JPH06138574A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide color photographic sensitive material containing a methine compound making residual color compatible with graininess or sensitivity with residual color in development processing. CONSTITUTION:The silver halide color photographic sensitive material has photographic constituent layers comprising one or more photosensitive silver halide emulsion layers and one or more nonphotosensitive layers and at least one of the constituent layers contains at least one of the methine compounds represented by formula I and the average silver iodide content of the total photosensitive silver halide grains in this photographic sensitive material is controlled to >=4mol%. In formula I, R<1> is -(CH2)r-CONHSO2-R<3>, -(CH2)s-SO2 NHCOR<4>, -(CH2)t-CONHCO-R<5>, or -(CH2)u-SO2NHSO2-R<6>; each of R<3>-R<6> is alkyl or the like; each of r, s, t, and u is an integer of 1-5; R<2> is same as R<1> or alkyl; each of Z<1> and Z<2> is a nonmetallic atomic group necessary to form a 5- or 6-membered hetero ring; each of p and q is 0 or 1; each of L1-L3 is a methine group; m is 0, 1, 2 and X1 is an anion; and k is a number necessary to adjust a charge.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color light-sensitive material, and more particularly to a color light-sensitive material containing a methine compound having excellent sensitivity / granularity and having improved residual color after development processing.

[0002]

2. Description of the Related Art In recent years, with the speeding up of development processing and the addition of large amounts of sensitizing dyes, the sensitizing dyes contained in silver halide light-sensitive materials are not completely dissolved during the processing and coloring remains in the light-sensitive materials ( There is a problem of so-called residual color or a problem of desilvering in which developed silver formed in the developing process is not dissolved and removed in the desilvering and fixing processes.

Sensitizing dyes having less residual color have a hydrophilic substituent such as a sulfamoyl group or a carbamoyl group (for example, JP-A-1-147451 and JP-A-61-29).
No. 4429, Japanese Patent Publication No. 32749/1985, Japanese Patent Laid-Open No. 61-
No. 77843) has been investigated, but if the hydrophilicity of the sensitizing dye is increased, the adsorptivity is generally lowered, and thus the sensitivity is not sufficient in any case. In addition, the residual color is not sufficiently satisfactory. Further, the sensitizing dye described in U.S. Pat. No. 3,822,933 also has the effect of improving the residual color, but in terms of compatibility of the residual color and the sensitivity, it is sufficient in terms of coping with the speeding up of development processing. Not obtained.

As means for improving the desilvering failure, US Pat. No. 3,893,858, British Patent No. 1,138,842, mercapto compounds described in JP-A-53-141623 and JP-A-53-95630 are described. Compounds having a disulfide bond, JP-B-45-8
There are thiourea derivatives described in Japanese Patent Publication No. 506 and Japanese Patent Publication No. 49-26586.

Although some of these bleaching accelerators certainly exhibit a bleaching promoting effect, they are expensive and the bleaching promoting effect itself is still insufficient, so that they are not practically used.
I'm not satisfied.

In contrast, Research. Disclosure Item No. Nos. 24241 and 11449 and JP-A-61-201247 describe a bleach-accelerating release coupler.

On the other hand, it is known that graininess is improved by using a high iodine emulsion having a high silver iodide content as the silver halide emulsion.

It is also known that when the silver iodide content in a silver halide color light-sensitive material is increased, the desilvering property is deteriorated.

On the other hand, in parallel with the recent trend toward higher image quality, higher sensitivity is also in progress. Although a high-sensitivity light-sensitive material having ISO 400 or higher has been released, the performance deterioration range is larger than that of a conventional type having a sensitivity of about ISO 100, and development of means for improving the above is urgent.

[0010]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a methine compound capable of achieving both the residual color and the sensitivity or the residual color and the granularity during development processing, and a silver halide color photographic light-sensitive material containing the compound. It is in.

[0011]

The above objects of the present invention are as follows.
(1) having a photographic constituent layer containing at least one photosensitive silver halide emulsion layer and at least one non-photosensitive layer,
Further, in a color photographic light-sensitive material containing at least one methine compound represented by the following general formula (I) in at least one of the photographic constituent layers, all light-sensitive silver halide grains contained in the color photographic light-sensitive material are used. A silver halide color photographic light-sensitive material having an average silver iodide content of 4 mol% or more.

[0012]

[Chemical 2] In the formula, R ¹ is — (CH ₂ ) _r —CONHSO ₂ —
_{^{R 3, - (CH 2)}} s -SO 2 NHCO-R 4, -
_{(CH 2) t -CONHCO-R} 5 or, - (CH
₂₎ represents a _u -SO ₂ NHSO ₂ -R ^6. Here, R ³ , R ⁴ , R ⁵ , or R ⁶ represents an alkyl group, an alkoxy group, or an amino group, and r, s, t, or u
Represents an integer from 1 to 5. R ² has the same meaning as R ¹ or represents an alkyl group. Z ¹ and Z ² represent a group of non-metal atoms necessary for forming a 5- or 6-membered heterocycle, and p and q represent 0 or 1.

L ₁ , L ₂ or L ₃ represents a methine group, and m represents 0, 1 or 2. X ₁ represents an anion, and k represents the number required to adjust the charge in the molecule to zero. And (2) ISO speed of the silver halide color photographic light-sensitive material in daylight illuminant is 160
This is achieved by the color photographic light-sensitive material described in (1) above.

The present invention will be described in more detail below.

The methine compound of the general formula (I) will be described in detail below.

The alkyl group represented by R ³ , R ⁴ , R ⁵ or R ⁶ may be substituted and is preferably one having 4 or less carbon atoms, particularly preferably methyl, ethyl, hydroxyalkyl or aminoethyl. Is. The alkoxy group may be substituted and is preferably one having 4 or less carbon atoms, particularly preferably methoxy, ethoxy, methoxyethoxy or hydroxyethoxy. The amino group may be substituted with an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group or the like, and the substituents may form a ring, and those having 8 or less carbon atoms are preferable. Particularly preferred are methylamino, dimethylamino,
It is ethylamino, diethylamino, hydroxyethylamino, morpholino, or pyrrolidino. The alkyl group represented by R ² may be substituted and is preferably one having 5 or less carbon atoms, particularly preferably 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl or 3-sulfobutyl. Preferred values of r, s, t, or u are 1, 2, and 3.

