JP2559254B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a multilayer silver halide color photographic light-sensitive material, and more specifically, it contains an improved development inhibitor releasing compound to improve sharpness. The present invention also relates to a multilayer silver halide color photographic light-sensitive material and a processing method in which the replenishment amount of the developing solution is reduced.

<< Conventional technology >> In recent years, with the spread of small-sized cameras (for example, 110 cameras), image quality enlarged from a small-sized screen is equivalent to image quality enlarged from a larger normal 35-mm-sized screen. Came to be required. In order to satisfy such demands, it is necessary to develop a color photographic light-sensitive material having both granularity and sharpness such that print quality is not impaired even when the enlargement magnification is increased.

Conventionally, various methods for improving the sharpness of image quality have been known, but it is widely known that a large effect can be obtained especially by increasing the edge effect and reducing the light scattering in the photographic light-sensitive material. . Of these, the edge effect utilizes the concentration gradient of the development-inhibiting substance present during development. As the development inhibitor in this case,
For example, there may be mentioned iodide ions, bromide ions or oxidation products of a developing agent released when silver halide is developed in a developer. In addition, the edge effect is described in U.S. Patent Nos. 3,227,554, 3,615,506,
It is also known that it can be increased by using the compounds described in 617,291 and 3,701,783, etc., or the so-called DIR compounds and DIR couplers described in JP-B-55-34933. Also, JP-A-62-166334 and JP-A-63-37346
It is also known that the effects can be further enhanced by using the further improved DIR compounds and DIR couplers described in the above publication.

However, even when the above DIR coupler is used, a large amount of the DIR coupler must be used when a strong edge effect is required, which inevitably greatly suppresses development. Inevitably, the maximum density of the obtained image and the sensitivity are reduced.Therefore, the amount of the DIR coupler to be used is naturally limited.
There is a disadvantage that the edge effect due to the IR coupler or the like must be limited. When the coating amount of silver is increased in order to solve such a drawback, not only the product cost is increased but also the MTF curve in the high spatial frequency region is lowered due to the large light scattering by silver halide. , DIR coupler added layer, as well as the lower layer sharpness is deteriorated (For the MTF curve, see Mies's “The The
ory of Photographi Process ", 3rd Edition, published by Macmillan, Inc.).

Japanese Unexamined Patent Publication No. 59-131934 has developed a DIR compound that can improve the above-mentioned conventional drawbacks and can particularly enhance the edge effect while maintaining a constant maximum image density. Although a light-sensitive material capable of increasing the sharpness in a region is provided, the above-mentioned present invention contains a development-inhibitor-releasing compound capable of reacting with an oxidation product of a developing agent during development to release a development-inhibiting substance. And a silver halide color photographic light-sensitive material.

Japanese Patent Application Laid-Open No. 61-173248 relates to the improvement of the above invention.In the case where a DIR coupler is used, the MTF value in the low frequency region generally increases, and as a result, the psychological sharpness increases. Nevertheless, the image sharpness and the layering effect are not sufficient, and further, the MTF in the low frequency region is to be improved.

Further, in JP-A-62-166334, an improved DIR compound was provided, and the sharpness and color reproducibility were improved by controlling the dry film thickness of the emulsion layer.

Most recently, the improved DI described in JP-A-63-37346
It is described that the use of the R compound further improves the sharpness as compared with the case of using the conventional DIR coupler.

Also, from the demand of simplifying the processing method, there is a strong demand for a method that requires a small amount of replenishment of the processing solution in the development processing step by the replenishing method.

In continuous development processing, the replenishing amount of the developing solution is slightly different depending on the type of the light-sensitive material to be processed, but in the case of silver halide color photographic light-sensitive material for photography, it is usually 1 per 1 m ^2.
It is about 300-1100 ml.

From the viewpoint as described above, it is desired to reduce the replenishment amount, but the reduction of the replenishment amount deteriorates the photographic characteristics.
The reduction is generally very difficult.

On the other hand, in order to meet the demand for environmental protection, various color developing solution recycling methods have been tried in the color development processing step.

For example, Journal of Applied Photographic Engineering (J.Appl.Phot.Eng.), 5 ,
208 (1979); Monthly Lab, 15 , 113 (1979); SMPTE Journal (SMPTE.J). 88 , 165 (1979); J.Appl.Phot.Eng.,
5 , 32 (1974); SMPTE.J., 88 , 168 (1979); JP-A-52.
-143018; 52-146236; 53-149331; 54-9629.
No .; J.Appl.Phot.Eng., 5 , 216 (1979) and the like.

Further, generally, when the replenishment amount is reduced, the amount of eluate from the silver halide photographic light-sensitive material becomes relatively large (for example, halogen ions generated by decomposition of silver halide), and the sensitivity is lowered. is there.

With respect to the problem of decreased sensitivity, attempts have been made to increase the processing temperature to prevent the sensitivity from decreasing and to reduce the amount of replenishment.

