JPH02221958A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance graininess and pressure resistance of the photosensitive material by incorporating a specified core/shell type silver iodobromide emulsion and a specified compound. CONSTITUTION:At least one of the emulsion layers of this photosensitive material contains the core/shell type silver iodobromide emulsion composed of the core consisting substantially of silver iodobromide containing >=5mol% silver iodide and the shell covering the core and consisting of silver iodobromide or bromide containing silver iodide less than that in the iodobromide of the core. The layer containing the emulsion or the like contains the compound of formula I in which X is halogen. In addition, the emulsion layer can contain a compound of formula II in which each of Z<1> and Z<2> is an atomic group necessary to form a naphthalene ring; each of R<1> and R<2> is optionally substituted alkyl; R<3> is H, optionally substituted alkyl or the like; X1<-> is an acid anion; and n is 0 or 1.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material with excellent graininess and improved pressure resistance. It is.

(Prior Art) In recent years, demands on the performance of silver halide glass photographic light-sensitive materials have become increasingly strict, and there is a demand for the development of light-sensitive materials with high sensitivity and excellent graininess and color reproducibility. In order to meet these demands, a wide range of studies have been made to improve the sensitivity and graininess of silver halide emulsions. In particular, as disclosed in US 4.728,602, the inner part (core part) is made of silver iodobromide with a high silver iodide content, and the outer part (shell part) is made of silver iodobromide or silver iodobromide with a low silver iodide content. A core/shell type silver halide emulsion made of silver bromide is effective in realizing a light-sensitive material with high sensitivity and excellent graininess.

One reason is the recent spread of cameras with automatic film winding mechanisms.
As the speed of development processing in photo labs increases, there is a tendency for photosensitive materials to be handled less carefully, and requirements for the pressure resistance of photosensitive materials are also becoming stricter. Pressure fog in an emulsion is caused by electrons generated in emulsion grains due to pressure and
It is thought to occur by reducing g" ions and forming a developable latent image (J, Photogr.
, Sci, 1i153 (1984)), emulsions that are highly efficient in forming latent images by electrons generated by light incident on emulsion grains, that is, highly sensitive emulsions, are also highly efficient in forming latent images by pressure electrons, and are less prone to pressure fog. The above-mentioned core/shell type silver halide emulsions, which often have a large resistance, also have a problem in that they do not have sufficient pressure fog resistance and cannot meet the recent strict demands for pressure resistance.

(Issues to be Solved by the Invention) An object of the present invention is to provide a silver halide color photographic material which has excellent graininess and improved pressure resistance.

(Means for Solving the Problems) The object of the present invention is to provide a color photograph having at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support. In a light-sensitive material, a core consisting essentially of silver iodobromide containing 5 mol % or more of silver iodide in at least one emulsion layer, and a core consisting essentially of silver iodobromide containing 5 mol % or more of silver iodide, which covers the core and has a lower silver iodide content than the silver iodobromide of the core. containing a core/shell type silver iodobromide emulsion consisting of a shell consisting essentially of silver iodobromide or silver bromide, and having at least one layer represented by the following general formula (1). This can be achieved by a silver halide color photographic light-sensitive material characterized by containing at least one type of compound.

General formula (1) (In the formula, X represents a halogen atom.) Specific examples of the compound of general formula (1) used in the silver halide color photographic light-sensitive material of the present invention are shown below.

The compound represented by the general formula (summer) of the present invention is a known compound, and is commercially available as PCMX (Mitsubishi Gas Chemical ■), Hopegin F60 (Hokuko Chemical ■), Hokubarin E400 (same), etc., and can be easily prepared manually. be able to.

The layer to which the compound of general formula (I) is added is preferably an emulsion layer containing the core/shell type silver halide emulsion of the present invention, but it is more preferably contained in all layers.

The amount of the compound of general formula (1) added is preferably 10 ppm or more and 5000 ppm or less, more preferably 100 ppm or more and 3000 ppm or less, based on the dry weight of the total gelatin in the layer to which it is added. There are no particular restrictions on the method of addition. However, it is convenient to add it as a methanol solution.

The core/shell type silver halide grains of the silver halide color photographic light-sensitive material of the present invention include a core consisting essentially of silver iodobromide containing 5 mol% or more of silver iodide;
It has a core/shell structure constituted by a shell consisting essentially of silver iodobromide or silver bromide, the silver iodide content of which is lower than that of the core. The silver iodide content of the core is 1
It is more preferably 0 mol% or more, and most preferably 20 mol% or more and 44 mol% or less.

