JPH03253852A - Method for processing silver halide photographic sensitive material and final processing composition - Google Patents

Abstract

PURPOSE:To prevent staining caused by rapid processing and to restrain promotion of color fading by incorporating a specified compound in the photosensitive material after a fixing step. CONSTITUTION:The compound to be incorporated after the fixing step in the photosensitive material is represented by formula I in which each of R<1>-R<4> is H, or an aliphatic, aromatic, or heterocyclic group, independent of each other, and each may combined with an other to form a ring, where possible, and each of M<1> and M<2> is H or a cation. That the compound is incorporated means that it is contained in the finally obtained photosensitive material and it is preferred that it is not perfectly eluted in a rinsing step and the like after it has been incorporated, thus permitting staining to be prevented at the time of the rapid processing and promotion of color fading to be reduced.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a processing method and a final processing bath composition for silver halide photographic materials. Novel processing method of silver halide photographic material for making prints and final processing bath &amp;
II Concerning the precepts.

(Conventional technology) In recent years, there has been a high demand for faster processing of photographic materials.

In order to speed up processing, it is natural that shortening the time from the start of processing to the end of processing (dry state) is important as a product value. Therefore, more developer components and bleach-fixer components remain in the photosensitive material than in conventional processing.

It has been known for some time that residual developer and bleaching solution components on photosensitive materials affect the shelf life of prints.

Residual color developing agent reacts with unreacted coupler over time, resulting in undesirable staining. Further, if bleaching acid remains, the sensitive material becomes an oxidizing atmosphere, resulting in yellow stain, especially under high humidity and high temperature. These stains tend to be improved by keeping the pH low, but fading of cyan and yellow colors becomes worse under high humidity and high temperature. Japanese Patent Publication No. 5814
No. 834, JP 61-20864, JP 60-2
No. 63939, JP-A-61-170742, JP-A-5
No. 8-132743 and Japanese Patent Application Laid-open No. 151538/1984 disclose techniques for preventing coloring components from being brought into the sensitive material or rendering it colorless when washing with water is insufficient. For example, JP-A-62-958, JP-A-62-1
No. 27741, JP-A-61228445, JP-A-60
No. 256143 and Japanese Patent Application Laid-Open No. 60-239750 disclose that a chelating agent is contained in a stabilizing bath to remove colored components in a fixing bleaching solution.

(Problem to be solved by the invention) However, some of these compounds are effective for staining, but may worsen fading, and in ultra-rapid processing, the washing time and amount of washing are extremely difficult. This tends to result in insufficient effects as it inevitably brings in larger amounts of developer and bleach-fixer components than conventional washing with water.Especially in continuous processing, even more coloring components from the bleach-fix bath are brought in. Because the coloring components remain in the photosensitive material, if the finished print is stored at high temperatures and high humidity, the product value will decrease, such as staining in the white areas and fading of the image area. It was put away.

In particular, it is advantageous to shorten the development time in terms of processing time, and for photosensitive materials for color printing (hereinafter referred to as color printing paper), chloride odor with a high silver bromide content, which has been conventionally used, is advantageous. A method of processing a color photographic material containing an emulsion mainly composed of silver chloride instead of a silver chloride emulsion is known. For example, International Patent Publication WO37
No. 04534 discloses a method for rapidly processing a color photographic material made of a silver chloride emulsion with a color developer substantially free of sulfite ions and benzyl alcohol.

For such color photographic materials that can be processed rapidly, there is a strong demand for shortening the time from the start of processing to the end of processing, and therefore it is necessary to prevent staining that may occur due to such rapid processing. It is becoming even more important to suppress the deterioration of fading.

As is clear from the above description, the object of the present invention is to provide a method for processing silver halide photographic materials that provides high quality images and excellent storage stability under high temperature and/or high humidity conditions. The goal is to provide the following.

In particular, it is an object of the present invention to provide a method for processing silver halide color photographic materials that can be processed extremely rapidly and achieve the above objects.

(Means for Solving the Problems) The above object of the present invention is to provide a silver halide photographic light-sensitive material, which is characterized in that a compound represented by the following general formula (I) is incorporated into the light-sensitive material after a fixing process. It has been found that this can be achieved by using a processing method.

General formula (1) % formula %) [In general formula (1), R+, R2, R3 and R4 each independently represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and if possible, may be connected to each other to form a ring. Ml and Ml each represent a hydrogen atom or a cation. ] That is, by incorporating the chelating agent represented by the above general formula (1) into the light-sensitive material after the fixing process, it is surprisingly possible to prevent staining, which is a problem especially in the rapid processing of color photographic light-sensitive materials. It was found that it is effective in preventing staining.

The requirements for an effective chelating agent are not clear, but first, it must be able to exchange iron ions from bleaches such as EDTA-Fe(III), and second, the newly formed iron complex is colorless. Thirdly, it can be inferred that both the key agent and the complex have high water solubility. In addition, there may be other preferable forms in which the molecular structure and shape of the chelating agent are more likely to react during complex formation. Furthermore, it must satisfy requirements such that there is no adverse effect on other properties of the photosensitive material, for example, there is no aggravation of fading under high temperature, high humidity, and heat.

Although the reason for the compound of general formula (1) of the present invention is not clear, it has been found that it has a significantly greater effect of improving bestein compared to conventionally used chelating agents and has no adverse effect on fading. Furthermore, it has been found that even when the compound of the present invention is incorporated into a photosensitive material and then allowed to age at high temperature and high humidity, there is little precipitation or crystallization on the surface, and high quality images are not impaired.

General formula (1) will be explained in detail below.

R3, Rt, R, and R4 are each independently a hydrogen atom,
Represents an aliphatic group, an aromatic group or a heterocyclic group.

The aliphatic groups represented by R1, R2, R1 and R4 are preferably chain, branched or cyclic alkyl groups having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Preferred alkyl groups include, for example, methyl, ethyl, propyl, and isopropyl groups.

The aromatic group is preferably monocyclic or bicyclic, such as phenyl group and naphthyl group.

The heterocyclic group is a cyclic compound containing at least one of a nitrogen atom, an oxygen atom, and a sulfur atom, and is preferably a nitrogen-containing heterocyclic compound.

Preferred heterocycles include morpholine ring, pyrrolidine ring, piperidine ring, imidazolidine ring, pyridine ring, igodazole ring, and indazole ring.

R3, Rz, Rs and R4 may be linked to each other to form a ring, if possible.

The ring formed by R1, R2, R1 and R4 is
It may be a cyclic hydrocarbon or a heterocycle.

Examples of the cyclic hydrocarbon include a cyclobencune ring, a cyclohexane ring, and a cyclohexene ring. The heterocycle is a cyclic compound containing at least one of a nitrogen atom, an oxygen atom, and a sulfur atom, and is preferably a 5- or 6-membered ring, such as a pyrrolidine ring, an imidazolidine ring, a piperidine ring, or a morpholine ring. , a piperazine ring, a virol ring, an imidazole ring, a pyrazole ring, an indole ring, a purine ring, a pyrazolidine ring, an imidazolidine ring, a pyrroline ring, and the like.

Also, I? ,, IT,, R8 and R4 may have a substituent, and examples of the substituent include an alkyl group,
Aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, azilamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group , sulfinyl group, hydroxyl group, halogen atom, cyano group, sulfo group, carboxyl group, phosphono group, aryloxycarboxyl group, acyl group, alkoxycarbonyl group, acyloxy group, alfonamide group, sulfonamide group, nitro group, etc. can be mentioned.

M1 and M1 represent a hydrogen atom or a cation.

