JPH03194552A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To suppress variation of sensitivity fog even at the time of using a developing solution regenerated with an anion exchange resin and to reduce deterioration of the ion exchange resin by using a color photographic sensitive material containing an emulsion high in silver chloride content and having a coated silver amount of a specified value or less. CONSTITUTION:The color photographic sensitive material has at least one emulsion layer containing >=80 mol% silver chloride, and a coated silver amout is regulated to <=0.6 g/m<2>. This photosensitive material is processed with a color developing solution regenerated by bringing it into contact with the ion exchange resin. If the coated silver amount exceeds the above-mentioned limit and regeneration of the developing solution is continued for a long period, the stabilities of sensitivity and the minimum density are lowered, deterioration of exchange resin due to extracts is made remarkable. If the coated silver amount becomes below a prescribed value, such as 0.1 g/m<2>, sufficient image density becomes unable to be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and in particular reduces the amount of processing waste liquid by reusing color developing solution. The present invention relates to a treatment method that causes less deterioration in the performance of an anion exchanger and provides stable treatment performance.

(Prior Art) Since environmental pollution caused by industrial wastewater has become a problem in recent years, various efforts have been made to reduce the amount of wastewater in the processing of photographic materials in order to reduce the pollution load. Among these, reducing the amount of color developer discharged, which has a large BOD (biochemical oxygen demand) and C0D (chemical oxygen demand) load, has become the most important issue. To date, roughly two methods have been proposed to address this problem. One is a method called a low replenishment processing method, which reduces the amount of color developer refilled while preventing a decrease in color development activity by increasing the color development processing temperature. This is a method called a regeneration processing method in which accumulated halogen is removed from the solution to restore development activity and then the solution is reused.

The former compensates for the decrease in developer activity due to the accumulation of halogen ions, such as iodine ions, bromine ions, and chloride ions released from the photosensitive material during development, by increasing the temperature, pH, and color developing agent. Although it is simple, there are limits to compensation, and it is difficult to drastically reduce the amount of replenishment and get close to zero emissions.

The latter regeneration treatment method is described in Journal of the SMPTE Vol. 65, 4 as a means of removing 4 tons of accumulated halogen.
The anion exchange resin method described on pages 78 to 484 (May issue, 1956) and JP-A-119-1989
There is an electrodialysis method described in No. 934, and although each method has the disadvantage of requiring special equipment, research has been carried out as a method that can reduce the discharge of color developer.

In particular, methods using anion exchange resins are less effective than electrodialysis.
Because the device cost is low, it is relatively widely used, and its use is also described in Journal of the Applied Photographic Engineering, Vol. 5, N.
α4. Pages 216 to 219 (1979, Autumn issue) describes a method for preventing performance deterioration of anion exchange resin by treating a color developer pretreated with an adsorbent with an anion exchange resin, and the journal Improvement research is underway, including the development of a miniaturized system that uses anion exchange resin, as described in Of Image Technology, Vol. 13, Nα3.85-89 (June 1987 issue). It is coming.

(Problem to be Solved by the Invention) However, when a color developer is repeatedly reused using an anion exchange resin, oxidative decomposition products of the color developer composition and elution from silver halide color photographic light-sensitive materials occur. It has been found that these substances accumulate in the color developer and change the finishing performance of silver halide color photographic light-sensitive materials, and that the anion exchange resin deteriorates significantly due to the eluates, making long-term use difficult.

For this reason, it is difficult to continue reusing it for a long period of time, and some of the color developer must be replaced with fresh color developer at regular intervals, or some of the used color developer must be discarded and a certain amount of new color developer must be constantly replenished. This required complicated management, such as adjusting the pH and composition of the color developer in order to reuse it and compensate for changes in performance.

Therefore, an object of the present invention is to suppress fluctuations in sensitivity fog and reduce deterioration of the anion exchanger in a method of repeatedly reusing (hereinafter referred to as regeneration) a color developer using an anion exchanger. The object of the present invention is to provide a method for processing silver halide color photographic materials that does not require complicated management (substantially zero discharge of color developer is possible).

(Means for solving problems) The above object was achieved by the following method.

That is, in a method of processing a silver halide color photographic light-sensitive material having at least one layer of a silver halide emulsion containing 80 mol % or more of silver chloride with a color developer, the silver halide color photographic light-sensitive material The coating silver I is 0.
6 g/rrf or less, and the color developer used for processing is brought into contact with an anion exchanger and then reused for processing the silver halide color photographic light-sensitive material. This was achieved using the following processing method.

The amount of coated silver in the silver halide color photographic light-sensitive material used in the present invention is 0.6 g/IT or less, more preferably 0.57 g/IT? per 1 rrr of the light-sensitive material. Less than 0.10g/
Should be at least m2. If the amount of coated silver exceeds 0.60 g/m2, the stability of photographic performance, which is the objective of the present invention, will deteriorate, especially when the color developer is continuously regenerated with an anion exchanger for a long period of time. Sensitivity and stability at the lowest concentration decrease, and deterioration of the anion exchanger due to eluates becomes significant. On the other hand, if it is less than 0.1 g/-, sufficient image density cannot be obtained, which is undesirable.

In an embodiment of the light-sensitive material of the present invention, a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer are formed on a support, and it is preferable that the red-sensitive layer is the uppermost layer. Preferably, the layer is the lowest layer. The amount of silver in the red-sensitive layer, which is the top layer, is o
, preferably 25g/m2 or less, 0.20g/m2 or less
．． More preferably 10 g/endurance or more. If the amount of silver in the top layer is too large, the desilvering performance will deteriorate, which is undesirable, and yellow color turbidity will likely occur in the bottom layer.

In at least one layer of the silver halide color photographic light-sensitive material used in the present invention, silver halide contains 80%
It contains silver chloride in an amount of mol % or more, preferably 95 mol % or more, more preferably 96 to 99.5%.

Furthermore, preferably in the multicolor photographic material,
The color sensitivity of the entire layer is such that the silver chloride content is 80 mol% or more, preferably 95 mol% or more.

Next, a method for regenerating a color developer using an anion exchanger according to the present invention will be described.

The present invention is applied to a method of continuously processing a silver halide color photographic material while adding a replenisher to a color developer.

Usually, the overflow from the image tank is collected and used.

As the anion exchanger, various anion exchange resins,
Although anion exchange latex and the like are used, it is preferable to use a strongly basic anion exchange resin having a quaternary ammonium salt type exchange group because it has a particularly large exchange capacity for halogen ions.

These anion exchange resins have a styrene-divinylbenzene copolymer as a base, and preferably have a divinylbenzene content of 3 to 12%.

The quaternary ammonium salt type exchange group will be further explained.

The following shows the basic structure of anion exchange resin.

(Structural formula A) →Color developer replenisher, that is, a used color developer is subjected to the above treatment and reused as a replenisher. The used color developing solution is color developed by supplying a replenisher.

Examples include trimethylammonium, tributylammonium, trihexylammonium, and trioctylammonium types.

Among these, trimethylammonium type resin is particularly preferred because it is easily available as a commercial product and in the structure of the present invention.
Amberlite IRA-400, I manufactured by & Haas
RA-410, Revatirad M600 manufactured by Bayer. Diaion 5A-10A, PA-41 manufactured by Mitsubishi Chemical Corporation
I can give 8th grade.

The counter ion of the ion exchange group can be exchanged into various types by contacting it with a solution of the salt of the ion, but when it is exchanged with the halogen ion in the color developer and eluted into the solution, processing performance may be affected. From this point of view, specific examples include carbonate ion, bicarbonate ion, hydroxide ion, sulfate ion, nitrate ion, phosphate ion, hydrogen phosphate ion, oxalate ion, etc. However, carbonate ion, bicarbonate ion, hydroxide ion,
Phosphate ions are preferred.

To retain these counterions, use sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, sodium phosphate, potassium phosphate solutions and resins at concentrations of 0.1N to 4N. bring into contact with.

Any method may be used to bring the anion exchange resin containing counterions into contact with the used color developer, but from the viewpoint of ease of operation and efficiency of ion exchange, it is preferable to A color developer is passed through the packed column,
A method of continuous contact is preferred. In this case, the flow rate of the color developer is preferably in the range of 0.3 to 10 times the volume of the resin layer per hour, particularly 0.5 to 5 times the volume of the resin layer per hour, in order to increase the efficiency of the ion exchange reaction. Furthermore, 0.5 to 3 times is preferable. After processing with an anion exchange resin, the color developer is supplemented with the corresponding component to compensate for the consumption of the component due to processing and the decrease in component due to adsorption to the anion exchange resin. The amount of component to be supplemented can be ascertained by chemical analytical means.