The silver iodide content of the shell is preferably 5 mol% or less.

The core may contain silver iodide uniformly or may have a multilayer structure consisting of phases with different silver iodide contents; The silver iodide content of the phase is 5 mol% or more, more preferably 10
mol% or more, and the silver iodide content of the shell is lower than that of the highest silver iodide content phase of the core, and
"Substantially consisting of silver iodobromide" means that it mainly consists of silver iodobromide, but may also contain up to about 1 mol % of other components.

In a further preferred embodiment of the silver halide grains used in the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention, the silver halide grains have a diffraction angle (2θ) in the range of 38 to 42°, and the silver halide grains are When we obtain the diffraction intensity vs. diffraction angle curve for the (220) plane, we find that there are two diffraction maxima, a diffraction peak corresponding to the core part and a peak corresponding to the shell part, and one minimum between them. The particles have a structure in which the diffraction intensity corresponding to the core portion is 171 to 3/1 that of the shell portion. Particularly preferably, the diffraction intensity ratio is 115 to 3/1, more preferably 1/3 to 3/1.

Such core/shell structuring makes it possible to use a high-iodine silver iodobromide emulsion without causing a delay in development speed, and it is possible to achieve a light-sensitive material with excellent graininess.

The silver halide photographic light-sensitive material of the present invention preferably contains an emulsion composed of monodisperse silver halide grains in at least one emulsion layer. is the value obtained by dividing the standard deviation S of the particle size by the average particle size, as defined by the following formula.
The value multiplied by 00 (hereinafter referred to as the coefficient of variation) is 1
It means an emulsion consisting of 6% or less silver halide grains.

xioo≦16% Note that S is the general standard deviation used in statistics,
It is expressed by the following formula.

In addition, the grain size referred to here refers to the diameter in the case of spherical silver halide grains, and in the case of grains with shapes other than spherical, the diameter when the projected image is converted to a circular image of the same area. Particle size is its average value, and the number of particles with particle size r is n,
When , the average particle size r is defined by the following formula.

General formula (n) Σn It is desirable that the core/shell type silver halide emulsion grains of the present invention have a uniform halogen composition distribution among the grains, and the relative standard deviation of the silver iodide content of each grain of the emulsion is is 20%
The silver iodide content of the individual grains is preferably 12% or less, more preferably 12% or less, for example.
It can be measured with an X-ray microanalyzer as described in No. 4,728,602.

The core/shell type silver halide emulsion of the present invention is, for example, U
It can be prepared by the method described in S4.728,602.

In the color photographic material of the present invention, it is particularly desirable to contain a compound represented by the following general formula (n) in at least one layer in order to improve pressure resistance.

ill et (X, θ).

In the formula, Z- and 21 represent an atomic group necessary to form an optionally substituted naphthalene ring, and may be the same or different. R1 and R1 each represent an optionally substituted alkyl group. R2 represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, Xe represents an acid anion, and n is 0.
or 1 and 0 in the case of an inner salt.

For details of the compound of general formula (■), please refer to JP-A No. 63-21474.
You can refer to No. 5. Specific compound examples are shown below.

Compound example ■ t-7 ■ :) LlsK )u3 ■-4 ■ ■-6 nt.

■-11 ■-12 ow to S02 ■ ■-14 ■-15 thK ■-19 ■-20 ■-21 50s ■-16 ■-17 ■-18 0i to SO3 ■-22 ■ General formula (II) Compounds that are formed by Halogen per mole of silver oxide, lXl0-'~5X1 3 moles, Preferably 3 x 1 O-h to 2.5 x 103 mol, especially Preferably axto-'-txi In a proportion of 3 moles, Contained in silver halide photographic emulsions.

