JPS63146032A - Silver halide photographic sensitive material capable of rapid processing - Google Patents

Abstract

PURPOSE:To obtain the titled material having a rapid development property to which processing stability such as sensitivity and gradient is increased, even in case of processing the titled material with a color developer which does not contain benzyl alcohol by incorporating a silver halide particles contg. >=80mol% silver chloride and a specific spectral sensitizing dye to a silver halide emulsion layer. CONSTITUTION:The titled material contains the silver halide particles contg. >=80mol% silver halide and the spectral sensitizing dye to at least one layer of the silver halide emulsion layer. At least one layer of the photographic constituting layer contains a water soluble chloride, and the total amount of the water soluble chloride is 15-50mol% per the amount of the silver halide which is contained in the same layer to that contg. the spectral sensitizing dye shown by formula I wherein X1-X4 are each hydrogen or halogen atom, alkyl, alkoxy, aryl or hydroxy group, R1 and R2 are each alkyl group, X<-> is a pair anion, (n) is 0 or 1. Thus, the rapid processing of the titled material is made possible, and the processing stability thereof can be increased.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a silver halide photographic material. More specifically, silver halide grains having a silver chloride content of 80 mol 56 or more are used, and are suitable for rapid development processing, and even when the light-sensitive material is stored over time, fogging and changes in the legs of the characteristic curve are avoided. Soft 141 (Relating to a silver halide photographic light-sensitive material that prevents scratches. [Background of the Invention] In a method for forming a dye image using a silver halide photographic light-sensitive material, a ii!! image that has been subjected to imagewise exposure is usually In this method, a 5ytiiD color reproduction method is applied, and cyan, magenta, and yellow dye images corresponding to red, green, and blue are formed on their respective photosensitive layers. In recent years, in order to shorten the development processing time when forming such dye images, high-temperature development processing and the omission of processing steps have become common.In particular, In order to shorten the development processing time through high-temperature development processing, it is extremely important to increase the development speed in color development.The development speed in zero-color development is influenced by two directions.One is: One is a silver halide photographic photosensitive T4 $1, and the other is a color developing solution. The latter has a strong influence on the development speed, and the latter is greatly influenced by the conditions of the color developing solution, especially the type of development inhibitor.
It has been found that under certain conditions it exhibits significantly higher development rates. Haloro' with high silver chloride content: /Silver emulsion, especially tR chloride
In a halide photosensitive material having an emulsion layer consisting of silver halide grains having a content of 80 mol% or more, such as a silver halide color photographic light-sensitive material, a fog prevention 1F is used for high-temperature rapid development processing. , jmInstead of the commonly used bromides such as potassium bromide and sodium bromide (bromide ions act as anti-fogging agents), chlorides such as sodium chloride and potassium chloride, and specific organic development inhibitors are used. , for example, 5- and 6-membered adenine, guanine, benzimidazole, benzotriazole and derivatives thereof.
By using nitrogen-containing or fused nitrogen-containing heterocyclic compounds, extremely high development rates can be obtained while maintaining good photographic performance. For example, water-soluble chloride or adenine are particularly preferred development inhibitors. Therefore, the silver halide countable photosensitive material C having a silver halide emulsion layer containing silver halide grains having a silver chloride content of 10 mol % or more is hereinafter referred to as a silver chloride photographic material. ) as water-soluble chloride or adenine as current Ck
When processed with a color developer containing p-phenylenediamine-based color developing agent as an inhibitor, the development time can be significantly shortened compared to conventional color development. This is of great practical value as it is possible to reduce the size of automatic processors, reduce the amount of developer replenisher required, and reduce the pollution load.On the other hand, in silver halide photographic materials processed quickly at high temperatures, In image formation, the photographic performance (fogging,
(sensitivity, gradation, etc.) fluctuate, making it difficult to obtain photographic images of constant quality. For this reason, for example, when developing a color photographic light-sensitive material, the replenishment rate of the developing e+tl solution must be closely controlled. On the one hand, even when processing with a color developing solution of It was not possible to obtain a photographic image with satisfactory photographic performance against changes in the developer composition, [)1 (1, etc.), and there was room for improvement. The applicant filed the earlier application (
In Japanese Unexamined Patent Publication No. 59-232.342), it was discovered that by carrying out color development treatment in the coexistence of a specific organic development inhibitor and adenine, stabilization of the process to a degree of 1+ was achieved. However, in recent years, when processing silver halide photosensitive +A rice, in order to reduce the pollution load as much as possible,
In particular, there is a growing tendency to remove benzyl alcohol, which is an IL improving agent, from color developing solutions, and under such color developing processing conditions, the treated carbon C of the silver chloride photographic material is further expanded, Even with the technology described in Section 2, there was still room for improvement. The photosensitive silver halide grains have a silver chloride content of 80%.
Developing a photographic material consisting of silver chloride having mol% or more of
) II, this problem will be significantly exacerbated if storage is carried out over time.