Examples of cations include alkali metals (lithium, sodium, potassium, etc.), ammonium, pyridinium, and the like.

Among the compounds represented by the general formula (1), the following formula (
The compound represented by It) is more preferable in terms of stain prevention effect.

General formula (If) may also be used. Examples of preferable nitrogen-containing heterocycles include a pyrrolidine ring, an imidasilidine ring, and a piperidine ring.

Specific examples of compounds represented by general formula (1) are shown below, but the present invention is not limited to the following exemplified compounds.

1, PO, lI.

cut -c-OH NHz P(hHz 2°03H2 [In formula (I[),) 11 and MZ have the same meanings as those in general formula (■). Q represents -C1 (represents a nitrogen-containing heterocycle formed including an -NH- bond). The nitrogen-containing heterocycle is preferably a 5- or 6-membered ring, and there is no other heterocycle in the heterocycle. Contains terror atoms (nitrogen, oxygen, or sulfur atoms) 3゜oiHt CHz COH 1 5゜0sHz co, -c-01 ( 6゜0sHt ■ 11゜0Jz 7゜0sL 8゜POs) 1g 13 4 17゜POsHt The compound represented by the general formula (1) is disclosed in JP-A-54611
It can be synthesized according to the method described in No. 25.

In the present invention, the compound of the general formula (I) is incorporated into the light-sensitive material after the fixing process. Here, "incorporated" means that it is contained in the final photosensitive material, and it is preferable that it is not completely eluted, for example, during a washing step after being incorporated.

A method for incorporating the compound of the present invention into a photosensitive material will be described.

First, it can be incorporated in at least one processing step after the fixing process, preferably in the final processing bath or its pre-processing bath.

The fixing treatment referred to herein also includes bleach-fixing treatment.

Preferably, it can be contained in a water washing and/or stabilization treatment bath (unless otherwise specified, the water washing treatment includes a so-called stabilization treatment).

It is particularly preferable to include it in the final treatment bath,
Therefore, a final treatment composition characterized by containing a compound represented by formula (I) above also constitutes an embodiment of the present invention.

The amount added in the processing bath after the fixing process can be arbitrarily selected depending on the required stain improvement level, but is preferably 4.8 to 500 mmol/j! It is desirable to add . More preferably 25 to 250 m5+o
The amount added is 1/1.

According to the present invention, one of the preferred methods for incorporating it into a photosensitive material is to apply it onto the photosensitive material using a roller or the like immediately after the water washing process is completed. In this case, the coating process can use conventionally known dip coating, bar coating, loft coating, air knife coating, and the like. In this case, the coating amount can be arbitrarily selected depending on the required stain improvement level, but preferably the coating amount is from 5 x 10-'' to 100 mmol/n.

More preferably, the coating amount is 3 x 10-' to 50 nmol/bo.

The method of the present invention is effective for photosensitive materials having any halogen composition, whether color photosensitive materials or black and white photosensitive materials, negatives, prints, etc. For example, color negative film, color reversal film, color paper, color reversal paper,
It can be applied to color photosensitive materials such as direct positive color paper and film, photosensitive materials for printing, black and white photosensitive materials such as X-ray film, black and white film, and black and white printing paper. In particular, in the case of a color print light-sensitive material, this method is particularly effective when rapid processing is performed using a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer containing 90 mol % or more of silver chloride.

The case of a color print photosensitive material will be explained below as a representative example.

Furthermore, in the case of printed photosensitive materials, the "
By setting the alkali consumption amount to 2.6 mmol/bo or less, ultra-fast processing becomes possible, and the stain prevention effect becomes effective.

In the present invention, the "alkali consumption amount" of a photosensitive material is measured and calculated by the following measuring method.

178 The means for calculating the "alkali consumption" is to first sample a certain area (specifically, 1 area) of the photosensitive material of the present invention and peel it off between the support and the coating layer. A typical support is paper laminated with polyethylene, and the layers can be separated. Next, crush the coating layer side finely and add it to a certain amount of water (specifically 100ml).
．． ). Next, this liquid was mixed with an alkaline aqueous solution (
Specifically, 0. Titrated with IN potassium hydroxide solution) and p
The amount of potassium hydroxide required to reach pH 10.0 from l+6.0 is defined as "alkali consumption" in millimole units.

If the support contains an acid component and cannot be peeled off as described above, evaluation can be made by subtracting the measured value of the support alone.

This alkali consumption rate evaluates the acid component contained in the photosensitive material and its pn buffering ability.
Specifically, it is affected by gelatin, which is a hydrophilic binder, and other organic compounds in the photosensitive material.

In the present invention, if the amount of alkali consumed is large, it is not possible to maintain high alkalinity during initial development, which delays the initial development and makes it impossible to shorten the development processing time. It is thought that this may also affect the occurrence of staining during treatment, and by using it in combination with reverse osmosis membrane treatment, unexpected effects were obtained.

In order to reduce "alkali consumption" which is a feature of the present invention, the following method is preferred.

First, hydrophilic colloids having acidic groups in the sensitive material layer are reduced.

Gelatin is most preferably used as the hydrophilic colloid in a color photographic light-sensitive material using a silver halide emulsion as a photosensor. However, due to its functional groups, gelatin has a pH$i resistance to the penetration of alkaline solutions.

Lowering this buffering capacity is important for speeding up the initial development in rapid processing, and a method of reducing the amount of gelatin is preferred.

Second, gelatin reduction alone may deteriorate membrane physical properties, and therefore is used in combination with a hydrophilic polymer that does not have acidic functional groups.

As the hydrophilic polymer that can be used in the present invention, those exemplified herein can be used, and polyacrylamide, polydextran, polyvinyl alcohol, and the like are particularly preferably used.

Thirdly, the type of gelatin used as the hydrophilic colloid is changed.

Specifically, by changing the processing method during gelatin production, or by using esterified gelatin or amidated gelatin that removes the acid groups of gelatin, we can change the number of functional groups and change the isoelectric point, thereby reducing alkali consumption. It can be suppressed.

Fourth, the amount of organic compound materials other than gelatin (specifically, couplers, hydroquinone, phenolic compounds, etc.) used is reduced. When such means are used in combination with a hardening agent, it is also possible to form a photosensitive material with a rapid initial swelling rate.

Fifth, by adjusting the pKa value of the organic compound mentioned in the fourth section, the amount of alkali consumption can be reduced.

As described above, it is important to suppress the "alkali consumption" of photosensitive materials, which is the solution of the present invention. The alkali consumption is 2.6 mmol/n? Below, preferably 1
．． It is 9 mmol/rrf.

Further, the present invention is particularly effective when aiming at quick and simple processing as described above, and it is desired to reduce the amount of replenishment and waste liquid as much as possible. The inventors calculated that the development time was within 20 seconds, the total time from color development to drying was within 100 seconds, and the replenishment amount was 150 seconds.
It is particularly preferable that In1/rrf or less, and for simplicity, it is even more preferable that the water washing treatment be carried out in 2 to 5 baths.

For this reason, washing with water is not sufficient, and bleaching components and the like remain in some of the photosensitive materials. However, according to the present invention, image storage stability can be improved using this as a prerequisite. The present invention provides a method that is completely different from conventional methods in that it is possible to aim at improving performance in such a limited area.

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.

Imaging systems including the useable photosensitive materials and processes of the present invention can be used for the rapid processing of commonly used color prints, but can also be used for intelligent color hardcopy applications where speed is more desirable.

In particular, as an embodiment of the intelligent color hard copy, an embodiment in which scanning exposure is performed using high-density light such as a laser (for example, a semiconductor laser) or a light emitting diode is preferable.

