JPH06230511A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity and contrast and to improve graininess and reciprocity law characteristics and to reduce fluctuation due to processing by incorporating the specified amount of a DIR compound, and specified amounts of compounds in an emulsion layer. CONSTITUTION:The silver halide color photographic sensitive material has at least one silver halide emulsion layer and it contains the DIR compound in the amount of >=5X10<-3>mol in the emulsion layer and its adjacent layer, and the compound represented by formula I in the amount of 1X10<-7> to 1X10<-3> mol/mol of silver halide in the emulsion layer and the compound represented by formula II or III in the amount of 5X10<-5> to 1X10<-2>mol/mol of the silver halide both in the emulsion layer, and in formulae I-III, Z is a nonmetallic atomic group necessary to form a ring; R<1> is H or the like; R<2> is a halogen or the like; X<-> is a counter anion; and each of R<11>-R<14> is, independently, H or an optionally substituted alkyl or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, more specifically with high sensitivity and high contrast,
The present invention relates to a silver halide color photographic light-sensitive material having good graininess and reciprocity law characteristics and having little process variation.

[0002]

2. Description of the Related Art Silver halide color photographic light-sensitive materials are desired to have high sensitivity and good graininess. Conventionally, development inhibitor releasing couplers (DIR couplers) have been used to improve graininess. In recent years, a large amount of DIR couplers have been used especially for improving graininess. For this reason, the graininess is improved in the medium illuminance region near the exposure time 1/100 "which is usually used, but on the other hand, there is a problem that the sensitivity is lowered and the softening occurs in the region of 1/10" to 10 ". Furthermore, 1/10000 ″, which is commonly used in flash photography,
In the high illuminance area of 1/1000 ″ area, sensitivity deterioration and softening also occur. Also, a large amount of DI
The treatment liquid is contaminated by the R coupler, which causes a problem that the performance of the treatment liquid tends to vary.

[0003]

The object of the present invention is to achieve high sensitivity, high contrast, and It is an object of the present invention to provide a silver halide color photographic light-sensitive material having good graininess and reciprocity law characteristics and having little process variation.

[0004]

[Means for solving the problem] As a result of earnest studies,
The object of the present invention can be achieved by the following means. That is, (1) a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the DIR compound contained in the emulsion layer and a layer adjacent to the emulsion layer is 5 ×. 10 is a ^-3 mol, 1 × 10 ^-7 mol to 1 × 10 ^-3 mol of the compound represented by the general formula (I) contained in the emulsion layer per mol of silver halide in the emulsion layer The amount of the compound represented by the general formula (II) or the general formula (III) contained in the emulsion layer is 5 × 10 ⁻⁵ mol or more and 1 × 10 ⁵ mol or more with respect to 1 mol of silver halide in the emulsion layer. ^A silver halide color photographic light-sensitive material characterized by being ^-2 mol or less. General formula (I)

[0005]

[Chemical 3]

In the formula, Z is a non-metal atom group necessary for forming an aromatic ring, R ¹ is H, an alkyl group having 1 to 5 carbon atoms,
R ² is a halogen atom, a hydroxyl group, a carboxyl group, or an alkyl group having 1 to 8 carbon atoms which may be substituted with a sulfo group, and X ⁻ is a counter anion. However, when forming betaine with N ⁺ -R ² , X
^- is not required. General formula (II) General formula (III)

[0007]

[Chemical 4]

In both formulas, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are
The same or different, each hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted amino group, a hydroxy group,
It represents an alkoxy group, an alkylthio group, an optionally substituted carbamoyl group, a halogen atom, a cyano group, a carboxy group, an alkoxycarbonyl group, or a heterocyclic residue, and R ¹¹ and R ¹² or R ¹² and R ¹³ are linked to each other. However, a 5- or 6-membered ring may be formed. However, at least one of R ¹¹ and R ¹³ represents a hydroxy group. (2) 1 × 1 with respect to 1 mol of silver halide in the emulsion layer
0 the containing ^-10 mol or more of Ir (1) A silver halide color photographic light-sensitive material as described. (3) The silver halide according to the above (1), wherein the DIR compound is a DIR coupler having a development inhibitor or a development inhibitor precursor that loses the development inhibiting ability in an alkaline developer after being eliminated from the coupling active position. Color photographic light-sensitive material.

The details of the present invention will be described below. (1) Silver Halide Emulsion Grain The silver halide constituting the silver halide grain used in the present invention includes silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide,
Silver iodobromide and silver chloroiodobromide. Other silver salts such as silver rhodanide, silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains. When it is desired to accelerate the development / desilvering (bleaching, fixing and bleach-fixing) steps, silver halide grains having a high silver chloride content are desirable.
Further, in the case of suppressing development appropriately, it is preferable to contain silver iodide. The preferred silver iodide content varies depending on the intended light-sensitive material. For example, in the case of a color photographic light-sensitive material typified by a color negative, it is preferably a silver halide containing 1 to 30 mol% of silver iodide, more preferably 5 to 5.
It is 20 mol%, particularly preferably 8 to 15 mol%. It is preferable that the silver iodobromide grains contain silver chloride in order to reduce lattice strain.

The grain size of the emulsion used in the present invention is the equivalent circle diameter of the projected area using an electron microscope, the equivalent sphere diameter of the grain volume calculated from the projected area and the grain thickness, or the equivalent sphere diameter of the volume determined by the Coulter counter method. Can be evaluated by As a scale representing the size distribution, a coefficient of variation of a projected area circle equivalent diameter of a particle or a sphere equivalent diameter of a volume may be used. When a monodisperse emulsion is used, it is preferable to use an emulsion having a size distribution with a coefficient of variation of 22% or less, more preferably 18% or less, and further preferably 15% or less.

The silver halide emulsion of the present invention preferably has a distribution or structure with respect to the halogen composition in its grains. The typical one is Japanese Patent Publication No. 43-1316.
2, JP-A-61-215540, and JP-A-60-22.
2845, JP-A-60-143331, JP-A-61
It is a core-shell type or double structure type grain having a halogen composition in which the inside and the surface layer of the grain are different as disclosed in, for example, -75337. Further, it is not a simple double structure, but a triple structure as disclosed in JP-A-60-222844 or a multilayer structure of more than that, or a different composition on the surface of the core shell double structure particles. The silver halide can be thinly applied. In order to give a structure to the inside of the particle, not only the wrapping structure as described above but also a so-called junction structure can be formed. Examples of these are disclosed in JP-A-59-133.
540, JP-A-58-108526, European Patent No. 1
99,290A2, JP-B-58-24772, and JP-A-59-16254.

In the case of silver halide grains in which two or more silver halides exist as a mixed crystal or have a structure, it is important to control the halogen composition distribution between grains. The method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. A uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a variation coefficient of 20% or less is preferable.
Another preferred form is an emulsion where there is a correlation between grain size and halogen composition. For example, there is a correlation in which larger size particles have a higher iodine content, while smaller particles have a lower iodine content. Depending on the purpose, an inverse correlation or a correlation with another halogen composition can be selected. For this purpose, it is preferable to mix two or more emulsions having different compositions.

It is important to control the halogen composition near the surface of the grain. Increase the content of silver iodide near the surface,
Alternatively, increasing the silver chloride content changes the adsorbability of the dye and the developing rate, and can be selected according to the purpose.
A normal crystal which does not contain twin planes is one of the preferable forms as the silver halide grains used in the present invention. In the case of a normal crystal, a cube having a (100) plane, an octahedron having a (111) plane, JP-B-55-42737, and JP-A-60-22.
12 composed of (110) plane disclosed in No. 2842
Faced grains can be used. Furthermore, Journa
l of Imaging Science Vol. 30 2
As reported on page 47 (1986) (2
11) is a (hll) plane particle, (331) is a (hhl) plane particle, (210) is a (hk0) plane particle, and (321) is a (hk) plane particle.
1) The surface particles also require a devised preparation method, but can be selected and used according to the purpose. The value obtained by dividing the circle-equivalent diameter of the projected area by the grain thickness is called the aspect ratio, and defines the shape of tabular grains. It is preferred to use tabular grains having aspect ratios greater than 1 in the present invention.

When tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitization efficiency by the sensitizing dye, and the above-cited US Pat. No. 4,434,226
The issue is detailed. 80% of the total projected area of the grain
The above average aspect ratio is preferably 1 or more and less than 100. It is more preferably 2 or more and less than 20, and particularly preferably 3 or more and less than 10. The shape of tabular grains can be selected from triangles, hexagons, circles, and the like. A regular hexagon with approximately six sides of equal length, as described in U.S. Pat. No. 4,797,354, is a preferred form.
Dislocation lines can be observed with a transmission electron microscope.
Particles containing no dislocation lines, particles containing several dislocations or particles containing many dislocations can be selected according to the purpose, but particles containing dislocations are preferred.

