JPH07119995B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide color photographic light-sensitive material, and more specifically to a silver halide color photographic light-sensitive material having improved color reproducibility and improved formalin resistance. It is about.

(Prior Art) In order to form a color photographic image, a color-addition method and a color-subtraction method can be roughly classified.
A photographic coupler capable of developing three colors of magenta and cyan is contained in the photosensitive layer, and the light-sensitive material of the image exposing material is color-developed with a color developing agent.

Upon color development, an aromatic primary amine as a color developing agent and an photographic coupler undergo an oxidative coupling reaction, and as a result, an indophenol-based or azomethine-based coloring dye is produced. It is essential that the color forming dye is a fresh cyan, magenta, or yellow dye having a small amount of secondary absorption in order to obtain a color photographic image with good color reproducibility. Among these, as a magenta color image forming bone nucleus to reduce the yellow component, pyrazolobenzimidazole bone nucleus described in British Patent 1,047,612, pyrazolotriazole bone nucleus described in U.S. Patent 3,725,067, It has been known.

On the other hand, in recent years, high-sensitivity and small format silver halide color negative films have been developed, and a color negative photographic light-sensitive material having high sensitivity and excellent image quality is strongly desired. For this reason, the demand for silver halide emulsions for photography is becoming more and more stringent, and there is an even higher demand for photographic performance such as high sensitivity, high contrast, excellent graininess and sharpness.

In order to meet such demands, a technique for using tabular grains intended to improve sensitivity including improvement of color sensitizing efficiency by a sensitizing dye, improve sensitivity / granularity relationship, improve sharpness, and improve covering power has been developed. U.S. Pat.Nos. 4,434,226 and 4,41
4,310, 4,433,048, 4,414,306, 4,459,353
No.

Further, JP-A-58-113930, JP-A-58-113934, and JP-A-59-11935.
No. 0 also discloses a multi-layer color photographic light-sensitive material having high sensitivity and improved graininess and sharpness, which uses a tabular silver halide emulsion having an aspect ratio of 8: 1 or more as a high sensitivity layer. .

However, the pyrazoloazole-based magenta couplers relating to the present invention having excellent color image fastness are disclosed in JP-A-59-162548, JP-A-59-171956, JP-A-60-33552, and JP-A-60-43659.
In the subsequent studies, these di-equivalent couplers did not cause poor color development in the presence of aldehyde gas, but significantly increased fog, especially spectral sensitization by sensitizing dyes. It became clear when I felt it.

In order to prevent the deterioration of photographic performance due to such formaldehyde gas, it has been attempted to incorporate a compound capable of reacting with formaldehyde in the internal silver halide color photographic light-sensitive material.

JP-B-46 for preventing deterioration of photographic performance due to formaldehyde gas in silver halide color photographic light-sensitive materials
-34675, 48-38418, 51-23908, U.S. Pat.
0,431, 4,414,309, 4,411,987, 4,490,460
No. 4,435,503, Research Disclosure (R
The compounds described in esearch Disclosure, Vol. 101, No. 10133, etc. do not provide sufficient effects, and when added in a large amount, they deteriorate the physical properties of the film of the light-sensitive material and deteriorate the storage stability.

(Problems to be Solved by the Invention) The present invention is intended to solve the above problems of a silver halide color photographic light-sensitive material.

An object of the present invention is to provide a silver halide color light-sensitive material capable of improving the color reproducibility of the obtained print even if the color-correcting coupler is greatly reduced because the secondary absorption of the magenta coloring dye is small. Secondly, to provide a silver halide color light-sensitive material in which formalin fog caused by the use of a sensitizing dye is suppressed.

(Means for Solving Problems) The present invention has been made for the purpose of solving the above problems, and means for this is to provide a silver halide color photographic light-sensitive material as described below. is there.

In a silver halide photographic light-sensitive material having at least one layer containing a silver halide emulsion on a support, at least one of the layers has a coupler represented by the following general formula (I) and the following (A): A silver halide color photographic light-sensitive material containing the silver halide emulsion shown.

In the above general formula (I), R ₁ represents a hydrogen atom or a substituent (including a substituent), and Y ₁ represents a hydrogen atom or a group capable of splitting off during the coupling reaction with the oxidized product of the developing agent (elimination). ), And Za, Zb and Zc represent methine, substituted methine, = N- or -NH-. One of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. When Zb-Zc is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring. Further, a dimer or higher multimer coupler may be formed by one group in the group consisting of R ₁ , Y ₁ and Za, Zb, Zc representing a substituted methine.

(A) 70% or more of the total projected area of the silver halide emulsion grains are tabular grains having a diameter of 0.15 μm or more, the average aspect ratio of the tabular grains is 8.0 or less, and the tabular grains have There are 50% or more (number) of all tabular grains in which the ratio (b / a) of the longest distance (a) between two or more parallel twin planes and the grain thickness (b) is 5 or more. Silver halide emulsion.

The present invention will be described in more detail below.

