JPH06186662A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material high in sensitivity and small in fog and drop of sensitivity during storage by incorporating a specified silver halide emulsion and a specified compound in an emulsion layer. CONSTITUTION:The silver halide color photographic sensitive material has on a support at least one photosensitive silver halide emulsion layer, and this emulsion layer contains in an emulsion silver halid grains comprising >=50% flat grains having an aspect ratio >=2 in the total silver halide grains, and the compound represented by formula in which each of R1-R4 is alkyl, aryl, or a heterocyclic group, and each of the adjacent groups of R1 and R2, R3 and R4, R1 and R3, and R2 and R4 may combine with each other to form a ring but not an aromatic ring, and each carbon atom directly combined with the N atom of the hydrazine is not substituted by an oxo group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having high sensitivity and high storage stability.

[0002]

2. Description of the Related Art Conventionally, it has been desired to increase the sensitivity of silver halide light-sensitive materials. Further, there has been a strong demand for higher sensitivity of spectrally sensitized silver halide light-sensitive materials. The spectral sensitization technique is a very important and essential technique for producing a light-sensitive material having high sensitivity and excellent color reproducibility. Spectral sensitizers have the function of absorbing light in the long wavelength range, which is essentially not absorbed by silver halide photographic emulsions, and transmitting the light absorption energy to silver halide. Therefore, an increase in the amount of light captured by the spectral sensitizer is advantageous for increasing photographic sensitivity. Therefore, attempts have been made to increase the amount of light trapped by increasing the amount added to the silver halide emulsion. However, if the amount of the spectral sensitizer added to the silver halide emulsion exceeds the optimum amount, it causes rather great desensitization. This is generally called dye desensitization, which is a phenomenon in which desensitization occurs in the light-sensitive region peculiar to silver halide, where light is not substantially absorbed by the sensitizing dye. If the dye desensitization is large, there is a spectral sensitization effect, but the overall sensitivity is low. In other words,
As the dye desensitization decreases, the sensitivity (that is, spectral sensitization) in the light absorption region by the sensitizing dye also increases correspondingly. Therefore, in the spectral sensitization technique, improvement of dye desensitization is a major issue. Further, the dye desensitization is generally larger as the sensitizing dye having a light-sensitive region at a longer wavelength. These things are CEK Mees
Written, "The Theory of the Photographic
Process (The Theory of the Photographic Process) "
Pp. 1067-1069 (published by Macmillan Co. 1942).

Methods for reducing dye desensitization and increasing sensitivity are described in JP-A-47-28916 and JP-A-49-4673.
No. 8, No. 54-118236, U.S. Pat. No. 4,011,
No. 083 is known. However, the above-mentioned techniques have limited sensitizing dyes that can be used, and their effects are still unsatisfactory. Currently, the most effective means for improving dye desensitization is, for example, Japanese Patent Publication No. 45-2.
2189, JP-A-54-18726, JP-A-52-
A method is known in which a bisaminostilbene compound substituted with a pyrimidine derivative or a triazine derivative described in JP-A No. 4822, JP-A No. 52-151026 and US Pat. No. 2,945,762 is used in combination. However, the sensitizing dyes for which the above-mentioned compounds are effective are usually so-called M-bands which exhibit a gentle sensitizing maximum such as dicarbocyanine, tricarbocyanine, rhodacyanine and merocyanine.
It is limited to dyes that are sensitizing dyes and have maximum sensitization in a relatively long wavelength region.

In US Pat. No. 3,695,888, a combination of a specific tricarbocyanine and ascorbic acid is sensitized in the infrared region, and British Patent 1,255,08.
In No. 4, the negative blue sensitivity was increased by using a specific dye in combination with ascorbic acid, and British Patent 1,06
No. 4,193, it is possible to increase the sensitivity by using a specific dye in combination with ascorbic acid, and US Pat.
No. 561 describes the combined use of a desensitizing nucleus-containing cyanine dye with a supersensitizer such as ascorbic acid. However, in the above-mentioned conventional techniques, there are still few dyes whose sensitizing effect is sufficiently satisfactory, and those having a high sensitizing effect tend to increase fog.

Attempts to add hydrazines to silver halide light-sensitive materials or developing solutions have been made for various purposes. U.S. Pat. No. 2,419,975, JP-A-63
In JP-A-261362 and JP-B-51-15745, hydrazines are added to a developer and used. Japanese Patent Office Sho 58
In Nos. 9410 and 58-9411, acylhydrazines are added to a light-sensitive material in order to obtain a high-contrast silver halide light-sensitive material. The addition of hydrazines has a small sensitizing effect, but increases fog. JP-A-6
Nos. 3-95444 and 63-43145 use a magenta coupler in combination with a specific hydrazine compound to improve the stability of a dye image to heat and light. JP-A-63-220142, 63-256951, 63
In No. 229455, photobleaching is prevented by using an organic coloring substance and a specific hydrazine in combination. on the other hand,
As a technique for providing a color light-sensitive material having high sensitivity and excellent image quality, it is possible to use tabular silver halide grains having a diameter-to-thickness ratio (aspect ratio) of silver halide grains of 8: 1 or more. Although it is proposed in JP-A-58-113934, it is still unsatisfactory in terms of high sensitivity, image quality, storability of light-sensitive material, stability of color development processing, and further improvement is desired. Heretofore, no example has been known in which a specific effect is found by using hydrazine having a specific structure of the present invention and a tabular silver halide emulsion.

[0006]

SUMMARY OF THE INVENTION The first object of the present invention is to:
Another object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity and less fog, particularly a spectrally sensitized silver halide photographic light-sensitive material. The second is to provide a silver halide light-sensitive material having high storage stability.

[0007]

[Means for Solving the Problems] As a result of repeated studies for achieving the above-mentioned objects, the objects could be achieved by the means described below. (1) In a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, silver halide grains having an aspect ratio of 2 or more are 50% of all silver halide grains in the emulsion layer. % Of silver tabular grains, and a compound represented by the following general formula (I). General formula (I)

[0008]

[Chemical 2]

In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent an alkyl group, an aryl group or a heterocyclic group. Also, R
₁ and R ₂ , R ₃ and R ₄ , R ₁ and R ₃ , and R ₂ and R ₄
May combine with each other to form a ring, but they do not form an aromatic ring. Provided that R ₁ , R ₂ , R ₃ and R
Of the _four , the oxo group does not substitute for the carbon atom directly bonded to the nitrogen atom of hydrazine.

(2) The silver halide emulsion described in (1) above has a coefficient of variation of 0.25 for the grain size of silver halide grains.
The silver halide photographic light-sensitive material as described in (1) above, which is a silver halide emulsion consisting of the following monodisperse grains.

(3) The silver halide emulsion described in (1) or (2) above is 50% of the total projected area of silver halide grains.
A silver halide emulsion comprising hexagonal tabular grains having parallel two surfaces as outer surfaces and having a ratio of the length of the side having the maximum length to the length of the side having the minimum length of 2 or less. The silver halide photographic light-sensitive material as described in (1) or (2) above, wherein

(4) The silver halide emulsion described in (1) or (3) above has at least 5 of the number of silver halide grains.
The silver halide photographic light-sensitive material as described in (1) or (3) above, wherein 0% is a silver halide emulsion consisting of grains having 10 or more dislocations per grain.

(5) The silver halide emulsion described in (1) or (4) above comprises silver halide grains having a relative standard deviation of the silver iodide content of each silver halide grain of 30% or less. The silver halide photographic light-sensitive material as described in (1) or (4) above, which is a silver halide emulsion. (6) The silver halide photographic light-sensitive material according to any one of claims 1 to 5, wherein the silver halide emulsion is spectrally sensitized with a sensitizing dye. Further, when the compound represented by the general formula (I) is a compound selected from the following general formulas (II), (III) and (IV), it is particularly preferable for high sensitivity. General formula (II)

[0014]

[Chemical 3]

General formula (III)

[0016]

[Chemical 4]

General formula (IV)

[0018]

[Chemical 5]

In the formula, R ₅ , R ₆ , R ₇ and R ₈ represent an alkyl group, an aryl group or a heterocyclic group. Z ₁ represents an alkylene group having 4 or 6 carbon atoms. Z ₂ represents an alkylene group having 2 carbon atoms. Z ₃ represents an alkylene group having 1 or 2 carbon atoms. Z ₄ and Z ₅ represent an alkylene group having 3 carbon atoms. L ₁ and L ₂
Represents a methine group. However, R ₅ , R ₆ , R ₇ ,
Among R _8, Z _1, Z ₄ and Z _5, does not oxo group to the carbon atom directly bonded to the nitrogen atom of the hydrazine is substituted. Compounds selected from general formulas (II) and (III) are more preferable, and compounds selected from general formula (II) are particularly preferable.

