JP2597140B2 - Silver halide color photographic materials - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a multi-layer silver halide color photographic light-sensitive material, and more particularly, to a compound containing an improved development inhibitor releasing compound and having improved sharpness. A multi-layer silver halide color photographic light-sensitive material.

<< 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.

Hitherto, various methods for increasing the sharpness of an image have been known. It is widely known that a great effect can be obtained by increasing the edge effect and reducing light scattering in a photographic material. . Among them, the edge effect utilizes a concentration gradient of a development inhibitor present at the time of 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 does the product cost increase, but also the MTF curve in a high spatial frequency region decreases because light scattering by silver halide increases. In addition to the DIR coupler-added layer, the sharpness of the lower layer as well as the lower layer is deteriorated.
ory of Photographic Process ", 3rd Edition, Macmillan, Inc.).

Japanese Patent Application No. 58-7150 has developed a DIR compound that can improve the above-mentioned conventional disadvantages and enhance the Ez effect especially while maintaining the maximum density of the image. Although the present invention provides a photosensitive material capable of increasing the sharpness in the region, the present invention contains a development inhibitor releasing compound that can react with an oxidation product of a developing agent during development to release a development inhibitor. 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.

Japanese Patent Application Laid-Open No. 62-166334 also provides an improved DIR compound, and aims to improve sharpness and color reproducibility by controlling the dry film thickness of the emulsion layer. No. 63-37346 provides further improved DIR compounds,
Various proposals have been made for solving problems. However, these conventional techniques are not satisfactory, and further improvement is strongly desired.

The present inventors have conducted intensive studies from the above-mentioned viewpoints, and as a result of including the improved development inhibitor-releasing compound of the present invention, and further reducing the swelling film thickness during development of the photosensitive material to a certain thickness or less, The present inventors have found that the MTF value of a region can be improved, thereby improving the clarity of the outline of an image, and arrived at the present invention. This fact is unexpected from the conventional knowledge that when the film thickness of the photosensitive material is reduced, the MTF value in the high-frequency region increases due to a decrease in optical scattering. In addition, the layering effect was increased, and the possibility of obtaining a photosensitive material having excellent color reproducibility became wider.

Therefore, a first object of the present invention is to provide a multi-layer silver halide color photograph which is extremely excellent in image sharpness without deteriorating the image quality of a print even when the enlargement magnification is increased. Provided is a photosensitive material.

A second object of the present invention is to provide a multilayer silver halide color photographic light-sensitive material in which the MTF value in the high frequency region is raised, and the MTF value in the low frequency region is raised, and the clarity of the outline of the image is particularly improved. It is in.

A third object of the present invention is to provide a multilayer silver halide color photographic light-sensitive material which enhances the so-called multilayer effect and has excellent color reproducibility.

<< Means for Solving the Problem >> The present invention reacts with an oxidation product of a developing agent during development,
A multilayer silver halide color photographic light-sensitive material containing a development inhibitor releasing compound capable of releasing a development inhibitor, and
A multilayer silver halide color photographic light-sensitive material characterized in that the total film thickness during development does not exceed 40 μm.

Here, the total film thickness at the time of development means a swelled film thickness in a developing solution, and the measurement is performed by A. Green and GI PLevennson.
nson), Journal of Photographic Science (J. Phot. Sci.), 20 , 205 (1972). That is, the swollen film thickness in the developer in the present invention means a value obtained by subtracting the dry film thickness from the equilibrium value of the total swollen film thickness in the developer kept at 38.0 ° C.

 The developing solutions are shown in Examples.

The compound for releasing a development inhibitor referred to in the present invention is a compound that reacts with an oxidized form of a color developing agent to release a development inhibitor or a precursor thereof and / or a compound that is cleaved after reacting with an oxidized form of the color developing agent to further form color development. It is a compound that cleaves the development inhibitor by reacting with the main drug.

Such a compound is represented by the following general formula (I).

General formula (I) AL ₁ -L ₂ -DI The reaction process in which the compound represented by formula (I) releases DI during development is represented by the following reaction formula.

 Where A, L₁, L_Two, DI are described in the general formula (I)
Has the same meaning as Means oxidized developer
I do.

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 residues (for example, coupler residues such as 5-pyrazolone type, pyrazolotriazole type or pyrazoloimidazole type), cyan coupler residues (for example, phenol type, naphthol type or European patent publication No. 249,
No. 453) and non-colored coupler residues (for example, coupler residues such as indanone type and acetophenone type). 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 a redox group, the redox group is a group that can be cross-oxidized by an oxidized developing agent, and examples thereof include hydroquinones, catechols, pyrogallols,
Examples thereof include 4-naphthohydroquinones, 1,2-naphthohydroquinones, sulfonamidophenols, hydrazides and sulfonamidonaphthols. These groups are specifically described, for example, in JP-A-61-230135 and JP-A-62-251746.
Nos. 61-278,852; U.S. Pat.Nos. 3,364,022; 3,37
9,529, 3,639,417, 4,684,604 or J.Org.C
hem., 29 , 588 (1964).