Many semiconductor lasers have high photosensitivity in the infrared region, and in the photosensitive material used for this purpose, 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 silver halide emulsions sensitive to respective wavelength ranges, and dyes that are complementary colors to the light to which they are exposed - yellow for blue, magenta for green, and cyan for red. By containing a so-called color coupler, subtractive color reproduction can be performed. However, the coloring hues of the photosensitive layer and the coupler may not correspond as described above.

Furthermore, depending on the required image quality and quality, the color coupler may be of two colors. In this case, the number of silver halide emulsion layers corresponding to each layer may be two.

In this case, although a full color image is not obtained, it is possible to form an image more quickly.

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 equal 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 grains, and cores (cores) inside the silver halide grains.
and a shell (-layer or multiple layers) that surrounds it, and the particles have a so-called layered structure in which halogen [power] is different, or a structure in which there are parts with different halogen compositions in a non-layered manner inside or on the surface of the particle (layers or layers). In some cases, particles with a structure in which parts of different compositions are joined on the edges, corners, or surfaces of the particles can be appropriately selected and used. 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 silver halide grains have the above-mentioned structure, even if the boundaries between parts with different halogen compositions are clear boundaries, the boundaries may be unclear due to the formation of mixed crystals due to compositional differences. It is also possible to actively have continuous structural changes.

Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide/silver chloride ratio can be used. 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 localized silver bromide layer is provided 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 edges, corners, or surfaces of the grain surface, but one preferred example is one grown epitaxially on a part of the corner of the grain25 26 .

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 98 mol% to 10
Emulsions of almost pure silver chloride, such as 0 mol %, are also preferably used.

Average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the 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 preferably 0.1 μ to 2 μ.

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) those with crystal shapes, those with irregular crystal shapes such as spherical, plate-like, etc.
Alternatively, a composite form of these 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.

The silver chlorobromide emulsion used in the present invention is P, GIafkide.
Written by Chimie et Ph1sique Photo
ographique (Published by Pau1Monte1,
(1967), Photog by G. F. Duffin.
rapic emulsion chemistry
(Published by Focal Press, 1966)
, V.L., Zelikman et al. Maki
ng and Coating Photography
c Emulsion (Focal Press
It can be prepared using the method described in, for example, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any method such as one-sided mixing method, simultaneous mixing method, or a combination thereof. May be used. A method in which particles are formed in an atmosphere containing excess silver ions (so-called back mixing method) can also be used. As one type of simultaneous mixing method, a method in which the pag in the liquid phase in which silver halide is produced can be kept constant, that is, the so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

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 and purpose, but it is preferably 10@-9 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-62-215272.
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 in each bath 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 90 spectral sensitivity. Spectral sensitizing dyes used at this time include, for example, F, M, Har
Heterocyclic compound by mer
dsCyanine dies and related
d compounds (John Wiley &
5ons CNe5 (York, London), 1964). As specific examples of compounds and spectral sensitization methods, those described in the above-mentioned JP-A-62-215272 specification, page 22, upper right column to page 38, are preferably used.

The silver halide emulsion used in the present invention has the following properties:
Alternatively, various compounds or their precursors can be added for the purpose of stabilizing photographic performance. As specific examples of these compounds, those described on pages 39 to 72 of the specification of JP-A-62-215272 mentioned above are preferably used.

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 have the following formulas (C-1), (C-11), (M-■), (M-11).
and (Y).

General formula (C-I) 1 General formula (C-11) General formula (M-1) 9 General formula (M-11) General formula (Y) CH3Y.

In the general formula ((, I) and (C-I[), R1,
R7 and R4 represent a substituted or unsubstituted aliphatic, aromatic or heterocyclic group, R3, R3 and R6 represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or an acylamino group, and R3 together with R2 It may also represent a group of nonmetallic atoms forming a nitrogen-containing 5-membered ring or 6R ring. Y3
, Y2 represents a hydrogen atom or a group that leaves during the coupling reaction with the oxidized product of the developing agent. n represents O or 1.

R5 in the general formula (C-I[) is preferably an aliphatic group, such as a methyl group, ethyl group, propyl group, butyl group, pentadecyl group, tert-butyl group, cyclohexyl group, or cyclohexylmethyl group. , phenylthiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, methoxymethyl group, and the like.

Preferred examples of the cyan coupler represented by formula (C-1) or (C-11) are as follows.

- In formula (C-1), preferable Ro 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 a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or an aryl group substituted with a cyano group.

- When R3 and R2 do not form a ring in formula (C-1), R2 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 the general formula (C-It), R4 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-I[), R6 preferably has 2 to 2 carbon atoms.
It is a methyl group having 15 alkyl groups 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 formula (C-■), R5 is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

- In formula (C-II), preferred Rh is a hydrogen atom,
A halogen atom, with chlorine and fluorine atoms being particularly preferred. - Preferred Yl and Y2 in formulas (C-1) 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, R8 represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group,
Y3 represents a hydrogen atom or a leaving group.

Aryl group (preferably phenyl group) for R1 and R7
The substituents allowed for are the same as the substituents allowed for the substituent R, and when there are two or more substituents, they may be the same or different. R8 is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, particularly preferably a hydrogen atom.

Preferred Y3 is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, for example as described in U.S. Pat.
Particularly preferred are sulfur atom dissociative types as described in No. 51,897 and International Publication No. WO 38104795.

In general formula (M-II), RIG represents a hydrogen atom or a substituent. Y4 represents a hydrogen atom or a leaving group, and is particularly preferably a halogen atom or an arylthio group. Za,
Zb and Zc are methine, substituted methine, =N- or -N
i1-, 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. R1° or Y.

When forming a dimer or more multimer, Za, zb
Alternatively, when Zc is a substituted methine, this includes the case where the substituted methine forms a dimer or more multimer.

Among the pyrazoloazole couplers represented by the general formula (M-It), the imidazo[1,2-b ) pyrazoles are preferred;
Pyrazolo (1
, 5-b) [1,2,4) Triazoles are 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 or aryloxy group in the 6-position, such as those described in No. 849 and No. 294.785.

In Formula 11 (Y), R1° represents a halogen atom, an alkoxy group, a trifluoromethyl group, or an aryl group, and l? , □ represents a hydrogen atom, a halogen atom or an alkoxy group. A represents -NHCORl3,I4. However, R13 and Ro are each an alkyl group,
Represents an aryl group or an acyl group. Y represents a leaving group. The substituents for R, □ and R13, RI4 are the same as those allowed for R8, and the leaving group Y is preferably of the type that leaves at either an oxygen atom or a nitrogen atom. However, the nitrogen atom detachment type is particularly preferable.

General formula (C-1), (C-II), (M-1), (M-
Specific examples of couplers represented by 11) and (Y) are listed below.

I (C 6) I (C 7) (C-8) I 1 (C-13) (C 14) (C 15) (C 16) (C 20) (C 21) (C 22) (C-17 ) (C 18) (C 19) (M 1) (,! (M 2) I (M 3) 1 6 9- 50 1 52 (Y-3) (Y-4) (Y 5) 7- (Y 1) (Y 2) (Y 6) (Y 7) (Y 8) B (Y-9) The couplers represented by formulas (C-1) to (Y) above are:
In the silver halide emulsion layer constituting the photosensitive layer, usually 0.1 to 1.0 mol per mol of silver halide, preferably,
It is contained in an amount of 0.1 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℃)
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 (B) W+ Coo Wz General formula (D) General formula (E) +v, -ow.