Ingredients that normally need to be supplemented include color developing agents, sulfites, preservatives such as hydroxylamines, and if necessary, chelating agents, carbonates, phosphates, potassium hydroxide, sodium hydroxide, etc. Replenish buffering agent and alkaline agent.

The color developing replenisher prepared after replenishing these components contains each component at a higher concentration than the concentration that should be maintained in the color developing tank, and the concentration ratio of the replenisher to that in the color developing tank is Usually 1.0 to 2.0. This ratio varies depending on the set replenishment amount, and increases as the replenishment amount is reduced. Replenishment amount is 1 per rrr of photosensitive material
00 m1 or more, this ratio is 1. The range of 0 to 1.5 is preferred. The same applies to the pH, and the pH within the color developing tank is 0. Normally, the value is 1 to 1.0 higher, and the relationship with the replenishment amount is the same as above.

In the recycling process carried out in the present invention, when the photosensitive material is a print material such as color paper, the replenishment amount of the color developer is 50 ml to 300 ml per rrr of the photosensitive material.
mI! Preferably it is 100 ml to 250 ml, most preferably 130 ml to 220 yd. The larger the amount of replenishment, the easier it is to stabilize the performance, but conversely the frequency of regeneration processing increases, so the above-mentioned preferred range is set as a range that provides an appropriate balance between the two.

In the pre-process of contact treatment between the anion exchange resin and the color developer described above, Journal of Applied Photographic Engineering Vol. 5, NcL4 (197
Providing the contact treatment step between the adsorbent and the color developer as described on pages 216 to 219 (Autumn issue, 9th issue) is a preferred embodiment because it further enhances the effect of the present invention of reducing sensitivity fluctuations.

As an adsorbent that can be used in the present invention, JP-A-53-132
In addition to the phenol formaldehyde type adsorptive resin, activated carbon, and surface-modified activated carbon described in No. 343, Mitsubishi Chemical Corporation ■
Published by Diamond Aeon Manual (n) (1985,
Examples include polystyrene-type adsorptive resins described on pages 64 to 66 (8th edition).

In the present invention, the anion exchange resin whose exchange capacity has decreased is recycled. The regeneration treatment of anion exchange resin can be carried out by known methods, such as Mitsubishi Chemical Industries (Diaion Manual (1) published by Kiki (1986, 14th edition)).
Examples include the operating method described on pages 19 to 21.

The liquid used for regenerating the anion exchange resin can be the same as that used for retaining the preferred counter ions described above.

However, in order to increase the regeneration efficiency, for example, a sodium chloride solution is used to elute the iodine ions and bromine ions collected on the resin, and then a solution of sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, etc. is used to elute the preferred counter ions. It is also possible to carry out processing for exchanging it.

Through the process described above, the accumulated halogen ions in the color developer are removed, and the developing activity is restored by replenishing the consumable components. oxides and decomposition products of preservatives such as hydroxylamine or chelating agents such as aminopolyphosphonic acid and aminopolycarboxylic acid, anti-irradiation dyes eluted from silver halide color photographic materials, and color enhancers. A wide variety of components such as dye-sensitive dyes, surfactants, antifoggants, etc. are not removed or are only removed unreliably, and accumulate in the color developer each time reproduction is repeated. Moreover, the accumulation of these components affects the degree of fatigue of the anion exchange resin, the color developer flow rate,
It varies depending on the method of regenerating the anion exchange resin and the presence or absence of an adsorbent in the previous process, and causes variations in sensitivity and fog as final photographic performance in color development processing.

Furthermore, the degree of fatigue of the anion exchange resin is greatly influenced by the manner in which the eluate accumulates. The present inventors have found that these changes in photographic performance and, in particular, the life of the anion-exchange resin are significant when the silver coating amount is 0°60 g/d or less in a photosensitive material having an emulsion containing 80 mol% or more of silver chloride. We have discovered that the use of a certain photosensitive material can greatly improve this.

Color photographic materials used in the present invention and
The processing liquid will be explained in detail.

The color photographic light-sensitive material of the present invention can be constructed by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support. In general color photographic paper, the layers are usually coated on the support in the above order, but they may be applied in a different order. Furthermore, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. These photosensitive emulsion layers contain a silver halide emulsion sensitive to each wavelength range, and dyes that are complementary colors to the sensitizing light - yellow for blue, magenta for green, and cyan for red.
By containing a so-called color coupler that forms a color, subtractive color reproduction can be performed. However, the coloring hues of the photosensitive layer and the coupler may not correspond as described above.

As the silver halide emulsion used in the present invention, one consisting of silver chlorobromide or silver chloride that does not substantially contain silver iodide can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same among the grains, but if an emulsion having the same halogen composition among the grains is used, it is easy to make the properties of each grain uniform. In addition, regarding the halogen composition distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grain, and grains with a core inside the silver halide grain and a shell surrounding it. (shell) [-layer or multiple layers] Particles with a so-called layered structure in which the halogen composition is different, or
Particles with a structure that has parts with different halogen compositions in a non-layered manner inside or on the particle surface (if on the particle surface, parts with different compositions are joined on the edge, corner, or surface of the particle) are appropriately selected and used. be able to. In order to obtain high sensitivity, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the above structure, the boundaries between the parts that differ in halogen composition are
It may be a clear boundary, or it may be an unclear boundary due to the formation of mixed crystals due to compositional differences (or it may be one that does not actively have a continuous structural change).

Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide/silver chloride ratio can be used in combination. Although this ratio can vary widely depending on the purpose, a silver chloride ratio of 2% or more is preferably used.

Furthermore, so-called high-silver chloride emulsions having a high silver chloride content are preferably used in light-sensitive materials suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more,
More preferably 95 mol% or more.

Such a high silver chloride emulsion preferably has a structure in which the silver bromide localized phase is present inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described above. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, and more preferably exceeds 20 mol%. These localized phases can be located inside the grain, or on the edge, corner, or surface of the grain surface, but one preferred example is one in which it is epitaxially grown on a part of the corner of the grain.

On the other hand, in order to minimize the decrease in sensitivity when a photosensitive material is subjected to pressure, even in high silver chloride emulsions with a silver chloride content of 90 mol% or more, grains with a uniform structure with a small distribution of halogen composition within the grains are used. It is also preferable to use

Furthermore, it is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of replenishment of the development processing solution.

In such cases, the silver chloride content is between 9i mol% and 10
Emulsions of almost pure silver chloride, such as 0 mol %, are also preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken) is 0. 1μ to 2μ is preferable.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%.
Hereinafter, a so-called monodisperse material having a content of 15% or less is preferable. At this time, in order to obtain a wide latitude, it is preferable to blend the above-mentioned monodispersed emulsions in the same layer or to apply multilayer coating.

The shape of silver halide grains contained in photographic emulsions is regular (cubic, tetradecahedral, or octahedral).
lar), irregular crystal shapes such as spherical or plate-like, or a combination of these shapes can be used. Moreover, it may be made of a mixture of crystals having various crystal forms.

In the present invention, among these particles, it is preferable to contain particles having the above-mentioned regular crystal shape in an amount of 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition to these, the average aspect ratio (yen equivalent diameter/
Emulsions in which the projected area of tabular grains having a thickness of 5 or more, preferably 8 or more, exceeds 50% of the total grains can also be preferably used.

Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the process of emulsion grain formation or physical ripening.

Examples of compounds used include cadmium, zinc, lead,
Salts such as copper and thallium, or iron, which is a group II element,
Examples include salts or complex salts of ruthenium, rhodium, palladium, osmium, iridium, platinum, and the like. In particular, the above-mentioned Group Ⅰ elements can be preferably used. The amount of these compounds added varies widely depending on the purpose, but is preferably 10-' to 10-2 mol relative to silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

Regarding the chemical sensitization method, sulfur sensitization typified by the addition of unstable sulfur compounds, noble metal sensitization typified by gold sensitization, or reduction sensitization can be used alone or in combination. Regarding compounds used for chemical sensitization, see the lower right column on page 18 of the specification of JP-A No. 61-215272.
Those described in the upper right column of page 22 are preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a spectral sensitizing dye that absorbs light in a wavelength range corresponding to the desired spectral sensitivity. Spectral sensitizing dyes used at this time include, for example, Hete by F., M.
rocyclic compounds - Cyani
ne dies and related comp
ounds (John Wiley & 5ons
[Published by New York, London 1, 1964
2013).