The 5- or 6-membered heterocyclic nucleus represented by Z ¹ and Z ² is a thiazole nucleus, {thiazole nucleus (eg thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4 , 5-diphenylthiazole), a benzothiazole nucleus (for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole,
5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-
Phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole,
5-chloro-6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5,6-dimethoxybenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydroxybenzothiazole, 4-phenylbenzothiazole), naphthothiazole Nuclei (eg naphtho [2,1-d] thiazole, naphtho [1,2-d]
Thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole , 5-methoxynaphtho [2,
3-d] thiazole)}, thiazoline nucleus (for example, thiazoline, 4-methylthiazoline, 4-nitrothiazoline), oxazole nucleus {oxazole nucleus (for example, oxazole, 4-methyloxazole, 4-nitroxazole, 5-methyloxazole) , 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole), benzoxazole nucleus (eg, benzoxazole, 5-chlorobenzoxazole, 5-
Methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5- Carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole,
5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole), naphthoxazole nucleus (eg, naphtho [2,1
-D] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, 5-nitronaphtho [2,1-d] oxazole)}, oxazoline nucleus (eg, 4,4-dimethyloxazoline) ), Selenazole nuclei {selenazole nuclei (for example, 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole), benzoselenazole nuclei (for example, benzoselenazole, 5-chlorobenzoselenazole, 5-nitro) Benzoselenazole, 5-methoxybenzoselenazole,
5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole, 5,6-dimethylbenzoselenazole), naphthoselenazole nucleus (for example, naphtho [2,1-d]) Selenazole, naphtho [1,2-d] selenazole)}, selenazoline nucleus (eg, selenazoline, 4-methylselenazoline), tellurazole nucleus {terrazole nucleus (eg,
Tellurazole, 4-methylterrazole, 4-phenylterrazole), benzoterrazole nucleus (for example, benzoterrazole, 5-chlorobenzoterrazole, 5-
Methylbenzoterrazole, 5,6-dimethylbenzotelrazole, 6-methoxybenzotelrazole), naphthoterrazole nucleus (for example, naphtho [2,1-d] telrazole, naphtho [1,2-d] telrazole)} , A tellrazoline nucleus (for example, tellrazoline, 4-methylterrazoline), 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5- Cyanoindolenine, 3,3-dimethyl-6-nitroindolenine,
3,3-dimethyl-5-nitroindolenine, 3,3-
Dimethyl-5-methoxyindolenine, 3,3,5-trimethylindolenine, 3,3-dimethyl-5-chloroindolenine), imidazole nucleus {imidazole nucleus (for example, 1-alkylimidazole, 1-alkyl-4-
Phenylimidazole, 1-arylimidazole),
Benzimidazole nuclei (for example, 1-alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole, 1-alkyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-alkyl-5- Cyanobenzimidazole, 1
-Alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole,
1-alkyl-6-chloro-5-cyanobenzimidazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzo Imidazole, 1-arylbenzimidazole, 1-
Aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole, 1-aryl-
5-cyanobenzimidazole), naphthoimidazole nucleus (for example, alkylnaphtho [1,2-d] imidazole, 1-arylnaphtho [1,2-d] imidazole), the above-mentioned alkyl group has 1 to 8 carbon atoms. The one
For example, methyl, ethyl, propyl, isopropyl,
An unsubstituted alkyl group such as butyl or a hydroxyalkyl group (eg, 2-hydroxyethyl, 3-hydroxypropyl) is preferable. Particularly preferred are methyl and ethyl. The aforementioned aryl group represents phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl. }, A pyridine nucleus (for example, 2-pyridine, 4
-Pyridine, 5-methyl-2-pyridine, 3-methyl-
4-pyridine), quinoline nucleus {quinoline nucleus (for example, 2
-Quinoline, 3-methyl-2-quinoline, 5-ethyl-
2-quinoline, 6-methyl-2-quinoline, 6-nitro-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2- Quinoline, 4-quinoline, 6-ethoxy-4-quinoline, 6-nitro-4-quinoline, 8
-Chloro-4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4-quinoline, 8-methoxy-4-quinoline, 6-methyl-4-quinoline, 6-methoxy-4
-Quinoline, 6-chloro-4-quinoline), isoquinoline nucleus (e.g. 6-nitro-1-isoquinoline, 3,4
-Dihydro-1-isoquinoline, 6-nitro-3-isoquinoline)}, imidazo [4,5-b] quinoxaline nucleus (eg 1,3-diethylimidazo [4,5-b] quinoxaline, 6-chloro-1 , 3-diallylimidazo [4,5-b] quinoxaline), oxadiazole nucleus,
Examples thereof include thiadiazole nucleus, tetrazole nucleus, and pyrimidine nucleus.

Among these heterocyclic nuclei, preferred are thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzimidazole nucleus, naphthimidazole nucleus and quinoline nucleus, Most preferably, it is a benzothiazole nucleus, a benzoselenazole nucleus, or a quinoline nucleus.

The methine group represented by L ₁ , L ₂ and L ₃ may be substituted, and the substituent may be an optionally substituted alkyl group (eg, methyl, ethyl, 2-carboxyethyl), or may be substituted. Good aryl groups (eg phenyl, o-carboxyphenyl), halogen atoms (eg chlorine, bromine), alkoxy groups (eg methoxy, ethoxy), alkylthio groups (eg methylthio, ethylthio) and the like, and other methine groups May form a ring, or may form a ring with the auxochrome.
The anion represented by X ₁ is an inorganic or organic acid anion (for example, chloride, bromide, iodide, p-toluenesulfonate, naphthalenedisulfonate, methanesulfonate, methylsulfate, ethylsulfate, perchlorate, etc.). Can be mentioned.

The value of m is preferably 0 or 1.

Specific examples of the methine compound represented by formula (I) are shown below, but the scope of the present invention is not limited thereto.

[0022]

[Chemical 3]

[0023]

[Chemical 4]

[0024]

[Chemical 5]

[0025]

[Chemical 6]

[0026]

[Chemical 7]

[0027]

[Chemical 8]

[0028]

[Chemical 9]

[0029]

[Chemical 10] The methine compound represented by the general formula (I) can be synthesized according to the method shown below. Synthesis Example 1 Synthesis of 5-chloro-3-methanesulfonylaminocarbonylmethyl-2-methylbenzothiazolium bromide N- (bromoacetyl) methanesulfonamide 5 synthesized according to the method described in US Pat. No. 3,282,933.
0 g, 5-chloro-2-methylbenzothiazole 36.
6 g, and 10 ml of 4 ml of methyl ethyl ketone
Stir for 5 hours on a 5 ° C. oil bath. Acetone 20 in the reaction solution
0 ml was added and the mixture was refluxed for 1 hour and then cooled with water.
After 1 hour, the crystals were suction filtered, washed with 100 ml of acetone and dried to give 59.6 g (7%) of the title compound.
4.7%) was obtained. Synthesis of Exemplified Compound I-1 5-Chloro-3-methanesulfonylaminocarbonylmethyl-2-methylbenzothiazolium bromide 38.
06 g and 4- {5-chloro-2- (ethoxy-1-
Butenyl) -3-benzothiazolio} butane sulfonate (40.46 g) was added with methanol (477 ml) and the mixture was stirred.
Add 1 ml dropwise and stir for 1 hour. 82 ml of acetic acid is added to the reaction solution, stirred for 20 minutes, and cooled with water.
After 1 hour, the crystals were suction filtered, washed with 150 ml of methanol, and dried to give crude crystals of I-1 of 48.
7 g are obtained.