It is useful to use a silver halide solvent in the emulsion manufacturing process. Examples of the silver halide solvent include ammonia, thiocyanates (eg, rhodan potassium, rhodan ammonium), organic thioether compounds (eg,
US Pat. Nos. 3,574,628 and 3,021,21
No. 5, No. 3,057,724, No. 3,038,805
Nos. 4,276,374 and 4,297,439.
Issue No. 3,704,130 Issue No. 4,782,013
No. 5, compounds described in JP-A-57-104926) and thione compounds (for example, JP-A-53-82408, JP-A-53-84208).
4-Substituted thiourea described in US Pat. No. 4,221,863 and JP-A-53-14.
4319) and JP-A-57-
Examples thereof include a mercapto compound and an amine compound (for example, JP-A No. 54-100717) capable of promoting the growth of silver halide grains described in No. 202531.

In the present invention, it is preferable to incorporate an Ir salt in the emulsion layer as one of means for eliminating the sensitivity decrease and softening which occur when the exposure time is in the high illuminance region. The Ir salt may be added during the step of preparing the silver halide emulsion or during the step of preparing the coating solution, but it may be added during the step of preparing the silver halide emulsion to dope the silver halide grains. Preferably. Regarding the position of Ir doping, it may be doped once in any step of silver halide emulsion preparation, or may be doped several times. The preferred dope position is preferably after the nucleation of silver halide grains and before the end of chemical sensitization, and particularly preferably after the nucleation and before the desalting step. The total amount of Ir salt to be doped may be 1 × 10 ^-10 mol or more, preferably 1 × 10 ^-9 mol or more, per 1 mol of the total Ag amount of the silver halide emulsion. It is particularly preferable that the amount is 10 ^-8 mol or more. The silver halide emulsion of the present invention can be doped with an Ir salt in any form. In the present invention, it is preferable to dope the silver halide grains as a tetravalent or trivalent cation in a silver halide emulsion preparation solution,
It is particularly preferred to dope the silver halide grains as tetravalent cations.

The silver halide emulsion used in the present invention is
Sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization (for example, gold sensitization, palladium sensitization), or reduction sensitization can be combined for sensitization. Various types of emulsions can be prepared depending on which step is chemically sensitized. There are a type in which chemically sensitized nuclei are embedded inside a grain, a type in which a chemical sensitized nucleus is embedded at a shallow position from the grain surface, or a type in which a chemically sensitized nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemically sensitized nuclei can be selected according to the purpose, but it is generally preferable to form at least one chemically sensitized nucleus near the surface. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide can be used. The palladium compound means a divalent or tetravalent palladium salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
711, 4,266,018 and 4,05
The sulfur-containing compounds described in 4,457 can be used. It is also possible to carry out chemical sensitization in the presence of a so-called chemical sensitization aid. Useful compound sensitization aids include compounds known to suppress fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine and azapyrimidine. In the selenium sensitization, a known unstable selenium compound is used, and specific examples thereof include colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea), Selenium compounds such as selenoketones and selenoamides can be used. In some cases, seleno sensitization is preferably used in combination with sulfur sensitization, precious metal sensitization, or both.

The silver halide emulsion used in the present invention is
It is preferable to carry out reduction sensitization during grain formation, after grain formation and before or during chemical sensitization, or after chemical sensitization. Here, the reduction sensitization means a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing or ripening in a low pAg atmosphere of pAg1 to 7 called silver ripening, a high p
Any method of growing or aging in a high pH atmosphere of pH 8 to 11 called H aging can be selected. Also, two or more methods can be used in combination. The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted. Known reduction sensitizers include stannous salt, ascorbic acid and its derivatives, amines and polyamides, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds.

During the production process of the emulsion used in the present invention,
It is preferable to use an oxidizing agent for silver. The oxidizing agent for silver refers to a compound that acts on metallic silver to convert it into silver ions. Preferred oxidizing agents in the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents such as thiosulfonates, and organic oxidizing agents such as quinones.

The photographic emulsion used in the present invention is preferably spectrally sensitized with a methine dye or the like in order to exert the effects of the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styrin dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, pyrroline, oxazoline, thiazoline,
Pyrrole, oxazole, thiazole, selenazole,
Nuclei such as imidazole, tetrazole, pyridine; nuclei in which these rings are fused with alicyclic hydrocarbon rings; and nuclei in which these nuclei are fused with aromatic hydrocarbon rings, that is, indolenine, benzindolenine, indole , Nuclei such as benzoxadol, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole and quinoline can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, for example,
Pyrazolin-5-one, thiohydantoin, 2-thiooxazolidine-2,4-dione, thiazolidine-2,4
-5- to 6-membered heterocyclic nuclei of dione, rhodanine, thiobarbituric acid can be applied. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. A typical example thereof is US Pat. No. 2,688,
No. 545, No. 2,977,229, No. 3,397,0
No. 60, No. 3,522,052, No. 3,527,64
No. 1, No. 3,617, 293, No. 3,628, 964
Issue 3, Issue 3,666,480, Issue 3,672,898
Issue No. 3,679,428 Issue 3,703,377
Issue No. 3,769,301 Issue No. 3,814,609
No. 3,837,862, 4,026,707
No., British Patent Nos. 1,344,281 and 1,507,
No. 803, Japanese Patent Publication No. 43-4936, No. 53-12, 3
No. 75, JP-A Nos. 52-110,618 and 52-10.
No. 9,925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. The sensitizing dye may be added to the emulsion at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,628,969.
No. 58-113,928, the spectral sensitization can be carried out simultaneously with the chemical sensitization by adding the chemical sensitizer at the same time as described in JP-A-58-113,928. It can also be carried out prior to chemical sensitization as described in US Pat. Furthermore, as taught in U.S. Pat. No. 4,225,666, it is possible to add these said compounds separately, i.e. to add some of these compounds prior to chemical sensitization and the balance to the chemical It is also possible to add it after the sensitization, and it is possible to add it to US Pat.
It may be at any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 183,756. The addition amount is 4 × 10 ⁻⁶ to 8 × 10 per mol of silver halide.
^-3 mol can be used, but it is about 5 x 10 in the case of a more preferable silver halide grain size of 0.2 to 1.2 µm.
^{-5 to} 2 x 10 ^-3 mol is more effective.

(2) Compound Represented by General Formula (I) and Compound Represented by General Formula (II) or (III) In the present invention, low illuminance and high intensity which occur in an emulsion layer containing a large amount of DIR couplers. As means for eliminating sensitivity deterioration and softening that occur when exposed for an exposure time in the illuminance region, at least one compound represented by the general formula (I) and the general formula (II) or (II) are contained in the emulsion layer.
It contains at least one compound represented by I). These compounds are used in the manufacturing process of the light-sensitive material, during storage,
Alternatively, it is a stabilizer used for the purpose of preventing fogging during photographic processing or stabilizing photographic performance. The present invention is particularly directed to the general formula (I) among various stabilizers.
By using the compound represented by the formula (II) or the compound represented by the general formula (II) or (III) in an appropriate addition amount, it is possible to remarkably reduce sensitivity deterioration and softening in low illuminance and high illuminance regions, and The photographic sensitivity when exposed for the exposure time is also increased.

With respect to the compound of the general formula (I), the addition amount is from 1 × 10 ⁻⁷ mol to 1 × 10 ⁻³ mol per mol of silver halide in the silver halide emulsion layer to be added. It may be present, but 2 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol is preferable, and 5 × 10 ⁻⁶ to 1 × 10 ⁻⁴ is particularly preferable. The compound represented by the general formula (II) or (III) is added in an amount of 5 × 10 ⁻⁵ mol or more and 1 × 10 ⁻² mol or less with respect to 1 mol of silver halide in the silver halide emulsion layer to be added. It may be present, but it is preferably 1 × 10 ⁻⁴ to 4 × 10 ⁻³ mol. Further, the compound of the general formula (II) and the compound of the general formula (III) have slightly different arrangements of nitrogen atoms in the heterocycle, but in the present invention, both can be treated almost equivalently.

By controlling the addition amount of the compound of the general formula (I) and the general formula (II) or (III) within the above-mentioned range, the advantages possessed by the individual stabilizers can be expressed together. Instead, when only the individual stabilizers are added, an unexpected effect is exhibited. The advantages and disadvantages of the individual stabilizers are that when only the compound represented by the general formula (I) is added, the sensitivity decrease and the softening that occur when the exposure is performed in the low illuminance region are eliminated, Fogging is high, and the normal exposure time (1/10
0 ″) also shows low sensitivity and soft photographic properties. On the other hand, when only the compound represented by the general formula (II) or (III) is added, the fog is low and the ordinary exposure time is long. When exposed, it exhibits high sensitivity and high contrast photographic properties, but it does not eliminate the decrease in sensitivity and softening that occur when exposure is performed for an exposure time in the low illuminance region.