In the results, it was found that the deterioration of the above-mentioned processing fluctuations when a silver chloride photographic material is stored over time depends on the sensitizing dye used, especially the species n1 of the blue-sensitive sensitizing dye. [Object of the Invention] The present invention has been made in view of the above-mentioned circumstances, and its first object is to remove benzyl alcohol from a color developer when forming a dye image using a silver chloride color photographic material. The object of the present invention is to provide a silver halide photographic light-sensitive material having rapid developability with increased processing stability in sensitivity and gradation even when the above is excluded. The second object of the present invention is that even when silver chloride photographic materials are stored for a long period of time,
It is an object of the present invention to provide a silver halide photographic material which prevents an increase in fog and a change in gradation when the developer conditions are changed. Halogen' having a 3r true constituent layer including at least one silver halide emulsion layer
Grudge photosensitive material! In Mi 1, at least one of the silver halide emulsion layers No. 111 contains silver halide grains containing 80 moles or more of silver chloride and a spectral sensitizing dye represented by the following general formula (1), and the photographic structure is At least one of the layers contains water-soluble chloride, and the total amount of water-soluble chloride contained in the photographic constituent layer is equal to the halogen contained in the same layer as the spectral sensitizing dye represented by the general formula (1'l). This is achieved by using a silver halide photographic light-sensitive material having a concentration of 15 to 50 mol % based on silver oxide. General formula (1) In the formula, XI, Xz, Xi and X4 each represent a hydrogen atom, a halogen atom, or an alkyl group. , does not represent an alkoxy group, aryl group or hydroxyl group.R1, and R2
each represents an alkyl group, Xo does not represent a counter anion, and n does not represent O or l. Hereinafter, the configuration of the present invention will be explained in more detail. In the compound represented by general formula [I], XI. The halogen atoms represented by X, X, and X are,
An alkyl group having 1 to 4 carbon atoms such as an ethyl group, a propyl group, a butyl group, and a methyl group are particularly preferred. A phenyl group is particularly preferred as the 7-aryl group represented by 1°X2. Examples of the alkyl group represented by R3 and R8 include a methyl group, an edyl group, a butyl group, a butyl group, and a pentyl group, and these may be branched or linear. Furthermore, these alkyl groups include those having substituents, such as sulfoconvex, hydroxyl, carboxyl, and alkylsulfonylamino groups. Below, compounds represented by general formula (1) A representative example of 6 (H) is shown below.Of course, the compounds used in the present invention are not limited thereto. 66
0408''S, each specification of U.S. Patent No. 3149105 or Japanese Patent Application Laid-Open No. 50-4127, or ``1' Cyanine Soybean Related Compounder'' written by I\-Mar.・Jens Publishers, New York, l!309) (F
, M, Ilamer+ “The Cyanine
DyeSandRpliedCoI! 1pI)u
+uls' rnte*1encc Publicis
hers, New York. 1969) can be easily synthesized according to the methods described in Items 32 to 76. The sensitizing dye represented by the above general formula [I] is preferably 0.1 mmol to 2 mmol per mole of 1 = 1 compound,
More preferably, it is added in an amount of 0.2 mmol to 1 mmol. These sensitizing dyes are preferably added at any time after the formation of silver halide grains and before coating, but particularly preferably after the formation of halide root grains and after the completion of the desalting process.・It is added before the color coupler is added. The water-soluble chlorides added to the silver halide photographic photosensitive layer of the present invention (the photographic constituent layer of rice grains include water-soluble inorganic salts such as sodium chloride, potassium chloride, calcium chloride, and magnesium chloride, and p++ of the coating solution) It includes hydrochloric acid used for jJM adjustment, water-soluble chloride produced as a result of hardening of gelatin film, etc. Furthermore, it also includes water-soluble chloride that is pre-contained in the silver halide emulsion. These water-soluble chlorides are added in such a way that the M of all the photographic constituent layers to which they are added, that is, the total content, is the added amount of the present invention, that is, the silver halide in the photographic constituent layers to which they are added, which is expressed by the general formula (1). The water-soluble chloride is added in an amount of 15 to 50 mol% to the silver halide in the layer containing the compound.Preferably it is 20 to 40 mol%. 15 mol%
If it is less than 20%, the effect of the present invention, that is, the effect of preventing increase in processing variation due to storage over time, will hardly be obtained;
If the amount exceeds 50 mol%, even when using the sensitizing dye represented by the -4J formula [I], not only will high sensitivity not be achieved, but the high phenomenon inherent to silver chloride will occur. There is a tendency to reduce sexuality. The total amount of water-soluble chloride added is calculated based on the amount of halogen 1
Arsenic photographic material is soaked in a certain amount of pure water rIJ for 7iJ (approximately 1 to 2 minutes), and the eluted chloride is subjected to potentiometric titration with a water-soluble silver salt (for example, Til'l aqueous solution, etc.). This can be easily confirmed by The silver chloride composition used in the silver chloride photographic material of the present invention is 80%
The silver halide emulsion containing 110 mol % or more of silver chloride, preferably 90 mol % or more, more preferably 955 mol % or more of silver chloride, preferably contains 2 mol % or more of silver chloride.
They are silver particles or silver chloride particles. It is preferable that the silver iodide grains having a chloride content of 80 mol % or more do not substantially contain silver iodide. The silver iodide ratio is preferably 2 mol % or less, more preferably 0.5 mol % or less, particularly preferably 0 mol %. It is preferable that the weight percent of the total -C halide grains in the silver emulsion layer is 80 or more, and more preferably 100 or more.
% is preferable. Further, the average silver chloride content of the emulsion layer containing such silver halide grains is preferably 80 mol% or more, more preferably 85 mol% or more. When the silver halide grains of the present invention having a silver chloride composition of 80 mol % or more have a silver bromide composition, the silver bromide U region can be localized within the halide 2R grains. Localization here means at least 70 mol% or more preferably 90 mol% or more of hv bromide when the silver halide emulsion is analyzed by X-ray diffraction.
It refers to a silver halide emulsion in which the peak corresponding to the silver halide composition having the &H structure is clearly separated from the peak of the silver chloride composition. Such silver halide grains in which silver bromide is localized are silver halide grains having a layered structure of silver bromide and silver chloride, and silver chloride grains having a ratio of 1. This refers to silver halide grains in which 1R bromide grains are epitaxially bonded. Such silver halide grains are disclosed in, for example, JP-A-59-162.
It can be formed according to the method described in Japanese Patent No. 540, Japanese Patent No. 60-136735, and the like. The silver halide emulsion containing 80 mol% or more of silver chloride according to the present invention is preferably used as a blue-sensitive silver halide emulsion containing a compound represented by the general formula (1). When the silver halide photographic material is a multilayer color photographic material, in addition to the blue-sensitive silver halide emulsion layer, it has a green-sensitive silver halide emulsion layer and a red-sensitive halide 5E1i layer. It is preferable. Preferably, the silver halide composition of the silver halide emulsion used in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer is monochrome light-sensitive silver L1.
It is preferable to use silver chloride bromide containing 0 mol% or more or silver chloride emulsion 1 (silver chloride composition similar to the silver gene emulsion layer) (1N)
The halogenation particles used in the halogenation limiting agent of the present invention, which are preferred for the acid method, neutral method, and ammonia? It may be 1q in either law. The particles may grow all at once, or they may grow after forming seed particles. l・may be,
The method of creating seed particles and the method of growing them are the same.