The crude crystals are dissolved in 600 ml of methanol and 30 ml of triethylamine, and the insoluble matter is filtered off with suction. After washing with 300 ml of methanol, the filtrate is concentrated under normal pressure, and 400 ml is distilled off. 40 ml of acetic acid is added to the residual liquid at 55 ° C., stirred for 20 minutes, and then cooled with water. After 1 hour, the crystals were suction filtered and washed with 250 ml of methanol,
Upon drying, 36.2 g (56.1%) of I-1 was obtained.

Λmax (MeOH) 554 nm (1.1
4 × 10 ⁵ ) Melting point> 300 ° C. Synthesis example 2 Synthesis of 5-chloro-3-methanesulfonylaminocarbonylethyl-2-methylbenzothiazolium bromide Synthesized according to the method described in US Pat. No. 3,282,933. 46 g of N- (β-bromopropionyl) methanesulfonamide and 20 g of 5-chloro-2-methylbenzothiazole are stirred on an oil bath at 115 ° C. for 60 hours. 200 ml of ethyl acetate was added to the reaction solution, and the mixture was stirred for 20 minutes, and crystals were filtered to obtain 40.8 g of the title compound.
(82%) was obtained. Synthesis of Exemplified Compound I-3 5-Chloro-3-methanesulfonylaminocarbonylethyl-2-methylbenzothiazolium bromide 2.1
1. g and 4- {5-chloro-2- (ethoxy-1-butenyl) -3-benzothiazolio} butane sulfonate 2.
Dissolve 4 g in 20 ml of benzyl alcohol,
2 ml of triethylamine is added to this solution at room temperature, and the mixture is stirred for 1 hour. The insoluble matter is filtered off from the reaction solution, 100 ml of ethyl acetate and 10 ml of glacial acetic acid are added to the filtrate, and the mixture is stirred for 10 minutes. The obtained crystals are dissolved in methanol-triethylamine, the insoluble matter is filtered off, 10 ml of glacial acetic acid is added to the filtrate, methanol is distilled off under atmospheric pressure to 1/3, and the mixture is cooled with water. The obtained crystals were filtered out to obtain 0.6 g of I-3 (17.4%).

Λmax (MeOH) 553 nm (ε1.
33 × 10 ⁵ ) Melting point> 300 ° C. The physical properties of the methine compound of the present invention synthesized by the same method are shown below.

Exemplified Compound λmax (MeOH) Melting Point I-2 550 (1.20 × 10 ⁵ )> 300 ° C. I-4 551 (1.21 × 10 ⁵ ) 〃 I-5 551 (1.13 × 10 ⁵⁾ ) 〃 I-6 551 (1.30 × 10 ⁵ ) 〃 I-7 551 (1.19 × 10 ⁵ ) 〃 I-8 560 (1.22 × 10 ⁵ ) 〃 I-9 552 (1.30 ×) 10 ⁵ ) 〃 I-10 538 (4.51 × 10 ⁵ ) 〃 I-11 503 (1.37 × 10 ⁵ ) 〃 I-12 500 (1.42 × 10 ⁵ ) 〃 The average silver iodide content of the silver halide grains in one or two of the silver halide emulsion layers is 4 mol% or more, and the average silver iodide content in the silver halide emulsion layer is 4 mol% or more. Is 4 mol%
Although it may be the following, in all light-sensitive silver halide emulsions,
The average silver iodide content of the silver halide grains is preferably 4 mol% or more.

The average silver iodide content of all the photosensitive silver halide grains is preferably 4 mol% or more and 15 mol% or less, more preferably 6 mol% or more and 10 mol% or less.

The ISO speed of the daylight illuminant of the present invention is exposed by the method described in 3.1 of JIS standard 7602 and measured by the method described in JIS standard 7613.

The ISO speed of daylight illuminant of the silver halide color light-sensitive material of the present invention is preferably ISO 160 or more and ISO 6400 or less.

The photographic emulsion used in the present invention may be spectrally sensitized with other methine dyes and the like together with the compound represented by the general formula (I) of the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl 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, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nucleus of aromatic hydrocarbon ring fused to nuclei of indolenin, benzoindolenin, indole, benzoxazole, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole A nucleus, a quinoline nucleus, etc. 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, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, and a thiazolidine-2,4-
A 5-6 membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus or a thiobarbituric acid nucleus can be applied.

The compound of the present invention may be used alone,
A combination thereof may be used, and a combination of sensitizing dyes is often used particularly for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,977,2.
No. 29, No. 3,397,060, No. 3,522,05
No. 2, No. 3,527, 641, No. 3, 617, 293
No. 3,628,964, 3,666,480
Issue 3, Issue 3,672,898, Issue 3,679,428
No. 3,03,377, No. 3,769,301,
Nos. 3,814,609, 3,837,862, 4,026,707, and British Patent 1,344,281.
No. 1,507,803, JP-B-43-49336
No. 53-12,375, JP-A No. 52-110,6.
18 and 52-109,925.

Along with the compound of the present invention, 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 compound of the present invention may be added to the emulsion at any stage in the preparation of the emulsion which has heretofore been known to be useful. Most commonly, it is performed after the completion of chemical sensitization and before coating, but U.S. Pat. Nos. 3,628,969 and 4,225,666.
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A-58-58.
It can be carried out prior to chemical sensitization as described in JP-A-113,928, or it can be added before the completion of silver halide grain precipitation to start spectral sensitization. It is also possible to add these said compounds separately, as taught in U.S. Pat. No. 4,225,666, i.e. to add some of these compounds prior to chemical sensitization and the rest to chemical sensitization. It can be added after the sensation and can be added at any time during silver halide grain formation, including the method taught in US Pat. No. 4,183,756.

Further, the compound of the present invention may be added to a non-photosensitive emulsion layer or a non-photosensitive layer and used as a light-absorbing dye for the purpose of improving image sharpness, as is well known.

The amount of addition is 4 × per mol of silver halide.
It can be used in an amount of 10 ⁻⁶ to 8 × 10 ⁻³ mol, but in the case of a more preferable silver halide grain size of 0.2 to 1.2 μm, about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is more effective. Is.

The silver halide used in the present invention is 0.1
Silver iodobromide, silver iodochloride, or silver iodochlorobromide containing ~ 30 mol% of silver iodide. Particularly, it is effective in combination with the compound represented by the general formula (I) and silver iodobromide or silver iodochlorobromide having a silver iodide content of 3 to 25 mol%.

The silver halide emulsion used in the present invention may have any grain size distribution, but the maximum grain size (average)
The weight of silver halide contained in the grain size range of ± 20% centered on r is preferably 60% or more, more preferably 80% or more of the total weight of silver halide grains.