The light-sensitive material of the present invention has at least IN of silver halide emulsion layers of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support.
There is no particular restriction on the number or order of the silver halide emulsion layer and the non-photosensitive layer.A typical example is to provide a silver halide emulsion layer and a non-photosensitive layer with substantially the same color sensitivity. A silver halide photographic material having at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having different light sensitivities, and the light-sensitive layer is one of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers in -g is a red-sensitive layer, a green-sensitive layer in order from the support side. , are arranged in order of blue sensitivity. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

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

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler as described in No. 037, No. 61-20038, DI)? Compounds etc. may be included, and a color mixing inhibitor may be included as commonly used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121.470 or British Patent No. 923.045. A two-layer structure can be preferably used0
Usually, it is preferable to arrange the halogen emulsion in a pattern in which the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.
No. 112751, No. 62-200350, No. 62-2
As described in Nos. 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support: low-sensitivity blue-sensitive layer (BL) / high-sensitivity blue-sensitive WA (BH) / high-sensitivity green-sensitive layer (GH) / low-sensitivity green-sensitive layer (GL) /
High-sensitivity red-sensitive JIJ (RH) / low-sensitivity red-sensitive layer (RL), or BH/BL/GL/GH/RH/
RL order or mouth H/BL/GH/GL/RL/R1
They can be installed in the order of 1, etc.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/Gll/
They can also be arranged in the order of RH/GL/RL. Also, as described in JP-A-56-25738 and JP-A-62-63936, the side farthest from the support.

They can also be arranged in the order of blue sensitivity 1i/GL/RL/GH/R1+.

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer with a low density is disposed and is composed of 3Ns having different photosensitivity, the photosensitivity of which is sequentially lowered toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, the medium-sensitivity emulsion layer/high-sensitivity emulsion FJ/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The 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 mole percent to about 25 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, (RD) Na17643, available from Research Desk.
(December 1978), pp. 22-23, "1. Emulsion preparation a.
nd types)'', and 1B716 (19
November 1979), 648 pages, Graphic "Physics and Chemistry of Photography", published by Beaumontel (P, Glafki
des, Chemic et Ph1siqu
e Photograph-ique, Paul
Montel+ 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Ouffin
.

Photographic Emulsion C
hemistry (Focal Press.

1966)), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L, Zalilv)
anet a+, + Making and Coat
ing Photographic Esulsion
, Focal Press, 1964).

U.S. Patent Nos. 3,574,628 and 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science
ence and Engineering), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4
, 434.226, 4,414.310, 4,
No. 433.048, No. 4,439.520 and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral enhancement. Additives used in such processes are subject to Research Disclosure Na
17643 and 18716, and the relevant sections 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 descriptions are shown in the table below.

Attached nail plate■ 肚UzuL 藚月 連 1 Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity enhancers Same as above 3 Spectral sensitizers,
Pages 23-24 Page 648 Right column ~ Super sensitizer
Page 649 right side 4 Brightener page 24 5 Anti-fogging agent pages 24-25 Page 649 right (fund)
- and stabilizer 6 Light absorber, pages 25-26 Page 649 right column - Filter dye, page 650 left column Ultraviolet absorber 7 Stain inhibitor Page 25 right 41jl Page 650 left-right column 8 Dye image stabilizer Page 25 9 Hardener page 26 page 651 left column 10
Binder, page 26 Same as above 11 Plasticizer, lubricant, page 27 Page 650, right column 12 Coating aid, pages 26-27 Page 650, right column Surfactant 13 Static, page 27 Same as above Patch agent Also, photographic performance improvement with formaldehyde gas In order to prevent deterioration, US Patent No. 4,411.987 and US Pat.
．． It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 435,503.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) Nα17643, described in the patent described in ■-C-C.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4.3
No. 26,024, No. 4.401.752, No. 4.
248,961, Japanese Patent Publication No. 5B-10739, British Patent No. 1.425,020, British Patent No. 1.476.760, U.S. Patent No. 3.973,968, British Patent No. 4.314,
No. 023, No. 4.511,649, European Patent No. 24
9.4738, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0.619, No. 4.351,897, European Patent No. 73.636, US Patent No. 3.061.432, US Patent No. 3.725,067, Research Disclosure No. 24220 (June 1984) month), JP-A-60-3
No. 3552, Research Disclosure Sou 2423
0 (June 1984), Japanese Patent Publication No. 60-43659,
No. 61-72238, No. 60-35730, No. 55
-118034, US Patent No. 6G-185951, US Patent No. 4.500,630, US Patent No. 4.540.654, US Pat. ．． No. 556.630, International Publication-o8810
Particularly preferred are those described in No. 4795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. 4.052.212.
No. 4,146.396, No. 4,228.23
No. 3, No. 4.296.200, No. 2.369.9
No. 29, No. 2.801.171, No. 2.772.
No. 162, No. 2,895.826, No. 3.772
．． No. 002, No. 3,758.308, No. 4,33
No. 4.011, No. 4.327,173, West German Patent Publication No. 3゜329.729, European Patent No. 121,365
No. 8, No. 249°453A, U.S. Patent No. 3,446
．． No. 622, No. 4,333.999, No. 4,77
5.616, 4,451.559, 4.4
No. 27.767, No. 4.690,889, No. 4.
Preferably, those described in No. 254°212, No. 4,296,199, and JP-A-61-42658 are preferred.