Linking group represented by L ₁ and L ₂ in the general formula (I), for example, U.S. Patent No. 4,146,396, Use group cleavage reactions hemiacetal with a described in the 4,652,516 Patent, or Nos 4,698,297, U.S. Patent 4,248,962 The timing group which causes a cleavage reaction using an intramolecular nucleophilic reaction described in No. 4, a timing group which causes a cleavage reaction using an electron transfer reaction described in U.S. Pat.No. 4,409,323 or 4,421,845, U.S. Pat.No. 4,546,073 describes a group that initiates a cleavage reaction by utilizing an imino ketal hydrolysis reaction or a group that initiates a cleavage reaction by utilizing an ester hydrolysis described in German Patent Publication No. 2,626,317. Is mentioned. L ₁ and L ₂ are each bonded to A or AL ₁ -L ₂ or the like at a hetero atom, preferably an oxygen atom, a sulfur atom or a nitrogen atom contained therein.

The group represented by DI in the general formula (I) is, for example, a tetrazolylthio group, a thiadiazolylthio group, an oxadiazolylthio group, a triazolylthio group, a benzimidazolylthio group, a benzthiazolylthio group, a tetrazolylseleno group, A benzoxazolylthio group, a benzotriazolyl group, a triazolyl group or a benzoindazolyl group. These groups are, for example, U.S. Pat.No. 3,227,554,
3,384,657, 3,615,506, 3,617,291, 3,7
33,201, 3,933,500, 3,958,993, 3,961,95
9, 4,149,886, 4,259,437, 4,095,984,
No. 4,477,563 or British Patent No. 1,450,479.

Next, preferred ranges of the compound represented by the formula (I) will be described.

In the formula, the linking groups represented by L ₁ and L ₂ include a methyleneoxy group, a 4-methylene-3-pyrazolyloxy group,
Preferred examples are a 2 (or 4) -methylene phenoxy group or a 2-carbonylaminomethyl phenoxy group.
In these oxygen atoms, L ₁ or L ₂ of the general formula (I)
To the left hand. Further, these divalent groups may have a substituent at a substitutable position (for example, in a methylene group or a benzene ring), and a typical substituent is an alkyl group (for example, methyl, ethyl, isopropyl, Dodecyl), acyl groups (eg, benzoyl, acetyl), alkoxy groups (eg, methoxy, ethoxy),
Alkoxycarbonyl group (for example, methoxycarbonyl,
Butoxycarbonyl), a carbamoyl group (for example, ethylcarbamoyl), a nitro group, a carboxyl group, a sulfonyl group (for example, methanesulfonyl), an aryl group (for example, 4-nitrophenyl, 4-carboxyphenyl), a halogen atom (for example, a chlorine atom or a fluorine atom) ) Or a sulfamoyl group (eg, butylsulfamoyl).

The compound represented by the general formula (I) is preferably a diffusion-resistant type, and particularly preferably, the diffusion-resistant group is A, L ₁ or L ₂
Is included.

A particularly preferred compound in formula (I) is when A represents a coupler residue.

For examples of the compound represented by the general formula (I) and a synthesis method, a known patent or literature cited for the description of A, L ₁ , L ₂ and DI in the general formula (I) is disclosed in JP-A-63-37346. And No. 61-156127.

Specific compounds are shown below, but are not limited to these compounds.

(4) to (6), (10), (13) to (20) show reference examples.

(Compound example) The addition amount of the development inhibitor releasing compound used in the present invention is 0.00001 to 0.5 mol, preferably 0.1 mol per mol of silver.
001-0.05 mole.

Since the thickness of the light-sensitive material considered in the present invention is related to the degree of diffusion of the development inhibitor, the developer used (usually pH
9 to 14, preferably 10 to 12), the maximum swollen film thickness swollen during development must be considered.

As described above, conventionally, only the fact that when the film thickness of the photosensitive material is reduced, the MTF in a high frequency region increases due to a decrease in optical scattering has been noticed. The currently known maximum swelling film thickness of a photosensitive material containing a DIR coupler in a developer is about 42 to 43 μm. However,
When the development inhibitor releasing compound of the present invention is used, the MTF in the low frequency region can be increased by reducing the maximum swelling film thickness in the developer.
In the case of the light-sensitive material used in the present invention, the film thickness of the light-sensitive material is reduced by 2 to 4 μm from the conventionally known maximum swelling film thickness of 40 μm in a developing solution, so that the MTF in a low frequency region is reduced.
The value can be increased by about 5.

Therefore, in the present invention, the maximum swelling film thickness of the photosensitive material in the developer is preferably about 35 μm or less, and about 30 μm or less.
It is more preferable that the thickness be equal to or less than μm. The maximum swelling film thickness of such a photosensitive material can be specified as the maximum swelling film thickness in a developer used for the development processing.