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

The silver halide used in the present invention is 0.1
Silver iodobromide, silver iodochloride, or silver iodochlorobromide containing ˜30 mol% silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 25 mol% silver iodide.

The silver halide grains used in the present invention have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

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

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation and types",
Id. No. 18716 (November 1979), p.648, ibid.
No. 307105 (November 1989), 863-86
P.Glafkides.Chemie et Phisique Photograp, P.Glafkides.Chemie et Phisique Photograp
hique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photog
raphic EmulsionChemistry, Focal Press, 196
6), and "Production and Coating of Photographic Emulsions" by Zelikmann et al.,
Published by Focal Press (VLZelikman et al., Making a
nd Coating Photographic Emulsion, Focal Press, 19
64) and the like.

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent 1,413,748.
The monodisperse emulsions described in JP-A No. 1989-2000 are also preferable.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention contains silver iodobromide, silver iodochloride, or iodochlorobromide containing not more than about 30 mol% of silver iodide. It is silver. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

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

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No. 17
643 (Dec. 1978), pp. 22-23, "I. Emulsion production (Emulsi
on preparation and types) ”, and No. 18716 (19)
Nov. 1979), pp. 648, ibid. 307105 (Nov. 1989), 863-
Page 865, and "Graphics and Chemistry" by Graphide, published by Paul Montel (P.Glafkides, Chemie et Phisique
Photographique, PaulMontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Ph
otographic Emulsion Chemistry (Focal Press, 196
6)), "Production and Coating of Photographic Emulsions" by Zelikman et al., Published by Focal Press (VL Zelikman et al., Making and
Coating Photographic Emulsion, Focal Press, 1964)
And the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and E.
14: 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048,
It can be easily prepared by the method described in U.S. Pat. No. 4,439,520 and British Patent No. 2,112,157.

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

The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed, or a type having a latent image on both the surface and the inside. Must be a type of emulsion. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The shell thickness of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

As the silver halide emulsion, those which have been physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the relevant portions are summarized in the table below.

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.

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

The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.75 μm,
In particular, 0.05 to 0.6 μm is preferable. The grain shape is not particularly limited and may be regular grains or polydisperse emulsions, but monodisperse grains (at least 95% of the weight or the number of silver halide grains are ± 40% of the average grain size). %) Is preferable).

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

The fine grain silver halide has a silver iodide content of
It is 0 to 100 mol%, and may contain silver chloride and / or silver iodide, if necessary. Preferably silver iodide is 0.5
~ 10 mol% is contained.

The fine grain silver halide preferably has an average grain diameter (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.

The coated silver amount of the light-sensitive material of the present invention is 6.0 g / m ^2.
The following is preferable, and 4.5 g / m ² or less is most preferable.

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

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

For the intermediate layer, JP-A-61-43748 and 59-1 are used.
13438, 59-113440, 61-20037, 61-20038
The couplers as described in the specification, DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as is commonly used.

The plural silver halide emulsion layers constituting each unit light-sensitive layer are composed of two layers of high-sensitivity emulsion layer and low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. Can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition, JP-A-57-11275
1, No. 62-200350, No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer on the side farther from the support and a high-sensitivity emulsion layer on the side closer to the support. May be installed.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / Low sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / RH / RL order, or BH / BL / GH /
It can be installed in the order of GL / RL / RH.

Further, as described in JP-B-55-34932, the blue-sensitive layer / GH from the side farthest from the support.
It can also be arranged in the order of / RH / GL / RL. In addition,
56-25738 and 62-63936, the blue-sensitive layer / GL / RL from the side farthest from the support.
It can also be arranged in the order of / GH / RH.

As described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity,
The middle layer is a silver halide emulsion layer having a lower photosensitivity, and the lower layer is a silver halide emulsion layer having a lower photosensitivity than the middle layer. The photosensitivity is gradually reduced toward the support. An arrangement composed of three layers can be mentioned. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side distant 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, 4
In the case of more than one layer, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat.
No. 663,271, No. 4,705,744, No. 4,707,436, and JP-A Nos. 62-160448 and 63-89850.
It is preferable to arrange a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, or RL, adjacent to or in proximity to the main photosensitive layer.

As described above, various layer structures and arrangements can be selected according to the purpose of each light-sensitive material.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table.

Types of Additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 Page 868 Supersensitizer ~ page 649 Right column 4. Whitening agent page 24 647 Page right column 868 page 5. Fogging prevention 24 ~ 25 page 649 Page right column 868 ~ 870 Agent, stabilizer 6. Light absorber , Pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dyes, ultraviolet absorbers, stain 7. stain, page 25, right column, page 650, left column, page 872, inhibitor, right column 8. dye image, page 25, page 650, left Column page 872 Stabilizer 9. Hardener page 26 651 page left column 874 to 875 page 10. Binder page 26 page 651 page left column 873 to 874 page 11. Plasticizer, page 27 page 650 right column page 876 lubricant 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surface active agent, 13. static, page 27, page 650, right column, pages 876 to 877, inhibitor, matting agent, pages 878 to 879, and formaldehyde. In order to prevent the deterioration of photographic performance due to vinegar, US Pat. No. 4,411,987 and the 4,435,503
It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde described in No.

The light-sensitive material of the present invention can be incorporated into US Pat. No. 4,740,4
54, No. 4,788,132, JP-A-62-18539, JP-A-1-
It is preferable to contain the mercapto compound described in No. 283551.

To the light-sensitive material of the present invention, a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof described in JP-A 1-106052, irrespective of the amount of developed silver produced by the development processing. It is preferable to include a releasing compound.

The light-sensitive material of the present invention has the international publication WO88 / 04794.
It is preferable to incorporate the dyes dispersed by the method described in JP-A No. 1-502912 or the dyes described in EP 317,308A, US Pat. No. 4,420,555 and JP-A 1-259358.

Various color couplers can be used in the light-sensitive material of the present invention. Specific examples thereof are Research Disclosure Nos. 17643, VII-C to G and 307105, VII-C. To the patents listed in G.