may also be different. Silver halide emulsions can be prepared by mixing dove ions and ions at the same time, or by mixing one in a solution where the other is present, but the critical growth rate of silver halide crystals is In addition, C7 is preferable in order to uniform the particle size distribution by sequentially and simultaneously adding halide ions and root ions while controlling the PL+ and pAg in the mixing pot. Further, it is also possible to carbonize the halogen composition of the particles by using a convergence run method after the growth, within a range that does not impair the effects of the present invention. In this case, the amount of bromide/ion to be added later is usually 5 mol % or less, preferably 3 mol % or less, based on the total silver halide. The silver halide emulsion of the present invention is the! l! During production, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled by using a silver halide solvent if necessary. Examples of the halogenated tl'RII include ammonia, thiourea derivatives such as thiourea, thiourea, and 4-substituted thiourea, and imiguzole derivatives. Regarding thioethers, U.S. Pat. No. 3,271°157;
You can refer to the same No. 3.790,387, the same No. 3.574,628, etc. When using a solvent, is there a reaction if the solvent is other than ammonia? 10-1 to 1°0 weight of 8 liquids! ! 9i, especially 10-2
~10-1% is preferred. In the case of ammonia, it can be selected arbitrarily. Halogenated SN used in the silver halide emulsion of the present invention
The particles may have regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, or may have irregular crystal shapes such as C7, spherical, or plate shapes. In these particles, any ratio of the (100) plane to the (111) plane can be used. The average grain size of the silver halide grains of the present invention (grain size
1° represents the diameter of a circle having an area equal to the projected area) is preferably 3 μm or less, particularly preferably 1 μm or less, most preferably 0.8 μm or more. For the silver halide grains of the present invention, /41, it is necessary to chemically sensitize the silver halide grains by a conventional method. In other words, more sulfur! 8 methods, seleno sensitization method, 'J magen sensitization method,
A noble metal sensitization method using gold or other noble metal compounds may be used alone or in combination, but it is particularly preferred to use at least a sulfur sensitizer. Suitable chemical sensitization methods include, for example, British Patent No. 618.
No. 061, No. 1,315,755, No. 1 + 3',
US Pat. , No. 083, 2,410,613:)
No. 2,419. ! No. 174, 2. =148,06
No. 0, No. 2 + 487,830, No. 2.51 Fl. C198, 2,521.926, 2. ! '54
No. 21361, No. 2゜' J911,637, No. 2,
No. 728.668, No. 2,739,060, No. 217
43+18= issue, 2,743. IFi3-sweat, same 2
, 98:'i, No. 609, 2,983,610
Month, No. 31021.215, No. 3,026゜203
No. 3,297,446, No. 3,297. =I4
No. 7, No. 3゜361.564, No. 3t4'-1,9
14, q, No. 3,554.757, r'W +115
6 tl 1631 +, 3 + 56J + 63
J No. 3+591. +385- issue, same ζ! 165
ti 1 'J 5 +', 1 issue, 1 Tsukasa, '1,76
No. 1,267, same +++7721 (No. 131,: Tsukasa
, No. G57+771, 3. a9L446, 3°90, i, 714, 3. ! 104.・No. 115, No. 3,130,167, No. 3,984,249, Tsukasa 4.05, 1.・No. 157, No. 4,067.740,
Research Disclosure (Re: r r
r:, hlliclosure) No. 12008, No. 13452, No. 13654, r, )1. James “The Theory of Photography Inc.” (Ding,!1.PanXe5: TheTh
eory of thp r'hQLographic
Proce:S,) (4thRd, Macmill
It is preferable to sensitize using the chemical sensitizers and sensitization methods described in J. Ian, 1977), pages 67 to 76. When a front window optical silver halide emulsion having 10 mol % or more of the above-mentioned silver chloride composition of the present invention is subjected to blue spectral sensitivity using the 12 colors I expressed by the formula (1), It is also possible to carry out spectral sensitization using a known η jj15 dye other than the sensitizing dye represented by the general formula C1). In this case - the window color scheme, which is subtracted by the form rl), contains 40 moles of the total blue sensitizing dye used in the halogenated 1rL milk 11 - preferably 60 mol% L Be used above. A useful sensitizing dye used with the sensitizing dye represented by the general formula C1) is, for example, West German Patent No. 929.080. , U.S. Patent No. 2,231,658, U.S. Patent No. 2,49
3.748, F! No. 2.503,776, No. 2,51
No. 9,001-, No. 2,912,329, No. 3, 6
56, No. 959, No. 3,672.8 No. 7, No. 3.6
! 14゜217, 4,025,319, 4,0
No. 46,572, British Patent 1.2 = 12.538 ”1
, described in Special Publication No. 44-1.1000, No. 52-24844, etc.! I can give back what is given to me. In addition, green-sensitive sensitizing dyes [useful sensitizing dyes used in raw silver halide emulsions include, for example, U.S. Pat.
No. 2,945°763, British Patent No. 505,979
Representative examples thereof include dianine dyes, merocyanine dyes, and complex cyanine dyes as described in No. Furthermore, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat. , No. 454, 629, 2
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in No. 1, etc. Examples of dyes that do not absorb visible light or substances that do not substantially absorb visible light and exhibit supersensitization include formaldehyde condensates of aromatic organic acids (for example, those described in U.S. Pat. No. 3,437,510). ), cadmium salt,
azaindene compounds, aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat. No. 2,933,
No. 390 and No. 3,635°721). Fangoku Patent No. 3゜615.613, No. 3,61
No. 5.641, No. 3,617.2, No. 5, No. 3,635
．． Plowing-1 described in No. 721 is useful for one rod. The purpose of the halogenated emulsion of the present invention is to prevent solubility during the manufacturing process, storage, or photographic processing of photosensitive materials, or to maintain stable rotational performance. during chemical ripening, at the end of chemical ripening, and/or at chemical μ
After completion of the formation and before coating the silver halide emulsion, compounds known in the photographic industry as anti-fogging agents or stabilizers can be added. Although it is advantageous to use gelatin as the binder (or protective colloid) for the silver halide emulsion of the present invention, gelatin may be used as the binder (or protective colloid) for the silver halide emulsion of the invention. Proteins, spear-induced 2! bodies, cellulose derivatives, mounds or co-1 (1) bodies 1111kii)・
♀Jl aqueous colloids such as aqueous polymeric substances can also be used. Examples of gelatin include lime-processed ceratin, acid-processed gelatin, Bretch, C. of Science of Japan (Bul.
l, Sac,, S+:1. PI+oL, Japa
n): 4o. 16, p. 30 (1966). j; Enzyme-treated ze and margin Latin may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. Examples of gelatin 414 include gelatin, for example, acid halides, acid halides; Epoxy compounds such as those obtained by reacting various epoxy compounds are used.Specific examples thereof include U.S. Patent No. 2,6t4,92 [
No. 1, No. 3,132,945, No. 3.186.846
No. 3.312.553, British Patent 8G1.414
No. 1゜ (j33. IFt No. 9, No. 1. O05, 71
No. 14, Japanese Patent Publication No. 42-26845, etc. Proteins include albumin, casein, se/L/
For the rJ-su conductor and 1.7, sulfuric acid esters of bitroxyethyl cellulose and carboxymethyl cellulose are preferred, and as the four conductors, sodium alginate and starch primary conductors are preferred. The graft polymer of gelatin and other polymers may be a single (homo) or copolymer of vinyl monomers such as gelatin, acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc. A grafted material can be used. Particularly preferred are graft polymers of seratin with polymers having some degree of compatibility, such as acrylic acid, acrylamide, methacrylamide, hydroxyalkylmethacrylate-1-, examples of which are described in U.S. Pat. No. 2,763. , No. 625, No. 2,831,767,
Same 2. 956, No. 884, etc. Typical synthetic hydrophilic polymer substances include polyvinyl alcohol, polyvinyl alcohol partial acetal, and poly-N-
Single or copolymers of vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinyl alcohol, etc.