The light-sensitive material of the present invention only needs to have at least one layer of a silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support. There is no particular limitation on the number and order of the emulsion layers and the non-light-sensitive layers. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. Wherein the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to any of red light and a multilayer silver halide color photographic light-sensitive material. In general, the arrangement of the unit light-sensitive layers is, in order from the support side, a red light-sensitive layer, 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.

Non-photosensitive layers 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-A-61-43748, JP-A-59-113438,
No. 59-113440, No. 61-20037, couplers as described in the specification of No. 61-20038, and may contain a DIR compound, etc., and contain a color mixing inhibitor as usually used. Is also 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 the high-speed emulsion layer and the low-speed emulsion layer
A layer configuration can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. In addition, JP-A-57-112751, JP-A-57-112751
200350, 62-206541, 62-206543 and the like, a low-speed emulsion layer may be provided on the side farther from the support, and a high-speed emulsion layer may be provided on the side closer to the support. .

As specific examples, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL) or BH / BL /
They can be installed in the order of GL / GH / RH / RL or BH / BL / GH / GL / RL / RH.

Also, as described in Japanese Patent Publication No. 55-34932,
From the farthest side from the support, blue light-sensitive layers / GH / RH / GL / RL can be arranged in this order. JP-A-56-25738, 62
As described in -63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

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 when such a three-layer structure having different sensitivities is used, Japanese Patent Application Laid-Open No.
As described in the specification of JP-A No. 464, a medium-speed emulsion layer / a high-speed emulsion layer / a low-speed emulsion layer may be arranged in the same color-sensitive layer from the side away from the support.

As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive 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 be one having regular crystals such as tetradecahedron, one having irregular crystal forms such as spherical or plate-like, one having crystal defects such as twin planes, or a complex form thereof.

The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion usable in the present invention is described, for example, in Research Disclosure (RD), No. 17643 (1978).
December 23, p. 22-23, "I. Emulsion production (Emulsion prepara
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), Photographic Emulsion Chemistry by Duffin, Focal Press (GFDuffin, Photo)
graphic Emulsion Chemistry (Focal Press, 1966)),
"Manufacture and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VLZelikman et al. Making and Coating)
Photographic Emulsion, Focal Press, 1964).

Monodisperse emulsions described in U.S. 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 provided by Gaft, Gutoff Photographic Science and Engineerin
g), 14, 248-257 (1970); U.S. Pat.
4,226, 4,414,310, 4,433,048, 4,439,520
And British Patent No. 2,112,157.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, may have a layered structure, and even if silver halides having different compositions are joined by epitaxial junction. Also, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide.

 Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are described in the aforementioned Research Disclosure Nos. 17643 and 18716, and the relevant 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 4,435,5
It is preferable to add a compound which can react with formaldehyde described in No. 03 and can be fixed to the photosensitive material.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in Research Disclosure (RD) No. 17643, VII-C to G mentioned above.

As a 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
No., Research Disclosure No.24230 (June 1984)
Mon), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730
No. 55-118034, No. 60-185951, U.S. Pat.
Nos. 630, 4,540,654 and 4,556,630 are particularly preferred.

Cyan couplers include phenolic and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200,
No. 2,369,929, No. 2,801,171, No. 2,772,162
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,
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 for correcting unwanted absorption of coloring dyes are described in Research Disclosure No. 17643, VII-
Section G, U.S. Patent No. 4,163,670, JP-B-57-39413, U.S. Patent Nos. 4,004,929, 4,138,258, UK Patent No. 1,14
Those described in 6,368 are preferred.

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are 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 (Published) No. 3,234,533.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 4,409,320, No. 4,576,910, UK 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. DIR couplers that release development inhibitors are described in the aforementioned RD17643, Patents described in VII-F, JP-A-57-151944 and JP-A-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 UK Patent Nos. 2,097,140 and 2,1
Preferred are those described in JP-A-31-188, JP-A-59-157638 and JP-A-59-170840.

In addition, as couplers that can be used in the light-sensitive material of the present invention, competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472 and 4,338,393,
No. 4,310,618, multi-equivalent couplers described in
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 a 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 high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (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-ethylhexylphenylphosphonate, etc.), benzoates (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N, N-diethyllaurylamide) , N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-t-
Aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2) -Butoxy-5-t-
Octylaniline, etc.) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). 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 include, for example, those described above.
From page 28 of RD.No.17643, and from the right column of page 647 of No.18716
It is described in the left column on page 648.

The color photographic light-sensitive material according to the present invention is described in RD.
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 in the development of the photosensitive material of the present invention is
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.
Phenylenediamine 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-N
-Β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. These compounds can be used in combination of two or more depending on the purpose.

Color developing solutions are pH buffers such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
It generally contains a development inhibitor or an antifoggant such as a benzimidazole, a benzothiazole or a mercapto compound. 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,
Viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, 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 salts thereof can be mentioned as representative examples.

When the reversal process is performed, color development is usually performed after black and white development. The black-and-white developer includes 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 color developing solution and the black-and-white developing solution generally have a pH of 9 to 12. The replenishment amounts of these developers are
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 means for suppressing the accumulation of bromide ions in the developer.

