JPH05107670A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material good in sensitivity/graininess ratio and reduced in fog, and prevented from occurrence of fog during storage. CONSTITUTION:The silver halide photographic sensitive material has at least one silver halide emulsion layer containing regular silver halide emulsifying agent each having (111) face and (100) face; an average silver iodide content of >=2mol%; 10 dislocation lines per 1 grain in the >=50 number % of the total grains; and a relative standard deviation of silver iodide content of <=30%; and these grains are formed in the presence of thiosulfonate compound represented by formula I in which R is an aliphatic or aromatic or heterocyclic group and M is a cation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material having high sensitivity and improved fog.

[0002]

2. Description of the Related Art In recent years, demands for the performance of photographic light-sensitive materials have become more and more strict, and demands for sensitivity, contrast, fog prevention and the like have become higher and higher.
Therefore, various studies have so far been made on silver halide emulsions in order to meet these demands.

For example, by a laminated type silver halide grain in which a plurality of outer shells (shells) are attached to the outside of the inner shell,
To improve the developing activity and to increase the sensitivity, it is disclosed in Japanese Patent Laid-Open No.
No. 3-22408, Japanese Patent Publication No. 43-1316, J. Phot
o. Sci., 24 (1976) 198 etc. JP-A-6
0-143331, J. Imaging Sci., 29 (1985) 193.
And the like disclose that a high iodine phase is provided inside the particles to enhance the sensitivity. Further, JP-A-60-143
No. 332 discloses that an emulsion having high sensitivity and high contrast can be obtained by using an emulsion having a small iodine distribution between grains.

Further, JP-A-60-35726 and JP-A-6-35726
No. 3-220238 discloses that a silver halide emulsion having a high sensitivity / graininess ratio with less pressure fog can be obtained by providing a portion having a high silver iodide content inside the grain. However, when a dislocation line is introduced by providing a portion with a high silver iodide content inside the regular grain, even if it is sensitized, even if it is used for a practical silver halide photographic material, the granular portion of the highlight portion due to the decrease in contrast is formed. Cause deterioration. Therefore, satisfactory results have not been obtained for the current high standards.

It is also possible to add thiosulfonic acid as a chemical sensitizer for surface latent image type emulsions in US Pat. No. 2,39.
No. 4,198, JP-A No. 54-1019, etc., it is possible to reduce fog, especially when it is applied to a silver halide having a portion having a high silver iodide content inside a regular grain. Reduction of fog during storage of the film could not be achieved. When the emulsion is fogged in this way, the color density of the light-sensitive material subjected to the reversal process is lowered.

[0006]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a silver halide light-sensitive material having a good sensitivity / granularity ratio. A second object of the present invention is to provide a silver halide light-sensitive material which, in addition to the above-mentioned sensitivity / granularity ratio, has reduced fog and further prevented fog from occurring during storage.

[0007]

DISCLOSURE OF THE INVENTION As a result of intensive studies conducted by the present inventors in order to overcome the above-mentioned drawbacks of conventional silver halide light-sensitive materials, as a result, silver iodide content was increased inside regular grains of silver halide. If dislocations are introduced, there are large variations in the intergranular iodine distribution of the emulsion grains, which impairs photographic performance. It was found that the presence of the above thiosulfonic acid compound was effective, and based on this finding, further research was conducted to complete the present invention.

That is, the present invention provides a light-sensitive material having at least one silver halide emulsion layer on a support,
In a regular silver halide emulsion having (111) faces and (100) faces, the average silver iodide content of the silver halide emulsion is 2 mol% or more, and based on the number of silver halide grains. 50% or more has 10 or more dislocation lines per grain, and the relative standard deviation of the silver iodide content of each grain is 3
An emulsion layer having a silver halide emulsion in which the content is 0% or less and the silver halide grains are grains formed in the presence of a compound represented by any one of the following general formulas (I) to (III). The present invention provides a silver halide light-sensitive material characterized by comprising:

General formula (I) R-SO ₂ S-M General formula (II) R-SO ₂ S-R ¹ General formula (III) RSO ₂ S-L-SSO ₂ -R ² (wherein R, R ¹ and R ² represent an aliphatic group, an aromatic group or a heterocyclic group, L represents a divalent linking group, and M represents a cation.)

The photosensitive silver halide emulsion used in the light-sensitive material of the present invention preferably has a portion having a higher silver iodide content than the surface of the grain inside the silver halide grain.

In the silver halide emulsion used in the present invention, normal crystal silver halide grains mainly composed of (111) plane and (100) plane are (111) plane, (10
0) The surface occupies 60% or more. Regular silver halide emulsions used in the present invention are mainly (11
It consists of 1) plane and (100) plane, but the ratio of plane index is (1
00) / (111) is 0.5 or more, preferably 1 or more, and more preferably 2 or more.

The silver halide grains of the present invention may be octahedral, cubic or tetradecahedral. Also EP
-0096727B1, EP-0064412B1 and the like, particles having rounded corners, or DE-2306447C2, JP-A-60-221320.
It may also be surface modified particles as disclosed in US Pat.

The dislocations of regular silver halide grains are described, for example, in JF Hamilton, Photo. Sci. Eng., 11, 57, (196
7) and T. Shiozawa, J. Soc. Photo. Sci. Japan, 35, 21
It can be observed by a direct method using a transmission electron microscope at low temperature described in 3, (1972). In other words, the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocation to the grains from the emulsion are placed on the mesh for electron microscope observation, and the sample to prevent damage (printout etc.) due to electron beam In the cooled state, observation is performed by the transmission method. The number and position of dislocation lines of each grain can be determined from the photograph of the grain obtained by such a method.

The number of dislocation lines in the grain of the present invention is 1
It is preferable that 50% by number or more of grains containing 0 or more dislocation lines are present. More preferably, the number of grains containing 10 or more dislocation lines is 80% or more, and the number of grains containing 20 or more dislocation lines is particularly preferably 80% or more. The number of dislocation lines existing in one grain, that is, the dislocation line density is measured as follows. A series of particle photographs with different tilt angles with respect to the incident electrons were taken for each particle,
Confirm the presence of dislocation lines. At this time, the number of dislocation lines that can be counted is counted. When the dislocation lines are densely present and the number of dislocation lines per grain cannot be counted, it is counted that many dislocation lines exist. The distribution of dislocation line densities between particles is determined by measuring the dislocation line density for 200 or more particles, more preferably 300 or more particles, and creating a frequency distribution thereof.

The silver halide grains of the present invention may be fine grains having a grain size of silver halide of about 0.1 μm or less or large grains having a projected area diameter of up to about 10 μm.

The relative standard deviation of the silver iodide content of each grain in the present invention is 30% or less, preferably 20% or less, more preferably 15% or less.

The silver iodide content of each emulsion grain can be measured by analyzing the composition of each grain using, for example, an X-ray microanalyzer described in JP-A-60-254032. Here, "relative standard deviation of silver iodide content of individual grains" means, for example, a standard of silver iodide content when the silver iodide content of at least 100 emulsion grains is measured by an X-ray microanalyzer. It is a value obtained by multiplying the value obtained by dividing the deviation by the average silver iodide content by 100. A specific method for measuring the silver iodide content of individual emulsion grains is described in, for example, European Patent 147,868A.