(In the formula, 1, h2, and 6 each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group, or heterocyclic group, and h.

represents hl, 0-1 or S-W, n is an integer from 0 to 5, and when n is 2 or more, - may be the same or different from each other, - in formula (E) ,W,
and 6 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'
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 impregnated into rhodapuru latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling 4Il&solvents mentioned above, or made water-insoluble and organic solvent-soluble. It can be dissolved in a polymer and emulsified and dispersed in an aqueous hydrophilic colloid solution.

Homopolymers or copolymers described on pages 12 to 30 of WO-088100723 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 atomphenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, organic antifading agents for cyan, magenta and/or yellow images mainly include f2 hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, and bisphenols. Representative examples include hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

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

Hydroquinones are disclosed in U.S. Patent No. 2,360,290;
Same No. 2,418,613, Same No. 2,700.453, Same No. 2,701゜197, Same No. 2,728,659
No. 2,732,300, No. 2,735,76
No. 5, No. 3,982,944, No. 4,430,4
No. 25, British Patent No. 1,363,921, U.S. Patent No. 2.710801, U.S. Patent No. 2,816,028, etc., 6-hydroxychromans, 5-hydroxycoumarans, and spirochromans are covered by U.S. patents. No. 3,432,300
No. 3,573,050, No. 3,574,62
No. 7, No. 3,698,909, No. 3,764,3
No. 37, JP-A No. 52-152225, spiroindanes are described in U.S. Patent No. 4,360,589, and p-alkoxyphenols are described in U.S. Patent No. 2,735°765.
No., British Patent No. 2,066.975, Japanese Unexamined Patent Publication No. 1987-1
No. 0539, Japanese Patent Publication No. 57-19765, etc., and hindered phenols are disclosed in U.S. Patent No. 3,700,455,
JP 52-72224, U.S. Patent No. 4,228,23
No. 5, Japanese Patent Publication No. 52-6623, etc., and gallic acid derivatives, methylenedioxybenzenes, and acid diphenols are disclosed in U.S. Patent No. 3.457,079 and U.S. Pat. No. 4.3, respectively.
No. 32.886, Japanese Patent Publication No. 56-21144, etc., and hindered amines are disclosed in U.S. Patent No. 3.336.135,
No. 4,268,593, British Patent No. 1,326,8
No. 89, No. 1,354,313, No. 1,410,
No. 846, JP 51-1420, JP 58-11
No. 4036, No. 59-53846, No. 59-78
No. 344, etc., and metal complexes are disclosed in U.S. Patent No. 4.050,9.
No. 38, No. 4.241,155, British Patent No. 2, 0
27,731 (A), etc., respectively.

The purpose of these compounds can be achieved by co-emulsifying them with the respective color couplers and adding them to the photosensitive layer, usually in an amount of 5 to 100 ffi. 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 to it.

As ultraviolet absorbers, benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533.9
74, 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314,794, U.S. Pat. No. 3,352,6)
81), benzophenone compounds (e.g., those described in JP-A No. 46-2784), cinnamic acid ester compounds (e.g., U.S. Pat. No. 3,705,805,
No. 3,707,395), butadiene compounds (as described in U.S. Pat. No. 4,045,229), or benzoxidole compounds (e.g., U.S. Pat. No. 3,406,070, U.S. Pat. 3,677.672 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 coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

A preferred S 6 compound (F) has a second-order reaction rate constant with p-anisidine of 2 (in trioctyl phosphate at 80°C) of 1. OI! , /ll1o1・sec~1
×10-' i! , /mol + Sec.

Incidentally, the second-order reaction rate constant can be measured by the method described in JP-A-63-158545.

When R2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if R2 is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, it may not be possible to prevent side effects of the remaining aromatic amine developing agent.

A more preferable compound (F) can be represented by the following formula (Fl) or (FII).

General formula (Fl) R+ (A)nX General formula (F I[) In the formula, R1 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,
Y represents a group that promotes addition of an aromatic adanone-based developing agent to the compound of general formula (Fn). Here, R8 and 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-62-2.
83338, European Patent Publication No. 298321, European Patent Publication No. 277
Those described in specifications such as No. 589 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 shown below - Formula (CI ).

General formula (Gl) -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. - The compound represented by the formula (Gl) has a Z value of Pearson's nucleophilicity "CH,I value (
R,G,Pe'arson,et al,+J,Am,
chen+.

Soc, 90.319 (1968) is preferably a group having 5 or more, or a group derived therefrom.

Specific examples of compounds represented by the general formula (GI) are disclosed in European Patent Publication No. 255722 and Japanese Patent Application Laid-Open No. 6214304.
No. 8, No. 62-229145, patent application No. 63-1367
No. 24, No. 62-214681, European Patent Publication No. 298
Those described in No. 321, 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 and halide. 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 Book, The Story of Gelatin, written by Arthur Vuis (Academic Press, published in 196490).

Hydrophilic colloids other than gelatin that can be used in the present invention include, for example, derivatives of gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein; Cellulose derivatives such as propylcellulose and cellulose sulfate;
Sugar derivatives such as sodium alginate, pyrodextran, and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinyl alcohol modified with anionic and cationic compounds, poly-
Synthetic hydrophilic polymeric substances consisting of homopolymers such as N-vinylpyrrolidone, polyacrylic acid and its neutralized products, polymethacrylic acid and its neutralized products, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. and their respective copolymers. I can do it.

Hydrophilic polymers, including gelatin, can be used with appropriate crosslinking to increase initial swelling.

The total hydrophilic colloid used in the photosensitive material is 2.0 to 8.0.
g/rrT is preferred, more preferably 3.5 to 6.
0 g/n (.If the amount of hydrophilic colloid is too large, development, especially the initial development, will be delayed, and if it is too small, it will affect the physical properties of the film during wetting, which is undesirable.

In the present invention, any conventionally known hardening agent can be used alone or in combination.

i.e. chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes (formaldehyde, glyoxal,
geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl (1,3,5-)lyacryloyl-hexahydro 2-triazine, 1,3-vinylsulfonyl-2propanol, etc.), active halogen compounds (2
, 4dichloro-6-hydroxy-3-triazine, etc.)
, mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.) can be used.

Hardeners that can be preferably used include aldehyde compounds such as formaldehyde, glyoxal, S-triazine compounds such as 2-hydroxy 4,6-cyclotriazine sodium salt, and vinylsulfone compounds.

The amount of hardening agent used is influenced by the presence of a hardening agent or hardening agent, but is preferably I
−'a+ol/ggelatin~I Xl0−”mol/g
Used in a range of gelatin. More preferably 5×10
-Smol/g gelatin ~5 X 10-3 mol/g
Used in a range of gelatin.

Examples of hardeners include the following:

■ HCHO ■ 0fIC+CHz +r (IJIO■ (Jl:
JIzCONHCOCHzCI■ CZCILzCOO
CHzCH200CCflzCZ■ CHaCOCl [Phase] CH3coC■z C1 Na C1(0 ■ CH2CHO t 3 Fee■ CHz=CI(OCR=Cfh [Phase] C) Iz=CH5O□(CHtll+5OtC
H=CHsCHz=CH-3(h-N9N-5OtCt
l=Cth[phase] C(CHzSOzCH=CHz)4
COCH=CHg @ CHt = CHCOOCOCH= COt@
(C1,= CH5O Examples include hydrogen bond breakers and aromatic hydrocarbons with hydroxyl groups such as hydroquinone.

Furthermore, only the added layer can be hardened by polymerizing the hardening agent.