For example, CP-L, a color paper treatment agent for Hunt
P treatment agent (specifically, Photographic Bulletin No. 49, published by Hunt, Inc.)
49) Page 6 Color Print Chemistries (Co
lor Print Chemistries)], and the methods described in Proceedings of the Photographic Society of Japan, A-7, "Low Replenishment of Color Paper Processing" (1980) and the like. The former processing agent reduces the replenishment amount of the color developing solution to 1/2 to 2/3.

However, since these are processing agents for color paper, they cannot be immediately applied to color photographic light-sensitive materials for photography because of problems in photographic characteristics such as sensitivity, gradation and color reproduction.

In the processing of color negative films, the above-mentioned Hunt's treatment agent (issued by Hunt, described in Photographik Bretein No.55) has a low replenishment formula of 754 ml per 1 m ^2, but the treatment is stable. In terms of sex, it is not enough.

This is a DI that is often used to improve the layering effect and sharpness, which is a problem peculiar to color photographic light-sensitive materials for photography.
It is speculated that one of the causes is that the released development inhibitor flows out and accumulates in the developer after the coupling reaction of the R (development inhibitor releasing type) coupler.

In particular, in the DIR compound described in JP-A-63-37346, by having a plurality of timing groups, it is possible to increase the diffusion distance of the detachment development inhibitor precursor, and enhance the interlayer effect and edge effect. It has become clear that when the low replenishment process as described above is applied, the release inhibitor accumulates in the developing solution, which causes a great problem that the photographic property is changed.

JP-A-62-148951 discloses a combination of a DIR coupler having a group capable of being decomposed in a developer and a low replenishing treatment in order to maintain stable photographic performance.
With the DIR couplers described in 63-37346, there was a need for even faster degradation times.

<Problems to be Solved by the Invention> Accordingly, an object of the present invention is to provide a processing method of a color photographic light-sensitive material having excellent sharpness and less contamination of a developing solution. A second object is to provide a processing method of a silver halide color photographic light-sensitive material which does not cause fluctuations in photographic performance such as desensitization even in a low replenishment continuous processing with a reduced replenishment amount.

<< Means for Solving the Problems >> As a result of earnest research, the present inventors have found that the object of the present invention can be achieved by the following things.

(1) At least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, and blue-sensitive silver halide emulsion layer are provided on a support, which is represented by the following general formula (I) at the time of development. A development inhibitor releasing coupler capable of reacting with an oxidation product of a developing agent to finally release a development inhibitor,
The development inhibitor has a group having a property of changing to a compound that does not substantially affect the photographic properties after the development inhibitor flows out into the developing solution, and further, the development inhibitor has a half at pH 10 In a method of continuously processing a silver halide color photographic light-sensitive material containing a coupler having a period of 2 hours or less, the replenishment amount of the developer is 1 m ^{2 of the} light-sensitive material to be developed. A method of processing a silver halide color photographic light-sensitive material, which is 700 ml or less.

In the general formula _{(I) A-L 1 -L} 2 -DI formula, A represents a group which reacts with an oxidation product of an aromatic primary amine developing agent cleaves the L ₁ -L ₂ -DI, L ₁ represents a group in which after the bond with A is cleaved, the bond with L ₂ is cleaved without reacting with the oxidation product of the aromatic primary amine developer, and L ₂ is cleaved with the bond with L ₁ . It represents a group in which the bond with the subsequent DI is cleaved, and DI represents a development inhibitor that loses the development inhibiting action when it flows into the developing solution without reacting with the oxidation product of the aromatic primary amine developing agent.

Next, the compound represented by formula (I) will be described in detail below.

In the general formula (I), 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),
Magenta coupler residue (for example, 5-pyrazolone type, pyrazolotriazole type or pyrazoloimidazole type coupler residue, cyan coupler residue (for example, phenol type, naphthol type or European Patent Publication No. 249,45)
No. 3 coupler group such as imidazole type) and a colorless coupler residue (for example, indanone type or acetophenone type coupler residue). Also, U.S. Pat.Nos. 4,315,070, 4,183,752, 4,174,
It may be a heterocyclic coupler residue described in 969, 3,961,959 or 4,171,223.

When A represents an oxidized ring group, the redox group is a group that 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, hydrazides or sulfonamide naphthols. These groups are specifically described, for example, in JP-A-61-230135 and JP-A-62-251746.
No. 61-278852, U.S. Pat.Nos. 3,364,022, 3,379,
No. 529, No. 3,639,417, No. 4,684,604 or J.Org.Che
m., 29 , 588 (1964).

Examples of the groups represented by L ₁ and L ₂ in the general formula (I) include the following.

(1) Group Utilizing Cleavage Reaction of Hemiacetal For example, a group described in US Pat. No. 4,146,396 and JP-A-60-249148 and 60-249149 and represented by the following general formula. Here, the * mark represents the position bonded to the left side of the group represented by L ₁ or L ₂ of the compound represented by the general formula [I], and the ** mark represents the position bonded to the right side of the group represented by L ₁ or L _2. Indicates the position to

General formula (T-1) In the formula, W is an oxygen atom, a sulfur atom or Represents a group, R ₁₁ and R ₁₂ represent a hydrogen atom or a substituent, R ₁₃ represents a substituent, and represents t1 or 2.
When t is 2, two Represents the same or different. R ₁₁ and R
_{When 12} represents a substituent and typical examples of R ₁₃ are R ₁₅ group, R ₁₅ CO— group, R ₁₅ SO ₂ — group, Base or Groups. Here, R ₁₅ represents an aliphatic group, an aromatic group or a heterocyclic group, and R 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 the following groups.

