adjusting the membrane pH suitable for dye stabilization, and ammonium compounds. It will be done. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

Furthermore, a surfactant, a fluorescent brightener, and a hardening agent can also be added. In the processing of the photosensitive material of the present invention, when stabilization is achieved directly without going through a water washing process, JP-A-Sho! 7-
♂j4t3, jr-74tr39, 6Q-co203
the law of nature! All known methods described in No. 1 and Isobaric can be used.

In addition, it is also a preferable embodiment to use chelating agents such as /-hydroxyethylidene-/, /-diphosphonic acid and ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds.

The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is to allow the overflow of washing water, which is reduced by a multi-stage counter-current system, to flow into the white-fixing bath during the pre-bath, and replenishing the bleach-fixing bath with concentrated liquid to reduce the amount of waste liquid. .

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any of silver iodochlorobromide, silver chlorobromide and silver chloride containing 70 moles or more of silver chloride may be used as silver halide. The preferred silver halide is silver chlorobromide or silver chloride containing less than 120 moles of silver bromide.

゛In a preferred embodiment, the silver halide in the blue-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer substantially contains silver chloride at least 0 mol, and the silver halide emulsion layer contains silver chloride in the green-sensitive silver halide emulsion layer. The silver halide contains 70 moles or more of silver chloride, and the green-sensitive silver halide emulsion layer has the following general formula (I
) containing a magenta dye-forming coupler represented by
It is a silver halide color photographic material.

The average grain size of silver halide grains in a photographic emulsion (the grain size is the grain diameter for spherical or approximately spherical grains, and the edge length for cubic grains, expressed as an average based on the projected area) is the grain size distribution It doesn't matter if it's narrow or wide.

The particle size is θ, 07~! It is preferable to have a thickness of about μ.

Silver halide grains in photographic emulsions may have regular crystal structures such as cubes and octahedrons, or irregular crystal structures such as spherical and plate shapes.
It may have a crystalline form (gular) or a composite form of these crystalline forms.

It may also consist of a mixture of particles of various crystalline forms.

The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.

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 particle.

The photographic emulsion used in the present invention is P, Glafkide.
Written by Chimie et Physique Photo
ographique (published by Paul Monte1,
It can be prepared using the method described in, et al.

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

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, see, for example, Di, edited by H. Frleser.
e Grundlagen der Photogra
phischenProzesse mit Silb
Erhalogeniden (Akademische
Verlagsgesllschaft.

/Rini/) The method described on pages 7r to 73 can be used.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used.

The photographic emulsions used in this invention may be spectrally sensitized with methine dyes and others. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization.

Useful sensitizing dyes, dye combinations exhibiting supersensitization, and substances exhibiting supersensitization are disclosed in Research Disclosure (Res.
7 volumes/
2g4tj (Published in /ri7/year/month) Page 23 ■-5
It is described in the section.

In the magenta dye-forming coupler represented by the general formula (I) contained in the green-sensitive silver halide emulsion layer of the photographic light-sensitive material of the present invention, a multimer is defined as λ or more of the general formula (represented by R) in 7 molecules. It means a monomer having a group represented by the general formula (1) (preferably a vinyl group) and also includes a bis compound and a polymer coupler. (hereinafter referred to as vinyl monomer), or a copolymer with a non-color-forming ethylene-like monomer that does not couple with the oxidized aromatic primary amine developer. It's okay.

Among the magenta dye-forming couplers represented by the general formula (1), preferable ones are those represented by the following general formulas (It) and (III).
, (■), (V), (Vl), (■) and (■).

(u) (nl) (IV) (V) (■)
(■) Among couplers represented by general formulas (If) to (■),
Preferred for the purpose of the present invention are general formulas (rl), (V)
and (M), and more preferable ones are general formula (M
).

In the general formulas ([) to (■), R11, R12, and R may be the same or different, and each may be a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, or an aryloxy group. group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imido group, sulfamoylamino group, carbamoylamino group, alkylthio group,
Represents an arylthio group, a heterocyclic thio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, a 71J-ruoxycarbonyl group. ,
X represents a hydrogen atom, a halogen atom, a carboxy group, or a group that is bonded to the carbon at the coupling position via an oxygen atom, nitrogen atom, or sulfur atom and is decoupled. R, R, R! l or X may serve as a covalent group to form a bis form.

It may also be in the form of a polymer coupler in which the coupler residues represented by the general formulas (U) to (■) are present in the main chain or side chain of the polymer, and especially those derived from vinyl monomers having the moiety represented by the general formula. Polymers are preferred, in which case R, R, R or X represent a vinyl group or a linking group.

More specifically, R11, R12 and R13 are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group,
Heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imido group, sulfamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonyl represents an amino group, an aryloxycarbonylamino group, a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and X is a hydrogen atom, a halogen atom, a carboxy group, or a group linked by an oxygen atom (
For example, acetoxy group, propanoyloxy group, benzoyloxy group,
ami)' group, N-ethyltoluenesulfonamide group, haptafluorobutanamide group, 2,3,4t, j.

6-pentafluorobenzamide group), an arylazo group, a group linked by a sulfur atom (e.g., a phenylthio group,
Cocarpoxyphenylthio group, -1methoxy r-t
-octylphenylthio group, etc.).