The general formula (I) will be described in detail below. Examples of R ₁ , R ₂ , R ₃ and R ₄ include unsubstituted alkyl groups (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, dodecyl group, octadecyl group). Group, cyclopentyl group, cyclopropyl group, cyclohexyl group), substituted alkyl group (wherein the substituent is V, the substituent represented by V is not particularly limited, and examples thereof include a carboxy group, a sulfo group, a cyano group, a halogen atom ( For example, fluorine atom, chlorine atom, bromine atom, iodine atom), hydroxy group, alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group), alkoxy group (eg methoxy group, ethoxy group, Benzyloxy group, phenethyloxy group), carbon number 18 or more The lower aryloxy group (for example, phenoxy group, 4-methylphenoxy group, α-
Naphthoxy group), acyloxy group (eg acetyloxy group, propionyloxy group), acyl group (eg acetyl group, propionyl group, benzoyl group, mesyl group),
Carbamoyl group (eg, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group), sulfamoyl group (eg, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinyl group Nosulfonyl group), an aryl group (for example, a phenyl group, a 4-chlorophenyl group,
4-methylphenyl group, α-naphthyl group), heterocyclic group (for example, 2-pyridyl group, tetrahydrofurfuryl group, morpholino group, 2-thiopheno group), amino group (for example, amino group, dimethylamino group, anilino group) Group, diphenylamino group), alkylthio group (eg, methylthio group, ethylthio group), alkylsulfonyl group (eg,
Methylsulfonyl group, propylsulfonyl group), alkylsulfinyl group (eg methylsulfinyl group), nitro group, phosphoric acid group, acylamino group (eg acetylamino group), ammonium group (eg trimethylammonium group, tributylammonium group), mercapto group ,
Hydrasino group (eg trimethylhydrazino group), ureido group (eg ureido group, N, N-dimethylureido group), imide group, unsaturated hydrocarbon group (eg vinyl group, ethynyl group, 1-cyclohexenyl group, benzilidine Group, a benzylidene group). The number of carbon atoms of the substituent V is preferably 18 or less. Further, V may be further substituted on these substituents.

More specifically, an alkyl group (eg, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group) , 3-sulfobutyl group, 2-hydroxy-3-sulfopropyl group, 2-cyanoethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-hydroxyethyl group, 3
-Hydroxypropyl group, hydroxymethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-ethoxycarbonylethyl group, methoxycarbonylmethyl group, 2-methoxyethyl group, 2-ethoxyethyl group , 2-phenoxyethyl group, 2-acetyloxyethyl group, 2-propionyloxyethyl group,
2-acetylethyl group, 3-benzoylpropyl group, 2
-Carbamoylethyl group, 2-morpholinocarbonylethyl group, sulfamoylmethyl group, 2- (N, N-dimethylsulfamoyl) ethyl group, benzyl group, 2-naphthylethyl group, 2- (2-pyridyl) ethyl group Group, allyl group, 3-aminopropyl group, 3-ditylaminopropyl group, methylthiomethyl group, 2-methylsulfonylethyl group, methylsulfinylmethyl group, 2-acetylaminoethyl group, 3-trimethylammoniumethyl group, 2-
Mercaptoethyl group, 2-trimethylhydrazinoethyl group, methylsulfonylcarbamoylmethyl group, (2-methoxy) ethoxymethyl group, and the like}, aryl group (for example, phenyl group, α-naphthyl group, β-naphthyl group, For example, a phenyl group substituted with the above-mentioned substituent V, a naphthyl group, a heterocyclic group (for example, 2-pyridyl group,
A 2-thiazolyl group and a 2-pyridyl group substituted with the above-mentioned substituent V) are preferable.

Further, R ₁ and R ₂ , R ₃ and R ₄ , R ₁ and R
₃ , and R ₂ and R ₄ may combine with each other to form a ring. However, it does not form an aromatic ring. These rings may be substituted, for example, by the aforementioned substituent V. However, the carbon atom directly bonded to the nitrogen atom of hydrazine in R ₁ , R ₂ , R ₃ and R ₄ is not substituted with the oxo group. For example, R ₁ , R ₂ , R
₃ and R ₄ are acetyl group, carboxy group, benzoyl group, formyl group, malonyl group when two form a ring,
It is not a succinyl group, a glutaryl group, or an adipoyl group. In addition, a carbon atom of R ₁ , R ₂ , R ₃ and R ₄ directly bonded to the nitrogen atom of hydrazine is substituted with a thioxo group (eg, thioacetyl group, thioaldehyde group, thiocarboxy group, thiobenzoyl group). It is preferable not to do it.

More preferably, R ₁ , R ₂ , R ₃ and R ₄ are the above-mentioned unsubstituted alkyl group, substituted alkyl group, and R ₁ and R ₂ , R ₃ and R ₄ , R ₁ and R ₃ , and R ₂ and R ₄ are bonded to each other to form a ring atom other than carbon atom (eg, oxygen atom, sulfur atom, nitrogen atom)
In the case of forming an alkylene group that does not include (the alkylene group may be substituted (for example, the above-mentioned substituent V)). Further preferred as R ₁ , R ₂ , R ₃ and R ₄ is a case where the carbon atom directly bonded to the nitrogen atom of hydrazine is an unsubstituted methylene group. Particularly preferably, an unsubstituted alkyl group (eg, methyl group, ethyl group, propyl group, butyl group), substituted alkyl group {eg, sulfoalkyl group (eg, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3 -Sulfobutyl group),
Carboxyalkyl group (eg, carboxymethyl group, 2
-Carboxyethyl group), hydroxyalkyl group (for example, 2-hydroxyethyl group)}, and R ₁ and R ₂ , R
_{In this case, 3} and R ₄ , R ₁ and R ₃ and R ₂ and R ₄ are bonded to each other by an alkylene chain to form a 5-membered ring and a 7-membered ring.

The hydrazine compound represented by the general formula (I) may be isolated as a salt if it is advantageous in terms of synthesis and storage. In such a case, any compound may be used as long as it can form a salt with hydrazines, but preferable salts include the following. For example, an aryl sulfonate (eg, p-toluene sulfonate, p-chlorobenzene sulfonate),
Aryl disulfonates (eg 1,3-benzenedisulfonate, 1,5-naphthalenedisulfonate, 2,
6-naphthalenedisulfonate), thiocyanate, picrate, carboxylate (eg oxalate, acetate, benzoate, hydrogen oxalate), halogenate (eg hydrochloride, fluorinated salt) (Hydrogen salt, hydrobromide salt, hydroiodide salt), sulfate salt, perchlorate salt, tetrafluoroborate salt, sulfite salt, nitrate salt, phosphate salt, carbonate salt, and bicarbonate salt. Preferred are hydrogen oxalate, oxalate and hydrochlorate.

The general formula (II) will be described in detail below. R ₅ and R ₆ have the same meanings as R ₁ , R ₂ , R ₃ and R ₄ , and the preferred ranges are also the same. Particularly preferred is the case where a methyl group and R ₅ and R ₆ are bonded to each other to form an unsubstituted tetramethylene group. Z ₁ represents an alkylene group having 4 or 6 carbon atoms, preferably an alkylene group having 4 carbon atoms. However, the oxo group is not substituted for the carbon atom by directly bonding to the nitrogen atom of hydrazine. The alkylene group may be unsubstituted or substituted. Examples of the substituent include the above-mentioned substituent V, but it is preferable that the carbon atom directly bonded to the nitrogen atom of hydrazine is an unsubstituted methylene group. An unsubstituted tetramethylene group is particularly preferable as Z ₁ .

The general formula (III) will be described in detail below. R ₇ and R ₈ have the same meanings as R ₁ , R ₂ , R ₃ and R ₄ , and preferred ranges are also the same. Particularly preferred is the case where the methyl group and R ₇ and R ₈ are bonded to each other to form a trimethylene group. Z ₂ represents an alkylene group having 2 carbon atoms. Z ₃ represents an alkylene group having 1 or 2 carbon atoms. Further, these alkylene groups may be unsubstituted or substituted. Examples of the substituent include the above-mentioned substituent V. Z ₂ is more preferably an unsubstituted ethylene group. Z ₃ is more preferably an unsubstituted methylene group or an ethylene group. L ₁ and L ₂ represent a methine group or a substituted methine group. Examples of the substituent include the above-mentioned substituent V, and preferably an unsubstituted alkyl group (eg, methyl group, t
-Butyl group). More preferably, it is an unsubstituted methine group.