Examples of yellow couplers include US Pat. Nos. 3,933,501, 4,022,620 and 4,326,024.
No. 4,401,752, No. 4,248,961, No. 58-
10739, British Patents 1,425,020, 1,476,760
U.S. Pat.Nos. 3,973,968, 4,314,023, and
Those described in 4,511,649, European Patent 249,473A, etc. are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,63 are preferred.
6, US Pat. Nos. 3,061,432, 3,725,067, Research Disclosure No. 24220 (June 1984),
JP-A-60-33552, Research Disclosure No.2
4230 (June 1984), JP-A-60-43659, 61-72238
No. 60, No. 60-35730, No. 55-118034, No. 60-185951,
U.S. Pat.Nos. 4,500,630, 4,540,654, 4,5
Those described in 56,630, International Publication WO88 / 04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
2,212, 4,146,396, 4,228,233, and
4,296,200, 2,369,929, 2,801,171,
No. 2,772,162, No. 2,895,826, No. 3,772,002
No. 3, No. 3,758,308, No. 4,334,011, No. 4,32
7,173, West German Patent Publication 3,329,729, European Patent 12
1,365A, 249,453A, U.S. Pat.No. 3,446,622
No. 4, No. 4,333,999, No. 4,775,616, No. 4,45
1,559, 4,427,767, 4,690,889, and
Those described in 4,254,212, 4,296,199 and JP-A-61-42658 are preferable. Furthermore, JP-A-64-553,
Pyrazoloazole couplers described in JP-A Nos. 64-554, 64-555 and 64-556 and imidazole couplers described in US 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, 4,080,211, 4,367,282, 4,409,320 and 4,576,910.
, British Patent 2,102,137, European Patent 341,188A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,12.
5,570, European Patent 96,570, West German Patent (Publication)
Those described in 3,234,533 are preferable.

Colored couplers for correcting unnecessary absorption of color-forming dyes are Research Disclosure No. 1
7643, VII-G, No. 307105, VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat.
Those described in 4,929, 4,138,258 and British Patent 1,146,368 are preferable. Also, U.S. Pat.
And a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.
It is also preferable to use a coupler having a dye precursor group as a leaving group capable of reacting with a developing agent to form a dye as described in 4,777,120.

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 RD 176 above.
43, VII-F and No. 307105, patents described in VII-F, JP-A-57-151944, 57-154234 and 60-
184248, 63-37346, 63-37350, U.S. Pat.
Those described in 48,962 and 4,782,012 are preferable.

RD No. 11449 and 24241, JP-A-61-20124
The bleaching accelerator releasing couplers described in No. 7 and the like are effective for shortening the time of the processing step having a bleaching ability, and in particular,
The effect is great when it is added to the light-sensitive material using the tabular silver halide grains described above. As a coupler that releases a nucleating agent or a development accelerator imagewise during development,
British Patent Nos. 2,097,140 and 2,131,188, JP Sho 59
-157638 and 59-170840 are preferable.
Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-
Compounds releasing a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in 44940 and 1-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,3.
38,393, 4,310,618 and the like, multi-equivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds described in JP-A-60-185950 and JP-A-62-24252. Alternatively, DIR redox-releasing redox compounds, couplers that release dyes that undergo color restoration after separation described in European Patents 173,302A and 313,308A, ligand-releasing couplers described in U.S. Pat. -75747 couplers releasing leuco dyes, U.S. Pat.
Examples thereof include couplers that release the fluorescent dye described in No. 181.

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

Examples of high boiling point 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 (dibutyl phthalate, dicyclohexyl phthalate,
Di-2-ethylhexyl phthalate, decyl phthalate,
Of 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 (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc. ), Benzoic acid esters (2-
Ethylhexyl benzoate, dodecyl benzoate,
2-ethylhexyl-p-hydroxybenzoate etc.),
Amides (N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), Aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-butoxy-5-) tert-octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363,
West German Patent Application (OLS) Nos. 2,541,274 and 2,541,23
No. 0 etc.

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

Suitable supports which can be used in the present invention are described in, for example, RD. No. 17643, page 28, No. 18716, page 647, right column to page 648, left column, and No. 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, further preferably 18 μm or less, and 16 μm or less. Particularly preferred. 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, Photographic Science and Engineering by A. Green et al.
(Photogr.Sci.Eng.), Vol. 19, No. 2, p. 124-129. A swellometer of the type described can be used for the measurement, and T _1/2 is 30 in a color developer. The saturated film thickness is defined as 90% of the maximum swollen film thickness reached when the film is treated at ℃ for 3 minutes and 15 seconds, and 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 the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness.

The photosensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
In this back layer, the above-mentioned light absorber, filter dye,
It is preferable to contain an ultraviolet absorber, an antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, a surface active agent and the like. The swelling ratio of this back layer is 150-50.
0% is preferable.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, aminophenol compounds are also useful, but 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, 4-amino-3-methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N-
(3-Hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (2-hydroxypropyl) aniline, 4-
Amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-
Hydroxypropyl) aniline, 4-amino-3-propyl
-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-methyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-ethyl-N -(4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl
-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-
Hydroxypentyl) aniline, 4-amino-3-methyl-N
-(5-hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N, Examples thereof include N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, especially 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl)
Aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline and their hydrochlorides, p-toluenesulphonates or sulphates are preferred. Two or more of these compounds can be used in combination depending on the purpose.

The color developing solution contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt,
It generally contains a development inhibitor such as bromide salt, iodide salt, benzimidazole, benzothiazole or mercapto compound, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-
Auxiliary developing agents such as phenyl-3-pyrazolidone, viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, Typical examples are N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

Next, the processing solutions and processing steps for the color reversal light-sensitive material of the present invention other than the color developing solution will be described.

Among the processing steps of the color reversal light-sensitive material of the present invention, the steps from black development to color development are as follows.

1) Black-white development-water washing-reversal-color development 2) Black-white development-water washing-light reversal-color development 3) Black-white development-water washing-color development Steps 1) to 3) are all performed in US patents. 4,8
In place of the rinse process described in No. 04,616, it is possible to simplify the process and reduce waste liquid.

Next, the steps after color development will be described.

4) Color development-adjustment-bleaching-fixing-washing-
Stable 5) Color development-washing-bleaching-fixing-washing-stable 6) Color development-adjusting-bleaching-washing-fixing-washing-stable 7) Coloring development-washing-bleaching-washing-fixing-washing-stable 8) Color development Development-bleaching-fixing-washing-stable 9) Color development-bleaching-bleaching fixing-washing-stable 10) Coloring development-bleaching-bleaching fixing-fixing-washing-stable 11) Color development-bleaching-washing-fixing-washing- Stable 12) Color development-adjustment-bleach-fix-washing-stable 13) Color development-wash-bleach-fix-wash-stable 14) Color development-bleach-fix-wash-stable 15) Color development-fix-bleach-fix-wash- In the treatment steps of Stability 4) to 15), the washing step immediately before the stabilizing step may be removed, or conversely, the stabilizing step of the final step may not be performed. Any one of the above steps 1) to 3) and any one of steps 4) to 15) are connected to form a color reversal step.

Next, the processing liquid in the color reversal processing step of the present invention will be described.

Known developing agents can be used in the black and white developing solution used in the present invention. As a developing agent,
Dihydroxybenzenes (eg hydroquinone),
3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-aminophenol), 1-phenyl-3-pyrazolines, ascorbic acid and U.S. Pat. No. 4,067,8.
A heterocyclic compound such as 1,2,3,4-tetrahydroquinoline ring and an indrene ring described in No. 72 can be used alone or in combination.

