JPH0682994A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide color photographic sensitive material containing an internal latent image type and negative type silver halide emulsion high in sensitivity and superior in graininess. CONSTITUTION:The silver halide color photographic sensitive material has on a support at least one negative type silver halide emulsion layer and contains a bleach-promoter-releasing compound in this emulsion layer, and an emulsion capable of forming a latent image in silver halide grains in the depth of 2-100nm from the surfaces of them in at least one photo-sensitive emulsion layer for forming the photosensitive material and this latent image can be developed with a color negative type surface developing type developing solution.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material containing a compound capable of releasing a compound having a bleach accelerating action and having an internal latent image type negative type silver halide emulsion.

[0002]

2. Description of the Related Art In recent years, demands on silver halide photographic light-sensitive materials have become more and more severe, and development of light-sensitive materials having higher sensitivity and excellent graininess has been desired. In order to improve the sensitivity and the image quality of the silver halide photographic light-sensitive material, it is necessary to improve the light absorption, quantum efficiency and developability of the silver halide emulsion. The silver halide emulsion can be spectrally sensitized with a dye, and in that case, it is advantageous in terms of light absorption that the dye is adsorbed on the silver halide emulsion as much as possible. However, the dye also has a property of desensitizing the silver halide emulsion, and the optimum spectral sensitization is usually achieved only in an amount considerably smaller than the amount of the dye producing a continuous monolayer on the emulsion grain surface. I couldn't do it. In order to solve this problem, so-called internal latent type emulsions having aging nuclei capable of forming a developable latent image by exposure (hereinafter referred to as "photosensitive nuclei") inside grains are effective. Are known.
For example, in U.S. Pat. No. 3,979,213, the intrinsic desensitization of an internal latent image type silver halide emulsion during color sensitization is significantly smaller than that of a chemically sensitized silver halide emulsion having an equal grain size, As a result, it is disclosed that color sensitization can be effectively performed by using a large amount of sensitizing dye.

Many studies have been made on such an inner latent type emulsion as a means for forming a positive image by developing with a developer having a fogging action as disclosed in JP-A-55-21067. It has been done. However, in these internal latent emulsions, the position of the latent image is 1 from the grain surface.
It is generally inside a grain having a depth of 00 nm or more, and it cannot be developed with a surface developing type developing solution such as a color negative. Further, the combined use of an inner latent type emulsion and a desilvering accelerator releasing type compound (hereinafter referred to as BAR compound) for a direct positive color light-sensitive material is disclosed in JP-A-1-245256, in which the inner latent image is a surface developing solution. It is a type that is not developed. On the other hand, JP-A-1-138551 discloses that the effect of improving the sensitivity can be obtained even by a surface developing type developer by controlling the depth of the photosensitive nucleus from the surface of the particle and the ratio of surface and internal sensitivity. It is described that when the photosensitizing nucleus is present at a deep position of 50 nm or more, practical surface development type processing causes insufficient development and substantial sensitivity is impaired. It was difficult to make the most of it. As a result of intensive studies to obtain the effect of further improving sensitivity and graininess by internal latent image formation in a surface development type processing such as a color negative type, as a result, the objective was achieved by combining an internal latent type emulsion with a BAR compound. I found that I could be. Although it is known that the sensitivity and graininess can be improved by controlling the internalization of photonuclei shallowly as described above,
For the first time, it was found that the combination with the BAR compound can bring out the effect of internalization sufficient to reach the original purpose.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material containing an internal latent image type negative type silver halide emulsion having high sensitivity and excellent graininess.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a bleach accelerator releasing compound in a silver halide color photographic light-sensitive material having at least one negative-working silver halide emulsion layer on a support. BAR compound), and at least one of the photosensitive emulsion layers constituting the light-sensitive material contains an emulsion capable of forming a latent image inside the grain at a depth of 2 nm to less than 100 nm from the grain surface, and It was achieved by a silver halide color photographic light-sensitive material characterized in that the image was developable with a color negative surface developing type developer. The contents of the present invention will be described in detail below. The light-sensitive material of the present invention comprises a ripening nucleus (“photosensitive nucleus”) capable of forming a latent image which can be developed by exposure on at least one emulsion layer.
Synonymous with) inside the grain (referred to as "internal latent emulsion"). The embodiment of the inner latent type emulsion of the present invention is as follows. That is, there is one local maximum in the latent image distribution in the particle, and the position where this local maximum exists is 2 nm or more and 100 nm or less from the particle surface, and more preferably 5 nm or more and 70 nm.
It is at the following depth, and the number of latent images on the surface of the particles is 1/10 or more and 5/10 or less of the maximum value. The "intra-particle latent image distribution" as used herein means the depth (xnm) of the latent image from the particle surface on the horizontal axis and the number of latent images (y) on the vertical axis, where x is

[0006]

[Equation 1]