However, by controlling the addition amount of each stabilizer within the above-mentioned range shown in the present invention, only the advantages of each stabilizer can be exhibited, and in addition, only each stabilizer can be expressed. There was an unexpected effect that the photographic sensitivity was specifically higher than that in the case of using, and the decrease in sensitivity and the softening that occurred when the exposure was performed for the exposure time in the high illuminance region were eliminated. If the amount of the compound of the general formula (I) and the compound of the general formula (II) or (III) added is too large or too small, the drawbacks of the individual stabilizers will appear, and The specific increase in photographic sensitivity and the effect of improving the reciprocity law characteristic in the high illuminance region, which are obtained when an appropriate addition amount is used in the invention, are lost.

The compound represented by the general formula (I) and the compound represented by the general formula (II) or (III) may be added at any position in the process for producing the silver halide emulsion and the process for producing the coating solution. However, it is preferably added in the step of producing a silver halide emulsion. Further, it is preferably added at the time of chemical sensitization in the production process of a silver halide emulsion, and particularly preferably at the end of chemical sensitization.
Further, the compound represented by the general formula (I) has the general formula (I
It is preferably added before the compound represented by I) or (III). In the compound represented by the general formula (I), the preferred structure is the general formula (IV)

[0029]

[Chemical 5]

(In the formula, R ² is CH ₃ , C ₂ H ₅ , C _{3
H 7, C 4 H 9,} C 5 H 11, (CH 2) 3 SO 3 -,
(CH ₂ ) ₄ SO ₃ ⁻ , and X ⁻ are Br ⁻ , I ⁻ ,
_{H 3 C-C 6 H 4} -SO 3 - represent. ) General formula (V)

[0031]

[Chemical 6]

(Wherein R ¹ is H, CH ₃ , and R ²
Represents (CH ₂ ) ₃ SO ₃ ⁻ and (CH ₂ ) ₄ SO ₃ ⁻ . ) Can be mentioned, but the following FC-1 to 6 can be mentioned as particularly preferable examples.

[0033]

[Chemical 7]

Preferred examples of the compound represented by the general formula (II) or (III) include the following TAII-1 to TAII-1.
0 and TAIII-1 to 3.

[0035]

[Chemical 8]

[0036]

[Chemical 9]

[0037]

[Chemical 10]

Further, the compound represented by the general formula (I) and the compound represented by the general formula (II) or (III) may be used in combination with other stabilizers. Other stabilizers include nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, and benzo. Known as antifoggants or stabilizers such as triazoles, nitrobenzotriazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, thioketo compounds such as oxadrinethione, triazaindenes and pentaazaindenes. Is a compound. For example, US Pat.
No. 954,474, No. 3,982,947, Japanese Patent Publication No. 5
Those described in 2-28660 can be used. These stabilizers are used for various purposes before grain formation, during grain formation, after grain formation, during washing step, during dispersion after washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. Can be added according to In addition to exhibiting the original antifoggant and stabilizing effects by adding during emulsion preparation, it also controls the crystal habit of silver halide grains, reduces the grain size, reduces the solubility of grains, and chemical sensitization. It can be used for various purposes such as controlling and controlling the arrangement of dyes.

(3) DIR Compound In the present invention, the DIR compound is a compound which releases a development inhibitor by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. As such a DIR compound, a DIR coupler is preferably used. DIR
The structure of the coupler is not particularly limited, and those well known in the art can be appropriately used. Other preferred examples of DIR compounds include DIR hydroquinone. Further, as one type of DIR compound, hydrolysis type D
There are IR compounds, but these compounds have unique properties, so they will be explained in another section. The amount of DIR compound is
The total amount (c mole) of the DIR compound contained in the silver halide emulsion layer containing the compound of the above general formula (I) and the layer adjacent to the emulsion layer and the silver halide contained in the emulsion layer (a mole). The ratio (c / a) may be 5 × 10 ⁻³ or more, preferably 8 × 10 ⁻³ or more, 1.3 × 1
It is particularly preferably 0 ^-2 or more. In the present invention,
The DIR compound may be contained in either or both of the emulsion layer and the layer adjacent to the emulsion layer, and thus the amount of the DIR compound is the total amount of both layers.

The DIR coupler preferably used as the DIR compound in the present invention is represented by the following general formula (VI) and general formula (VIII). In the general formula (VI) A- (TIME) _n -B, A represents a coupler residue which leaves (TIME) _n -B by a coupling reaction with an oxidation product of an aromatic primary amine developing agent, TIME represents a timing group that binds to the coupling active position of A and releases B after being separated from A by the coupling reaction, and B represents the following general formulas (VIIa), (VIIb), (VIIc), (VI
Id), (VIIe), (VIIf), (VIIg),
(VIIh), (VIIi), (VIIj), (VII
k), (VIIl), (VIIm), (VIIn),
It represents a group represented by (VIIo) or (VIIp), and n represents an integer of 0 or 1. However, when n is 0, B is directly bonded to A.

[0041]

[Chemical 11]

[0042]

[Chemical 12]

In the formula, X ₁ represents a substituted or unsubstituted aliphatic group having 1 to 4 carbon atoms or a substituted phenyl group. X ₂
Is a hydrogen atom, aliphatic group, halogen atom, hydroxyl group, alkoxy group, alkylthio group, alkoxycarbonyl group, acylamino group, carbamoyl group, sulfonyl group, sulfonamide group, sulfamoyl group, acyloxy group, ureido group, cyano group, nitro group. Represents a group, an amino group, an alkoxycarbonylamino group, an aryloxycarbonyl group or an acyl group, X ₃ represents an oxygen atom, a sulfur atom or an imino group having 4 or less carbon atoms, and m represents an integer of 1 or 2. However, the total number of carbon atoms contained in m X ₂ is 8 or less, and when m is 2, the two X ₂ may be the same or different. General formula (VII
I)

[0044]

[Chemical 13]

In the formula, Y reacts with the oxidized product of the developing agent (L
_{1) v} -Z- (L ₂₎ represents a group which cleaves _w -DI,
L ₁ represents a linking group in which the bond with Y is cleaved and then the bond with Z is cleaved, and Z reacts with an oxidized product of a developing agent (L ₂ )
represents a group that cleaves _w- DI, L ₂ represents a group that cleaves DI after the bond with Z is cleaved, DI represents a development inhibitor, and v and w each represent an integer of 0 to 2, When they represent 2, two L _1's and two L _2's respectively represent different or the same.

(4) Hydrolyzable DIR Compound In the present invention, the hydrolyzable DIR compound is a fragment of a development inhibitor or a development inhibitor precursor which loses its inhibitory property after being released from the coupling active site by the reaction of color development. As long as it has the above-mentioned active position.
In the present invention, as the hydrolyzable compound, those represented by the following general formula (IX) can be preferably used. General formula (IX)

[0047]

[Chemical 14]

In the formula, m is 0,1, n is 1,2, C _p is a coupler, Z is the whole or main structure of the development inhibitor, and the coupling position of the coupler is when m = 0. Is bonded directly through T when m = 1, and Y is a linking group L
Is a substituent that binds to Z via Z to develop the development inhibitory action of Z, L is a linking group containing a chemical bond that is cleaved in the developer, and when n = 2, L and Y are different from each other. Or they may be the same. Among the couplers represented by the general formula (IX), preferred are the following general formulas (X) to (XVI).
It is represented by II).

[0049]

[Chemical 15]

[0050]

[Chemical 16]

In the above formulas (X) to (XVIII), R ₁ is hydrogen atom, halogen atom, alkyl group, alkenyl group, aralkyl group, alkoxy group, alkoxycarbonyl group, anilino group, acylamino group, ureido group, cyano group. Group, nitro group, sulfonamide group, sulfamoyl group, carbamoyl group, aryl group, carboxyl group, sulfo group, cycloalkyl group, alkanesulfonyl group, arylsulfonyl group or acyl group, R
₂ represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group or an aryl group,

K is 1 or 2, and when k is 2, a plurality of R _{1 s} may form a heterocycle, and X is included in the Z moiety in the general formula (IX). There
Hydrogen atom, halogen atom, alkyl group, alkenyl group,
Alkaneamide group, alkenamide group, alkoxy group,
It represents a sulfonamide group or an aryl group, Y represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, an aralkyl group or a heterocyclic group, and L is a linking group. Examples of the linking group preferable as L are shown below together with the substitution position of Z and the substitution position of Y.

[0053]

[Chemical 17]

[0054]

[Chemical 18]

However, d is 0 to 10, preferably 0 to 5
And W ₁ is, for example, a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, preferably an alkoxy group having 1 to 5 carbon atoms, and 1 carbon atom. -10, preferably 1 to 5 alkoxycarbonyl group, aryloxycarbonyl group, carbon number 1 to
10, preferably 1 to 5 alkanesulfonamide groups,
An aryl group, a carbamoyl group, an N-alkylcarbamoyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, a nitro group,
Selected from a cyano group, an aryl sulfonamide group, a sulfamoyl group and an imide group, W ₂ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or an alkenyl group, and W ₃ represents a halogen atom, a nitro group or a carbon atom. Number 1-6
Represents an alkoxy group.