In the present invention, the particle surface means 5 from the surface.
It refers to a region up to a depth of about 0A. The silver halide emulsion composition in such a region can be usually measured by the ESCA method. The inside of a particle refers to a region other than the above-mentioned surface region.

The dislocation lines in the present invention are those which reach the surface from the inside of 0.1 μm or more from the surface of the grain,
The existing position may exist on a plane, on a side, or on a vertex.

The size distribution of the regular silver halide grains used in the present invention is preferably as narrow as possible in order to further narrow the grain-to-grain iodine distribution of the silver iodide content. The standard deviation is preferably 20% or less, particularly preferably 10% or less.

The silver halide emulsion composition of the grains of the present invention is preferably silver iodobromide or silver chloroiodobromide, and particularly has a silver iodide content of 2 to 20 mol%, preferably 2
The amount of silver iodobromide is -10 mol%, more preferably 2-5 mol%.

The method for producing the regular silver halide grains of the present invention can be achieved by appropriately combining the methods known in the art. For example, Research Disclosure, Vol. 176, No. 17643 (November 1979)
Mon.), page 648.

The dislocation line of the regular silver halide grain of the present invention can be introduced by a known method, and can be controlled by, for example, providing a specific high iodine phase inside the grain. The internal high iodine phase refers to a silver halide solid solution containing iodine. The silver halide in this case is preferably silver iodide, silver iodobromide or high silver iodobromide, but is more preferably silver iodide or silver iodobromide (iodine content 20 to 40 mol%). Silver iodide is preferable, and silver iodide is particularly preferable.

The internal high iodine phase may be uniformly deposited on the plane of the substrate particles, or may be locally present. Such localization may occur anywhere on the plane, edges, or corners of the substrate particles. Further, the internal high iodine phase may be selectively and epitaxially coordinated to such a site.

As a method for this, a so-called conversion method in which, for example, an iodide salt is added alone, or in, for example, JP-A-59-133540 and JP-A-58-10852.
No. 6, JP-A-59-162540, an epitaxial bonding method may be used. The pAg at the time of adding the iodide salt is more preferably in the range of 8.5 to 10.5, and particularly preferably in the range of 9.0 to 10.5. The temperature is
It is preferable to keep the temperature in the range of 50 to 30 ° C. The silver iodide content of the substrate grains is lower than that in the high iodine phase, and is preferably 0.
˜12 mol%, more preferably 0 to 10 mol%.

The outer phase covering the high iodine phase is lower than the iodine content of the high iodine phase, preferably 0-12.
Mol%, more preferably 0 to 10 mol%, and most preferably 0 to 3 mol%.

This internal high iodine phase is 5 to 80 mol% in terms of silver amount from the center of the regular silver halide grain to the total grain.
Is preferably present in the range of 20 to 70 mol%, more preferably in the range of 20 to 70 mol%, particularly preferably in the range of 30 to 70 mol%.

The iodine content of the internal high iodine phase is higher than the average iodine content of silver iodide, silver iodobromide or silver chloroiodobromide present on the grain surface, preferably 5 times or more, particularly preferably. It is more than 20 times.

Further, the amount of silver halide forming the internal high iodine phase is 50 mol% or less, more preferably 10 mol% or less, and particularly preferably 5 mol% or less of the silver amount of the whole grains in terms of silver amount. Is.

In the present invention, the properties of the silver halide grains can be controlled by allowing various compounds to be present in the silver halide precipitation forming process. Such compounds may be initially present in the reactor.

In addition, one or more salts can be added together with the salt according to a conventional method. U.S. Pat. Nos. 2,448,060, 2,628,167, 3,737,313, 3,772,031, and Research Disclosure, Vol. 134, 1975.
June, 133752, copper, iridium, lead, bismuth, cadmium, zinc (eg sulfur,
Chalcogen compounds of selenium and tellurium), gold and VII
The characteristics of silver halide can be controlled by allowing a compound such as a compound of a group noble metal to be present during the silver halide precipitation formation process. As described in JP-B-58-1410, Moisar et al., Journal of Photographic Science, Vol. 25, 1977, pp. 19-27, a silver halide emulsion has a grain-forming property during the precipitation process. The inside can be sensitized by reduction.

In the regular silver halide grains used in the present invention, silver halides having different compositions may be bonded by epitaxial bonding, and, for example, silver rhodanide, lead oxide and a compound other than silver halide may be bonded. It may have been done. These emulsion grains are described, for example, in U.S. Pat. Nos. 4,094,684 and 4,142,900.
No. 4,459,353, British Patent No. 2,038,
792, U.S. Pat. Nos. 4,349,622 and 4,3.
95,478, 4,433,501, 4,46
No. 3,087, No. 3,656,962, No. 3,85
2,067 and JP-A-59-162540.

The silver halide grains of the silver halide emulsion used in the present invention have the above general formula (I), (II) or (II).
Particles are formed in the presence of the compound of I).

Here, forming in the presence of these compounds specifically means adding these compounds before the completion of the formation of the silver halide grains.
It may be added when forming a core of a silver halide grain having a shell structure, or when forming a shell.

Next, the compounds of the general formulas (I), (II) and (III) will be described in more detail. When R, R ¹ and R ² are aliphatic groups, saturated or unsaturated, straight chain, A branched or cyclic aliphatic hydrocarbon group, preferably having 1 carbon atom
To 22 alkyl groups, alkenyl groups having 2 to 22 carbon atoms, and alkynyl groups, which may have a substituent, and examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, and hexyl. , Octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl,
t-butyl may be mentioned.

As the alkenyl group, for example, allyl,
Butenyl is given. Examples of the alkyl group include a propargyl group and butynyl. R, R ¹ and R
The aromatic group of ² includes a monocyclic or condensed ring aromatic group, preferably having 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl. These may be substituted.

The heterocyclic group for R, R ¹ and R ² includes
A 3- to 15-membered ring having at least one element selected from nitrogen, oxygen, sulfur, selenium, and tellurium and having at least one carbon atom, preferably 3 to 6
Member rings are preferred, for example pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole, tetrazole, oxadiazole, An example is the thiadiazole ring.

Substituents for R, R ¹ and R ² include, for example, alkyl groups (eg, methyl, ethyl, hexyl),
Alkoxy group (eg methoxy, ethoxy, octyl), aryl group (eg phenyl, naphthyl, tolyl), hydroxy group, halogen atom (fluorine, chlorine, bromine, iodine), aryloxy group (eg phenoxy),
An alkylthio group (eg, methylthio, butylthio),
Arylthio group (eg, phenylthio), acyl group (eg, acetyl, propionyl, butyryl, valeryl), sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), acylamino group (eg, acetylamino, benzoylamino), sulfonylamino group ( Examples thereof include methanesulfonylamino, benzenesulfonylamino), an acyloxy group (eg acetoxy, benzoxy), a carboxyl group, a cyano group, a sulfo group, an amino group, a —SO ₂ SM group, and a —SO ₂ R ¹ group.