S: average grain size (nm) of silver halide emulsion Ag ₁ : residual silver amount after unexposed emulsion coating sample is subjected to the following treatment Ag ₀ : coating silver amount before treatment, and y After 1/100 second white exposure,
It is the reciprocal of the exposure amount that gives the density of (fog + 0.1) when the following process is performed. The processing conditions for obtaining the latent image distribution are as follows: N-methyl-p-aminophenol sulfate 2.5 g L-sodium ascorbate 10 g sodium metaborate 35 g potassium bromide 1 g Water added 1 liter (pH 9.6). Sodium thiosulfate is added to the treatment liquid in an amount of 0 to 10 g / liter and treated at 20 ° C for 7 minutes. By changing the amount of sodium thiosulfate to 0 to 10 g / liter, the depth from the surface of the latent image in the silver halide grains developed during processing is changed, and the number of latent images in the depth direction is changed. You can know the changes. This method is preferably carried out on a light-sensitive material obtained by simply coating an emulsion on a support such as an undercoated cellulose triacetate film, but peeling off one layer of the light-sensitive material coated in multiple layers. Then, the emulsion is extracted, and the depth of the photosensitive nucleus may be determined by a method of performing the same treatment on a light-sensitive material obtained by re-coating only the emulsion. The photonucleus depth determined as described above is 10 from the surface.
When it is present at a deep position of 0 nm or more, even if it is developed with a developing solution that is practically used for color negative, the development becomes insufficient and the substantial sensitivity is impaired. According to the method of preparing an internal latent image type emulsion which has been reported so far, controlling the shell thickness results in changing the ratio of surface sensitivity to internal sensitivity. However, from the results of this study, the particle formation conditions must be controlled, and the latent image distribution mode and the ratio of surface sensitivity to internal sensitivity must be controlled independently in order to develop the optimum sensitivity for a certain treatment. For example, even if the latent image distribution maximum value is less than 100 nm, if the latent image distribution on the surface becomes 5/10 or more of the maximum value,
The effect on the color sensitization of the internal latent image type emulsion as described in US Pat. No. 3,979,213 becomes insufficient. Further, when the latent image distribution on the surface is one-tenth or less of the maximum value, the development with a substantial processing solution is insufficient and the sensitivity is substantially impaired. On the other hand, the conventional design criteria for internal latent image type silver halide grains, which focus only on the difference between the sensitivity when surface development is performed and the sensitivity when internal development is performed, are also required to achieve optimum sensitivity. It turned out to be insufficient. That is, even if the ratio of the surface sensitivity to the internal sensitivity is the same (for example, the surface sensitivity is ½ of the internal sensitivity), when the maximum of the latent image distribution exists at a deep position of 100 nm or more, practical processing is performed. In some cases, development is insufficient and the potential optimum sensitivity of the particles cannot be obtained. As described above, in order to develop the optimum sensitivity, the position where the latent image distribution maximum exists,
It has become clear that internal latent image type silver halide grains must be designed in consideration of both the maximum value and the difference in the number of latent images on the surface. The practical processing solution mentioned above means a developing solution containing a large amount of a silver halide solvent intended to develop a developing solution excluding a silver halide solvent for the purpose of developing only a surface latent image and an internal latent image. It is not a liquid, but has the following composition, for example. Diethylenetriamine pentaacetic acid 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 g Sodium sulfite 3.9 g Potassium carbonate 37.5 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 g 4 -(N-ethyl-N-β-hydroxylethylamino) -2-methylaniline sulfate 4.5 g Water was added to 1.0 liter pH 10.05 (25 ° C) A method for preparing an internal latent image type emulsion is US Pat. No. 3,97
9,213, 3,966,476 and 3,20
No. 6,313, No. 3,917,485, Japanese Patent Publication No. 43-
29405, Japanese Patent Publication No. 45-13259 and the like can be used. In any method, in order to obtain an emulsion having a latent image distribution within the scope of the claims, a chemical sensitization method or a method of chemical sensitization is used. The amount of silver halide precipitated after chemical sensitization and the conditions of precipitation must be adjusted. Specifically, in U.S. Pat. No. 3,979,213, an internal latent image type emulsion is prepared by a method of reprecipitating silver halide on the emulsion grains whose surfaces are chemically sensitized by the control double jet method. When precipitating silver halide on emulsion grains whose surface has been chemically sensitized, the emulsion p
H is from 5.0 to 7.5, more preferably from 5.5 to 7.
It is desirable to keep the range of 0. At that time, it is desirable to maintain the conductivity (in μmho / cm unit) of the emulsion in the range of 1000 to 8000, and more preferably 1500 to 5000. At that time, the temperature of the emulsion is preferably maintained in the range of 30 to 75 ° C, more preferably 35 to 65 ° C.
The pAg of the emulsion at that time is preferably maintained in the range of 7.0 to 10.0, more preferably 8.0 to 9.0. Further, when precipitating silver halide, it is desirable to allow a tetrazaindene compound or a water-soluble mercapto compound described in JP-A-58-251821 to be present. The amount of the tetrazaindene compound is 10 ^-6 to 10 ^-2 mol, and more preferably 10 mol per mol of silver halide.
It is preferably ^-5 to 10 ^-3 mol. The preferred amount of the water-soluble mercapto compound is 10 ^-6 to 10 ^-3 mol per mol of silver halide. The above conditions are extremely important in controlling the latent image distribution. The above items are closely related to each other, and it is necessary to control each condition in a balanced manner. The bleaching accelerator releasing compound used in the present invention can be preferably represented by the following general formula (B).

The general formula (B) A- (L ₁ ) _k -Z A represents a group which cleaves (L ₁ ) _k -Z by reacting with an oxidized product of a developing agent, and L ₁ is a bond with A. Represents a group capable of cleaving Z, then k represents 0 or 1, and Z represents a bleaching accelerator.

Next, the general formula (B) will be described.

In the general formula (B), A specifically represents a coupler residue or a redox group.

Examples of the coupler residue represented by A include yellow coupler residues (for example, open-chain ketomethylene type coupler residues such as acylacetanilide and malondianilide) and magenta coupler residues (for example, 5-pyrazolone type and pyrazolotriazole). Type or an imidazopyrazole type coupler residue), a cyan coupler residue (for example, phenol type, naphthol type, imidazole type or the same type as described in European Patent Publication 249,453).
No. 4,001, such as a pyrazolopyrimidine type coupler residue) and a colorless coupler residue (for example, an indanone type or acetophenone type coupler residue). Also, U.S. Pat. Nos. 4,315,070, 4,183,752, 4,174,969, 3,961,959, 4,171,223 or JP-A-52-82423. It may be a heterocyclic coupler residue described in No.

When A represents a redox group, the redox group is a group which can be cross-oxidized by an oxidized product of a developing agent, and examples thereof include hydroquinones, catechols, pyrogallols, 1,4-naphthohydroquinones, 1 , 2-naphthohydroquinones, sulfonamide phenols,
Examples include hydrazides or sulfonamide naphthols. These groups are specifically described in, for example, JP-A-61-2.
30135, 62-251746, 61-27.
8852, U.S. Pat. Nos. 3,364,022 and 3,
379,529, 3,639,417, 4,6
84,604 or J.Org.Chem., 29,588 (1
964).