The general formula (I) represents a magenta coloring coupler having a pyrazoloazole bone nucleus, R ₁ represents an arbitrary group which can be substituted at the 3-position of the pyrazole ring, and is a hydrogen atom and R ₀ shown below. R ₀ is an aliphatic, aromatic, heterocyclic group or aliphatic oxy group (eg, methoxy, 2-methoxyethoxy, 2
-Propenyloxy), an aromatic oxy group (for example, 2,4-
Di-tert-amylphenoxy, 2-chlorophenoxy,
4-cyanophenoxy), an acyl group (eg, acetyl,
Benzoyl), ester group (eg butoxycarbonyl, phenoxycarbonyl, benzoyloxy, butoxysulfonyl, toluenesulfonyloxy), amide group (eg acetylamino, methanesulfonamide, ethylcarbamoyl, diethylcarbamoyl, butylsulfamoyl), imide (Eg succinimide, hydantoinyl), ureido (eg phenylureido, dimethylureido), sulfamoylamino group (eg dipropylsulfamoylamino), aliphatic, aromatic or heterocyclic sulfonyl group (eg methanesulfonyl, phenylsulfonyl), Aliphatic, aromatic or heterocyclic thio groups (eg ethylthio, phenylthio), substituted amino groups (eg diethylamino, anilino), silyl groups (eg trimethylsilyl) Hydroxyl group, a cyano group, a carboxyl group, a sulfonic acid group, a nitro group, a thiocyanato group, is a halogen atom (fluorine, chlorine, bromine, iodine).

In the general formula (I), when Y ₁ is not a hydrogen atom but represents a coupling leaving group (hereinafter referred to as a leaving group),
The leaving group is coupled with activated carbon through an oxygen, nitrogen, sulfur or carbon atom, an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic / aromatic or heterocyclic sulfonyl group, an aliphatic / aromatic group or A group capable of binding to a heterocyclic carbonyl group, a halogen atom, an aromatic azo group, etc., and the aliphatic, aromatic or heterocyclic group contained in these leaving groups may be substituted with R _0. Well, when these substituents are 2 or more, they may be the same or different.

Specific examples of the leaving group include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkoxyl group (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxylpropyloxy, methylsulfonylethoxy, etc.), aryloxy A group (for example, 4-chlorophenoxy, 4-methoxyphenoxy,
4-carboxyphenoxy etc.), an acyloxy group (eg acetoxy, tetradecanoyloxy, benzoyloxy etc.), an aliphatic or aromatic sulfonyloxy group (eg methanesulfonyloxy, toluenesulfonyloxy etc.), an acylamino group (eg dioxy). Chloroacetylamino, heptafluorobutyrylamino etc.), an aliphatic or aromatic sulfonamide group (eg methanesulfonamino, p-toluenesulfonylamino etc.),
An alkoxycarbonyloxy group (eg, ethoxycarbonyloxy, benzyloxycarbonyloxy, etc.),
Aryloxycarbonyloxy group (eg, phenoxycarbonyloxy), aliphatic / aromatic or heterocyclic thio group (eg, ethylthio, phenylthio, tetrazolylthio, etc.), carbamoylamino group (eg, N-methylcarbamoylamino, N-phenyl) A 5- or 6-membered nitrogen-containing heterocyclic group (eg, imidazoline, pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl, etc.), imide group (eg, succinimide, hydantoinyl, etc.) ), And aromatic azo groups (such as phenylazo). Further, there is a bis-type coupler obtained by binding a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom.

Among the pyrazoloazole compounds represented by the general formula (I), preferred photographic couplers are 1H-imidazo [1,2-b] pyrazoles represented by the following general formula (II) and general formula (III) 1H-pyrazolo [1,5-b] pyrazoles represented by the formula 1H-pyrazolo [5,1] represented by the general formula (IV)
-E] [1,2,4] triazoles, 1H-pyrazolo [1,5-b] [1,2,4] triazoles represented by general formula (V), 1H represented by general formula (VI) -Pyrazolo [1,5-
d] tetrazole and 1 represented by the general formula (VII)
H-pyrazolo [1,5-a] benzimidazoles.

The substituents in the general formulas (II) to (VII) will be described in detail. R ¹¹ , R ¹² and R ¹³ represent an aliphatic group, an aromatic group or a heterocyclic group, and these groups may be substituted with at least one of R ⁰ (the above substituent groups are referred to as R To). R ¹¹ , R ¹² and R ¹³ are each further RO−, RSO−, RSO ₂ −, RSO ₂ NH−, It may be a hydrogen atom, a halogen atom, a cyano group or an imide group. R ¹¹ , R ¹² and R ¹³ may further be a carbamoyl group, a sulfamoyl group, a ureido group or a sulfamoylamino group, and the nitrogen atom of these groups is R.
_It may be substituted with ₀ . X has the same meaning as Y _2, and either R ¹¹ , R ¹² , R ¹³ or X may be a divalent group to form a dimer, or a polymer main chain and a coupler chromophore may be combined. It may be a divalent group for connection.