The time for the color development processing is usually set to 2 to 5 minutes, but the processing time can be further shortened by using a high temperature, a high pH and using a high concentration of the color developing agent.

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. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive 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.
Representative bleaches include ferricyanide; dichromate; organic complexes of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3- Aminopolycarboxylic acids such as diaminopropanetetraacetic acid and glycol ether diaminetetraacetic 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, iron (III) complex salts of aminopolycarboxylic acid, such as iron (III) complex salt of ethylenediaminetetraacetate, and persulfate are preferred from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually
5.5 to 8, but lower p for faster processing
H can also be processed.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and 2,059,98.
No. 8, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418
Nos. 53-72623, 53-95630, 53-95631, 53
-104232, 53-124424, 53-141623, 53-2842
No. 6, Research Disclosure No. 17129 (1978
A compound having a mercapto group or a disulfide group described in, for example, July, 1983; a thiazolidine derivative described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832,
Nos. 53-32735, U.S. Pat. No. 3,706,561; thiourea derivatives; West German Patent No. 1,127,715; iodide salts described in JP-A-58-16235; West German Patents 966,410, 2,748,430
No. 45-883
No. 6 polyamine compound; other JP-A-49-42434
Nos. 49-59644, 53-94927, 54-35727, 55-2
Compounds described in Nos. 6506 and 58-163940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858 and West German Patent No. 1,290,812
And compounds described in JP-A-53-95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. 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, a large amount of iodide salts, and the use of thiosulfates is common.
In particular, ammonium thiosulfate can be used most widely. As a preservative of the bleach-fixing solution, a sulfite, a bisulfite or a 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 step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Of these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture and
It can be determined by the method described in Television Engineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. 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. Sanitizing agents described in "Sterilization, disinfection and fungicide technology of microorganisms" edited by the Sanitary Technology Society, and "Encyclopedia of antibacterial and antifungal agents" edited by the Japan Society of Antifungals and Fungi can also be used.

In the processing of the light-sensitive material of the present invention, the pH of the washing water is from 4 to
9, preferably 5 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, application, etc., but are generally 20 seconds to 10 minutes at 15 to 45 ° C, and preferably 30
A range from seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. 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 fungicides can be added to the stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a 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 speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. 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 may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.
No. etc. are described.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to. Further, in order to save silver of the light-sensitive material, a process 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.

The silver halide light-sensitive material of the present invention is disclosed in U.S. Pat.
No. 500,626, JP-A-60-133449, 59-218443, 61-
No. 2,38056, European Patent No. 210,660A2 and the like.

<< Effects of the Invention >> The present invention merely reduces the film thickness of the photosensitive material when swollen, and further improves the conventional MTF in the low frequency region improved by using the development inhibitor releasing compound of the present invention. Further improvements can be made, so that the outline of the image can be made very clear.

Thus, there is no doubt that the present invention, which can improve the psychological sharpness of an image by a simple method, is extremely useful in the photographic industry.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 On a cellulose triacetate film support having an undercoat, Sample 01, which is a multilayer color photosensitive material composed of layers having the following compositions, was prepared.

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 dyes are shown in terms of moles per mole of silver halide in the same layer.