, for example, West German patent application (01.5) 2,312,708
No. 3,620,715, U.S. Patent No. 3,879,
No. 205 and Japanese Patent Publication No. 43-7561. The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention are formed by crosslinking binder (or protective colloid) molecules and forming rIIl. Hardening can be achieved by using one or more hardening agents that increase strength. A hardening agent can be added to the processing solution to harden the photosensitive material to such an extent that it is not necessary to add a hardening agent, but it is also possible to add a hardening agent to the processing solution. As a hardening agent, aldehyde type, aziridine type (for example, PB Report, 19,921, U.S. Pat. No. 2,950)
, No. 197, No. 2.964.404, No. 2.98
No. 3,611, No. 3,271,175, Japanese Patent Publication No. 16-40898, Japanese Patent Application Publication No. 16-9131
5), isoxazole systems (for example, those described in U.S. Pat. No. 331,609), epoxy systems (for example, those described in U.S. Pat. No. 3,047,39,
No. 1, West German Patent No. 1,085,663, British Patent No. 1
．． Specifications of No. 033,518, Japanese Patent Publication No. 48-3549
5), vinyl sulfone type (for example, PB Revo-1-19,920, West German Patent No. 100,942, West German Patent No. 2,337,412, West German Patent No. 2,5
No. 45,722, No. 2,635,518, No. 2,74
No. 2,308, No. 2,749,260, British Patent No. 1
．． No. 251.091, Patent Application No. 4236, 1973, No. 4
8-110996, U.S. Pat. No. 3,539,644, and U.S. Pat. No. 3,490,911)
, acrylic loyl type (for example, Japanese Patent Application No. 40-27949)
No. 3,640,720), carbodiimides (e.g., those described in U.S. Patent No. 2.
No. 9311.892, No. 4,043,818, No. 4,
No. 061,499, each detail indented, Japanese Patent Publication No. 46-38715, Japanese Patent Application No. 4! Q-15095), triazine type (for example, West German Patent No. 2.41n,
No. 973, No. 2,553.915, U.S. Patent No. 3, 3
Details of No. 25,287, JP-A-52-12722
No. 822,061, US Pat. No. 3.623.13
No. 78, 3,396. Specifications G of No. 029, No. 3,226, 23, 1, Japanese Patent Publication No. 47-18578, No. 8579, No. 47-4
8896) and others, ``reimide type, γ-cetylene type, methanesulfonic acid ester type, (
N-methylol-based hardeners can be used in combination with Chinese and German hardeners. Useful combination techniques include, for example, i
German Patent No. 2+ 4'17, 5th 7? ,, same 2,50
No. 5,746, No. 2,514.245, U.S. Patent No. 4
, No. 047,957, No. 3,832, 181, No. 3
, 840, 370, special specification 1, 1977-433
No. 19, No. 50-63062, No. 52-127329
Examples include combinations described in Japanese Patent Publication No. 4B-32364. When color development is carried out using the halogenated emulsion of the present invention, the oxidized form of an aromatic primary amine phenomenon agent (for example, r--, diamine, nylenediamine, aminophenol derivatives, etc.) is used for compounding. A dye-forming coupler is used that reacts to form a dye. The dye-forming couplers are typically selected for each emulsion layer so that a dye is formed that absorbs the angry spectrum light of the emulsion layer;
A yellow dye-forming coupler is used in the blue-sensitive emulsion layer, a magenta dye-forming coupler is used in the green-sensitive emulsion layer, and a fluorescent dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, photosensitive materials capable of photographing with silver halide can be produced using different combinations from the above combinations.17. But that's fine. It is preferable that these dye-forming couplers have a group called balas i in the molecule, which has 8 or more carbon atoms and which makes the cabbage non-diffusive.
Either 2-equivalent coupler may be used because it only forms a molecular dye, but in the color photographic material of the present invention, a 2-equivalent coupler is preferable from the viewpoint of rapid processing. By coupling with oxidants, development accelerators, bleaching accelerators, development agents, halogenated eye melts,!
Containing compounds that release photographically useful fragments such as PI colorants, hardeners, fogging agents, antifogging agents, chemical sensitizers, spectral sensitizers, and deformation. I can do it. Colored couplers that have a color correction effect on these dye-forming couplers, or
■This festival, DIR coupler, which releases an inhibitor and improves image sharpness and image graininess, may be used in combination.
It is preferable that the dye formed from the IR coupler is of the same type as the dye formed from the dye-forming coupler used in the same emulsion layer ζ, but if the color turbidity is not noticeable, a different method may be used. In place of the DIR coupler, a DIR compound which, when used with or in combination with the coupler, undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used. May be used. The Dln couplers and DIR compounds used include those in which an inhibitor is directly attached to the coupling chain, and those in which the inhibitor is directly attached to the coupling chain.
1! It is bonded to the camping position via the i group, and the inhibitor is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular premature transfer reaction at the base circle separated by the coupling reaction. (referred to as timing DIR couplers and timing DIR compounds). Further, depending on the purpose, inhibitors that are diffusible after release and those that are not so diffusible can be used alone or in combination. Aromatic number one? Although a coupling reaction is carried out with the oxidized product of a dye-forming developer, a colorless coupler that forms a dye can also be used in combination with a dye-forming coupler. As the yellow dye-forming coupler to be used in combination with a general silver halide emulsion sensitized with the sensitizing dye represented by formula (I) of the present invention, various acylacetanilide couplers are preferably used. Can be used. Among these, benzoyljcetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used are given in British Patent No. 1.07'
7.1174, Japanese Patent Publication No. 45-40757, Japanese Patent Publication No. 4
No. 7-1031, No. 47-26133, No. 4B-94
No. 432, No. 50-8765θ, No. 51-3631, No. 52-115219, No. 54-99433, No. 54-133329, No. 56-30127, U.S. Special Fraud No. 2,875.057, No. 3,253.924,
3,265.506, 3,408.194, 3,551,155, 3,551,156, 3
, 664°841, 3,725.072, 3,
730.722, 3゜891.445, 3.9
00.483, 3.929.484, 3.93
No. 3,500, No. 3,973.968, No. 3,990
, No. 896, No. 4,012,259, No. 4,022,
No. 620, No. 4,029゜No. 508, No. 4,057,4
No. 32, No. 4,106,942, No. 4゜133, 95
No. 8, No. 4,269.936, No. 4, 286, 0
No. 53, No. 4,304,845, No. 4,314,02
No. 3, No. 1, 336, No. 327, No. 4,356,
No. 258, No. 4,386.155, No. 4,401, 7
This is described in No. 52, etc. In addition, as the magenta color hole-forming cover, 5-pyrazolono couplers, virazole...\F1° midazole couplers, pyrazoloazole couplers, and closed acyl nitrile couplers are preferably used. Specific examples of magenta couplers that can be used advantageously are disclosed in Japanese Patent Application No. 5O-1640EI2, Japanese Patent Application No. 5B-167326,
No. 5B-206321, No. 58-214863, No. 58-217339, No. 59-24653, Tokuko No. 40-6031, No. 40-6035 Gin, No. 45-4
075'/No. 47-27411-, No. 49.37
No. 854, Japanese Patent Application Publication No. 5013041, No. 51-2654
No. 1, No. 51-37646, No. 51-105820, No. 52-42121, No. 53-123+29, No. 53.125B35, No. 53-129035, No. 54-485.10, No. 56- No. 29236, 56
-75648, 57-17950, 57-35
No. 858, No. 57-146251, No. 59-9943
No. 7, British Patent No. 1,252.418, U.S. Patent No. 2
．． No. 600.788, No. 3,005,712, No. 3,
No. 062,653, No. 3.127.269, No. 3.2
No. 14,437, No. 3,253.924, No. 3,31
No. 1,476, No. 3,419.39L, No. 3.519
．． 3') No. 1, No. 3,558,319, No. 3,582
．． No. 322, No. 3,615,506, No. 3,658.