* -OCH ₂ -** ＊ －SCH ₂ － ＊＊ (2) A group that causes a cleavage reaction by utilizing an intramolecular nucleophilic substitution reaction. For example, a timing group described in US Pat. No. 4,248,962 may be mentioned. It can be represented by the following general formula.

General formula (T-2) * -Nu-Link-E-** In the formula, Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, E represents an electrophilic group, Nu A group that can be more nucleophilically attacked to cleave the bond with **
Link represents a linking group that sterically links Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction. General formula (T
Specific examples of the group represented by -2) are as follows.

(3) A group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system.

For example, U.S. Pat.
57-188035, 58-98728, 58-209736, 58-209
No. 737, No. 58-209738, etc., the following general formula (T
-3) is a group.

General formula (T-3) In the formula, *, **, W, R ₁₁ , R ₁₂ and t are (T
-1) has the same meaning as described above. However, R ₁₁ and R ₁₂ may be combined to form a benzene ring or a heterocyclic ring. Specific examples include the following groups.

(4) A group that utilizes a cleavage reaction due to hydrolysis of an ester.

For example, the following groups are the connecting groups described in West German Published Patent No. 2,626,315. In the formula, asterisks and asterisks have the same meanings as described for the general formula (T-1).

(5) A group that utilizes an imino ketal cleavage reaction.

For example, it is a linking group described in US Pat. No. 4,546,073 and is a group represented by the following general formula.

General formula (T-6) In the formula, *, ** and W have the same meanings as described in formula (T-1), and R ₁₄ has the same meaning as R ₁₃ . Specific examples of the group represented by formula (T-6) include the following groups.

Examples of the development inhibitor represented by DI in the general formula (I) include U.S. Pat. No. 4,477,563, JP-A-60-218644,
Examples thereof include those described in Nos. 60-217,750, 60-233650 and 61-11743.

What is preferable as DI is represented by the following general formula (II).

Formula _{(II) * -Y 1 - (} L 3 -Y 2) a wherein Y ₁ represents the basic skeleton of the development inhibitor, L _3, a compound represented by the general formula (I) is flowed in the developer When
Represents a group containing a bond which is cleaved in a developing solution, Y ₂
Represents a group for exhibiting a development inhibiting effect. a represents an integer of 1 to 3.

Examples of the group represented by Y ₁ include a tetrazolylthio group, a thiadiazolylthio group, an oxadiazolylthio group, a triazolylthio group, a benzimidazolylthio group, a benzthiazolylthio group, a tetrazolylseleno group, a benzoxazolylthio group, Typical examples are a benzotriazolyl group, a triazolyl group substituted with an alkylthio group, a benzoindazolyl group or an imidazolylthio group.

Particularly preferred development inhibitors represented by DI in formula (I) are listed below.

For example, U.S. Pat.No. 4,477,563, JP-A-60-218,644
No. 60, No. 60-211,750, No. 60-233,650, or No. 61-11,
The development inhibitors described in No. 743 can be mentioned, preferably the following general formulas (D-1), (D-2), (D-3) and (D
-4), (D-5), (D-6), (D-7), (D-
8), (D-9), (D-10) or (D-11).

In the formula, the * mark represents the position at which L ₃ is bonded in the general formula (I), X ₃ represents a hydrogen atom or a substituent, and h
Represents 1 or 2, L ₄ represents a group containing a chemical bond which is cleaved in a developing solution, Y ₃ represents a substituent which exerts a development inhibiting action, and represents an aliphatic group, an aromatic group or a heterocyclic group. Represent.

After being cleaved from L _{3, the} development inhibitor diffuses in the photographic layer while exhibiting a development inhibiting action, and partially flows out to the color development processing solution. The development inhibitor that has flowed out into the processing solution reacts with hydroxyl ions or hydroxyamines generally contained in the processing solution to rapidly decompose (for example, hydrolyze an ester bond) in the chemical bond portion contained in L _4. That is, the group represented by Y ₃ is cleaved to become a highly water-soluble compound having a small development-inhibiting property, and the development-inhibiting action is substantially eliminated.

X ₃ is preferably a hydrogen atom, but may represent a substituent, and the substituent may be an aliphatic group (eg, methyl group,
Ethyl group), acylamino group (eg acetamide group,
Propionamide group), alkoxy group (eg methoxy group, ethoxy group), halogen atom (eg chloro atom,
Representative examples include a bromo atom), a nitro group, and a sulfonamide group (eg, a methanesulfonamide group).

The linking group represented by L ₄ includes a chemical bond that is cleaved in the developing solution. Examples of such chemical bonds include the examples given in the table below. Each of these is cleaved by a nucleophile such as hydroxy ion or hydroxylamine which is a component in the color developing solution.

