JPH0540333A - Color developing solution for silver halide color photographic sensitive material and processing method using same solution - Google Patents

Abstract

PURPOSE:To provide the color developing solution small in malodor, adapted to operation environment, superior in preservability, small in crystal precipitation to the inside wall of the tank of an automatic developing machine, superior in color developability, capable of processing 2 kinds of photosensitive materials different in halogen composition by incorporating a combination of a specified preservative and a specified chelating agent in the color developing solution. CONSTITUTION:This combination is at least one of the compounds represented by formula [and the like and at least one of the chelating agents represented by formula II and the like. In formulae I and II, oxygen or -R1-N<; R1 is H, OH, or optionally substituted lower alkyl; n is 0, l, car 2; each of A1 and A2 is, independently, -COOM, -PO3M2, or -CH2OH; and II is H or an alkali metal atom. The photosensitive materials different in halogen composition are processed with this color developing solution in the case of using a common color developing solution.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color developing solution for silver halide color photographic light-sensitive materials and a processing method using the color developing solution. More specifically, it is difficult to cause crystal precipitation on the wall surface of a tank of an automatic processor. The present invention relates to a color developer and a processing method suitable for processing two types of light-sensitive materials having improved fog in the exposed area and having different halogen compositions.

[0002]

BACKGROUND OF THE INVENTION Silver halide color photographic light-sensitive materials (hereinafter abbreviated as color light-sensitive materials as necessary) are used for photographing color light-sensitive materials represented by color negative films and print color light-sensitive materials represented by color paper. Broadly divided.

In the color developing solution for the present color negative film processing, 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate (usually CD-4) is used as a color developing agent. ) Has been used.
However, recent studies have shown that the use of CD-4 in color negative films has some inherent problems. One problem is that the dye formed by reacting with CD-4 generally has poor light fastness, and therefore the imagewise exposed developed film used to set the exposure conditions of the automatic printer is While the exposure is repeated many times to set the print condition, the fading occurs and the correct exposure condition cannot be set.

Conventionally, color light-sensitive materials have been processed only in large-scale developing laboratories, but in recent years, small-sized processing devices for processing at storefronts such as photo shops have rapidly become popular.
These small stores often have a minimum of two processing units for color film and color paper, even though the inside of the store is small. Therefore, a lot of space is required for the processing units. Therefore, it is extremely important to install and widen the work space, and it has been strongly desired to develop a processing method that achieves further downsizing of the processing apparatus and simplification of the processing work.

On the other hand, as a recent trend, there is a tendency that the replenishment amount of the processing liquid is low due to the economical viewpoint, the viewpoint of preventing pollution, and the need for labor saving in the developing station by reducing the dissolution frequency of the processing liquid. .. This low replenishment has made it possible to reduce the frequency of dissolution of the processing solution and downsize the processing equipment, but with only low replenishment technology, at least two processing equipment, a film developing machine and a print developing machine, are still available. is necessary.

In view of this, Japanese Patent Application Laid-Open No. 64-15741 proposes a technique in which a film developing function and a print printing developing function are provided in a single processing apparatus to achieve downsizing of the processing apparatus. However, since the processing liquid is divided into the color photosensitive material for photography and the color photosensitive material for printing, a circulation pump, a filter case, a heater unit, a replenishing pump, etc. are required for each processing liquid tank, and the size of the automatic developing machine is reduced. Is also insufficient, and it is not sufficient to reduce the types of processing liquids and simplify the work.

On the other hand, JP-A-60-129741 and JP-A-60-129748
No. 60-147148, No. 61-134759, JP-A-1-154153
No. 1, No. 1-244449, etc. process color photosensitive materials for photography and color photosensitive materials for printing, which were conventionally processed in different processing units, in the same processing liquid tank in some or all processing steps. Techniques for completing it have been proposed.

If these proposals can be embodied, only one processing unit will be required and the installation space will be greatly reduced. Further, since the types of processing liquids used are also reduced, the stock space for the processing liquids is greatly reduced, and the work can be simplified.

In recent years, as a color light-sensitive material for printing, a material using a silver halide emulsion mainly containing silver chloride has been widespread from the viewpoint of rapid processing. When a hydroxylamine salt, which has been generally used in the past, is used as a preservative for the developing agent in the color developing solution used when processing these color light-sensitive materials for printing, the development of the print is suppressed and it becomes practical. Cannot be used for. Therefore, an organic preservative such as diethylhydroxylamine has been used. When processed with a developer containing this diethylhydroxylamine, a color developing material for photography and a color developing material for printing are commonly developed. It turned out that there is a big problem when treating with liquid. It is obtained by processing a silver iodobromide-containing color light-sensitive material with the above-mentioned diethylhydroxylamine-containing color developing solution which is conventionally used for processing a silver chloride-based color photographic light-sensitive material. In the case of a color light-sensitive material, development suppression will occur.

As another problem, when the silver iodobromide light-sensitive material is processed with the color developer containing diethylhydroxylamine as described above, dyeing occurs on the lower turn roller of the color developing tank, and this dyeing occurs. It has been found that the coloring dye adheres to the light-sensitive material to be processed and causes a failure.

Further, in recent years, the replenishment amount has been reduced from the viewpoint of reducing pollution, but the above problems are becoming more serious when applying such a low replenishment amount to a common treatment.

Further, looking at the color developing solution itself, that is, because the preservability of the processing solution itself deteriorates regardless of the photosensitive material to be processed, crystals are deposited on the wall surface or the roller portion in the tank of the automatic developing machine. Also, the color developing solution is colored and further blackened, and when applied to the processing of the photosensitive material, stains and scratches are likely to occur on the photosensitive material. Also, in the case of a small-scale store that uses a normal small-sized processing device, the switch is turned on in the morning to raise the processing temperature, and after the development processing is completed, it is turned off at night to save power.
Therefore, the temperature in the tank of the automatic processor repeatedly rises and falls in a cycle of 24 hours, and this temperature difference is large in cold regions in winter, and in some cases, the temperature difference becomes close to 30 ° C. Under such circumstances, p in the color developing solution
It has been found that phenylenediamines (mainly color bases) have the drawback that they tend to precipitate as crystals.

Furthermore, when the color developing solution is left to stand for several days, odor is generated due to concentration of the processing solution, which causes a problem of deteriorating the working environment.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color developing solution for a silver halide color photographic light-sensitive material and a processing method, which has little odor and is suitable for working environment. A second object is to provide a color developing solution for silver halide color photographic light-sensitive material and a processing method which are excellent in preservability, have less crystal precipitation on the wall surface of an automatic developing machine tank, etc. and have excellent colorability. The third purpose is to provide a color developer for silver halide color photographic light-sensitive materials and a processing method capable of processing two kinds of light-sensitive materials having different halogen compositions, and the fourth purpose is to enable rapid processing. Another object of the present invention is to provide a color developing solution for a silver halide color photographic light-sensitive material having stable photographic performance and a processing method using the color developing solution.

[0015]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a specific preservative and a chelating agent are contained in a color developing solution in combination. The inventors have found that the above problems can be solved, and completed the present invention.

That is, the color developing solution for a silver halide color photographic light-sensitive material according to the present invention comprises the following general formulas [A] and [B].
Alternatively, at least one compound represented by [C] and at least one compound represented by the following general formula [I] or [II] are used in combination. General formula [A]

[0017]

[Chemical 8] [In the formula, X represents an oxygen atom or R ₁ -N <, and R ₁ represents a hydrogen atom, a hydroxyl group or a lower alkyl group which may have a substituent (for example, a methyl group, an ethyl group, an ethanol group, -CH ₂ PO
₃ H ₂ , —CH ₂ CH ₂ SO ₃ H, —CH ₂ CH ₂ COOH, etc.). N represents 0, 1 or 2. ] General formula [B]

[0018]

[Chemical 9] [In the formula, R ₂ and R ₃ represent a hydrogen atom or an alkyl group (including a substituent), and at least one of R ₂ and R ₃ is an alkyl group having 1 to 5 carbon atoms substituted with an alkoxy group,
An alkyl group having 1 to 5 carbon atoms substituted with a sulfonic acid group,
It represents an alkyl group having 1 to 5 carbon atoms substituted with phosphonic acid, an alkyl group having 1 to 5 carbon atoms substituted with carboxylic acid, or an alkyl group having 1 to 5 carbon atoms substituted with an ammonium group. ] General formula [C]