No. 544, No. 3,705,896, No. 3.725.
+167, 3.158.30, 3,823,
t: ; No. 6, No. 3,834.9118, I, 89
1+445, 3.907,571, 3,926
, 6; No. 31, No. 3,928,044, No. 3,935
, No. 015, No. 3,9 (io, No. 571, No. 4.076
．． No. 5r+3-, No. 4,133,6 (No. 16, No. 4+2
No. 37+217-, No. 4,241゜168, No. 4,
264. 'l? , No. 3, No. 4.3 (iL, No. 235, No. 4.310,623, etc.). Furthermore, as the cyan dye-forming coupler, naphthol couplers and phenol couplers are preferably used. Specific examples of cyan couplers that may be advantageously used are given in British Patent No. 1,038,331;

[. No. 543.040, Japanese Patent Publication No. 18-36894, Japanese Patent Publication No. 1983-9838, No. 50-137137, No. 5
l-14682E! No. 5. J-] No. 05226, No. 54-115230, No. 56-29235, No. 56
-104333, 56-126833, 57-
No. 133650, No. 57-155538, No. 57-2
No. 04545, No. 58-118643, No. 59-3
No. 1953, No. 59-31954, No. 59-1965
No. 6, No. 59-124341, No. 59-166956
No. 2, U.S. Patent No. 2,369.929, U.S. Patent No. 2,423,
No. 730, No. 4,434,272, No. 2.47. i,
No. 293, No. 2,698,794, No. 2,772,1
No. 62, No. 2,801,171, No. 2,895,82
No. 6, No. 3,253.924, No. 3,311,476
No. 3,458,315, No. 3,476, 563, No. 3,591,383, No. 3,373.316,
Same, No. 3,758,308, No. 3,767.411,
3,790,384, 3,880.661, 3,926.634, 4,004.929, 4
, No. 009,035, No. 4,012,258, No. 4.
No. 052.212, No. 4,124,396, No. 4,
134, No. 766, 4. I, '18.258,
4,146,396, 4,149.886, 4.178.183, 4,205,990, 4
, 254.212, 4,264.722, 4,
No. 288,532, 4°296.19! 'I No. 4
, No. 296,200-, No. 4,299,914, No. 4
, No. 333,999, No. 4,334,011, No. 4,
No. 386.155, No. 4,401,752, No. 4,4
No. 27,767 etc. are listed here. In addition to the above-mentioned compounds, various photographic additives can be added to the silver halide photographic light-sensitive material containing the abrasive emulsion of the present invention. As an example of such, for example, ultraviolet absorbing side (e.g., hesiphenone compounds, benzotriazole compounds, etc.)
, development accelerator (e.g. 1-aryl-3-pyrazolito'
surfactants (e.g. alkylnaphthalene sulfonates, alkyl succinate sulfonates, itaconate sulfonates, polyalkylene oxide compounds, etc.), water-soluble anti-irradiation dyes (e.g. azo type compounds, styryl type compounds, oxonol type compounds, anthraquinone type compounds, triphenylmethane type compounds, etc.), film property improvers (e.g. glycerin, polyalkylene glycol, polymer latex,
solid or liquid paraffin, etc.) color turbidity inhibitors (diffusion-resistant hydroquinone compounds, etc.), dye image stabilizers (e.g. hydroquinone derivatives, gallic derivatives, phenol compounds, hydroxychroman compounds, polyalkylpiperidine compounds, aromatic compounds) amine compounds, etc.), water-soluble or oil-soluble fluorescent whitening agents, ground color tone regulators (diffusion-resistant colored dyes, etc.), and the like. In particular, when the above-mentioned diffusion-resistant hydroquinone compound used as a color clouding preventive agent is used as a stain preventive agent in a silver halide emulsion layer, treatment when stored over time with the silver halide photographic light-sensitive material of the present invention It has the advantage that the amount of variation during improvement further increases. Examples of preferably used diffusion-resistant halodroquinone compounds include US Pat. No. 2,360,296. No. 2,728,659, No. 3,700.453, Japanese Patent Publication No. 50-23813, Japanese Patent Application Publication No. 97021-1987,
Compounds described in Japanese Patent Publication No. 58-24141, Japanese Patent Publication No. 5B-47702, and Japanese Patent Publication No. 54-29637 are included. In the following margin, typical examples of the compound will be listed. The amount of the hydroquinone compound is 0.001 to 0 per mole of silver halide in the emulsion layer containing the compound.