The general formula (IV) will be described in detail. Z
₄ and Z ₅ represent an alkylene group having 3 carbon atoms.
However, the carbon atom directly bonded to the nitrogen atom of hydrazine is not substituted with the oxo group. Further, these alkylene groups may be unsubstituted or substituted. Examples of the substituent include the above-mentioned substituent V, but the carbon atom directly bonded to the nitrogen atom of hydrazine is preferably an unsubstituted methylene group. Z ₄ and Z ₅
Particularly preferably, it is an unsubstituted trimethylene group or an unsubstituted alkyl group-substituted trimethylene group (eg, 2,2-dimethyltrimethylene group). The compounds represented by the general formulas (II), (III) and (IV) can be isolated as salts similarly to the compounds represented by the general formula (I). Examples of the salt include those similar to the salt represented by the general formula (I). Preferred are hydrogen oxalate, oxalate and hydrochlorate. Below, general formulas (I) and (I
Typical examples of the compounds represented by I), (III) and (IV) are shown below, but the invention is not limited thereto. The compound represented by the general formula (I) (the compound represented by the general formula (I) includes the compounds represented by the general formulas (II), (III) and (IV). The compound represented by the general formula (II), (III) and (IV)
An example excluding the compound represented by )

[0028]

[Chemical 6]

[0029]

[Chemical 7]

[0030]

[Chemical 8]

[0031]

[Chemical 9]

[0032]

[Chemical 10]

[0033]

[Chemical 11]

[0034]

[Chemical 12]

Compound represented by general formula (II)

[0036]

[Chemical 13]

[0037]

[Chemical 14]

[0038]

[Chemical 15]

[0039]

[Chemical 16]

[0040]

[Chemical 17]

[0041]

[Chemical 18]

Compound represented by general formula (III)

[0043]

[Chemical 19]

[0044]

[Chemical 20]

[0045]

[Chemical 21]

[0046]

[Chemical formula 22]

Compound represented by general formula (IV)

[0048]

[Chemical formula 23]

[0049]

[Chemical formula 24]

[0050]

[Chemical 25]

The hydrazines of the present invention can be synthesized by various methods. For example, it can be synthesized by a method of alkylating hydrazine. Alkylation methods include direct alkylation with alkyl halides and sulfonic acid alkyl esters, reductive alkylation with carbonyl compounds and sodium cyanoborohydride, and acylation followed by hydrogenation. A method of reducing with lithium aluminum is known. For example, SR Sandler, W
W. Karo, "Organic Functional Group Preparations (Organic Fanctional Gro
up Preparation) ", Volume 1, Chapter 14, 434-465
Page (1968), Academic Press (Academ
ic Press) Described in company publications. The compound represented by the general formula (I) is, for example, E.L.
L. Clennan, etc.Journal of the American Che
mical Society) Vol. 112, No. 13, p. 5080 (199
0 years) and can be synthesized by referring to them.

The compound represented by the general formula (II) can be obtained, for example, from S. F. Nelsen, Journal of the American Chemical Society (J.
ournal of The American Chemical Society) Volume 98, 1
No. 2, page 5269 (1976), SF Nelsen, G. R. Weissmann (GR.
Weisman), Tetrahedron Letter (Tetrahed)
ron Letter) No. 26, page 2321 (1973) and the like, and can be synthesized by referring to them. The synthesis examples of typical compounds are described below.

(Synthesis Example 1) Synthesis of Compound (2-3) Synthesis Route

[0054]

[Chemical formula 26]

(A) 20 g (0.163 mol), (a)
16.3 g (0.163 mol) and 80 ml acetic acid
After heating under reflux for 5 hours, 50 ml of water and 100 ml of 5% aqueous sodium hydroxide solution are added, and the mixture is extracted with 200 ml of chloroform. After drying over anhydrous sodium sulfate, the solvent is distilled off under reduced pressure. 200 ml of ethyl acetate was added to the obtained oil, and 200 ml of hexane was further added to precipitate crystals. After filtering off with suction filtration, it is dried (c) (colorless crystals, 8.65).
g, yield 32%) was obtained. Lithium aluminum hydride 8.9 g (0.235 mol), tetrahydrofuran 10
Cool 0 ml to 0 ° C., and with stirring, (c) 7.9 g
A (0.047 mol) / tetrahydrofuran 70 ml solution is slowly added dropwise. At this time, the reaction solution is kept at 5 ° C. or lower.
After stirring at room temperature for 4 hours, the reaction solution was cooled to 0 ° C. again, and 9 ml of water, 9 ml of 15% aqueous sodium hydroxide solution, and water 2
The mixture was added dropwise in the order of 7 ml, and the precipitated colorless crystals were filtered off with suction and removed. The filtrate was dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure, followed by vacuum distillation (2-3) (colorless liquid, 1.44 g, 85-90 ° C / 25 mmHg, yield 17).
%) Was obtained.

(Synthesis Example 2) Synthesis of compound (2-1) 6 g (0.043 mol) of (2-3), ethyl acetate 100
A solution of 4.3 g (0.048 mol) of oxalic acid / 120 ml of ethyl acetate was added to ml, and the mixture was stirred. The precipitated crystals were filtered by suction filtration and dried (2-1) (9.3 g of colorless crystals, mp.
129-131 ° C., yield 94%).

The compound represented by the general formula (III) is, for example, HRSnycler, J
R), JG Michels, Journal of Organic Chemistry (Journal o
f Organic Chemistry) 28, 1144 (1963)
Year), JE Anderson,
JMLehn, Journal of The Amer
ican Chemistry) Vol. 89, No. 1, p. 81 (1967)
Year), Hermann Stetter, Peter Woernle Justus LiebigsAmmalen
der Chemie) No. 724, p. 150 (1969), SF Nelsen et al., Tetrahedron
(Tetrahedron), Vol. 42, No. 6, 1769 (1986)
, Etc.) and can be synthesized by referring to them.

The compound represented by the general formula (IV) can be obtained by, for example, SF Nelsen et al., Journal of the American Chemistry.
eAmerican Chemical Society), Vol. 96, No. 9, 291
Page 6 (1974), EL Buhle
Etc., Journal of the American Chemistry
(Journal of The American Chemical Society), No. 6
5, p. 29 (1943) and the like, and can be synthesized by referring to them.

The tabular silver halide grains of the present invention can be spectrally sensitized with methine dyes and the like, if necessary. In addition to the above-mentioned improvement in sharpness, a high spectral speed is also a feature of the tabular silver halide grains of the present invention. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes,
Included are 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.

Examples of useful sensitizing dyes include German Patent 929,080 and US Pat. No. 2,493,748.
No. 2,503,776, No. 2,519,00
No. 1, No. 2,912,329, No. 3,656,9
No. 59, No. 3,672,897, No. 4,025.
349, British Patent No. 1,242,588, Japanese Patent Publication No. 4
The thing described in 4-14030 can be mentioned.

These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,5
No. 22,052, No. 3,527,641, No. 3,
617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,728, 3,814,609.
No. 4,026,707, British Patent No. 1,344,2
No. 81, Japanese Patent Publication No. 43-4936, No. 53-12375.
Nos. 52-109925 and 52-110618.
No. Particularly preferred sensitizing dyes have an oxidation potential of 0.95 (V _vs SCE) or less. It is known that these dyes generally have large dye desensitization. More preferably, the oxidation potential is 0.95 (V
_vs SCE) or less and spectral sensitivity maximum is 600 nm
It is a dye that spectrally sensitizes the above panchromatic and near-infrared regions.

The oxidation potential was measured by a phase discrimination type second high frequency AC polarography. The details are described below. Acetonitrile (spectral grade) dried in 4A-1 / 16 molecular sieves was used as a solvent, and normal tetrapropylammonium perchlorate (special reagent for polarograph) was used as a supporting electrolyte. The sample solution was prepared by dissolving a sensitizing dye at 10 ⁻³ to 10 ⁻⁵ mol / liter in acetonitrile containing 0.1 M of supporting electrolyte, and a high alkaline aqueous solution of pyrogallol was added to the solution before the measurement, and calcium chloride was passed through the solution. It was deoxygenated with high-purity argon gas (99.999%) for 15 minutes or more. The working electrode was a rotating platinum electrode, the reference electrode was a saturated calomel electrode (SCE), and the counter electrode was platinum. The reference electrode and the sample solution were connected with a Luggin tube filled with acetonitrile containing 0.1 M indicator electrolyte, and Vycor glass was used for the liquid junction. The tip of the Luggin tube and the tip of the rotating platinum electrode were measured at 25 ° C. with a distance of 5 mm to 8 mm. The measurement of the oxidation potential by the phase discriminating oni hard harmonic AC voltammetry is described in "Journal
Of Imaging Science "(Journal of Imagi
ng Science), Vol. 30, pp. 27-35 (1986).
It is described in. Under this condition, the dye (XIV-
The oxidation potential of 9) was 0.915 V (vsSCE). The sensitizing dyes satisfying the conditions of the above-mentioned oxidation potential and the maximum spectral sensitivity and represented by the following general formulas (XI), (XII) and (XIII) are particularly preferably used. General formula (XI)

[0063]

[Chemical 27]

General formula (XII)

[0065]

[Chemical 28]

General formula (XIII)

[0067]

[Chemical 29]

In the formula, Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ , Z ₁₅ and Z ₁₆ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. D and D'represent an atomic group necessary for forming an acyclic or cyclic acidic nucleus.
R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₆ represent an alkyl group. R ₁₅ represents an alkyl group, an aryl group or a heterocyclic group. L ₁₁ , L ₁₂ , L ₁₃ , L ₁₄ , L ₁₅ , L ₁₆ , L ₁₇ , L
₁₈ , L ₁₉ , L ₂₀ , L ₂₁ , L ₂₂ , L ₂₃ , L ₂₄ , L ₂₅ ,
L ₂₆ , L ₂₇ , L ₂₈ , L ₂₉ and L ₃₀ represent a methine group. M ₁₁ , M ₁₂ and M ₁₃ represent charge-neutralizing counterions, and m ₁₁ , m ₁₂ and m ₁₃ are a number of 0 or more necessary for neutralizing the charge in the molecule. n ₁₁ , n ₁₃ , n ₁₄ , n
₁₆ and n ₁₉ represent 0 or 1. n ₁₂ represents 1, 2 or 3. n ₁₅ represents 2 or 3. n ₁₇ and n ₁₈
Each is an integer of 0 or more, and the total represents 1, 2, 3 or 4. More preferred are sensitizing dyes represented by the general formula (XI).