First layer (anti-halation layer) Black colloidal silver ・ ・ ・ 0.2 Gelatin ・ ・ ・ 1.3 ExM-8 ・ ・ ・ 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) Silver coating amount 1.2 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3
μ, coefficient of variation of equivalent sphere diameter 15%, spherical particles, diameter / thickness ratio
1.0) Silver coating ・ ・ ・ 0.6 Gelatin ・ ・ ・ 1.6 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 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6mol%, internal shell A with core shell ratio 1: 1)
gI type, sphere-corresponding diameter 0.7 .mu.m, coefficient of variation of 15% of the sphere-equivalent diameter, the plate-like particles, diameter / thickness ratio 5.0) coating silver amount ... 0.7 Gelatin ··· 1.6 ExS-1 ··· 3 × 10 - ⁴ ExS-2 ・ ・ ・ 2.3 × 10 ^-5 ExC-5 ・ ・ ・ 0.11 ExC-6 ・ ・ ・ 0.05 ExC-4 ・ ・ ・ 0.05 Solv-1 ・ ・ ・ 0.05 Solv-3 ・ ・ ・ 0.05 5th layer (Intermediate layer) Gelatin: 0.5 Cpd-1: 0.1 Solv-1: 0.05 Sixth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core shell ratio: 1: 1) Surface height A
gI type, sphere equivalent diameter 0.5μ, coefficient of variation of sphere equivalent diameter 15%, plate-like grain, diameter / thickness ratio 4.0) Silver coating amount: 0.35 silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, sphere) Equivalent diameter 0.3
μ, coefficient of variation of equivalent sphere diameter 25%, spherical particles, diameter / thickness ratio
1.0) Silver coating ・ ・ ・ 0.20 Gelatin ・ ・ ・ 1.6 ExS-3 ・ ・ ・ 5 × 10 ^-4 ExS-4 ・ ・ ・ 3 × 10 ^-4 ExS-5 ・ ・ ・ 1 × 10 ^-4 ExM-7・ ・ ・ 0.4 ExM-8 ・ ・ ・ 0.07 ExM-9 ・ ・ ・ 0.02 ExY-10 ・ ・ ・ 0.03 Solv-1 ・ ・ ・ 0.3 Solv-4 ・ ・ ・ 0.05 7th layer (high sensitivity green sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core shell ratio 1: 3, internal high A
gI type, sphere-corresponding diameter 0.7 .mu.m, variation coefficient of 20% of the equivalent spherical diameter, the plate-like particles, diameter / thickness ratio 5.0) coating silver amount ... 0.8 Gelatin ··· 0.8 ExS-3 ··· 5 × 10 - ⁴ ExS-4 ・ ・ ・ 3 × 10 ^-4 ExS-5 ・ ・ ・ 1 × 10 ^-4 ExM-8 ・ ・ ・ 0.1 ExM-9 ・ ・ ・ 0.02 ExY-10 ・ ・ ・ 0.03 ExC-2 ・ ・ ・0.03 ExM-13 ・ ・ ・ 0.01 Solv-1 ・ ・ ・ 0.2 Solv-4 ・ ・ ・ 0.01 8th layer (intermediate layer) Gelatin ・ ・ ・ 0.5 Cpd-1 ・ ・ ・ 0.05 Solv-1 ・ ・ ・ 0.02 9th Layer (donor layer of multilayer effect on red-sensitive layer) Silver iodobromide emulsion (AgI 2 mol%, internal shell A with core shell ratio 2: 1)
gI type, equivalent diameter of sphere 1.0μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter / thickness ratio 6.0) Silver coating amount ・ ・ ・ 0.35 Silver iodobromide emulsion (AgI 2mol%, core shell ratio 1: 1) Inside height A
gI 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 ··· 0.8 ExS-3 ··· 8 × 10 - ⁴ ExY-12 ・ ・ ・ 0.11 ExM-11 ・ ・ ・ 0.03 ExM-13 ・ ・ ・ 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 sphere diameter) 0.7
μ, coefficient of variation of equivalent sphere diameter 15%, plate-like particles, diameter / thickness ratio
7.0) Silver coating 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) Silver coating ・ ・ ・ 0.15 Gelatin ・ ・ ・ 2.0 ExS-6 ・ ・ ・ 2 × 10 ^-4 ExC-2 ・ ・ ・ 0.10 ExY-14 ・ ・ ・ 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 sphere diameter 1.
0μ, coefficient of variation of sphere equivalent diameter 25%, multiple twin plate-like grains, diameter / thickness ratio 2.0) Coating silver amount: 0.5 gelatin: 0.8 ExS-6: 1 × 10 ^-4 ExY-14・ ・ ・ 0.20 Solv-1 ・ ・ ・ 0.10 13th layer (first 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 (2 mol% AgI, uniform AgI type, equivalent sphere diameter 0.07μ) ・ ・ ・ 0.5
Gelatin ・ ・ ・ 0.45 Polymethyl methacrylate particles 1.5μ diameter ・ ・ ・ 0.2 H-1 ・ ・ ・ 0.4 Cpd-5 ・ ・ ・ 0.5 Cpd-6 ・ ・ ・ 0.5 In each layer, in addition to the above components, stabilization of emulsion Agent Cpd-3 (0.0
4 g / m ² ) Surfactant Cpd-4 (0.02 g / m ² ) was added as a coating aid. The total thickness of the thus-prepared silver halide multilayer color light-sensitive material excluding the support was 18.0 μm.

Solv-1 Tricresyl phosphate Solv-2 Dibutyl phthalate The total thickness of the thus prepared silver halide multilayer color light-sensitive material excluding the support was 18.0 μm.

Next, as shown in Table 1, the development inhibitor releasing coupler used in Sample 01 was replaced with another comparative coupler and the coupler of the present invention in an equimolar amount to prepare samples. These samples are referred to as samples 02 to 06.

On the other hand, by reducing the amount of gelatin by keeping the total emulsion film thickness at a fixed gelatin / hardener ratio,
Samples were made in the same manner using the same couplers from 01 to 06. These are referred to as samples 07 to 12 and samples 13 to 18 (see Table 1).

The obtained samples 01 to 18 were exposed to white light through a pattern for MTF measurement, and the following processing steps were performed.

Coupler described in JP-A-62-166334 Coupler described in JP-A-63-37346 Example 29 Example 32 Table 2 Processing method Process Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C Bleaching 6 minutes 30 seconds 38 ° C Rinse 2 minutes 10 seconds 24 ° C Settled 4 minutes 20 seconds 38 ° C Rinse (1) 1 minute 05 seconds 24 ° C water washing (2) 1 minute 00 seconds 24 ° C Stabilized 1 minute 05 seconds 38 ° C Drying 4 minutes 20 seconds 55 ° C Next, the composition of the processing solution is described.