Colored couplers to correct unnecessary absorption of coloring dyes are listed in Research Disclosure 17643.
- Section G, U.S. Patent No. 4.163.670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4.004.929, U.S. Patent No. 4.138.258, British Patent No. 1.146.36
No. 8 is preferred, and also US Pat. No. 4,7
No. 74,181, a coupler that corrects unnecessary absorption of a color-forming dye by a fluorescent dye released upon coupling, and a coupler that can react with a developing agent to form a dye, as described in U.S. Pat. No. 4,777,120. It is also preferred to use couplers having a dye precursor group as a leaving group.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
．． 570, EP 96,570 and DE 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4.576°910, British Patent No. 2.102.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD 17643.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
No. 63-37346, U.S. Patent No. 4,248.96
No. 2, No. 4°782.012 is preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
No. 2,131,188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , DIR redox compound releasing couplers described in JP-A-60-185950, JP-A-62-24252, etc., DIR coupler-releasing couplers,
DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173゜3
Couplers that release dyes that undergo discoloration after separation as described in No. 02A, Il, D, N111449, 24241, bleaching accelerator-releasing couplers as described in JP-A No. 61-201247, etc., U.S. Pat. No. 4,553.477 Gantt-emitting couplers described in JP-A-63-75747, leuco dye-releasing couplers described in US Pat.
Examples include couplers that emit fluorescent dyes as described in No. 181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in U.S. Pat. No. 2,322.027 and the like.

The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high boiling point organic solvents include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-L-amyl phenyl) phthalate, bis(2,4-di-L-amyl phenyl) phthalate, esters of phosphoric or phosphonic acids (triphenyl phosphate, tricresyl phosphate, 2-
(ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.), benzoic acid ester! a (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.) amide @ (N,N-diethyldodecanamide, N,N-diethyllaurylamide, totitradecylpyrrolidone, etc.), Alcohols or phenol N (isostearyl alcohol, 2.4-
di-lert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sepagate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N- diptyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. Further, 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, -Ethoxyethyl acetate, dimethylformamide and the like.

Specific examples of latex dispersion process steps, effects, and latex for impregnation are disclosed in U.S. Pat. No. 4,199,363, West German Pat. It is described in No. 230, etc.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, stone 17643, page 28, and the same? 4111871
6, from the right column on page 647 to the left column on page 648 (capital).

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, and the film swelling rate Tl/l is preferably 30 seconds or less.

The film thickness means the film thickness measured at 25°C and 55% relative humidity (2 days), and the film swelling rate T17. can be measured according to techniques known in the art. For example, according to Green, A. et al. ,
2, pp. 124-129 (
71/1 is a saturated film thickness that is 90% of the maximum swollen film thickness reached when treated with a color developer for 13 minutes and 15 seconds at 30°C.
/t is defined as the time required to reach the film thickness.

The membrane swelling rate T+/x can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling rate can be calculated from the maximum swollen film thickness under the above-mentioned conditions according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

The color photographic material according to the present invention includes the above-mentioned RD,
Ha 17643, pages 28-29, and the same Nu 1B
716, 615 left column to right column can be used for development processing.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl -4-amino-N-ethyl-N-
f-hydroxyethylaniline, 3-methyl-4-aminoethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochloric acid Examples include salts and p-toluenesulfonates. These compounds can be used depending on the purpose. One or more can also be used together.

The color developer may contain pH 1 additives such as alkali metal carbonates, borates or phosphates, development inhibitors such as bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds, or fogging agents. It generally contains an inhibitor. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfites, hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfone Mat, etc.)
Liethylenediamine (1,4-diazabicyclo(2,2
, 2) various preservatives such as octane), 1a solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, and competitive couplers. , fogging agents such as sodium boron hydride, auxiliary developing agents such as l-phenyl-3-pyrazolidone, viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids. Various chelating agents such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N
-) Rimethylenephosphonic acid, ethylenediamine-N, N
, N,N-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as l-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. It can be used alone or in combination.