The general formulas (XI), (XII) and (XIII) are shown below.
Will be described in more detail. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₆ are preferably unsubstituted alkyl groups having 18 or less carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl), or substituted. Alkyl group (As a substituent, for example, a carboxy group, a sulfo group, a cyano group, a halogen atom (eg, fluorine, chlorine, bromine), a hydroxy group, an alkoxycarbonyl group having 8 or less carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, Phenoxycarbonyl, benzyloxycarbonyl), an alkoxy group having 8 or less carbon atoms (eg, methoxy, ethoxy, benzyloxy, phenethyloxy), a monocyclic aryloxy group having 10 or less carbon atoms (eg, phenoxy, p-tolyloxy), carbon Acyloxy groups of 3 or less (eg acetyl , Propionyloxy), no more than 8 acyl group carbons (e.g., acetyl, propionyl, benzoyl, mesyl), a carbamoyl group (e.g. carbamoyl, N, N-
Dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), sulfamoyl group (eg, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), aryl group having 10 or less carbon atoms (eg, phenyl, 4-chloro) Phenyl,
4-methylphenyl, α-naphthyl) -substituted alkyl groups having 18 or less carbon atoms}. Preferably, an unsubstituted alkyl group (eg, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group), carboxyalkyl group (eg, 2-carboxyethyl group, carboxymethyl group) ), A sulfoalkyl group (for example, a 2-sulfoethyl group, a 3-sulfopropyl group, a 4-sulfobutyl group, a 3-sulfobutyl group) and a methanesulfonylcarbamoylmethyl group. M ₁₁ m ₁₁ ,
M ₁₂ m ₁₂ and M ₁₃ m ₁₃ are included in the formula to indicate the presence or absence of a cation or anion when required to neutralize the ionic charge of the dye. Whether a dye is a cation, an anion, or has a net ionic charge depends on its auxochrome and substituents. Typical cations are inorganic or organic ammonium and alkali metal ions, while the anion may be either an inorganic or organic anion, for example a halogen anion (eg a fluoride ion, (Chlorine ion, bromine ion, iodine ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulfonate ion (for example, 1,3-benzene disulfonate ion, 1, 5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetic acid Ion, trifluoromethane Preferably sulfonic acid ion and the like, ammonium ion, an iodine ion, a p- toluenesulfonic acid ion.

The nucleus formed by Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ and Z ₁₆ 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-methylthiobenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole,
5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 6-methylthiobenzothiazole, 5-ethoxybenzothiazole, 5- Ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5,6
-Dimethylthiobenzothiazole, 5,6-dimethoxybenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole), naphthothiazole nucleus (for example, naphtho [2,1-d] thiazole) , Naft [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-phenyl) Oxazole, 4,5-diphenyloxazole, 4
-Ethyloxazole), a benzoxazole nucleus (for example, 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 (for example, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, 5-
Nitronaphtho [2,1-d] oxazole)}, an oxazoline nucleus (eg, 4,4-dimethyloxazoline),
Selenazole nucleus (selenazole nucleus (for example, 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole), benzoselenazole nucleus (for example, benzoselenazole, 5-chlorobenzoselenazole, 5-
Nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole, 5,6-dimethylbenzoselenazole), naphthoselenazole Nuclear (eg naphtho [2,1
-D] selenazole, naphtho [1,2-d] selenazole)}, selenazoline nucleus (for example, selenazoline, 4-
Methyl selenazoline), tellurazole nucleus {terrazole nucleus (eg, tellurazole, 4-methylterrazole,
4-phenylterrazole), a benzoterrazole nucleus (for example, benzoterrazole, 5-chlorobenzoterrazole, 5-methylbenzoterrazole, 5,6-dimethylbenzotelrazole, 6-methoxybenzoterrazole), naphtho Tellurazole nucleus (for example, naphtho [2,1-d] telrazole, naphtho [1,2-d] telrazole)}, 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-trimethyl Indolenine, 3,3-dimethyl-5-chloroindolenine), imidazole nucleus (imidazole nucleus (for example, 1-alkylimidazole, 1-alkyl-4-phenylimidazole, 1-arylimidazole), benzimidazole nucleus (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-chlorobenzimidazole, 1-arylbenzimidazole, 1-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1- Aryl-5-methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole), naphthimidazole nucleus (for example, alkylnaphtho [1,2-d] imidazole, 1-arylnaphtho [1,2-d] imidazole), The aforementioned alkyl groups have 1 to 8 carbon atoms, such as methyl, ethyl,
Unsubstituted alkyl groups such as propyl, isopropyl, butyl and hydroxyalkyl groups (eg, 2-hydroxyethyl, 3-hydroxypropyl) are preferred. Particularly preferred are methyl group and ethyl group. The aforementioned aryl group represents phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl. }, 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 (for example, 6-nitro-1-isoquinoline, 3,4-dihydro-1-isoquinoline, 6-nitro-3-) Isoquinoline)}, an imidazo [4,5-b] quinoxaline nucleus (for example, 1,3-diethylimidazo [4,5-b] quinoxaline, 6-chloro-1,3-diallylimidazo [4,5-b] quinoxaline. ), An oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, and a pyrimidine nucleus. However, in the general formula, when n ₁₂ is 1, neither Z ₁₁ nor Z ₁₂ is an oxazole nucleus or an imidazole nucleus. The nucleus formed by Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ and Z ₁₆ is preferably a benzothiazole nucleus, a naphthothiazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzimidazole nucleus, a 2-quinoline nucleus, 4-
It is a quinoline nucleus.

D and D'represent the atomic groups necessary to form acidic nuclei, but can take the form of the acidic nuclei of any common merocyanine dye. The acidic nucleus here is
For example, The Theory of the Photographic Process, edited by James.
Photographic Process) 4th edition, Macmillan Publishers,
1977, defined by page 198. In a preferred form, the substituent involved in D resonance is, for example, a carbonyl group, a cyano group, a sulfonyl group, or a sulfenyl group. D'represents the remaining atomic group necessary for forming an acidic nucleus. Specifically, US Pat. No. 3,567,7
19, No. 3,575,869, No. 3,804,63
No. 4, No. 3,837,862, No. 4,002,480
No. 4,925,777, JP-A-3-167546.
The items listed in the No. etc. are listed. When the acidic nucleus is acyclic, the end of the methine bond is malononitrile,
A group such as alkanesulfonylacetonitrile, cyanomethyl benzofuranyl ketone, or cyanomethyl phenyl ketone. When D and D'are cyclic, carbon, nitrogen, and chalcogen (typically oxygen, sulfur,
It forms a 5- or 6-membered heterocycle consisting of selenium and tellurium) atoms.

The following cores are preferred. 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidin-4-one, 2-oxazolin-5-one, 2- Thiooxazolidin-2,4-dione, isoxazolin-5-one,
2-thiazolin-4-one, thiazolidin-4-one,
Thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indane-
1,3-dione, thiophen-3-one, thiophene-
3-one-1,1-dioxide, indoline-2-one, indoline-3-one, indazoline-3-one,
2-oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, cyclohexane-1,3-
Dione, 3,4-dihydroisoquinolin-4-one,
1,3-dioxane-4,4-dione, barbituric acid, 2-thiobarbituric acid, chroman-2,4-dione, indazoline-2-one, or pyrido [1,2-
a] Pyrimidine-1,3-dione nucleus. More preferably, 3-alkyl rhodanine, 3-alkyl-2-thiooxazolidine-2,4-dione, 3-alkyl-2-
It is thiohydantoin.

The substituent bonded to the nitrogen atom contained in the nucleus and R ₁₅ are a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and particularly preferably 1 to 4 carbon atoms (eg, methyl group). , Ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups (eg aralkyl groups (eg benzyl, 2-phenylethyl), hydroxyalkyl groups (eg 2-hydroxyethyl, 3- Hydroxypropyl), carboxyalkyl group (for example, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl group (for example, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl) , A sulfoalkyl group (for example, 2-
Sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy]
Ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfatoalkyl group (eg, 3-sulfatopropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl group (eg, 2- (pyrrolidine) 2-On-1-yl) ethyl, tetrahydrofurfuryl, 2-morpholinoethyl), 2-acetoxyethyl, carbomethoxymethyl, 2-methanesulfonylaminoethyl}, allyl group, aryl group (eg phenyl,
2-naphthyl), substituted aryl groups (eg 4-carboxyphenyl, 4-sulfophenyl, 3-chlorophenyl, 3-methylphenyl), heterocyclic groups (eg 2-pyridyl, 2-thiazolyl), preferred. More preferably, an unsubstituted alkyl group (eg, methyl, ethyl, n-
Propyl, n-butyl, n-pentyl, n-hexyl) and carboxyalkyl group (for example, carboxymethyl, 2-carboxyethyl, sulfoalkyl group (for example, 2-sulfoethyl)).