The black-and-white developer used in the present invention may further contain a preservative (eg, sulfite, bisulfite, etc.), a buffer (eg, carbonate, boric acid, borate, alkanolamine), an alkaline agent, if necessary. (Eg, hydroxide, carbonate), dissolution tablet (eg, polyethylene glycols,
These esters), pH adjusters (for example, organic acids such as acetic acid), sensitizers (for example, quaternary ammonium salts), development accelerators, surfactants, defoamers, hardeners, viscosity imparting agents, etc. Can be included.

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

The pH value of the developer thus adjusted is selected to an extent sufficient to give a desired density and contrast, but is in the range of about 8.5 to about 11.5.

In order to carry out the sensitizing process using such a black-and-white developing solution, it is usually necessary to extend the time up to about 3 times the standard process. At this time, if the processing temperature is raised, the extension time for the sensitization processing can be shortened.

The pH of these color developing solution and black-and-white developing solution is generally 9-12. The replenishment amount of these developers depends on the color photographic light-sensitive material to be processed,
Generally, it is 3 liters or less per square meter of the light-sensitive material, and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. When the replenishment 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 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 (c ^m2 )] ÷ [volume of treatment liquid (c ^m3 )] The above aperture ratio is preferably 0.1 or less, more preferably It is 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit development processing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as 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 reversal bath used after black and white development may contain a known fogging agent. That is, stannous ion-organic phosphoric acid complex salt (US Pat. No. 3,617,282), stannous ion organic phosphonocarboxylic acid complex salt (Japanese Patent Publication No. 56-32616), stannous ion-
Aminopolycarboxylic acid complex salt (US Pat. No. 1,209,0
50), stannous ion complex salts, borohydride compounds (US Pat. No. 2,984,567),
Heterocyclic amine borane compounds (UK Patent No. 1,011,0
No. 00 specification) and the like, and the like. The fogging bath (reversal bath) has a wide pH range from the acidic side to the alkaline side, and has a pH of 2 to 12, preferably 2.5 to 10, and particularly preferably 3 to 9.
A light reversal process by re-exposure may be performed instead of the reversal bath, and the reversal step may be omitted by adding the fogging agent to the color developing solution.

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

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

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patent 1,290,812.
No. 2,059,988, JP-A-53-32736, and JP-A-53-57831
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53
-95631, 53-104232, 53-124424, 53-141
623, 53-28426, Research Disclosure
Compounds having a mercapto group or a disulfide group described in No. 17129 (July 1978), etc .; JP-A-50-140129
Thiazolidine derivatives described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, and US Pat. No. 3,706,561.
Thiourea derivative described in Japanese Patent No. 1,127,715, West German Patent
Iodide salts described in JP-A-58-16,235; West German Patent No. 966,
Polyoxyethylene compounds described in JP-A Nos. 410 and 2,748,430; polyamine compounds described in JP-B-45-8836; Other JP-A-49-40,943, 49-59,644, 53-94,92
No. 7, No. 54-35,727, No. 55-26,506, No. 58-163,940
Compounds described in No. 1; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, US Pat.
3,858, West German Patent 1,290,812, JP-A-53-95,630
Compounds described in US Pat. Further, U.S. Pat.
The compounds described in No. 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 has an acid dissociation constant (p
Ka) is a compound of 2 to 5, and specifically, acetic acid, propionic acid, hydroxyacetic acid and the like are preferable.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Use of thiosulfates Are generally used, and ammonium thiosulfate is most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like 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 and the bleach-fixing solution for the purpose of stabilizing the solution. 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 treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to
45 ° C. In the preferable temperature range, the desilvering rate is improved, and 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. Specific examples of the method for strengthening stirring include a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and JP-A-62-1834.
A method of increasing the stirring effect using the rotating means of No. 61, and further moving the photosensitive material while bringing the emulsion surface into contact with the wiper blade provided in the liquid to make the emulsion surface turbulent, thereby further improving the stirring effect. Examples thereof include a method for improving the method and a method for increasing the circulation flow rate of the entire processing solution. 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, JP-A-60-191258, and JP-A-60-191258.
It is preferable to have the photosensitive material conveying means described in 60-191259. As described in JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath and has a high effect of preventing the deterioration of the performance of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture a
nd Television Engineers Volume 64, P. 248-253 (1955)
May May issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to this problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be very effectively used. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antibacterial and fungicide" (1986) Sankyo Publishing, Sanitary Technology Society, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society for Antibacterial and Antifungal, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) The disinfectants described can also be used.

Rinsing water in processing the light-sensitive material of the present invention
The pH is 4-9, preferably 5-8. The washing water temperature and the washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but in general, it is 20 seconds to 10 minutes at 15 to 45 ° C., preferably
A range of 30 seconds to 5 minutes at 25-40 ° C is selected. 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, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used.

In addition, there is a case where a stabilizing treatment is further carried out after the water washing treatment, and as an example thereof, a stabilizer containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing is used. You can mention the bath. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution resulting from the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

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 U.S. Pat.
42,597 Indoaniline compounds, 3,342,5
99, Research Disclosure 14,850 and 1
Examples thereof include Schiff base type compounds described in 5,159, aldol compounds described in 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628.

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 Nos. 56-64339, 57-144547, and
58-115438, etc.

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

[0133]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Preparation of Sample 101 A sample 101 was prepared by preparing a multi-layer color light-sensitive material having the following composition on a cellulose triacetate film support having a thickness of 205 μ having undercoat on both sides of the film.