In the general formula (B), L ₁ is preferably the following. (1) Group utilizing cleavage reaction of hemiacetal For example, US Pat. No. 4,146,396, JP-A-60-
No. 249148 and No. 60-249149, which are groups represented by the following general formula. Here, the * mark represents the position of bonding with A of the compound represented by the general formula (B), and the ** mark represents the position of bonding with Z. Formula (T-1) * - ( W-CR 11 (R 12)) t - ** In formula, W is an oxygen atom, a sulfur atom or -NR ₁₃ - represents a group, R ₁₁ and R ₁₂ are a hydrogen atom Or a substituent, R ₁₃ represents a substituent, and t represents 1 or 2.
When t is 2, two -W-CR ₁₁ (R ₁₂ ) represent the same or different. When R ₁₁ and R ₁₂ represent a substituent and typical examples of R ₁₃ are R ₁₅ group and R ₁₃ respectively.
Examples thereof include a ₁₅ CO- group, an R ₁₅ SO ₂ -group, an R ₁₅ (R ₁₆ ) NCO- group and an R ₁₅ (R ₁₆ ) NSO ₂ -group. Here, R ₁₅ represents an aliphatic group, an aromatic group or a heterocyclic group, and R _15
16 represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. The case where each of R ₁₁ , R ₁₂ and R ₁₃ represents a divalent group and is linked to form a cyclic structure is also included. Specific examples of the group represented by formula (T-1) include groups represented by the following "Chemical formula 1" to "Chemical formula 3".

[0014]

[Chemical 1]

[0015]

[Chemical 2]

[0016]

[Chemical 3]

(2) Group that causes cleavage reaction by utilizing intramolecular nucleophilic substitution reaction For example, a timing group described in US Pat. No. 4,248,292 can be mentioned. It can be represented by the following general formula. General formula (T-2) * -Nu-Link-E-** In the formula, * mark and ** mark represent the same meaning as described for general formula (T-1), and Nu represents a nucleophilic group. Represents an example of a nucleophilic species such as an oxygen atom or a sulfur atom, E represents an electrophilic group, and is a group capable of undergoing a nucleophilic attack from Nu and cleaving the bond with the ** mark. Represents a linking group that is sterically related so that it can undergo an intramolecular nucleophilic substitution reaction. Specific examples of the group represented by formula (T-2) include those represented by the following "Chemical formula 4" and "Chemical formula 5".

[0018]

[Chemical 4]

[0019]

[Chemical 5]

(3) A group which causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system, for example, US Pat. Nos. 4,409,323 and 4,42.
1,845, JP-A-57-188035, 58-
98728, 58-209736, 58-20.
9737, 58-209738 and the like,
It is a group represented by the general formula (T-3) represented by the following "Chemical Formula 6".

[0021]

[Chemical 6]

In the formula, *, **, W, R ₁₁ , R ₁₂ and t have the same meanings as described for (T-1). However, R ₁₁ and R ₁₂ may be bonded to each other to form a benzene ring or a heterocyclic ring. Further, R ₁₁ or R ₁₂ and W may combine with each other to form a benzene ring or a heterocycle. Z ₁ and Z ₂ each independently represent a carbon atom or a nitrogen atom, and x and y represent 0 or 1. When Z ₁ is a carbon atom, x is 1, and when Z ₁ is a nitrogen atom, x is 0. The relationship between Z ₂ and y is the same as the relationship between Z ₁ and x. Also, t represents 1 or 2,
t is two in the case of 2 - _{[Z 1 (R 11) x =} Z 2 (R 12) y ]
The-may be the same or different. The -CH ₂ adjacent to the mark ** - group may be substituted with an alkyl group or a phenyl group having 1 to 6 carbon atoms.

In the following "Chemical formula 7" to "Chemical formula 10" (T-
Specific examples of 3) will be given.

[0024]

[Chemical 7]

[0025]

[Chemical 8]

[0026]

[Chemical 9]

[0027]

[Chemical 10]

(4) Group Utilizing Cleavage Reaction by Ester Hydrolysis For example, the following groups are the linking groups described in West German Laid-Open Patent No. 2,626,315. In the formula, asterisks and asterisks have the same meanings as described for the general formula (T-1). General formula (T-4) * -OCO-** General formula (T-5) * -SCS-** (5) Group utilizing cleavage reaction of imino ketal For example, described in U.S. Pat. No. 4,546,073. It is a linking group, and is represented by the following general formula (T 11) (T-
It is a group represented by 6).

[0029]

[Chemical 11]

In the formula, *, ** and W are general formulas (T
-1) has the same meaning as described above, and R ₁₄ is R
Has the same meaning as ₁₃ . Specific examples of the group represented by formula (T-6) include groups represented by the following "Chemical Formula 12".

[0031]

[Chemical 12]

(6) A compound that becomes a coupler residue or a redox group after being cleaved from A. For example, JP-A-63-21
No. 4752, which is represented by B in the general formula (I), more preferably a redox group. In the general formula (B), L ₁ is preferably (T-1) to (T-5).
And is particularly preferably (T-1) (T
-3) and (T-4).

The group represented by Z in the general formula (B) includes, in detail, a known bleaching accelerator group. For example, U.S. Pat. No. 3,893,858, British Patent No. 1138842, JP-A-53-141623.
Various mercapto compounds as described in Japanese Patent Publication No.
Compounds having a disulfide bond as described in JP-A-53-95630, JP-B-53-9854
Thiazolidine derivatives as described in JP-B No. 53-94927, isothiourea derivatives as described in JP-A-53-94927, JP-B-45-8506, and JP-B-4.
Thiourea derivatives as described in JP-A No. 9-26586, thioamide compounds as described in JP-A-49-42349, dithiocarbamate salts as described in JP-A-55-26506, An arylenediamine compound such as those described in U.S. Pat. No. 4,552,834. These compounds have a substitutable heteroatom contained in the molecule,
Formula A- in _{(B) (L 1) k} - as preferred examples for binding.

The group represented by Z is preferably a group represented by the following general formula (V), (VI) or (VII).

[0035]

[Chemical 13]