Sensitizing dyes preferably used in the present invention include:
Compounds of the following general formula are mentioned. When these sensitizing dyes are used, stable photographic performance can be obtained even when using a color developing solution that has been regenerated over a long period of time.

General formula (S) (wherein, Z represents a nitrogen atom, an oxygen atom, a sulfur atom, or a selenium atom, and Z represents an oxygen atom, a sulfur atom, or a selenium atom.

L1, L2, L3, L4 and RI represent a methine group. This methine group may be substituted or may form a ring with another methine group.

R1 and R1 represent an alkyl group which may be the same or different. Also, R1 is connected to L+ and R7 is connected to Ls to form 5
Alternatively, a 6-membered carbon ring may be formed.

vl, v2, v3, v4, ■6, ■0, v7 and V,
are a hydrogen atom, a halogen atom, an alkyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a carboxy group, a cyan group, a hydroxy group, an amino group, an acylamino group, an alkoxy group, an alkylthio group, and an alkyl group, respectively. It represents a sulfonyl group, a sulfonic acid group, an aryloxy group, or an aryl group, or two of (1) to (V) bonded to adjacent carbon atoms may form a fused ring with each other.

(XI), , represents a charge-balancing counterion, and 71 represents the value necessary to neutralize charges of 0 or more. ) General formula (
Among the red-sensitive sensitizing dyes represented by S), more preferable red-sensitive sensitizing dyes have the following general formulas (S-I) and (S-
If). Among these, the general formula (S-I
) are preferred.

General Formula (S-1) General Formula (S-n) In General Formula (S-1), Z represents an oxygen atom or a sulfur atom.

R6 and R7 represent methine groups.

R3 and R1 have the same meanings as R1 and Rt in general formula (S). R1 represents that R6 and R4 can be combined with R1 to form a 5- or 6-membered carbon ring.

■,,V+6,VII% VIS,VIS,VI4,v
l and vl are each a hydrogen atom or the general formula (S
) represents a substituent defined in vl, ■2, ■3, ■1, vs1v6, v7, and V, and V.

~V1. Two that are bonded to adjacent carbon atoms in cannot form a fused ring with each other, and if each Hammett's σ value is σp+ (t=9 to 16), then Y:σpl+
σplO + σe + aplt + σpH + σp 10σpI
, +σ, 16, then Z is an oxygen atom, then Y≦−0,0
8, and on the other hand, if Z is a sulfur atom, Y
It is preferable that ≦−0,15. More preferably, the value of Y is Y≦−0,15 if Z is an oxygen atom,
If Z is a sulfur atom, Y≦−0,30. A particularly preferable value of Y is -0,90≦Y≦- if Z is an oxygen atom
At 0°17, if Z8 is a sulfur atom, -1,05≦Y≦-
It is 0.34.

Here, σ2 is from the Structure-Activity Relationship of Drugs - Guidelines for Drug Design and Mechanism Research, pp. 96-103 of Structure-Activity Relationship Conversation Kinsuk's "Region of Chemistry" Special Issue No. 122, published by Nankodosha, Colvin Hanks ( Corwin Hansch
), by Albert Leo, ``The State of Constance for...
Correlation Φ Analysis in Chemistry
and Biology” (Substituent C
on5tants for Correlation
Analyzing Chemistry and
Biology) pages 69-161 John Wiley
John Wileyand 5on
s) Represents the value shown in the company publication. The method for measuring σ is described in "Chemical Review J".
ews), Vol. 17, pp. 125-136 (1935)
Listed in Saletail. Preferably 41VI, v, , Vl
1% VatsVo, ■1, VIS and VIS are hydrogen atoms, unsubstituted alkyl groups having 6 or less carbon atoms (for example,
Methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl), carbon number 8
Substituted alkyl groups such as carboxymethyl, 2
-carboxyethyl, benzyl, phenethyl, dimethylaminopropyl), hydroxy groups, amino groups (e.g.
amino, hydroxyamino, methylamino, dimethylamine, diphenylamino), alkoxy groups (e.g. methoxy, ethoxy, isopropoxy, propoxy, butoxy, pentoxy), aryloxy groups (e.g. fenoquine) and aryl groups (e.g. phenyl). be.

(X,). 2 has the same meaning as (L)-1 in general formula (S).

In the general formula (S -n), Ll, L, ,L,. , L and Ll2 have the same meanings as Ll, R7, R8, L and R5 in general formula (S). More preferably, a methine group is substituted with a substituent having a negative Hammett's σ value, and the substituent is a substituted or unsubstituted alkyl group (for example, methyl,
ethyl). More preferably, L and L 1
1 are preferably connected to each other to form a 5- or 6-membered carbon ring.

R5 and R8 have the same meanings as R and R2 in general formula (S).

Vl2, V I I, Vl. , vgo, v28, V! I
The two bonded to adjacent carbon atoms in XLs and V, 4 are at least one pair bonded to each other to form a benzene ring or a heterocycle (e.g., pyrrole, thiophene, furan, pyridine, imidazole, triazole, thiazole). ) to form. These rings may be further substituted. Other VI, ~V, which are not involved in this are synonymous with general formula (S) 17) Vl ~Vl.

(Xs)-= has the same meaning as (X+) in general formula (S).

Specific examples of the dyes represented by the general formulas (S), (S-I) and (S-n) of the present invention include, for example, Japanese Patent Application No. 63
Examples include (S-1) to (S-43) described on pages 61 to 68 of No. 249246, but are not limited to these.

The emulsion used in the present invention may be either a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface or a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Also good.

When the present invention is applied to a color photosensitive material, the color photosensitive material includes a yellow coupler, a magenta coupler, and a cyan coupler that form yellow, magenta, and cyan colors respectively by coupling with an oxidized product of an aromatic amine color developer. is usually used.

Cyan couplers, magenta couplers and yellow couplers preferably used in the present invention are represented by the following general formulas (C-1), (C-II), (M-■), (M-n) and (Y). It is something.

General formula (C-I) General formula (C-n) Y.

General formula (M-1) R1 General formula (M-n) General formula (Y) In general formulas (C-I) and (C-n), Rt, R
t and R4 represent a substituted or unsubstituted aliphatic, aromatic or heterocyclic group, Rt, Rs and Ro represent a hydrogen atom, halogen atom, aliphatic group, aromatic group or acylamino group, R8 together with R2 It may also represent a group of nonmetallic atoms forming a nitrogen-containing 5- or 6-membered ring. YYY
2 represents a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized product of a developing agent. n represents 0 or I.

R6 in general formula (C-II) is preferably an aliphatic group, such as methyl group, ethyl group, propyl group, butyl group, pentadecyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, phenyl group. Examples include thiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, and methoxymethyl group.

Preferred examples of the cyan coupler represented by the general formula (C-1) or (C-II) are as follows.

In general formula (C-1), preferable R1 is an aryl group,
A heterocyclic group, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
More preferably, it is an aryl group substituted with a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group.

When R1 and R2 do not form a ring in general formula (C-I), R7 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R8 is Preferably it is a hydrogen atom.

In general formula (C-n), R1 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (C-n), R6 preferably has 2 to 1 carbon atoms.
It is a methyl group having an alkyl group of 5 and a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In general formula (C-II), R6 is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

In the general formula (C-n), R6 is preferably a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred. Preferred Yl and Y in general formulas (C-I) and (C-n) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In general formula (M-1), R7 and R1 represent an aryl group, R represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group,
Y represents a hydrogen atom or a leaving group. The substituents allowed for R7 and R9 on the aryl group (preferably the phenyl group) are the same as the substituents allowed on the substituent R1, and when there are two or more substituents, they may be the same or different. You can. R8 is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, particularly preferably a hydrogen atom. Preferred Y is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, such as those described in US Pat. No. 4,351,897 and International Publication WO 3810479.
The sulfur atom detachment type as described in No. 5 is particularly preferred.

In general formula (M-n), RIG represents a hydrogen atom or a substituent. Y represents a hydrogen atom or a leaving group, and particularly preferably a halogen atom or an arylthio group. ZaSZb
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. The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. This includes the case where a dimer or more multimer is formed with RIG or Y4, and when Za, Zb or Zc is a substituted methine, the case where a dimer or more multimer is formed with the substituted methine.

Among the pyrazoloazole couplers represented by the general formula (M-11), imidazo (1,2 -b) pyrazoles are preferred;
Pyrazolo (1
,5-bl (1°2.4) triazole is particularly preferred.