The 5- or 6-membered nitrogen-containing heterocycle formed by Z ₁₅ is a cyclic heterocycle represented by D or D ′, from which an oxo group or a thiooxo group at an appropriate position is removed. Is. More preferably, the thiooxo group of the rhodanine nucleus is removed.

L ₁₁ , L ₁₂ , L ₁₃ , L ₁₄ , L ₁₅ , L ₁₆ , L
₁₇ , L ₁₈ , L ₁₉ , L ₂₀ , L ₂₁ , L ₂₂ , L ₂₃ , L ₂₄ ,
L ₂₅ , L ₂₆ , L ₂₇ , L ₂₈ , L ₂₉ and L ₃₀ are methine groups or substituted methine groups (eg, substituted or unsubstituted alkyl groups (eg, methyl, ethyl, 2-carboxyethyl), substituted or unsubstituted) Aryl group (eg phenyl, o-carboxyphenyl), heterocyclic group (eg barbituric acid), halogen atom (eg chlorine atom, bromine atom), alkoxy group (eg methoxy, ethoxy), amino group (eg N, N-diphenylamino, N
-Methyl-N-phenylamino, N-methylpiperazino), those substituted with an alkylthio group (eg, methylthio, ethylthio), etc.}, and may form a ring with another methine group, or It is also possible to form a ring with the chromophore. L ₁₁ , L ₁₂ , L ₁₆ , L ₁₇ , L
₁₈ , L ₁₉ , L ₂₂ , L ₂₃ , L ₂₉ and L ₃₀ are preferably unsubstituted methine groups. L ₁₃ , L ₁₄ and L ₁₅ form trimethine, pentamethine and heptamethine dyes. The units of L ₁₃ and L ₁₄ are repeated when n ₁₂ is 2 or 3, but need not be the same. Below L ₁₃ , L ₁₄
And preferred examples of the methine chain formed by L ₁₅ .

[0076]

[Chemical 30]

L ₂₀ and L ₂₁ form the tetramethylene and hexamethine dyes. The units of L ₂₀ and L ₂₁ are repeated but need not be the same. L ₂₀ and L
Preferred examples of the methine chain formed by ₂₁ are given below.

[0078]

[Chemical 31]

L ₂₄ and L ₂₅ form dimethine, tetramethine, hexamethine and the like. The units of L ₂₄ and L ₂₅ are repeated when n ₁₇ is 2 or more, but need not be the same. Preferred examples of the methine chain formed by L ₂₄ and L ₂₅ will be given.

[0080]

[Chemical 32]

A preferred example when n ₁₇ is 2 or more is
The same as 1). L ₂₆ , L ₂₇ and L ₂₈ form monomethine, trimethine, pentamethine and the like. L ₂₆
The units of L ₂₇ and L ₂₇ are repeated when n ₁₈ is 2 or more, but need not be the same. Preferred examples of the methine chain formed by L ₂₆ , L ₂₇ and L ₂₈ will be given.

[0082]

[Chemical 33]

In addition to this, the example shown in (Chemical Formula 30) is preferable. Among the compounds represented by the general formula (XI), the compound represented by the following general formula (XIV) is more preferably used. General formula (XIV)

[0084]

[Chemical 34]

In the formula, Z ₁₇ and Z ₁₈ represent a sulfur atom or a selenium atom. R ₁₇ and R ₁₈ represent an alkyl group. R ₁₉ , V ₁₁ , V ₁₂ , V ₁₃ , V ₁₄ , V ₁₅ , V ₁₆ , V ₁₇
And V ₁₈ represent a hydrogen atom or a monovalent substituent. M
₁₄ represents a charge neutralizing counterion, and m ₁₄ is a number of 0 or more necessary for neutralizing the charge in the molecule. General formula (XI
V) will be explained in more detail. R ₁₇ and R ₁₈ are preferably the same as R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₆ . R ₁₉ , V ₁₁ , V ₁₂ , V ₁₃ , V ₁₄ , V ₁₅ , V
_The substituents represented by ₁₆ , V ₁₇ and V ₁₈ are not particularly limited, and examples thereof include the substituents represented by V described above. Also, V ₁₁ , V ₁₂ , V ₁₃ , V ₁₄ , V ₁₅ , V ₁₆ , V ₁₇ and V ₁₈
Among them, two bonded to adjacent carbon atoms may form a condensed ring with each other. For example, as the condensed ring, a benzene ring and a heterocycle (for example, pyrrole, thiophene,
Furan, pyridine, imidazole, triazole, thiazole). R ₁₉ is preferably a methyl group, an ethyl group, a propyl group or a cyclopropyl group.
More preferably, it is an ethyl group. V ₁₁ , V ₁₂ , V ₁₄ ,
V ₁₅ , V ₁₆ and V ₁₈ are preferably hydrogen atoms. V ₁₃ and V ₁₇ are preferably a chloro group, a methyl group, a methoxy group, a phenyl group and a carboxy group. It is also preferable that V ₁₃ and V ₁₄ and V ₁₇ and V ₁₈ are bonded to each other to form a benzene ring. M ₁₄ m ₁₄ is M
Synonymous with ₁₁ m ₁₁ , M ₁₂ m ₁₂ and M ₁₃ m ₁₃ . The typical examples of the sensitizing dyes used in the invention are shown below, but the invention is not limited thereto. The sensitizing dyes of the higher concept are illustrated in order, and the sensitizing dye of the lower concept, which is more preferable, is excluded. (1) Sensitizing dye used in the present invention

[0086]

[Chemical 35]

[0087]

[Chemical 36]

[0088]

[Chemical 37]

[0089]

[Chemical 38]

[0090]

[Chemical Formula 39]

[0091]

[Chemical 40]

(2) Sensitizing dye having an oxidation potential of 0.95 (V _vs SCE) or less

[0093]

[Chemical 41]

[0094]

[Chemical 42]

[0095]

[Chemical 43]

[0096]

[Chemical 44]

[0097]

[Chemical formula 45]

(3) Sensitizing dye having an oxidation potential of 0.95 (V _vs SCE) or less and a spectral sensitivity maximum of 600 nm or more.

[0099]

[Chemical formula 46]

[0100]

[Chemical 47]

(4) The conditions of the above (3) regarding the oxidation potential and the spectral sensitivity maximum are satisfied, and the general formulas (XI), (XII) and (X
Sensitizing dye represented by III) (4-1) Sensitizing dye represented by general formula (XI)

[0102]

[Chemical 48]

[0103]

[Chemical 49]

[0104]

[Chemical 50]

[0105]

[Chemical 51]

[0106]

[Chemical 52]

[0107]

[Chemical 53]

[0108]

[Chemical 54]

[0109]

[Chemical 55]

(4-2) Sensitizing dye represented by the general formula (XII)

[0111]

[Chemical 56]

[0112]

[Chemical 57]

[0113]

[Chemical 58]

(4-3) Sensitizing dye represented by the general formula (XIII)

[0115]

[Chemical 59]

[0116]

[Chemical 60]

[0117]

[Chemical formula 61]

(5) A sensitizing dye represented by the general formula (XIV), which satisfies the condition (3) concerning the oxidation potential and the spectral sensitivity maximum.

[0119]

[Chemical formula 62]

[0120]

[Chemical formula 63]

[0121]

[Chemical 64]

[0122]

[Chemical 65]

[0123]

[Chemical formula 66]

[0124]

[Chemical formula 67]

[0125]

[Chemical 68]

The sensitizing dye used in the present invention is F.M.
FM Hamer, "Heterocyclic Compounds-Cyanine Dyes-Cyanine Dyes and Related Compounds-Cyanine Dyes
and Related Compounds (John & Sons Inc.-New York, London, 1)
964). , Day M Starmer (DMSturme
r), “Heterocyclic Compounds-Special topics in he
terocyclic chemistry-) ", Chapter 18, Section 14, pp. 482-515, John Wiley & Sons, New York, London,
(Published in 1977). , "Rods Chemistry of
Carbon Compounds (Rodd's Chemistry of Carbon C
ompounds) ”, (2nd.Ed.vol.IV, part B, 1977), Chapter 15, 369-422; (2nd.Ed.vol.I)
V, part B, 1985), Chapter 15, 267-29
Page 6, Elsvier Science Publishing Company, Inc.
Inc.) Annual, New York, etc.