These color developing solutions and black and white developing solutions generally have a pi of 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
It can also be less than d. When reducing the amount of replenishment, it is preferable to prevent evaporation of the solution and air oxidation by reducing the contact area with the air in the processing tank, and also to use means to suppress the M#R of bromide ions in the developer. This also allows the amount of replenishment to be reduced.

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

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately (bleach-fixing process), or in order to speed up the process, it may be carried out in two ways: bleach-fixing process after bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents include iron (■) and cobalt (nl).
), compounds of polyvalent metals such as chromium (IV), copper (n), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide-dichromate; organic complex salts of iron (II) or cobalt (III);
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; Persulfates; bromates; manganates; nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron (I [I) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (III) complex salts, are preferable from the viewpoint of rapid processing and environmental pollution prevention. 1) Complex salts are particularly useful in both bleach and bleach-fix solutions. p of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron (II) complex salts.
l+ is usually 5.5 to 8, but to speed up the process, it is also possible to process at a lower pH.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, West German Patent Section 1.
．． No. 290.812, No. 2,059.988, JP-A No. 53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group as described in JP-A No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. Na17129 (July 1978), etc.; JP-A-50-140129 Thiazolidine derivatives described in No.
Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832,
No. 53-32735, U.S. Patent Box 3,706.561
Thiourea derivatives described in West German Patent Section 1,127.7
No. 15, iodide salts described in JP-A-58-16.235;
Polyoxyethylene compounds described in No. 1973-
Polyamine compounds described in No. 8836; other JP-A-49
-42.434, 49-59,644, 53-
No. 94.927, No. 54-35.727, No. 55-2
Compounds described in No. 6.506 and No. 58-163.940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as disclosed in US Patent No. 3,893.858.
No. 1, West Patent No. 1゜290.812, JP-A-53-95
．． The compounds described in U.S. Pat. No. 630 are preferred, and the compounds described in U.S. Pat. These bleach accelerators are particularly effective when bleach-fixing.

Examples of fixing agents include thiosulfates, thiocyanates, 1,000-onythyl compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most commonly used. Can be used widely. As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urn-al of the 5ociety of
Motion Picture and Te1e-v
ision Engineers Volume 64, P, 24
8-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, such problems can be solved by:
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288.838 can be used very effectively. Also, JP-A-57-8,542
Isothiazolone compounds, cyabendazole, chlorine-based sterilizers such as chlorinated sodium isocyanurate, and other benzotriazoles, as well as benzotriazoles, etc. It is also possible to use disinfectants described in "Sterilization, Disinfection, and Anti-Mildew Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Japan Antibacterial and Antifungal Society.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but generally it is in the range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out; an example of this is a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photographic materials for imaging. can.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

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 processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. U.S. Patent No. 3,342.59
Indoaniline compounds described in No. 7, No. 3.342.
No. 599, Research Disclosure 14.850
Schiff base-type compounds described in No. and No. 15.159, Fuldol compounds described in No. 13,924, U.S. Patent No. 3
．． Metal salt complex described in No. 719.492, JP-A-53-i
Examples include urethane compounds described in No. 35628.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-
Pyrazolidones may also be incorporated.

Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 58-115438.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Usually, the standard temperature is 33°C to 38°C, but it is possible to use a higher temperature to accelerate the processing and shorten the processing time. Or, conversely, by lowering the temperature, it is possible to improve the image quality and the stability of the processing solution.

In addition, West German Patent No. 2.226.7 due to the nodal line of the photosensitive material
70 or U.S. Pat. No. 3,674.499 using cobalt or hydrogen peroxide intensification.

Further, the silver halide photosensitive material of the present invention is disclosed in US Patent No. 4.
No. 500.626, JP-A No. 60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in European Patent No. 9-218443, European Patent No. 61-238056, and European Patent No. 210,66082.

(Left below) (Example 1) On an undercoated cellulose triacetate film support,
Samples 101-108, which are multilayer color photosensitive materials each having the composition shown below, were prepared.

(Composition of photosensitive layer) The coating amount is expressed in g/rd unit of silver for silver halide and colloidal silver, and the amount expressed in g/rd unit for coupler additive and gelatin. Regarding the dye, the number of moles is expressed per 111 moles of halogen in the same layer.