As the divalent linking group represented by L,
It is an atom or atomic group containing at least one selected from C, N, S and O. Specifically, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-,-
S-, NH -, - CO - , - SO 2 - or the like is made of a single or a combination of these sets of. L is preferably a divalent aliphatic group or a divalent aromatic group. As the divalent aliphatic group of L, for example,

[Chemical 1] Examples thereof include a xylylene group. Examples of the divalent aromatic group of L include a phenylene group and a naphthylene group.

These substituents may be further substituted with the above-mentioned substituents. M is preferably a metal ion or an organic cation. Examples of the metal ion include lithium ion, sodium ion and potassium ion. Examples of the organic cation include ammonium ion (for example, ammonium, tetramethylammonium, tetrabutylammonium), phosphonium ion (tetraphenylphosphonium), guanidyl group and the like.

When the general formulas (I) to (III) are polymers, examples of the repeating units are as follows.

[0042]

[Chemical 2]

These polymers may be homopolymers or copolymers with other copolymerizable monomers. Specific examples of the compound represented by formula (I), (II) or (III) are shown below, but the invention is not limited thereto.

[0044]

[Chemical 3]

[0045]

[Chemical 4]

[0046]

[Chemical 5]

[0047]

[Chemical 6]

[0048]

[Chemical 7]

[0049]

[Chemical 8]

[0050]

[Chemical 9]

[0051]

[Chemical 10]

[0052]

[Chemical 11]

The compounds of the general formulas (I), (II) and (III) are described in JP-A-54-1019; British Patent 972,211.
Issue, Journal of Organic Chemistry, 53, 396 (1)
988) and Chemical Abstracts (Chemical Abstracts), Vol. 59, 9776e.

The compound represented by the general formula (I), (II) or (III) is 10 ^-7 to 10 ^-1 per mol of silver halide.
It is preferable to add them in moles. From 10 ^-6 to 10 ^-2 ,
Particularly, the addition amount of 10 ⁻⁵ to 10 ⁻³ mol / mol Ag is preferable.

In order to add the compounds represented by the general formulas (I) to (III) during the production process, a method which is usually used when adding an additive to a photographic emulsion can be applied. For example, a water-soluble compound is an aqueous solution having an appropriate concentration, and a water-insoluble or sparingly-soluble compound is a suitable organic solvent that is miscible with water, such as alcohols, glycols, ketones, esters, amides, etc. Of these, it can be dissolved in a solvent that does not adversely affect the photographic characteristics and added as a solution.

Chemical sensitization is performed by James (TH James).
Written by The Theory of Photographic Process, 4th Edition, published by Macmillan, 1977 (TH Jame
s, The Theory of the Photographic Process, 4 th e
d, Macmillan, 1977) pp. 67-76, with active gelatin. Research Disclosure, Volume 120, April 1974,
12008; Research Disclosure, Volume 34,
June 1975, 13452, U.S. Pat. No. 2,642,
361, 3,297,446, 3,772,0
No. 31, No. 3,857,711, No. 3,901,71
No. 4, No. 4,266,018 and No. 3,904,41
5 and pAg 5-10, pH 5-8 and temperature 30-as described in British Patent 1,315,755.
Chemical sensitization can be performed at 80 ° C. with sulfur, selenium, tellurium, gold, platinum, iridium or combinations of these sensitizers. The chemical sensitization is optimally carried out in the presence of a gold compound and a thiocyanate compound, or US Pat. Nos. 3,857,711 and 4,266,018.
And the sulfur-containing compounds described in JP-A No. 4,054,457 or the sulfur-containing compounds of hypo, thiourea compounds, and rhodanine compounds.

Chemical sensitization can also be carried out in the presence of a chemical sensitization aid. As the chemical sensitization aid, compounds such as azaindene, azapyridazine and azapyrimidine which are known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aid modifiers are:
US Pat. Nos. 2,131,038 and 3,411,91
No. 4, 3,554, 757, JP-A-58-1265.
No. 26 and Duffin, "Photoemulsion Chemistry", 138-14.
It is described on page 3. In addition to or as an alternative to chemical sensitization, US Pat. Nos. 3,891,446 and 3,9
For example, hydrogen can be used for reduction sensitization as described in No. 84,249. Also, US Pat.
18,698, 2,743,182 and 2,7
Reduction with reducing agents such as stannous chloride, thiourea dioxide, polyamines or by treatment with low pAg (eg less than 5) and / or high pH (eg greater than 8) as described in US Pat. Can be sensitized. Further, the color sensitization can be improved by the chemical sensitization method described in U.S. Pat. Nos. 3,917,485 and 3,966,476.

Further, JP-A-61-3134 and 61-3
The sensitization method using an oxidant described in JP-A-136-136 can also be applied to the chemical sensitization of the present invention.

The emulsion comprising regular silver halide grains of the present invention should be used in combination with an emulsion comprising ordinary chemically sensitized silver halide grains (tabular grains, non-tabular grains) in the same silver halide emulsion layer. You can

The tabular grain silver halide may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. A preferred silver halide is silver iodobromide or silver iodochlorobromide containing 30 mol% or less of silver iodide. Particularly preferably 2 mol%
Of silver iodobromide containing up to 25 mol% of silver iodide.

The particle size of the tabular grains used here is
Even with fine particles of 0.1 micron or less, the projected area diameter is 10
It may be large-sized grains down to micron, and may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution.

As a general method for producing the above-mentioned tabular grains, US Pat. Nos. 4,434,226 and 4,439,52 are used.
No. 0, No. 4,414, 310, No. 4,399, 2
No. 15, No. 4,433,048, No. 4,386.
No. 156, No. 4,400, 463, No. 4,41
It can be made by appropriately combining the methods described in No. 4,306, No. 4,435,501 and the like. As the non-tabular grains, for example, cubic grains, octahedra, regular grains having a regular crystal such as a tetradecahedron,
For example, particles having an irregular crystal shape such as a spherical shape or a potato shape can be mentioned.

The non-tabular grains used in the present invention are described in, for example, "The Physics and Chemistry of Photography" by Graphide, published by P. Montefel (P. Glafkides, Chemie et Phisique Photograp.
hique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photogra
phic Emulsion Chemistry (Focal Press, 1966)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., VL Zelikman et al., Making and Coating P
It can be prepared using the method described in hotographic Emulsion, Focal Press, 1964). That is, any of the acidic method, the neutral method, the ammonia method, etc. may be used.
As a method of reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a controlled double jet method can be used.
According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained. 2 formed separately
A mixture of two or more silver halide emulsions may be used.

The silver halide emulsion consisting of the regular grains can be obtained by controlling the pAg and pH during grain formation. For details, see, for example, Photographic Science and Engineering (Photographic S
Cience and Engineering, Volume 6, 159-165 (1962); Journal of Photographic Science 1
Volume 2, Pages 242-251 (1964), U.S. Pat.
655,394 and British Patent 1,413,748.

Regarding the monodisperse emulsion, for example, JP-A-48-8600, JP-A-51-39027 and JP-A-51-39027.
-83097, 53-137133, 54-4
No. 8521, No. 54-99419, No. 58-3763.
No. 5, No. 58-49938, Japanese Patent Publication No. 47-11386
No. 3,655,394 and British Patent No. 1,413,748.