The silver halide emulsion of the present invention contains the compound represented by formula (I), (II), (III) or (IV) of the present invention and the sensitizing dye used in the present invention. , They may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol. , 3-methoxy-1-propanol, 3-methoxy-
1-butanol, 1-methoxy-2-propanol,
It may be added to the emulsion by dissolving it in a solvent such as N, N-dimethylformamide alone or in a mixed solvent. Further, as described in US Pat. No. 3,469,987, the dye or the compounds (I) to (IV) of the present invention are dissolved in a volatile organic solvent, and the solution is dissolved in water or a hydrophilic colloid. And then adding this dispersion to the emulsion, JP-B-46-
No. 24,185, etc., a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding this dispersion to an emulsion, JP-B-44-23389.
JP-B-44-27,555, JP-B-57-22,09
No. 1, etc., a method in which a dye is dissolved in an acid and the solution is added to the emulsion, or an acid or a base is coexisted to form an aqueous solution and the solution is added to the emulsion, US Pat. No. 3,82.
No. 2,135, US Pat. No. 4,006,026, etc., a method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant into an emulsion,
JP-A-53-102,733, JP-A-58-105,
No. 141, a method in which a dye is directly dispersed in a hydrophilic colloid and the dispersion is added to an emulsion, and a compound for red-shifting is used, as described in JP-A-51-74624. It is also possible to use a method of dissolving the dye and adding the solution to the emulsion. Also, ultrasonic waves can be used for dissolution.

The timing of adding the sensitizing dye used in the present invention or the compounds (I) to (IV) of the present invention to the silver halide emulsion of the present invention has been found to be useful so far. Any of the steps may be performed. For example, US Pat. No. 2,735,766 and US Pat. No. 3,628,96.
No. 0, US Pat. No. 4,183,756, US Pat.
25,666, JP-A-58-184,142, JP-A-60-196,749 and the like, as disclosed in the specification, before the grain forming step of silver halide and / or before desalting. Timing, during the desalting step and / or from after desalting to before the start of chemical ripening, as disclosed in the specification of JP-A-58-113,920 or the like, immediately before or during the chemical aging. No., and may be added at any time in any step before the emulsion is coated before the coating after the chemical ripening and before the coating. Also, U.S. Pat. No. 4,225,666, JP-A-58.
No. 7,629, and the like, the same compound alone or in combination with a compound having a different structure, for example, during the grain formation step and during the chemical ripening step or after the chemical ripening step is completed. The compounds may be added in divided portions, such as before or after chemical aging, or during the process and after completion, or the compound and the combination of compounds may be added in different types.

The addition amount of the sensitizing dye used in the present invention varies depending on the shape and size of silver halide grains,
Preferably 4 × 10 ⁻⁸ to ⁸ per mol of silver halide
It can be used at × 10 ^-2 mol. The compound represented by the general formula (I), (II), (III) or (IV) of the present invention may be added before or after the sensitizing dye, and preferably 1 × 10 5 mol / mol of silver halide. ^{-6 to} 5 x 10
^-1 mol, more preferably 1 × 10 ^-5 to 2 × 10 ^-2 mol, and particularly preferably 1 × 10 ^{-4 to} 1.6 × 10 ² -mol in the silver halide emulsion. The ratio (molar ratio) of the sensitizing dye to the compound represented by the general formula (I), (II), (III) or (IV) may be any value, but the ratio of the sensitizing dye / (I), (II ), (III) or (IV) = 10/1 to 1/10
The range of 00 is preferably used, in particular the range of 1/1 to 1/100 is used.

The tabular silver halide emulsion used in the present invention will be described in detail below.

The emulsion of the present invention is a tabular silver halide grain having an aspect ratio of 2 or more. Here, 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. When viewed from above, the tabular grains have a triangular shape, a hexagonal shape, or a rounded circular shape.The triangular shape is a triangular shape, the hexagonal shape is a hexagonal shape, and a circular shape. Have circular outer surfaces parallel to each other.

The tabular grain aspect ratio in the present invention means a value obtained by dividing the grain diameter of each tabular grain having a grain diameter of 0.1 μm or more by the thickness. The thickness of the particles is measured by evaporating the metal from the diagonal direction of the particles together with the latex for reference, measuring the shadow length on an electron micrograph, and calculating by referring to the shadow length of the latex. You can easily.

The particle diameter in the present invention is the diameter of a circle having an area equal to the projected area of the parallel outer surfaces of the particles.

The projected area of particles is obtained by measuring the area on an electron micrograph and correcting the photographing magnification.

The average aspect ratio is obtained as the arithmetic mean of the aspect ratios of each grain for at least 100 silver halide grains. It can also be obtained as the ratio of the average diameter to the average thickness of the particles.

In the tabular silver halide grains used in the silver halide emulsion of the present invention, the grain diameter is 2 times or more the grain thickness, preferably 3 to 20 times, more preferably 4 to 15 times, It is particularly preferably 5 to 10 times. The proportion of tabular silver halide grains in the projected area of all silver halide grains is 50% or more, preferably 70% or more, particularly preferably 85% or more.

By using such an emulsion, a silver halide photographic light-sensitive material having excellent sharpness can be obtained. The sharpness is excellent because the light scattering in the emulsion layer using such an emulsion is extremely small as compared with the conventional emulsion layer. This can be easily confirmed by those skilled in the art by experimental methods that can be routinely used. It is not clear why the light scattering of the emulsion layer using the tabular silver halide emulsion is small, but the main surface of the tabular silver halide emulsion is
It is considered that this is because the orientation is parallel to the support surface.

The diameter of tabular silver halide grains is
0.02 to 20 μm, preferably 0.3 to 10.0 μm
And particularly preferably 0.4 to 5.0 μm. The thickness of the particles is 0.7 μm or less, preferably 0.5 μm or less.

In the present invention, more preferable tabular silver halide grains have a grain diameter of 0.3 μm or more and 10.
The particle size is 0 μm or less, the particle thickness is 0.3 μm or less, and the average (diameter / thickness) is 5 or more and 10 or less. 1
When it is greater than 0, the photographic performance may be abnormal when the light-sensitive material is bent, tightly wound, or touched with a sharp object, which is not preferable. More preferred is a silver halide having a grain diameter of 0.4 μm or more and 5.0 μm or less and an average (diameter / thickness) of 5 or more occupying 85% or more of the total projected area of all silver halide grains. This is the case for emulsions.

The tabular silver halide grains used in the present invention may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide, but they are silver bromide or iodide. Silver iodobromide containing 15 mol% or less of silver, or 50 mol% or less of silver chloride and 2 mol% of silver iodide
The following silver chloroiodobromide and silver chlorobromide are more preferable, and the composition distribution in the mixed silver halide may be uniform or localized.

The tabular silver halide emulsions used in the present invention are reported by Cgnac and Chateau, and Duf.
Fin “Photographic Emulsio”
nChemistry ”(published by Focal Press,
New York 1966) pp. 66-72, and A. P. H. Trivelli, W.C. F. Smith edited "Phot.Jouranl" 80 (1940) 28
As described on page 5, JP-A-58-113927
No. 58-113928, No. 58-127921, it can be easily prepared.

For example, if pBr is 1.3 or less, a relatively high p
It can be obtained by forming a seed crystal in which tabular grains are present in an amount of 40% or more by weight in an atmosphere of Ag value, and growing the seed crystal while simultaneously adding silver and a halogen solution while keeping the same pBr. In this particle growth process,
It is desirable to add silver and halogen solutions so that new crystal nuclei are not generated.

The size of the tabular silver halide grains can be adjusted by controlling the temperature, selecting the kind and quality of the solvent, the addition rate of the silver salt used during grain growth, and the halide.

During the production of the tabular silver halide grains of the present invention, a silver halide solvent may be used, if necessary, so that the grain size, grain shape (diameter / thickness ratio, etc.), grain size distribution, grain size You can control the growth rate. The amount of the solvent used is 10 ^{−3 to} 1.0 of the reaction solution.
The range of wt% is preferable, and the range of 10 ^-2 to 10 ^-1 wt% is particularly preferable. In the present invention, as the amount of solvent used increases, the particle size distribution can be made monodisperse and the growth rate can be promoted, while the thickness of particles also tends to increase with the amount of solvent used.

In the present invention, known silver halide solvents can be used. Examples of frequently used silver halide solvents include ammonia, thioethers, thioureas, thiocyanate salts and thiazoline thiones. Regarding thioethers, US Pat. Nos. 3,271,157 and 3,57
No. 4,628 and No. 3,790,387 can be referred to. Further, regarding thioureas, Japanese Patent Laid-Open No. Sho 5
3-82408, 55-77737, and thiocyanate salts, U.S. Pat. Nos. 2,222,264, 2,448,534, 3,320,069,
Regarding thiazoline thiones, JP-A-53-1443
No. 19 can be referred to respectively.

In the process of formation or physical ripening of silver halide grains, for example, cadmium salt, zinc salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may be present together. .

In the production of tabular silver halide grains used in the present invention, the addition rate and the addition amount of a silver salt solution (eg AgNO ₃ aqueous solution) and a halide solution (eg KBr aqueous solution) which are added to accelerate grain growth. The method of increasing the addition concentration is preferably used. Regarding these methods, for example, U.S. Pat. Nos. 1,335,925, 3,650,757, 3,672,900, 4,242,445 and JP-A-55-142329.
No. 55-158124, etc. can be referred to.

The tabular silver halide grain of the present invention can be chemically sensitized if necessary. For chemical sensitization,
For example, H.264. Frieser ed "Die Grundl
agen der Photogrophischen
Process MitSilberhalage
niden ”(Akademishe Verlag
sgesellschaft. 1968) 675 pages ~
The method described on page 735 can be used.