．． 2 mol, preferably in the range of 0.005 to 0.1 mol. Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
Compounds, image stabilizers, color capri inhibitors, ultraviolet absorbers,
Among fluorescent brighteners, various methods such as solid dispersion method, latex dispersion method, and oil-in-ice emulsion dispersion method can be used for dispersing hydrophobic compounds such as couplers. It can be selected as appropriate depending on the chemical structure and the like. The oil-in-ice emulsion dispersion method can be applied to various methods for dispersing hydrophobic additives such as couplers, and usually has a boiling point of about 1
A high boiling point organic solvent of 50°C or higher, if necessary, a low boiling point,
and/or dissolved in combination with a water-soluble organic solvent, using a surfactant in a hydrophilic binder such as gelatin, and dispersing it using a stirrer, homogenizer, colloid mill, flow jet mixer, ultrasonic device, etc. After emulsifying and dispersing the colloid, it may be added to the desired hydrophilic colloid layer. A step of removing the low-boiling organic solvent may be included simultaneously with the dispersion or dispersion. The ratio of high boiling point organic solvent to low boiling point organic solvent is preferably 1:0.1 to 1:50, more preferably 1:1 to 1:20. High boiling point oils include organic compounds with a boiling point of 150°C or higher, such as phenol derivatives, phthalate alkyl esters, phosphate esters, citric acid esters, benzoate esters, alkylamides, fatty acid esters, and trimesic acid esters, which do not react with the oxidized form of the developing agent. A solvent is used. Examples of high-boiling organic solvents that can be used include U.S. Pat.
, No. 353,262, No. 2,852,383, No. 3,
No. 554,755, No. 3,676.137, No. 3,6
76.142, 3,700゜454, 3,74
8゜141, 3,779.765, 3,837
, No. 863, British Patent No. 958,441, No. 1,222
, No. 753, 0LS2.538,889, Japanese Unexamined Patent Publication No. 1973-
No. 103'1, No. 49-90523, No. 5O-23F
i23 No. 51-26037, No. 51-27921
No. 51-27922, No. 51-26035, No. 51-26036, No. 50-62632, No. 53-
No. 1520, No. 53-1521, No. 53-15127
No. 54-119921, No. 54-119922, No. 55-25057, No. 55-36869, No. 5
No. 6-19049, No. 56-81836, Special Publication Showa 4B
-29060 etc. Low-boiling or water-soluble organic solvents that can be used in conjunction with or in place of high-boiling solvents are disclosed in U.S. Pat.
1, No. 2,949.360, and the like. Organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, Hensen, etc.
Water-soluble organic solvents include acetone, methyl isobutyl ketone, β-ethoxyethyl acetate, methoxy glycol acetate, methanol, ethanol, acetonitrile, dioxane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, diethylene glycol monophenyl Examples include ethyl and phenoxyethanol. Surfactants can be used as dispersion aids, such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfonates, alkyl sulfates, alkyl phosphates, sulfosuccinates, and sulfoalkyl polyesters. Anionic surfactants such as oxyethylene alkylphenyl ethers, steroidal saponins, nonionic surfactants such as alkylene oxide derivatives and glycidol tM iB forms, amino 6X1ffiJ? It is preferred to use amphoteric surfactants such as , aminoalkyl sulfone Ruff, and alkylhetaines, and cationic surfactants such as quaternary ammonium salts. Specific examples of these surfactants can be found in the "Surfactant Handbook"
(Sangyo Tosho, 1966) and "Emulsifier/Emulsifier Research/Technical Data Collection" (Science Panronsha, 1978). For example, US Pat. No. 4, 1
No. 99.363, 4,214. (No. 147, 4, 2
No. 03,716, No. 4,247.627, Japanese Unexamined Patent Publication No. 1973
-74538, 51 1st layer 9942, 51 1st layer 9
The methods described in No. 943, No. 54-32552, etc. are preferred. When carrying out color development using the silver halide color photographic light-sensitive material of the present invention, a color development process, a bleaching process, a fixing process, and if necessary a water washing process and/or a stabilizing process are carried out. Instead of the processing process using a bleaching solution and the processing process using a fixing solution, it is also possible to carry out the bleach-fixing processing process using a bath bleach-fix solution, and color development, bleaching, and fixing can be carried out in one bath. It is also possible to carry out a monobath processing step using a one-bath development, bleach-fixing treatment solution that can be carried out in the following manner. In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development process, an activator treatment process may be performed in which a color developing agent or its precursor is contained in the material and the development process is performed using an activator solution, or an activator treatment process may be performed instead of the monobath process. The treatment, bleaching, and fixing treatments may be performed simultaneously. Representative treatments among these treatments are shown below. (These treatments are carried out as the final step, which is either a washing process, a stabilization process, a washing process, or a stabilization process.) (1) Color development process - bleaching process, fixed fixation process (2) ) Color development process - Bleach-fixing process (3) Pre-hardening process - Neutralization process - Color development process - Stop fixing process - Water washing process - Bleaching process Constant fixing process - Washing process - Post hardening process (4) Color development process - Water washing process - Supplementary color development process - Stop process - Bleach process Constant fixation process (5) Monobath process (6) Activator process - Bleach fixing Processing process (7
) Finishing process - Bleaching process Constant fixation process Below, when the present invention is applied to a silver halide color photographic light-sensitive material, the above-mentioned process (2) which is preferably used when processing the material will be described in detail. do. The color developing agent used in the color developing solution is typically an aromatic primary amine compound, especially a P-phenylene diamine compound, and preferred examples include N, N-
Diethyl-P-phenylenediamine hydrochloride, N-ethyl-■)-phenylenediamine salt fi salt, N,N-dimethyl-P-phenylenediamine hydrochloride, 2-amino monolayer-
(N-ethyl-N-dodecylamino)-toluene, N-
Ethyl-N-(β-methanesulfonamidoethyl)-3
-Methyl-4-aminoaniline sulfate, N-ethyl-N
-β-hydroxyethylaminoaniline, 4-amino-
N-(2-methoxyethyl)-N-ethyl-3-methyl? Examples include niline-p-+-luenesulfonate, N,N-diethyl-3-methyl-4-aminoaniline, N-ethyl-N-(β-hydroxyethyl)-3-methyl-4-aminoaniline, etc. . These color developing crude drugs may be used alone or in combination of two or more, and one or more of these color developing agents and other black and white developing agents such as hydroquinone, 1-phenyl-3-pyrazolidone , N-methyl-P-aminophenols. This color developing agent may be included in the silver chloride color photographic light-sensitive material of the present invention. In this case, the amount of the color developing agent added is in the range of 0.2 mol to 2 mol, preferably 0.2 mol to 2 mol, per 1 mol of gl halide contained in the silver chloride color photographic light-sensitive material.
．． It ranges from 4 mol to 0.7 mol. When the silver halide color photographic light-sensitive material to which the present invention is applied is subjected to color development processing, N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl- Particularly preferred is 4-aminoaniline sulfate. In addition to the above-mentioned color developing solution, the color developing solution may contain alkaline agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, tribasic sodium phosphate, potassium carbonate, potassium hydrogen carbonate, N, N-bis(methoxy), etc. Preservatives such as ethyl) hydroxylamine, N, N-diethylhydroxylamine, triethanolamine, jetanolamine, glucose, organic solvents such as methanol, ethanol, butanol, ethylene glycol, diethylene glycol, citrazic acid and polyethylene glycol, etc. Development regulators, optical brighteners, heavy metal ion hiding agents, development accelerators, etc. Photography → When containing various photographic additives known in the field as necessary, silver chloride color photographic sensitizers The development speed of the material is drastically reduced, and the object of the present invention cannot be achieved. The bromide ion concentration in the color developer is approximately O, 1g or less, preferably 0.05g, per 12 color developer in terms of potassium bromide.