The crystal structure of these non-tabular grains may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains can be obtained, for example, from British Patent No. 1,027,146,
U.S. Pat. No. 3,505,068, 4,444,8
77 and JP-A-60-143331.

In the present invention, a non-photosensitive fine grain emulsion having a grain size of 0.6 μm or less, preferably 0.2 μm or less is used as a silver halide emulsion layer or an intermediate layer for the purpose of promoting development, improving storability and effectively utilizing reflected light. It may be added to the layer or the protective layer.

The regular silver halide grains of the present invention are preferably used in color photographic light-sensitive materials. Known photographic additives that can be used in the present invention are described in Research Disclosure No. 17643 and No. 18716, and the locations described in Table 1 are shown.

Various color couplers can be used in the photographic light-sensitive material of the present invention. A specific example is Research Disclosure (RD) No. 1764 mentioned above.
3, VII-C to G.
As the dye-forming coupler, a coupler which gives the three primary colors of the subtractive method (that is, yellow, magenta and cyan) by color development is important. Diffusion resistant, 4 equivalents or 2
Specific examples of equivalent couplers include RDNo. 176 described above.
In addition to the couplers described in the patents described in paragraphs 43, VII-C and G, the following can be preferably used in the present invention.

A typical example of the yellow coupler which can be used in the photographic light-sensitive material of the present invention is a hydrophobic acylacetamide coupler having a ballast group. Specific examples thereof include, for example, US Pat. No. 2,407,21.
No. 0, No. 2,875,057 and No. 3,265,
No. 506. The use of 2-equivalent yellow couplers in the present invention is preferred, eg US Pat.
No. 8,194, No. 3,447,928, No. 3,9
Nos. 33,501 and 4,022,620, or oxygen atom elimination type yellow couplers, or, for example, Japanese Patent Publication No. 58-10739, U.S. Pat. No. 4,401,7.
52, No. 4,326,024, RD No.1803
5 (April 1979), British Patent No. 1,425,020
No. 2, West German Application Publication No. 2,219,917, No. 2,2
No. 61,361, No. 2,329,587, and No. 2,433,812, the nitrogen atom-releasing yellow couplers are mentioned as typical examples. α-
Pivaloyl acetanilide couplers are excellent in color fastness of coloring dyes, particularly light fastness, while α-benzoyl acetanilide couplers can obtain high color density.

Examples of the magenta coupler which can be used in the photographic light-sensitive material of the present invention include hydrophobic, indazolone or cyanoacetyl, preferably 5-pyrazolone and pyrazoloazole couplers having a ballast group. Be done. The 5-pyrazolone coupler is 3-
A coupler in which the position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and color density of the color forming dye, and typical examples thereof include US Pat.
082, 2,343,703, 2,60
0,788, 2,908,573, 3,0
62,653, 3,152,896 and 3,936,015. 2 equivalents of 5-
As a leaving group of a pyrazolone-based coupler, US Pat.
Particularly preferred are the nitrogen atom leaving groups described in 310,619 or the arylthio groups described in U.S. Pat. No. 4,351,897. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density. As the pyrazoloazole coupler, pyrazolobenzimidazoles described in US Pat. No. 3,061,432, preferably pyrazolone [5,1 described in US Pat. No. 3,725,067.
-C] [1,2,4] triazoles, Research Disclosure 24220 (June 1984) and pyrazolotetrazoles and Research Disclosure 24230 (1) described in JP-A-60-33552.
(June 984) and the pyrazolopyrazoles described in JP-A-60-43659. The imidazo [1,2-as described in U.S. Pat. No. 4,500,630, in view of low yellow sub-absorption of the coloring dye and light fastness.
b] Pyrazoles are preferred, and US Pat. No. 4,540,
Pyrazolo [1,5-b] [1,2,4] described in No. 654
Triazole is especially preferred.

Cyan couplers that can be used in the photographic light-sensitive material of the present invention include hydrophobic and diffusion resistant naphthol-type and phenol-type couplers, and the naphthol-type couplers described in US Pat. No. 2,474,293. ,
Preferably, US Pat. Nos. 4,052,212 and 4,4
Representative examples thereof include oxygen atom-eliminating type 2-equivalent naphthol couplers described in JP-A Nos. 146,396, 4,228,233 and 4,296,200. Further, specific examples of the phenol-based coupler are, for example,
US Pat. Nos. 2,369,929 and 2,801,1
No. 71, No. 2,772, 162, No. 2,895.
No. 826.

Couplers capable of forming cyan dyes that are fast to humidity and temperature are preferably used in the present invention,
Typical examples thereof include phenolic cyan couplers having an alkyl group of ethyl or higher at the meta position of the phenol nucleus described in US Pat. No. 3,772,002, for example,
US Pat. Nos. 2,772,162 and 3,758,3
08, 4,126,396, 4,334,
011, 4,327,173, West German Patent Publication 3,329,729 and European Patent 121,365.
2,5-diacylamino-substituted phenolic couplers described in US Pat. No. 3,446,622,
Phenols having a phenylureido group at the 2-position and an acylamino group at the 5-position described in Nos. 4,333,999, 4,451,559 and 4,427,767. It is a coupler. European Patent No. 16
A cyan coupler in which the sulfonamide group or the amide group is substituted at the 5-position of naphthol described in No. 1,626A is also excellent in the fastness of a color image and can be preferably used in the present invention.

In order to correct the unnecessary absorption of the color forming dye, it is preferable to mask the color sensitive material for photographing with a colored coupler. For example, U.S. Pat. No. 4,
No. 163,670 and Japanese Patent Publication No. 57-39413, or yellow colored magenta couplers, or, for example, U.S. Pat. Nos. 4,004,929 and 4,138,25.
Typical examples are magenta colored cyan couplers described in No. 8 and British Patent No. 1,146,368.
Other colored couplers are RD17643, VII
-G section.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. As such couplers, specific examples of magenta couplers are disclosed in U.S. Pat. No. 4,366,237 and British Patent No. 2,125,570, and European Patent 96,570 and West German Patent Publication No. 3,234. No. 533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye-forming couplers are described in US Pat.
451 and 820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent 2,102,173 and U.S. Patent 4,367,282.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler releasing a development inhibitor is the above-mentioned R
The couplers of the patents described in D17643, Section VII-F are useful.

Preferred in combination with the present invention are:
Developer inactivation type represented by JP-A-57-151944; US Pat. No. 4,248,962 and JP-A-57.
Timing type typified by JP-A-154234;
The reaction type represented by 0-184248, and particularly preferable ones are, for example, JP-A-57-151944, JP-A-58-217932, JP-A-60-218645,
No. 60-225156, No. 59-82214 and No. 60-233650, deactivating developer DI.
R couplers and reactive DIR couplers described in, for example, JP-A-60-184248.

In the photographic light-sensitive material of the present invention, a coupler which releases a nucleating agent or a development accelerator or a precursor thereof imagewise during development can be used. Specific examples of such compounds include British Patent No. 2,097,140,
No. 2,131,188. A coupler which releases a nucleating agent having an adsorbing action on silver halide is particularly preferable, and specific examples thereof include, for example, JP-A-59-157638 and JP-A-59-170840.
No.

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, for example, US Pat. No. 2,322,027.