The above-mentioned emulsion may be used alone in the light-sensitive emulsion layer, or may be mixed with two or more kinds of emulsions having different average grain sizes or two or more kinds of emulsions having different average silver iodide contents to obtain the same light-sensitivity. You may use in a layer. The use of a mixture of emulsions controls gradation, controls graininess from low to high exposure regions, and depends on color development (time and, for example, color developing agent sodium sulfite developer). It is preferable from the viewpoint of control of internal composition dependence and pH dependence. The light-sensitive material of the present invention is
It suffices that at least one layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive silver halide emulsion layer is provided on the support, and a silver halide emulsion layer and a non-light-sensitive layer can be provided. There is no particular limitation on the number of layers and the order of layers. As a typical example, at least one photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities is provided on a support.
Which is a unit photosensitive layer having a color sensitivity to any of blue light, green light, and red light, and is a unit in a multilayer silver halide color photographic light-sensitive material. Is generally a unit photosensitive layer arrangement,
The red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer may include, for example, JP-A-61-437.
No. 48, No. 59-113438, No. 59-11344.
No. 0, No. 61-20037 and No. 61-20038 may contain a coupler and a DIR compound, and may contain a color mixing inhibitor as commonly used. As described in West German Patent No. 1,121,470 or British Patent No. 923,045, a plurality of silver halide emulsion layers constituting each unit photosensitive layer are used as high-sensitivity emulsion layers and low-sensitivity emulsion layers. The two-layer structure can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each silver halide emulsion layer. Further, for example, Japanese Patent Application Laid-Open No. 57-112751
No. 62-200350, No. 62-206541.
No. 62-206543,
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, the low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (B
H) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH
/ RL, or BH / BL / GH / GL / RL / R
It can be installed in the order of H. In addition, Japanese Examined Sho 55-3
As described in JP-A-4932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Also, JP-A-56-2573
No. 8, 62-63936, the blue-sensitive layer / GL / R from the side farthest from the support.
It can also be arranged in the order of L / GH / RH.

As described in JP-B-49-15495, a silver halide emulsion layer having the highest photosensitivity in the upper layer, a silver halide emulsion layer having a lower photosensitivity in the middle layer, and a lower layer in the lower layer. An example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity than the middle layer is arranged and the photosensitivity is gradually decreased toward the support, and the three layers have different sensitivities. 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. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order. In addition, the layers 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 can be changed as described above. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The light-sensitive material of the present invention comprises a photosensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer. In the present invention, it is preferable to use 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 it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferably, it contains 0.5 to 10 mol% of silver iodide. 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 chemically sensitized,
Also, spectral sensitization is not necessary. 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, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the three Research Disclosures, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 (December 1978) (November 1979) (November 1989) 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer, to page 649, right column 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Fogging prevention 24 to 25 pages 649 right column 868 to 870 Agents and stabilizers 6. Light absorber, page 25-26, page 649, right column, page 873, filter dye, page-650, left column, ultraviolet absorber, page 872 7. Stain prevention page 25 right column page 650 left column Stopping agent to right column 8. Dye image safety Page 25 Page 650 Left column Page 872 Fixed agent 9. Hardener, page 26, page 651, left column, pages 874-875 10. Binder page 26 page 651 left column page 873-874 11. Plasticizers and lubricants Page 27 Page 650 Right column Page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Static page 27 page 650 right column 876 to 877 inhibitor 14. Matting agent pp. 878-879

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,98
It is preferable to add to the light-sensitive material the compounds described in No. 7 and No. 4,435,503, which can be immobilized by reacting with formaldehyde. To the light-sensitive material of the present invention, a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, which is described in JP-A-1-106052, is released irrespective of the amount of developed silver. It is preferable to include a compound. The light-sensitive material of the present invention includes
International publication WO88 / 04794, Japanese Patent Laid-Open No. 1-5029
Dye or EP3 dispersed by the method described in No. 12
It is preferable that the dyes described in 17,308A, U.S. Pat. No. 4,420,555, and JP-A-1-259358 are contained.

Various color couplers can be used in the present invention. Specific examples thereof are Research Disclosure No. 17643, VII-CG, and N
o. 307105, VII-C to G. As a yellow coupler, for example,
U.S. Pat. Nos. 3,933,501 and 4,022,6
No. 20, No. 4,326,024, No. 4,401,
No. 752, No. 4,248,961, Japanese Patent Publication No. 58-1
0739, British Patents 1,425,020, 1,476,760, U.S. Patent 3,973,968.
No. 4, No. 4,314, 023, No. 4, 511, 64
Those described in No. 9 and EP 249,473A are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and examples thereof include US Pat. Nos. 4,310,619 and 4,35.
No. 1,897, European Patent No. 73,636, US Patent Nos. 3,061,432, 3,725,067, Research Disclosure No. 24220 (198
June, 4), JP-A-60-33552, Research Disclosure No. 24230 (June 1984)
Mon), JP-A-60-43659, JP-A 61-72238.
No. 60-35730, No. 55-118034,
No. 60-185951, U.S. Pat. No. 4,500,63.
No. 0, No. 4,540, 654, No. 4,556, 6
No. 30, those described in International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers. Examples thereof include US Pat. Nos. 4,052,212 and 4,146,396.
No. 4,228,233, No. 4,296,200
No. 2, No. 2,369,929, No. 2,801,17
No. 1, No. 2,772, 162, No. 2,895, 8
No. 26, No. 3,772,002, No. 3,758,
No. 308, No. 4,334, 011 and No. 4,32
7,173, West German Patent Publication No. 3,329,729,
European Patent Nos. 121,365A and 249,453A
U.S. Pat. Nos. 3,446,622 and 4,33.
No. 3,999, No. 4,775,616, No. 4,4
No. 51,559, No. 4,427,767, No. 4,
Those described in 690,889, 4,254,212, 4,296,199, and JP-A-61-42658 are preferable. Furthermore, JP-A-64-553,
No. 64-554, No. 64-555, and No. 64-556.
The pyrazoloazole-based couplers described in U.S. Pat. No. 4,849,639 and the imidazole-based couplers described in U.S. Pat. No. 4,818,672 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,08.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, and European Patent 341,188A. Examples of couplers in which the color forming dye has an appropriate diffusibility include U.S. Pat. No. 4,366,237, British Patent 2,125,570, and European Patent 96,57.
Those described in No. 0 and West German Patent (Publication) No. 3,234,533 are preferable. Colored couplers for correcting unwanted absorption of color forming dyes are Research Disclosure No. 17643, Item VII-G, ibid. 307
105 VII-G, U.S. Pat. No. 4,163,670.
No. 57/39413, U.S. Pat. No. 4,000
Those described in 4,929, 4,138,258 and British Patent 1,146,368 are preferable. Also,
The coupler described in US Pat. No. 4,774,181 which corrects unnecessary absorption of a coloring dye by the fluorescent dye released during coupling, and the reaction with the developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are described in RD1 above.
7643, VII-F section and No. 307105, V
Patents described in the section II-F, JP-A-57-15194
No. 4, No. 57-154234, No. 60-184248.
Nos. 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patents 2,097,140 and 2,131,188.
Nos. 59-157638 and 59-17084.
Those described in No. 0 are preferable. In addition, JP-A-60-10
7029, 60-252340, JP-A-1-44.
The compounds described in JP-A No. 940 and JP-A No. 1-45687, which release a fogging agent, a development accelerator, and a silver halide solvent by a redox reaction with an oxidized product of a developing agent are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include, for example, US Pat.
Competitive couplers described in US Pat. No. 30,427, for example, US Pat. Nos. 4,283,472 and 4,338,393,
Multiequivalent couplers described in JP-A No. 4,310,618, such as JP-A-60-185950 and JP-A-62-242.
52, etc., DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent Nos. 173,302A, 31
No. 3,308A, which is a coupler that releases a dye that recovers color after release, for example, a ligand-releasing coupler described in US Pat. No. 4,555,477, and a leuco dye described in JP-A-63-75747. The couplers and the couplers emitting a fluorescent dye described in US Pat. No. 4,774,181 can be mentioned.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods. Examples of high boiling solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling-point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (eg, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl). Phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or phosphonic acid Esters of (eg,
Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate), benzoic acid Esters (eg, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg, N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone) ,
Alcohols or phenols (for example, isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, Isostearyl lactate, trioctyl citrate), aniline derivatives (eg N, N-dibutyl-2-butoxy-5-te)
rt-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, for example, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-Ethoxyethyl acetate and dimethylformamide can be mentioned.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230. In the color light-sensitive material of the present invention, for example, phenethyl alcohol, JP-A-63-257747 and JP-A-62-257747 are used.
272248, and 1,2-benzisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol described in JP-A No. 1-80941. It is preferable to add various preservatives or antifungal agents such as 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.
Suitable supports that can be used in the present invention are described, for example, in RD. No. 17643, page 28, ibid. 187
16, page 647, right column to page 648, left column, and No. 16 of the same.
307105, page 879.