In the couplers of general formulas (It) and (I[[), R12 and R13 are bonded! It may form a negative or Z shell ring.

When R11, R12, R13 or X becomes a divalent group to form a bis body, preferably R11, R12, R1
3 is a substituted or unsubstituted alkylene group (e.g., methylene group, ethylene group, /, 10-decylene group, -CH2C
H2-O-CH2CH2-, etc.), substituted or unsubstituted phenylene groups (e.g. /, q-phenylene group, /, 3-
Phenylene group, -NHCO-R14-C0NH- group (R represents tit or unsubstituted alkylene group or phenylene group, for example -NHCOC) I2CH2CONH-1H3 -NHCOCH2C-CH2CONH-CH3 -8-R14-8- group ( R14 represents a substituted or unsubstituted alkylene group, for example, -8-CH2CH2-8
, CH3 -8-CH2C-CH2-8-, etc.), and X represents the above CH3 heptavalent group converted into a divalent group at an appropriate position.

General formulas (II), (III), (f'/), (V), (
■), (■) and (■) are vinyl □ R11, R12, R13 when included in the monomer
or the linking group represented by X is an alkylene group, a phenylene group, -NHCO-1CONH-1-〇-1-OC
It includes a group formed by a combination of O- and aralkylene groups.

Preferred linking groups include the following.

-NHCO-2-CH2CH2-5 -CII2CH20-CH2CH2-NHCO-1 The vinyl group has the general formula (II), (III), (F/), (
V), (1, substituents other than those represented by (■) or (■) may be used, and preferred substituents are hydrogen atoms,
Represents a chlorine atom or a lower alkyl group (for example, a methyl group or an ethyl group) having 1 to 3 carbon atoms.

General formula (II), (I[[), (IV), (V), (M
), (■) and (■) may be copolymerized with non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic primary amine developers. good.

Acrylic acid, α
- chloroacrylic acid, α-alkylacrylic acid (such as methacrylic acid) and esters or amides derived from these acrylic acids, such as acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide,
Methyl acrylate, ethyl acrylate), n-propyl acrylate, n-butyl acrylate, t-butyl acrylate), 1so-butyl acrylate, coethylhexyl acrylate), n-octyl acrylate,
Lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-
hydroxymethacrylate), methylene dibisacrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylateryl, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene,
divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid,
Vinylidene chloride, vinyl alkyl ether (e.g.
Examples include t-vinyl ethyl ether), maleic acid, m-hydric maleic acid, maleic ester, N-vinyl-J-pyrrolidone, N-vinylpyridine, and 2- and dervinylpyridine. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used together.

For example, n-butyl acrylate and methyl acrylate,
These include styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetone acrylamide, etc.

As is well known in the polymeric color coupler art, non-chromogenic ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomeric couplers depend on the physical and/or chemical properties of the copolymer formed, e.g. solubility, compatibility of the photographic colloidal composition with binders such as gelatin, its flexibility,
It can be selected so that thermal stability etc. are favorably influenced.

The polymer coupler used in the present invention may be water-soluble or water-insoluble, but polymer coupler latex is particularly preferred.

Specific examples and synthesis methods of the pyrazoloazole magenta coupler represented by general formula (1) used in the present invention are as follows:
Tokukai Akira! 9-/buλz4tr, samego 0-4136! the law of nature,
same! Tar/2/rijg, same θ-/77! R/Co, same 〇-33!6.2 and US patent! ,0/s/,443
2 isobaric is described.

Specific examples of typical magenta couplers and vinyl monomers thereof according to the present invention are shown below, but the invention is not limited thereto.

(M-λ) ti3 (M-J) (M-<') H2CH3 (M-s) (M-, g) (M-7) (M-/) (M-?) (M-/I H2CH3 exposure (M-//) l (M-/ko) (M-/J) (M-/lt) (M-/r) (M-it) (M-//) (M-ko/) (M-4,2) (M-koJ) (M-koq) (M-kogo) (M-,27) H3 (M-,251) N=N (M-3o) 5tillftノ( M-J/) (M-32) (M-33) (M-34t) (M-jj) (to M-3) These magenta dye-forming couplers may be used alone, but the following magenta/ Examples of magenta couplers to be used in combination include yoichi pyrazolone couplers, pyrazolopenzimidazole couplers, cyanoacetylcoumarone couplers, and open-chain acylacetonitrile couplers.

The blue-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer of the photographic material of the present invention may contain the following dye-forming couplers. For example, yellow couplers include acylacetamide couplers (eg, benzoylacetanilides, piparoylacetanilides), etc., and cyan couplers include naphthol couplers, phenol couplers, and the like.

These couplers, including the magenta coupler used in combination, are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either commercial or co-equivalent with respect to silver ion. Also, colored couplers that have a color correction effect, or Kab2- (so-called D) that releases a development inhibitor during development.
IR coupler). 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.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling point organic solvents used in the oil-in-water dispersion method are U.S. Pat.
It is stated in issue 7 etc.

Further, the process and effects of the latex dispersion method, and specific examples of the latex for impregnation, are described in US Patent No. Q./Wata.

3g3, West German Patent Application (OLS) No. 2. j4t/.

No. 274 and No. 274, Jr4t/, No. 230, etc.

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization.