[0019]

[Chemical 10] [Wherein R ₄ , R ₅ and R ₆ each represent a hydrogen atom, an alkyl group (including a substituent), an aryl group (including a substituent) or a heterocyclic group (including a substituent), and R ₈ is a hydroxy group, Hydroxyamino group, alkyl group (including substituted),
An aryl group (including a substituent), a heterocyclic group (including a substituent), an alkoxy group (including a substituent), an aryloxy group (including a substituent), a carbamoyl group (including a substituent) or an amino group (including a substituent) Represent R ₇ is -CO-, -S
Represents a divalent group selected from O ₂ — or> C═NH,
n is 0 or 1. ] General formula [I]

[0020]

[Chemical 11] Wherein, A ₁ to A ₅ are, -COOM, -PO ₃ M ₂ or -C
H ₂ OH, all of which may be the same or different, represent a hydrogen atom or an alkali metal (eg, sodium, potassium, lithium). ] General formula [II]

[0021]

[Chemical formula 12] Wherein, A ₆ represents -OH or -NH _2, M represents a hydrogen atom or an alkali metal (e.g. sodium, potassium, lithium). R ₁ is _{-CH 3, -C 2 H 5,} -CH 2 C
It represents H ₂ OH or a lower alkyl group having a substituent. ]
A preferred embodiment of the present invention is that the color developer contains at least one compound represented by the following general formula [E]. General formula [E]

[0022]

[Chemical 13] [Wherein X ₂ , X ₃ , Y ₁ and Y ₂ are each a hydroxyl group, a halogen atom, an alkyl group, an aryl group,

[0023]

[Chemical 14] Alternatively, it represents -OR ₂₅ . Here, R ₂₁ and R ₂₂ are each a hydrogen atom, an alkyl group (including a substituent) or an aryl group (including a substituent), R ₂₃ and R ₂₄ are an alkylene group (including a substituent), R ₂₅ Represents a hydrogen atom, an alkyl group (including a substituent) or an aryl group (including a substituent), and M represents a cation].

Further, the method of processing a halogen color photographic light-sensitive material according to the present invention is a silver halide color photographic light-sensitive material in which the average silver iodide content of the silver halide emulsion layer coated on the support is 3 mol% or more. (A) and a silver halide color photographic light-sensitive material (b) in which at least one silver halide emulsion layer coated on a support has a silver chloride content of 80 mol% or more, treated with a common color developer. In the method for processing a silver halide color photographic light-sensitive material, the processing is performed with the above-mentioned color developing solution for a silver halide color photographic light-sensitive material.

[0025]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, at least one compound selected from the compounds represented by the above formulas [A], [B] and [C] is selected and used in the color developing solution.

Specific examples of the compound represented by the general formula [A] are shown below, but the invention is not limited thereto.

[0027]

[Outer 1]

The compound represented by the general formula [A] may be a salt, and specifically, a sulfate, a hydrochloride, an oxalate, a phosphate of the compound represented by the general formula [A], Nitrate or the like can be used.

In the above general formula [B], the details of R ₂ and R ₃ have the same meanings as R ₁ and R _{2 in} the general formula [I] described in JP-A-63-43143. Specific examples of the compound represented by the general formula [B] are shown below, but the invention is not limited thereto.

[0030]

[Outside 2]

The compounds represented by the general formula [B] are
It is usually used in the form of free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, acetate and the like.

In the above general formula [C], R _Four~ R ₉Details of
For details, refer to Japanese Patent Application No. 2-127444, page 15, lines 1-16
R in formula [I '] ₁₁~ R ₁₄Is synonymous with. Below, the general formula
Specific examples of the compound represented by [C] are shown below, but are not limited thereto.
Not determined.

[0033]

[Outside 3]

[0034]

[Outside 4]

[0035]

[Chemical 15]

The compounds represented by the general formula [C] are
It is usually used in the form of free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, acetate and the like.

The compounds represented by the above general formulas [A], [B] and [C] are preferably in the range of 0.4 to 100 g, more preferably 1.0 to 60 g, still more preferably 2 to 30 g per liter of color developing solution. Used in.

Next, the compound represented by the general formula [I] will be described. Specific examples of the compound represented by the general formula [I] are shown below, but the invention is not limited thereto.

[0039]

[Outside 9]

Among the above-mentioned compound examples, the one particularly preferably used in the present invention is (I-1).

Next, the compound represented by the general formula [II] will be described. Specific examples of the compound represented by the general formula [II] are shown below, but the invention is not limited thereto.

[0042]

[Outside 10]

Among the above-mentioned compound examples, the one particularly preferably used in the present invention is (II-1).

The addition amount of the compounds represented by the general formulas [I] and [II] is 0.1 to 20 per liter of the color developing solution.
The range of g is preferable, and the range of 0.2 to 8 g is more preferable.

Next, the compound represented by the general formula [E] will be described. The details of each group of the general formula [E] or the substituents thereof are the same as those described in Japanese Patent Application No. 2-240400, page 63 to page 8, line 8 to page 64, page 3 to page 3. Specific examples of the compound represented by the general formula [E] are shown below.

[0046]

[Outside 11]

[0047]

[Outside 12]

[0048]

[Outside 13]

[0049]

[Outside 14]

[0050]

[Outside 15]

The color developing solution may contain a commonly used color developing agent, but in the present invention, it is preferable to use the color developing agent represented by the following general formula [III]. General formula [III]

[0052]

[Chemical 17] [In the formula, R ₁₀ , R ₁₁ and R ₁₂ may be the same or different and each represents a methyl group, an ethyl group, a propyl group, a hydroxyethyl group, a sulfone alkyl group or a β-methanesulfonamidoethyl group. However, R ₁₀ and R ₁₁
And at least one of R ₁₂ is a β-methanesulfonamidoethyl group. X ₁ represents sulfuric acid, hydrochloric acid, p-toluenesulfonic acid or phosphoric acid. ] The following general formula [II
Specific examples of the compound represented by the formula [I] are shown below, but the present invention is not limited thereto.

[0053]

[Outside 16]

Among the compounds represented by the general formula [III], (III-1) is particularly preferably used. These compounds are preferably 1 × 1 per liter of color developer.
It is used at a concentration of 0 ^{-2 to} 2 x 10 ^-1 mol, but from the viewpoint of rapid treatment, it is particularly preferably used at a concentration of 1.5 x 10 ^-2 to 2 x 10 ^-1 mol.

Further, the development inhibitors preferably used in the color developing solution include halides such as sodium chloride, potassium chloride, sodium bromide and potassium bromide, as well as organic inhibitors, and the addition amount thereof is 0.005. ~ 30g
It is preferably used in the range of 0.01 to 20 g / liter, more preferably 0.01 to 20 g / liter. Examples of the organic inhibitor include a nitrogen-containing heterocyclic compound, a compound containing a mercapto group, an aromatic compound, an onium compound and a compound having an iodine atom as a substituent.

Further, the color developing solution used in the present invention contains, if necessary, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other Japanese Patent Publication Nos. 47-33378 and 44-9509. The compounds described in the publication can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developing agent may be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol hexalphate (methol), phenidone, and N, N-diethyl-p-.
Aminophenol hydrochloride, N, N, N ′, N′-tetramethyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably 0.01 to 1.0 g / liter.

Further, various additives such as stain inhibitors, sludge inhibitors, and stacking effect accelerators can be used.

More generally, a plurality of components which can coexist stably can be used as a concentrated aqueous solution or in a solid state which is previously prepared in a small container and added to water and stirred to be adjusted. it can.

In the present invention, the pH of the color developer is
Is preferably pH 9.5 to 13.0, more preferably pH 9.8 to 12.0. The processing temperature is 33.0 ° C. or higher, more preferably 36.0 to 43.0 ° C., particularly preferably 39.0 to 42.0 ° C., and the processing time is preferably 20 seconds to 4 minutes for the color light-sensitive material (a), and more preferably Is 50 seconds to 2 minutes and 30 seconds. For the color light-sensitive material (b), it is preferably 5 seconds to 1 minute, more preferably 8 seconds to 35 seconds.

One of the preferred embodiments of the processing method of the present invention is a method of flowing a part or all of the overflow solution of the color developing solution into the bleaching solution in the next bleaching step. This is because when a certain amount of the color developing solution is flowed into the bleaching solution, the generation of sludge due to silver in the bleaching solution is suppressed.