1st layer (antihalation layer) Black colloidal silver ・Old 0.15 gelatin 1.5E x
M -8--,0,08 UV-1-...-0,03 UV-2--...0.06 S o Iv-2-0,08 UV-3, Old,, 0,07 Cp d -5-kawa3X10-' pd-6 2nd layer (intermediate layer) Gelatin V-1 V-2 V-3 xF-1 pd-6 olv-2 pd-5 3rd layer (First red-sensitive emulsion layer) Silver iodobromide emulsion (Agr 2 mol%, equivalent sphere diameter 0.3μ
m, coefficient of variation of equivalent sphere diameter 29%, twin grains, diameter/thickness ratio 2.5) Coated silver amount ・・・・・・0.5 ・・・・・・ 1.5 ・・・・・・0.03 ・・・・・・ 0.06 ・・・・・・ 0.07 ・・・・・・ 0.004 ・・・・・・ 3X10-” ・・・・・・ 0.07 ・・・...3X10-'0XIO-' ...... lXl0-5 ...... 0.22 Cpd-5... 1.6X10-'Cpd-6
...... 1.6X10-"E x C-4---
---0,02 4th layer (second red-sensitivity lactite I) Silver iodobromide emulsion (Ag (4 mol%, equivalent sphere diameter 0.55 μm
, coefficient of variation of equivalent sphere diameter 20%, normal crystal grains, diameter/thickness ratio l) Coated silver amount...0.7 Gelatin...1.26
E x S -1...txto-'E x S
-2--3xlO-' Snake x S -3--lXl0-' E x C-3-0,33 E x C-4= 0.01 E x C-7-0,04 E x C-2-・-・0.08 S o I v l −-0,0
3Cpd-5...2.5X10-'Cpd-6
・・・・・・2.5 Cpd-6 olv-2 Cpd-5 6th layer (middle layer) Cpd-6 Gelatin Cpd-5 Cpd-1 Cpd-4 olv-1 ・・・・・・ 0.7 ・・・・・・ 0.8 ...... lXl0-' ...... 3X10-' ...... lXl0-5 ...... 0.05 ...... 0.06 ......・ 0,15 ...... 1.6X10-' ...... 0.08 ...... 1.6X10-' ...... 2XIO-3 ...... 1.0...2XIO-'...0.lO...l, 23...0.05 Cpd-3...0. 25 Seventh layer (first green emulsion layer) Silver iodobromide emulsion (Ag1 2 mol%, equivalent sphere diameter 0.3 μm
, coefficient of variation of equivalent sphere diameter 28%, twinned particles, diameter/thickness ratio 2.5) Coating il! ...0.30 Gelatin ...0.4 x S -4--5X10-' Ex S-6''-0.3xlO-' Exemplary Compound 11
-2...2 X 10-'
ExM-9...0.2 E x Y -14-0,03 Ex M -8-0,03 Cpd-6...8X10-' S o I v -1... ...0.2Cpd-5.
...8 X 10-' 8th layer (second green-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 4 mol%, equivalent sphere diameter 0.55μ
m, coefficient of variation of equivalent sphere diameter 20%, normal crystal grains, diameter/thickness ratio l) Coated silver amount Gelatin xS-4 Exemplary compound n-2 xS-6 xM-9 xM-8 xM-10 xY-14 Cpd- 6 olv-1 Cpd-5 9th layer (third green-sensitive emulsion layer) Silver iodobromide emulsion coating 11! Gelatin xS-4 Exemplary compound ■-2 xS-6 xS-7 ...... 0.6 ...... 0.8 ...... 5XIO-' ...... 2X10- ' ・・・・・・ 0.3XlO-' ・・・・・・ 0.25 ・・・・・・ 0.03 ・・・・・・ o, ois ・・・・・・ 0.04 ・・・...1.6xlo-' ...0.2 ...1.6. X10-' ...0.85 ...1.0 ...2.0X10-'...2.0X10-' ...0 .2xlO-' ...... 3.0XIO-' E x M -12-0,06 E x M -13...0.02E x M
-8-------0,02Cpd-6...2
X10-”Cpd-5...2XIO-'S
o l v -1・old...0.20S o l v -
2-0,05 1st θ layer (yellow filter layer) Gelatin ・Old...0.9 Yellow colloidal silver...0.05Cp
d-1...0.2 Cpd-6...2 X IG-'S o l
v-1...0.15Cpd-5...
2X10-' 11th layer (first blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag! 4 mol%, equivalent sphere diameter 0.5μ
m, coefficient of variation of equivalent sphere diameter 15%, octahedral particles) Amount of silver coated: 0.4 gelatin
......l, 0ExS-8...2X
lO-' ExY-16...0.9 Ex Y -14--0,09 Cpd-6...2X10-" So Iv-1-0,3 Cpd-5.・・・・・・ 2XIQ-'12th layer (2nd
Blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 10 mol%, equivalent sphere diameter 1.3μ
m, coefficient of variation of equivalent sphere diameter 25%, twin grains, diameter/thickness ratio 4.5) Coated silver amount...0.5 Gelatin...0.6E
x S -8-1xlG-' E x Y -16--0,12 Cpd-6...1.2XlO-'S o l
v -1-"・0.04 Cpd-5...1.2X10-' 13th layer (first protective layer) Fine grain silver iodobromide (average grain size 0.07 μm, heg 11 mol%) ...0.2 gelatin
...0.8V-3 V-4 V-5 olv-3 Cpd-5 Cpd-6 14th layer (second protective layer) Gelatin polymethyl methacrylate (1.5 μm in diameter) Cpd-5 Cpd-6 to particle...0.1...0.1...0.2...0.04...5xto-' ...... 5X10-" 0.9 ...0.2 5X10-' X10-2 V-t H-1...0.4 In addition to the above components, each layer contains A surfactant was added as a coating aid.