Additives used in such processes are described in Research Disclosure, Vol. 1, Vol. 4, A/744t3 (7922,
72) and volume 1r7, black/♂7/4 (/ri7
The relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

Additive type RD/7t4ti RDit2/l/
Chemical sensitizers page 23 ta4t/page right column Co-lateralization increasing agent Same as above 3 Spectral sensitizers page 3 to J4 L64t page 1 right column to q
Super sensitizer 6ri9 left and right column! Masuhaku
Agent 2q page? Capra-2j page? Organic solvent page 2j IO ultraviolet absorber// anti-stin agent - page 5 right column 6!0 page left to right column/2 dye image stabilizer, page 2j/3 hardener, page 2J 61/page left column/4t Binder, page 26 Same as above/j Plasticizer, lubricant, page 22 4jO Right column The method of the present invention can be applied to any processing process as long as it uses a color developer. For example, it can be applied to the processing of color developer, color reversal paper, color direct positive photosensitive material, color positive film, color negative film, color reversal film, etc., but in particular, color can be applied to -par, color reversal base/e- It is preferable to apply

(Example) Hereinafter, the present invention will be explained in detail with reference to Examples.

Example/Silver chlorobromide emulsion containing a yellow coupler emulsified dispersion on a paper support with a resin coating (silver chloride 3θ morch grain size/
A silver chlorobromide emulsion (silver chloride g0
A green-sensitive layer consisting of silver chloride, grain size 0.7μ), an intermediate layer consisting of gelatin, and a silver chlorobromide emulsion containing a cyan coupler emulsified dispersion (silver chloride 60 mole, grain size 0.7μ).
) and a gelatin layer containing an ultraviolet absorber were coated to produce a color bar/guy. Each coupler emulsion used in this color packer was prepared by dissolving each coupler in a mixture of dibutyl phthalate and tricresyl 7 phosphate, dispersing sorbitan moclarate, funnel oil, and sodium dodecylbenzenesulfonate as dispersing emulsifiers, and adding the coupler to a gelatin solution. It is dispersed in a 0/w type.

As a coupler, (M-/9) magenta coupler, 2
-(2,4t-di-monoamylphenoxyacetamide)
-<t,l-dichloro-! -Methylphenol, α-(
comethylpenzoyl)-ace)-(2'-chloro-s
Three types of '-doderoxycarbonyl)anilides were used. Also, as an ultraviolet absorber, Tokko Sho 4tj-9!
For r, the one described in the publication was used. Furthermore, the emulsion contains 2, z-dichloro-6-hydroxy-/, 3. ,
! r-triazine sodium salt was added. The color thus produced was subjected to the following two-part process after exposure. (33°C processing) Processing corporation color development - bleach fixing - washing with water (running water/21/m2;
/tank) 3.5 minutes /, 1 minute 3 minutes Processing method B (invention) Color development - bleach fixing - stabilization processing (replenishment 0.217 m
2; 3.6 minutes /, 6 minutes 7 minutes 3 tanks countercurrent)
The processing liquid used in each step is as follows.

Color developer diethylene glycol 3 ml Potassium carbonate 23 g Sodium chloride θ,/g Sodium bromide
0.2g anhydrous sodium sulfite
2g hydroxylamine
2 g N-ethyl-N-β-methanesulfonamide ethyl-3-methyl-9-aminoaniline sulfate 4 tg water is added/l and the pH is adjusted to 10.o using sodium hydroxide.

Bleach-fix ammonium thiosulfate /,! ＜＜ , jg
Sodium metabisulfite /3.3g anhydrous sodium sulfite u, 7gBDTA ferric ammonium salt +rg Add water to make /l.

Pour the color developer with the above recipe into a container with a large opening.
~Fatigue liquid j left for 3 weeks and air foamed for 7 hours
Add 00cc and add water to make up to /l.

Stabilization treatment liquid acetone O/ccEDT
A2Na -2H20sg Compound E-/-2g Add water to make up to /l The sample thus treated was examined for stability over time as follows. That is, each sample is 4o'C, 2ochiR
After aging for 3 to 2 days under H conditions, the stain concentration was measured using a densitometer to evaluate the change in concentration (change in stain concentration). The results of changes in stain concentration are shown in Table 1.

According to the method of the present invention, as can be seen from Table 1, the increase in stain concentration was able to be significantly suppressed, even though the amount of liquid used was smaller, compared to the conventional method (processing A) in which washing was performed with running water. .

Silver halide color photographic light-sensitive materials containing a magenta dye-forming coupler represented by the general formula (R) have a significant amount of staining even in conventional processing, making it difficult to put them into practical use as commercial products.

However, when a stabilizer containing a compound of the present invention is combined with a magenta dye-forming coupler represented by general formula (I),
Surprisingly, the stain was significantly reduced, and we were able to bring it to a commercially viable level.

That is, a highly stable color photographic image was obtained by simply processing in a bath of aminopolycarboxylic acid and a chlorotriazine compound without washing with water after bleach-fixing.

Example 2 EDT A 2 used in the stabilization treatment bath of Example/
Sodium citrate/g/l and / , , 2-Bis(,2', 3/-
epoxyprepoxy) -propane 2
When the same procedure as in Example 1 was carried out using g/l, favorable results were obtained as in Example 2.