As the support used in the present invention, transparent films such as cellulose nitrate film and polyethylene hand phthalate, 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.
The above is preferable, and it is also preferable to roughen the metal surface or use metal powder to make it diffusely reflective. The metal may be aluminum, tin, silver, magnesium, or an alloy thereof, and the surface may be a 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. Preferably, a layer of water-resistant resin, particularly thermoplastic resin, is provided on the metal surface. It is preferable to provide an antistatic layer on the side opposite to the side having the metal surface of the support 7 8 of the present invention. For details of such supports, see e.g.
JP-A-61-210346, JP-A No. 63-24247,
It is described in 63-24251 and 63-24255.

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 most typically calculated by dividing the observed area into adjacent unit areas of 6μ x 6μ and projecting onto that unit area. It can be determined by measuring the occupied area ratio (%) (Ri) of fine particles. The coefficient of variation of the occupied area ratio (%) can be determined by the ratio S/π of the standard deviation S of R1 to the average value (IT) of R1. The number (n) of target and area unit areas is preferably 6 or more. Therefore, the coefficient of variation S
/N can be found by

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 photographic material used in the present invention is preferably subjected to color development, bleach-fixing, and water washing treatment (or stabilization treatment). Bleaching and fixing may be carried out separately instead of in one bath as described above.

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-I N, lll-diethyl-p-phenylenediamine D-22-amino-5-dinithylaminotri-
32-amino-5-(N-ethyl-N-lauryl)
) Toluene D-44-(N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-52-Methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-62- Methyl-4-[N-ethyl-N-(3-hydroxypropyl)amino]aniline D-74-amino-3-methyl-N-ethyl-N-(β
-(methanesulfonamido)ethyl)-aniline D-8N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-9N, N-dimethyl-p-phenylenecyagon D-104-amo no 3 -Medyl~N-ethyl N-methoxyethylaniline D-114-agono 3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-124-amino-3-methyl-N-ethyl N-β-
Butoxyethylaniline Among the above p-phenylenediamine derivatives, particularly preferred are exemplary compounds D-4 and D-6.

Further, salts of these p-phenylene cyano derivatives such as sulfates, hydrochlorides, sulfites, and P-)luenesulfonates may be used. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g per liter of developer solution.
, more preferably at a concentration of about 0.5 g to about 12 g.

In practicing the present invention, it is preferred to use a developer solution that is substantially free of benzyl alcohol. Here, "not substantially containing" preferably means 2d11. More preferably, the benzyl alcohol concentration is 0.5 rtrl/1 or less, and most preferably, no benzyl alcohol is contained at all.

More preferably, the developer used in the present invention does not substantially contain 1 2 sulfite ions. The sulfite ion functions as a preservative for the developing agent, and at the same time has the effect of dissolving silver halide and reacting with the oxidized product of the developing agent to reduce the dye formation efficiency.

Such an effect is presumed to be one of the causes of increased fluctuations in photographic characteristics due to continuous processing. Here, "substantially no content" means preferably 3.0 x 10-' mol/I! ,
The sulfite ion concentration is as follows, most preferably no sulfite ion at all.

However, in the present invention, a very small amount of sulfite ion used to prevent oxidation of the processing agent kit in which the developing agent is concentrated before being adjusted to a working solution is excluded.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. This is because hydroxylamine functions as a preservative for the developing solution and also has silver developing activity itself, and it is thought that fluctuations in the concentration of hydroxylamine greatly affect photographic properties.

The term "substantially free of hydroxylamine" as used herein means preferably a hydroxylamine concentration of 5.0 x 10-' mol/l or less, and most preferably no hydroxylamine at all.

It is more preferable that the developer used in the present invention contains an organic preservative instead of the hydroxylamine or sulfite ion.

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, it is an organic compound that has the function of preventing the oxidation of color developing agents by air and other factors, and among them, hydroxylamine derivatives (excluding hydroxylamine, the same shall apply hereinafter), hydroxamic acids, hydrazines, hydrazides, and phenols. α-hydroxyketones, α-aminoketones,
Particularly effective organic preservatives include sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and fused cyclic amines. These are JP-A-6
No. 3-4235, No. 6330845, No. 63-216
No. 47, No. 63-44655, No. 63-53551, No. 63-43140, No. 63-56654, No. 6
No. 3-58346, No. 63-43138, No. 63-1
No. 46041, No. 6344657, No. 63-4465
No. 6, U.S. Patent No. 3,615,503, U.S. Patent No. 2,494
, No. 903, JP-A No. 52-143020, JP-A No. 1973
-30496, etc.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicyl M class described in No. 180588, JP-A-54-35
Alkanol ξ-anes described in No. 32, JP-A-56-94
Polyethyleneimines described in US Pat. No. 349, US Pat.
If necessary, aromatic polyhydroxy compounds described in No. 746,544 and the like may be contained. In particular, alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine,
Preferably, a hydrazine derivative or an aromatic polyhydroxy compound is added.

Among the above-mentioned organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferred.
No. 5270, No. 63-9713, No. 639714,
It is described in No. 63-11300.

Further, it is more preferable to use the above-mentioned hydroxylamine derivative or hydrazine derivative in combination with amines from the viewpoint of improving the stability of the color developer and further improving the stability during continuous processing.

Examples of the amines include cyclic amines as described in JP-A-63-239447 and JP-A-634283.
Amines such as those described in No. 40 and other patent applications of 1982
Examples include amines such as those described in No. -9713 and No. 63-11300.

In the present invention, 3.5% of chloride ions are added to the color developer.
It is preferable to contain Xl0-2 to 1.5 mol/l of XIO. Particularly preferred is 4XIO-2 to 1x10 mol/IV. Chlorine ion concentration is 1.5X10-'
If the amount is more than 10-1 mol/l, it has the disadvantage of delaying development, which is undesirable in distantly achieving the object of the present invention of rapid development and high maximum density. Also, 3.5xio-”
If it is less than 5 6 mol/1, it is not preferable in terms of preventing fogging.

In the present invention, 3.0% bromine ion is added to the color developer.
X10-'mol/I! ,~1. OXIO Tsukasa Mol/I! ,
It is preferable to contain. More preferably, s, ox
10-5 to 5×10-' mol/l. If the bromide ion concentration is more than 1X10-' mol/i, the development will be delayed and the maximum density and sensitivity will be reduced, and if it is less than 3.OX10-' mol/1, fog cannot be sufficiently prevented.

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

When added directly to a color developer, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, among which preferred ones are preferred. are sodium chloride and potassium chloride.

Alternatively, it may be supplied from an optical brightener added to the developer.

Substances that supply bromide ions include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, and krillam bromide. Among these, preferred are potassium bromide and sodium bromide.

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

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 carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt,
N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-
Methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates have a solubility of pl+9.
These buffers have the advantage of having excellent buffering ability in the high pH range of 0 or higher, having no adverse effect on photographic performance (such as capri) when added to color developers, and being inexpensive. is particularly preferred.

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

The amount of the buffer added to the color developer is 0.1 mol/1
It is preferable that the amount is more than 0.1 mol/1-0.
4 mol/I! It is particularly preferable that

In addition, various caloric acid agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or for improving the stability of the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Ethylenecyaminetetraacetic acid, N, N, N-)rimethylenephosphonic acid, ethylenecyamine-N,N,N', N'-
Tetramethylene sulfonic acid, transsilohexanetetraacetic acid, 1,2 cyanopropane tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-L2,4
- tricarboxylic acid, 1-hydroxyethylidene-1,
Examples include 1-diphosphonic acid, N,N'-bis(2-hydroxyhensyl)ethylenediamine-N,N'-diacetic acid, and the like.

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 11
It is about 0.1g to Log per unit.