(Color developing solution) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-hydroxyethylidene 3.0-1,1-diphosphonic acid Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- (N- Ethyl-N-β-hi 4.5 Droxyethylamino) -2-methylaniline sulfate Add water 1.0l pH 10.05 (Bleaching solution) (Unit: g) Ferric ethylenediaminetetraacetate 100.0 Sodium trihydrate Ethylenediaminetetraacetic acid 2 10.0 Sodium salt Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5m Add water 1.0l pH 6.0 (fixing solution) (Unit: g) Ethylenediaminetetraacetic acid 0.5 Disodium salt Sodium sulfite 7.0 Sodium bisulfite 5.0 Ammonium thiosulfate Aqueous solution 170.0ml (70%) Add water and add 1.0l pH 6.7 (stabilizer) G) Formalin (37%) 2.0 ml Polyoxyethylene-p-0.3 monononylphenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid 0.05 disodium salt Water is added 1.0 l pH 5.0-8.0 For the sample, the MTF value was determined at the spatial frequency of 5 cycles / mm and 20 cycles / mm for the cyan image.
The MTF values are shown in Table 3.

On the other hand, the results of measuring the maximum swelling film thickness in the developer are also shown in Table 3.

From the results shown in Table 3, it can be seen that, in general, when the emulsion film thickness is reduced, the effect of light scattering by the emulsion grains is reduced and the sharpness is improved. However, this effect appears only for about 20 cycles.
It is known that the high frequency region is not less than 5 to 10 cycles / mm, in which the so-called Etsu effect is remarkably exhibited. Nevertheless, as shown in Table 3,
The fact that there is a difference in MTF values is surprising. This is due to the difference in the type of the development inhibitor releasing coupler added, and can be interpreted as follows.

When the swollen film thickness in the developer is small, it is considered that the difference in the diffusibility of the development inhibitor appears more remarkably,
The effect of the compound of the present invention is thought to be due to the fact that the development inhibitor released from the DIR coupler has a large diffusibility and the swelling thickness of the emulsion layer in the developing solution is small. Can be

Samples 01 to 06 having a swelled film thickness of more than 40 μm have a development inhibiting effect, but the degree of the effect is not so large, but samples 10 using the DIR coupler of the present invention and having a swelled film thickness of 40 μm or less are used. It was evident that the development inhibitory effect was improved in Nos. ~ 12 and markedly improved in Samples 16-18 having a small swollen film thickness.

In addition, Japanese Patent Application Laid-Open Nos. 62-166334 and 63-37346
It was found that the comparative coupler No. had a slightly lower development inhibitory effect than the coupler of the present invention. This is thought to be due to the difference in the structure of the coupler of the present invention and the comparative coupler, that is, the effect differs due to the difference in the release speed at the time of color development and the diffusivity after release, but from the realization of the actual effect. It has been found that the compounds of the present invention are superior.

Example 2 On a subbed cellulose triacetate film support prepared by the production method described in JP-A-62-115035,
Sample 21 which was a multilayer color photographic material composed of each layer having the following composition was prepared.

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 dyes are shown in terms of moles per mole of silver halide in the same layer.