In the formula, the * mark represents the position at which A- (L ₁ ) _k- is bonded, R ₃₁ represents a divalent aliphatic group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and R ₃₂ represents R _32. A group having the same meaning as R ₃₁ ,
Represents a divalent aromatic group having 6 to 10 carbon atoms or a divalent heterocyclic group having a 3- to 8-membered ring, preferably a 5- or 6-membered ring, and X ₁ represents -O-, -S-,-. COO-, -SO _{2
-, - NR 33 -, -} NR 33 -CO -, - NR 33 -SO 2
-, -S-CO-, -CO-, -NR ₃₃ -COO-,-
_{N = CR 33 -, - NR} 33 CO-NR 34 -, or -NR
₃₃ SO ₂ NR ₃₄ — group, X ₂ represents an aromatic group having 6 to 10 carbon atoms, X ₃ is a 3-membered to 8-membered ring having at least one carbon atom bonded to S in the ring. Preferably a 5- or 6-membered heterocyclic group, Y ₁ is a carboxyl group or a salt thereof, a sulfo group or a salt thereof,
A hydroxyl group, a phosphonic acid group or a salt thereof, an amino group (which may be substituted with an aliphatic group having 1 to 4 carbon atoms),-
NHSO ₂ —R ₃₅ or —SO ₂ NH—R ₃₅ group (salt means sodium salt, potassium salt, ammonium salt or the like), and Y ₂ has the same meaning as described for Y _1. Alternatively, it represents a hydrogen atom, r represents 0 or 1, i represents an integer of 0 to 4, j represents an integer of 1 to 4, and k represents an integer of 0 to 4. However, j Y ₁ is R ₃₁ − {(X ₁ ) _r −R ₃₂ } _i
And X ₂ -{(X ₁ ) _r −R ₃₂ } _i are bonded at substitutable positions, and k Y ₁ are X ₃ − {(X ₁ ) _r −R ₃₂ }.
_When bonded to a substitutable position of _i , when k and j are plural, k and j Y ₁ 's each represent the same or different, and when i is plural, i (X ₁ ) _r- R ₃₂ Represents the same or different. Where R ₃₃ and R ₃₄
And R ₃₅ each represents a hydrogen atom or an aliphatic group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. When R ₃₁ to R ₃₅ represent an aliphatic group, they may be linear or cyclic, linear or branched, saturated or unsaturated, substituted or unsubstituted. Although it is preferably unsubstituted, examples of the substituent include a halogen atom, an alkoxy group (eg, methoxy, ethoxy), and an alkylthio group (eg, methylthio, ethylthio).

The aromatic group represented by X ₂ and the aromatic group when R ₃₂ represents an aromatic group may have a substituent. Examples of the substituent include those enumerated above as the aliphatic group substituents.

The heterocyclic group represented by X ₃ and the heterocyclic group when R ₃₂ represents a heterocyclic group are a saturated or unsaturated, substituted or unsubstituted heterocyclic group having an oxygen atom, a sulfur atom or a nitrogen atom as a hetero atom. It is a cyclic group. For example, pyridine, imidazole, piperidine, oxirane,
Mention may be made of sulfolane, imidazolidine, thiazepine or pyrazole. Examples of the substituent include those enumerated above as the aliphatic group substituents.

Specific examples of the group represented by the general formula (V) include the followings.

[0040]

[Chemical 14]

[0041]

[Chemical 15]

Specific examples of the group represented by the general formula (VI) include the followings.

[0043]

[Chemical 16]

Specific examples of the group represented by the general formula (VII) include the followings.

[0045]

[Chemical 17]

[0046]

[Chemical 18]

Next, specific examples of the bleaching accelerator-releasing compound preferably used in the present invention will be given, but the present invention is not limited thereto.

[0048]

[Chemical 19]

[0049]

[Chemical 20]

[0050]

[Chemical 21]

[0051]

[Chemical formula 22]

[0052]

[Chemical formula 23]

[0053]

[Chemical formula 24]

[0054]

[Chemical 25]

[0055]

[Chemical formula 26]

[0056]

[Chemical 27]

[0057]

[Chemical 28]

[0058]

[Chemical 29]

[0059]

[Chemical 30]

Others, Research Disclosure I
tem No. 24241, No. 11449, JP-A-61-
201247, 63-106749, 63-121843, 63-121844, 63-2144752 and 2-93.
The compounds described in Japanese Patent No. 454 are also used in the same manner.

The bleaching accelerator releasing compound used in the present invention can be easily synthesized based on the description in the above-mentioned patent specification.

The compound of the general formula (B) may be added to any layer, but a layer containing an emulsion capable of forming a latent image inside the grain at a depth of 2 nm or more and less than 100 nm from the grain surface or adjacent thereto. It is preferably added to the layer. General formula (B)
The amount of the compound to be added varies depending on the structure of the compound, but is preferably 1 × 10 ⁻⁵ to 1 mol, and particularly preferably 1 × 10 ⁻⁴ to 0.5 mol per mol of silver present in the same layer or an adjacent layer. is there.