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-phenylenesia fruit compounds shown in JP-A-52-49829 and JP-A-5015554, JP-A-50-1
No. 37726, Japanese Patent Publication No. 1977-30074, Japanese Patent Publication No. 1983
-156826 and 52-43429, etc., U.S. Patent No. 2,494,9
No. 03, No. 3,128,182, No. 4,230,79
No. 6, No. 3,253,919, Special Publication No. 41-1143
No. 1, U.S. Patent No. 2,482,546, U.S. Patent No. 2,596
, 926 and 3,582,346, etc., Japanese Patent Publication No. 37-16088, 42-25
No. 201, U.S. Patent No. 3.128.183, Special Publication No. 4
1-11431, 42-23883, U.S. Pat. No. 3,532,501, etc., other l-phenyl-3-pyrazolidones, imidazoles, etc. may be added as necessary. I can do it.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidrohenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-hensitriazole, 2-thiazolyl-benzimidazole, Typical examples include nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer applicable to the present invention preferably contains an optical brightener. As an optical brightener, 4,4'
-Cya-2,2'-disulfostilbene compounds are preferred. Addition amount is 0-5 g/l, preferably 0.1 g
~47 years old.

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

The processing temperature of the color developer that can be applied to the present invention is 20~
50°C, preferably 30 to 45°C. Processing time is 2
Within 0 seconds, preferably within 15 seconds. It is preferable that the amount of replenishment is small, but it is 20 to 600 per m2 of photosensitive material.
- is suitable, preferably 30 to 300 d. More preferably 40ml to 200-1, most preferably 60ml
d-150d.

Next, a desilvering process that can be applied to the present invention will be explained.

The desilvering step may generally include any process such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step, or a bleach-fixing step.

The bleaching solution, bleach-fixing solution, and fixing solution that can be applied to the present invention will be explained below.

As the bleaching agent used in the bleach or bleach-fix solution, any bleaching agent can be used, but especially iron (
III) organic complex salts (e.g. ethylenediaminetetraacetic acid,
complex salts with aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acids) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; hydrogen peroxide, etc. preferable.

Among these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. 72 noboricarboxylic acids useful for forming organic complexes of iron(III);
Aminopolyphosphonic acids, organic phosphonic acids, or salts thereof include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-cyanopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid,
Cyclohexanediaminetetraacetic acid, methylynononiacetic acid,
Examples include iminodiacetic acid, glycol ether cyagonitetraacetic acid, and the like. These compounds include sodium,
Any potassium, lithium or ammonium salt may be used. Among these compounds, ethylenediaminetetraacetic acid,
The iron (mNf salt) of diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-cyanoprobanetetraacetic acid, and methyliminodiacetic acid is preferred because it has a high bleaching edge.These ferric ion complex salts are used in the form of complex salts. Also, ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc. and aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc. Second in solution using a chelating agent such as an acid.
An iron ion complex salt may be formed. Further, the chelating agent may be used in excess of the amount required to form the ferric ion complex. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/i! ,, preferably 0.05 to 0.50 mol/l.

Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. For example, U.S. Pat.
Publication No. 630, Research Disclosure No. 1712
No. 9 (July 1978 issue), compounds having a mercapto group or disulfide bond, and Japanese Patent Publication No. 45-85
No. 06, JP-A-52-20832, JP-A No. 53-3273
Thiourea compounds described in No. 5 and US Pat. No. 3,706,561, or halides such as iodine and bromide ions are preferred because they have excellent bleaching properties.

In addition, the bleaching solution or bleach-fixing solution that can be applied to the present invention contains bromides (for example, potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide) or chlorides (eg, potassium chloride, sodium chloride, ammonium chloride) or iodides (eg, ammonium iodide) can be included. 111 with pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. as required.
Inorganic acids, organic acids, alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The fixing agent used in the bleach-fixing solution or fixing solution is a known fixing agent, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid. , 3,6-sithia-1,8-octanediol, and other water-soluble silver halide solubilizers such as thioureas, and these can be used alone or in combination of two or more. Further, a special bleach-fixing solution consisting 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 can also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of fixing agent per 11 is 0.3
-2 mol is preferable, and the range of 0.5-1.0 mol is more preferable. The pH range of the bleach-fix solution or fix solution is
3 to 10 are preferred, and 5 to 9 are particularly preferred.

Further, the bleach-fix solution may contain various other optical brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

Bleach-fix solutions and fixing solutions contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives.
, metabisulfite (eg, potassium metabisulfite, potassium metabisulfite, ammonium metabisulfite, etc.).

These compounds are approximately 0.02 to 0.02 in terms of sulfite ion.
The content of poor gold is preferably 0.05 mol/l, more preferably 0.04 to 0.40 mol/l.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

7 9δ Furthermore, a buffering agent, a fluorescent whitening agent, a chelating agent, an antifoaming agent, an antifungal agent, etc. may be added as necessary.

Furthermore, if necessary, a known chelating agent other than the compound of general formula (1) may be included.

After desilvering treatment such as fixing or bleach-fixing, water washing and/or stabilization treatment is performed (hereinafter, unless otherwise specified, water washing includes stabilization treatment).

The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers (Jour
nalof the 5ociety of Moti
on Picture and Televi-sio
n Engineers) Volume 64, p, 248-25
3 (May 1955 issue).

Normally, the number of stages in the multistage countercurrent system is preferably 2 to 6.9 2 to 5 are particularly preferred.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, it is possible to reduce the amount of water used for washing the photosensitive material (0.4M to 11 or less per unit), and the effect of the present invention is remarkable. The increase in residence time causes problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material.As a solution to this problem, calcium and magnesium as described in JP-A No. 62-288838 have been proposed. It is possible to use a method of reducing this extremely effectively.
Isothiazolone compounds and thiahendazoles described in No. 542, chlorine-based disinfectants such as chlorinated sodium isocyanurate described in No. 61-120145, JP-A No. 61-1201-
Henctriazole, copper ion, etc. described in No. 267761, Hiroshi Horiguchi, Chemistry of antibacterial and antifungal (1986)
Sankyo Publishing, Hygiene Technology complete volume "Sterilization, sterilization, and anti-mold technology of microorganisms" (1982) Edited by Society of Industrial Engineers, Japan Society of Antibacterial and Anti-Mold "
Bactericidal agents described in Encyclopedia of Antibacterial and Antifungal Agents, (1986) can also be used.

Further, in the washing water, surfactant 00 can be used as a draining agent, and a chelating agent such as EDTA can be used as a water softener.

The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing liquid, such as an aldehyde compound such as formalin, or a film suitable for stabilizing the dye.
Examples include buffers for preparing H and ammonium compounds. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

Furthermore, surfactants, optical brighteners, and hardeners can also be added.

Furthermore, in water washing and/or stabilization treatment,
The introduction of coloring components into the photosensitive material may be reduced by using a reverse osmosis membrane as shown in No. 241053 and No. 62-254151.

Further, the washing treatment bath of the present invention can also contain a known chelating agent other than the compound of the present invention.

The preferred pH of the water washing step or stabilization step is 4 to 10, more preferably 5 to 8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but -119 is 30 to 4
The temperature is 5°C, preferably 35-42°C. Although the time can be set arbitrarily, a shorter time is preferable from the viewpoint of reducing processing time. Preferably 10 seconds to 45 seconds, more preferably 10 seconds to 3 seconds
It is 5 seconds. The smaller the amount of replenishment, the lower the running cost.
Preferable from the viewpoints of reduced emissions, ease of handling, etc.

A specific preferable replenishment amount is 0.5 to 50 times, preferably 2 to 15 times, the amount brought in from the previous bath per unit area of the photosensitive material. Or in photosensitive material? 300ml per serving
It is preferably 150 or less. Further, replenishment may be performed continuously or intermittently.