Further, in addition to the above system, when a part or all of the overflow solution of the stabilizing solution in the subsequent step is poured into the bleach-fixing solution or the fixing solution, the silver recovery efficiency is improved.

From the viewpoint of the effect of the present invention, the replenishing amount of the color developing solution in the present invention is 1.5 per 1.0 m ² of the color photosensitive material (a) when the color photosensitive material (a) is processed.
It is preferably less than 1 liter, and 300 ml to 700 ml more effectively achieves the object of the present invention. When processing the color photosensitive material (b), the color photosensitive material (b) 1.0m
^It is preferably 300 ml or less per ² and more preferably 20 ml to
180 ml, more preferably 30 to 100 ml.

Main examples of preferable processing steps in the processing method using the color developing solution of the present invention are shown in FIGS. 1 and 2, but the present invention is not limited thereto.

In the figure, the broken line means the processing flow of the color photosensitive material (a), and the solid line means the processing flow of the color photosensitive material (b). Among these steps, (1), (2), (6), (7) and (10) are preferably used.

The bleaching agent preferably used in the processing solution having a bleaching ability according to the present invention is a ferric iron complex salt of an organic acid represented by the following general formula [IV].

[0067]

Embedded image General formula [IV] [In the formula, A _{1 to} A ₄ may be the same or different,
-CH ₂ OH, represents a -COOM or -PO ₃ M ₁ M _2. M, M ₁ , M ₂
Each represents a hydrogen atom, an alkali metal or ammonium. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms. ] The compound represented by formula [IV] is described in detail below. In the formula, A _{1 to} A ₄ are Japanese Patent Application No. 1-260628.
The description is omitted because it has the same meaning as A _{1 to} A ₄ described on page 12, line 15 to page 15, line 3 from page 15. The preferred specific examples of the compound represented by the general formula [IV] are shown below.

[0068]

[Outside 17]

As the ferric complex salt of these compounds (IV-1) to (IV-12), any of sodium salt, potassium salt and ammonium salt of these ferric complex salts can be used. From the viewpoint of the effect of the present invention and solubility, ammonium salts of these ferric complex salts are preferably used.

Of the above-mentioned compound examples, those particularly preferably used in the present invention include (IV-1) and (IV-
3), (IV-4), (IV-5) and (IV-9), with (IV-1) being particularly preferred.

In the present invention, the bleaching solution or the bleach-fixing solution may contain, as a bleaching agent, a ferric complex salt of the following compound in addition to the iron complex salt of the compound represented by the above general formula [IV]. You may use together. [A'-1] ethylenediaminetetraacetic acid [A'-2] trans-1,2-cyclohexanediaminetetraacetic acid [A'-3] dihydroxyethylglycinic acid [A'-4] ethylenediaminetetrakismethylenephosphonic acid [A'- 5] Nitrilotrismethylenephosphonic acid [A′-6] diethylenetriaminepentakismethylenephosphonic acid [A′-7] diethylenetriaminepentaacetic acid [A′-8] ethylenediaminedioltohydroxyphenylacetic acid [A′-9] hydroxyethylethylenediamine Acetic acid [A'-10] ethylenediamine dipropionic acid [A'-11] ethylenediamine diacetic acid [A'-12] hydroxyethyliminodiacetic acid [A'-13] nitrilotriacetic acid [A'-14] nitrilotripropionic acid [A'-12] A'-15] Triethylene tet Min hexaacetic acid [A'-16] ethylenediaminetetraacetic propionic acid

The amount of the ferric organic acid complex salt added is preferably in the range of 0.1 mol to 2.0 mol, more preferably 0.15 to 1.5 mol / l, per liter of the bleaching solution or the bleach-fixing solution. ..

The bleaching solution, the bleach-fixing solution and the fixing solution include imidazole and its derivatives described in JP-A No. 64-295258, and general formulas [I] to [I] described in the same.
By containing the compound represented by the formula [X] and at least one of these exemplified compounds, an effect can be exerted on the rapidity.

In addition to the above-mentioned accelerators, the exemplified compounds described on pages 51 to 115 of JP-A-62-123459 and pages 22 to 25 of JP-A-63-17445. The exemplified compounds described in JP-A-53-95630 and JP-A-53-28426 can also be used in the same manner.

The temperature of the bleaching solution or the bleach-fixing solution is 20 ° C to 50 ° C.
However, the temperature is preferably 25 ° C to 45 ° C.

The pH of the bleaching solution is preferably 6.0 or less, more preferably 1.0 or more and 5.5 or less. The pH of the bleach-fixing solution is preferably 5.0 to 9.0, more preferably 6.0.
~ 8.5. The pH of the bleaching solution or the bleach-fixing solution is the pH of the processing tank at the time of processing the silver halide light-sensitive material,
It can be clearly distinguished from the so-called replenisher pH.

In addition to the above, the bleaching solution or the bleach-fixing solution may contain halides such as ammonium bromide, potassium bromide and sodium bromide, various fluorescent whitening agents, defoaming agents or surfactants. it can.

The replenishing amount of the bleaching solution or the bleach-fixing solution is preferably 500 ml or less, preferably 20 ml to 400 ml, and most preferably 40 ml to 350 ml per 1 m ^{2 of the} silver halide color photographic light-sensitive material, which is a low replenishing amount. The more significant, the more remarkable the effect of the present invention becomes.

In the present invention, in order to enhance the activity of the bleaching solution or the bleach-fixing solution, air may be blown or oxygen may be blown in the processing bath and the storage tank of the processing replenisher, if desired, or appropriate oxidation is carried out. Agents, such as hydrogen peroxide,
Bromate, persulfate and the like may be added appropriately.

As the fixing agent used in the fixing solution or the bleach-fixing solution according to the present invention, thiocyanates and thiosulfates are preferably used. The content of thiocyanate is preferably at least 0.1 mol / liter or more, more preferably 0.5 mol / liter or more, and particularly preferably 1.0 mol / liter or more when processing a color negative film. The content of thiosulfate is at least 0.2
The amount is preferably mol / liter or more, more preferably 0.5 mol / liter or more when processing a color negative film. Further, in the present invention, the object of the present invention can be achieved more effectively by using thiocyanate and thiosulfate in combination.

The fixing solution or the bleach-fixing solution according to the present invention may contain, in addition to these fixing agents, a pH buffering agent comprising various salts, either alone or in combination of two or more. Further, it is desirable to add a large amount of alkali halide or ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride or ammonium bromide. In addition, compounds known to be added to ordinary fixing solutions or bleach-fixing solutions such as alkylamines and polyethylene oxides can be appropriately added.

Silver may be recovered from the fixing solution or the bleach-fixing solution according to the present invention by a known method.

The replenishing amount of the fixing solution is preferably 900 mol / l or less per 1 m ² of the light-sensitive material, more preferably 20 mol / l to 750 mol / l per m ² of the light-sensitive material, particularly preferably 50 to 620 mol / l. It is a liter.

The pH of the fixing solution is preferably in the range of 4-8.

A fixing solution or a bleach-fixing solution is described in JP-A-64-2
It is preferable to add the compound represented by the general formula [FA] described on page 56 of the specification of No. 95258 and its exemplified compounds,
Not only the effect of the present invention is better exhibited, but also when a small amount of a light-sensitive material is processed for a long period of time, an extremely small amount of sludge is generated in a processing solution having fixing ability.

The processing time with the bleaching solution and the fixing solution is optional, but is preferably 3 minutes and 30 seconds or less, more preferably 10 seconds to 2 minutes and 20 seconds, and particularly preferably 20 seconds to 1 minute.
It is in the range of 20 seconds. The processing time with the bleach-fix solution is 4
Minutes or less are preferable, and more preferably 10 seconds to 2 minutes and 20 seconds.

In the present invention, the stabilizing solution preferably contains a chelating agent having a chelate stability constant for ferric ions of 8 or more. Here, the chelate stability constant is the "Stability Constant" by LG Sillen / AEMartell.
s of Metal-ion Complexes ", The Chemical Society, Lond
on (1964). S. Chaberek AEMartell, "Organic Seq
uestering Agents ", Wiley (1959) and others.

As a chelating agent having a chelate stability constant for ferric ions of 8 or more, Japanese Patent Application No. 2-234776
Nos. 1-324507 and the like.