The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red color-sensitive layer and the green color. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-113.
No. 438, No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound and the like as described in the specification, and an anti-color mixing agent may be used as usual. May be included. The plural silver halide emulsion layers constituting each unit light-sensitive layer are preferably composed of two layers of high-sensitivity emulsion layer and low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. be able to. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition,
57-112751, 62-200350, 62-206541, 62-2
As described in No. 06543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / Low sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / RH / RL order, or BH / BL / GH /
It can be installed in the order of GL / RL / RH. In addition,
As described in JP-A-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. In addition, JP-A-56-25738 and 62-63936
It is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support, as described in the specification. Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and the layer is composed of three layers having different sensitivities in which the sensitivities are gradually lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four or more layers, the arrangement may be changed as described above. In order to improve color reproducibility, U.S. Pat.Nos. 4,663,271 and 4,70
5,744, 4,707,436, JP-A-62-160448, 6
3- 89850, it is preferable to arrange a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, RL, adjacent to or in proximity to the main photosensitive layer. . As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention contains silver iodobromide, silver iodochloride, or iodochlorobromide containing about 30 mol% or less of silver iodide. It is silver. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. The silver halide grains in a photographic emulsion are those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal shapes such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about
It may be fine particles of 0.2 μm or less or large-sized grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o.17643 (December 1978), pp. 22-23, "I. Emulsion production (Emu
lsion preparation and types) ”, and the same No.18716
(November 1979), p. 648, ibid. No. 307105 (November 1989), 863.
-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Glafkides, Chemie et P
hisique Photographique, PaulMontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF D
uffin, Photographic Emulsion Chemistry (Focal Pres
s, 1966)), "Production and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (VL Zelikman et al.,
Making and Coating Photographic Emulsion, Focal Pr
ess, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff, PhotographicScience
and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,0
It can be easily prepared by the method described in 48, 4,439,520 and British Patent 2,112,157. The crystal structure may be uniform, may have different halogen compositions in the inside and the outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which forms a latent image inside the grain, or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The shell thickness of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion,
It can be used by mixing in the same layer. US Patent No.
No. 4,082,553, the surface of which is covered with a silver halide grain, U.S. Pat. It can be preferably used in the silver emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface is a silver halide grain that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat.
It is described in No. 9-214852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but as the average grain size,
0.01 to 0.75 μm, particularly 0.05 to 0.6 μm is preferable. Also,
The grain shape is not particularly limited, and may be regular grains or polydisperse emulsion, but monodisperse grains (at least 95% of the weight or number of silver halide grains are within ± 40% of the average grain size) (Having a particle size of 1).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866 2. Sensitivity enhancer 3. Spectral sensitizer, page 23 to 24, page 648, right column, page 866 to 868 Supersensitizer Page 649 Right column 4. Brightener page 24 Page 647 Right column Page 868 5. Fogging prevention page 24 to 25 Page 649 Right column 868 to 870 Agent, stabilizer 6. Light absorber, Page 25 to 26 Page 649 Right column Page 873 Filter to page 650 Left column Dye, UV absorber 7. Stain 25 Page right column 650 Page left column 872 Inhibitor to right column 8. Dye image Page 25 Page 650 Left column Page 872 Stabilizer 9. Hardener page 26 page 651 left column 874 to 875 10. Binder page 26 page 651 left column 873 to 874 page 11. Plasticizer, page 27 650 page right column 876 lubricant 12. Coating aid, 26 to 27 Page 650 page right column 875 to 876 surface active agent 13. static page 27 page 650 right column 876 to 877 inhibitor 14. matting agent page 878 to 879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add to the light-sensitive material a compound capable of reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. . In the light-sensitive material of the present invention, U.S. Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-28
It is preferable to contain the mercapto compound described in No. 3551. A compound which, in the light-sensitive material of the present invention, releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. In the light-sensitive material of the present invention, a dye dispersed by the method described in International Publication WO88 / 04794 or JP-A-1-502912 or
EP 317,308A, U.S. Pat.No. 4,420,555, JP 1-2593
It is preferable to include the dye described in No. 58. Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 1764 mentioned above.
3, VII-CG, and No. 307105, VII-CG
Are described in the patents listed in. Yellow couplers include, for example, U.S. Patents 3,933,501 and 4,02.
No. 2,620, No. 4,326,024, No. 4,401,752, No.
4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,
No. 020, No. 1,476,760, U.S. Patent No. 3,973,968,
No. 4,314,023, No. 4,511,649, European Patent No. 24
Those described in No. 9,473A, etc. are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,63 are preferred.
6, U.S. Pat.Nos. 3,061,432 and 3,725,067,
Research Disclosure No. 24220 (June 1984
Month), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A 61-7.
No. 2238, No. 60-35730, No. 55-118034, No. 60-185951
U.S. Pat.Nos. 4,500,630, 4,540,654, and
Those described in 4,556,630 and International Publication WO88 / 04795 are particularly preferable. Examples of cyan couplers include phenol-based and naphthol-based couplers, and US Pat.
52,212, 4,146,396, 4,228,233, and
4,296,200, 2,369,929, 2,801,171,
No. 2,772,162, No. 2,895,826, No. 3,772,002
No. 3, No. 3,758,308, No. 4,334,011, No. 4,32
7,173, West German Patent Publication 3,329,729, European Patent 12
1,365A, 249,453A, U.S. Pat.No. 3,446,622
No. 4, No. 4,333,999, No. 4,775,616, No. 4,45
1,559, 4,427,767, 4,690,889, and
Those described in 4,254,212, 4,296,199 and JP-A-61-42658 are preferable. Furthermore, JP-A-64-553,
Pyrazoloazole couplers described in JP-A Nos. 64-554, 64-555 and 64-556 and imidazole couplers described in US Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in US Pat.
3,451,820, 4,080,211 and 4,367,282,
No. 4,409,320, No. 4,576,910, British patent 2,1
No. 02,137 and European Patent No. 341,188A.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,12.
5,570, European Patent 96,570, West German Patent (Publication)
Those described in 3,234,533 are preferable. Colored couplers for correcting unnecessary absorption of color forming dyes are described in Research Disclosure No. 17643, Item VII-G, No. 307.
105 VII-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57
-39413, U.S. Pat.Nos. 4,004,929, 4,138,258
And those described in British Patent No. 1,146,368 are preferred.
Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181, and a dye capable of reacting with a developing agent described in U.S. Pat.No. 4,777,120 to form a dye. It is also preferable to use a coupler having a precursor group as a leaving group.
Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are described in RD 17643, VII-F above.
And Patent Nos. 307105 and VII-F, JP-A-57-151944, 57-154234, 60-184248,
63-37346, 63-37350, U.S. Patent 4,248,962,
Those described in JP-A-4,782,012 are preferable. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patents 2,097,140 and 2,131,188.
And those described in JP-A Nos. 59-157638 and 59-170840. In addition, JP-A-60-107029 and 60-252340
Compounds releasing a fog agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in JP-A Nos. 1-444940 and 1-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,3.
38,393, 4,310,618 and the like, multi-equivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds described in JP-A-60-185950 and JP-A-62-24252. Alternatively, DIR redox-releasing redox compounds, couplers that release dyes that undergo color restoration after withdrawal described in European Patents 173,302A and 313,308A, ligand-releasing couplers described in U.S. Pat. -75747 couplers releasing leuco dyes, U.S. Pat.
Examples thereof include couplers that release the fluorescent dye described in No. 181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling-point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate. (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di
-2-Ethylhexyl phenylphosphonate, etc., Benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecane amide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctylazese) Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate, etc., aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
Organic solvents above 160 ° C can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-272248,
And 1,2-benzisothiazolin-3-one described in JP-A-1-80941, n-butyl p-hydroxybenzoate,
It is preferable to add various preservatives or antifungal agents such as phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole. The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.
Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D. No.17643, page 28, No.18716, page 647 From right column 648
It is described on the left column of the page and on page 879 of the same No. 307105. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, particularly preferably 16 μm or less. Also the film swelling speed T
_1/2 is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured under a humidity condition of 25 ° C. and 55% relative humidity (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, A. Green et al., Photographic Science and Engineering (Photog
r.Sci.Eng.), No. 19, No. 2, pages 124 to 129 can be measured by using a swellometer (swelling meter) of the type described, and T _1/2 is 30 ° C. in a color developer. , 90% of the maximum swollen film thickness reached after treatment for 3 minutes and 15 seconds is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness. Membrane swelling speed T
_1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness. The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
In this back layer, the above-mentioned light absorber, filter dye,
It is preferable to contain an ultraviolet absorber, an antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, a surface active agent and the like. The swelling ratio of this back layer is 150-500
% Is preferred.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28 to 29, No. 18716, 651 left column to right column, and No. 307105, pages 880 to 881 can be developed by a usual method. The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As this color developing agent,
Aminophenol-based compounds are also useful, but p-phenylenediamine-based compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N diethylaniline and 3-methyl-4-amino-N-. Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline, 4-amino-3-
Methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl- N-
(2-hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-
Amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino-3-propyl-N-methyl-N- (3-
Hydroxypropyl) aniline, 4-amino-3-methyl-N
-Methyl-N- (4-hydroxybutyl) aniline, 4-amino
-3-Methyl-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N -Ethyl -N-
(3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-hydroxy Pentyl) aniline, 4-amino-3-methyl-N- (5-hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl ) Aniline, 4-amino-3-ethoxy-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates and hydrochlorides Alternatively, p-toluenesulfonate may be used.
Among these, especially 3-methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 4-amino-3-methyl-
N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, and their hydrochlorides, p-toluenesulfonate or sulfuric acid Salt is preferred. Two or more of these compounds can be used in combination depending on the purpose. Color developers include alkaline metal carbonates, borates or phosphates.
It is common to include a pH buffer, a chloride salt, a bromide salt, an iodide salt, a development inhibitor such as a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agent, aminopolycarboxylic acid,
Aminopolyphosphonic acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1- Hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and them Can be mentioned as a representative example.