In the case of a heterocyclic ring or a benzene condensed ring constituting a development inhibitor, the chemical bonding modes shown in the above table are directly linked to the benzene ring portion or via an alkylene group and / or a phenylene group, while Y ₃ Connect directly to.
When connecting via an alkylene group or a phenylene group, the intervening divalent group may contain an ether bond, an amide bond, a carbonyl group, a thioether bond, a sulfone group, a sulfonamide bond, and a urea bond.

When Y ₃ represents an aliphatic group, it is a saturated or unsaturated, linear or branched, linear or cyclic, substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Examples of hydrocarbon groups include, for example, methyl, ethyl, propyl, butyl, isopropyl, allyl, propargyl, cyclohexyl, hexyl, isobutyl or octyl.

When Y ₃ represents an aromatic group, it is substituted or unsubstituted phenyl or substituted or unsubstituted naphthyl.

When Y ₃ represents a heterocyclic group, it is a 4- to 8-membered heterocyclic group containing a sulfur atom, an oxygen atom or a nitrogen atom as a hetero atom.

Examples of the heterocycle include pyridyl, imidazolyl, furyl, tetrahydrofuryl, pyrazolyl, oxazolyl,
Examples thereof include thiazolyl, thiadiazolyl, phthalimide, triazolyl, diazolidinyl, and dianidyl.

When the aliphatic hydrocarbon group, the aromatic group, and the heterocyclic group have a substituent, the substituent is a halogen atom, a nitro group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, Alkanesulfonyl group having 1 to 10 carbon atoms, arylsulfonyl group having 6 to 10 carbon atoms, 1 to 1 carbon atoms
10, alkanamide group, anilino group, benzamide group,
Alkylcarbamoyl group having 1 to 10 carbon atoms, carbamoyl group, arylcarbamoyl group having 6 to 10 carbon atoms, 1 carbon atom
To 10 alkyl sulfonamide group, 6 to 10 carbon aryl sulfonamide group, 1 to 10 carbon alkylthio group, 6 to 10 carbon arylthio group, phthalimide group, succinimide group, imidazolyl group, 1,2, 4-triazolyl group, pyrazolyl group, benztriazolyl group, furyl group, benzthiazolyl group, alkylamino group having 1 to 10 carbon atoms, alkanoyl group having 1 to 10 carbon atoms, benzoyl group, alkanoyloxy having 1 to 10 carbon atoms Group, benzoyloxy group, perfluoroalkyl group having 1 to 5 carbon atoms, cyano group, tetrazolyl group, hydroxyl group, mercapto group, amino group, sulfamoyl group having 1 to 10 carbon atoms, arylsulfur group having 6 to 10 carbon atoms Moyl group, morpholino group,
C6-C10 aryl group, pyrrolidinyl group, ureido group, urethane group, C1-C10 alkoxycarbonyl group, C6-C10 aryloxycarbonyl group, imidazolidinyl group or C1-C10 alkylideneamino And the like.

Examples of the compound of the present invention are shown below, but the present invention is not limited thereto.

(Compound example) The couplers of this invention can be synthesized by commonly known methods or by analogous methods. For example, U.S. Patent Nos. 4,698,297, 4,248,962, and 4,40
9,323, 4,421,845, JP-A-63-37346, 61-156
It can be synthesized by the method described in No. 127 or No. 60-218645. For the development inhibitor, see US Pat.
It can be synthesized by the method described in 7,563 or JP-A-60-233650.

The half-life of the compound of the present invention is described in JP-A-57-151944.
No. 62-148951 and the like.

The compound of the present invention may be added to either the light-sensitive emulsion layer or the non-light-sensitive emulsion layer. The addition amount is preferably 1 × 10 ^-5 mol% to 1 × 10 ^-1 mol% of the total coated silver amount.

The compound of the present invention may be used alone in one layer, or may be used in combination with a known coupler. When used in combination with another color image-forming coupler, the molar ratio of the compound of the present invention to the other color image-forming coupler (the compound of the present invention (general formula (I)
And the other color image-forming couplers)
It is 0.1 / 99.9 to 90/10, preferably 1/99 to 50/50.

To add the DIR coupler of the present invention to a light-sensitive material, a conventionally known method for adding or dispersing the coupler to an emulsion and its addition method to a gelatin / silver halide emulsion or a hydrophilic colloid are applied. It For example, high boiling organic solvent
Dibutyl phthalate, tricresyl phosphate, wax, a method of mixing and dispersing a coupler with a higher fatty acid and its ester or the like, for example, U.S. Pat.No. 2,304,939,
The method described in No. 2,322,027. Also, a method in which a coupler having a low boiling point organic solvent or a water-soluble organic solvent is mixed and dispersed. A method of dispersing the coupler in combination with a high boiling point organic solvent. For example, US Patent Nos. 2,801,170 and 2,8
The method described in 01,171 and 2,949,360. The coupler itself has a sufficiently low melting point (for example, 75 ° C or less)
In the case of, the dispersion is carried out alone or in combination with other couplers to be used in combination, for example, colored couplers or uncolored couplers. For example German Patent No. 1,143,707
No. etc. description is applied.