Preferred R ¹¹ , R ¹² and R ¹³ are a hydrogen atom, a halogen atom, a substituent defined by R, RO-, RCONH-, RSO ₂ NH.
A R-, RNH-, RS- or ROCONH group. Preferred X
Is a hydrogen atom, a halogen atom, an acylamino group, an imide group, an aliphatic or aromatic sulfonamide group, a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom, an aryloxy group and an alkoxy group. Is.

The couplers of general formula (I) may be dimers, multimers or polymers.

Any group selected from the group consisting of the general formulas R ¹¹ , R ¹² , R ¹³ and X in (II) to (VII) may be a divalent or higher polyvalent group, or They may form a polymer chain with each other and contain a chromophore in the side chain or in the polymer main chain. The polymer coupler can make the coupler-containing layer thin and improve the sharpness.

The magenta coupler represented by the general formula (I), preferably the general formulas (II) to (VII), usually has a ballast group that makes the coupler self-diffusing. In addition, the coloring group formed from a coupler whose leaving group is a ballast group is designed to have appropriate diffusivity,
The graininess can be improved.

The synthetic methods or compound examples of the couplers represented by the general formulas (II) to (VII) are described in the following documents. Compounds of general formula (II) are disclosed in Japanese Patent Application Nos. 58-23434 and 58
-145331 and other compounds of general formula (III) are disclosed in Japanese Patent Application No. 58-151.
354 and the like, the compound of the general formula (IV) is shown in Japanese Patent Publication No. 47-27411 and Japanese Patent Application No. 58-103336, and the compound of the general formula (V) is shown in Japanese Patent Applications No. 58-45512, 59-27,745 and 59-27. 45601, 59-53443
And 59-70146, the compound of general formula (VI) is described in Japanese Patent Application No. 58-142801, and the compound of general formula (VII) is US Patent
There are detailed descriptions in 3,061,432, etc.

Further, as a magenta ballast group of the present invention, JP-A-58-4
02045, Japanese Patent Application Nos. 58-88940, 58-52923, 58-52924, 58-52927 and the like can be used to obtain a high color density or a high color development rate by using a high color-forming ballast group.

Hereinafter, examples of the magenta coupler according to the present invention (M-1)
It is shown below.

Next, the emulsion A will be described.

The tabular grains used in the present invention may be any of silver bromide, silver iodobromide, silver chloride, silver chlorobromide, and silver iodochloride.

The tabular photographic emulsion of the present invention may have at least two layered structures having substantially different halogen compositions in silver halide grains or may have a uniform composition.

In emulsions having a layered structure with different halogen compositions,
It may be an emulsion containing a high iodine layer in the core part and a low iodine layer in the outermost layer, or an emulsion containing a low iodine layer in the core part and a high iodine layer in the outermost layer. Further, the layered structure may be composed of three or more layers, and it is preferable that the layered structure has low iodine as it is located on the outer side.

The average aspect ratio of the tabular silver halide emulsion of the present invention is 8.0 or less, preferably 5.0 or less, and particularly preferably
It is preferably 1.1 to 5.0.

The tabular silver halide emulsion of the present invention can be prepared by the following precipitation forming method. The dispersion medium is placed in a commonly used reactor for producing a silver halide precipitate, which is equipped with a stirring mechanism.
Usually the amount of dispersion medium introduced into the reactor in the first stage is at least about 10%, preferably 20-80% of the amount of dispersion medium present in the silver iodobromide emulsion in the final grain precipitation forming stage.
Water or a peptizer in water is used as a dispersion medium to be initially charged in the reactor, and the dispersion medium may optionally contain other components such as one or more silver halide ripening agents and And / or a metal doping agent, which will be described in detail later, is added.
When the peptizer is initially present, its concentration is preferably at least 10%, especially at least 20% of the total peptizer present at the final stage of silver iodobromide precipitation formation.
An additional dispersion medium is added into the reactor with the silver and halide salts, which can be introduced from another jet. Generally, the proportion of dispersion medium is adjusted after completion of the halide salt introduction, especially in order to increase the proportion of peptizer.

Usually less than 10% by weight of the bromide salt used to form the silver iodobromide grains is first present in the reactor to control the bromide ion concentration in the dispersion medium at the beginning of silver iodobromide precipitation formation. Further, the dispersion medium in the reactor is initially substantially free of iodine ions. Here, "substantially free of iodine ions" means that iodine ions are present in an amount insufficient to precipitate as another silver iodide phase as compared with bromide ions. It is desirable that the iodine concentration in the reactor before introducing the silver salt be kept printed at less than 0.5 mol% of the total halide ion concentration in the reactor.