The coating amount of each composition is the value per 1 m ² of the sample. For silver halide and colloidal silver, the equivalent weight of silver is shown. First layer: antihalation layer Black colloidal silver 0.25 g Gelatin 1.9 g UV absorber U-1 0.2 g UV absorber U-3 0.1 g UV absorber U-4 0.2 g High boiling point Organic solvent Oil-1 0.1 g Microcrystalline solid dispersion of dye E-1 0.1 g Second layer: intermediate layer Non-photosensitive fine grain silver iodobromide emulsion (average grain size 0.1 μm, AgI content 1 mol) %) Silver amount 0.15 g Surface- and internal-fogged fine grain silver iodobromide emulsion (average grain size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) Silver amount 0.05 g Compound Cpd-A 0. 1 g Compound Cpd-M 0.05 g Gelatin 0.4 g Third layer: Intermediate layer Gelatin 0.40 g Compound Cpd-C 1 mg Compound Cpd-D 3 mg Dye D-4 0.4 mg High boiling point organic solvent Oil-3 40 mg No. 4 layers: low sensitivity red Emulsion layer Emulsion A Silver amount 0.3 g Emulsion B Silver amount 0.4 g Gelatin 0.8 g Coupler C-1 0.09 g Coupler C-2 0.03 g Coupler C-3 0.02 g Coupler C-100 .02 g Compound Cpd-D 1 mg Compound Cpd-K 0.05 g High-boiling point organic solvent Oil-2 0.10 g Ethyl acrylate latex dispersion 0.5 g Fifth layer: medium-speed red-sensitive emulsion layer Emulsion B Silver amount 0. 2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-3 0.2 g High boiling point organic solvent Oil-2 0.1 g Ethyl Latex dispersion of acrylate 0.05 g Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-2 0.1 g Cap -C-3 0.1 g Additive P-1 0.02 g Ethyl acrylate latex dispersion 0.1 g Seventh layer: Intermediate layer Gelatin 1.0 g Compound Cpd-J 0.2 g Compound Cpd-L 0 0.05 g Compound Cpd-N 0.02 g Additive P-1 0.05 g Dye D-1 0.02 g Eighth layer: intermediate layer Silver iodobromide emulsion with a fogged surface and inside (average grain size 0.06 μm, Coefficient of variation 16%, AgI content 0.3 mol%) Silver amount 0.02 g Gelatin 0.4 g Compound Cpd-A 0.1 g Compound Cpd-D 1 mg Compound Cpd-M 0.05 g Layer 9: Low sensitivity Green-sensitive emulsion layer Silver iodobromide emulsion with fog inside (average grain size 0.1 μm, AgI content 0.1 mol%) Silver amount 0.15 g Emulsion E silver amount 0.3 g Emulsion F silver amount 0. 1 g Emulsion G Silver amount 0.1 g Gelatin 2.0 g Coupler C-4 0.03 g Coupler C-7 0.05 g Coupler C-8 0.02 g Coupler C-9 0.05 g Coupler C-12 0.2 g Compound Cpd-B 0.03 g Compound Cpd- D 1 mg Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-H 0.02 g High-boiling point organic solvent Oil-2 0.2 g 10th layer: Medium sensitivity green sensitive emulsion Layer Emulsion G Silver amount 0.3 g Emulsion H Silver amount 0.1 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-7 0.05 g Coupler C-8 0.05 g Coupler C-9 0. 02g Coupler C-12 0.20g Compound Cpd-B 0.03g Compound Cpd-E 0.02g Compound Cpd-F 0.02g Compound Cpd-G 0.05g Compound Cp d-H 0.05 g Additive F-5 0.08 mg High-boiling-point organic solvent Oil-2 0.01 g 11th layer: high-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion with fog inside (average grain size 0 0.2 μm, AgI content 0.1 mol%) Silver amount 0.05 g Emulsion I Silver amount 0.5 g Gelatin 1.1 g Coupler C-4 0.1 g Coupler C-7 0.3 g Coupler C-80 0.07 g Coupler C-9 0.05 g Coupler C-12 0.1 g Compound Cpd-B 0.08 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-H 0 0.02 g High boiling point organic solvent Oil-2 0.04 g 12th layer: Intermediate layer Gelatin 0.4 g Ethyl acrylate latex dispersion 0.15 g Dye D-1 0.1 g Dye D-2 0.05 g Dye D -3 0.07 g 13th layer: Yellow filter layer Yellow colloidal silver Silver amount 0.08 g Gelatin 1.0 g Compound Cpd-A 0.04 g High boiling point organic solvent Oil-1 0.01 g Microcrystalline solid of dye E-2 Dispersion 0.05 g 14th layer: intermediate layer Gelatin 0.6 g 15th layer: low-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion with fog inside (average grain size 0.2 μm, AgI content 0.1) Mol%) Silver amount 0.1 g Emulsion J Silver amount 0.4 g Emulsion K Silver amount 0.1 g Emulsion L Silver amount 0.1 g Gelatin 1.0 g Coupler C-5 0.5 g Coupler C-6 0.1 g Coupler C-11 0.1 g Compound Cpd-K 0.1 g 16th layer: Middle speed blue sensitive emulsion layer Emulsion L Silver amount 0.1 g Emulsion M Silver amount 0.1 g Gelatin 0.6 g Coupler C-5 0.02g Coupler C-60 0.002 g Coupler C-11 0.02 g 17th layer: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.6 g Gelatin 1.4 g Coupler C-5 0.05 g Coupler C-6 0.08 g Coupler C-11 0.8 g Eighteenth layer: First protective layer Gelatin 0.9 g UV absorber U-1 0.4 g UV absorber U-2 0.01 g UV absorber U-3 0.03 g UV absorber U- 4 0.03 g UV absorber U-5 0.05 g UV absorber U-6 0.05 g High boiling point organic solvent Oil-1 0.02 g Formalin scavenger Cpd-C 0.2 g Cpd-I 0.4 g Ethyl acrylate Latex dispersion of 0.05 g Dye D-3 0.05 g Compound Cpd-A 0.02 g Compound Cpd-J 0.02 g Compound Cpd-N 0.01 g 19th layer: second protective layer Colloidal silver Silver amount 0.05 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver amount 0.05 g Gelatin 0.3 g 20th layer: third protective layer Colloidal silver silver amount 0 .05 mg Fine grain silver iodobromide emulsion (average particle size 0.07 μm, AgI content 1 mol%) Silver amount 0.05 g Gelatin 0.6 g Polymethylmethacrylate (average particle size 1.5 μm) 0.1 g Methyl methacrylate Acrylic acid 4: 6 copolymer (average particle size 1.5 μm) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g Each silver halide emulsion Additives F-1 to F-1 to
F-4 and F-6 to F-9 were added.

In addition to the above composition, gelatin hardener H-1, coating surfactants W-3, W-4 and W-5, and emulsifying surfactant W-6 were added to each layer.

Further, as an antiseptic / antifungal agent, phenol, 1,
2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenyl isothiocyanate, and phenethyl alcohol were added.

[0137]

[Table 1]

[0138]

[Table 2]

[0139]

[Table 3]

[0140]

[Chemical 11]

[0141]

[Chemical 12]

[0142]

[Chemical 13]

[0143]

[Chemical 14]

[0144]

[Chemical 15]

[0145]

[Chemical 16]

[0146]

[Chemical 17]

[0147]

[Chemical 18]

[0148]

[Chemical 19]

[0149]

[Chemical 20]

[0150]

[Chemical 21]

[0151]

[Chemical formula 22]

[0152]

[Chemical formula 23]

[0153]

[Chemical formula 24]

[0154]

[Chemical 25]

[0155]

[Chemical formula 26] Samples 102 to 105, and 107 to 109 are emulsion A
Sample Nos. 1 to D were prepared in the same manner as in Sample 101 except that the sensitizing dyes used were changed as shown in Table 4.

Sample 106 was prepared in the same manner as sample 102 except that the iodine content of the emulsions A to N was 3 mol%.

Sample 110 was prepared in the same manner as Sample 102 except that the iodine content of the emulsions A to N was 6 mol%.

Sample 111 was prepared in the same manner as Sample 102 except that the grain sizes of emulsions A to N were adjusted as shown in Table 6.