The steps and effects of the latex dispersion method, and specific examples of the latex for impregnation are described in, for example, US Pat.
199,363, West German Patent Application (OLS) No. 2,54
No. 1,274 and No. 2,541,230.

Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, page 28 and ibid., N.
No. 187116, page 647, right column to page 648, left column.

The color photographic light-sensitive material according to the present invention has the RD. 28-29 of No. 17643 and ibid., N.
The development can be carried out by a usual method described in the left column to the right column on page 651 of O.18716.

The color photographic light-sensitive material of the present invention is usually subjected to washing treatment or stabilizing treatment after development, bleach-fixing or fixing treatment.

In the water washing step, it is general to carry out countercurrent water washing of two or more tanks to save water. As stabilization processing,
A typical example is a multi-stage countercurrent stabilization treatment as described in JP-A-57-8543 instead of the water washing step. In the case of this step, a countercurrent bath of 2 to 9 tanks is required. Various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, various buffers (eg borate, etc.) to adjust the membrane pH (eg pH 3-8).
(A combination of metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia water, monocarboxylic acid, dicarboxylic acid, and polycarboxylic acid)
Typical examples thereof include formalin and the like.
In addition, if necessary, for example, a water softener (for example, inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid), bactericide (for example, benzisothiazolinone, isothiazolone, 4-thiazoline benzimidazole, halogenated phenol), various additives such as surfactants, optical brighteners and hardeners may be used, or two or more kinds of the same or different target compounds may be used in combination. ..

Further, it is preferable to add, for example, various ammonium salts of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as the film pH adjuster after the treatment.

The present invention can be applied to various color light-sensitive materials. Representative 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. The present invention can also be applied to a black-and-white light-sensitive material utilizing a three-color coupler mixture described in Research Disclosure No. 17123 (July 1978).

The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color-sensitive layer and the blue color-sensitive layer are installed in this order.
However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038, the couplers, the DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as is usually used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high sensitivity emulsion layer and a low sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure of emulsion layers can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Further, JP-A-57-112751, JP-A-62-20035.
No. 0, No. 62-206541, No. 62-206543
As described in the publications, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
Can be installed in order.

Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Further, an arrangement in which a silver halide emulsion layer having a low photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support can be mentioned. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. It may be arranged in the order of layer / high-speed emulsion layer / low-speed emulsion layer. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four or more layers, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448 are used.
No. 63-89580, BL, G
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL, adjacent to or in proximity to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
Silver iodobromide, silver iodochloride, or silver iodochlorobromide, including the following silver iodides. About 2 mol% is particularly preferred.
To silver iodobromide or silver iodochlorobromide containing up to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, and irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof. The grain size of silver halide is about 0.2 μm
The following fine particles may also be large-sized particles having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23, "
I. Emulsion preparation and types ",
And No. 18716 (November 1979), 648.
Pp. 307105 (November 1989), 863.
-865 and Graphide, "Physics and Chemistry of Photography," published by Paul Montel (P.Glafkides, Chemie et Phisique
Photographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duff
in, Photographic Emulsion Chemistry (FocalPress, 19
66)), "Manufacturing and coating of photographic emulsions" by Zelikman et al., Published by Focal Press (VL Zelikman et al., Making
and Coating Photographic Emulsion, Focal Press, 19
64) and the like.

US Pat. Nos. 3,574,628 and 3,
Monodisperse emulsions described in 655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff,
Photographic Science and Engineering), Volume 14,
248-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,43
It can be easily prepared by the method described in 3,048, 4,439,520 and British Patent 2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and silver halide having different compositions may be bonded by epitaxial bonding. May be
Further, it may be bonded with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed, or a type having a latent image on both the surface and the inside. Must be a type of emulsion. Among the internal latent image types, the cores described in JP-A-63-264740 /
It may be a shell type internal latent image type emulsion. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-13.
3542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643, No. 18716, and No. 30.
No. 7105, the relevant parts are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion are mixed in the same layer. Can be used.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. What is a silver halide grain whose inside or surface is fogged?
It is a silver halide grain that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
It is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited and may be regular grains or polydisperse emulsion, but monodisperse grains (at least 95% of the weight or the number of silver halide grains are within ± 40% of the average grain size). It is preferable that the particles have a particle size of

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that the fog is not fogged in advance. ..

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in the layer containing the fine grain silver halide grains. The silver coating amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less,
It is most preferably 4.5 g / m ² or less.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1 Chemical sensitizer Page 23 648 Right column Page 866 2 Sensitivity enhancer Page 648 Right column 3 Spectral sensitizer, Page 23 to 24 Page 648 Right column 866 to 868 Supersensitization Agent ~ page 649 right column 4 brightener page 24 647 page right column 868 page 5 antifoggant page 24 ~ 25 page 649 right column 868 ~ 870 page and stabilizer 6 light absorber, page 25 ~ 26 page 649 right column ~ Page 873 Filter dye page 650 Left column UV absorber 7 Anti-stain agent page 25 Right column page 650 Left column page 872 ~ Right column 8 Dye image stabilizer page 25 650 page left column page 872 9 Hardener 26 page 651 page Left column 874 to 875 page 10 Binder page 26 same as above 873 to 874 page 11 Plasticizer and lubricant page 27 page 650 right column page 876 page 12 Coating aid, page 26 to 27 page 875 to 876 surface active agent 13 Static prevention 27 Page Same as above 876 to 877 Stop agent 14 Matting agent 878 to 879

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,9
It is preferable to add a compound capable of being immobilized by reacting with formaldehyde described in No. 87 and No. 4,435,503 to the light-sensitive material. The light-sensitive material of the present invention can be incorporated into U.S. Pat.
JP-A-62-18539, JP-A-1-28355
It is preferable that the mercapto compound described in No. 1 is contained. A compound described in JP-A No. 1-106052, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, to the light-sensitive material of the present invention, irrespective of the amount of developed silver produced by the development processing. Is preferably contained. In the light-sensitive material of the present invention, the international publication WO88 / 04
No. 794, Dyes dispersed by the method described in JP-A-1-502912 or EP317,308A, US Pat. No. 4,420,555, JP-A-1-259358.
It is preferable to incorporate the dyes described in No.

The color light-sensitive material of the present invention contains phenethyl alcohol, JP-A-63-257747 and JP-A-62-1257.
272248 and 1,2-benzisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol described in JP-A 1-80941. It is preferable to add various antiseptics or antifungal agents such as 2- (4-thiazolyl) benzimidazole.

Suitable supports which can be used in the present invention are, for example, those described in RD. No. 17643, page 28, No. 18
716, right column, page 647 to left column, page 648, and No. 3 of the same.
07105, page 897.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable. The film swelling speed T _1/2 is preferably 30 seconds or less,
20 seconds or less is more preferable. The film thickness is 25 ° C and relative humidity is 5
Means the film thickness measured under 5% humidity control (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, A Green (A. G
Reen) et al., Photographic Science and Engineering (Photogr. Sci., Eng.), 19
It can be measured by using a swellometer (swelling meter) of the type described in Vol. 2, No. 2, pp. 124-129, T _1/2
Is 90% of the maximum swollen film thickness reached when the film is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds, and the saturated film thickness is defined as 1% of the saturated film thickness.
It is defined as the time to reach / 2.