During the precipitation, the silver, bromide and iodo salts are added to the reactor according to techniques well known for the precipitation of silver iodobromide grains. Usually, an aqueous solution of a soluble silver salt such as silver nitrate is introduced into the reactor at the same time as the introduction of the bromide and iodo salt. In addition, the bromide and iodine salts are introduced as an aqueous salt solution such as an aqueous solution of soluble ammonium, alkali metal (eg sodium or potassium) or alkaline earth metal (eg magnesium or calcium) halide salts. The silver salt is introduced into the reactor separately from the bromide salt and the iodo salt, at least initially. The bromide salt and iodo salt may be added separately or introduced as a mixture.

Introducing the silver salt into the reaction vessel initiates the grain nucleation step. Continued introduction of silver, bromide and iodo salts forms a population of silver bromides and grain nuclei that serve as precipitation sites for silver iodide. The grain enters the growth stage due to the precipitation of silver bromide and silver iodide on the existing grain nuclei. The average value of the equivalent circle diameters of the projected area of the tabular grains before entering the grain growth stage is preferably 0.6 μm or less, and more preferably 0.4 μm or less. The conditions for nucleation may be based on the method described in Japanese Patent Application No. 61-48950, but the method is not limited to this method, and the nucleation temperature may be in the range of 5 to 55 ° C. You can

The size distribution of the tabular grains formed according to the present invention is
It is greatly influenced by the bromide and iodo salt concentrations during the growth stage. If pBr is too low, tabular grains with a high aspect ratio are formed, but the coefficient of variation of the projected area becomes significantly large. By maintaining pBr in the range of about 2.2 to 5, preferably 2.5 to 4, tabular grains having a small variation coefficient of projected area can be formed.

The concentration and introduction rate of silver, bromide and iodo salts may be the same as those conventionally used, provided that the above-mentioned pBr condition is satisfied. The silver and halide salts are preferably introduced at a concentration of 0.1 to 5 mol per liter, but a wider concentration range conventionally used, for example, a range from 0.01 mol per liter to the degree of saturation can be employed. A particularly preferred precipitation generation technique is
Increasing the introduction rate of silver and halide salts to shorten the precipitation formation time. The introduction rate of silver and halide salts can be increased by increasing the dispersion medium and the introduction rate of silver and halide salts, or by increasing the concentration of silver and halide salts in the introduced dispersion medium. You can By keeping the addition rates of silver and halide salts near the limit value at which the formation of new grain nuclei occurs as described in JP-A-55-142329, the coefficient of variation of the projected area of grains can be further reduced. .

The amount of gelatin in the reaction vessel during nucleation greatly influences the particle size distribution. When the amount of gelatin is not optimally selected, the nucleation becomes non-uniform, and b / a greatly varies among grains in the observation of twin planes by the above-mentioned method. The gelatin concentration is preferably 0.5-10 wt%, more preferably 0.5-6 wt%.

Here, the tabular grains are a general term for grains having one twin plane or two or more parallel twin planes. In this case, the twin plane means the (111) plane when ions at all lattice points on both sides of the (111) plane have a mirror image relationship.

Here, the particle thickness (b) is a distance between outer surfaces parallel to each other, and the thickness of the particle is measured by vapor-depositing a metal from a diagonal direction along with the latex for reference and measuring the shadow length by an electron micrograph. This can be easily done by measuring above and calculating with reference to the shadow length of the latex.

The grain diameter in the present invention is the diameter of a circle having an area equal to the projected area of the parallel outer surface of the grain.

The method for measuring the twin plane spacing a of the present invention will be described.

The twin plane spacing a is the distance between two twin planes in a grain having two twin planes, and the twin plane in a grain having three or more twin planes. The longest distance among them.

The twin plane can be observed by a transmission electron microscope.

Specifically, an emulsion consisting of tabular grains is coated on a support to prepare a sample in which the tabular grains are arranged substantially parallel to the support, and the sample is cut with a diamond knife to give a thickness. A section of about 0.1 μm is prepared.

The twin planes of the tabular grains can be detected by observing this section with a transmission electron microscope.

When the electron beam passes through the twin plane, a phase shift occurs in the electron wave, so that its existence is recognized.

Here, the aspect ratio is the tabular grain diameter (denoted as D) divided by the tabular grain thickness (b) (D / b).
Is. The average aspect ratio is the number average of the aspect ratios of the tabular grains.

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

The present invention will be described below with reference to examples.

Example 1 Emulsion A. (Step A) Aqueous gelatin solution (water 1350 ml, gelatin 17
g, AgNO ₃ 0.9 while maintaining the KBr3.7g), the temperature of the solution to 45 ° C.
67.7 ml of AgNO ₃ aqueous solution containing 0 mol / l and KBr 0.85 mol / l, KI
67.7 ml of an aqueous solution containing 0.04 mol / l was added simultaneously at a constant flow rate for 45 seconds and then left for 5 minutes. The solution temperature was raised to 65 ° C., 241 g of 10% gelatin was added, and the mixture was allowed to stand for 30 minutes.

(Step B) Subsequently, ₃ AgNO ₃ aqueous solutions containing AgNO ₃ 1.76 mol / l and KBr 2.72 mol / l and KI 0.249 mol / l were added.
While maintaining pBr at 3.5 per minute, a constant flow rate was added until the consumption of the aqueous AgNO ₃ solution reached 310 ml.