Example 3 The triazine compound in the stabilization bath of Example 9/, j-di-1sopropyl-
carbodiimide / , r g / ll
The same procedure was carried out by adding 100% of the total amount of alcohol, but the results were almost the same as those of Example 1.

In place of the (M-/ri) magenta coupler in Example/Example/(
A 2-equivalent magenta coupler of Mr.

When the thus obtained color photosensitive material was similarly processed using processing method A in Example 1 and subjected to forced aging for 7 days to0c<toqb, magentastin was noticeably generated, but with processing method B, the magentastin was approximately /2.

Furthermore, in processing method B, compound E-/
When 2 g/l of was added and treated in the same manner, the magentastin was reduced to about 3 to 4 tons compared to Processing Method A.

Example: Similar effects were obtained by using magenta coupler (M-/, 2) instead of magenta coupler (M-/) in Example 4'.

Example 6 /-Hydroxy-,2-N-r-(,2,4
t-di-t-amylphenoxybutyl) naphthamide is emulsified and mixed, and a green-sensitive silver iodobromide emulsion (silver iodide grams per mole) is emulsified with (M-+) as a magenta coupler. Yellow caprateite α-benzoyl-[cochloride!] −
A reversal color paper photographic material was prepared by emulsifying and mixing .alpha.-(dodecyloxycarbonyl)propyloxycarbonyl]acedoanilide and sequentially coating the resin coating on a single .xi. layer.

For emulsification of each coupler, diptylphthalate and tricresyl phosphate were used as coupler solvents, sorbitan monolaurate and sodium dodecylbenzenesulfonate were used as emulsifiers, and other K/-(p-nonylphenoxyditrioxy Sodium ethylene)butane-9-sulfonate and lauric acid ester of sucrose were added as coating aids.

Furthermore, a filter layer of yellow colloidal silver containing potassium iodide was placed between the shore-sensitive emulsion layer and the blue-sensitive emulsion layer in the sample, and di-t-amylhydroquinone was dispersed between the green-sensitive emulsion layer and the red-sensitive emulsion layer. An intermediate layer comprising gelatin contained therein and a protective layer mainly comprising gelatin are provided on the blue-sensitive emulsion layer.

This silver halide color photographic light-sensitive material was exposed to light according to the sensitometric method, and then processed at a temperature of 3♂0C using the following processing solution according to the processing steps (processing method A).

Processing step 1st development (black and white development) 3♂0C 7 minutes 30 seconds water washing 3♂00 2 minutes color development
310C 2 minutes water wash 3♂ 0C 30 seconds bleach-fix solution 3er0c 3 minutes water wash
3t 0c x minutes (3/sl/m2
: /tank) Stabilizing bath 3!0C/min Total 72 minutes [Processing liquid composition] First developer (black and white development) Sodium tetrapolyphosphate 3.0g Sodium hydrogen carbonate λ, jg/-Phenyl-3
-Pyrazolidone 0.4tJ-g
Anhydrous potassium sulfite 4♂7g hydroquinone to g potassium carbonate cosg sodium bromide
/, 41g potassium iodide (0.7%
) 3 ml diethylene glycol
0, Oml polyethylene glycol→<10θ j, add 0g water, add /l hydric soda (pH: 10.2), and boil.

Color developer Benzyl alcohol /2'rr/1 Sodium tetrapolyphosphate 3.0g Anhydrous sodium sulfite 7.5g Potassium carbonate
3 pieces, 0g potassium bromide
0.3g potassium iodide (0,/ti)
Ta θ, Om/1 caustic soda
2.3g3-methyl-q-amino-N-ethyl-N-β-methanesulfonamidoethylaniline //・θgKodak RA-/θ, +2g ethylene glycol Add 20ml water
/1 (pH: /θ, 7) Bleach-fix solution Bisthiourea 3.0g Aqueous ammonia (2♂H) 30.0ml Ethylenediaminetetraacetate iron (I [I) ammonium / water salt gjg Ethylenediaminetetraacetate cosodium co Water salt 2g anhydrous sodium sulfite 10g ammonium thiosulfate / 40.0ml glacial acetic acid
Add 5.9ml water
/1 (pH: d, 7) Stable liquid zinc sulfate crystals 7g tartaric acid
Add 7g sodium metaborate/4tg water
/1 (pH:, r, θ) In order to compare with the above treatment method A, the running water of the final washing of the above treatment was lowered to /, 017 m2, and methanol, 2 ml/l, p-Phenylenebis was added to the stabilizing solution.
(di (/-aziridinyl)phosph
onate]/, sg/l (processing method B
).

■These processed sensitive materials? Under the condition of θ'Cdry,■
606C under 170% RH condition, under fluorescent light (room temperature) for 7 days -? A daily aging test was conducted to examine the fading of color images.

Visually judge the obtained results and select treatment method A and treatment method B.
compared with. The results are shown in Table 2.

Processing method B (the present invention) was able to significantly suppress the increase in maginta stain (M stain) compared to conventional processing companies, and was able to maintain the same level of fading in color images.

Example 7 In place of the stabilizing bath in Example B, /, j-di (methane
esulfonoxy) -b'utane / ,
r g /12 methanol 3ml//l, z% solution of polyethylene oxide with a molecular weight of about 30.0 2ml//l
Although a /73 stabilizing bath was used, almost the same performance as in Example j was obtained.