1st layer (anti-halation 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) Silver coating amount 1.2 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3
μ, coefficient of variation of equivalent sphere diameter 15%, spherical particles, diameter / thickness ratio
1.0) Silver coating ・ ・ ・ 0.6 Gelatin ・ ・ ・ 1.6 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 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, internal height of core shell ratio 1: 1) A
gI type, sphere-corresponding diameter 0.7 .mu.m, coefficient of variation of 15% of the sphere-equivalent diameter, the plate-like particles, diameter / thickness ratio 5.0) coating silver amount ... 0.7 Gelatin ··· 1.6 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 5th layer (Intermediate layer) Gelatin: 0.5 Cpd-1: 0.1 Solv-1: 0.05 Sixth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core shell ratio: 1: 1) Surface height A
gI type, sphere equivalent diameter 0.5μ, coefficient of variation of sphere equivalent diameter 15%, plate-like grain, diameter / thickness ratio 4.0) Silver coating amount: 0.35 silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, sphere) Equivalent diameter 0.3
μ, coefficient of variation of equivalent sphere diameter 25%, spherical particles, diameter / thickness ratio
1.0) Silver coating ・ ・ ・ 0.20 Gelatin ・ ・ ・ 1.6 ExS-3 ・ ・ ・ 5 × 10 ^-4 ExS-4 ・ ・ ・ 3 × 10 ^-4 ExS-5 ・ ・ ・ 1 × 10 ^-4 ExM-8・ ・ ・ 0.4 ExM-9 ・ ・ ・ 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%, core shell ratio 1: 3, internal high A
gI type, sphere-corresponding diameter 0.7 .mu.m, variation coefficient of 20% of the equivalent spherical diameter, the plate-like particles, diameter / thickness ratio 5.0) coating silver amount ... 0.8 Gelatin ··· 0.8 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 ・ ・ ・ 0.01 Solv-1 ・ ・ ・ 0.2 Solv-4 ・ ・ ・ 0.01 8th layer (intermediate layer) Gelatin ・ ・ ・ 0.5 Cpd-1 ・ ・ ・ 0.05 Solv-1 ・ ・ ・ 0.02 9th Layer (donor layer of multilayer effect on red-sensitive layer) Silver iodobromide emulsion (AgI 2 mol%, internal shell A with core shell ratio 2: 1)
gI type, 1.0μ after sphere equivalent, coefficient of variation of sphere equivalent diameter 15%, plate-like grain, diameter / thickness ratio 6.0) Silver coating amount ・ ・ ・ 0.35 Silver iodobromide emulsion (AgI 2mol%, core shell ratio 1: 1) Inside height A
gI 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 ··· 0.8 ExS-3 ··· 8 × 10 - ⁴ ExY-13 ・ ・ ・ 0.11 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 sphere diameter) 0.7
μ, coefficient of variation of equivalent sphere diameter 15%, plate-like particles, diameter / thickness ratio
7.0) Silver coating 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) Silver coating ・ ・ ・ 0.15 Gelatin ・ ・ ・ 2.0 ExS-6 ・ ・ ・ 2 × 10 ^-4 ExC-16 ・ ・ ・ 0.05 ExC-2 ・ ・ ・ 0.10 ExC-3 ・ ・ ・ 0.02 ExY-13 ・..0.07 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 sphere diameter 1.
0μ, coefficient of variation of sphere equivalent diameter 25%, multiple twin plate-like grains, diameter / thickness ratio 2.0) Silver coating ・ ・ ・ 0.5 gelatin ・ ・ ・ 0.8 ExS-6 ・ ・ ・ 1 × 10 ^-4 ExY-15・ ・ ・ 0.20 ExY-13 ・ ・ ・ 0.01 Solv-1 0.10 13th layer (first 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 (AgI2mol%, uniform AgI type, equivalent sphere diameter 0.07μ) ・ ・ ・ 0.5
Gelatin ・ ・ ・ 0.45 Polymethyl methacrylate particles 1.5μ diameter ・ ・ ・ 0.2 H-1 ・ ・ ・ 0.4 Cpd-5 ・ ・ ・ 0.5 Cpd-6 ・ ・ ・ 0.5 In each layer, in addition to the above components, stabilization of emulsion Agent Cpd-3 (0.0
4 g / m ² ) Surfactant Cpd-4 (0.02 g / m ² ) was added as a coating aid.

 The structures of the compounds described above are shown below.

Solv-1 Tricresyl phosphate Solv-2 Dibutyl phthalate The total thickness of the emulsion of the sample prepared as described above was 18.0.
μm.

Next, as shown in Table 4, the DIR coupler used in Sample 21 was replaced with the compound of the present invention in an equimolar amount to prepare samples. These samples are designated as 22-24.

On the other hand, by adjusting the total film thickness of the emulsion by adjusting the amount of gelatin and the amount of the gelatin hardener, the same compound as in the above samples 21 to 24 was used, and the total emulsion film thickness was reduced by exactly the same method. ~ 32 were prepared.

The obtained Samples 21 to 32 were exposed to white light through a pattern for MTF measurement, and subjected to the following development processing.

Table 5 Processing method Process Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C Bleaching 1 minute 00 seconds 38 ° C Bleaching and fixing 3 minutes 15 seconds 38 ° C Rinse (1) 40 seconds 35 ° C Rinse (2) 1 minute 00 seconds 35 ° C Stability 40 seconds 38 ° C Drying 1 minute 15 seconds 55 ° C Next, the composition of the processing solution is described.

(Color developing solution) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-hydroxyethylidene 3.0-1,1-diphosphonic acid Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- (N- Ethyl-N-β-4.5 hydroxyethylamino) -2-methylaniline sulfate 1.0 l pH 10.05 by adding water (bleach) (unit: g) Ethylenediaminetetraacetic acid 122.0 Iron ammonium dihydrate Ethylenediaminetetraacetic acid 10.0 Sodium salt Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol Ammonia water (27%) 15.0ml Add water 1.0l pH 6.3 (Bleaching / fixing solution) (unit: g) Ferric ethylenediaminetetraacetate 50.0 Ammonium dihydrate 5.0 Disodium salt ethylenediaminetetraacetic acid 5.0 Sodium sulfite 12.0 Aqueous ammonium thiosulfate solution 240.0 ml (70%) Ammonia water (27%) 6.0ml Add water 1.0l pH 7.2 (Washing solution) Tap water is replaced with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH Water through a mixed-bed column packed with an anion-exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentration to 3 mg / l or less, followed by 20 mg / l of sodium diisocyanurate dichloride 0.15 / l of sodium sulfate was added.