(Step C) Further, subsequently, AgNO ₃ 1.76 mol / l is contained.
The AgNO ₃ aqueous solution and the aqueous solution containing KBr2.72 mol / l were added for 15 minutes.
While keeping Br at 3.5, the consumption of AgNO ₃ aqueous solution was 34 at a constant flow rate.
Add to 5 ml.

(Step D) After completion of precipitation, the emulsion was cooled to 40 ° C. and phthalated Ge
1.65 L of 15.3% solution was added and the emulsion was washed twice by the coagulation method described in US Pat. No. 2,614,929. Then add 0.55 l of 10.5% bone gelatin solution, adjust the pH of the emulsion to 5.5 and pBr.
Each was adjusted to 3.1 at 40 ° C.

Emulsion B. In Emulsion A, the iodine composition of the aqueous halogen solution was adjusted so as to have a uniform iodine composition.

Emulsions C. and D Emulsions B can be prepared by adjusting the pBr of steps B, C.

Each of these emulsions was optimally chemically sensitized, and then optimally spectrally sensitized with a dye in which a sensitizing dye ExS-3,4,5 was mixed at a molar ratio of 1: 2: 1.

The triacetyl cellulose film support provided with an undercoat layer was coated with emulsions A to D in coating amounts shown in Table 2.

Table 2. Emulsion coating conditions (1) (1) Emulsion layer Emulsion ... Emulsions A to D shown in Table 1 (Silver 2.1 × 10 ⁻² mol / m ² ) Coupler (1.5 × 10 ⁻³ mol / m ² ) Tricresyl phosphate (1.10 g / m ² ) Gelatin (2.30 g / m ² ) (2) Protective layer 2,4-dichlorotriazine-6-hydroxy-s-triazine sodium salt (0.08 g / m ² ) Gelatin ( 1.80 g / m ² ) Further, formalin scavenger (Cpd-5) was added to the protective layer of Sample D so that the coating amount was 0.3 g / m ² to obtain Sample E.

After leaving these samples for 14 hours under the conditions of 40 ° C and 70% relative humidity, sample A ... formalin resistance test (40 ° C, relative humidity
It was exposed to 20 ppm of folimaldehyde vapor under the condition of 70% for 1 day. Reference sample (R) is not exposed to formaldehyde vapor under the same conditions) and test B ... Forced deterioration aging test (3 days under conditions of 50 ° C. and 60% relative humidity) and then A
Develop and expose the light source with a color temperature conversion filter of 4800 ° K and the above green filter so that the maximum exposure amount becomes 10 CMS,
The following color development processing was performed.

The developing treatment used here was carried out at 38 ° C. under the following conditions.

1. Color development ………… 2 minutes 45 seconds 2. Bleaching ………… 6 minutes 30 seconds 3. Washing ………… 3 minutes 15 seconds 4. Settling ………… 6 minutes 30 seconds 5. Washing with water 3 minutes 15 seconds 6. Stability 3 minutes 15 seconds The composition of the treatment liquid used in each process is as follows.

Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4- (N-ethyl-N-β-hydroxyethylamino)
2-Methyl-aniline sulfate 4.5 g Water added 1 Bleach Ammonium bromide 160.0 g Ammonia water (28%) 25.0 ml Ethylenediamine-tetraacetic acid sodium iron salt 130 g Glacial acetic acid 14 ml Water added 1 Fixer Tetrapolyline Sodium acid salt 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 g Sodium bisulfite 4.6 g Water was added 1 Stabilizer Formalin 3.0 ml Water was added 1 The concentration of the sample thus developed was measured.

Table 2 shows the sensitivity of the reference sample S _0.2 (relative value of the logarithm of the exposure dose that gives the density of fog + 0.2), the difference in fog between the reference sample and the test sample in Test A, ΔFog, and S in Test B.
Shows the change [Delta] S _{0.2 0.2.}

From these results, it was found that Samples A to C had a relatively small increase in fog due to formalin and a small decrease in sensitivity due to the time of forced deterioration. This is because formalin fog is caused by the sensitizing dye, and the emulsion of the present invention, which can reduce the sensitizing dye without impairing the sensitivity, exhibited excellent performance. Also, sample E including scavenger
It was found that the increase in fog caused by formalin was suppressed, but the sensitivity was significantly decreased with the lapse of forced deterioration.

Example 2 By introducing the emulsion prepared in Example 1 into a color light-sensitive material having a multilayer constitution as shown in Table 3, Table 4
Four types of samples shown in were prepared.

Table 3. Multi-layered color light-sensitive material (1) The coating amount is silver halide and colloidal silver.
The amount represented in units of g / m ^2, also couplers, moles per 1 mol of silver halide in the same layer for the amount for the additives and gelatin represented in units of g / m ^2, also the sensitizing dye Indicated by.