In addition, a branched alkyl group as described in JP-A No. 61-65245 is directly connected to the 2.3 or 6-position of the pyrazolotriazole ring to create a pyrazolotriazole coupler, which is described in JP-A No. 61-65246. pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, European Patent Publication No. 226, It is preferred to use pyrazolotriazole couplers having an alkoxy group or an aryloquine group at the 6-position, such as those described in No. 849 and No. 294,785.

In general formula (Y), R11 represents a halogen atom, an alkoxy group, a trifluoromethyl group, or an aryl group, and R+2 represents a hydrogen atom, a halogen atom, or an alkoxy group. A is -NHCOR, , NH302-R, ,
-8O□NHR,,,C0OR,, -502N-R,
, represents. However, R11 and R11 each represent an alkyl group, an aryl group, or an acyl group. Y5 represents a leaving group.

The substituents for R1□, R11, and R8 are the same as the substituents allowed for R3, and the leaving group Y5 is preferably one that leaves at either an oxygen atom or a nitrogen atom; Particularly preferred is the atomic dissociation type.

General formula (C-I), (C-II), (M-1), (M=
Specific examples of couplers represented by II) and (Y) are listed below.

(C-1) (C-5) (C-6) tHs 1 (C-7) 1 (C-4) (C-8) M (C-17) (C-18) (C-19 ) (C-13) (C-14) (C-15) (C-16) (C-20) (C-21) (C-22) (M-1) (M-2) (M-3 ) (M-7) (M-8) I Shil C! t Shil Shil (M-4) (M-6) Shil (Y 1) (Y-2) (Y-3) Sui (Y-4) (Y-5) (Y-6) (Y -9) (Y-7) (Y-8) The couplers represented by the above general formulas (C-I) to (Y) are:
The silver halide emulsion layer constituting the photosensitive layer usually contains 0.1-1.0 mol per mol of silver halide, preferably O.
, 1 to 0.5 mol.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by the oil-in-water dispersion method known as the oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water droplet dispersion with phase inversion.

Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. From the coupler dispersion,
The low-boiling organic solvent may be removed by distillation, noodle washing, ultrafiltration, or the like, and then mixed with the photographic emulsion.

As a dispersion medium for such a coupler, the dielectric constant (25℃)
2-20. It is preferable to use a high boiling point organic solvent and/or a water-insoluble polymer compound having a refractive index (25° C.) of 1.5 to 1.7.

As the high boiling point organic solvent, preferably the following general formula (A) ~
A high boiling point organic solvent represented by (E) is used.

General formula (A) W w2-o-p=.

W.

2 \ / General formula (E) W, -0-W2 (wherein, W, , W2 and W each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group) , W4 is W, ,
represents OW or S-W, n is an integer from ■ to 5, and when n is 2 or more, W may be the same or different from each other, and in the general formula (E), Wl and W2 may form a fused ring).

The high boiling point organic solvent that can be used in the present invention also has a melting point of 100°C or less and a boiling point of 140°C, even if it is other than the general formula (A) or E).
It can be used as long as it is a water-immiscible compound of C or higher and is a good solvent for the coupler. The melting point of the high-boiling organic solvent is preferably 80°C or lower. The boiling point of the high boiling point organic solvent is preferably 160°C or higher, more preferably 170°C or higher.

For details on these high boiling point organic solvents, please refer to JP-A-62
-215272 Publication Specification, page 137, lower right column ~ 14
It is written in the upper right column of page 4.

These couplers can also be synthesized with rhodapul latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a polymer (for example, US Pat. No. 4,203,716) or by dissolving it in a water-insoluble but organic solvent-soluble polymer.

Homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO 38100723 are preferably used, and acrylamide polymers are particularly preferred from the viewpoint of color image stabilization.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and silylation and alkylation of the phenolic hydroxyl groups of these compounds. Typical examples include ether or ester derivatives. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiorubamato)nickel complex can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hydroquinones are covered by U.S. Patent No. 2. 360. 290
No. 2,418,613, No. 2,700.45
No. 3, No. 2,701,197, No. 2,728,6
No. 59, same No. 2. 732. No. 300, No. 2,73
No. 5,765, No. 3,982.944, No. 4,4
30.425, British Patent No. 1,363,921, U.S. Patent No. 2,710.801, U.S. Patent No. 2,816,02
No. 8, etc., 6-hydroxychromans, 5-hydroxycoumarans, and spirochromans are disclosed in U.S. Patent No. 3゜43.
2.300, 3,573,050, 3,5
No. 74,627, same No. 3. 698. No. 909, No. 3,764,337, and JP-A-52-152225, spiroindanes are disclosed in U.S. Patent No. 4,360,58.
No. 9, p-alkoxyphenols are disclosed in U.S. Patent No. 2,
735,765, British Patent No. 2,066.975;
Hindered phenols are disclosed in U.S. Pat.
0.455, Japanese Unexamined Patent Publication No. 52-72224, U.S. Patent No. 4,228,235, Japanese Patent Publication No. 526623, etc.
Gallic acid derivatives, methylenedioxybenzenes, and aminophenols are each disclosed in U.S. Patent No. 3,457,079.
No. 4,332.886, Special Publication No. 56-2114
No. 4, etc., and hindered amines are disclosed in U.S. Patent No. 3.33.
6°135, British Patent No. 4,268,593, British Patent No. 1,326,889, British Patent No. 1. 354. No. 313, No. 1.410,846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 114036-1987, No. 59-53846
Metal complexes are described in U.S. Pat. No. 4,050,938, U.S. Pat. ing. These compounds are usually used in an amount of 5 to 100% by weight relative to the corresponding color coupler.
By co-emulsifying with a coupler and adding it to the photosensitive layer,
Able to achieve purpose. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto.

As ultraviolet absorbers, benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533,7
94), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314°794, U.S. Pat. No. 3,352,
681), benzophenone compounds (e.g., those described in JP-A No. 46-2784), cinnamic acid ester compounds (e.g., those described in U.S. Pat. Nos. 3,705,805 and 3,707,375), ), butadiene compounds (such as those described in U.S. Pat.
For example, U.S. Patent No. 3. 406. No. 070, 3,6
77.672 and 4,271°307) 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.

Among these, benzotriazole compounds substituted with the aforementioned aryl group are preferred.

In addition to the above-mentioned couplers, it is particularly preferable to use the following compounds. Particularly preferred is the combination with a pyrazoloazole coupler.

That is, a compound (F) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, in storage after processing, the compound (G) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent staining and other side effects caused by the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

A preferable compound (F) has a second-order reaction rate constant with p-anisidine of 2 (in trioctyl phosphate at 80°C) of 1.0//mol·sec ~1
It is a compound that reacts in the range of x l O-J/mol-sec. Note that the second-order reaction rate constant is based on JP-A-63
It can be measured by the method described in No.-158545.

When k2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if k2 is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, side effects of the remaining aromatic amine developing agent may not be prevented.

A more preferable compound (F) can be represented by the following general formula (FI) or (Fn).

General formula (FI) R, -(A). -X General formula (F III) R, -C=Y In the formula, R, and R2 each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group that reacts with the aromatic amine developer to form a chemical bond, and X represents a group that reacts with the aromatic amine developer and leaves. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y promotes the addition of an aromatic amine developing agent to the compound of general formula (Fil). represents a group that Here R1, X, Y
and R2 or B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine developing agent, the typical ones are substitution reaction and addition reaction.

For specific examples of compounds represented by general formulas (Fl) and (FII), see JP-A-63-158545 and JP-A-62-
283338, European Patent Publication No. 298321, European Patent Publication No. 27
Those described in specifications such as No. 7589 are preferred.

On the other hand, a more preferable compound (G) that chemically bonds with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inert and colorless compound is the following general formula (GI ).

General formula (GI) -Z In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the photosensitive material to release a nucleophilic group. In the compound represented by the general formula (GT), Z has Pearson's nucleophilicity 'CH,I value (
R.G. Pearson et at.

J, Am, Chem, Soc,,90. 319
(1968) ) is preferably 5 or more, or a group derived therefrom.

Specific examples of compounds represented by the general formula (Gl) are disclosed in European Patent Publication No. 255722 and Japanese Patent Application Laid-Open No. 1983-1.43.
No. 048, No. 62-229145, Patent Application No. 63-13
No. 6724, No. 62-214681, European Patent Publication 2
Those described in No. 98321, No. 277589, etc. are preferred.

Further, details of the combination of the above-mentioned compound (G) and compound (F) are described in European Patent Publication No. 277589.

The photosensitive material produced using the present invention contains a water-soluble dye or a dye that becomes water-soluble through photographic processing as a filter dye in the hydrophilic colloid layer or for various purposes such as preventing irradiation or halation. You can leave it there. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or 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 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 1964).