That is, a sulfur sensitizing method using a compound containing sulfur capable of reacting with active gelatin or silver (eg, thiosulfates, thioureas, mercapto compounds, rhodanins); a reducing substance (eg, stannous salt) , An amine, a hydrazine derivative, a formamidinesulfinic acid, a silane compound); a noble metal compound (for example, a gold complex salt, or a complex salt of a metal of Group VIII of the periodic table such as Pt, Ir, Pd, etc. Noble metal sensitization method and the like can be used alone or in combination.

These specific examples are described in US Pat. Nos. 1,574,944 and 2,278,9 concerning the sulfur sensitization method.
No. 47, No. 2,410,689, No. 2,728,
Nos. 668 and 3,656,955, and US Pat. Nos. 2,419,974 and 2,9 for reduction sensitization.
No. 83,609, No. 4,054,458, etc., and noble metal sensitization methods are described in US Pat. Nos. 2,399,083, 2,448,060, and British Patent 618,061. It is described in the specification.

From the viewpoint of silver saving, the tabular silver halide grains of the present invention are preferably gold-sensitized or sulfur-sensitized, or a combination thereof is preferable.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, and stabilizing photographic performance. it can. That is, azoles such as benzothiazolium salts, nitroimidazoles,
Triazoles, benzotriazoles, benzimidazoles (especially nitro or halogen-substituted); heterocyclic mercapto compounds, such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group and a sulfone group; thioketo compounds such as oxadrinethione; azaindenes, for example triazain Denes, tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes);
Many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acids; benzenesulfinic acid; and the like. For more detailed specific examples of these and methods for using them, see, for example, US Pat. Nos. 3,954,474 and 3,982,947,
The respective specifications of No. 4,021,248, or Japanese Examined Patent Publication No. 52
The description in Japanese Patent Publication No. 28660 can be referred to.

The emulsion of the present invention is preferably a monodisperse emulsion.

The monodisperse emulsion according to the present invention is an emulsion having a grain size distribution in which the variation coefficient relating to the grain size of silver halide grains is 0.25 or less. Here, the coefficient of variation is a value obtained by dividing the standard deviation regarding the particle diameter by the average particle diameter. That is, the grain size of each emulsion grain is ri, and the number is ni.
, The mean particle size is

[0155]

[Equation 1]

And its standard deviation is

[0157]

[Equation 2]

Is defined as

The term "individual grain size" as used in the present invention means that a silver halide emulsion is referred to as TH James (TH Jam).
es) et al., "The Theory of the Photographic Process" (The Theory of the
e Photographic Process) No. 3
Corresponding to the projected area when microscopically photographed by a method well known in the art (usually electron microscope photography), as described in pp. 36-43, published by Macmillan (1966). It is the diameter equivalent to the projected area. Here, the projected equivalent diameter of a silver halide grain is defined by the diameter of a circle equal to the projected area of a silver halide grain, as shown in the above-mentioned book. Therefore, the average grain size r and its deviation S can be obtained as described above even when the silver halide grains are other than spherical (eg, cubic, octahedral, tetradecahedral, tabular, potato-like, etc.). is there.

The coefficient of variation relating to the grain size of silver halide grains is 0.25 or less, preferably 0.20 or less,
It is more preferably 0.15 or less.

The tabular silver halide emulsion of the present invention is particularly preferably a monodisperse hexagonal tabular silver halide emulsion described in JP-A-63-151618.

Here, the hexagonal tabular silver halide grain is
The {1,1,1} plane is hexagonal, and the adjacent side ratio is 2 or less. Here, the adjacent side ratio is the ratio of the length of the side having the maximum length to the length of the side having the minimum length forming a hexagon. The hexagonal tabular silver halide grains of the present invention may have some rounded corners as long as the ratio of adjacent sides is 2 or less. The length of a side when the corner is rounded is represented by the distance between the intersections of the straight line portion of the side and the line obtained by extending the straight line portion of the adjacent side. It is preferable that 1/2 or more of each side forming the hexagon of the hexagonal tabular grain of the present invention is substantially a straight line, and particularly 4/5 or more is substantially a straight line. In the present invention, the ratio of adjacent sides is preferably 1 to 1.5.

The hexagonal tabular silver halide emulsion of the present invention comprises
The hexagonal tabular silver halide grains occupy 50% or more, preferably 70% or more, more preferably 90% or more of the total projected area of the silver halide grains, the dispersion medium and the silver halide grains. There is.

The halogen composition of the hexagonal tabular silver halide grains in the present invention may be any of silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide. And silver iodobromide are preferred. In the case of silver iodobromide, the silver iodide content is 0.
It is -30 mol%, preferably 2-15%, more preferably 4-12 mol%. The distribution of silver iodide within a grain is
It may be uniform throughout the grain, or the silver iodide content may differ between the inside of the grain and the surface layer. Further, it may have a so-called multiple structure in which there are several layers having different silver iodide contents inside the grain, but so-called internal iodine type grains in which the silver iodide content is smaller on the grain surface than inside the grain are preferred. .

Regarding the method for producing a hexagonal tabular silver halide emulsion, US Pat. No. 4,797,354 can be referred to.

As a method for producing a monodisperse hexagonal tabular silver halide emulsion, the production process is divided into nucleation, Ostwald ripening and grain growth. At the time of nucleation, pBr was 1.
The supersaturation conditions (temperature, temperature, 0 to 2.5) are set so that nuclei (tabular grain nuclei) having twin planes as parallel as possible are formed.
Nucleation is performed based on the gelatin concentration, the addition rate of the aqueous solution of silver salt and the aqueous solution of alkali halide, pBr, the content of iodide ions, the rotation speed of stirring, pH, the amount of silver halide solvent, the salt concentration, and the like. During Ostwald ripening, in order to eliminate grains other than tabular grain nuclei formed during nucleation, to grow only tabular grain nuclei and to form nuclei with good monodispersity, temperature,
Adjust pBr, pH, gelatin concentration, amount of silver halide solvent, etc. During grain growth, hexagonal tabular silver halide grains having a desired aspect ratio and grain size can be obtained by adjusting pBr and the amount of added silver ions and halogen ions. During grain growth, the addition rate of silver ions and halogen ions is set to 3 of the crystal critical growth rate.
It is preferably 0 to 100%.

In the emulsion of the present invention, 50% of the number of silver halide grains preferably contains 10 or more dislocations per grain.

The dislocations of tabular grains are described, for example, in J. F. Ha
milton, Photo. Sci. Eng. , 11, 5
7, (1967) and T.S. Shiozawa, J .; So
c. Photo. Sci Japan, 35, 213 (1
It can be observed by a direct method using a transmission electron microscope at a low temperature described in 972). That is,
Carefully remove the silver halide grains from the emulsion so as not to apply dislocation pressure to the grains, place them on a mesh for electron microscope observation, and set the sample to prevent damage (printout, etc.) due to electron beams. In the cooled state, observation is performed by the transmission method. At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough. Therefore, it is possible to observe more clearly by using a high-voltage type (200 kV for a particle having a thickness of 0.25 μm) electron microscope. From the photograph of the grains obtained by such a method, the position and number of dislocations for each grain when viewed from the direction perpendicular to the main plane can be used.

The positions of dislocations in the tabular grains of the present invention occur from the distance x% of the length from the center of the tabular grain in the major axis direction to the side to the side. The value of x is preferably 1
0 ≦ x <100, more preferably 30 ≦ x <98
And more preferably 50 ≦ x <95. At this time, the shape formed by connecting the positions where the dislocations start is close to a particle shape, but may not be a perfect shape and may be distorted. The direction of the dislocation line is from the center to the side, but it often meanders.

Regarding the number of dislocations in the tabular grains of the present invention,
It is preferable that 50% by number or more of grains containing 10 or more dislocations exist. More preferably, 80% by number or more of particles containing 10 or more dislocations are present, and particularly preferably 80% by number or more of particles containing 20 or more dislocations.

Further, 50% by number of the silver halide grains preferably used in the tabular silver halide grains of the present invention.
In the case of silver halide grains containing 10 or more dislocations per grain, the relative standard deviation of the individual silver iodide content of the silver halide grains is particularly preferably 30% or less, further preferably 20%. % Or less is preferable.

The silver iodide content of each emulsion grain can be measured by analyzing the composition of each grain using, for example, an X-ray micro analyzer. The term "relative standard deviation of the silver iodide content of individual grains" as used herein means, for example, the silver iodide content when the silver iodide content of at least 100 emulsion grains is measured by an X-ray microanalyzer. It is a value obtained by multiplying the value obtained by dividing the standard deviation of by the average silver iodide content by 100. Specific methods for measuring the silver iodide content of individual emulsion grains are described in, for example, European Patent 147,8.
48A.

If the relative standard deviation of the silver iodide content of individual grains is large, the appropriate points of chemical sensitization of individual grains are different, and it becomes impossible to bring out the performance of all emulsion grains.
Further, the relative standard deviation of the number of dislocations between grains also tends to increase.