Sample 112 is dye D-1, D-2, D-.
Adjust the coating amount of 3 as follows to ISO speed 200
I made a sensitive material.

D-1: coating amount of seventh layer 0.02 → 0 g / m ² twelfth layer 0.1 → 0.05 g / m ² D-2: twelfth layer 0.05 → 0 g / m ² D -3: twelfth layer 0.07 → 0.05g / m ² 18th layer 0.05 → 0g / m ² sample 113, a sensitizing dye is used in the emulsion A~D adjusted according to Table 4 Other than that, it was created in the same manner as the sample 111.

Regarding the ISO speed of the sample prepared as described above, the sample exposed by the method described in 3.1 of JIS standard 7602 is processed by the following method to obtain ISO standard 76.
The sensitivity was measured and determined by the method described in 13. At the same time, J
The sensitivity of exposure according to item 3.2 of IS Standard 7602 (tungsten exposure with a color temperature of 3200K) was also obtained.

[0162]

[Table 4]

[0163]

[Table 5]

[0164]

[Table 6] Treatment process time Temperature First development 6 minutes 38 ° C Water wash 2 minutes 38 ° C Inversion 2 minutes 38 ° C Color development 6 minutes 38 ° C adjustment 2 minutes 38 ° C Bleach 6 minutes 38 ° C Settling 4 minutes 38 ° C Water wash 4 minutes 38 ° C stability 1 minute 25 ° C The composition of each treatment solution was as follows. (First developer) Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 g Sodium sulfite 30 g Hydroquinone / potassium monosulfonate 20 g Potassium carbonate 33 g 1-Phenyl-4-methyl-4-hydroxymethyl -3-Pyrazolidone 2.0 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide 2.0 mg Water was added to 1000 ml pH 9.60 pH was adjusted with hydrochloric acid or potassium hydroxide. (Inversion solution) Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 3.0 g Stannous chloride dihydrate 1.0 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water 1000 ml pH 6.00 The pH was adjusted with hydrochloric acid or potassium hydroxide. (Color developer) Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 g Sodium sulfite 7.0 g Trisodium phosphate 12-hydrate 36 g Potassium bromide 1.0 g Potassium iodide 90 mg Hydroxyl hydroxide Sodium 3.0 g Citrazine acid 1.5 g N-Ethyl- (β-methanesulfonamidoethyl) 3-methyl-4-aminoaniline sulfate 11 g 3,6-dithiaoctane-1,8-diol 1.0 g Water was added. 1000 ml pH 11.80 The pH was adjusted with hydrochloric acid or potassium hydroxide. (Preparation Solution) Ethylenediaminetetraacetic acid / disodium salt / dihydrate 8.0 g Sodium sulfite 12 g 1-Thioglycerin 0.4 ml Water was added to 1000 ml pH 6.20 pH was adjusted with hydrochloric acid or sodium hydroxide. (Bleaching solution) Ethylenediaminetetraacetic acid ・ sodium salt ・ dihydrate 2.0 g Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ammonium ・ dihydrate 120 g Potassium bromide 100 g Ammonium nitrate 10 g Water is added 1000 ml pH 5.70 pH Was adjusted with hydrochloric acid or sodium hydroxide. (Fixer) Ammonium thiosulfate 80 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml pH 6.60 The pH was adjusted with hydrochloric acid or aqueous ammonia. (Stabilizer) Formalin (37%) 5.0 ml Polyoxyethylene-p-monononyl 0.5 ml Phenyl ether (average degree of polymerization 10) 1000 ml by adding water No pH adjustment Residual silver amount has been developed Maximum exposure of sample (20CM
The amount of residual silver in part S) was measured by fluorescent X-ray.

For RMS, a sample exposed through a pattern for RMS value measurement using the light source of the method described in 3.1 of JIS standard 7602 was subjected to the above-mentioned treatment and measured.

The results are summarized in Table 5. (Regarding the RMS value, edited by TH James, The Theor
y ofthe Photographic Proce
ss 4th edition, Macmillan, page 619. ) A measuring aperture having a diameter of 48 μm was used.

GL Dmin is the maximum exposure amount (20 CM
It is a value obtained by measuring the green ISO status M diffuse transmission density of the treated sample exposed in S) according to JISK7605.

The RMS values of R, G and B of the sample 102 and the MTF values of R, G and B exposed through the MTF measurement pattern were as follows.

RMS Granularity MTF (density 1.0) (at a density of 1.0, spatial frequency 20 lines / mm) R G B R G B 17 20 30 0.5 0.5 0.6 0.8 The dry film thickness is 24 μm. Met.

MTF measurement aperture is 2 × 400 μm
I used the one.

From the comparison with Samples 101 to 105 and 107 to 109, the present invention shows that sensitivity, RMS, Dmin of GL,
It can be seen that the amount of residual silver is effective.

From a comparison between Samples 106 and 102, it can be seen that when the average silver iodide content is low, graininess becomes poor.

It can be seen that the sample 110 having a high iodine content is excellent in sensitivity, granularity, residual color, and residual silver amount.

By comparing the samples 101, 102 and 111, 113, it is understood that the effect of the present invention is more remarkable when the sensitivity is higher.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 6, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

[0025]

[Chemical 6]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

[0027]

[Chemical 8]

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0149

[Correction method] Change

[Correction content]

[0149]

[Chemical 20]

Claims (2)

[Claims] 1. A photographic constituent layer comprising at least one photosensitive silver halide emulsion layer and at least one non-photosensitive layer, wherein at least one photographic constituent layer has the following general formula (I): In a color photographic light-sensitive material containing at least one methine compound represented by the formula 1, the average silver iodide content of all light-sensitive silver halide grains contained in the color photographic light-sensitive material is 4 mol% or more. And a silver halide color photographic light-sensitive material. [Chemical 1] In the formula, R ¹ is — (CH ₂ ) _r —CONHSO ₂ —
_{^{R 3, - (CH 2)}} s -SO 2 NHCO-R 4, -
_{(CH 2) t -CONHCO-R} 5 or, - (CH
₂₎ represents a _u -SO ₂ NHSO ₂ -R ^6. Here, R ³ , R ⁴ , R ⁵ , or R ⁶ represents an alkyl group, an alkoxy group, or an amino group, and r, s, t, or u
Represents an integer from 1 to 5. R ² has the same meaning as R ¹ or represents an alkyl group. Z ¹ and Z ² represent a group of non-metal atoms necessary for forming a 5- or 6-membered heterocycle, and p and q represent 0 or 1. L ₁ , L ₂ , or L ₃
Represents a methine group, and m represents 0, 1 or 2. X
₁ represents an anion, and k represents the number necessary for adjusting the charge in the molecule to 0. 2. The color photographic light-sensitive material according to claim 1, wherein the silver halide color photographic light-sensitive material has an ISO speed of 160 or more in daylight illuminant.