It is as follows. The effects of the present invention are particularly remarkable when a water-soluble chloride is used as a development regulator in the color developing solution. The water-soluble chloride used is used in an amount of 0.5 g to 5 g, preferably 1 g to 3 g, per 11 parts of the color developing solution in terms of potassium chloride. In the color developing solution, an organic development inhibitor described in Japanese Patent Application Laid-open No. 58-95345 can be further used as long as it does not impair the present invention. Preferably, adenine and guanine are used in the color developing solution in an amount of O to 0.02 g/1. The pH of the developer of the present invention is 9.5 or higher, preferably 13 or lower. It has been known that development can be accelerated by increasing the pH of the developer, but in the silver halide color photographic light-sensitive material of the present invention, even if the pH is 11 or less, the development can be accelerated at a sufficient temperature of 40°C. It will be done. The bleaching agent used in the bleach-fixing process that is carried out subsequent to the color development process is preferably a metal complex salt of an organic acid, and an organic acid such as aminopolycarboxylic acid or oxalic acid or citric acid is used to bleach metals such as iron, cobalt, or copper. It is a coordinated ion. The most preferred organic acids used to form such metal complexes include polycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these include the following. (1) Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N, N', N'
-) diacetic acid [4] propylene diaminetetraacetic acid [5] nitrilotriacetic acid [6] cyclohexanecyaminthi-1-l-acetic acid [7] iminodiacetic acid [8] dihydroxyethylglycine citric acid (or tartaric acid)

[9] Ethyl etherdiaminetetraacetic acid (10) Glycol etherdiaminetetraacetic acid [I1] Ethylenediaminetetrapropionic acid [I2] Phenylenediaminetetraacetic acid [I3] Ethylenediaminetetraacetic acid disodium salt [I4] Ethylenediaminetetraacetic acid tetra(trimethylammonium) ) salt [I5] Ethylenediaminetetraacetic acid tetrasodium salt [I6] Diethylenetriaminepentaacetic acid pentasodium salt [I7] Ethylenediamine-N-(β-oxyethyl)
-l. N',N'-Triacetic acid sodium salt [I8] Propylene diamine tetraacetic acid sodium salt [I9] Nitriloacetic acid sodium salt [20] Schiff 1. ] Hexanediaminetetraacetic acid sodium salt These bleaches are 5-450g/j! , more preferably 20 to 250 g/12. The bleach-fix solution contains a halogenation-limiting binder in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. In addition, a bleach-fix solution consisting of an ethylenediaminetetraacetate iron (I [[) complex salt bleach and a small amount of a halide such as ammonium bromide other than the above-mentioned halogenation-limiting adhesive, or conversely, a bleach-fix solution containing a small amount of a halide such as ammonium bromide or A bleach-fix solution with a composition containing a large amount of a halide, such as a bleach-fix solution, and a special composition consisting of a combination of an ethylenediaminetetraacetate iron (I) complex salt bleach and a large amount of a halide such as ammonium bromide. A bleach-fix solution or the like can also be used. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can. The halogenation-limiting adhesive contained in the bleach-fix solution includes compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium periosulfate, etc., which are used in ordinary fixing processes. Typical examples include periosulfates such as ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, and thioethers. These fixing agents are used in an amount of 5 g/1 or more, within the range that can be dissolved, but generally 70 g to 250 g/7
! Use with. The bleach-fix solution contains boric acid, borax, sodium hydroxide,
Various pH 11 buffering agents such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide can be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, and organic A solvent and the like can be contained as appropriate. The bleaching constant M'tfl used in the present invention includes JP-A No. 46-2
No. 80, Special Publication No. 45-8506, No. 46-1 layer No. 56,
Belgian Patent No. 770,910, Special Publication No. 45-883
6, No. 53-9854, JP-A-54-71634 and JP-A-49-42349, etc., can be added. The bleach-fix solution is used at a pH of 4.0 or higher, but is generally used at a pH of 5.0 or higher and 9.5 or lower, preferably at a pH of 5.5 or higher and a pH of 8.5 or higher and 1-2 for processing. The temperature is 80°C or less, which is 3°C or more, preferably 5°C or more lower than the processing temperature of the color developer, but preferably 55°C or less to prevent evaporation. . The bleach-fixing time is within 90 seconds, preferably within 60 seconds. Color photosensitive materials that have been subjected to color development and bleach-fixing processes must be washed with water to remove unnecessary processing chemicals. 58434634 and 5
No. 848631 and Japanese Patent Application No. 58-2709 and No. 59
A stabilization treatment as an alternative to water washing as shown in Japanese Patent Application No.-89288 may also be performed. When each of the color development, bleach-fixing, and stabilization methods of the present invention is processed while continuously replenishing, the replenishment rate of each replenisher is 100 to 10 QOmN per color photosensitive material In (preferably 150 to 500 mJ!). [Example] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these. Example-1 One side of a 170 g/rrf paper support polyethylene,
On the other side of a support laminated with polyethylene containing II weight percent of anatase titanium dioxide, corona discharge is applied to the titanium dioxide-containing polyethylene side, and the following layers are sequentially applied. The amounts added are expressed per liter unless otherwise specified. Layer 1: 1.2 g of gelatin, 0.28 g (in terms of iN, the same applies hereinafter) of I-Mimeisei photosensitive chlorobromide emulsion (Note 1)
, AgBr2 mol%, average particle size 0.73 μm), 0.5
0.78 g of yellow coupler (Y-1) dissolved in 0 g of dibutyl phthalate (hereinafter abbreviated as DBP),
0.35g of the following image stabilizers 5TB-1 and 0.04
A layer containing the color stain inhibitor HQ-11 of g. Layer 2...0.7g gelatin, 15mg anti-irradiation dye (AI-1), 10mg (AI
-2) and 05 g of sail dissolved in 0.05 g of HQ-11
An intermediate layer containing di-2-ethylhexyl phthalate (DOP). Layer 3: 1.25 g of gelatin, 0.29 g of green-sensitive silver chlorobromide emulsion (Note-2, HegBr 1.2 mol%, average particle size 0.40 μm) dissolved in 0.30 g of DOP 0,
45 g of magenta coupler (M-1) 0.20 g of light stabilizer 5TB-2,0, 15 g of light stabilizer 5TB-3
and 0. Layer containing IQ-11 of Olg. 1 is 4...1.2g of gelatin, 0.08g! IQ
Intermediate Jffl containing 0.35 g of DOP in which -11 and 0.4 g of ultraviolet absorber (UV-1) are dissolved. Layer 5: 1.4 g gelatin, 0.20 g red-sensitive silver chlorobromide emulsion (Note 2, 8 g [LRO, 5 mol%, average grain size 0.37/1 m2), 0.20 g I) 0.25 g of cyan coupler (C-2) dissolved in OP,
0.15g of 5TB-1 and 0.0]g of IIQ-11
A layer containing. Layer 6...1.0g pyratine and 0.208 DOP
To? tJ V −1 and 0.0 of dissolved 0, 3 (Ig
Layer containing 5g of polyvinylpyrrolidone. ) Beat 7: layer containing 0.5 g of gelatin. pt fIll! As a ++q agent, bisvinylsulfonyl methyl ether was added to layers 2 and 7 above. (Note-1) Blue-sensitive silver chlorobromide emulsion containing sodium thiosulfate at 3.1% per mole of silver halide.