Example 1 In the stabilization treatment solution of Example/, aziridyl compound D
When the same procedure as in Example/ was carried out using a treatment solution containing zg/l of each of -/ and D-B, substantially the same results as in Example/ were obtained.

In place of the stabilizing bath in Processing Method B of Example/Example/
:/When the same procedure as in Example/ was carried out using a stabilizing bath in a tank, substantially the same results as in Example/ were obtained.

Example 10 In place of the stabilizing treatment solution used in Treatment Method B of Example 1, the following procedure was carried out in the same manner, and favorable results were obtained.

Washing liquid compound E −/2 g/
1 Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment Date: 77/1930, H, 98 Kay 1, Indication of the Case: Showa A2, Patent Application No. rtoyi No. 2, Title of the Invention: Processing of color photographic light-sensitive materials Method 3: Relationship with the case of the person making the amendment Patent applicant Address: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Contact address: 2-chome, Nishiazabu, Minato-ku, Tokyo 106 [I26-30-4, Subject of amendment: Details of the invention in the description The description in Column 5 of "Detailed Explanation of the Invention" and "Detailed Explanation of the Invention" in the Description of Contents of the Amendment is amended as follows.

l) After the structural formula (M-J4) on page ≠r, “(M-37
) 6H13 (M-3, r) Fully insert.

K) 4th! Insert a separate sheet after the 7th line of the page.

Attachment Example-// A multilayer photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene.

Four coating solutions were prepared as follows.

(Preparation of first layer coating solution) Yellow coupler (ExY-/)/ri, /p and color image stabilizer (("pd-/)≠, HiroPK ethyl acetate yb2
7.2cc and high boiling point solvent (Solv-/)? 7.7 CC (%, Oy) was added and dissolved, and this solution was diluted with 10
4 Sodium dodecylbenzenesulfonate! It was emulsified and dispersed in a 1Qt4 gelatin aqueous solution irzσ containing cc'6.

This emulsified dispersion and emulsions EM 7 and EM! A first layer coating solution was prepared by mixing and dissolving the gelatin Df and adjusting the gelatin Df to have the following composition. Coating solutions for the second to seventh layers were also prepared in the same manner as the single-layer coating solution. The gelatin hardening agent for each layer is /-oxy-3,! -dichloro5-) riazine sodium salt was used.

(Cpd-co) was used as the thickener.

(Layer structure) The composition of each layer is shown below. The numbers are coated f(ri/FF12
). The silver halide emulsion is expressed as a silver conversion coating.

Support polyethylene laminate paper [white pigment (TiOz) and background dye on polyethylene on the single layer side? include. ] First layer (blue-sensitive layer) Monodisperse silver chlorobromide emulsion (EM7) spectrally sensitized with a sensitizing dye (ExS-/) ...
Monodisperse silver chlorobromide emulsion (EM, r) spectrally sensitized with o, it sensitizing dye (ExS-/)...・・・・・・・・・・・・・・・・・・
・・・Yu・・・・・・・・・・・・0. /! gelatin························
・・・・・・・・・・・・・・・・・・／, fj yellow coupler (ExY-/)・・・・・・・・・o, r
J color image stabilizer (Cpd-J)・・・・・・・・・・・・
・・・・・・・・・0. / Solvent (Solv-/)...
・・・・・・・・・・・・・・・・・・・・・・・・
...0.31 Second layer (color mixing prevention layer) Gelatin... River...
・・・・・・・・・・・・・・・・・・・O+Tata color mixture prevention agent (
Cpd-j)・・・・・・・・・・・・・・・・・・
・・o, or third layer (green sensitivity l-) Monodisperse silver chlorobromide emulsion (EM) spectrally sensitized with sensitizing dye (ExS-2, 3)...・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0. / Monodispersed silver chlorobromide emulsion (EMzO) spectrally sensitized with sensitizing dyes (ExS-2, 3) ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・O, Kohiro Gelatin・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・1.2μ Magenta coupler (M-/ri)・・・・・・・・・・・・0.32
Color image stabilizer (Cpd-≠)・・・・・・・・・・・・・
River...0.2! Color image stabilizer (Cpd-j)...
・・・・・・・・・・・・・・・・・・O, ta solvent (
Solv-2)・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0. λ! Fourth layer (ultraviolet absorption layer) Gelatin・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・／, 40 UV absorber (Cpd-J/Cpd-7/Cpd-rwg
J/co/l: weight ratio) - River - - 0,70 Wet color inhibitor (Cpd-2)...
...0.0! Solvent (Solv J)
・・・・・・・・・・・・・・・・・・・・・・・・0.
4IJ 5th N (red sensitive layer) Monodisperse silver chlorobromide emulsion (EM//) spectrally sensitized with a sensitizing dye (ExS-Hiroshi, j)...・・・・・・
・・・・・・・・・・・・・・・・・・ 0.07 sensitizing dye (ExS- monodisperse silver chlorobromide emulsion spectrally sensitized (EM/J)...・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・o, it gelatin
・・・・・・・・・・・・φ・・・・・・・・・・・・・・・・
・・・・・・・・・0. FJ cyan coupler (ExC-
/)・・・・・・・・・・・・・・・／、44 Cyan coupler (ExC-J)・・・・・・・・・・・・・・・・・・
・/, 144 color image stabilizer (Cpd-7/Cpd-t/
('pd-10=3/reference/J: weight ratio)...
・・0.17 Polymer for dispersion (Cpd-//)・・・・
・・・・・・・・・0. /Solvent (SOIV-/)...
・・・・・・・・・・・・・・・・・・・・・・・・
・・Oo－〇Sixth layer (ultraviolet absorption layer) Gelatin ・・・・・・・・・・・・・Fist-Fist・・・・・・・・・・
......0. ! UV absorber (Cpd-6/Cp
d-1/Cpd-#) Wealth//! /J”, weight ratio)...
......O, co/solvent (Solv-≠) ...
・・・・・・・・・・・・・・・・River・・・・・・o, o
r Seventh layer (protective layer) Gelatin・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・／、JJ Acrylic modified copolymer of polyvinyl alcohol (modified Fll/71)・・・・・・0. /
7 Liquid paraffin・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・0.01 but at this time, as the irradiation prevention dye, (Cpd-
/Cpd-/J')t- was used.