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, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (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. Gr
een) and others in Photographic Science and Engineering (Photogr. Sci. E.
ng. ), Vol. 19, No. 2, can be measured by using a type of Swellometer described (swelling meter) pp 124-129, T _1/2 is 30 ° C. with a color developing solution, and treated for 3 minutes 15 seconds 90% of the maximum swollen film thickness that reaches at time is the saturated film thickness,
It is defined as the time required to reach 1/2 of the saturated film thickness. The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing aging conditions after coating. The swelling rate is 15
0 to 400% is preferable. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula: (maximum swollen film thickness-film thickness)
/ Film thickness.

The light-sensitive 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.
~ 500% is preferred. The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29,
Same No. 18716, page 651, left column to right column, and N.
o. Development processing can be performed by a usual method described on pages 880 to 881 of 307105.

The color developing solution used in the development processing of the light-sensitive material in the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3- Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline,
3-Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p- Toluene sulfonate may be mentioned. Among these, especially 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. These compounds are 2 depending on the purpose.
It is also possible to use together more than one species.

The color developing solution contains, for example, a pH buffering agent such as an alkali metal carbonate, borate or phosphate,
It is common to include development inhibitors or antifoggants such as chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catacolsulfonic acids, ethylene glycol. , Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonos. Various chelating agents represented by carboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo. -N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N,
N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts can be used.

When the reversing process is carried out, the black and white development is usually carried out before the color development. This black-and-white developer contains known black-and-white developing agents, for example, dihydroxybenzenes such as hydroquinone, 2-pyrazolidones such as 1-phenyl-3-pyrazolidone, or amino acids such as N-methyl-p-aminophenol. Phenols can be used alone or in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 L (liter) or less per square meter of the light-sensitive material, and 500 ml can be obtained by reducing the bromide ion concentration in the replenishing solution. It can also be: When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air.

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 aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 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 is available.
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps,
For example, it is preferably applied in all steps of bleaching, bleach-fixing, fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The time of color development processing is usually set between 2 and 5 minutes, but by using a high temperature and high pH and using a color developing agent at a high concentration,
Further, the processing time can be shortened.

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 can be optionally carried out according to the purpose. As the bleaching agent, for example, polyvalent metal compounds such as iron (III), peracids, quinones, and nitro compounds are used. Typical bleaching agents are iron (III) complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid,
Complex salts of aminopolycarboxylic acids such as glycol ether diamine tetraacetic acid, citric acid, tartaric acid, or malic acid can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts 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 iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but it is also possible to process at a lower pH 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 include, for example, U.S. Pat. No. 3,893,858 and West German Patent 1,290,81.
2, No. 2,059,988, JP-A-53-3273.
No. 6, No. 53-57831, No. 53-37418,
53-72623, 53-95630, 53
-95631, No. 53-104232, No. 53-1
No. 24424, No. 53-141623, No. 53-28
426, Research Disclosure No. 171
No. 29 (July 1978), a compound having a mercapto group or a disulfide group; JP-A-50-140.
No. 129, a thiazolidine derivative; JP-B-45-8
No. 506, JP-A Nos. 52-20832 and 53-327.
35, U.S. Pat. No. 3,706,561; thiourea derivatives; West German Patent No. 1,127,715, JP-A-58-16,235; Iodide Salts; West German Patent No. 9
66,410 and 2,748,430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40,943.
No. 49-59,644, and 53-94,927.
No. 54, 35-727, 55-26, 506.
No. 58-163, 940; and bromide ions. Of these, compounds having a mercapto group or a disulfide group are preferred because of their large accelerating effect, and are particularly described in U.S. Pat. The compounds mentioned are preferred. Further, US Pat. No. 4,55
The compounds described in No. 2,834 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 photography.

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. The fixer used in the fixer and the bleach-fixer is thiosulfate,
Thiocyanates, thioether compounds, thioureas,
Although a large amount of iodide salt and the like can be mentioned, thiosulfate is generally used, and ammonium thiosulfate is most widely used. Further, for example, a combined use of a thiosulfate solution and a thiocyanate, a thioether compound, or thiourea is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2- It is preferable to add imidazoles such as methylimidazole in an amount of 0.1 to 10 mol / L. The total time of the desilvering process is preferably as short as possible in the range where desilvering failure does not occur. The preferred time is 1 to 3 minutes, more preferably 1 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 process, it is preferable that the stirring is strengthened as much as possible. As a specific method for strengthening stirring, a method of causing a jet of a processing solution to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and a rotating means described in JP-A-62-183461 are used. To improve the stirring effect, and further to move the light-sensitive material while bringing the emulsion surface into contact with the wiper blade provided in the solution to make the emulsion surface turbulent, thereby further improving the stirring effect. There is a method of increasing the circulation flow rate of. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the 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 consequently the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19.
It is preferable to have the photosensitive material conveying means described in Nos. 1258 and 60-191259. The above-mentioned JP-A-6
As described in No. 0-191257, 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 photographic light-sensitive material in the present invention is generally subjected to a desilvering processing solution, washing with water and / or a stabilizing step. The amount of washing water in the washing process is
Characteristics of photosensitive material (for example, depending on materials used such as couplers),
It can be set in a wide range depending on the application, the washing water temperature, the number of washing tanks (the number of stages), the replenishment method such as countercurrent and forward flow, and various other conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is as follows.
the Society of Motion Pic
ture and television vision engine
ers, 64, 248-253 (May 1955 issue).

According to the multistage countercurrent system described in the above-mentioned document,
Although the amount of washing water can be significantly reduced, bacteria increase due to an increase in the residence time of water in the tank, for example, a problem arises in that the produced suspended matter adheres 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. Also,
The isothiazolone compounds described in JP-A-57-8542, siabendazoles, chlorine-based germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents (1986)
Sankyo Publishing, Sanitary Technology Society, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982), Industrial Technology Association, Japan Antibacterial and Antifungal Society, "Microbial and Antifungal Encyclopedia" (1986) Can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can be set variously depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C. and 20 seconds to 10 seconds.
Minutes, preferably at 25-40 ° C. for 30 seconds-5 minutes. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No. 57-8543
All known methods described in Nos. 58-14834 and 60-220345 can be used. Also,
In some cases, further stabilization treatment may be performed following the water washing treatment,
An example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. 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 also be added to this stabilizing bath.

The overflow solution that accompanies 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. No. 3,342,597
No. 3,342,5
No. 99, Research Disclosure No. 14,8
50 and No. 50. Examples of the Schiff base type compounds described in JP-A No. 15,159, 15, aldol compounds described in JP-A No. 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A No. 53-135628. be able to.

The silver halide color light-sensitive material of the present invention comprises
If necessary, various 1-phenyl-3-pyrazolidones may be incorporated for the purpose of promoting color development. Typical compounds are JP-A-56-64339 and JP-A-57-144.
547 and 58-115438. Various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature 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. The silver halide light-sensitive material of the present invention is disclosed in, for example, US Pat.
626, JP-A-60-133449, and JP-A-59-21.
No. 8443, No. 61-238056, European Patent 21.
It can also be applied to the photothermographic material described in No. 0,660A2.

[0089]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. (Preparation of Emulsion A) To 1 liter of water, 4.5 g of low molecular weight gelatin and 3.8 × 10 ^-2 mol of potassium bromide were added.
An aqueous solution of silver nitrate (1.9 mol / l) and an aqueous solution of potassium bromide (2.0 mol / l) were simultaneously added at 23 cc / m while stirring in a container which was dissolved at 0 ° C. and then heated to 60 ° C.
In for 1 minute (addition 1). Thereafter, 270 g of a gelatin solution (12 wt%) was added, the temperature was raised to 75 ° C., and the same solution of silver nitrate was added to this container at 7.7 cc / min for 2 minutes (addition 2), and then 0.3 mol of ammonium nitrate, After 4.7 × 10 ^-2 mol of sodium hydroxide was added and Ostwald ripening was performed for 10 minutes, 6.6 × 10 ^-2 mol of acetic acid was added to stop the aging process. Then, a solution of silver nitrate (1.9 mol / l), potassium bromide and potassium iodide (molar ratio of potassium bromide to potassium iodide 9: 1).
Then, in total, 1.8 mol / l) was used as the initial flow rate of 4 cc /
min At a final flow rate of 14 cc / min, primary acceleration was performed simultaneously for 40 minutes by the double jet method (addition 3).

Thereafter, the temperature was lowered to 55 ° C., an aqueous solution of silver nitrate (0.18 mol / l) was 40 cc / min, and an aqueous solution of potassium iodide (0.18 mol / l) was 30 cc / mi.
n at the same time by the double jet method (addition 4),
After further adding 0.06 mol of an aqueous potassium bromide solution, an aqueous solution of silver nitrate (1.9 mol / l) and an aqueous solution of potassium bromide (2.0 mol / l) were simultaneously added at a rate of 18 cc / min by the double jet method (addition 5). Then, after desalting by a usual flocculation method, gold sensitization, sulfur sensitization and selenium sensitization were optimized in the presence of a spectral sensitizing dye and sodium thiocyanate according to the example of JP-A-3-237450. After completion of the chemical sensitization, a mercapto compound (formula MER-1 below) was added as a stabilizer in an amount of 1.8 × 10 ⁻⁴ mol per mol of silver halide in the emulsion. According to the above procedure, the coefficient of variation of the grain size distribution is 26%, the average aspect ratio of grains having an aspect ratio of 2 or more is 4.8, and the emulsion is composed of tabular silver halide grains having a spherical equivalent diameter of 0.63 micrometers. A was prepared.