The amount of the above chelating agent used is preferably 0.01 to 50 g, and more preferably 0.05 to 20 g, per liter of the stabilizing solution.
Good results are obtained in the range of g.

As a preferable compound to be added to the stabilizing solution, an ammonium compound can be mentioned. These are supplied by ammonium salts of various inorganic compounds. Addition amount of ammonium compound is 0.0 per liter of stabilizer.
The range of 01 mol to 1.0 mol is preferable, and more preferably
It is in the range of 0.002 to 2.0 mol.

Further, the stabilizing solution preferably contains sulfite.

Furthermore, it is preferable that the stabilizing solution contains a metal salt in combination with the chelating agent. Such metal salts include Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb,
Sn, Zn, Ti, Zr, Mg, There is a metal salt of Al or Sr, which can be supplied as an inorganic salt such as a halide, a hydroxide, a sulfate, a carbonate, a phosphate, an acetate or a water-soluble chelating agent. The amount used is 1 x 10 ^-4 to 1 x 10 per liter of stabilizing solution.
^-1 mol range is preferable, more preferably 4 × 10 ^-4 ~ 2
It is in the range of × 10 ^-2 mol.

To the stabilizing solution, organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH adjusting agents (phosphate salts, borate salts, hydrochloric acid, sulfate salts, etc.) are added. can do. In the present invention, known antifungal agents can be used alone or in combination as long as the effects of the present invention are not impaired. Further, in the treatment of the present invention, silver may be recovered from the stabilizing solution by a known method.

Further, the stabilizing solution is subjected to ion exchange treatment, electrodialysis treatment (see JP-A-61-28949) and reverse osmosis treatment (JP-A-60).
-240153 and JP-A-62-254151).
Further, it is also preferable to use deionized water used in the stabilizing solution in advance. That is, the mildew resistance of the stabilizing solution, the stability of the stabilizing solution, and the image storability are improved. As the deionization treatment means, Ca and M of the rinse water after the treatment are treated.
Any material may be used as long as it has a g-ion content of 5 ppm or less. For example, it is preferable to use treatment with an ion exchange resin or a reverse osmosis membrane alone or in combination. Ion exchange resins and reverse osmosis membranes are described in detail in Public Technical Report 87-1984 and Public Technical Report 89-20511.

No washing treatment is required after the stabilizing treatment, but rinsing by a small amount of washing in a very short time, surface washing and the like can be optionally performed.

In the present invention, the pH of the stabilizing solution is 5.5 to 1
A range of 0.0 is preferred. The pH adjusting agent that can be contained in the stabilizing solution may be any of commonly known alkaline agents or acid agents.

The treatment temperature for the stabilization treatment is 15 ° C to 70 ° C.
C is preferable, and more preferably in the range of 20 to 55 ° C. The treatment time is preferably 120 seconds or less, more preferably 3 seconds to 90 seconds, and most preferably 6 seconds to 50 seconds.

The replenishing amount of the stabilizing solution is preferably from 0.1 to 50 times, more preferably from 0.5 to 50 times the carrying amount of the pre-bath (fixing solution or bleach-fixing solution) per unit area of the light-sensitive material from the viewpoint of rapid processing property and storability of dye image. 30 times is preferable.

The stabilizing tank is preferably composed of a plurality of tanks, preferably 2 to 6 tanks, and particularly preferably 2 to 3 tanks in a counter current system (supplied to the post-bath. It is preferable to adopt a method of overflowing from the previous bath).

In the processing method of the present invention, it is preferable as an embodiment of the present invention to apply forced liquid agitation to the stabilizing solution, the bleach-fixing solution or the fixing solution. The reason is that not only the effect of the object of the present invention is better achieved, but also the suitability for rapid processing is improved. Here, the forced liquid agitation means not a normal liquid agitation movement but a liquid agitation means for agitation. As the forced stirring means, the means described in JP-A No. 64-222259 and JP-A No. 1-206343 can be adopted.

In the present invention, the effect different from that of the present invention is obtained when the crossover time from the color developing tank to the bleaching tank or the bleach-fixing tank is preferably within 10 seconds, more preferably within 7 seconds. Effective against bleached fog.

Next, the color photographic material to which the color developing solution or processing method of the present invention is applied will be described.

As the silver halide grains in the light-sensitive material, silver iodobromide or silver iodochloride having an average silver iodide content of 3 mol% or more is preferably used, and particularly from 4 mol%.
Silver iodobromide containing up to 15 mol% silver iodide is preferred. Among them, the average silver iodide content of the present invention is preferably 5 mol% to 12 mol%, and most preferably 8 mol% to 11 mol%.

In the color photographic light-sensitive material (a) used in the present invention, as the silver halide emulsion, those described in Research Disclosure 308119 (hereinafter abbreviated as RD308119) can be used. The table below shows the locations. [Items] [Page of RD308119] Iodine structure 993 I-A item Manufacturing method 993 I-A item and 994 E item Crystal habit Normal crystal 993 I-A item Twin 〃 Epitaxial 〃 Halogen composition uniform 993 IB item Uniform Not 〃 Halogen conversion 994 I-C 〃 Substitution 〃 Metal-containing 994 I-D Item Monodispersion 995 I-F Item Solvent addition 〃 Latent image forming position Surface 995 I-G Internal 〃 Applied Sensitive Material Negative 995 I-H Item Positive (including internal fog particles) 〃 Used by mixing emulsions 995 I-J item Desalting 995 II-A item

In the present invention, the silver halide emulsion is used after physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are
Disclosure No. 17643, No. 18716 and No. 308119 (hereinafter abbreviated as RD17643, RD18716 and RD308119, respectively).

The places described in the table below are shown. [Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-AA, B, C, D, E, H, I, J Item 23-24 648-9 Supersensitizer 996 IV-AE, J Item 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649

Known photographic additives that can be used in the present invention are also described in the above Research Disclosure. The following table shows the relevant locations. [Items] [Page of RD308119] [RD 17643] [RD 18716] Color turbidity inhibitor 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Whitening agent 998 V 24 UV absorber 1003 VIII C, Section XIII C 25-26 Light absorber 1003 VIII 25-26 Light-scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26-27 650 Matting agent 1007 X VI Developer (contained in light-sensitive material) 1011 XX-B Item

Various couplers can be used in the light-sensitive material used in the present invention, specific examples of which are described in the above-mentioned Research Disclosure. The following table shows the relevant locations. [Item] [Page of RD308119] [RD 17643] [RD 18716] Yellow coupler 1001 VII-D item VII C to G magenta coupler 1001 VII-D item VII C to G item Cyan coupler 1001 VII-D item VII C to Item G DIR coupler 1001 VII-F item VII F item BAR coupler 1002 VII-F item Other useful residue releasing coupler 1001 VII-F item Alkali-soluble coupler 1001 VII-E item

The additive used in the present invention is RD308119.
It can be added by the dispersion method described in XIV.

In the present invention, the above-mentioned RD17643 28
The supports described on page RD18716 pp. 647-8 and RD308119 XIX can be used.

For the light-sensitive material, the above-mentioned RD308119 VII is used.
An auxiliary layer such as a filter layer or an intermediate layer described in the section -K can be provided. The photosensitive material is RD3081 described above.
Various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the section 19VII-K can be adopted.

Next, the color photosensitive material (b) to which the present invention is applied will be described.

As the silver halide grains in the light-sensitive material, silver halide grains mainly containing silver chloride containing at least 80 mol% of silver chloride are used, preferably 90 mol% or more,
Particularly preferably, those containing 95 mol% or more are used, and most preferably those containing 99 mol% or more.

The silver halide emulsion mainly composed of silver chloride can contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride. In this case, the silver bromide content is 20 mol% or less. Is preferable, more preferably 10 mol% or less, further preferably 3 mol% or less, and when silver iodide is present, it is preferably 1 mol% or less, more preferably 0.5 mol%.
Below, it is most preferably zero. Such silver chloride 50
The silver halide grains mainly composed of silver chloride containing more than mol% are
It may be applied to at least one silver halide emulsion layer, but is preferably applied to all light-sensitive silver halide emulsion layers.

The crystal of the silver halide grain may be a normal crystal, a twin crystal, or another crystal, and has a [1.0.0] plane and a [1.1.1] plane.
Any surface ratio can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside or may have a layer (phase) -like structure (core-shell type) in which the inside and the outside are heterogeneous. Good. Also,
These silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain.
Further, tabular silver halide grains (JP-A-58-113934,
It is also possible to use Japanese Patent Application No. 59-170070). Further, silver halides described in JP-A 64-26837, 64-26838, 64-77047 and the like can be used.