The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is reducing the wash water overflow by a multi-stage counter-current system to flow into a bleach-fixing bath as a pre-bath, replenishing the bleach-fixing bath with concentrated liquid, and freezing the waste liquid volume.

A drying process that can be used in the present invention will be explained.

In order to complete an image using the ultra-quick processing of the present invention, a drying time of 20 to 40 seconds is desired.

As a means for shortening this drying time, it is possible to improve the drying time by reducing the amount of water carried into the film by reducing the amount of a hydrophilic binder such as gelatin. In addition, from the perspective of reducing the amount carried in, it is possible to speed up drying by absorbing water with a squeeze roller or cloth immediately after leaving the washing bath. Of course, as an improvement from the dryer, it is possible to speed up drying by increasing the temperature or increasing the drying air. Furthermore, drying can be accelerated by adjusting the angle at which the drying air is irradiated onto the photosensitive material or by removing the exhaust air.

(Examples) Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 Multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. Six coating solutions were prepared as follows.

19.1 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1), and color image stabilizer (Cpd-1) were prepared.
-7) Add and dissolve 27.2 cc of ethyl acetate and 8.2 g of solvent (Solv-1) to 1.4 g, and emulsify and disperse this solution in 185 cc of a 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylhenzenesulfonate. I let it happen. On the other hand, silver chlorobromide emulsion (cubic, average grain size 0.88
3=7 mixture (silver molar ratio) of 0.70+1m and 0.70+1m. The coefficient of variation of particle size distribution is 0.08 and 0.08.
10. Each emulsion contains 0.2 mol % of silver bromide locally on the grain surface), and the following blue-sensitive sensitizing dyes are added to each mol of silver at 2.0 x 10-' mol for large-sized emulsions. In addition, for small size emulsions, 2.5X
A sulfur sensitized product was prepared after adding 10-' moles. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below.

The blue-sensitive emulsion layer 103 04 contains 5.6 Xl0-' mol) and (2.0 X 10-' mol each for large size emulsions and 2.0x10-' mol each for small size emulsions, per mole of silver halide). 5X10-' mol) SO,OS03+1・N(CJs)3 (per mol of silver halide, 7.0X10-5 mol for large size emulsions and 1 for small size emulsions)
．． 0-5 moles of OXl) red-sensitive emulsion layer (per mole of silver halide, 4.0XIO-' moles for large emulsions, for small emulsions (per mole of silver halide, for large emulsions) It is 0.9X
10-' moles, or 1.0-' mole for small size emulsions. IX
10-' mol) For the red-sensitive emulsion layer, the following compounds were added in an amount of 2.6 x 10-3 mol per mol of silver halide.

And also for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added at 8.5×10−5 mol and 7 mol per mol of halogenated material, respectively. .7 Xl0-' moles, 2.
Added 5X10-4 moles.

Furthermore, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4hydroxy-6-methyl-1,3,3a, ? -Tetrazaindene were added in 1X10-' mol and 2X10-' mol, respectively, per mole of silver halide.

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

07- (Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/bo). The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiOz) and a bluish dye (ulmarine blue)] -th layer (blue-sensitive layer) Said silver chlorobromide emulsion 0.27 Gelatin 0.74 Yellow Coupler (ExY) 0.67 color image stabilizer (
Cpd-1) 0.19 solvent (So
lv-1) 0.3508- Color image stabilizer (Cpd-7) 0.0
6 Second layer (color mixing prevention layer) Gelatin 0.75 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08
Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, 1:3 mixture of one with an average grain size of 0.55μ and one with an average grain size of 0.394 (Ag molar ratio). Coefficient of variation of grain size distribution are 0.10 and 0.08,
(Each emulsion contained 8 mol% of AgBrO locally on the grain surface) 0.12 Gelatin
0.66 magenta coupler (ExM)
0.26 color image stabilizer (Cpd-2)
0.03 color image stabilizer (Cpd-3)
0.15 color image stabilizer (Cpd-4)
0.02 color image stabilizer (Cpd-9
) 0.02 solvent (Solv-2)
0.40 Fourth layer (ultraviolet absorption layer) Gelatin 0.63 Ultraviolet absorber (UV-1) 0.47 Color mixing inhibitor (cpd-5) 0.05 Solvent (
Solv-5) 0.24 Fifth layer (redness N) Silver chlorobromide emulsion (cubic, 1:4?M compound of one with an average grain size of 0.58-micron and one with an average grain size of 0.45μ) (Ag molar ratio).The coefficient of variation of particle size distribution is 0.09 and 0.11.
, each emulsion locally contained 6 mol% of AgBrO on a part of the grain surface) 0.20 gelatin
1.00 cyan coupler (IExC)
0.32 color image stabilizer (Cpd-6)
0.17 color image stabilizer (Cpd-7)
0.40 color image stabilizer (Cpd-8)
0.04 solvent (Solv-6)
0.15 Sixth layer (ultraviolet absorption layer) Gelatin 0.48 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (
Sol Sea 5) 0.08 Seventh layer (protective layer) Gelatin 1.26 Acrylic of polyvinyl alcohol 0.17 Modified copolymer (degree of modification 17%) Liquid paraffin 0.03 1 with (ExY) yellow coupler: ■ Mixture (molar ratio) -111, - 1:1 mixture (molar ratio) of (Cpd-1) color image stabilizer (Cpd-2) color image stabilizer (Cpd-3) color image stabilizer (ExM) magenta coupler A 2:4:4 mixture of R"'CtHs, aNq, and 11 liters by weight, respectively (Cpd-5) Color mixture inhibitor H (Cpd-6) A 2:4:4 mixture of color image stabilizer (by weight) ) (Cpd-7) Color image stabilizer + C11I CH → Co (Cpd-8) Color image stabilizer H (cpd-9) Color image stabilizer (Sol Sea 1) Solvent (UV-1) Ultraviolet absorber ( Solv-2) 7 medium 41'19 (L) (Solv-5) Solvent 15 16 (Solv-5) Solvent COOC8+117 (CI+2)B COOCR1117 (Solv-6) ?Volume Prepare sample 101 in this way did.

The sample was subjected to gradation exposure of a three-color separation filter for sensitometry using a sensitometer (Model FWH manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3200''K).The exposure at this time was 0. The exposure time was 1 second and the exposure amount was 250 CMS.

After the exposure, the sample was subjected to continuous processing (running test) using a paper processing machine until twice the capacity of the color development tank was replenished in the next processing step.

Processing process: Direct peel, crushed field, ixi”-mu raw volume, 1 color development, 40'C, 15 seconds, 60ml, 54!
Bleach fixing 40'C 15 seconds 60ml 51 rinse ■ 40'C 15 seconds -5 rinse ■ 4
0°C 15 seconds -5 Rinse ■ 40°C 15 seconds
60mQ 5j2 Dry 70~80℃2
0 seconds *The replenishment amount was per 1M of photosensitive material (3 tank countercurrent method was used from rinsing ■ to ■.) The composition of each processing solution was as follows.