The film swelling speed T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.
The photosensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150 to 500%
Is preferred.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, an aminophenol compound is also useful, but a p-phenylenediamine compound is preferably used, and a typical example thereof is 3-methyl-4-amino-N,
N-diethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-
Examples thereof include ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more kinds of these compounds can be used in combination depending on the purpose.

The color developing solution contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt,
It generally contains a development inhibitor such as a bromide salt, an iodide salt, benzimidazoles, benzothiazoles or a mercapto compound, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclo Hexane diamine tetraacetic 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.

Next, processing solutions and processing steps for the color reversal photosensitive material of the present invention other than the color developing solution will be described. Among the processing steps of the color reversal light-sensitive material of the present invention, the steps from black development to color development are as follows. 1) Black development-water washing-reversal-color development 2) Black development-water washing-photo reversal-color development 3) Black development-water washing-color development Steps 1) to 3) are all performed in US Pat.
In place of the rinse process described in No. 804,616, it is possible to simplify the process and reduce waste liquid.

Next, the steps after color development will be described. 4) Color development-adjustment-bleaching-fixing-washing-stable 5) Color development-washing-bleaching-fixing-washing-stable 6) Color development-adjusting-bleaching-washing-fixing-washing-stable 7) Color development-washing -Bleaching-washing-fixing-washing-stable 8) Color development-bleaching-fixing-washing-stable 9) Color development-bleaching-bleach-fixing-washing-stable 10) Color development-bleaching-bleach-fixing-fixing-washing-stable 11) Color development-bleaching-washing-fixing-washing-stable 12) Color development-adjusting-bleaching fixing-washing-stable 13) Color developing-washing-bleaching fixing-washing-stable 14) Color development-bleaching fixing-washing- Stable 15) Color development-fixing-bleach-fixing-washing-stable 4) to 15), the washing step immediately before the stabilizing step may be omitted, and conversely the final stabilizing step is not performed. May be. Any one of the above steps 1) to 3) and any one of steps 4) to 15) are connected to form a color reversal step.

Next, the processing liquid in the color reversal processing step of the present invention will be described. Known developing agents can be used in the black-and-white developing solution used in the present invention. Examples of developing agents include dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol), 1-phenyl-
3-pyrazolines, ascorbic acid and US Pat.
The heterocyclic compounds such as 1,2,3,4-tetrahydroquinoline ring and indrene ring described in No. 067,872 can be used alone or in combination.

In the black-and-white developer used in the present invention, other preservatives (eg, sulfite, bisulfite, etc.), buffers (eg, carbonate, boric acid, borate, alkanolamine), alkaline agents may be added, if necessary. (Eg, hydroxide, carbonate), dissolving tablets (eg, polyethylene glycols,
These esters), pH adjusters (for example, organic acids such as acetic acid), sensitizers (for example, quaternary ammonium salts), development accelerators, surfactants, defoamers, hardening agents, viscosity imparting agents, etc. Can be included.

The black-and-white developing solution used in the present invention must contain a compound which acts as a silver halide solvent.
The sulfite, which is usually added as a preservative, plays the role. The sulfite and other silver halide solvents that can be used are specifically KSCN, NaSCN, K
₂ SO ₂ , Na ₂ SO ₃ , K ₂ S ₂ O ₅ , Na ₂ S ₂ O ₅
, K ₂ S ₂ O ₃ , Na ₂ S ₂ O _{3 and the} like.

The pH of the developer thus adjusted is
The value is chosen to be sufficient to provide the desired density and contrast, but is in the range of about 8.5 to about 11.5. In order to carry out the sensitizing process using such a black-and-white developing solution, it is usually necessary to extend the time up to about 3 times the standard process. At this time, if the processing temperature is increased, the extension time for the sensitization processing can be shortened.

PH of these color developing solution and black and white developing solution
Is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally 3 liters or less per 1 square meter of the light-sensitive material, and it is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area with the air in the processing tank.

The contact area between the photographic processing liquid and the air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, more preferably 0.1. It is 001-0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-82
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. To reduce the aperture ratio, not only the steps of color development and black and white development, but also the subsequent steps,
For example, it is preferably applied in all steps such as bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The reversal bath used in the black and white developer may contain a known fogging agent. That is, stannous ion-organic phosphoric acid complex salt (US Pat. No. 3,617,282), stannous ion organic phosphonocarboxylic acid complex salt (Japanese Patent Publication No. 56-32616), stannous ion-
Aminopolycarboxylic acid complex salt (US Pat. No. 1,209,0
50), stannous ion complex salts, borohydride compounds (US Pat. No. 2,984,567),
Heterocyclic amine borane compounds (UK Patent No. 1,011,0
No. 00 specification) and the like, and the like. The fogging bath (reversal bath) has a wide pH range from the acidic side to the alkaline side and has a pH of 2 to 12, preferably 2.5 to 10, and particularly preferably 3 to 9.
A light reversal process by re-exposure may be performed instead of the reversal bath, and the reversal step may be omitted by adding the fogging agent to the color developing solution.

The silver halide color photographic light-sensitive material of the present invention is subjected to bleaching treatment or bleach-fixing after color development. These treatments may be carried out immediately after the color development without passing through other processing steps, in order to prevent unnecessary post-development, air fog and reduce the carry-in of the color developing solution to the desilvering process. In addition, in order to wash out and detoxify the sensitizing dyes and dyes contained in the photographic light-sensitive material and the color-developing agent impregnated in the photographic light-sensitive material, stop, adjust, and wash with water after the color-developing process. A bleaching treatment or a bleach-fixing treatment may be carried out after the treatment steps such as.

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

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. 17129 (July 1978), and the like, compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A-50-140129; JP-B-45. -8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5
Thiourea derivatives described in No. 61; West German Patent No. 1,12
No. 7,715, iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,4.
Polyoxyethylene compounds described in No. 30; Japanese Patent Publication No. 4
Polyamine compounds described in JP-A-5-8836; Others, JP-A-49-40943, JP-A-49-59644, and JP-A-53-
94927, 54-35727, 55-265.
Compounds described in No. 06 and No. 58-163940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Pat. No. 3,893,858, West German Patent No. 1,290,812, and JP-A-53-95630.
Compounds described in US Pat. Furthermore, US Pat.
The compounds described in No. 552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid is a compound having an acid dissociation constant (pka) of 2 to 5, specifically, acetic acid,
Propionic acid, hydroxyacetic acid and the like are preferred.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Use of thiosulfates Is generally used, and ammonium thiosulfate is most widely used. Further, it is also preferable to use thiosulfate in combination with thiocyanate, thioether compound, thiourea and the like. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

The total time for the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferred temperature range, the desilvering rate is improved,
In addition, the stain generation after the processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening the stirring, there is a method described in JP-A-62-183460, in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material, and JP-A-6-63.
No. 2-183461, a method of increasing the stirring effect, and further, moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to make the emulsion surface turbulent, thereby stirring the effect. And a method of increasing the circulation flow rate of the whole treatment liquid. Such a stirring improving means is effective in any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the agitation improving means is
It is more effective when a bleaching accelerator is used, and the accelerating effect can be remarkably increased and the fixing inhibiting effect of the bleaching accelerator can be eliminated.