[0091]

[Chemical 19]

Emulsion A was prepared as J. F. Hamilton Ph
ot. Sci. Eng. , 11, 57 (1967) and T.W. Shiozawa, J .; Soc. Photo. Sc
i. It was observed by the method using a transmission electron microscope described in Japan, 35, 213 (1972). The electron microscope uses JEM-2000FX manufactured by JEOL Ltd. 2
It was observed at a liquid nitrogen temperature with an acceleration voltage of 00 kV. As a result, tabular silver halide grains having 10 or more dislocation lines per grain on the periphery of grains having a diameter of 0.3 μm or more and an aspect ratio of 2 or more were 70% of the total amount of silver halide grains.
Accounted for more than%.

(Preparation of emulsion B) In preparation of emulsion A,
Same as Emulsion A except that MER-1 added at the end of chemical sensitization was replaced with compound FC-1 of the general formula (I) (7 × 10 ⁻⁵ mol per mol of silver halide in the emulsion). To prepare Emulsion B. (Preparation of Emulsion C) In the preparation of Emulsion A, MER-1 added at the end of the chemical sensitization was added to compound TAII-1 of the above-mentioned general formula (II) (5 × per mol of silver halide in the emulsion).
Emulsion C was prepared in exactly the same manner as Emulsion A except that the amount was changed to 10 ^-4 mol). (Preparation of Emulsion D) In the preparation of Emulsion B, 3 minutes after the addition of the compound FC-1 of the general formula (I), the compound TAII-1 of the general formula (II) (the silver halide in the emulsion) Emulsion C was prepared in exactly the same manner as Emulsion A except that 7 × 10 ⁻⁵ mol per mol) was added.

Example 1 This example shows the relationship between the DIR coupler amount and the photographic sensitivity, fog, granularity, and reciprocity law characteristics for the embodiments of the present invention. On the undercoated cellulose triacetate film support, samples 101 to 116, which are multilayer color light-sensitive materials composed of layers having the compositions shown below and in Table 1, were prepared. These samples 10
1 to 116 were imagewise exposed to white light with a shutter speed of 10 ⁻⁴ ″ to 10 ″, and subjected to the color development processing shown in the following processing method-1. After the development processing, the photographic sensitivity, fog and granularity at a shutter speed of 10 ^-2 "were examined and shown in Table 2. Here, the photographic sensitivity is a relative sensitivity of a yellow density and a fog optical density of 1.3. The relative sensitivity is the exposure amount E corresponding to the position where the optical density on fog is 1.3.
Using (CMS) and the exposure amount Es of the reference sample, (relative sensitivity) = (Es / E) × 100. Regarding the granularity, R.I. M. S. The granularity was measured, and the relative value of its reciprocal was defined as a measure of granularity. Also, the reciprocity law characteristics were evaluated by determining the photographic sensitivity at a shutter speed of 10 ^-4 ″, 1 ″, and 10 ″ when the photographic sensitivity at the shutter speed of 10 ⁻² ″ of each sample is set to 1.0. The values are shown in Table 2. The optical density of the sample was measured through a filter having the optical characteristics shown in FIG.

(Composition of photosensitive layer) Unless otherwise specified, the coating amount is the amount expressed in g / m ² of silver for silver halide and colloidal silver, and g for couplers, additives and gelatin. / M ² units, and for sensitizing dyes, the number is expressed in mol per mol of silver halide in the same layer. DIR-Cp- in the 12th layer
The coating amounts of 1 and 2 are shown in Table 1 in terms of the molar ratio to the coating amount of silver iodobromide emulsion Bu in the layer. UV; UV absorber, S
olv; high boiling organic solvent, ExF; dye, ExS; sensitizing dye, ExC; cyan coupler; ExM; magenta coupler, ExY; yellow coupler, Cpd; additive

First Layer (Antihalation Layer) Black Colloidal Silver 0.15 Gelatin 2.33 ExM-2 0.11 UV-1 3.0 × 10 ^-2 UV-2 6.0 × 10 ^-2 UV-3 7.0 × 10 ^-2 Solv-1 0.16 Solv-2 0.10 ExF-1 1.0 × 10 ^-2 ExF-2 4.0 × 10 ^-2 ExF-3 5.0 × 10 ^-3 Cpd -7 1.0 x 10 ^-3

Second Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.2 mol%, uniform AgI type, sphere equivalent diameter 0.4 μm, variation coefficient of sphere equivalent diameter 35%, plate-like grain , Aspect ratio 3.1) coating amount of silver 0.35 silver iodobromide emulsion (AgI 6.0 mol%, core-shell ratio 1: 2, internal high AgI type, sphere equivalent diameter 0.45 μm, variation coefficient of sphere equivalent diameter 23%, plate-like particles, aspect ratio 2.0) coated silver amount 0.18 gelatin 0.77 ExS-1 2.4 × 10 ⁻⁴ ExS-2 1.4 × 10 ⁻⁴ ExS-5 2.3 × 10 ⁻⁴ ExS-7 4.1 × 10 ⁻⁶ ExC-1 9.0 × 10 ⁻² ExC-2 2.0 × 10 ⁻² ExC-3 4.0 × 10 ⁻² ExC-4 2.0 × 10 ^-2 ExC-5 8.0 x 10 ^-2 ExC-6 2.0 x 10 ^-2 ExC-9 1.0 x 10 ^-2

Third Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 5.9 mol%, internal high AgI type with core-shell ratio 1: 2, equivalent sphere diameter 0.67 μm, variation in equivalent sphere diameter) Coefficient 35%, plate-like particles, aspect ratio 2.3) Coating amount 0.80 Gelatin 1.46 ExS-1 2.4 × 10 ⁻⁴ ExS-2 1.4 × 10 ⁻⁴ ExS-5 2.4 × 10 ^-4 ExS-7 4.3 × 10 ^-6 ExC-1 0.19 ExC-2 1.0 × 10 ^-2 ExC-3 2.5 × 10 ^-2 ExC-4 1.6 × 10 ^-2 ExC-5 0.19 ExC-6 2.0x10 ^-2 ExC-7 3.0x10 ^-2 ExC-8 1.0x10 ^-2 ExC-9 3.0x10 ^-2

Fourth Layer (High-Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 8.9 mol%, multi-structured grains having a core-shell ratio of 3: 4: 2, AgI content of 24, 0, 6 mol from the inside) %, Equivalent sphere diameter 0.80 μm, variation coefficient of equivalent sphere 42%, plate-like particles, aspect ratio 2.5) Coating amount of silver 1.05 Gelatin 1.38 ExS-1 2.0 × 10 ^-4 ExS- 2 1.1 × 10 ⁻⁴ ExS-5 1.9 × 10 ⁻⁴ ExS-7 1.4 × 10 ⁻⁵ ExC-1 8.0 × 10 ⁻² ExC-4 9.0 × 10 ⁻² ExC− 6 2.0 × 10 ^-2 ExC-9 1.0 × 10 ^-2 Solv-1 0.20 Solv-2 0.53

Fifth layer (intermediate layer) Gelatin 0.62 Cpd-1 0.13 Polyethyl acrylate latex 8.0 × 10 ^-2 Solv-1 8.0 × 10 ^-2 Sixth layer (low-sensitivity green-sensitive emulsion) Layer) Silver iodobromide emulsion (AgI 3.7 mol%, uniform AgI type, sphere-equivalent diameter 0.45 μm, variation coefficient of sphere-equivalent diameter 20%, plate-like grains, aspect ratio 4.5) Coating silver amount 13 Gelatin 0.31 ExS-3 1.0 × 10 ⁻⁴ ExS-4 3.1 × 10 ⁻⁴ ExS-5 6.4 × 10 ⁻⁵ ExM-1 0.12 ExM-4 2.1 × 10 ^{− 2} Solv-1 0.09 Solv-4 7.0x10 ^-3

Seventh Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.2 mol%, uniform AgI type, sphere equivalent diameter 0.69 μm, variation coefficient of sphere equivalent diameter 25%, plate-like particles , Aspect ratio 4.0) coated silver amount 0.31 gelatin 0.54 ExS-3 2.7 × 10 ⁻⁴ ExS-4 8.2 × 10 ⁻⁴ ExS-5 1.7 × 10 ⁻⁴ ExM-1 0.27 ExM-3 7.2 × 10 ^-2 ExY-1 5.4 × 10 ^-2 Solv-1 0.23 Solv-4 1.8 × 10 ^-2