When reversal processing is carried out, black and white development is usually carried out before color development. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and it is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. Is. As a method of reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit development processing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a color developing agent at a high concentration.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include organic complex salts of iron (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. . Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patent 1,290,812.
No. 2,059,988, JP-A-53-32736, and JP-A-53-57831
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53
-95631, 53-104232, 53-124424, 53-141
623, 53-28426, Research Disclosure
Compounds having a mercapto group or a disulfide group described in No. 17129 (July 1978), etc .; JP-A-50-140129
Thiazolidine derivatives described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, and US Pat. No. 3,706,561.
Thiourea derivative described in Japanese Patent No. 1,127,715, West German Patent
Iodide salts described in JP-A-58-16,235; West German Patent No. 966,
Polyoxyethylene compounds described in JP-A Nos. 410 and 2,748,430; polyamine compounds described in JP-B-45-8836; Other JP-A-49-40,943, 49-59,644, 53-94,92
No. 7, No. 54-35,727, No. 55-26,506, No. 58-163,940
Compounds described in No. 1; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, US Pat.
3,858, West German Patent 1,290,812, JP-A-53-95,630
Compounds described in US Pat. Further, U.S. Pat.
The compounds described in No. 834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acid has an acid dissociation constant (pKa) of 2
A compound of -5, specifically acetic acid, propionic acid,
Hydroxyacetic acid and the like are preferred. Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts, but the use of thiosulfates is common. In particular, ammonium thiosulfate can be used most widely. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or European Patent No. 294
The sulfinic acid compounds described in No. 769A are preferable. Furthermore,
For the purpose of stabilizing the solution, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution. In the present invention, the fixer or the bleach-fixer has a pH of
For adjustment, a compound having a pKa of 6.0 to 9.0, preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole.
It is preferable to add 1 to 10 mol / liter.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is as strong as possible.
As a specific method for strengthening stirring, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461 Method to increase the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution to further improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator. The automatic processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
No. 60-191258 and No. 60-191259. The above-mentioned JP-A-6
As described in No. 0-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture a
nd Television Engineers, Volume 64, P. 248-253 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, such a problem is solved as a solution.
The method of reducing calcium ion and magnesium ion described in 62-288,838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" (1986) Sankyo Publishing Co., Ltd., Hygiene Engineering Society, "Microbial sterilization, sterilization, and antifungal technology"
(1982) The sterilizing agent described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal can also be used. The pH of the washing water in the processing of the light-sensitive material of the present invention is 4
It is -9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the photosensitive material, the application, etc.
Generally, 15 seconds to 45 degrees Celsius for 20 seconds to 10 minutes, preferably 25 to 40 degrees Celsius
The range from 30 seconds to 5 minutes is selected with. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used. Further, there is a case where further stabilizing treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. be able to. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution associated with the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat.No. 3,342,597, No. 3,342,599, Schiff base compounds described in Research Disclosure Nos. 14,850 and No. 15,159, aldol compounds described in No. 13,924, U.S. Pat.No. 3,719,492. Metal salt complexes described, JP-A-53-135
The urethane compound described in No. 628 can be mentioned.
The silver halide color light-sensitive material of the present invention contains various 1-phenyl-3-methyl-3-phenyl-3-(-3-phenyl) -3-phenyl-3- (phenyl-3-phenyl) -3- (phenyl-3-phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3-(-3-phenyl-3-phenyl-3- (cyclohexyl) -3- (phenyl-3-phenyl-3-methyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3- (3-phenyl-3-phenyl-3- (3-phenyl-3- (phenyl-phenyl--3-one-
You may incorporate pyrazolidones. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, JP-A-58-115438 and the like. Various treatment liquids in the present invention are 10 °
Used at ~ 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

The silver halide color photographic light-sensitive material of the present invention is more likely to exhibit the effect when applied to the lens-fitted film unit described in JP-B-2-32615, JP-B-3-39784 and the like. It is valid.