Further, in each layer, as an emulsifying dispersant and a coating aid, Alkanol
? Using. As a stabilizer for silver halide, ((”pd
- / reference, /rit - were used.

Details of the emulsion used are as follows.

Emulsion name Shape Particle size (JA Br included 1) (motl)
Fluctuation wave tl”EM 7 Cube /, /
/, 0 0.10EM 1 cube
o, r l, o o, i.

EM ta cube O, da j /, no!
0.02EM10 Cube 0. J da
/,j O,0riEM// Cube
0.4! j /, j O, 0ri EM
/J cube 0. J4A /, t
The structural formula of the compound used in 0110 is as follows.

ExY-/ ('1 EXC-/ a ■Six S-/ 5O3HN(C2H5)3 ExS-λ ExS-J ExS-≠ ExS-j Cpd-/ cpd-ko cpct-jCpd-≠ し4MgLtJ Cpd-r Cpd -IO Cpd-// (nx/DO~1000) Cpd-/koCpd-/J Cpd-/Hiroshi CDd-/!5olv-/
Dibutyl phthalate 5olv-2 trioctyl phosphate 5ojv'
) Rifnyl phosphate 5olv-ttricresyl phosphate After exposing the above light-sensitive material to light,
Continuous processing (running test) was performed using the processing machine until the tank capacity of the colored monk was replenished by one time by the following processing workers & JC.

Treatment pd corporation (comparative example) Treatment process Temperature IL Replenishment amount Tank capacity Color Hi image J j 'C17 seconds /l/ml /
Bleach and fix 7 30~JA'C≠j seconds /l/yd
/71 Rinse ■ 30~37°CJt7 seconds -/a
t rinse ■ 30~37°C 30 seconds -ion rinse ■ 30~37°C 3D seconds JAOml /I
t Drying 7ONI00C 40 seconds Photosensitive material/m2 (3-tank countercurrent flow method from rinsing ■ to ■) The composition of each processing solution is as follows.

Water 100td l00
td ethylenediamine-N, N.

N,N-tetramethylenephosphonic acid i,sp t,rtatriethylenediamine (/.

Dah azabicyclo [ko.

1, Co]octane) j, O9l j, 09 Sodium chloride /, 4<1 - Potassium carbonate
N-ethyl-N-(β
-Methanesulfonamidoethyl)-3-methyl-Hiroshi- Aminoaniline sulfate! , 0ta 7. θtadiethylhydroxylamine ≠, 2pg
, OP Fluorescent brightener (4L, da'-diaminostilbene type) , Op J, JP Add water 1000 td 1000 scrap lp H
(ko r'c) 10. or io, a
T-mill fixing solution (tank solution and refill solution are the same) water
≠θ0j! /Ammonium thiosulfate (70th section) 100g1 Sodium sulfite /79 Iron ethylenediaminetetraacetate (DI) Ammonium jjpEthylenediaminetetraacetic acid disodiumjP Lium ammonium bromide Daθriglacial acetic acid
Tata water gold plus
1ooo, 1pH (-2yo'C)
z, a.

Rinse solution (tank solution and refill solution are the same) Ion exchange water (calcium, magnesium each 3 ppm)
Below) Treatment method B (this invention) Treatment process Temperature Time Replenishment amount Tank capacity color current P 360 (: Guj seconds l/mt
/'71 bleach fixing 30~3 Otsu0C Hiro! seconds //,
/ml /7t rinse ■ 30-37°C 30 seconds
-10t rinse ■ 30~J70C30 seconds -1
0tlJyx ■ 30~37°C 30 seconds J&0t
ttl 101 drying 7o-rooc to
Per second light-sensitive material/m2 (3-tank countercurrent system from rinsing ■ to ■) The composition of the processing solution used for the processing was the same as that of the processing corporation for the color developer and bleach-fix solution.

The composition of the rinse liquid is as follows.

Rinse solution (tank solution and refill solution are the same) Compound E-/2y Ion exchange water (calcium, magnesium each JpI m or less)? In addition, pH to /l (,2J-'C) 7.0 Regarding the photographic material subjected to the above treatment, fruitfulness = Example 1
The stability over time was investigated in the same manner. The results are shown in Table 3.

As is clear from the 43 vortices, in the case of the processing method of the present invention, a preferable image was obtained in which the increase in stain density was significantly suppressed compared to the comparative processing method.