Further, the silver halide grains are prepared by the acidic method,
It may be obtained by any preparation method such as a neutral method or an ammonia method.

Alternatively, for example, a method may be used in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size. When growing silver halide grains, the pH, pAg, etc. in the reaction vessel are controlled, and the amount of silver ions corresponding to the growth rate of silver halide grains as described in JP-A-54-48521 is used. It is preferable to sequentially and simultaneously inject and mix halide ions with halide ions.

The silver halide emulsion layer of the light-sensitive material processed according to the present invention contains a color coupler.

The red-sensitive layer can contain, for example, non-diffusible color couplers which produce cyan partial color images, generally phenol or α-naphthol based couplers. The green-sensitive layer is, for example, at least one non-diffusible color coupler, usually 5-, which produces a magenta partial color image.
A pyrazolone color coupler and a pyrazolotriazole can be included. The blue-sensitive layer can contain, for example, at least one non-diffusible color coupler that produces a yellow partial color image, typically a color coupler having open chain ketomethylene groups. Color couplers are 6, 4
Or it can be a two equivalent coupler.

In the present invention, 2-equivalent couplers are particularly preferable. Suitable couplers are disclosed, for example, in the following publication: Agfa's research report (Mitteilunglnausd).
en Forschungslaboratorien der Agfa), Leverkusen / Munchen, Vol.II
I.p.111 (1961) W. Pelz's "Color Coupler"(Farbkuppler); K. Venkataraman, "The Chemistry of Synthetic Soybean" (The Chemirsry of Synthe
tic Dyes), Vol. 4, 341-387, Academic Press (Ac
ademicPress), "The Theory of the Photograph Process"
ic Process), 4th edition, pp. 353-362; and Research Disclosure No.17643,
Section VII.

In the present invention, in particular, JP-A-63-10 is used.
No. 6655, page 26.
1] (the specific exemplary magenta couplers are described in JP-A-63-106655,
Examples include No. 1 to No. 77 described on pages 29 to 34. ), Also
The general formula [C-I] or [C-I] described on page 34
Cyan coupler represented by the formula [I] (Specific examples of the cyan coupler include (C'-
1) to (C'-82), (C "-1) to (C" -36)
And high-speed yellow couplers also described on page 20 (specifically exemplified yellow couplers include (Y'-1) to (Y'-39) described on pages 21 to 26 of the same specification). Is preferable from the viewpoint of the effect of the present invention.

Further, in order to more effectively achieve the object of the present invention, it is preferable to use a magenta coupler represented by the following general formula [MI] in the color light-sensitive materials (a) and (b). .. General formula [M-I]

[0123]

[Chemical 19] In the magenta coupler represented by, Z represents a non-metal atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent.

R represents a hydrogen atom or a substituent. In the general formula [M-I], the substituent represented by R is not particularly limited, but typically, each of alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl and the like. Examples thereof include a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, and the like.
Amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups, spiro compound residues, bridged hydrocarbon compound residues And so on.

The substituent represented by R, the group represented by X which can be removed by the reaction with the oxidation product of the color developing agent, the nitrogen-containing heterocycle formed by Z and the ring formed by Z may have. The preferred range and specific examples of the substituents, and the preferred range of the magenta coupler represented by the general formula [MI] are described in EP-A-0327272, page 5, line 23 to line 8.
Same as described on page 52, line 52. Below, the general formula [M
Typical examples of magenta couplers represented by -I] are shown below.

[0127]

[Chemical 20]

[0128]

[Chemical 21]

[0129]

[Chemical formula 22]

In addition to the typical examples described above, specific examples of the compound according to the present invention include those described in Japanese Patent Application No. 2-218720.
Of the compounds described on pages 63 to 82, No. 13, 3
4,42,57 to 59,61,62, 65 to 67, compounds disclosed in European Patent Publication No. 0327272, pages 10 to 28, No. 3,5 to 20,22 -33, 35-60, 62-77 and the compounds described in No. 0235913, pages 36-92, Nos. 1-4, 6, 8-17, 19-2
4, 26 ~ 43, 45 ~ 59, 61 ~ 104, 106 ~ 121, 123 ~ 162
, 164 to 223.

Further, the coupler is a Journal of the Chemical Society.
Society), Perkin I (1977), 2047-2
052, U.S. Patent 3,725,067, JP-A-59-99437, 58-
42045, 59-162548, 59-171956, 60-33552
No. 60, No. 60-43659, No. 60-172982, No. 60-190779, No. 6
It can be synthesized with reference to 2-209457 and 63-307453.

[0132] aforementioned couplers can also be used with other types of magenta couplers, usually 1 mol of silver halide per 1 × 10 ^-3 mol to 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10 ^- It can be used in the range of ¹ mol.

When a nitrogen-containing dicyclic mercapto compound is used in a light-sensitive material using an emulsion mainly composed of silver chloride, not only the effect of the present invention is satisfactorily achieved but also a bleach-fix solution is contained in a color developer. The effect on photographic performance that occurs when mixed,
Since it has another effect of making it extremely slight, it can be mentioned as a more preferable embodiment in the present invention.

Specific examples of these nitrogen-containing phosphine-containing mercapto compounds include (I'-1) to (I'-87) described in JP-A-63-106655, pages 42 to 45.

The silver halide emulsions can be prepared by conventional methods (eg, constant inflow or double inflow with constant acceleration of the material). Especially preferred is the double influx method of adjusting pAg; see Research Disclosure No. 17643, Sections I and II.

The silver halide emulsion can be chemically sensitized. Sulfur-containing compounds such as allyl isothiocyanate, allyl thiourea or thiosulfate are particularly preferred. Reducing agents can also be used as chemical sensitizers, for example Belgian Patent 493,464 and the same.
Silver compounds as described in 568,687, and polyamines such as diethylenetriamine according to Belgian patent 547,323 or aminomethylsulfinic acid derivatives.
Noble metals and noble metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium are also suitable sensitizers. This chemical sensitization method is based on Zeitschrift Fair Bissenscherich Photography (Z.W.
Iss. Photo.) 46 , 65-72 (1951), R. Kosiovsky's paper; and Research Disclosure No. 17643, section III above.
See also

The emulsion mainly composed of silver chloride is an optically known method,
It can be sensitized with conventional polymethine dyes such as neutraocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like: FM Hamer's "Cyanine Dyes and rel"
atedCompounds) (1964) Ullmanns E
nzyklpadie dertechnischen Chemie) 4th edition, 18 volumes, 431
Page and the following, and the above Research Disclosure
See No. 17643, Section IV.

For the emulsion mainly containing silver chloride, conventional antifoggants and stabilizers can be used. Azaindene is a particularly suitable stabilizer, tetra- and penta-azaindenes being preferred, especially those substituted with hydroxyl or amino groups. Compounds of this kind are described, for example, in Birr's paper, Z. Wiss. Phot.
o) 47, 1952, p.2-58, and Research Disclosure No. 17643, above, Section IV.

The components of the light-sensitive material can be incorporated by a conventional known method; for example, US Pat. No. 2,322,027.
Nos. 2,533,514, 3,689,271, 3,764,336 and 3,765,897. The components of the light-sensitive material, such as couplers and UV absorbers, can also be included in the form of charged latex; DE-A 2,541,274.
And European Patent Application No. 14,921. The components can also be fixed in the light-sensitive material as polymers; see, for example, DE-A 2,044,992, US Pat. Nos. 3,370,952 and 4,080,211.

The support for the color photographic light-sensitive materials (a) and (b) used in the present invention is, for example, baryta paper,
Polyethylene coated paper, polypropylene synthetic paper, transparent support provided with a reflective layer, or together with a reflector, for example, glass plate, cellulose acetate, cellulose nitrate, or polyester film such as polyethylene terephthalate, polyamide film, polycarbonate film, polystyrene Examples thereof include a film, and other usual transparent support may be used.

These supports were appropriately selected according to the purpose of use of the light-sensitive material, but in order to more effectively achieve the object of the present invention, the color light-sensitive material (a) contains cellulose acetate and cellulose nitrate. Or a transparent support such as a polyester film such as polyethylene terephthalate, a polyamide film, a polycarbonate film, or a polystyrene film, and a reflective support such as baryta paper, polyethylene-coated paper, or polypropylene synthesis for the color photosensitive material (b). It is preferable to use.