As the support used in the present invention, transparent films such as cellulose nitrace film and polyethylene terephthalate, which are usually used in photographic materials, and reflective supports can be used. For purposes of the present invention, the use of reflective supports is more preferred.

The "reflective support" used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Examples include those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film,
Examples include polystyrene film and vinyl chloride resin.

As other reflective supports, supports having a specular reflective or second type diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
(Also, it is preferable to roughen the metal surface or use metal powder to make it diffusely reflective. The metal should be aluminum, tin, silver, magnesium, or an alloy thereof, and the surface should be It may be the surface of a metal plate, metal foil, or thin metal layer obtained by rolling, vapor deposition, plating, or the like.

Among these, it is preferable to obtain the metal by vapor-depositing the metal onto another substrate. It is preferable to provide a water-resistant resin and a thermoplastic resin layer on the metal surface.An antistatic layer is preferably provided on the side opposite to the metal surface of the support of the present invention. For details of the support, see, for example, JP-A-61-210.
No. 346, No. 63-24247, No. 63-24251
No. 63-24255, etc.

These supports can be appropriately selected depending on the purpose of use.

As a light-reflecting substance, it is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with
It is preferable to use one treated with a tetrahydric alcohol.

The occupied area ratio (%) of white pigment fine particles per defined unit area is calculated by dividing the observed area into adjoining unit areas of 6 μm x 6 μm, and dividing the area of fine particles projected onto that unit area. It can be determined by measuring the occupied area ratio (%) (R+). The coefficient of variation of the occupied area ratio (%) can be determined by the ratio s/R of the standard deviation S of R1 to the average value (100) of R1. The number (n) of target unit areas is preferably 6 or more. Therefore, the coefficient of variation s/R can be found as follows.

In the present invention, the coefficient of variation of the occupied area ratio (%) of the pigment fine particles is preferably 0.15 or less, particularly 0.12 or less. If it is 0.08 or less, the dispersibility of the particles can be said to be "substantially uniform."

The color developer used in the present invention contains a known aromatic primary amine color developing agent.

Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N laurylamino)toluene D-44-(N-ethyl-N -(β-hydroxyethyl)aminecoaniline D-52-Methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-64-amino-3-methyl-N-ethylN-( β-
(Methanesulfonamide) Ethylcouaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl-N -ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-butoxyethylaniline Among the above-mentioned -phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N-[β-(
methanesulfonamido)ethyl]aniline (exemplified compound D-6) and 2-methyl-4-[N-ethyl-N-(
β-hydroxyethyl)aminocoaniline (exemplified compound D-5).

Moreover, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and p-)luenesulfonates. The amount of the aromatic-grade amine developing agent used is preferably about 0.1 g to about 20 g per developer solution 11,
More preferred is a concentration of about 0.5 g to about 15 g.

Various organic preservatives can be used to prevent oxidation of the developing agent. The term "organic preservative" as used herein refers to any organic compound that reduces the rate of deterioration of an aromatic primary amine color developing agent when added to a processing solution for a color photographic light-sensitive material. In other words, they are organic compounds that have the function of preventing color developing agents from being oxidized by air, among others, hydroxylamine derivatives (excluding hydroxylamine; the same shall apply hereinafter), hydroxamic acids, hydrazines,
Hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed rings Formula amines are particularly effective organic preservatives. These are Japanese Patent Application No. 147823/1983 and Japanese Patent Application No. 1983/1983.
No. 1173595, No. 61-165621, No. 61-
No. 188619, No. 61-197760, No. 61-1
No. 86561, No. 61-198987, No. 61-20
No. 1861, No. 61-186559, No. 61-170
No. 756, No. 61-188742, No. 61-1887
No. 41, U.S. Patent No. 3,615,503, U.S. Patent No. 2,49
No. 4,903, JP-A-52-143020, Special Publication No. 4, 1973
It is disclosed in No. 830496 and the like.

In addition, the amount of the following compounds added to the color developing solution is 0.00
It is desirable to add it at a concentration of 5 mol/l to 0.5 mol/l, preferably 0.03 mol/l to 1 mol/l.

Particularly preferred is the addition of hydroxylamine derivatives and/or hydrazine derivatives.

The hydroxylamine derivative is preferably one represented by the following general formula (1).

General formula (1) (wherein, L represents a linear or branched optionally substituted alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. Specifically, examples include methylene, ethylene, Preferable examples include trimethylene and propylene. Examples of substituents include carboxy groups, sulfo groups, phosphono groups, phosphinic acid residues, hydroxy groups, and ammonio groups which may be substituted with alkyl; Preferred examples include A group and hydroxy group.A
is a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be substituted with alkyl, an ammonio group which may be substituted with alkyl, a carbamoyl group which may be substituted with alkyl, a carbamoyl group which may be substituted with alkyl, Preferred examples include a carboxy group, a sulfo group, a hydroxy group, a phosphono group, and a carbamoyl group which may be substituted with alkyl. Examples of -LA include carboxymethyl group, carboxyethyl group,
Preferred examples include a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. A particularly preferred example is a phosphonoethyl group. R represents a hydrogen atom or a linear or branched optionally substituted alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. Examples of substituents include a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be substituted with alkyl, an ammonio group which may be substituted with alkyl, a carbamoyl group which may be substituted with alkyl, and an alkyl group. Represents an optionally substituted sulfamoyl group. There may be two or more substituents. R is a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group,
Preferred examples include a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group, and particularly preferred examples include a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group. be able to. L and R may be connected to form a ring.

) C1 H8 HI H CH.

CH.

CH.

Shit12 Shitll F(Js (19) H.O. CH CH2 CO2 ■ 0-NH CH2 CH.

O2 (21) 0-NH CHCO2 CH.

(22) 0-NH CH O2 2 5 (23) 0-NH CH O2 4 9 (24) H.O. CH CH-CH2 O2 CH.

(25) 0-NH CH2 CH-Co2 CH.

(26) 0-NH CH2 CH2 03 CH (27) 0-NH CH2 HCH2 SOL CH (28) H.O. CH- (CHI)3 SO8 (29) H.O. CH- (CH2).

03 (30) H.O. CH-CH2 Os 2 (31) 0 NH-CH-PO.

2 CH.

(32) 0 NH-CH.

CH2 ot 2 (33) H.O. CH CH2 CH2 CH (34) H.O. CH- (CH2).

CH (35) H.O. CH-CH2 P.O.

2 H (46) )(ONHC)I.

C)I (P.O.

R2)2 (54) HO-NHCHl CH2C-NHC(CH2LCH
2-SO3H1 In addition, as hydrazine derivatives, for example, the European patent (E
The compounds described in PO254280A2) are preferably used.

In the color developing solution according to the present invention, a compound represented by the following general formula [A] is more preferably used in order to improve the effects of the present invention.

General formula [A] (In the formula, RI 1 is a hydroxyalkyl group having 2 to 6 carbon atoms, R1□ and R13 are each a hydrogen atom, and 1 to 6 carbon atoms.
The alkyl group of 6, hydroxyl group having 2 to 6 carbon atoms, benzyl group, or formulas Xl and X' each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 2 to 6 carbon atoms. ) Preferred specific examples of the compound represented by the general formula (A) are as follows.

(A-1) Ethanolamine, (A=2) Jetanolamine, (A-3) Triethanolamine, (A-4) Di-
Isopropanolamine, (A-5) 2-methylaminoethanol, (A-6) 2-dithylaminoethanol,
(A-7) 2-dimethylaminoethanol, (A-8)
2-diethylaminoethanol, (A-9) l-diethylamino-2-propanol, (A-1o) 3-diethylamino-1-propanol, (A-11) 3-dimethylamino-1-propanol, (A -12) Isopropylaminoethanol, (A-1
3) 3-amino-1-propatol, (A-14)
2-Amino-2-methyl-1,3-propanediol, (A-15) Ethylenediaminetetraisopropanol, (A-16) Benzylethanolamine, (A-17)
2-amino-2-(hydroxymethyl)-1,3-
Propanediol, (A-18) 1,3-diaminopropanol, (A-1
9) 1,3-bis(2-hydroxyethylmethylamino)-propanol These compounds represented by the general formula (A) have an effect point of 3 g to 100 per 11 color developing solution.
It is preferably used in the range of 6g to 5g, more preferably 6g to 5g.
It is used in the range of 0g.

The color developer according to the present invention has the following general formula [B-I] and CB
A compound represented by -I[) is more preferably used.