As the dispersion aid, a commonly used anionic surfactant (for example, sodium alkylbenzene sulfonate, sodium dioctyl sulfosuccinate, sodium dodecyl sulfate, sodium alkylnaphthalene sulfonate, Fisher type coupler, etc.), zwitterionic A surfactant (for example, N-tetradecyl / N / N / dipolyethylene α-betaine) or a nonionic surfactant (for example, sorbitan, monolaurate, etc.) is used.

The amount of the coupler added to the light-sensitive material used in the present invention is 0.01 to 50 mol per mol of silver halide. It is preferably 0.1 to 5 mol.

The silver halide color light-sensitive material for photographing used in the present invention includes a color negative film and a color reversal film (which may or may not contain a dye-forming coupler). In particular, a color negative film for photographing is preferably used. The amount of silver coated on these light-sensitive materials is 1 to 15 g / m ² in terms of silver, but preferably 3 to 12 g / m ^2.
m ² .

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 of layers of the emulsion layer and the non-photosensitive layer and the layer order. 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 any of red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit light-sensitive layers is generally such that the red-sensitive layer, green The color-sensitive layer and the blue color-sensitive layer are provided 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 color-sensitive layers are sandwiched between the same color-sensitive layers.

A non-photosensitive layer such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer, JP 61-43748, 59-113438,
No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler as described in the specification, DIR compounds and the like, and contains a color mixing inhibitor as is commonly used. Good.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045.
No. 2 of high-speed emulsion layer and low-speed emulsion layer as described in No.
A layer structure can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition, JP-A-57-112751, JP-A-57-112751
As described in 200350, 62-206541, 62-206543, etc., 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-sensitive layer (RH) / Low-sensitivity red-sensitive layer (RL), or BH / BL / GL
It can be installed in the order of / GH / RH / RL or BH / BL / GH / GL / RL / RH.

Also, as described in Japanese Patent Publication No. 55-34932,
It is also possible to arrange in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. In addition, JP-A-56-25738 and 62
It is also possible to arrange in order of the blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support, as described in the specification of No. 63936.

Also, as described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the less sensitive silver halide emulsion layer, and the lower layer is more sensitive than the middle layer. A silver halide emulsion layer having a low degree is arranged,
There is an array composed of three layers having different sensitivities in which the sensitivities are sequentially decreased toward the support. Even in the case of being composed of three layers having different sensitivities as described above, JP-A-59-202
As described in Japanese Patent No. 464, the medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer may be arranged in this order from the side distant from the support in the same color-sensitive layer.

As described above, various layer configurations and arrangements can be selected according to the purpose of each sensitive material.

Preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 25 mol% silver iodide.

Silver halide grains in photographic emulsions are cubic, octahedral,
It may have a regular crystal such as a tetradecahedron, an irregular crystal form such as a sphere or a plate, a crystal defect such as a twin plane, or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less, or large 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), No. 17643 (1978).
December 23, p. 22-23, "I. Emulsion production (Emulsion prepara
and types) ”, and No. 18716 (November 1979)
Mon.), p.648, Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemie et Phisique P
hotographique Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photo
graphic Emulsion Chemistry (Focal Press, 1966)),
"Production and coating of photographic emulsions" by Zelikman et al., Published by Focal Press (VLZelikman et al. Making and Coating
Photographic Emulsion, Focal Press, 1964).

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gaft, Gutoff Photographic Science and Engineerin
g), Vol. 14, pp. 248-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,433,048, 4,439,520
It can be easily prepared by the method described in Japanese Patent No. 2,112,157 and the like.

The crystal structure may be uniform, may have different halogen compositions inside and 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.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such a process are described in Research Disclosure No. 17643 and No. 18716, and the corresponding portions are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Patent Nos. 4,411,987 and 4,435,503
It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde described in No.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG.

As the yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, JP-B-58-10739, UK Patent No. 1,425,020,
No. 1,476,760, U.S. Pat.No. 3,973,968, No. 4,314,
Nos. 023, 4,511,649 and EP 249,473A are preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
Nos. 619 and 4,351,897, European Patent No. 73,636, U.S. Patent Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552
Issue, Research Disclosure No. 24230 (June 1984
Mon), JP-A-60-43659, 61-72238, 60-35730
No. 55-118034, No. 60-185951, U.S. Pat.No. 4,500,
Nos. 630, 4,540,654 and 4,556,630 are particularly preferred.

Examples of cyan couplers include phenol-based and naphthol-based couplers, and U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200.
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2, No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, No. 249,453.
A, U.S. Pat.Nos. 3,446,622, 4,333,999, and
Nos. 4,451,559, 4,427,767, 4,690,889, 4,254,212, 4,296,199, and JP-A-61-42658 are preferred.

Colored couplers to correct unwanted absorption of colored dyes are VII of Research Disclosure No. 17643.
-G section, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413,
U.S. Patent Nos. 4,004,929, 4,138,258, British Patent No.
Those described in No. 1,146,368 are preferable.