Example 1 A multilayer photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with copolyethylene.

The coating solution was prepared as follows.

(Preparation of first layer coating solution) Yellow coupler (ExY-/) and (ExY-2)
10 each. -y, de, IP and color image stability (Cpd-
/) ≠, ethyl acetate 27.2 countries and high boiling point solvent (5olv-/) 7,7 CC (#.

ay)'r: Add and dissolve this solution t-104 sodium dodecylbenzenesulfonate! r Cc! r including tr
It was emulsified and dispersed in 704 gelatin aqueous solution/rzCc. This emulsified dispersion and emulsions EM/and EllilJ were completely mixed and dissolved, and the gelatin concentration was adjusted to have the following composition to prepare a first layer fIL. Coating liquids for the second to seventh layer phases were also prepared v4 in the same manner as the first layer coating liquid.

As the gelatin hardening agent for each layer, /-oxy-3°j-dichloro-3-triazine sodium salt was used.

Moreover, (Cpd-, 2) was used as a thickener.

(if3 configuration) The composition of each layer is shown below. The numbers are coating t(y/m2
). The silver chloride emulsion exhibits a silver stroke pattern.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiOz) and a bluish dye. ] First layer (blue-sensitive layer) Monodisperse silver chlorobromide emulsion (EM co) spectrally sensitized with a sensitizing dye (ExS-/)...0. /J gelatin
-,,,-1-0/, ! r A yellow coupler (ExY-/) 0. Hiro≠Yellow coupler (ExY-ko)・・・・・・・・・0.
Tricolor image stabilizer (Cpd-/) ・・・・・・・
・・0. Solvent (Solv-/)...
......0. Jj second layer (color mixing prevention layer) Gelatin ・・・・・・・・・0.
Polygonum color mixing prevention agent (Cpd-J) ・・・・・・
... o, or third layer (edge-sensitive layer) Monodisperse silver chlorobromide emulsion (EM 3) spectrally sensitized with a sensitizing dye (ExS-2, j) ...... 01
Monodisperse silver chlorobromide emulsion spectrally sensitized with aS sensitizing dye (ExS-2,j) (EM reference)... River... 0. /
/ Gelatin ...... Meeting... /
, 10 magenta coupler (M-/ri) ・・・・・・
...0. J-color image stabilizer (Cpd-≠)...
...0.20 color image stabilizer (Cpd-7)
・・・・・・・・・0.0 Color image stabilizer (Cpd
-4) ......0.03 solvent (S
olv-2) ・・・・・・・・・0. /
Co-solvent (So IV-J) ・---
---・-0, 2! Fourth layer (purple foreshadow absorption layer) Gelatin ・・・・・・・・・／
, 1.0 ultraviolet absorber (Cpd-7/Cpd-1/Cp
d-2=3/co/6:11Lt ratio) ・・・・・・0
．． 70 color mixing prevention agent (Cpd-10)...
...o, or solvent (So 1v-4c)
-・-...-0, 27 Fifth M (red-sensitive layer) Monodisperse silver chlorobromide emulsion (E M j ) spectrally sensitized with a sensitizing dye (ExS-da, /j) °-- ------
-- Monodisperse silver chlorobromide emulsion (EM-4) spectrally sensitized with 0.'' sensitizing dye (ExS-da, j) ・・・・・・・・・o
, it gelatin...
・・0. Taco cyan coupler (ExC-/)...
...0.32 color image stabilizer CCDd-1/Cp
d-ta/Cpd-ta=J/a/2:Ill ratio)...
・-・・・0, / 7 dispersion polymer (Cpd-/
/) ・・・・・・・・・0. λr solvent (So I
V −J ) −°−−−−− o−J
.

6th ft (ultraviolet absorption layer) Gelatin ・・・・・・・・・O0
! ≠Ultraviolet absorber (Cpd/-7/Cpd-ta/Cpd
−/2=//j/3: weight ratio)・・・・・・・・・0,
2/Soluka (So 1v-2) -・-・・
・-・-o, or Seventh layer (protective layer) Gelatin ・・・・・・・・・7.
33 Acrylic modified copolymer of polyvinyl alcohol (modified [77%)] ...0. /
7 Rough-in 9 Rough-in ・・・・・・・・・
At this time, (Cpd-/3.Cpd-/≠)t- was used as the irradiation preventing dye.

Each layer contains an emulsifying dispersant, coating aids such as alkanol B (T)uponHt), sodium alkylbenzene sulfonate, succinate ester and Marrefa.
cx F-/20 (manufactured by Dainippon Ink Co., Ltd.) 'Ik: Used. Silver halide stabilizer and [7te(Cpd-/!
, /1) was used.

Details of the emulsion used are as follows.

Emulsion base shape particle size (A pr@t<moL4)
Coefficient of variation EM/cube/, (7to
o, orEM, 2 Cube 0,71 10
θ, 07EMJ Cube o, s
r3 o,oyEM4' cube 0
．． 'I l'j O,10E M
j cube 0. ! 73 0
, 0ri EMJ cube 0. II 73
0,10 The structural formula of the compound used is as follows.