Chemical sensitization and spectral sensitization were carried out by adding 0.4 mmol of the blue sensitizing dye shown in Table 1 per mole of silver halide, followed by stabilization and -ζS'l°[(
-1 was added at 1.2 mmol per mole of silver halide. (Note-2) Green photosensitive silver chlorobromide emulsion 4X per mole of halogenated sodium thiolomer
Chemical sensitization and spectral sensitization were carried out by adding 0.2 mmol of IQ-'mol and the following green sensitizing dye GSD-1 per mol of silver halide, and adding S1'H-1 as a stabilizer to 1 mol of silver halide. Rigidity per mole 1. - Added 1 mmol. (Note-3) Red-sensitive silver chlorobromide emulsion sodium thiosulfate is halogenated with 4XI per mole.
For O-' moles and the red color below! S3(!!, cumulative 5D
Chemical sensitization and spectral sensitization were performed by adding 0.10 mol of -1.
As a stabilizer, 2.0 mmol of S'l'to1 was added per mole of silver halide. Itcho margin (Y-1) (M-1) I (C-1) ll Shi! (C-2) (STB-1) (S GoB-2) Below margin (STB-3) (UV-1) H Beyond, 1s white (AI-1) (AI-2) Below Kanayama (GSn- 1) (R3D -1) (STR-1) Sodium chloride is added as a water-soluble chloride in layer 2 (Table-1)
Samples 1 to 20 were prepared in which the sample was added only at the times shown in . The obtained sample was stored at 40° C. and 80% relative humidity for 24 hours to allow dura mater to reach the required level. I got R11 of the regulation fee! Potentiometric titration was performed with an aqueous solution of silver chloride to determine the amount of water-soluble chloride in the film. The results are shown in Table-1. On the other hand, each of the obtained samples was subjected to optical draft exposure.
&, processing was performed according to the processing steps below. (Process rll! Ii level) Color development Bleach fixation at 35"C for 45 seconds Wash with water at 35°C for 45 seconds Dry at 30-35°C for 90 seconds
Use 60-80°C for 60 seconds to prepare the Zco color developer and bleach-fixer. ) The reflection density of each of the obtained samples was measured using monochromatic blue light, and the results shown in Table 1 were obtained. It represents the relative sensitivity when the sensitivity at 1 is set to 100, and each gradation represents the slope of the reflection density from 0.4 to 0.9.The pH of the color developer is 9.8.10.1.10. It changed to .4.Table-1
From the results shown in , when the water-soluble chloride content of the sample using the sensitizing dye of the present invention is 15 mol % or less based on the blue-sensitive silver halide, there is no change in sensitivity with respect to a change in the pH of the color developing solution. It can be seen that, although water-soluble chloride tends to cause changes in sensitivity and gradation, changes in sensitivity and gradation are reduced within the scope of the present invention. Furthermore, it can be seen that when the water-soluble chloride content exceeds 50 mol %, the sensitivity decreases. Blue sensitizing dye I for comparison! 5DR-1 EISDR-2 Below margin Example-2 Samples 1 to 20 used in Example-1 were stored for one week under the conditions of 40°C and 45% relative humidity. Example after photo-visual exposure. The same treatment as 1 was carried out, and the results shown in Table 2 were obtained. From the results shown in Table 2, it can be seen that the effect of the present invention is particularly large when the photosensitive material is stored over time. Table 2 below: The pH of the color development solution was changed to 9.11.10.1.10.4. Example 3 In preparing Samples 11 to 15 of Example 1, the same conditions as Example 2 were followed except that the diffusion-resistant hydroquinone compound in layer 1 was changed from IIQ-11 as shown in Table 3. repeated. The results are shown in Table-3. From the results shown in Table 3, it can be seen that the effect of the present invention is particularly large when a diffusion-resistant hydroquinone compound is added to layer 1. Example-4 Examples 1-2 were repeated. However, in the preparation of Samples 16 to 20 of Example 1, bisvinylsulfonyl methyl ether and 2,4-dichloro-6-hydroxy-S-
Samples were prepared by adding triazine in combination and varying the ratio. As a result of processing under the conditions of Example 2, good results were obtained when the water-soluble chloride content was within the range of the present invention, that is, within the range of 15 to 50 mol% based on the blue-sensitive silver chlorobromide emulsion. Ta. The results are shown in Table-4. Margin below In this way, unlike inorganic salts such as sodium chloride, water-soluble chloride cannot It can be seen that the effects of the present invention can be preferably obtained if the amount measured as is within the range specified in the present invention. That is, the same effects of the present invention as in Examples 1 and 2 were confirmed. [Effects of the Invention] As mentioned above, the silver halide photographic material 4'4 of the present invention has the following:
It can be processed quickly and has increased processing stability in terms of sensitivity and gradation.This stability is outstanding even when benzyl alcohol is removed from the color developer, and when stored for a long period of time. However, it has the effect of preventing an increase in fog and changes in gradation due to changes in developer conditions.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having a photographic constituent layer including at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers contains 80 mol% of silver chloride. It contains silver halide grains containing the above and a spectral sensitizing dye represented by the following general formula [I], and at least one of the photographic constituent layers contains a water-soluble chloride,
The total amount of water-soluble chloride contained in the photographic constituent layer is 15 to 50 mol% based on the silver halide contained in the same layer as the spectral sensitizing dye represented by the general formula [I]. Characteristic silver halide photographic materials. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, X_1, X_2, X_3 and X_4 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a hydroxyl group. R_1 and R_2 represent an alkyl group, and X^■ represents a counter anion. n is 0
Or represents 1. ]