[0083]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 (Preparation of shallow inner latent silver halide emulsion) In the same manner as in Example 1 of JP-A-58-248473,
A monodisperse dispersion having a diameter of 1.1 μm, a grain size variation coefficient of 14%, an average silver iodide content of 20 mol%, an average silver iodide content of 0 mol% and an average silver iodide content of 10 mol%. A heavy-structured silver iodobromide emulsion was prepared, and after desalting by the θ conventional method, an aqueous solution of chloroauric acid and an aqueous solution of sodium thiosulfate were added,
Chemically aged. The obtained emulsion is designated as EM-11. Further subsequently, EM- corresponding to 1 mol of silver halide.
11 to 1.00M AgNO ₃ aqueous solution and 1.00M K
10 ml of each Br aqueous solution was added over 2 minutes. The obtained emulsion is designated as EM-12. Similarly, to EM-11 equivalent to 1 mol of silver halide, 1.0M AgNO ₃ aqueous solution and 1.0 were added.
40 ml each of 0M aqueous KBr solution was added over 5 minutes. The obtained emulsion is designated as EM-13. Similarly, silver halide 1
To EM-11 corresponding to a mole, 160 ml each of a 1.00 M AgNO ₃ aqueous solution and a 1.00 M KBr aqueous solution were added over 20 minutes. The obtained emulsion is designated as EM-14. Similarly, 1.00M Ag was added to EM-11 equivalent to 1 mol of silver halide.
260 ml of NO ₃ aqueous solution and 260 ml of 1.00 M KBr aqueous solution were added over 35 minutes. The obtained emulsion is designated as EM-15. Similarly, to EM-11 corresponding to 1 mol of silver halide, 360 ml each of 1.00 M AgNO ₃ aqueous solution and 1.00 M KBr aqueous solution were added over 50 minutes. The obtained emulsion is designated as EM-16. The above emulsions EM-11, 12, 1
3, 14, 15 and 16 were coated on a triacetyl cellulose support provided with an undercoat layer at a rate of 3.8 g / m ² in terms of silver amount and dried. The latent image distribution of each emulsion of EM-11 to 16 was determined by the method described in the text. Table 1 shows the distance from the surface of the emulsion grains to the maximum latent image distribution of each emulsion and the ratio of the latent image existing on the surface.

[0084]

[Table 1]

Example 2 Example 2 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 201 which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 201) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.20 ExM-1 0.18 ExF-1 2.0 × 10 ^-3

[0087]

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-4 0.17 ExC-6 0.020 UV-1 0.070 UV-2 0.050 UV-3 0.070 HBS-1 0.060 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.20 ExC-2 0.050 ExC-4 0.20 ExC-5 0.050 ExC-6 0.015 UV-1 0.070 UV-2 0.050 UV-3 0.070 Gelatin 1.30

Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.097 ExC-2 0.010 ExC-3 0.089 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63

6th layer (intermediate layer) Cpd-1 0.040 HBS-1 0.020 gelatin 0.80

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion C Silver 0.30 ExS-4 2.6 × 10 ^-5 ExS-5 1.8 × 10 ^-4 ExS-6 6.9 × 10 ^-4 ExM-1 0.021 ExM-2 0.28 ExM-3 0.030 ExY-1 0.025 HBS-1 0.10 HBS-3 0.010 Gelatin 0.63

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion D Silver 0.55 ExS-4 2.2 × 10 ^-5 ExS-5 1.5 × 10 ^-4 ExS-6 5.8 × 10 ^-4 ExM-2 0.094 ExM-3 0.026 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.50

Ninth layer (high-sensitivity green emulsion layer) Emulsion EM-11 (produced in Example 1) Silver 1.55 ExS-4 4.6 × 10 ⁻⁵ ExS-5 1.0 × 10 ⁻⁴ ExS-6 3.9 × 10 ^-4 ExC-1 0.015 ExM-1 0.013 ExM-4 0.067 ExM-5 0.016 HBS-1 0.25 HBS-2 0.10 Gelatin 1.60

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.035 Cpd-1 0.080 HBS-1 0.030 Gelatin 0.95

Eleventh Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.042 ExY-2 0.72 HBS-1 0.28 Gelatin 1.10

12th layer (medium-speed blue-sensitive emulsion layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-6 7.0 × 10 ^-3 ExY-2 0.15 HBS-1 0.050 Gelatin 0.78

13th layer (high sensitivity blue-sensitive emulsion layer) Emulsion F Silver 0.70 ExS-7 2.8 × 10 ^-4 ExY-2 0.20 HBS-1 0.070 Gelatin 0.69

14th layer (first protective layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt and rhodium salt.

[0102]

[Table 2]

In Table 2, (1) Emulsions A to F were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to F were prepared according to the examples of Japanese Patent Application No. 2-34090.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in Japanese Patent Application No. 2-34090 have been observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope.

[0104]

[Chemical 31]

[0105]

[Chemical 32]

[0106]

[Chemical 33]

[0107]

[Chemical 34]

[0108]

[Chemical 35]

[0109]

[Chemical 36]

[0110]

[Chemical 37]

[0111]

[Chemical 38]

[0112]

[Chemical Formula 39]

[0113]

[Chemical 40]

[0114]

[Chemical 41]

[0115]

[Chemical 42]

[0116]

[Chemical 43]

[0117]

[Table 3]

(Production of Samples 202 to 206) Sample 201
A sample 202 which is the same as the sample 201 except that the emulsion EM-11 of the ninth layer of was changed to EM-12. Sample 203 in which the emulsion EM-11 of the ninth layer of Sample 201 was changed to EM-13 to EM-16 as shown in Table 3 in exactly the same manner.
~ 206 were produced. (Preparation of Samples 211 to 216) 0.07 mmol / m ² of the bleaching accelerator releasing compound B-28 was added to the ninth layer of Samples 201 to 206, and the others were the same as Samples 201 to 206, respectively. 216 was produced. (Preparation of Samples 223, 233, 243) Sample ^{2 in} which B-20 was added to the ninth layer of Sample 203 in an amount of 0.07 mmol / m 2.
23 and ExC-3 0.07 of the fifth layer of sample 203
Except mmol / m ^2, to prepare a sixth layer to the B-26 0.07 mmol / m ² samples 243 added of B-32 0.07 mmol / m ² added samples 233 and the sample 203 in place . A list of the bleaching accelerator releasing compounds contained in these samples 201 to 243 and the emulsion of the ninth layer is shown in Table 3. (Evaluation method of each sample) After coating each sample of 201 to 243 for 8 days at 25 ° C. and 68% in temperature and humidity to harden the film, the film is exposed with an optical wedge at a color temperature of 4800 ° K for 1/100 seconds. Gave. Subsequently, it was developed by the (Processing A) described, exposed to white light, and the optical density was measured. The reciprocal of the exposure amount giving the density of fogging density + 0.2 was defined as the green-sensitive layer sensitivity, and it was expressed as a relative value when the value of Sample 201 was 100. For RMS granularity, after uniformly exposing the sample with a light amount giving a density of fog +0.2 and performing a developing process (Process A), "The Theory of Photographic Process", page 619, published by Macmillan Corporation. It measured using the green filter by the method described from. The result is Sample 2
It was expressed as a relative value when the RMS of 01 was 100. Further, the amount of silver remaining in the sample after being subjected to a white uniform exposure of 10 lux · sec for processing was quantified by a fluorescent X-ray method to evaluate the desilvering property. The above results are summarized in Table 3. As is clear from Table 3, the combination of a BAR compound, which lowers the sensitivity when combined with a non-internal latent emulsion, in combination with an internal latent emulsion, can significantly improve the sensitivity without substantially reducing the RMS. it can. The effects of the present invention were similarly exhibited by using (treatment B) and (treatment C) described below.