As a coupler in which the coloring dye has an appropriate diffusibility,
Those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570 and West German Patent (Publication) No. 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 4,409,320, No. 4,576,910, British Patent No. 2,
No. 102,173, etc.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. The DIR coupler releasing the development inhibitor is the above-mentioned RD17643, VII-F.
Patents described in paragraphs, JP-A-57-151944 and 57-154234
And Nos. 60-184248 and U.S. Pat. No. 4,248,962 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,1.
Those described in 31,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472, and 4,338,393,
Multi-equivalent couplers described in JP-A No. 4,310,618 and the like, JP-A-60-
No. 185950, DIR redox compound releasing coupler or DIR coupler releasing coupler or DIR coupler releasing redox compound or DIR redox compound releasing redox described in JP-A-62-24252, etc., and discoloration after disengagement described in EP 173,302A. RDN releasing coupler
o.11449 and 24241, and bleaching accelerator releasing couplers described in JP-A-61-201247 and the like, and ligand releasing couplers described in US Pat. No. 4,553,477 and the like.

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 for the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bisyl 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 ester (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-diethyllaurylamide) , N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-t-)
Aminophenol etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate etc.), aniline derivative (N, N-dibutyl-2) -Butoxy-5-t-
Octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-hexane. 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 U.S. Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

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 are, for example, those mentioned above.
RD.No. 17643, page 28, and RD.No. 18716, page 647 From the right column
See page 648, left column.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD.No.
Development can be carried out by the usual methods described in 17643, pp. 28-29, and No. 18716, 651 left column to right column.

The color developer used for the development processing of the light-sensitive material of the present invention,
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent, but p-
A phenylenediamine compound is preferably used, and typical examples thereof include 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-N
Examples include -β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

Color developing solutions include alkali metal carbonates, pH buffers such as borates or phosphates, bromide salts, iodide salts,
It is common to include a development inhibitor such as benzimidazoles, benzothiazoles or mercapto compounds, or an antifoggant. If necessary, such as hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, and triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers,
Fogging agent such as sodium boron hydride, 1
An auxiliary developing agent such as -phenyl-3-pyrazolidone,
Various chelating agents represented by viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid. , Hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenesulfonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine -Di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

When the reversal process is performed, black and white development is usually performed before color development. This black and white developer contains dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solution and black-and-white developing solution is generally 9 to 12. The replenishment amount of these developers is
Although it depends on the color photographic light-sensitive material to be processed, it is generally 3 l or less per square meter of the light-sensitive material, and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions during development.

The color development processing time is usually set to 2 to 5 minutes, but the processing time can be further shortened by setting the temperature and the pH to high and using the 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 processing with two continuous bleach-fix baths,
Fixing before bleach-fixing or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. Examples of the bleaching agent include iron (III) and cobalt (II
Compounds of polyvalent metals such as I), chromium (IV) and copper (II), peracids, quinones, nitro compounds and the like are used.
Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methylimininodiacetic acid, 1,3- Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. . Of these, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salts and persulfates 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 containing these aminopolycarboxylic acid iron (III) complex salts is usually
5.5 to 8, but lower p for faster processing
H can also be processed.

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 Patents 1,290,812, 2,059,98.
8, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418
No. 53, No. 53-72623, No. 53-95630, No. 53-95631, No. 53
-104232, 53-124424, 53-141623, 53-2842
No. 6, Research Disclosure No. 17129 (1978
Compounds having a mercapto group or a disulfide group described in JP-A No. 50-140129; JP-B-45-8506; JP-A-52-20832;
No. 53-32735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German patent 1,127,715, iodide salts described in JP-A-58-16235; West German patents 966,410, 2,748,430.
Compounds described in Japanese Patent Publication No. 45-883
No. 6 polyamine compound; other JP-A-49-42434
Nos. 49-59644, 53-94927, 54-35727, 55
-26506 and 58-163940, compounds such as bromide ion can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Pat. No. 3,893,858 and West German Patent 1,290,812.
And the compounds described in JP-A-53-95630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 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 photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but ammonium thiosulfate is generally used.
In particular, ammonium thiosulfate can be used most widely. As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, and the temperature of rinsing water, the number of rinsing tanks (number of stages), replenishment method such as countercurrent and 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 and
Television Engineers Vol. 64, pp. 248-253 (5 May 1955)
It can be obtained by the method described in (Month 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, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in Japanese Patent Application No. 131632/1986 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. It is also possible to use bactericides described in "Sterilization, Sterilization and Antifungal Techniques of Microorganisms" edited by the Society of Sanitary Engineers, and "Encyclopedia of Antifungal and Antifungal Agents" edited by the Japan Society of Antifungals and Fungi.

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4 to
9, and preferably 5-8. The washing water temperature and washing time may be variously set depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range from seconds to 5 minutes is selected. 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 a stabilization treatment, any of the known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be used.