The present invention can be applied to color films such as color papers, color negative films, color reversal films, color reversal papers, direct positive color papers, motion picture color films, color films for television, etc. which are used for general use or for movies. It can be applied to photosensitive materials.

[0143]

EXAMPLES Next, the present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited to these examples.

[0144]

Example 1 Experiments 1 to 3 were carried out using a color developer prepared as follows.

(Color developer) Water 700 ml Diethylene glycol 15.0 g Potassium bromide 23.0 g Potassium chloride 3.30 g Potassium sulfite (50% solution) 0.5 ml Potassium carbonate 30.0 g Color developing agent (Exemplary compound III-1) 1.2 × 10 ⁻² mol Preservative (listed in Table 1) 0.05 mol Optical brightener (exemplary compound E-44) 2.0 g Chelating agent (listed in Table 1) 2.0 g Water added to 1 liter And potassium hydroxide or 20
Adjust to pH 10.05 with% sulfuric acid.

Experiment 1 The above color developing solution was heated to 40 ° C., and it was investigated whether 30 monitors arbitrarily collected in-house felt an odor.

Evaluation of odor O: Less than 25% of people who feel odor Δ: 25 to 80% of people who feel odor X: More than 80% of people who feel odor

Experiment 2 The above color developing solution was placed in a container made of hard vinyl chloride having an air contact area of 25 cm ² per liter of the color developing solution, and 3
After standing at 8 ° C for 15 days, the state of crystal precipitation on the wall surface of the container was observed.

Evaluation of Crystal Precipitation ◯: No Precipitation Δ: Slight Precipitation ×: Precipitation

Experiment 3 The above color developing solution was put in the same container as used in Experiment 2 and allowed to stand at room temperature for 20 days, and the coloring property of the color developing solution was visually observed.

Evaluation of Colorability ◯: Almost no coloration Δ: Some coloration X: Coloring The above experimental results are shown in Table 1.

[0152]

[Table 1]

In the table, HAS is hydroxylamine sulfate,
DEHA means diethylhydroxylamine, MHA means methylhydroxylamine, EHA means ethylhydroxylamine, EDTA means ethylenediaminetetraacetic acid, NTA means nitrilotriacetic acid, and TPPS means sodium tripolyphosphate.

As is clear from Table 1 above, when a specific organic preservative and a specific chelating agent are used in combination,
It can be seen that the effects of the present invention are excellently exerted in terms of odor, crystal precipitation and coloring.

Example 2 Experiment No. 1 of Example 1 The same experiment as in Example 1 was conducted, except that the fluorescent whitening agent in the color developing solution 1-10 was changed to that shown in Table 2 below. The results are shown in Table 2.

[0156]

[Table 2]

[0157]

[Chemical 30]

From Table 2 above, it is understood that the effect of the present invention becomes more remarkable by using the optical brightening agent represented by the general formula [E] in combination with the present invention.

Example 3 Silver halide color light-sensitive materials (a) and (b) were prepared as follows.

Preparation of color light-sensitive material (a) In the following examples, the addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

One side (front surface) of the triacetyl cellulose film support was subjected to an undercoating treatment, then the support was sandwiched, and the surface opposite to the surface subjected to the undercoating treatment (rear surface) had the composition shown below. Each of the layers was sequentially formed from the support side. Backside first layer Aluminasol AS-100 (aluminum oxide) (manufactured by Nissan Chemical Industries, Ltd.) 0.8 g Backside second layer diacetylcellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle size 0.2 μm) 50 mg

Then, on the surface of the triacetyl cellulose film support which had been subjected to the undercoating, each layer having the composition shown below was sequentially formed from the support side to prepare a multilayer color photographic light-sensitive material sample (a-1). 1st layer: Antihalation layer (HC) Black colloidal silver 0.15 g UV absorber (UV-1) 0.20 g Colored cyan coupler (CC-1) 0.02 g High boiling point solvent (Oil-1) 0.20 g 〃 (Oil-2) 0.20 g Gelatin 1.63 g

Second Layer; Intermediate Layer (IL-1) Gelatin 1.31 g

Third layer; low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (average particle size 0.3 μm) 0.42 g 〃 (average particle size 0.4 μm) 0.3 g Sensitizing dye (S-1) 3.0 × 10 ^-4 (mol / silver 1 mol) 〃 (S-2) 3.2 × 10 ^-4 (mol / silver 1 mol) 〃 (S-3) 0.3 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-1) 0.52 g 〃 (C-2) 0.20 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1) 0.006 g 〃 (D-2) 0.01 g High boiling point solvent (Oil-1) 0.55 g Gelatin 1.0 g

Fourth layer: high-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average particle size 0.7 μm) 0.91 g Sensitizing dye (S-1) 1.7 × 10 ⁻⁴ ( Mol / silver 1 mol) 〃 (S-2) 1.6 × 10 ^-4 (mol / silver 1 mol) 〃 (S-3) 0.2 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C -2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D-2) 0.02 g High boiling point solvent (Oil-1) 0.30 g Gelatin 1.0 g

Fifth layer; Intermediate layer (IL-2) Gelatin 0.8 g

Sixth layer: low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (average particle size 0.4 μm) 0.58 g 〃 (average particle size 0.3 μm) 0.2 g Sensitizing dye (S-4) 6.7 × 10 ^-4 (mol / silver 1 mol) 〃 (S-5) 1.0 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (MA) 0.20 g 〃 (MB) 0.40 g Colored magenta coupler (CM-1) 0.10 g DIR compound (D-3) 0.02 g High boiling point solvent (Oil-2) 0.7 g Gelatin 1.0 g

Seventh layer: high-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (average grain size 0.7 μm) 0.92 g Sensitizing dye (S-6) 1.1 × 10 ⁻⁴ ( Mol / silver 1 mol) 〃 (S-7) 2.0 × 10 ^-4 (mol / silver 1 mol) 〃 (S-8) 0.5 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M -A) 0.5 g 〃 (MB) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) 0.004 g High boiling point solvent (Oil-2) 0.35 g Gelatin 1 0.0 g

Eighth layer: Yellow filter layer (YC) Yellow colloidal silver 0.11 g Additive (HS-1) 0.07 g 〃 (HS-2) 0.07 g 〃 (SC-1) 0.12 g High boiling point solvent (Oil-2) 0.15 g Gelatin 0.9 g

Ninth layer: low-sensitivity blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion (average particle size 0.3 μm) 0.25 g 〃 (average particle size 0.4 μm) 0.25 g Sensitizing dye ( S-9) 5.8 × 10 ⁻⁴ (mol / silver 1 mol) Yellow coupler (Y-1) 0.69 g 〃 (Y-2) 0.32 g DIR compound (D-1) 0.003 g 〃 (D -2) 0.006 g High boiling point solvent (Oil-2) 0.18 g Gelatin 1.2 g

Tenth layer: High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (average grain size 0.8 μm) 0.5 g Sensitizing dye (S-10) 3 × 10 ⁻⁴ (mol) / Silver 1 mol) 〃 (S-11) 1.2 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.18 g 〃 (Y-2) 0.20 g High boiling solvent (Oil- 2) 0.05 g gelatin 0.9 g

Eleventh layer; First protective layer (PRO-1) Silver iodobromide (average particle size 0.08 μm) 0.3 g Ultraviolet absorber (UV-1) 0.07 g 〃 (UV-2) 0 Additive (HS-1) 0.2 g 〃 (HS-2) 0.1 g High boiling point solvent (Oil-1) 0.07 g 〃 (Oil-3) 0.07 g Gelatin 0.85 g

Twelfth layer; Second protective layer (PRO-2) Compound A 0.04 g Compound B 0.004 g Polymethyl methacrylate (average particle size 3 μm) 0.02 g Methyl methacrylate: Ethyl methacrylate: Methacrylic acid = Copolymer of 3: 3: 4 (weight ratio) (average particle size 3 μm) 0.13 g

The above color light-sensitive material further comprises compounds Su-1, Su-2, a viscosity modifier, a film hardener H-1, and
H-2, stabilizer ST-1, antifoggant AF-1, AF
-2 (weight average molecular weight of 10,000 and 1,10
50,000), dyes AI-1, AI-2 and compound DI-1 (9.4 mg / m ² ).