(Processing A) Processing was carried out by the method described below using an automatic processor. Process Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ℃ 22 ml 20 liters Bleach 3 minutes 00 seconds 38 ℃ 25 ml 40 liters Water wash 30 seconds 24 ℃ 1200 ml 20 liters Fixed time 3 minutes 00 seconds 38 ℃ 25 ml 30 liter Water wash (1) 30 seconds 24 ℃ 10 liter from (2) to (1) Countercurrent piping system Water wash (2) 30 seconds 24 ℃ 1200 ml 10 liter Stability 30 seconds 38 ℃ 25 ml 10 Liter dry 4 minutes 20 seconds 55 ℃ Replenishment amount is 35mm width 1m length

Next, the composition of the processing liquid will be described. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.3 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 6.2 Water added 1.0 liter 1.0 liter pH 10.05 10.15

(Bleaching solution) Tank solution (g) Replenishing solution (g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 11.0 3-Mercapto-1,2,4-triazole 0.08 0.09 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5 ml 4.0 ml Add water 1.0 liter 1.0 liter pH 6.0 5.7

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ethylenediaminetetraacetic acid disodium salt 0.5 0.7 Ammonium sulfite 20.0 22.0 Ammonium thiosulfate aqueous solution (700 g / l) 290.0 ml 320.0 ml 1.0 liter 1.0 liter by adding water pH 6.7 7.0

(Stabilizing Solution) Common Tank Solution / Replenishing Solution (g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2 , 4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

(Processing B) Processing was carried out by the method described below using an automatic processor. Process Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ° C 45 ml 10 liters Bleaching 1 minute 00 seconds 38 ° C 20 ml 4 liters Bleaching fixing 3 minutes 15 seconds 38 ° C 30 ml 8 liters Washing (1) 40 seconds 35 ℃ 4 liters from (2) to (1) countercurrent piping system Washing with water (2) 1 minute 00 seconds 35 ℃ 30 milliliters 4 liters Stability 40 seconds 38 ℃ 20 milliliters 4 liters Drying 1 minute 15 seconds 55 ℃ Replenishment amount is 35mm width 1m per length

Next, the composition of the processing liquid will be described. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 5.5 Water was added to 1.0 liter 1.0 liter pH 10.05 10.10

(Bleaching Solution) Tank Solution and Replenishing Solution Common (Unit: g) Ethylenediaminetetraacetic acid Ammonium ferric dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol (CH ₃ ) _{2 N-CH 2 -CH 2 -SS} -CH 2 -CH 2 -N (CH 3) 2 · 2HCl aqueous ammonia (27%) was added to 15.0 ml water 1.0 liters pH 6.3

(Bleach-fixing solution) Tank solution (g) Replenishing solution (g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 50.0-Ethylenediaminetetraacetic acid disodium salt 5.0 2.0 Sodium sulfite 12.0 20.0 Ammonium thiosulfate aqueous solution (700 g / l) 240.0 ml 400.0 ml Ammonia water (27%) 6.0 ml-Add water 1.0 liter 1.0 liter pH 7.2 7.3

(Washing Solution) Common to Tank Solution and Replenishing Solution Tap water is used as H type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type anion exchange resin (Amberlite IR-400). Water was passed through a mixed bed column filled with to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then 20 mg / liter of sodium diisocyanurate dichloride and 0.15 g / liter of sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizing Solution) Common Tank Solution / Replenishing Solution (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

(Processing C) Processing was carried out under the following conditions using an automatic processor.

Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 600 ml 17 liters Bleach 50 seconds 38.0 ° C 140 ml 5 liters Bleach fixing 50 seconds 38.0 ° C-5 liters Fixed 50 seconds 38.0 ℃ 420 ml 5 liters Water wash 30 seconds 38.0 ℃ 980 ml 3 liters Stable (1) 20 seconds 38.0 ℃ −3 liters Stable (2) 20 seconds 38.0 ℃ 560 ml 3 liters Dry 1 minute 60 ℃ * Replenishment amount is photosensitive material Amount per 1 m ² The stabilizing solution was a countercurrent system from (2) to (1), and the overflow solution of washing water was all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank so that all of the overflow solution generated by supplying the replenishing solution to the bleaching tank and the fixing tank is added to the bleach-fixing bath. I was allowed to flow in. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the washing process were each per 1 m ² of the light-sensitive material. 65 ml, 50 ml, 50 ml, 5
It was 0 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. Further, each replenisher was replenished with the same liquid as the respective tank liquids.

The composition of the processing liquid is described below. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 Sodium sulfite 3.9 Potassium carbonate 37.5 Potassium bromide 1.4 Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 2-Methyl-4 -[N-Ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 Water was added to 1.0 liter pH 10.05

(Bleaching Solution) (Unit: g) 1,3-Diaminopropanetetraacetic acid Ammonium ferric acid monohydrate 130 Ammonium bromide 80 Ammonium nitrate 15 Hydroxyacetic acid 50 Acetic acid 40 Water was added to 1.0 liter pH [prepared with aqueous ammonia] ] 4.4

(Bleaching Fixing Solution) A 15:85 (volume ratio) mixture of the above bleaching solution and the following fixing solution. (PH 7.0)

(Fixer) (Unit: g) Ammonium sulfite 19 Ammonium thiosulfate aqueous solution (700 g / liter) 280 ml imidazole 15 Ethylenediaminetetraacetic acid 15 Water was added to 1.0 liter pH [Prepared with ammonia water and acetic acid] 7.4

(Washing Water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
/ Liter or less, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

(Stabilizing Solution) (Unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one negative type silver halide emulsion layer on a support, said emulsion layer containing a bleaching accelerator releasing compound,
Further, at least one of the light-sensitive emulsion layers constituting the light-sensitive material contains an emulsion capable of forming a latent image within the grains having a depth of 2 nm or more and less than 100 nm from the grain surface, and the latent image is a color negative surface. A silver halide color photographic light-sensitive material, which is developable with a developing type developer.