General formula CB-I:] 11 General formula CB-I11 In the formula, R14, RIIN RIS and R17 are each a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -OR, , a group represents. Also, R
11, Rte, R2O and R11 each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. however,
When RIS represents -OH or a hydrogen atom, R14 is a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, or 0R1e.

represents a group.

The alkyl groups represented by R1, R15, R16 and RIT include those having substituents, such as methyl group, ethyl group, 1so-propyl group, n-propyl group, t-butyl group, n-butyl group, hydroxymethyl group. group, hydroxyethyl group, methylcarboxylic acid group, benzyl group, etc., and R5. , R+e, R2° and R11 have the same meanings as above, and may further include an octyl group.

Also R 11, R15, RIS and Rl? Examples of the phenyl group represented by include a phenyl group, a 2-hydroxyphenyl group, and a 4-aminophenyl group.

Typical specific examples of the chelating agent of the present invention are listed below, but the invention is not limited thereto.

(B-I-1) 4-isopropyl-1,2-dihydroxybenzene (B-1-2) 1.2-dihydroxybenzene-3,5-disulfonic acid (B-1-3) 1.2.3- ) Dihydroxybenzene-5-carboxylic acid (B-1-4) 1.2.3-trihydroxybenzene-5-carboxymethyl ester (B-I-5) 1.2.3-trihydroxybenzene-5-carboxy n -Butyl ester (B-7-6) 5-t~butyl-1,2,3-trihydroxybenzene (B-I-7) 1,2-dihydroxybenzene-3,4,6-trisulfonic acid (B- I[-1) 2.3-dihydroxynaphthalene-6-sulfonic acid (B-II-2) 2.3.8-)lihydroxynaphthalene-6-sulfonic acid (B-n-3) 2.3-dihydroxy Naphthalene-6-carboxylic acid (B-n-4) 2.3-dihydroxy-8-isopropyl-naphthalene (B-n-5) 2.3-dihydroxy-8-chloro-naphthalene-6-
Among the above sulfonic acid compounds, compounds particularly preferably used in the present invention include 1,2-dihydroxybenzene-3,
Examples include 5-disulfonic acid, and it can also be used as alkali metal salts such as sodium salts and potassium salts. (Specific exemplary compound (B-I-2)).

In the present invention, the general formulas CB-1) and (B-II
) is 5 to 15 per liter of color developing solution.
It can be used in the range of 15 to 1 g, preferably 15 to 1
It is desirable to use the amount in the range of 0g/1, more preferably 25~7g.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate,
Sodium tetraborate (borax), potassium tetraborate, 0
-Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

The amount of the buffer added to the color developer is 0. 1 mole/
It is preferably 1 or more, particularly 0. 1 mol/l-
Particularly preferred is 0.4 mol/l.

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

Specific examples are shown below, but the invention is not limited to these. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid,
Nitrilo-N,N,N-tris (methylenephosphonic acid)
, ethylenediamine-N, N, N', N'-tetrakis (methylenephosphonic acid LL, 3-diamino-2
-propatoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, l, 2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid,
Glycol ether diamine tetraacetic acid, hydroxyethylene diamine triacetic acid, ethylene diamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-)licarponic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'bis(2 -hydroxybenzyl)
Ethylenediamine-N, N'-diacetic acid, catechol-
3,4,6-trisulfonic acid, catechol-3,5-disulfonic acid, 5-sulfosalicylic acid, 4-sulfosalicylic acid.

These chelating agents are preferably ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, ethylenediamine-N, N, N', N
'-Tetrakis (methylenephosphonic acid) and hydroxyethyliminodiacetic acid are good.

Two or more of these chelating agents may be used in combination, if necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example 14
It is about 0.1g-10g per 7.

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

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 38-7826, No. 44-123
No. 80, No. 45-9019 and U.S. Patent No. 3,813
, p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554;
Quaternary ammonium salts shown in Japanese Patent Publication No. 0-137726, Japanese Patent Publication No. 44-30074, Japanese Patent Application Publication No. 56-156826 and Japanese Patent Publication No. 52-43429, etc., U.S. Patent No. 2,6
No. 10,122 and p described in No. 4,119゜462
-Aminophenols, U.S. Patent No. 2,494,903
No. 3. 128. No. 182, 4,230,79
No. 6, No. 3,253゜919, Special Publication No. 41-1143
No. 1, U.S. Patent No. 2,482,546, U.S. Patent No. 2,596
, 926 and 3,582,346, etc.; Japanese Patent Publication No. 37-16088 and 42-2.
5201, U.S. Patent No. 3,128,183, Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883, and U.S. Patent No. 3,532.501, etc., and other 1-phenyl-3-pyrazolidones. hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added as necessary.

Preferably, the color developer is substantially free of benzyl alcohol. Substantially means 2 per 11 color developer
．． It is more preferable that it not be contained at all. When it is not substantially contained, fluctuations in photographic properties during continuous processing, particularly increases in staining, are smaller, and more favorable results can be obtained.

Chlorine ions and bromine ions are necessary in color developing solutions for purposes such as preventing fogging. In the present invention, preferably the chlorine ion is 1.0×10−2 to 1.5×1
0-'mol/l, preferably 5X10-2 to lXl0
Contains -'mol/l. Chlorine ion concentration is 1.5X10
If the amount is more than -' mole/1, it has the disadvantage of delaying development. Moreover, if the amount is less than 3,5 isn't it.

In the present invention, the color developer preferably contains bromine ions from 3.0 x 10-' mol/1 to 1.0 x 10-s mol/1. More preferably 5,0XIO-5-5
XIO-”mol/l, more preferably 1.0X1
0-' to 3X10-' mol/l. If the bromide ion concentration is greater than lXl0-' mol/l, development is delayed;
Maximum concentration and sensitivity decreased to 3.0XlO-'mol/1
If it is less than that, it is not possible to prevent staining, and furthermore, fluctuations in photographic properties due to continuous processing become large, and the object of the present invention cannot be achieved.

Here, chloride ions and bromine ions may be added directly to the developer, or may be eluted from the photosensitive material during development.

When added directly to a color developer, chloride ion supplying substances include sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride.
Among them, preferred are sodium chloride and potassium chloride.

It may also be supplied in the form of a countersalt of the fluorescent brightener added to the developer. As a supply material for bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide,
Examples include thallium bromide, of which potassium bromide and sodium bromide are preferred.

When eluted from the light-sensitive material during development, both chlorine ions and bromine ions may be supplied from the emulsion, or may be supplied from a source other than the emulsion.

In the present invention, in addition to chlorine ions and bromide ions, any antifoggant can be added as necessary. As antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-
Nitropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitropenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention preferably contains a fluorescent brightener. As a fluorescent whitening agent, 4.4'-
Diamino-2,2'-disulfostilbene compounds are preferred. Addition amount is 0-10g/l, preferably 0
．． 1 to 6 g/l.

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

The processing temperature of the color developer of the present invention is 10 seconds to 120 seconds,
Preferably, the effect of the present invention is significant in 20 seconds to 60 seconds. Further, the treatment temperature is 33 to 45°C, preferably 3
The effect of the present invention is particularly remarkable at 6 to 40°C.

The amount of replenishment of the color developer during continuous processing is preferably 20 to 220 mA', preferably 25 to 160 mA', and particularly preferably 30 m1 to 110 mA' per 1 d of light-sensitive material, since the effects of the present invention can be effectively exhibited.

Aperture ratio (air contact area (cj) of the color developer of the present invention
/liquid volume (car) ”) is 0 to 0, 1
cm is preferred. Practically speaking, 0゜0 in continuous processing.
The range is preferably from 0.01 to 0.05 cm-1, more preferably from 0.002 to 0.03 cm-1.

It is generally known that when hydroxylamine is used as a preservative, decomposition occurs due to heat or trace metals even if the aperture ratio of the color developer is reduced. However, when the compound represented by the general formula (1) or the compound represented by the general formula (A) or (B) according to the present invention is used in a color developer, the decomposition of these compounds is very small, and the color Even if the developer is stored for a long time or used as a replenisher for a long period of time, it is sufficiently practical. Therefore, in the case of long-term use, the aperture ratio is preferably small, preferably 0 to 0.002 cm. .

In the present invention, desilvering treatment is performed after color development.

The desilvering step generally consists of a bleaching step and a fixing step, but it is particularly preferable that they are carried out simultaneously.

The bleach or bleach-fix solutions used in the present invention may contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), or chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride), or iodides. (eg, ammonium iodide).

If necessary, one or more inorganic substances having pH buffering ability such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Acids, organic acids and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate, guanidine, etc. can be added.