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

(Stabilizing solution) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-0.3 monononylphenyl ether (average degree of polymerization: 10) Ethylenediaminetetraacetic acid 0.05 Disodium salt 8.0 With respect to these developed samples, the MTF values of the cyan image, the magenta image and the yellow image at a spatial frequency of 5 cycles / mm were measured. Table 6 shows the results.

Table 6 also shows the results of measuring the maximum swelling film thickness in the developer.

From the results shown in Table 6, firstly, the DIR coupler of the present invention is significantly improved in the etching effect due to the development suppression effect as compared with the conventional DIR coupler, and secondly, the emulsion film thickness is reduced. It has been clarified that the effect is more excellent by reducing the swelling film thickness during development, and it has become clear that the present invention makes a remarkable improvement.

Example 3 Samples 01 to 18 prepared in Example 1 were exposed to white light,
The processing was carried out using an automatic developing machine according to the method described below (until the cumulative replenishment amount of the solution became three times the capacity of the mother liquor tank).

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

(Color developing solution) (Bleach) (Fixer) (Washing solution) Common to mother liquor and replenisher 5-chloro-2-methyl-4-6.0mg isothiazolin-3-one 2-methyl-4-isothiazoli 3.0mg n-3-one Ethylene glycol 1.5 Add water 1.0l pH 5.0 -7.0 (Stabilizer) Common for mother liquor and replenisher Formalin (37%) 3.0ml Ethylene glycol 2.0g Surfactant 0.4g 1.0 l pH 5.0-8.0 was added to the water. The MTF value of the red-sensitive layer of the obtained developed sample was measured according to the method described in the above example. The results are similar to the results described in Table 3 of Example 1, showing that the DIR coupler of the present invention is excellent in the Ez effect, and that the samples 10 to 12 of the present invention whose swelling film thickness at the time of development is thinner are obtained. The effect has been improved,
It was confirmed that samples 16 to 18 of the present invention having a further reduced swelling film thickness exhibited a remarkable improvement effect.

Example 4 Samples 21 to 32 prepared in Example 2 were processed for a 110 camera to obtain a color photosensitive material for photographing, and various types of the same subject were photographed with a 110 camera (Fujifilm KK's Pocket Fujika Flash AW). Was photographed with the same camera. These photographed samples 21 to 32 were processed by the following method using an automatic developing machine (processing was performed using another sample until the cumulative replenishment amount of the solution became three times the mother liquor tank capacity).

The replenishment amount is 35 mm wide and 1 m long. Next, the composition of the processing solution is described.

(Color developing solution) (Bleaching solution) Common to mother liquor and replenisher (unit: g) Ferric ethylenediaminetetraacetate 120.0 Ammonium dihydrate Ethylenediaminetetraacetic acid 10.0 Sodium salt Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol Ammonia water (27%) 15.0ml Add water 1.0l pH 6.3 (Bleaching and fixing solution) Common for mother liquor and replenisher (unit: g) Ferric ethylenediaminetetraacetate 50.0 Ammonium dihydrate Ethylenediaminetetraacetic acid 5.0 Disodium salt Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution 240.0ml (70%) Ammonia water (27%) 6.0ml Add water 1.0l pH 7.2 (Washing solution) Common for mother liquor and replenisher Tap water is replaced with H type strongly acidic cation exchange resin (Rohm and Haas Co.) Amberlite IR-120B) and a mixed bed column filled with an OH type anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentrations to 3 mg / l or less. 20 mg / l of sodium isocyanurate dichloride and 0.15 / l of sodium sulfate were added.

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

(Stabilizer) Common to mother liquor and replenisher (unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-0.3 monononylphenyl ether (average degree of polymerization: 10) Ethylenediaminetetraacetic acid 0.05 Disodium salt Add water and add 1.0 l pH 5.0-8.0 The so-called negative material obtained in this way is
Fujicolor Hi-Tech Paper Type 21 with KK FPSR-2030
The sample using the DIR-coupler of the present invention was excellent in detail description, and the sample in which the swelling film thickness during development was thinner was improved and the detail description was improved, and the three-dimensional impression was obtained by comparing the detail description with the print of G in a cabinet size. It was shown that excellent prints could be obtained.

 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-61-173248 (JP, A) JP-A-62-166334 (JP, A) JP-A-61-236551 (JP, A) JP-A 62-166551 272246 (JP, A)

Claims (1)

(57) [Claims] 1. A red-sensitive silver halide emulsion layer containing at least one cyan color coupler, a green-sensitive silver halide emulsion layer containing at least one magenta color coupler, and at least one layer on a support. In a multilayer silver halide color photographic material having a blue-sensitive silver halide emulsion layer containing a yellow coupler, a development inhibitor is released by reacting with an oxidation product of a developing agent during development represented by the following general formula (I). A multi-layer silver halide color photographic light-sensitive material containing at least one kind of a development inhibitor-releasing compound, wherein the total thickness of the multi-layer silver halide color photographic light-sensitive material does not exceed 40 μm during development. General formula (I) AL ₁ -L ₂ -DI