Eighth Layer (High-Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 8.5 mol%, multi-structured grains with a silver amount ratio 3: 4: 2, AgI content of 24, 0, 3 Mol%, equivalent sphere diameter 0.69 μm, variation coefficient of equivalent sphere diameter 51%, multiple twinned plate-like particles, aspect ratio 2.7) Coating silver amount 0.49 Gelatin 0.61 ExS-4 4.3 × 10 ^-4 ExS-5 8.6x10 ^-5 ExS-8 2.8x10 ^-5 ExM-2 1.0x10 ^-2 ExM-5 1.0x10 ^-2 ExM-6 3.0x10 ^{-2 ExY-1 1.5 × 10 -2} ExC-1 0.4 × 10 -2 ExC-4 2.5 × 10 -3 ExC-6 0.5 × 10 -2 Solv-1 0.12 Cpd- 8 1.0 x 10 ^-2

Ninth layer (intermediate layer) Gelatin 0.56 Cpd-1 4.0 × 10 ^-2 polyethyl acrylate latex 5.0 × 10 ^-2 Solv-1 3.0 × 10 ^-2 UV-4 3. ^{0x10 -2} UV-5 4.0x10 ^-2

10th layer (donor layer having a multilayer effect for the red-sensitive layer) Silver iodobromide emulsion (AgI 7.5 mol%, core-shell ratio 1: 2, internal high AgI type particles, sphere equivalent diameter 0.70 μm, spheres Coefficient of variation of equivalent diameter 35%, multiple twin plate-like grains, aspect ratio 2.0) Coating silver amount 0.67 Silver iodobromide emulsion (AgI 10.0 mol%, core-shell ratio 1: 3, high internal AgI type) Particles, sphere equivalent diameter 0.45 μm, variation coefficient of sphere equivalent diameter 17%, normal crystal grains, coated silver amount 0.20 gelatin 0.87 ExS-3 6.7 × 10 ^-4 ExM-4 0.16 Solv- 1 0.30 Solv-6 3.0 × 10 ^-2

Eleventh Layer (Yellow Filter Layer) Yellow Colloidal Silver 9.0 × 10 ⁻² Gelatin 0.84 Cpd-2 0.13 Solv-1 0.13 Cpd-1 5.0 × 10 ⁻² Cpd-7 2.0 × 10 ⁻³ H-1 0.25 12th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion-Bu Coated silver amount 0.88 (8.16 × 10 ⁻³ mol / m ² ). Gelatin 2.18 ExS-6 7.4 × 10 ^-4 ExC-1 0.05 DIR-Cp-1 x DIR-Cp-2 y ExY-4 1.20 Solv-1 0.54

Thirteenth Layer (High Sensitivity Blue Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 14 mol%, internal high AgI type grain having a core-shell ratio of 1: 2, sphere equivalent diameter 1.4 μm, coefficient of variation of sphere equivalent diameter) 65%, twin) coated silver amount 0.40 gelatin 0.59 ExS-6 2.6 × 10 ⁻⁴ ExY-4 0.20 ExC-1 1.0 × 10 ⁻² Solv-1 9.0 × 10 ^-2

Fourteenth Layer (First Protective Layer) Fine grain silver iodobromide emulsion (AgI 2.0 mol%, uniform AgI type, sphere equivalent diameter 0.07 μm) Coating amount of silver 0.12 Gelatin 0.63 UV-4 0.11 UV-5 0.18 Solv-5 2.0 × 10 ^-2 Cpd-5 0.10 Polyethyl acrylate latex 9.0 × 10 ^-2 Fifteenth layer (second protective layer) Fine grain silver iodobromide Emulsion (AgI 2.0 mol%, uniform AgI type, spherical equivalent diameter 0.07 μm) Coating silver amount 0.36 Gelatin 0.85 B-1 (diameter 2.0 μm) 8.0 × 10 ^-2 B-2 ( Diameter 2.0 μm) 8.0 × 10 ⁻² B-3 2.0 × 10 ⁻² W-4 2.0 × 10 ⁻² H-1 0.18

In addition to the above, the samples thus prepared include
1,2-benzisothiazolin-3-one (average 200 ppm relative to gelatin), n-butyl-p-hydroxybenzoate (about 1000 ppm the same), and 2-phenoxyethanol (about 10,000 ppm the same) were added. Furthermore, B-4, B-5, F-1, F-2, F-
3, F-4, F-5, F-6, F-7, F-8, F-
9, F-10, F-11, F-12 and iron salts, lead salts,
It contains gold salt, platinum salt, and rhodium salt. In addition to the above components, each layer contains a surfactant W-1, W-2, W-3.
Was added as a coating aid or an emulsifying dispersant. The chemical formula of each compound added to each layer is shown below.

[0109]

[Chemical 20]

[0110]

[Chemical 21]

[0111]

[Chemical formula 22]

[0112]

[Chemical formula 23]

[0113]

[Chemical formula 24]

[0114]

[Chemical 25]

[0115]

[Chemical formula 26]

[0116]

[Chemical 27]

[0117]

[Chemical 28]

[0118]

[Chemical 29]

[0119]

[Chemical 30]

[0120]

[Chemical 31]

[0121]

[Chemical 32]

[0122]

[Chemical 33]

[0123]

[Chemical 34]

[0124]

[Chemical 35]

[0125]

[Chemical 36]

Using an automatic processor and the method described below,
It was processed (until the cumulative replenishment amount of the developer became three times its tank volume). Treatment method-1 step Treatment time Treatment temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ° C. 22 ml 20 liters Bleaching 3 minutes 00 seconds 38 ° C. 25 ml 40 liters Water washing 30 seconds 24 ° C. 1200 ml 20 liters Fixed arrival 3 minutes 00 seconds 38 ℃ 25 ml 30 liter Water wash (1) 30 s 24 ℃ 10 liter from (2) to (1) Countercurrent piping system Water wash (2) 30 s 24 ℃ 1200 ml 10 liter Stability 30 s 38 ℃ 25 ml 10 Liter Dry 4 minutes 20 seconds 55 ℃ Replenishment amount is 35mm width 1m length

Next, the composition of the processing liquid will be described. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.0 Carbonic acid Potassium 30.0 37.0 Potassium bromide 1.4 0.3 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2 -Methylaniline sulfate 4.5 6.2 Add water 1.0 liter 1.0 liter

(Bleaching Solution) Tank Solution (g) Replenishing Solution (g) Ethylenediaminetetraacetic Acid Sodium Ferric Acid Trihydrate 100.0 120.0 Ethylenediaminetetraacetic Acid Disodium Salt 10.0 11.0 3-Mercapto-1 , 2,4-Triazole 0.08 0.09 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5 ml 4.0 ml Water was added to 1.0 liter 1. 0 liter pH 6.7 5.7

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ethylenediaminetetraacetic acid disodium salt 0.5 0.7 Ammonium sulfite 20.0 22.0 Ammonium thiosulfate aqueous solution (700 g / liter) 290.0 ml 320. 0 ml Water was added 1.0 liter 1.0 liter pH 6.7 7.0 (stabilizing liquid) Tank liquid / replenishing liquid common (g) sodium p-toluenesulfinate 0.03 polyoxyethylene-p-monononyl Phenyl ether 0.2 (Average degree of polymerization: 10) Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0 Add 0.75 water 1.0 liter pH 8.5

[0130]

[Table 1]

In Table 1, * the addition amount of the compound of the general formula (I) and the compound of the general formula (II) or (III) is expressed by the molar amount with respect to the Ag amount (mol) in the silver iodobromide emulsion Bu. . The coating amounts X and Y of ** DIR-Cp-1 and 2 are expressed by the molar amount with respect to the Ag amount (mol) in the silver iodobromide emulsion Bu.

[0132]

[Table 2]

In Table 2, the photographic sensitivity at an optical density of 1.3 above the fogging of the yellow density of Sample 116 is 10
It is shown as a relative sensitivity when 0 is set. ** Average R.Y. of yellow density of sample 116 M. The value is shown when the relative value of the reciprocal of the S value is 100. *** The relative sensitivity is shown when the photographic sensitivity of each sample at a shutter speed of 10 ^-2 ″ is 1.0.

From Table 2 the samples according to the embodiments of the invention are D
It can be seen that even if the amount of IR coupler is increased and the granularity is improved, the change in photographic sensitivity at each shutter speed is small and the reciprocity law property is excellent. In addition, when the compound of the general formula (I) is lacking in the aspect of the present invention, the reciprocity law property of low illuminance is particularly deteriorated, and when the compound of the general formula (II) or (III) is lacking, the photographic sensitivity is lowered. It is also clear that it will rise. Further, the photographic sensitivity is specifically high when the compound of the general formula (I) and the compound of the general formula (II) or (III) are used in combination, and the reciprocity property of high illuminance is obtained by each stabilizer alone. You can see that it is better than the ones. Note that FIG. 1 is a graph showing the optical characteristics of the filters used in the optical measurement of these samples.