[0175]

[Chemical 31]

[0176]

[Chemical 32]

[0177]

[Chemical 33]

[0178]

[Chemical 34]

[0179]

[Chemical 35]

[0180]

[Chemical 36]

[0181]

[Chemical 37]

[0182]

[Chemical 38]

[0183]

[Chemical Formula 39]

[0184]

[Chemical 40] Component A: Component B: Component C = 50: 23: 20 (molar ratio)

[Preparation of Emulsion] The silver iodobromide emulsion used in the 10th layer was prepared by the following method.

A silver iodobromide emulsion was prepared by the double jet method using monodispersed silver iodobromide grains (silver iodide content 2 mol%) having an average grain size of 0.33 μm as seed crystals.

The solution <G-1> was heated at 70 ° C. and pAg7.
While maintaining pH 8 and pH 7.0 and stirring well, a seed emulsion corresponding to 0.34 mol was added. (Formation of internal high iodine phase-core phase) After that, <H-1>
And <S-1> were added at an accelerated flow rate (the flow rate at the end was 3.6 times the initial flow rate) for 86 minutes while maintaining the flow rate ratio of 1: 1. (Formation of External Low Iodity Phase-Shell Phase) Subsequently, pAg1
<H-2> and <S-, while maintaining 0.1 and pH 6.0.
2> was added at a flow rate accelerated by a flow rate ratio of 1: 1 (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes.

The pAg and pH during grain formation were controlled using an aqueous potassium bromide solution and a 56% aqueous acetic acid solution. After the particles were formed, they were washed with water by a conventional flocculation method, and then gelatin was added to redisperse them, and the pH and pAg were adjusted to 5.8 and 8.06 at 40 ° C., respectively.

The obtained emulsion had an average grain size of 0.80 μm,
It was a monodisperse emulsion containing octahedral silver iodobromide grains having a distribution of 12.4% and a silver iodide content of 9.0 mol%. <G-1> Ocein gelatin 100.0 g 10 wt% methanol solution of compound-1 25.0 ml 28% aqueous ammonia solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Finish with water 5000.0 ml <H-1> ossein Gelatin 82.4 g Potassium bromide 151.6 g Potassium iodide 90.6 g Finish with water 1030.5 ml <S-1> Silver nitrate 309.2 g 28% aqueous ammonia solution equivalent Finish with water 1030.5 ml <H-2> Ocein gelatin 302.1 g Potassium bromide 770.0 g Potassium iodide 33.2 g Finish with water 3776.8 ml <S-2> Silver nitrate 1133.0 g 28% aqueous ammonia solution Equivalent Finish with water 3776.8 ml Compound-1

[0190]

[Chemical 41]

By the same method, the average grain size of the seed crystal, the temperature,
The above emulsions having different average grain sizes and silver iodide contents were prepared by changing pAg, pH, flow rate, addition time, and halide composition.

All were core / shell type monodisperse emulsions having a distribution of 20% or less. Each emulsion was subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to obtain a sensitizing dye, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. ,
1-Phenyl-5-mercaptotetrazole was added.

However, the photosensitive material sample (a) was prepared so that the average silver iodide content was 8 mol%.

Preparation of color light-sensitive material (b) A support having a polyethylene support laminated on one side of a paper support and a polyethylene oxide containing titanium oxide on the other side of the support was coated with each layer having the following constitution. Then, a multilayer color light-sensitive material sample (b) was prepared. The coating liquid was prepared as follows.

First Layer Coating Solution Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, (ST-2) 6.67
g, 0.67 g of the additive (HQ-1) is added to the high boiling point solvent (DN
P) 60 ml of ethyl acetate was added to 6.67 g to dissolve, and this solution was emulsified and dispersed in 220 ml of 10% gelatin aqueous solution containing 7 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer to disperse the yellow coupler. A liquid was prepared. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a coating solution for the first layer. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a hardening agent, (H-1) was added to the second and fourth layers, and (H-2) was added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

[0197]

[Outside 18]

[0198]

[Outside 19]

[0199]

[Chemical 43]

[0200]

[Chemical 44]

[0201]

[Chemical 45]

[0202]

[Chemical 46]

[Method for preparing blue-sensitive silver halide emulsion] 4
The following (solution A) and (solution B) were added to 1000 ml of a 2% gelatin aqueous solution kept at 0 ° C. to obtain pAg = 6.5 and pH = 3.
While controlling to 0, it was added at the same time over 30 minutes.
Liquid) and (D liquid) were simultaneously added over 180 minutes while controlling pAg = 7.3 and pH = 5.5.

At this time, pAg control is described in JP-A-59-4.
According to the method described in No. 5437, pH control was performed using an aqueous solution of sulfuric acid or sodium hydroxide. (Liquid A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added 200 ml (Liquid B) Silver nitrate 10 g Water was added 200 ml (Liquid C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added 600 ml (D liquid) 300 g of silver nitrate 600 ml by adding water

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
Of 5% aqueous solution of magnesium sulfate and 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous solution of gelatin to have an average particle size of 0.85 μm, coefficient of variation (σ / r) = 0.07, and silver chloride content. A 99.5 mol% monodisperse cubic emulsion EMP-1 was obtained.

The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye (BS-1) 4 × 10 ⁻⁴ Mol / mol AgX 〃 (BS-2) 1 × 10 ^-4 mol / mol AgX

[Preparation Method of Green-Sensitive Silver Halide Emulsion]
(A solution) and (B solution) addition time and (C solution) and (D solution)
In the same manner as EMP-1 except that the addition time of
Average particle size 0.43 μm, coefficient of variation (σ / r) = 0.0
8. Monodisperse cubic emulsion E having a silver chloride content of 99.5 mol%
MP-2 was obtained.

The following compounds were used for EMP-2:
Chemical ripening was carried out at 5 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye (GS-1) 4 × 10 ⁻⁴ Mol / mol AgX

[Preparation Method of Red-Sensitive Silver Halide Emulsion]
(A solution) and (B solution) addition time and (C solution) and (D solution)
In the same manner as EMP-1 except that the addition time of
Average particle size 0.50 μm, coefficient of variation (σ / r) = 0.0
8. Monodisperse cubic emulsion E having a silver chloride content of 99.5 mol%
MP-3 was obtained.

The following compounds were used for EMP-3:
Chemical ripening was performed at 0 ° C. for 90 minutes to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye (RS-1) 4 × 10 ⁻⁴ Mol / mol AgX

[0214]

[Chemical 47]

However, the photosensitive material sample (b) was prepared so that the silver chloride content was 99.5 mol%.

The samples of the light-sensitive materials (a) and (b) thus prepared were subjected to wedge exposure according to a conventional method and then subjected to running processing according to the following processing steps. However, the running process was continuously carried out until the amount twice the capacity of the color developing tank tank was replenished (2R).

[0217]

[Table 4]

In the above, (a) is a photosensitive material (a).
(B) shows the processing conditions for the photosensitive material (b). Also,
Unless otherwise specified, the processing conditions are common to the light-sensitive material (a) and the light-sensitive material (b).

The first and second stabilizing tanks were of the calendar current type, and the replenisher was replenished in the second tank.
The treatment liquid used in each treatment step is as follows.

(Color developer) Water 700 ml Diethylene glycol 15.0 g Potassium bromide 11.0 mg Potassium chloride 3.00 g Potassium sulfite (50% solution) 0.5 ml Potassium carbonate 30.0 g Color developing agent (Exemplary compound III-1) 1.2 × 10 ⁻² mol Preservative (described in Table 3) 0.05 mol Optical brightener (described in Table 3) 2.0 g Chelating agent (described in Table 3) 2.0 g Water was added to make 1 liter, Potassium hydroxide or 20
Adjust to pH 10.05 with% sulfuric acid.

(Color development replenisher) Water 700 ml Diethylene glycol 15.0 g Potassium bromide 11.0 mg Potassium chloride 3.0 g Potassium sulfite (50% solution) 0.5 ml Potassium carbonate 30.0 g Color developing agent (Exemplified compound III-1) ) 1.3x10 ^-2 mol Preservative (listed in Table 3) 0.08 mol Optical brightener (listed in Table 3) 2.0 g Chelating agent (listed in Table 3) 2.0 g Water was added to make 1 liter. , Potassium hydroxide or 20
Adjust to pH 10.30 with% sulfuric acid.