The automatic developing machine used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after desilvering. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the material used such as couplers), the application, and the temperature of the rinsing water, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Pictur.
e and Television Engineers Volume 64, p. 248 ~
253 (May 1955 issue).

According to the multistage countercurrent method described in the above-mentioned document,
Although the amount of washing water can be significantly reduced, the increase in the residence time of water in the tank causes problems such as bacteria breeding and adhered floating substances to the photosensitive material. 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 ion and magnesium ion described in JP-A-62-288838 can be used very effectively. In addition, JP-A-57-
No. 8542, isothiazolone compounds, siabendazoles, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982)
It is also possible to use the bactericide described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal Society.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics and use of the light-sensitive material, but in general, the range of 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes is selected. To be done. Further, the light-sensitive material of the present invention, instead of the above water washing,
It is also possible to treat directly with the stabilizing solution. In such stabilizing treatment, JP-A-57-8543 and JP-A-5-543 have been used.
All the known methods described in JP-A-8-14834 and JP-A-60-220345 can be used.

In addition, the washing treatment may be followed by a further stabilizing treatment. As an example of the stabilizing treatment, a stabilizing agent containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing, is used. You can mention the bath. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can be added to this stabilizing bath.

The overflow solution accompanying the washing with water and / or the replenishment of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, US Pat.
Indoaniline compounds described in No. 342,597, No. 3,342,599, Schiff base type compounds described in Research Disclosure No. 14850 and No. 15159, Aldol compounds described in No. 13924. The metal salt complexes described in U.S. Pat. No. 3,719,492 and the urethane compounds described in JP-A-53-135628 can be mentioned.

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64339 and JP-A-57-14.
Nos. 4547 and 58-115438.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

[0140]

EXAMPLES Next, the present invention will be described in more detail by way of examples.

Example 1 <Preparation of Emulsion A> An aqueous silver nitrate solution and an aqueous potassium bromide solution were added to a gelatin aqueous solution kept at 75 ° C. at a pAg of 7.0 by the double jet method. This gives 0.24 μm
To obtain core grains of silver iodobromide (grain forming step 1). Further, an aqueous potassium iodide solution was added at 40 ° C. and pAg 9.5 (conversion). Further, at 75 ° C., an aqueous solution of silver nitrate and an aqueous solution of potassium bromide were added at pAg of 7.7 by the double jet method (grain growth stage 2). The compound of the general formula (I), (II) or (III) or S-3 was added immediately after the start of the double jet in the above step 1 or 2. The addition amount is 3 × 10 ^-4 mol / mol A
It was set to g.

Thereafter, emulsions A to H were washed with water at 35 ° C. by a known flocculation method, gelatin was added, and potassium chloroaurate and sodium thionitrate were added in optimum amounts to carry out chemical sensitization. Then, after adding optimum amounts of the sensitizing dyes S-1 and S-2, emulsions A to H were added to Japanese Patent Application No. 63-22.
According to the method described in Example 1- (2) of No. 0238, direct dislocation lines were observed using a transmission electron microscope. Further, regarding Emulsions A to H, European Patent No. 1
The intergranular iodine distribution was obtained according to the method described in No. 47868A. The results are shown in Table 1.

[0143]

[Chemical 12]

[0144]

[Table 1]

2 of the above emulsion per square centimeter
It was coated with a silver amount of μg. The above film was exposed as it was or after incubation (50 ° C., 80% RH for 3 days) for 1/100 seconds and the following treatment was performed. The sensitivity and fog of this sample were measured, and the results are shown in Table 2. The sensitivity was indicated by the relative value of the reciprocal of the exposure amount that gives the minimum density + 0.2.

Treatment liquid 1-Phenyl-3-pyrazolidone 0.5 g Hydroquinone 10 g Ethylenediaminetetraacetic acid / disodium 2 g Potassium sulfite 60 g Boric acid 4 g Potassium carbonate 20 g Sodium bromide 5 g Diethylene glycol 20 g Adjusted to pH 10.0 with sodium hydroxide Water Plus 1 liter

[0147]

[Table 2]

Example 2 Preparation of Sample 101 Undercoating 127 μm thick cellulose triacetate fill
Multi-layer color feeling consisting of each layer of the following composition on the support
An optical material was produced and used as a sample 101. Number is m² Hit
Represents the weight. The effects of the added compounds are as described above.
Not limited to the way.

First layer: antihalation layer Black colloidal silver 0.20 g Gelatin 1.9 g UV absorber U-1 0.1 g UV absorber U-3 0.04 g UV absorber U-4 0.1 g High boiling organic Solvent Oil-1 0.1 g Microcrystalline solid dispersion of Dye E-1 0.1 g

Second layer: intermediate layer Gelatin 0.40 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 3 mg High boiling point organic solvent Oil-3 0.1 g Dye D-4 0.4 mg

Third layer: intermediate layer Fine grained silver iodobromide emulsion with a fogged surface and inside (average grain size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) silver amount 0.05 g gelatin 0.4 g

Fourth Layer: Low Sensitivity Red Sensitive Emulsion Layer Emulsion A Silver amount 0.1 g Emulsion B Silver amount 0.4 g Gelatin 0.8 g Coupler C-1 0.15 g Coupler C-2 0.05 g Coupler C-30 0.05 g Coupler C-9 0.05 g Compound Cpd-C 10 mg High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g

Fifth Layer: Medium-Sensitivity Red-Sensitive Emulsion Layer Emulsion B Silver amount 0.2 g Emulsion C silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-30 .2 g High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion Ni silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-2 0.1 g Coupler C-3 0.7 g Additive P-1 0.1 g

Seventh layer: intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-I 2.6 mg UV absorber U-1 0.01 g UV absorber U-2 0.002 g UV absorber Agent U-5 0.01 g Dye D-1 0.02 Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 5 mg High boiling point organic solvent Oil-1 0.02 g

Eighth layer: intermediate layer Silver iodobromide emulsion with fogged surface and inside (average grain size 0.06 μm, coefficient of variation 16%, AgI content 0.3 mol%) silver amount 0.02 g gelatin 1. 0g Additive P-1 0.2g Color mixing inhibitor Cpd-A 0.1g

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion fo silver amount 0.1 g Emulsion he silver amount 0.2 g Emulsion to silver amount 0.2 g Gelatin 0.5 g Coupler C-4 0.1 g Coupler C-7 0 .05 g Coupler C-8 0.20 g Compound Cpd-B 0.03 g Compound Cpd-C 10 mg Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g High Boiling point organic solvent Oil-1 0.1 g High boiling point organic solvent Oil-2 0.1 g

The 10th layer: Medium-speed green-sensitive emulsion layer Emulsion to silver amount 0.3 g Emulsion to silver amount 0.1 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-7 0.2 g Coupler C-80 .1 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.05 g Compound Cpd-G 0.05 g High boiling point organic solvent Oil-2 0.01 g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.3 g Coupler C-7 0.1 g Coupler C-8 0.1 g Compound Cpd-B 0 0.08 g Compound Cpd-C 5 mg Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-J 5 mg Compound Cpd-K 5 mg High boiling point organic solvent Oil -1 0.02g High boiling point organic solvent Oil-2 0.02g