Example 2 In this example, the amount of the compound of the general formula (I) and the amount of the compound of the general formula (II) or (III) added in the range where the amount of the DIR coupler according to the embodiment of the present invention is relatively large. The relationship between the amount of compound added, photographic sensitivity, fog, contrast and reciprocity law characteristics is shown. In the above-mentioned preparation of emulsion D, emulsion E was prepared by changing the addition amount of the compound of general formula (I) or the addition amount of the compound of general formula (II) or (III) as shown in Table 3 below.
-1 to 6 and Emulsions F-1 to 4 were prepared. Further, in the preparation of the emulsion D, the types of the compound of the general formula (II) or (III) are changed from TAII-1 (the compound of the general formula (II)) to TAIII-1 (the compound of the general formula (III)).
Was prepared to prepare Emulsion G. Further, using these emulsions, in the same manner as in the method described in Example 1, Samples 201 to
211 was created.

Table 4 shows the results of examining the photographic sensitivity of yellow density, fog, contrast and reciprocity law characteristics by exposing and processing these samples in the same manner as in Example 1. Here, the contrast was evaluated by the magnitude of the value of [(maximum density)-(fog)]. From Table 4, compounds of general formula (I) and general formula (I
It can be seen that when the added amount of the compound I) or (III) is within the range described in the present invention, the photographic sensitivity is high, the fog is low, the contrast is high, and the reciprocity law property is good. In addition, the compound of the general formula (II) and the general formula (III)
It can be seen that the compound (1) has a similar effect although the arrangement of nitrogen atoms in the heterocycle is slightly different.

[0137]

[Table 3]

In Table 3, the addition amount of the compound of the general formula (I) and the compound of the general formula (II) or (III) is represented by the molar amount with respect to the Ag amount (mol) in the silver iodobromide emulsion Bu. . The coating amounts X and Y of ** DIR-Cp-1 and 2 are expressed by the molar amount with respect to the Ag amount (mol) in the silver iodobromide emulsion Bu.

[0139]

[Table 4]

In Table 4, the photographic sensitivity at an optical density of 1.3 above the fog of yellow density of Sample 116 is 10
It is shown as a relative sensitivity when 0 is set. ** The relative sensitivity is shown when the photographic sensitivity of each sample at a shutter speed of 10 ^-2 "is 1.0.

Example 3 In this example, a compound of the general formula (I) and a compound of the general formula (I) are used in accordance with an embodiment of the present invention.
When the addition amounts of the compound I) or (III) and the DIR coupler are determined, the relationship between the addition amount of the Ir salt and photographic sensitivity, fog and reciprocity law characteristics is shown. Emulsion D of Example 1
In the preparation of, the aqueous solution of K ₂ IrCl ₆ is added after the addition (4) of the grain formation step and before the addition (5), as shown in Table 5 below, relative to 1 mol of silver halide in the emulsion. Emulsions H-1 to 5 were prepared by adding in this manner. Furthermore, using these silver halide emulsions,
In the same manner as in the method described in Example 1, Samples 301 to 305
It was created. Table 5 shows the configuration of the twelfth layer of these samples. Table 6 shows the yellow density photographic sensitivity of these samples,
The results of examining fog and reciprocity law characteristics are shown. From Table 6, it is clear that in the embodiment of the present invention, the addition of Ir salt to the emulsion improves the reciprocity law characteristics under high illuminance, and addition of Ir salt is preferable.

[0142]

[Table 5]

[0143]

[Table 6]

Example 4 In this example, the effect of the hydrolyzable DIR compound on the process variation will be described. DIR-Cp-1, in Sample 304 of Example 3
Samples 401 to 406 were manufactured by changing 2 as shown in Table 7. This sample was continuously processed according to the following processing method-2. The treatment was carried out until the replenisher solution in the stabilizing tank was three times as large as that in the stabilizing tank. In this example, only one type of DIR-Cp was added in the twelfth layer. Table 8 shows the gradation variation (maximum absolute gamma difference | Δγ |) of yellow density when image-like white exposure is applied to Samples 401 to 406 at a shutter speed of 10 ^-2 in the same manner as in Example 3. Table 8
According to the above, by using the hydrolyzable DIR coupler, the gradation variation (maximum absolute gamma difference | Δγ |) due to the running treatment liquid is small, and a more stable image can be obtained.

Processing method-2 (Processing step) Process processing time Processing temperature Complementary amount Color development 1 minute 40 seconds 40 ° C. 50 ml Bleach 40 seconds 38 ° C. 5 ml settling 1 minute 20 seconds 38 ° C. 30 ml Stability (1) 20 seconds 38 ℃ -Stability (2) 20 seconds 38 ℃ -Stability (3) 20 seconds 38 ℃ 40ml Dry 1 minute 15 seconds 55 ℃ * Replenishment amount per 35mm width 1m length * Stable from (3) Countercurrent method to (1)

The composition of the processing liquid is shown below. (Color developer) Tank liquid Replenisher (g / liter) (g / liter) Hydroxyethyliminodiacetic acid 3.0 3.0 1,2-Dihydroxybenzene-3,5-disulfonate sodium 1.0 1.0 Sodium sulfite 3.0 4.0 Potassium carbonate 30.0 35.0 Potassium bromide 1.0 0.4 Hydroxylamine sulfate 2.5 3.5 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 6.5 7.5 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 0.02 0.03 5-nitroindazole 0.02 0.03 pH (potassium hydroxide And water) 10.50 10.70

(Bleaching Solution) Tank Solution Replenishing Solution (g / liter) (g / liter) 1,3-Diaminopropaneferric acid ammonium ferric dihydrate 60.0 75.0 Ethylenediaminetetraacetic acid ammonium ferric dichloride Water salt 120.0 140.0 Ammonium bromide 160.0 190.0 Ammonium nitrate 30.0 35.0 pH (using acetic acid and aqueous ammonia) 5.0 4.5

(Fixer) Tank solution Replenisher (g / l) (g / l) Ammonium thiosulfate aqueous solution (700 g / l) 400.0 ml 420.0 ml Sodium sulfite 12.0 15.0 Ethylenediaminetetraacetic acid disodium salt 1 0.0 1.0 pH (using acetic acid and aqueous ammonia) 7.1 7.5 (stabilizing solution) tank solution replenishing solution (g / l) (g / l) 5-chloro-2-methyl-4-isothiazoline -3-one 0.006 0.006 2-methyl-4-isothiazolin-3-one 0.003 0.003 formalin (37%) 1.0 ml 1.0 ml polyoxyethylene-p-monononylphenyl ether (average Polymerization degree 10) 0.05 0.05 pH 4.0-8.0 4.0-8.0

[0149]

[Table 7]

[0150]

[Table 8]

[0151]

As described above, according to the present invention, excellent graininess and low-illuminance / high-illuminance reciprocity law characteristics, and high sensitivity,
A silver halide color photographic light-sensitive material having a high contrast and little process variation can be obtained. In particular, when a large amount of DIR compound is made to exist in or near the emulsion layer in order to improve graininess, high sensitivity is maintained over a wide range of irradiation degree and softening does not occur. Produce an effect.

[Brief description of drawings]

FIG. 1 is a graph showing the optical characteristics of a filter used for measuring the optical density of a sample in an example of the present invention.

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein D is contained in the emulsion layer and a layer adjacent to the emulsion layer.
The IR compound is 5 × 10 ⁻³ mol or more, and the compound represented by the general formula (I) contained in the emulsion layer is 1 × 10 ⁻⁷ mol or more per 1 mol of silver halide in the emulsion layer. × 10 ^-3
The amount of the compound represented by the general formula (I
The compound represented by the formula (I) or the general formula (III) is 5 × 10 ⁻⁵ mol or more and 1 × with respect to 1 mol of silver halide in the emulsion layer.
A silver halide color photographic light-sensitive material characterized by being 10 ^-2 mol or less. General formula (I) In the formula, Z is a non-metal atom group necessary for forming an aromatic ring, R ¹ is H, an alkyl group having 1 to 5 carbon atoms, R ² is a halogen atom, a hydroxyl group, a carboxyl group, or a sulfo group. An optionally substituted alkyl group having 1 to 8 carbon atoms, X ⁻ is a counter anion. However, N ⁺ -R ²
When forming betaine with X, X ⁻ is unnecessary. General formula (II) General formula (III) In both formulas, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ may be the same or different and each is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or a substituted Optionally represents an amino group, a hydroxy group, an alkoxy group, an alkylthio group, an optionally substituted carbamoyl group, a halogen atom, a cyano group, a carboxy group, an alkoxycarbonyl group, or a heterocyclic residue, and R ¹¹ and R ¹² Alternatively, R ¹² and R ¹³ may combine to form a 5- or 6-membered ring. However, at least one of R ¹¹ and R ¹³ represents a hydroxy group. 2. The silver halide color photographic light-sensitive material according to claim 1, which contains 1 × 10 ⁻¹⁰ mol or more of Ir with respect to 1 mol of silver halide in the emulsion layer. 3. A D which has a development inhibitor or a development inhibitor precursor which loses its development inhibiting ability in an alkaline developer after the DIR compound is released from the coupling active position.
The silver halide color photographic light-sensitive material according to claim 1, which is an IR coupler.