(Bleaching Solution) Water 700 ml Bleach (ferric ammonium salt of Exemplified compound IV-1) 0.3 mol Ethylenediaminetetraacetic acid 2.0 g Sodium nitrate 40.0 g Ammonium bromide 150 g Glacial acetic acid 40.0 g Water In addition, the volume is adjusted to 1 liter, and the pH is adjusted to 4.4 with aqueous ammonia or glacial acetic acid.

(Bleach Replenisher) Water 700 ml Bleach (Ferric ammonium salt of Exemplified compound IV-1) 0.4 mol Ethylenediaminetetraacetic acid 2.0 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g Water was added 1 Adjust to pH 3.0 with aqueous ammonia or glacial acetic acid.

(Fixing Solution) Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2.0 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, water is added to make 1 liter.

(Fixing Replenisher) Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2.0 g After adjusting the pH to 6.5 using aqueous ammonia or glacial acetic acid, water is added to make 1 liter.

(Stabilizer and Replenisher) Water 900 ml Surfactant

[0227]

[Chemical 48] Hexamethylenetetramine 10.0g After adding water to make 1 liter, use ammonia water or 2
Adjust to pH 8.0 with 0% sulfuric acid.

After the continuous processing, the photosensitive material (a) was measured for the maximum density magenta density (hereinafter referred to as DmaxM) and the unexposed magenta density (hereinafter referred to as DminM) by the transmission density, and In (b), the DmaxM and the yellow density of the unexposed area (hereinafter referred to as DminY) were measured by the reflection density. Further, the color developing solution was allowed to stand for 15 days while being kept in the tank of the automatic developing machine, and the precipitation of crystals on the wall surface of the tank was observed and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0229]

[Table 5]

The effects of the present invention are clear from Table 3 above.

Example 4 The magenta couplers (MA), (MB) and (MC) of the photosensitive materials (a) and (b) used in Example 3 were replaced with the magenta couplers shown in Table 4. Experiment No. 3 of Example 3. 3-
After continuous processing in the same manner as in No. 10, DmaxM and DminM of the color light-sensitive material (a) were measured by transmission density,
DminM of the photosensitive material (b) was measured by reflection density. The results are shown in Table 4.

[0232]

[Table 6]

As is clear from the results of Table 4, in the present invention, the magenta coupler represented by the above general formula [MI] is used in combination with the present invention to obtain a sufficient magenta dye in the maximum density part. And that the magenta fog density in the unexposed area can be suppressed.

Example 5 The bleaching solution, bleach replenisher, fixing solution and fixing replenisher used in Example 3 were replaced with the bleach-fixing solution and bleach-fixing replenisher shown below,
When the samples (a) and (b) of the present invention were used in the following steps and the same treatment as in Example 3 was carried out, the same results as in Example 3 were obtained. It has been found that the objects of the invention can be achieved.

(Bleaching Fixing Solution) Water 800 ml Bleach [Ferric ammonium salt of A′-7] 180 g Ethylenediaminetetraacetic acid 2 g Sodium sulfite 20 g Ammonium thiosulfate 150 g Ammonium thiocyanate 120 g Ammonia water (25%) 12 ml Ammonia water or acetic acid After adjusting the pH to 7.0 with water, add water to make 1 liter.

(Bleach-fixing replenisher) Water 700 ml Bleach [A'-7 ferric ammonium salt] 280 g Ethylenediaminetetraacetic acid 2 g Sodium sulfite 30 g Ammonium thiosulfate 180 g Ammonium thiocyanate 150 g Ammonia water (25%) 15 ml Ammonia water or After adjusting the pH to 6.0 with acetic acid, water is added to make 1 liter.

[0237]

[Table 7]

Example 6 Experiment No. 3 of Example 3 An experiment was conducted in the same manner as in Example 3 except that the color developing agent used in 3-10 was replaced with the one shown below. The results are shown in Table 5.

[0239]

[Table 8] The following developing agents were used in the table.

[0240]

[Chemical 49]

From Table 5 above, when the color developing agent represented by the general formula [III] is used in combination with the present invention,
It can be seen that the effect of the present invention becomes better.

[0242]

EFFECTS OF THE INVENTION According to the present invention, firstly, it is possible to provide a color developing solution and processing method for silver halide color photographic light-sensitive materials which has little odor and is suitable for working environment. It is possible to provide a color developing solution and a processing method for a silver halide color photographic light-sensitive material that has less crystal precipitation on the wall surface of a developing machine tank and is excellent in colorability. Thirdly, a silver halide capable of processing two kinds of light-sensitive materials having different halogen compositions. A color developing solution for a color photographic light-sensitive material and a processing method can be provided. Fourth, a color developing solution for a silver halide color photographic light-sensitive material capable of rapid processing and stable in photographic performance, and a processing method using the color developing solution. Can be provided.

[Brief description of drawings]

FIG. 1 is an explanatory view showing a main example of preferable processing steps in a processing method of the present invention.

FIG. 2 is an explanatory diagram showing a main example of preferable processing steps in the processing method of the present invention.

Claims (3)

[Claims] 1. At least one compound represented by the following general formula [A], [B] or [C] and the following general formula [I]:
Alternatively, a color developing solution for a silver halide color photographic light-sensitive material, which is used in combination with at least one compound represented by [II]. General formula [A] [In the formula, X represents an oxygen atom or R ₁ -N <, and R ₁ represents a hydrogen atom, a hydroxyl group or a lower alkyl group which may have a substituent. N represents 0, 1 or 2. ] General formula [B] [In the formula, R ₂ and R ₃ represent a hydrogen atom or an alkyl group (including a substituent), and at least one of R ₂ and R ₃ is an alkyl group having 1 to 5 carbon atoms substituted with an alkoxy group,
An alkyl group having 1 to 5 carbon atoms substituted with a sulfonic acid group,
It represents an alkyl group having 1 to 5 carbon atoms substituted with phosphonic acid, an alkyl group having 1 to 5 carbon atoms substituted with carboxylic acid, or an alkyl group having 1 to 5 carbon atoms substituted with ammonium group. ] General formula [C] [Wherein R ₄ , R ₅ and R ₆ each represent a hydrogen atom, an alkyl group (including a substituent), an aryl group (including a substituent) or a heterocyclic group (including a substituent), and R ₈ is a hydroxy group, Hydroxyamino group, alkyl group (including substituted),
An aryl group (including a substituent), a heterocyclic group (including a substituent), an alkoxy group (including a substituent), an aryloxy group (including a substituent), a carbamoyl group (including a substituent) or an amino group (including a substituent) Represent R ₇ is -CO-, -S
Represents a divalent group selected from O ₂ — or> C═NH,
n is 0 or 1. ] General formula [I] Wherein, A ₁ to A ₅ are, -COOM, -PO ₃ M ₂ or -C
H ₂ OH, which may be the same or different. M
Represents a hydrogen atom or an alkali metal. ] General formula [II] [In the formula, A ₆ represents —OH or —NH ₂ , and M represents a hydrogen atom or an alkali metal. R ₁ is -CH ₃ , -C ₂ H
_5, a lower alkyl group having -CH ₂ CH ₂ OH or a substituent. ] 2. A color developer for a silver halide color photographic light-sensitive material according to claim 1, which contains at least one compound represented by the following general formula [E]. General formula [E] [Wherein, X ₂ , X ₃ , Y ₁ and Y ₂ are each a hydroxyl group, a halogen atom, an alkyl group, an aryl group, or Alternatively, it represents -OR ₂₅ . Here, R ₂₁ and R ₂₂ are each a hydrogen atom, an alkyl group (including a substituent) or an aryl group (including a substituent), R ₂₃ and R ₂₄ are an alkylene group (including a substituent), R ₂₅ Represents a hydrogen atom, an alkyl group (including a substituent) or an aryl group (including a substituent), and M represents a cation. ] 3. A silver halide color photographic light-sensitive material (a) having an average silver iodide content of 3 mol% or more in a silver halide emulsion layer coated on a support, and at least a silver halide emulsion layer coated on the support. In the processing method of a silver halide color light-sensitive material, a silver halide color photographic light-sensitive material (b) having a silver chloride content of one silver halide emulsion layer of 80 mol% or more is processed with a common color developer. A method for processing a silver halide color photographic light-sensitive material, which comprises processing with the color developing solution for a silver halide color photographic light-sensitive material according to claim 1.