Twelfth layer: Intermediate layer Gelatin 0.6 g

Thirteenth layer: Yellow filter layer Yellow colloidal silver Silver amount 0.07 g Gelatin 1.1 g Color mixing inhibitor Cpd-A 0.01 g High boiling point organic solvent Oil-1 0.01 g Dye E-2 microcrystalline solid dispersion Thing 0.05g

14th layer: Intermediate layer Gelatin 0.6 g

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion Nu Silver amount 0.2 g Emulsion silver amount 0.3 g Emulsion silver amount 0.1 g Gelatin 0.8 g Coupler C-5 0.2 g Coupler C-60 .1g Coupler C-10 0.4g

Sixteenth layer: Medium sensitivity blue-sensitive emulsion layer Emulsion amount of silver 0.1 g Emulsion amount of silver amount 0.4 g Gelatin 0.9 g Coupler C-5 0.3 g Coupler C-6 0.1 g Coupler C-100 .1 g

Seventeenth layer: High-sensitivity blue-sensitive emulsion layer Emulsion emulsion Silver amount 0.4 g Gelatin 1.2 g Coupler C-5 0.3 g Coupler C-6 0.6 g Coupler C-10 0.1 g

Eighteenth layer: First protective layer Gelatin 0.7 g UV absorber U-1 0.2 g UV absorber U-2 0.05 g UV absorber U-5 0.3 g Formalin scavenger Cpd-H 0.4 g Dye D-1 0.1g Dye D-2 0.05g Dye D-3 0.1g

19th layer: Second protective layer Colloidal silver Silver amount 0.1 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver amount 0.1 g Gelatin 0.4 g

20th layer: 3rd protective layer Gelatin 0.4 g Polymethylmethacrylate (average particle size 1.5 μ) 0.1 g Methyl methacrylate / acrylic acid 4: 6 copolymer (average particle size 1.5 μ) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g

Additives F-1 to F-8 were added to all emulsion layers in addition to the above composition. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer. Further, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and p-benzoic acid butyl ester were added as antiseptic and antifungal agents.

[0170]

[Table 3]

[0171]

[Table 4]

[0172]

[Table 5]

[0173]

[Chemical 13]

[0174]

[Chemical 14]

[0175]

[Chemical 15]

[0176]

[Chemical 16]

[0177]

[Chemical 17]

[0178]

[Chemical 18]

[0179]

[Chemical 19]

[0180]

[Chemical 20]

[0181]

[Chemical 21]

[0182]

[Chemical formula 22]

[0183]

[Chemical formula 23]

[0184]

[Chemical formula 24]

[0185]

[Chemical 25]

[0186]

[Chemical formula 26]

The silver halide color photographic light-sensitive material prepared as described above was exposed and then processed according to the following steps.

Treatment process time Temperature First development 6 minutes 38 ° C. Water wash 2 minutes 38 ° C. Inversion 2 minutes 38 ° C. Color development 6 minutes 38 ° C. adjustment 2 minutes 38 ° C. Bleach 6 minutes 38 ° C. fixation 4 minutes 38 ℃ water wash 4 minutes 38 ℃ stability 1 minute 25 ℃

The composition of each processing liquid was as follows. (First developer) Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 1.5 g Diethylenetriamine pentaacetic acid / 5 sodium salt 2.0 g Sodium sulfite 30 g Hydroquinone / potassium monosulfonate 20 g Potassium carbonate 15 g Bicarbonate Sodium 12 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide 2.0 mg Diethylene glycol 13 g Water was added to 1000 ml pH 9.60. The pH was adjusted with hydrochloric acid or potassium hydroxide.

(Inversion Solution) Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 3.0 g stannous chloride dihydrate 1.0 g p-aminophenol 0.1 g sodium hydroxide 8 g glacial acetic acid 15 ml water was added and 1000 ml pH 6.00 The pH was adjusted with hydrochloric acid or sodium hydroxide.

(Color Developer) Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 g sodium sulfite 7.0 g phosphoric acid trisodium dodecahydrate 36 g potassium bromide 1.0 g potassium iodide 90 mg Sodium hydroxide 3.0 g Citrazine acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 11 g 3,6-dithiaoctane -1,8-diol 1.0g Water was added and 1000 ml pH 11.80 pH was adjusted with hydrochloric acid or potassium hydroxide.

(Preparation Solution) Ethylenediaminetetraacetic acid • disodium salt • dihydrate 8.0 g Sodium sulfite 12 g 1-thioglycerol 0.4 g Sodium formaldehyde bisulfite adduct 30 g Water was added 1000 ml pH 6.20 pH was hydrochloric acid Or adjusted with sodium hydroxide.

(Bleach) Ethylenediaminetetraacetic acid / sodium salt / dihydrate 2.0 g Ethylenediaminetetraacetic acid / Fe (III) / ammonium / dihydrate 120 g Potassium bromide 100 g Ammonium nitrate 10 g Water 1000 ml pH 5. 70 pH was adjusted with hydrochloric acid or sodium hydroxide.

(Fixer) Ammonium thiosulfate 80 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml pH 6.60 The pH was adjusted with hydrochloric acid or aqueous ammonia.

(Stabilizing Solution) Benzisothiazolin-3-one 0.02 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Water was added to 1000 ml pH 7.0

Emulsion B of Sample 101 was replaced with Emulsions A to
Samples 102 to 108 were manufactured by replacing with H. Sample 1
01 to 108 with continuous wedge 2 for 1/100 seconds
White exposure was performed with an exposure amount of 0 CMS, or as it was, or after incubation, development processing was performed in a processing step shown on a separate sheet, and sensitometry was performed. Table 6 shows the sensitometry results.
Shown in.

[0197]

[Table 6]

Sample 101 using Emulsion A did not achieve the purpose because the RL color density was greatly reduced after fresh and incubation. The sample 108 has a small drop in RL color density, but has low sensitivity. Compared to these, the sample of the present invention has both sensitivity and a decrease in color density.

[0199]

The silver halide photographic light-sensitive material of the present invention comprises
It has excellent sensitivity / granularity ratio, reduces fog, and prevents fog from occurring during storage.

Claims (2)

[Claims] 1. A light-sensitive material having at least one silver halide emulsion layer on a support, which is a regular silver halide emulsion having (111) faces and (100) faces. Has an average silver iodide content of 2 mol% or more and is 50% based on the number of the silver halide grains.
The above has 10 or more dislocation lines per grain, the relative standard deviation of the silver iodide content of each grain is 30% or less, and the silver halide grains have the following general formula (I) to
A silver halide light-sensitive material comprising an emulsion layer having a silver halide emulsion which is a grain formed in the presence of the compound represented by any of (III). General formula (I) R-SO ₂ S-M General formula (II) R-SO ₂ S-R ¹ General formula (III) RSO ₂ S-L-SSO ₂ -R ² (wherein R, R ¹ , R ² represents an aliphatic group, an aromatic group or a heterocyclic group, L represents a divalent linking group, and M represents a cation.) 2. The photosensitive silver halide light-sensitive material according to claim 1, wherein the relative standard deviation of the grain size is 20% or less.