Further, after the water washing treatment, a stabilization treatment may be further performed. As an example, a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photography, can be mentioned. . Various chelating agents and antifungal agents can be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

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, 3,342,599, Schiff base-type compounds described in Research Disclosure 14850 and 15159, aldol compounds described in 13924, and metals described in U.S. Pat.No.3,719,492 Salt complex, JP 5
Examples thereof include urethane compounds described in 3-135628.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-containing compounds, if necessary, for the purpose of promoting color development.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.
No. etc. are described.

The various treatment liquids in the present invention are used at 10 ° C to 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. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

Further, the silver halide light-sensitive material of the present invention is described in US Pat.
500,626, JP-A-60-133449, 59-218443, 61-
It can also be applied to the photothermographic materials described in 238056 and European Patent 210,660A2.

Example A sample 101, which is a multilayer color light-sensitive material having the following compositions, was prepared on an undercoated cellulose triacetate film support.

The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer.

First layer (antihalation layer) Black colloidal silver 0.2 Gelatin 1.3 ExM-9 0.06 UV-1 0.03 UV-2 0.06 UV-3 0.06 Solv-1 0.15 Solv-2 0.15 Solv-3 0.05 Second layer (intermediate layer) Gelatin 1.0 UV-1 0.03 ExC-4 0.02 ExF-1 0.004 Solv-1 0.1 Solv-2 0.1 Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent spherical diameter 0.5)
μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter / thickness ratio
3.0) Coating silver amount 1.2 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, spherical equivalent diameter 0.3
μ, coefficient of variation of equivalent spherical diameter 15%, spherical particles, diameter / thickness ratio
1.0) Coating silver amount 0.6 Gelatin 1.0 ExS-1 4 × 10 ^-4 ExS-2 5 × 10 ^-5 ExC-1 0.05 ExC-2 0.50 ExC-3 0.03 ExC-4 0.12 ExC-5 0.01 ExC-8 0.03 4th Layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, internal high AgI type with 1: 1 core-shell ratio, sphere equivalent diameter 0.7μ, variation coefficient of sphere equivalent diameter 15%, tabular grains, diameter / Thickness ratio 5.0) Silver coating amount 0.7 Gelatin 1.0 ExS-1 3 × 10 ^-4 ExS-2 2.3 × 10 ^-5 ExC-6 0.11 ExC-7 0.05 ExC-4 0.05 Solv-1 0.05 Solv-3 0.05 Fifth layer (Intermediate layer) Gelatin 0.5 Cpd-1 0.1 Solv-1 0.05 Sixth layer (low-sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type with core-shell ratio 1: 1, equivalent spherical diameter 0.5) μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 4.0) Coating silver amount 0.35 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3)
μ, coefficient of variation of equivalent sphere diameter 25%, spherical particles, diameter / thickness ratio
1.0) Silver coating amount 0.20 Gelatin 1.0 ExS-3 5 × 10 ^-4 ExS-4 3 × 10 ^-4 ExS-5 1 × 10 ^-4 ExM-8 0.4 ExM-14 0.07 ExM-10 0.02 ExY-11 0.03 Solv- 1 0.3 Solv-4 0.05 7th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type with core-shell ratio 1: 3, spherical equivalent diameter 0.7 μ, variation coefficient of spherical equivalent diameter) 20%, plate-like particles, diameter / thickness ratio 5.0) Coating silver amount 0.8 Gelatin 0.5 ExS-3 5 × 10 ^-4 ExS-4 3 × 10 ^-4 ExS-5 1 × 10 ^-4 ExM-8 0.1 ExM-9 0.02 ExY-11 0.03 ExC-2 0.03 ExM-14 0.04 Solv-1 0.2 Solv-4 0.01 Eighth layer (intermediate layer) Gelatin 0.5 Cpd-1 0.05 Solv-1 0.02 Ninth layer (donor of multi-layer effect for red-sensitive layer) Layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type with core-shell ratio 2: 1, equivalent sphere diameter 1.0 μ, variation coefficient of equivalent sphere diameter 15%, tabular grains, diameter / thickness ratio 6.0) coated silver 0.35 silver iodobromide emulsion (AgI 2 mol%, core-shell ratio 1: 1 High AgI type, sphere-corresponding diameter 0.4 micron, a coefficient of variation of 20% of the sphere-equivalent diameter, the plate-like particles, diameter / thickness ratio 6.0) coating silver amount 0.20 Gelatin ^{0.5 ExS-3 8 × 10 -4} ExY-13 0.40 ExM-12 0.03 ExM-14 0.10 Solv-1 0.20 10th layer (yellow filter layer) Yellow colloidal silver 0.05 Gelatin 0.5 Cpd-2 0.13 Solv-1 0.13 Cpd-1 0.10 11th layer (low sensitivity blue sensitive emulsion layer) Silver iodobromide Emulsion (AgI 4.5 mol%, uniform AgI type, equivalent spherical diameter
0.7μ, variation coefficient of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 7.0) Coating silver amount 0.3 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3)
μ, coefficient of variation of sphere equivalent diameter 25%, plate-like particles, diameter / thickness ratio
7.0) Coating silver amount 0.15 Gelatin 1.6 ExS-6 2 × 10 ^-4 ExC-16 0.05 ExC-2 0.10 ExC-3 0.02 ExY-13 0.33 ExY-15 1.0 Solv-1 0.20 12th layer (high-sensitivity blue-sensitive emulsion layer) ) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent spherical diameter)
1.0μ, coefficient of variation of sphere equivalent diameter 25%, multiple twin plate-like particles,
Diameter / thickness ratio 2.0) Coating silver amount 0.5 Gelatin 0.5 ExS-6 1 × 10 ^-4 ExY-15 0.20 ExY-13 0.05 Solv-1 0.10 13th layer (1st protective layer) Gelatin 0.8 UV-4 0.1 UV-5 0.15 Solv-1 0.01 Solv-2 0.01 14th layer (2nd protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, equivalent spherical diameter)
0.07 μ) 0.5 Gelatin 0.45 Polymethylmethacrylate particles Diameter 1.5 μ 0.2 H-1 0.4 Cpd-5 0.5 Cpd-6 0.5 Cpd-8 0.2 In addition to the above-mentioned components, each layer contains emulsion stabilizer Cpd-3 (0.0
4 g / m ² ) Surfactant Cpd-4 (0.02 g / m ² ) was added as a coating aid.