1st layer (antihalation layer) Black colloidal silver …… 0.2 Gelatin …… 1.3 ExM-9 …… 0.06 UV-1 …… 0.03 UV-2 …… 0.06 UV-3 …… 0.06 Solv-1 …… 0.15 Solv− 2 …… 0.15 Solv-3 …… 0.05 Second layer (intermediate layer) Gelatin …… 1.0 UV-1 …… 0.03 ExC-4 …… 0.02 ExF-1 …… 0.004 Solv-1 …… 0.1 Solv-2 …… 0.1 Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent spherical diameter 0.5)
μ, coefficient of variation of equivalent spherical diameter 20%, plate-like particles, diameter / thickness ratio
30.) Amount of coated silver …… 1.2 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, spherical equivalent diameter 0.3
μ, coefficient of variation of equivalent spherical diameter 15%, spherical particles, diameter / thickness ratio
1.0) Silver coating amount …… 0.6 Gelatin …… 1.0 ExS-1 …… 4 × 10 ^-4 ExS-2 …… 5 × 10 ^-5 ExC-1 …… 0.05 ExC-2 …… 0.50 ExC-3 …… 0.03 ExC-4 ...... 0.12 ExC-5 ...... 0.01 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core shell ratio 1: 1 internal high A)
gI type, equivalent sphere diameter 0.7μ, variation coefficient of equivalent sphere diameter 15%, plate-like particles, diameter / thickness ratio 5.0) Coating silver amount …… 0.7 Gelatin …… 1.0 ExS-1 …… 3 × 10 ^-4 ExS- 2 …… 2.3 × 10 ^-5 ExC-6 …… 0.11 ExC-7 …… 0.05 ExC-4 …… 0.05 Solv-1 …… 0.05 Solv-3 …… 0.05 Fifth layer (intermediate layer) Gelatin …… 0.5 Cpd -1 ...... 0.1 Solv-1 ...... 0.05 Sixth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion Emulsion shown in Table 3 Silver coating amount ...... 0.45 Gelatin ...... 1.0 Exemplified compound (M-46) ・ ・ ・… 0.4 ExM-9 …… 0.07 ExM-10 …… 0.02 ExY-11 …… 0.03 Solv-1 …… 0.3 Solv-4 …… 0.05 7th layer (high sensitivity green emulsion layer) Silver iodobromide emulsion (AgI6 Internal high A with mol% and core shell ratio of 1: 1
gI type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter / thickness ratio 5.0) Silver coating amount …… 0.7 gelatin …… 0.5 ExS-3 …… 5 × 10 ^-4 ExS- 4 …… 3 × 10 ^-4 ExS-5 …… 1 × 10 ^-4 ExM-8 …… 0.1 ExM-9 …… 0.02 ExY-11 …… 0.03 ExC-2 …… 0.03 ExM-14 …… 0.01 Solv- 1 …… 0.2 Solv-4 …… 0.01 8th layer (intermediate layer) Gelatin …… 0.5 Cpd-1 …… 0.05 Solv-1 …… 0.02 9th layer (donor layer of the multi-layer effect for the red sensitive layer) Iodobromide Silver emulsion (AgI 2 mol%, core shell ratio 2: 1, internal high A
gI type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 6.0) Coating silver amount …… 0.35 Silver iodobromide emulsion (AgI 2 mol%, core shell ratio 1: 1) Internal height A
gI type, sphere equivalent diameter 0.4μ, variation coefficient of sphere equivalent diameter 20%, plate-like particles, diameter / thickness ratio 6.0) Coating silver amount …… 0.20 Gelatin …… 0.5 ExS-3 …… 8 × 10 ^-4 ExY- 13 …… 0.11 ExM-12 …… 0.03 ExM-14 …… 0.10 Solv-1 …… 0.20 10th layer (yellow filter layer) Yellow colloidal silver …… 0.05 Gelatin …… 0.5 Cpd-2 …… 0.13 Solv-1… ... 0.13 Cpd-1 ... 0.10 11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent spherical diameter 0.5)
μ, coefficient of variation of equivalent spherical diameter 25%, plate-shaped particles, diameter / thickness ratio
7.0) Coating silver amount …… 0.45 Gelatin …… 1.6 ExS-6 …… 2 × 10 ^-4 ExC-16 …… 0.05 ExC-2 …… 0.10 ExC-3 …… 0.02 ExY-13 …… 0.07 ExY-15… 1.0 Solv-1 0.20 12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, uniform AgI type, equivalent spherical diameter 1.0)
μ, coefficient of variation of spherical equivalent diameter 25%, multiple twin plate particles, diameter / thickness ratio 2.0) Coating silver amount …… 0.5 Gelatin …… 0.5 ExS-6 …… 1 × 10 ^-4 ExY-15 …… 0.20 ExY-13 …… 0.01 Solv-1 …… 0.10 13th layer (first protective layer) Gelatin …… 0.8 UV-4 …… 0.1 UV-5 …… 0.15 Solv-1 …… 0.01 Solv-2 …… 0.01 No. 14 layers (2nd protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, equivalent spherical diameter)
0.07μ) ...... 0.5 Gelatin ...... 0.45 Polymethylmethacrylate particles Diameter 1.5μ ...... 0.2 H-1 ...... 0.4 Cpd-5 ...... 0.5 Cpd-6 ...... 0.5 In addition to the above components in each layer emulsion stability Agent Cpd-3 (0.0
4 g / m ² ) Surfactant Cpd-4 (0.02 g / m ² ) surfactant was added as a coating aid.