The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, namely sodium thiosulfate,
Thiosulfates such as ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; water-soluble such as thioether compounds and thioureas such as ethylene bisthioglycolic acid and 3,6-cythia-1,8-octanediol These silver halide solubilizers can be used alone or in combination of two or more. It is also possible to use a special bleach-fix solution made of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354. In the present invention, preference is given to using thiosulfates, especially ammonium thiosulfates. The amount of fixing agent per 11 moles is preferably 0.3 to 2 moles, more preferably 0.5 to 1 mole. It is in the range of 0 mol.

The pH range of the bleach-fix solution or fixer solution in the present invention is as follows:
3 to 8 are preferred, and 4 to 7 are particularly preferred. p
If H is lower than this, the desilvering property will be improved, but the deterioration of the solution and the leucoization of the cyan dye will be promoted. On the other hand, if the pH is higher than this, desilvering is delayed and staining is more likely to occur.

In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary.

The bleach-fix solution may also contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fix solution and fixer solution used in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite,
ammonium sulfite, etc.), bisulfites (e.g. ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfites (e.g. potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) containing sulfite ion-releasing compounds. These compounds are approximately 0.0 in terms of sulfite ion.
The content is preferably 2 to 0.50 mol/l, more preferably 0.04 to 0.40 mol/l. Particularly preferred is the addition of ammonium sulfite.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Sulfinic acids, carbonyl compounds, sulfinic acids, etc. may be added.

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

The bleach-fix solution of the present invention has a processing time of 10 seconds to 120 seconds, preferably 20 seconds to 60 seconds. Also, the replenishment amount is 1M of photosensitive material.
30ml per hit! ~250ml, preferably 40ml1-1
It is 50ml. Generally, an increase in staining and poor desilvering tend to occur as the amount of replenishment is reduced, but according to the present invention, the amount of replenishment of the bleach-fix solution can be reduced without causing such problems. I can do it.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization process after fixing or desilvering treatment such as bleach-fixing.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. this house,
The relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal on the Society on Motion.
Picture and Television Engineers (
Journal of the 5ociety of
Motion Picture and Terevi
sion Engineers) Volume 64, p. 248
-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium and magnesium described in Japanese Patent Application No. 61-131632 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A No. 57-8542, "Chemistry of Antibacterial and Antifungal Agents" by Hiroshi Horiguchi It is also possible to use the disinfectants described in ``Microorganism Sterilization, Disinfection, and Anti-Mold Techniques'', a complete collection of sanitary techniques, and ``Encyclopedia of Anti-Bacterial and Anti-Mold Agents'' edited by the Japanese Society of Anti-Bacterial and Anti-Mold.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 9.
and preferably 5 to 8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 2 minutes at 15 to 45°C, preferably 25 to 45°C.
A range of 30 seconds to 1 minute and 30 seconds at 0°C is selected.

Even in such short-time water washing, according to the present invention, there is no increase in staining and good photographic performance can be obtained.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-open Nos. 57-8543 and 58-1
No. 4834, No. 59-184343, No. 60-220
No. 345, No. 60-238832, No. 60-2397
All known methods described in No. 84, No. 60-239749, No. 61-4054, No. 61-118749, etc. can be used. Especially l-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2-methyl-
A stabilizing bath containing 4-isothiazolin-3-one, a bismuth compound, an ammonium compound, etc. is preferably used.

Further, following the water washing process, a further stabilization process may be performed, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

The processing time of the present invention is defined as the time from when the photosensitive material comes into contact with the color developer until it leaves the final bath (generally water washing or stabilizing group).
The effects of the present invention can be significantly exhibited in a rapid treatment process in which the processing time is 30 seconds or less, preferably 3 minutes or less.

(Examples) The present invention will be explained below using Examples, but the present invention is not limited to these embodiments.

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

19.1 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (Cpd-7)
) to 0.7 g, 27.2 cc of ethyl acetate and solvent (So
lv-1) 8.2g was added and dissolved, and this solution was mixed with 10% sodium dodecylbenzenesulfonate containing 8cc.
% gelatin aqueous solution (185 cc). On the other hand, bulk silver bromide emulsion (cubic, 3=7 mixture of average grain sizes of 0.88 μm and 0.70 μm (silver molar ratio)
.

The coefficient of variation of the grain size distribution is 0.08 and 0.10, and each emulsion contains 0.2 mol% of silver bromide locally on the grain surface), and the blue-sensitive sensitizing dye shown below is added to the large size per mol of silver. For emulsions add 2.0 x 10-' moles each and for small size emulsions add 2.5 x 10-' moles each.
A sample was prepared in which sulfur sensitization was carried out after adding 'mol. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. l-oxy-3,5-dichloro-s-triazine sodium salt was used as the gelatin hardening agent for each layer.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer Green-sensitive emulsion layer Red-sensitive emulsion layer To the red-sensitive emulsion layer, the following compound was added in an amount of 2.6 X 1 O-' mol per mol of silver halide.

For the layer, 1-(5-methylureidophenyl)-5-
Mercaptotetrazole at 8.0% per mole of silver halide, respectively. 5 x 1 o-5 mol, 7.7XIO-
'mol, 2.5X10-'mol was added.

In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene was added per mole of silver halide, respectively, to lXl0-"
mol and 2 X IQ-t mol were added.

The following dyes were added to the emulsion layer to prevent irradiation.

Also, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion (layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/m2). The silver halide emulsion represents Coating I in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiOx and blue dye (ulmarine blue)]] -th layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion See Table 1 Ceratin 1.86 Yellow coupler (ExY) 0.82 color image stabilizer (Cpd-
1) 0.19 solvent (Solv-1)
0.35 color image stabilizer (Cpd-7)
0.06 Fifth layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv
-1) 0.16 solvent (Solv-4)
0.08 Fifth layer (green sensitive layer) Silver chlorobromide emulsion (cubic, 1:3 mixture (Ag molar ratio) of average grain size of 0.55 μm and 0.39 μm. Grain size distribution. The coefficient of variation is 0.10 and 0.0
8. Each emulsion contained 0.8 mol% of AgBr locally on the grain surface) See Table 1 Gelatin 1, 24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cpd
-2) 0.03 color image stabilizer (Cpd-3)
0.15 color image stabilizer (Cpd-4)
o, 02 color image stabilizer (Cpd-9)
0.02 Solvent (Solv-2) 0.4
0 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixing prevention agent (C
pd-5), 0.05 solvent (Solv-5
) 0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1:4 mixture (Ag molar ratio) of one with an average grain size of 0.58 μm and one with an average grain size of 0.45 μm. Grain size distribution The coefficient of variation is 0.09 and 0.I
(Each emulsion contained 0.6 mol% of A g B r locally on a part of the grain surface.) See Table 1 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6 ) 0. 17 color image stabilizer (C
pd-7) 0. 40 color image stabilizer (Cpd
-8) 0.04 solvent (Solv-6)
0.15 Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixture prevention agent (C
pd-5) o, 02 solvent (Solv-5)
'0.08 Seventh layer (protective layer) Seven'Latin 1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17%)
) 0.17 liquid paraffin (Ex Y) 1=l mixture (molar ratio) with yellow coupler (Ex M) magenta coupler (Ex C) cyan coupler R=C,H.

C4H.

a 2:4:4 mixture by weight of each (Cpd color image stabilizer l: l mixture (molar ratio) (Cpd-2) color image stabilizer C00C,H.

(Cpd-3) color image stabilizer (Cpd 4) color image stabilizer (Cpd-7) color image stabilizer Zu CH2 CH Gema C0NHC, He(t) average molecular weight 60° 00 (Cpd-8) color image stabilizer (Cpd-9) color image stabilizer CH CH.

Hs (Cpd-5) Color mixing prevention agent CH (Cpd-6) color image stabilizer Ct He(t) C4He(t) C4He(t) 2:4:4 mixture (weight ratio) of (UV-1) UV absorber 5H (1) Ct H, (t) C, H, (D 4:2:4 mixture (weight ratio) of (Solv-1) melt Medium (Solv-2) Solv. Medium The amount of silver coated is as follows.

A 2:1 mixture (by volume) of (Solv-5) Solvent C00C,H,.

(CHri 1 COOC, H.

Sample 1-A-1-E prepared as described above was subjected to imagewise exposure, and a small automatic developing machine was used for each sample, and while regenerating the color developer, the replenishment amount of the color developer was Processing was continued until the capacity of the developing tank became three times as large.