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

V ExM-8: v ExF-1D tricresyl phosphate olv 2: dibutyl phthalate 5olv-3: bis phthalate (2-ethylhexyl) C, Hs C.HS CgHsO5Oi xC 2: xC H H xC 3: S CHCOOCHi ExY-14: CH.

ExC-5: ExC 6: H ExC-7: υ CH2 ExM-12: ExM-13: ExM-9: Il xY l 6: Cpd l: CJ+3(n) Cpd-2: H ExS-1: ExS-2 : ExS-3; ExS-8: H-1: C11x=CI-501-CHz-CONH-C)lx
CI+,=C)I SOx-CHi-CONH-CHz cpa-3゜cpa-4゜ExS-4: ExS 6 : ExS-7: Cpd-57 Pd 6 : (CHi)zsOJa υ Samples 101 to 108 No. 5 The contents of the layers and the emulsion of the ninth layer are as shown in Table 1-1. Also, samples 105-10B
Compound 1-1 was added as shown in Table 1-1.

After coating each sample No. 101-108, it was aged for 8 days at 25°C and 68% humidity, and then optically (using rust, color temperature 48%).
An exposure of 1/100 second was given at 00°. Subsequently, the film was developed by processing method A described below, and the optical density was measured using a green filter. The reciprocal of the exposure amount that gives a density of fog density +0.2 was defined as the sensitivity, and the relative relationship was determined when the sensitivity of sample 101 was set as 100. Table 1 shows the results.
-2.

The RMS value was measured by a conventional method using a 48 μm diameter aperture after each sample was developed by processing method A in which each sample was exposed to light at a color temperature of 4800@20 lux for 1/100 seconds. The results are shown in Table 1-2.

The emulsion surface of each sample from 101 to 10B was
Scratching was performed with a μm sapphire needle at a rate of 5 C1 per second while applying a load of 8 g. Subsequently, development processing was performed using processing method A. The density of scratches caused by scratching with a needle was measured using a microdensitometer, and the difference in density from that when no scratching was performed was determined.

The results are shown in Table 1-2.

Processing method A Process Processing time Color development 3 minutes 15 seconds Bleach White 6 minutes 30 seconds Water wash 2 minutes 10 seconds Fixed arrival time: 4 minutes 20 seconds Washing with water (1) 1 minute 05 seconds Washing with water (2) 1 minute 00 seconds Stable 1 minute 05 seconds Drying 4 minutes 20 seconds Next, the composition of the treatment liquid will be described.

(Color developer) Processing temperature 38°C 38°C 24°C 38°C 24°C 24°C 38°C 55°C (Unit: g) Ethylenetriaminepentaacetic acid 1.01-Hydroxyethylidene-1,l-diphosphonic acid sulfite Sodium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl-N-β xyethylamino)-2-methylaniline sulfate Add H (bleach solution) Sodium ferric hydroethylenediaminetetraacetate Trihydrate Ethylenediamine Tetraacetic acid disodium Salt Ammonium bromide Ammonium nitrate 3.0 4.0 30.0 1.4 1.5 1973 2.4 4.5 1.01 10.05 (Unit g) 100.0 10. 0 140.0 30.0 Aqueous ammonia (27%) Add water and H (fixing fi) Ethylenediaminetetraacetic acid disodium salt Sodium sulfite Sodium bisulfite Ammonium thiosulfate aqueous solution (70%) Add water and H (stabilizing solution) Formalin (37%) Polyoxyethylene-p-7nononylphenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid 6.5- 1.01 6.0 (Unit g) 0.5 7.0 5.0 1?0 .0mff1 1, Ql 6.7 (unit: g) 2.0affi 0.3 0.05 Disodium salt water added H 1,02 5,0-8,0 As is clear from Table 1-2, the present invention The sample has excellent graininess and low scratch fogging value.