Solv-1 Tricresyl Phosphate Solv-2 Dibutyl Phthalate After performing a formalin resistance test and a forced deterioration aging test under the same conditions as in Example 1, a color development process (using the processing method shown in Example 1, a color development time of 3 minutes and 45 seconds) was carried out. Fog increase due to formalin ΔFog and decrease in sensitivity of green-sensitive layer after forced deterioration (ΔS _0.2 )
Is shown in Table 5.

Similar to the results of Example 1, emulsions having an ashtect ratio of 8 or less have less formalin fog than those of 8 or more. In addition, the addition of formalin scavenger enough to improve the formalin fog deteriorated the storage stability.

Further, a sample obtained by further adding 40 mg / m ^{2 of} poly (polymerization degree 10) oxyethylene poly (polymerization degree 3) glycidyl and p-nonylphenyl ether to the 14th layer of sample F also showed good performance. .

Example 3 Four kinds of samples shown in Table 7 were prepared by introducing the emulsion prepared in Example 1 into a color light-sensitive material having a multilayer structure as shown in Table 6.

Table 6 Color sensitive material having a multi-layered structure (2) The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver.
However, for sensitizing dyes, the same amount of silver halide 1
The coating amount per mol is shown in mol.

1st layer (antihalation layer) Black colloidal silver 0.2 Gelatin 2.6 Cpd-33 0.2 Solv-31 0.02 2nd layer (intermediate layer) Fine grain silver bromide (average particle size 0.07μ) 0.15 Gelatin 1.0 3rd layer (low sensitivity red) Emulsion-sensitive layer) Monodisperse silver iodobromide emulsion (5.5 mol% silver iodide, average grain size 0.3)
μ, coefficient of variation related to particle size (hereinafter simply referred to as coefficient of variation) 19
%) 1.5 Gelatin 3.0 ExS-31 2.0 × 10 ^-4 ExS-32 1.0 × 10 ^-4 ExS-33 0.3 × 10 ^-4 ExC-31 0.7 ExC-32 0.1 ExC-36 0.02 Cpd-31 0.01 Solv-31 0.8 Solv -32 0.2 Solv-34 0.1 4th layer (high sensitivity red emulsion layer) Monodisperse silver iodobromide emulsion (3.5 mol% silver iodide, average grain size 0.7)
μ, coefficient of variation 18%) 1.2 Gelatin 2.5 ExS-31 3 × 10 ^-4 ExS-32 1.5 × 10 ^-4 ExS-33 0.45 × 10 ^-4 ExC-34 0.15 Exc-35 0.05 ExC-32 0.03 ExC-36 0.01 Solv-31 0.05 Solv-32 0.3 Fifth layer (intermediate layer) Gelatin 0.8 Cpd-32 0.05 Solv-33 0.01 Sixth layer (low sensitivity green emulsion layer) Silver iodobromide emulsion Emulsion described in Table 1.0 Gelatin 3.0 ExM-39 0.2 ExM-37 0.4 ExM-40 0.16 ExC-39 0.05 Solv-32 1.2 Solv-34 0.05 Solv-35 0.01 7th layer (high sensitivity green sensitive emulsion layer) Silver iodobromide emulsion (3.5 mol silver iodide) %, Average particle size 0.7μ, coefficient of variation 18%) 0.9 Gelatin 1.6 ExS-34 0.7 × 10 ^-4 ExS-35 2.8 × 10 ^-4 ExS-36 0.7 × 10 ^-4 ExM-37 0.05 ExM-40 0.04 ExC- 39 0.01 Solv-31 0.08 Solv-32 0.3 Solv-34 0.03 8th layer (yellow filter layer) Yellow colloidal silver 0.2 Gelatin 0.9 Cpd-32 0.2 Solv-32 0.1 9th layer (low sensitivity blue emulsion layer) Monodisperse iodine Silver bromide emulsion (silver iodide 6 mol%, average grain size 0.3
μ, coefficient of variation 20%) 0.4 Monodisperse silver iodobromide emulsion (5 mol% silver iodide, average grain size 0.6
μ, coefficient of variation 17%) 0.4 Gelatin 2.9 ExS-37 1 × 10 ^-4 ExS-38 1 × 10 ^-4 ExY-40 0.8 ExY-41 0.4 ExC-33 0.05 Solv-32 0.4 Solv-34 0.1 10th layer ( High-sensitivity blue emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, average grain size 1.5)
μ, coefficient of variation 14%) 0.5 Gelatin 2.2 ExS-37 5 × 10 ^-5 ExS-38 5 × 10 ^-5 ExY-40 0.2 ExY-41 0.2 ExC-33 0.02 Solv-32 0.1 11th layer (1st protective layer) ) Gelatin 1.0 Cpd-33 0.1 Cpd-34 0.1 Cpd-35 0.1 Cpd-36 0.1 Solv-31 0.1 Solv-34 0.1 12th layer (second protective layer) Fine grain silver bromide emulsion (average grain size 0.07μ) 0.25 gelatin 1.0 Polymethylmethacrylate particles (diameter 1.5 μ) 0.2 0.5 In addition, a surfactant Cpd-37 and a hardener H-31 were added.