Every time the color developing tank capacity is replenished from the start of the above processing (that is, at the time when 0.1.2゜3 times the capacity has been replenished), a sample subjected to optical wedge exposure with an exposure dose of 250 CMS is The sensitivity and minimum density variations of yellow, magenta, and cyan (the difference between the maximum and minimum values of each from the start to the end of 3-fold replenishment, that is, during the maximum variation) were evaluated. Furthermore, when the color developer replenisher was filled to 3 times the capacity of the above tank, 4.8 liters of the color developer was passed through a column filled with an anion exchange resin, and the concentration of potassium chloride in the recovered solution was measured. The processing liquid and processing steps used are as follows.

Temperature Nawaterai Korigokan 9 Tank capacity Color development 35℃ 45 seconds 161d 6
1 Bleach-fixing 30-36℃ 45 seconds 215d
41 Rinse■ 30-37℃ 20 seconds
21 Rinse■ 30-37℃ 20 seconds
21 Rinse ■ 30-37°C 20 seconds 360
m1 21 drying 70-85℃ 60 seconds *Sensitive material lr+? The amount of replenishment per unit (a 4-tank countercurrent system from stable ■ to ■) was used. The composition of each treatment solution is as follows.

Tachinoji Rinner Liquid Ebei 2 Shikasui
800-ethylenediamine-N, N
.

N',N'-tetrakismethylenephosphonic acid 1.5g 2.0g
Potassium bromide 0.01g Potassium chloride 2.0g Optical brightener (4,4'-diaminostilbene type) 2.0g Potassium carbonate
25 g Triethanolamine 10 g N, N-bis(2-carboxyethyl) hydroxyl 2.5 g 5 g 1 g Plate 80〇- 8.5 g 11 g N-ethyl-N-(β-methanesulfonamidoethyl) 3 Methyl-4-aminoaniline sulfate 5.0 7.0 Add water 1000 d 1000
dpH (25°C) 10.05 Bleach-fix solution (tank solution and replenisher are the same) Water
400mj! Ammonium thiosulfate (70%) loOmj! sodium sulfite
17g ethylenediaminetetraacetic acid iron (I
I [) Ammonium 55g Disodium ethylenediaminetetraacetate 5g Glacial acetic acid
9 Add water
1000ml! pH (25°C)
5.40 Rinse solution (tank solution and replenishment solution are the same) Ion exchange water (calcium, magnesium each 10 and 4
5 3ppm or less) How to recycle color developer Color developer 6I! The recovered overflow liquid 4,81 was transferred to a plastic cylindrical column (inner diameter 12°) filled with anion exchange resin (Amberlite IRA-400 manufactured by Rohm & Haas) 51 which had been previously treated as described below. 5c+n, resin layer height approximately 40c
80 to 100 ml of liquid per minute was passed through the tank and collected.

N of this solution, N-bis(2-carboxyethyl)hydroxylamine, triethanolamine, N-ethyl-N
-(β-methanesulfonamidoethyl)-3-methyl-
When 4-aminoaniline sulfate, fluorescent brightener, and potassium carbonate were quantitatively determined and water was added to make the total amount 61, the replenisher composition was adjusted to have the above-mentioned composition. Also, ethylenediamine-N, N.

Total amount of N',N'-tetrakismethylenephosphonic acid 61
2.4g was added to the solution, and the pH was adjusted to the same value as the replenisher using potassium hydroxide and sulfuric acid.

The solution prepared in this way will be used as a replenisher from now on.
Each time one replenishment was completed, it was regenerated and used in the same manner as above.

Anion exchange resin treatment method Part 1: 0.5M/l sodium hydrogen carbonate solution 6
1 was passed through the column at a rate of 80 ml per minute, followed by washing with distilled water 61 at a rate of 60 ml per minute, and used to regenerate the developer.

2nd time onwards: After using developer solution 4.81 to regenerate, distilled water 6
No. 1 was washed by passing liquid through it at a rate of 160 ml per minute, and then treated in the same manner as the first time, and used for regenerating the developer.

(Results) As is clear from Table 2, when the amount of coated silver on the sample is less than 0.6 g/m2 (sample IC-IE), compared to the sample with a higher amount of coated silver (I A-IB). , Yellow, Magenta, and Cyan, the sensitivity changes and minimum density changes are small, and the KCI concentration after passing through the anion exchange resin is also small, indicating that a decrease in the exchange ability of the resin is suppressed.

(Nα3,4.5) Example 2 N used in the color developer and its replenisher in Example 1
, general formula % formula % described in the text instead of N-bis(2-carboxyethyl)hydroxylamine (a) Compound (b) of Nαfil in general formula (I)! /
(3)〃 (c) tt (7) tt(d
)〃(8)〃 (e) I/ (9) /〆(f
) ノ / (12 pieces
l/(g) ″(1■ l/(h) ” (I 滲 〃or,
As a hydrazine derivative, European patent (EPO25428
0A2) Using the compound (i) l-11 (j) l-34 (k) l-40 of the general formula (1) described in the text, in each case Example 1 A similar test was conducted on two samples, Sample 1-A and Sample 1-D, for comparative evaluation.

As a result, the use of sample 1-D according to the configuration of the present invention resulted in better results with smaller sensitivity changes, minimum concentration changes, and deterioration of the anion exchange resin than when using sample 1-A. was gotten.

Example 3 Samples 1-A to 1-E prepared in Example 1 were subjected to imagewise exposure, and a paper processor was used for each sample to develop color in the same manner as in Example I using the following processing steps and processing liquid composition. Processing was performed while regenerating the developer.

Processing process Temperature Toyo plate Can 5 members 8 Tank capacity Color development 38°C 45 seconds 109 d 17
N bleach fixing 35°0 45 seconds 215 d
l 71 Rinse ■ 35°C 20 seconds
101 Rinse ■ 35°C 20 seconds
10A rinse ■ 35°C 20 seconds 250 J
I O1 drying 80°0 60 seconds *Amount of replenishment per 1% of photosensitive material.

A three-tank countercurrent flow system was used for rinsing from ■ to ■.

In addition, the liquid aperture ratio of the color developer is on average 0.005 cm.
-'.

Second son of the left liquid tank liquid replenisher water
700 d 7
00 WI ethylenediamine-N, N.

N',N'-tetrakismethylenephosphonic acid 3.0g 3.3g
Triethanolamine 10g 12g Potassium bromide 0.015g O Potassium chloride 5.0g O Fluorescent brightener (WRITEX 4B, manufactured by Sumitomo Chemical) 1. Og 3.5
g Potassium carbonate 25g 25g
N,N-diethylhydroxylamine 50mM 70mM
N-Ethyl-N-(β-methanesulfonamidoethyl)-3 Monomethyl-4-aminoaniline sulfate 5.5 8.5 Add water 1000 d 1000 d
pH (25°C) 10.05 1
0.557 (tank fluid and refill fluid are the same) Water 400ml
lAmmonium thiosulfate (70%) loomj!
Sodium sulfite 17g Iron(III) ethylenediaminetetraacetate Ammonium 55g Disodium ethylenediaminetetraacetate 5g Acid
9 Add water
1000ml pH (25°C)
5.40 yen (tank liquid and replenisher are the same) Ion-exchanged water (calcium and magnesium are 3 ppm or less) Color developer regeneration method The composition of the color developer was analyzed and prepared in the same manner as in Example 1. . Ethylenediamine-N, N, N', N'-
4.0 g of tetrakismethylenephosphonic acid was added to the prepared replenisher 61.

However, Amberlite IRA is an anion exchange resin.
-Instead of 400, Mitsubishi Chemical Industries (Kikugi Diaion 5A)
-10 was used. The processing method is the same as in Example 1.

The results after treatment are shown in Table 3.

As is clear from Table 3, it can be seen that good results can be obtained if the configuration of the present invention is followed.

Example 4 Samples 1-A and 1-D used in Example 3 were subjected to the same treatment. The following anion exchange resins were compared.

■ Rohm and Haas Amberlight IRA-
400 (trimethylammonium type) ■ Revateit M600 manufactured by Bayer (trimethylammonium type) 〇 PA-418 manufactured by Mitsubishi Chemical Corporation (trimethylammonium type)

Claims (1)

[Claims] A method of processing a silver halide color photographic material having at least one layer of a silver halide emulsion containing 80 mol% or more of silver chloride with a color developer, wherein the amount of coated silver in the silver halide color photographic material is 0. .6 g/m^2 or less, and the color developer used for processing is brought into contact with an anion exchanger and then reused for processing the silver halide color photographic light-sensitive material. Method of processing photographic materials.