Solv-1 Tricresyl Phosphate Solv-2 Dibutyl Phthalate Preparation of Samples 102 to 106 Instead of the DIR coupler EXY-13 added to the ninth, eleventh and twelfth layers in Sample 101, comparative couplers A to C and the compounds (1) and (3) of the present invention were replaced by equimolar amounts. It was made.

The obtained samples 101 to 106 were cut to a width of 35 m / m and then subjected to wet exposure with white light, and for evaluation of sharpness, exposure was performed through an MTF chart, using an automatic processor, and according to the following processing steps, 38 ° C. The development process was carried out.

Also, for a running process, expose a standard subject,
Each photographic material was processed until the cumulative replenishment amount of the developing solution was double the tank volume of the mother liquor. Immediately after the running was completed, each sample 101 which had been subjected to the wet exposure was processed.

Next, the composition of the treatment liquid will be described.

(Bleach-fixing solution) Common for mother liquor and replenisher (unit: g) Ethylenediaminetetraacetic acid Ferric acid 50.0 Ammonium dihydrate Ethylenediaminetetraacetic acid 5.0 Disodium salt Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution 240.0 ml (70%) Ammonia water (27%) 6.0 L Water was added to 1.0 L pH 7.2 (Washing liquid) Mother liquor and replenishing liquid Common tap water was used for H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (same as above). Amberlite IR-400) is passed through a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / L or less, followed by sodium diisocyanurate dichloride 20 mg / L and sodium sulfate 0.15 g / L. Was added.

The pH of this solution was in the range of 6.5-7.5.

(Stabilizer) Mother liquor and replenisher common (unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-0.3 Monononylphenyl ether (Average degree of polymerization 10) Ethylenediaminetetraacetic acid 0.05 Disodium salt Water added 1.0 L pH 5.0-8.0 Next, the replenishing amount of the developing solution was set to 700 ml / m ² , the composition of the replenishing solution was concentrated, and a running test was conducted in the same manner.

After completion of each running test, the composition of the developing solution was analyzed, and the developing solution was prepared based on the analyzed value.

Next, the sensitivity of the developing solution prepared from the analytical values was evaluated by passing the sample 101 which was subjected to the wet exposure with white light.

 The results obtained are shown in Table 1.

With compounds outside the invention, in particular comparative coupler B,
When C is used, a high MTF is given, but a developing solution with a reduced replenishment amount causes a marked decrease in sensitivity due to the running process. It can be seen that in the decomposed development inhibitor releasing coupler of the present invention, there is no problem even if the replenishment amount is reduced.

Claims (1)

(57) [Claims] 1. A support having at least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer, which is represented by the following general formula (I): A development inhibitor releasing coupler capable of finally releasing a development inhibitor by reacting with an oxidation product of a developing agent at the time of development, wherein the development inhibitor flows into a developing solution after development. A silver halide color photographic light-sensitive material containing a coupler having a group having the property of changing to a compound that does not substantially affect photographic properties, and further containing a coupler having a half-life of 2 hours or less at pH 10 of the development inhibitor. In the method of continuously processing while replenishing the developing solution, the replenishing amount of the developing solution is 700 ml or less per 1 m ^{2 of the} light-sensitive material to be processed for development. Method. In the general formula _{(I) A-L 1 -L} 2 -DI formula, A represents a group which reacts with an oxidation product of an aromatic primary amine developing agent cleaves the L ₁ -L ₂ -DI, L ₁ represents a group bonding the cleavage of the L ₂ without reacting with an oxidation product of an aromatic primary amine developing agent after cleavage bond with a,
L ₂ represents a group in which the bond with DI is cleaved after the bond with L ₁ is cleaved, without reacting with the oxidation product of the aromatic primary amine developer, and DI is a development inhibitor when it flows into a developing solution. Represents a development inhibitor that loses its action.