The samples J to M were subjected to formalin resistance and forced deterioration aging test in the same manner as in Example 2. The results are shown in Table 8.

Example 4 Samples G to J produced in Example 2 were exposed to white light at 10 CMS, 1 /
After exposure for 100 seconds, the method described below gives the same results as in Example 3.
Table 9 Processing method Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° Bleaching 1 minute 00 seconds 38 ° Bleaching fixing 3 minutes 15 seconds 38 ° Water washing (1) 40 seconds 35 ° Water washing (2) 1 minute 00 seconds 35 ° Stability 40 seconds 38 ° Drying 1 minute 15 seconds 55 ° Next, describe the composition of the treatment liquid.

(Color developer) diethylenetriaminepentaacetic acid 1.0 1-hydroxyethylidene-1,1 diphosphonic acid 3.0 sodium sulfite 4.0 potassium carbonate 30.0 potassium bromide 1.4 potassium iodide 1.5 mg hydroxylamine sulfate 2.4 4- [N-ethyl-N- ( β-Hydroxyethyl) amino] -2-methylaniline sulphate 4.5 Water was added to 1.0 l pH 10.05 (bleaching solution) (unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 120.
0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol Ammonia water (27%) 15.0ml Add water 1.0l pH 6.3 (bleach-fixer) (unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0
Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240.0 ml Ammonia water (27%) 6.0 ml Water is added to 1.0 l pH 7.2 (Washing solution) Tap water is H type strong acidic cation exchange resin ( Amberlite IR-120B manufactured by Rohm and Haas Co., Ltd. and water are passed through a mixed bed column packed with OH type anion exchange resin (Amberlite IR-400) to treat calcium and magnesium ions at a concentration of 3 mg / l or less. Then, 20 g / l of sodium isocyanurate dichloride and 0.15 g / l of sodium sulfate were added subsequently.

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

(Stabilizer) (Unit: g) Formalin 2.0 ml Polyoxyethylene-p-monononylphenyl-ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water was added to 1.0 l pH 5.0-8.0 Example 7 Samples F to I prepared in Example 3 were exposed to white light at 10 CMS, 1 /
After exposure for 100 seconds, the same treatment as in Example 2 can be obtained by the method described below.

 Table 10 Processing method Processing time Processing temperature Color development 2 minutes 30 seconds 40 ℃ Bleach fixing 3 minutes 00 seconds 40 ℃ Water wash (1) 20 seconds 35 ℃ Water wash (2) 20 seconds 35 ℃ Stability 20 seconds 35 ℃ Dry 50 Second 65 ° C. Next, the composition of the treatment liquid will be described.

(Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N- Ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Water was added to 1.0 l pH 10.05 (bleach-fixing solution) (unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0
Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 260.0 ml Acetic acid (98%) 5.0 ml Bleach accelerator 0.0l mol 1.0l pH 6.0 (water washing solution) by adding water To tap water, use H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400). Water was passed through a packed mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / l or less, and then 20 mg / l sodium diisocyanurate dichloride and 0.15 g / l sodium sulfate were added.

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

(Stabilizer) (Unit: g) Foraline (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water was added to 1.0 l pH 5.0-8.0

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one layer containing a silver halide emulsion on a support, wherein at least one of the layers has a coupler represented by the following general formula (I): A silver halide color photographic light-sensitive material containing the silver halide emulsion shown in (A) below. In the above general formula (I), R ₁ represents a hydrogen atom or a substituent (including a substituent), and Y ₁ represents a hydrogen atom or a group capable of splitting off during the coupling reaction with the oxidized product of the developing agent (elimination). ), And Za, Zb and Zc represent methine, substituted methine, = N- or -NH-. One of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. When Zb-Zc is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring. Further, a dimer or higher multimer coupler may be formed by one group in the group consisting of R ₁ , Y ₁ and Za, Zb, Zc representing a substituted methine. (A) 70% or more of the total projected area of the silver halide emulsion grains are tabular grains having a diameter of 0.15 μm or more, the average aspect ratio of the tabular grains is 8.0 or less, and the tabular grains have There are 50% or more (number) of all tabular grains in which the ratio (b / a) of the longest distance (a) between two or more parallel twin planes and the grain thickness (b) is 5 or more. Silver halide emulsion.