ExY-/α ExY--2: ExS- same as ExY-/ of Example/l
/ 5O3HN(C2H5)3 Ex S-2 5OsNH(C2H5)3 ExS-j: Same as ExS--2 in Example //
S 4'', same ExS-4' as Example/l
j: F of implementation 913//, same Cpd-/ as xs-j:
Same Cpd-coni Example/l as Cpd-/ of Example//
Same Cpd-J as Cpd-co of Example //Cpd-
Cpd-μ toward j: same c as Cpd-μ on the implementation layer side/
pct-j 2H5 Cpd-7: Example // cpd-JK same cpct-
r: Same as Cpd-7 of Example // Cpd- Data: Same as cpct-r of Example II Cpd-10: Cod-YK of Example II Same Cpd-//: Example/ /(DCo
Cpd-/2 same as d-//: C'E of Example 11)
Same as d-10 5olv-/ Dibutyl phthalate 5olv-J Tricresyl phosphate 5olv-
3 trioctyl phosphate 5olv-μ trinonyl phosphate Cpd-/J Cpd-/gCpd-/! : IWI same Cpd-/4t on the Example layer side Cpd-/A : After imagewise exposure of the above photosensitive material same as Cpd-/z of Example 1/, using Fuji Color Paper Processing Machine PP
Using too, continuous processing (running test) is performed by refilling twice the color development tank capacity in the following processing steps.
) t” went.

Force'y -Jjl (jfi JroC1 minute 170 seconds 2POxl /7tlA White NN 1z0c
go second 1ro-trinsu ■ JJ ~J!
'C-2゜sec -44t rinse (wa 33~J!
0CJO seconds - dat rinse (J:3:+jJ~J!0
C 20 seconds 36≠ Dry Gohiro 70~lO°C10
Second tatami photosensitive material/? The composition of each treatment liquid is as follows.

Color developer tank liquid replenisher water
100yd 1r00td
Diethylenetriaminepentaacetic acid /, Op /, Op nitrilotriacetic acid co, op co, 0Pl-hydroxyethylidene-/, /-diphosphonic acid ,, z, op co, o1p Benzyl alcohol /Ad Coco-diethylene glycol 10101NI10 Sodium sulfite -0092,j potassium dibromide
o, zp - potassium carbonate JO
p JailN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl Kazuhiro-amine aniline sulfate #salt r, zta 7.3tahydroxylamine sulfate λ, OP Ko,! ! Fluorescent brightener (IT EX≠ Add water 100 Ddj 1000 pH (Koj'C) 10.Ko io3゜ Bleach waste solution Tank solution Replenishment solution water
3〇〇M ≠00d Ammonium thiosulfate (70) l0rd 9! rt
d Ammonium sulfite 2nd P 3.29 Iron(III) ethylenediaminetetraacetate Ammonium 309 ≠op Disodium ethylenediaminetetraacetate! Add Ta lO Risuke / 000 ml / 000 M
eρ1-i(2j'c) bu,to
t, o.

Rinse solution ionized or exchanged water (calcium, magnesium each jppl
n or less) Processing method B (present invention) Color development 3r0Ct%ao seconds -ta01111
/7t6;' Self-sufficiency N 3j ' CA 0 seconds /ro, g Tatrinsu ■ 33~Jj'C
20 seconds -$t rinse ■ 33~3!0C20 seconds
-Hirot rinse ■ 33~Jj0C20 seconds 34/l
J! Dry ≠ 70−♂o0c to
A 3-tank countercurrent flow system was adopted in which the flow rate per second ax photosensitive material/m2 (rinsing O)→■. ) The composition of the processing solution used in the processing was the same as that of the processing corporation for the color developer and bleach-fix solution. The composition of the rinse liquid is as follows.

Rinse solution (tank solution and replenishment solution are the same) Compound E-729 Add all ion exchange water (calcium, magnesium each below jppm) and adjust the pH to /l (
, 2j'C) 7-'The above processing was performed. Regarding photographic light-sensitive materials, Example 1
The stability over time was investigated in the same manner. The results are shown in Table ≠.

As is clear from Table 1, in the case of the processing method of the present invention, favorable images were obtained in which the increase in stain density was significantly suppressed compared to the comparative processing method.

In addition, as a magenta coupler used in the third layer of the multilayer photographic paper produced this time, K, M-37, and M-
A similar experiment was conducted using 3ryz, and favorable results were obtained.

Claims (1)

[Claims] (1) A silver halide color photographic light-sensitive material having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support and containing an aromatic primary amine compound. In the method of desilvering after color development, the green-sensitive silver halide emulsion layer is prepared by the following general formula (
I) contains a magenta dye-forming coupler represented by
And after color development, epoxy compound, aziridine compound,
It is characterized by treatment with a treatment liquid containing at least one compound selected from the group consisting of an acryloyl compound, a vinylsulfonyl compound, a triazine compound, an isoxazolium compound, a sulfonic acid ester compound, a carbodiimide compound, a maleimide compound, and an isocyanate compound. A method for processing color photographic materials. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a coupling with an oxidized aromatic primary amine developer. Represents a group that can be separated by reaction. Za, Zb
and Zc is methine, substituted methine, =N- or -NH
-, one of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. Zb-Zc
An aromatic ring may be fused there. It also includes the case where R^1 or X forms a dimer or more multimer. Also,
When Za, Zb or Zc is a substituted methine, it also includes the case where the substituted methine forms a dimer or more multimer. )