If the core/shell type halogenated emulsion of the present invention and the compound of general formula (1) are used in all emulsion layers, the effects of the present invention will be even greater.

(Example 2) Samples 107 and 307 in which the ninth layer of Samples 103 and 107 contained C and 1% sensitizing dye ExS-5, respectively, had the general formula (II
) The effect of the present invention is more pronounced than in Sample 207, which does not use a sensitizing dye.

Instead, samples 203 and 207 were created.

Samples 303 and 307 were obtained by replacing the sensitizing dye ExS-5 in the ninth layer of Samples 103 and 107 with compound ■-14, respectively.
It was created.

Samples 203, 207, 303 and 307 were tested for photographic properties in the same manner as in Example 1. The results are shown in Table 2-1.

As is clear from Table (2), the effect of the present invention on increasing general formula ([I) is similarly exhibited when Samples 101 to 108 are treated with the following treatment method B.

Processing method B Process Processing time Color development 3 minutes 15 seconds Bleach White 1 minute 00 seconds Bleach fixing 3 minutes 15 seconds Washing with water (1) 40 seconds Washing with water (2) 1 minute 00 seconds Stability 40 seconds Drying 1 minute 15 seconds Next, the composition of the treatment liquid will be described.

(Color developer) Processing temperature 38°C 38°C 38°C 35°C 35°C 38°C 55°C Ethylenetriaminepentaacetic acid l-hydroxyethylidene 1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide (unit: g) 1.0 3.0 4.0 30.0 1.4 Potassium iodide hydroxylamine sulfate 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate water was added and H (bleached) Liquid) Ethylenediaminetetraacetic acid Ferric ammonia water dihydrate Ethylenediaminetetraacetic acid disodium salt Ammonium bromide Ammonium nitrate Bleach accelerator Aqueous ammonia (27%) Add water 1.5■ 2.4 4.5 1.01 to , os (unit g) 120.0 1O10 100.0 1O80 0,005 mol 15.0d 1.0ffi P H6,3 (bleach-fix solution) (unit g) Ethylenediaminetetraacetic acid dibasic 50. O Iron ammonium dihydrate Ethylenediaminetetraacetic acid dis 5.0 Thorium salt Sodium sulfite 12.0 Ammonium thiosulfate water m? a 240.0sd (7
0%) Ammonia water (27%) Add 6.0d water to 1.01p H7
, 2 (Washing liquid) Tap water was mixed with an H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and an O) l-type anion exchange resin (Amberlite IR-400, manufactured by Rohm and Haas).
Water was passed through a mixed-bed column packed with water to reduce the concentration of calcium and magnesium ions to 3 sg/2 or less, and then 20 g/l of sodium isocyanurate dichloride and 0.15 g/l of sodium sulfate were added.

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

(stabilizer) Procedural amendment 1990! Month! (Unit: g) Formalin (37%) polyoxyethylene-p- seven-tononylphenyl ether (Average degree of polymerization 10) Ethylenediaminetetraacetic acid thorium salt add water pH 2.0d 0.3 0.05 1.On! 5.0-8.0 Display of incidents name of invention person who makes corrections Relationship with the incident 1999 Patent Application No. 42617 silver halide color photographic material

Claims (1)

[Scope of Claims] In a color photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support, at least one emulsion layer is provided. A core consisting essentially of silver iodobromide containing 5 mol% or more of silver iodide in the layer, and a silver iodobromide or silver iodobromide coating which covers the core and has a lower silver iodide content than the silver iodobromide of the core. Containing a core/shell type silver iodobromide emulsion consisting of a shell consisting essentially of silver bromide, and containing at least one of the compounds represented by the following general formula (I) in at least one layer. A silver halide color photographic light-sensitive material. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents a halogen atom.)