Imperial Niga-(4 liquids, replenishment water, 800ml)
800ml Ethylenediamine-NNNN Tetramethylenephosphonic acid Potassium bromide Triethanol Agon Sodium chloride Potassium carbonate N-ethyl-N-(3-hydroxypropyl)-3 1,5g 2.0g O,015g 8.0 g 12. 0 g 1.4 g 25 g 25 g Methyl 4-aminoaniline Civaradruene sulfonate N,N-bis(carboxymethyl) Hydrazine optical brightener (WIIITIEX 4B 6.8 g 5.5 g 9.5 g 7.0 g Lower A rinse solution prepared as shown in 1 to ■ in the table was prepared.The chelating agent used was added at a concentration of 32 mmol/l, and the pH was adjusted to 6.5 with thorium hydroxide.The water used was Magnesium adds water
10100O1000m#ρ11(2
5℃) 10.05 10
．． 45m liquid, (tank liquid and refill liquid are the same) water
400ml! Ammonium thiosulfate (70%)
100ml! 1-lium sulfite
17g Iron (I) ethylenediaminetetraacetate Ammonium 5g Disodium ethylenediaminetetraacetate g Add water to pH (25℃) 1□ (tank solution and replenisher are the same) 000m 6.0 Yellow after color development processing , magenta and cyan coloring densities were measured using a densitometer to obtain a so-called characteristic curve.

Furthermore, the processed photosensitive material 19 20 at the start and end of continuous processing was aged at 70°C and 70% for 8 days, and the increase in blue density due to the aging of the lowest density part was calculated as stain, and the initial density 2
．． The decrease in density at the 0 portion was evaluated as a fading value.

A sample 102 was created with only the following parts changed from sample 101.

Sample Nα Standard prescription Layer Contents 102
101 1st layer Gelatin 1.00 2nd layer
Gelatin 1.25 3rd N Gelatin 1.10 4th layer Gelatin 1.42 The "alkali consumption" of sensitive material sample 101 is 2.5 mmo
1/bo, and the sensitive material sample 102 had a concentration of 3.1 mmol/bo.

The table below shows the color density for the blue density at the start of continuous processing, staining for the sample at the start and end of continuous processing, and fading value for the blue density at the start and end of continuous processing. .

As is clear from Tables 1 to 4, it can be seen that the compounds of the present invention have a large stain improvement effect, and the fading caused by addition is less aggravated. Comparative Example (3) has good stain, but does not satisfy the <1.-tal performance of fading. Comparative example■
It can be seen that the improvement effect of STEIN is small for ~■.

For both rinse solutions No. and I to ■, the color density was sufficient after 95 seconds of treatment, but the adverse effects of rapid treatment led to deterioration of staining, etc., and it can be seen that the compounds of the present invention are particularly excellent in terms of total performance.

In addition, the surface of the sample using rinsing liquid (■) became cloudy after the stain test, which deteriorated the quality.

Furthermore, sample 10 with an alkali consumption of 3.1 mmol/bo
Sample No. 2 shows a stain improvement effect compared to the comparative example, and also has less deterioration in fading, but Sample 101 with an alkali consumption of 2.6 mmol/bo has better rapid processability and a greater stain improvement effect. I understand that.

Example 2 The same process was carried out using the sensitive material of sample 101 of Example 1 and rinsing liquid I, except that the temperature of the rinsing liquid was 30°C and 135°C. Table 5 shows the results of staining measured in the same manner as in Example 1.

(Table 5) (Table 6) 24 Although the effect of the present invention is great, it can be seen that under conditions of short water washing, the difference in water washing temperature affects the stain.

Example 3 The same process was carried out using the sensitive material of sample 101 in Example 1 and rinsing liquid I, except that the rinsing liquid was used in one bath and two baths. Table 6 shows the results of staining measured in the same manner as in Example 1.

Although the effect of the present invention is great, it can be seen that the difference in the number of washing tanks affects the stain under conditions of short washing.

Example 4 Using the sensitive material of sample 101 of Example 1 and rinsing liquid I, the replenishment amount of the rinsing liquid was set to 60/bo, 150 iffi/bo, 2
The same treatment was carried out except that the concentration was 00 ml/rIf. Table 7 shows the results of staining measured in the same manner as in Example 1.

(Table 7) The effect becomes smaller when the replenishment amount is 150 mff/m2 or more.

Moreover, if the amount of replenishment is large, the amount of waste liquid will increase, which is not preferable in terms of simplification.

Example 5 Sample 5 in which only the following parts were changed in sample 101
01 was created.

Sample Nα Layer 501 1st layer 3rd layer 5th layer 6th layer 7th N Contents Gelatin 0.51 Coupler coating amount 0.480.
38 0.1B0.35
0.220.20 0.38 The alkali consumption of this sample is 1.75 mmol/n?
Met. This sample and Sample 102 were treated with the following changes compared to the treatment of Example 1, and color density and stain were evaluated.

Item Development time Bleach-fixing time Rinse time Rinse liquid Changes 10 seconds 10 seconds 10 seconds Solution I, 3-tank solution ■ only (Table 8) Stin results (after continuous processing) Solution I (invention) Solution ■ (comparative example) ) Sample 501 1), 10 0.14 It can be seen that the present invention is superior when processing is further accelerated. It can also be seen that the amount of alkali consumed is also important.

Example 6 Color negative film 5HG400 (manufactured by Fuji Photo Film ■) was subjected to image exposure and then subjected to Fuji Color Process CN-16 processing (color development for 3 minutes and 15 seconds, bleaching for 6 minutes and 30 seconds, and washing for 2 minutes and 10 seconds) by Fuji Photo Film Co., Ltd. , fixing time 4 minutes 20 seconds,
After washing with water for 3 minutes and 15 seconds, washing with water for 1 minute and 127 seconds, and window treatment for 1 minute and 5 seconds, it was dried. Each treatment was performed at 38.0±0.2°C).

In addition, the compound of the present invention (
CN1 except that 12), (13) or (14) was added.
It was treated in the same way as the 6 process.

When each film of the processing agent was exposed to 80'C70% for 14 days, the increase in the lowest density (blue color) was evaluated, and it was found that the use of the chelating agent of the present invention was able to suppress the increase.

(Effects of the Invention) According to the present invention, it is possible to provide a method for processing a silver halide photographic material that effectively prevents staining and further reduces deterioration of fading, and a final processing composition for achieving the method.

In particular, the method and final processing composition of the present invention are effective in ultra-rapidly processing silver halide color photographic materials having a high silver chloride content and suitable for rapid processing.

) (3 others) 28 Procedural amendment September 21, 1990

Claims (5)

[Claims] (1) A method for processing a silver halide photographic light-sensitive material, which comprises incorporating a compound represented by the following general formula (I) into the light-sensitive material after a fixing process. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the general formula (I), R^1, R^2, R^3 and R
^4 each independently represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and if possible, may be linked to each other to form a ring. M^1 and M^2 each represent a hydrogen atom or a cation. ] (2) The compound represented by general formula (I) is incorporated into the photosensitive material by including it in the final processing bath or its pre-bath, and/or by coating it on the photosensitive material after the final bath processing. The processing method according to claim (1), characterized in that: (3) The silver halide photographic light-sensitive material has at least one silver halide emulsion layer containing 90 mol% or more of silver chloride.
It is a silver halide color photographic light-sensitive material having a layer, and the "alkali consumption" of the light-sensitive material is 2.6 mmol/m.
Claim (1) or (2) characterized in that the
) Processing method described. (4) In the processing of the silver halide color photographic light-sensitive material, the development time is substantially within 20 seconds, the time from the color development process to the end of the drying process is within 100 seconds, and the water washing process (stabilization process is also included). (including) the processing temperature of the bath is 35° C. or higher, the water washing process is a countercurrent method using 2 to 5 tanks, the water washing processing liquid is replenished in an amount of 150 ml or less per 1 m^2 of the sensitive material, and the water washing processing The total time for washing with water in the bath is 45
The processing method according to claim 3, wherein the processing time is within seconds. (5) A final processing composition for developing a silver halide photographic material, which contains a compound represented by the general formula (I) according to claim (1).