Silver iodide content of individual grains Yi (mol%)
And the sphere equivalent diameter Xi (micron) of each particle may or may not be correlated, but it is desirable that there is no correlation.

Regarding the structure relating to the halogen composition of the tabular grains, X-ray diffraction, EPMA method (also called XMA method; method of scanning silver halide grains with an electron beam to detect silver halide composition), ESCA Method (also called XPS method; method of irradiating X-ray to disperse photoelectrons emitted from particle surface) and the like.

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

An emulsion comprising tabular grains having the above dislocation lines is disclosed in JP-A-63-220238 and Japanese Patent Application No. 2-31.
It can be prepared based on the method described in No. 0862. The silver halide emulsion of the present invention preferably has a narrow grain size distribution, and is prepared through the steps of nucleation-Ostwald ripening and grain growth.
The method described in No. 151618 can be preferably used.

However, the silver iodide content of the individual grains of the emulsion tends to be non-uniform unless particularly precise control is performed.

In order to make the silver iodide content of individual grains of the emulsion uniform, it is important to make the size and shape of the grains after Ostwald ripening as uniform as possible. Further, in the growth stage, the aqueous solution of silver nitrate and the aqueous solution of alkali halide are added by the double jet method while keeping the pAg constant in the range of 6.0 to 10.0. It is preferable that the supersaturation degree of the solution therein is high. For example, in the method as described in U.S. Pat. No. 4,242,445, it is desirable to carry out the addition at a relatively high degree of supersaturation such that the crystal growth rate is 30 to 100% of the crystal critical growth rate. .

The dislocation of the tabular grain of the present invention can be controlled by providing a specific high iodine phase inside the grain. Specifically, it is obtained by preparing substrate particles, then providing a high iodine phase, and covering the outside thereof with a phase having a lower iodine content than the high iodine phase. Here, in order to make the silver iodide content of each grain uniform, it is important to appropriately select the conditions for forming the high iodine phase.

The internal high iodine phase is a silver halide solid solution containing iodine. The silver halide in this case is preferably silver iodide, silver iodobromide or silver chloroiodobromide, but is preferably silver iodide or silver iodobromide (iodine content 10 to 40 mol%). Especially, silver iodide is preferable.

It is important that the internal high iodine phase is not uniformly deposited on the plane of the tabular grains of the substrate, but rather localized. Such localization may occur on any of the principal planes, side surfaces, sides, and corners of the flat plate. Further, the internal high iodine phase may be selectively and epitaxially coordinated to such a site.

As a method for this purpose, a so-called conversion method in which an iodide salt is added alone, for example, JP-A-59-133540 and JP-A-58-108526,
The epitaxial bonding method as described in JP-A-59-162540 can be used. At that time, it is effective to select the following conditions in order to make the silver iodide content of each grain uniform. That is, the pAg at the time of adding the iodide salt is preferably in the range of 8.5 to 10.5, and particularly preferably in the range of 9.0 to 10.5. The temperature is
It is preferable to keep the temperature in the range of 50 ° C to 30 ° C. Addition of iodide salt is 1 with respect to the total amount of silver under sufficiently agitated conditions.
It is preferable to add mol% or more of iodide salt for 30 seconds to 5 minutes.

The iodine content of the tabular grains of the substrate is lower than that of the high iodine phase, preferably 0 to 12 mol%, more preferably 0 to 10 mol%.

The outer phase which covers the high iodine phase has a lower iodine content than that of the high iodine phase, preferably 0-12.
Mol%, more preferably 0 to 10 mol%, and most preferably 0 to 3 mol%.

The internal high iodine phase is 5 mol% to 8 in terms of silver amount from the center of the grain to the whole grain in the major axis direction of the average grain.
It is preferably present in an annular region centered on the particle center in the range of 0 mol%, more preferably in an annular region in the range of 10 mol% to 70 mol%, particularly 20 mol% to 60 mol%. Preferably present.

Here, the major axis direction of the grain means the diameter direction of the tabular grain, and the minor axis direction means the thickness direction of the tabular grain.

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

Furthermore, the amount of silver halide forming the internal high iodine phase is 50 mol% of the total amount of silver in terms of silver amount.
Or less, more preferably 10 mol% or less,
It is particularly preferably 5 mol% or less.

The properties of silver halide grains can be controlled by allowing various compounds to be present in the silver halide precipitation forming process. Such compounds may be initially present in the reactor. In addition, according to the conventional method, 1
Alternatively, it can be added together with two or more salts. U.S. Pat. Nos. 2,448,060 and 2,628,
No. 167, No. 3,737,313, No. 3,772,0
31 and Research Disclosure, 134
Vol., June 1975, 13452,
By allowing compounds such as copper, iridium, lead, bismuth, cadmium, zinc, chalcogen compounds (eg, compounds of sulfur, selenium and tellurium), gold and compounds of Group VII noble metals to be present during the silver halide precipitation process. , The characteristics of silver halide can be controlled. Japanese Patent Publication No. 58-1410, Moisar et al., Journal of Photographic Science, 25.
Vol. 1977, pp. 19-27, the silver halide emulsion is capable of reduction-sensitizing the inside of the grain during the precipitation formation process.

In the tabular grains used in the present invention,
Silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halide such as silver rhodanide and lead oxide. These emulsion grains are described, for example, in US Pat.
094,684, 4,142,900, 4,4
59,353, British Patent 2,038,792, U.S. Patents 4,349,622, 4,395,478.
Issue No. 4,433,501 Issue 4,463,087
Issue 3, Issue 3,656,962, Issue 3,852,067
And JP-A-59-162540.

The tabular silver halide emulsion of the present invention is usually chemically sensitized.

The chemical sensitization is carried out after forming the silver halide emulsion, but the emulsion may be washed with water during the chemical sensitization after forming the silver halide emulsion.

Regarding the chemical sensitization, Research Disclosure No. 17643 (December 1978: 23
Page) and the same No. 18716 (November 1979: 648)
Page right column), pAg 5-10, pH 5-8 and temperature 30-80 ℃ sulfur, selenium, tellurium,
It can be carried out using gold, platinum, palladium, iridium or a combination of plural sensitizers.

The tabular silver halide emulsion of the present invention is preferably chemically sensitized in the presence of a spectral sensitizing dye. The method of chemically sensitizing in the presence of a spectral sensitizing dye is described in, for example, U.S. Pat. Nos. 4,425,426 and 4,442.
No. 201, JP-A-59-9658 and JP-A-61-11031.
49, 61-133941 and the like. The spectral sensitizing dye to be used may be any spectral sensitizing dye usually used in silver halide photographic light-sensitive materials, and the spectral sensitizing dye may be Research Disclosure No. 17643, pages 23-24 and N
o. 18716, page 648, right column to page 649, right column. The spectral sensitizing dye may be used alone or in combination of several kinds.

The spectral sensitizing dye may be added before the start of chemical sensitization (during grain formation, after grain formation, after water washing), during chemical sensitization or after chemical sensitization. However, it is preferably after the grain formation and before the chemical sensitization or at the end of the chemical sensitization.

The amount of the spectral sensitizing dye to be added is arbitrary, but 30 to 100% of the saturated adsorption amount is preferable, and 50 to 90% is more preferable.

The tabular silver halide emulsion of the present invention is usually spectrally sensitized. Examples of spectral sensitizing dyes used are:
Similar to the above, it is described in the above two Research Disclosures. In the emulsion in which the spectral sensitizing dye is present during the chemical sensitization as described above, the dye of the same kind or another kind may be further added or not in order to perform the spectral sensitization.

The emulsion of the present invention may be used alone in the light-sensitive emulsion layer, or two or more kinds of emulsions having different average grain sizes may be used in combination. When two or more emulsions are used, they may be used in different layers, but it is preferable to use them by mixing them in the same photosensitive layer. Further, when two or more kinds of emulsions are used, an emulsion having an average aspect ratio defined in the present invention and an emulsion not having the average aspect ratio may be used. As described above, the use of a mixture of emulsions controls gradation, control of graininess from the low exposure area to the high exposure area,
Also, it is preferable from the viewpoints of controlling color development dependency (time and color developing agent / composition in developer such as sodium sulfite, pH dependency).

Further, the emulsion of the present invention is disclosed in JP-A-60-143.
No. 332, 60-254032,
The relative standard deviation of the silver iodide content between grains is particularly preferably 20% or less.

In the present invention, it is preferable to use a nitrogen-containing heterocyclic compound substituted with a mercapto group in order to improve the sensitivity, graininess and desilvering property. These compounds are known and are described in the following documents.

US Pat. Nos. 2,585,388 and 2,
No. 541,924, Japanese Examined Patent Publication No. 42-21842, Japanese Patent Laid-Open No. 53-50169, British Patent No. 1,275,701.
No., D.I. A. Barges et al., “Journal of Heterocyclic Chemistry” (DA Berges).
et. al. , "Journal of the H
“Etherocyclic Chemistry”) No. 1
Volume 5, No. 981 (1978), "The Chemistry of Heterocyclic Chemistry", Imidazole
And Derivatives Part I ("The Che
mistry of Heterocyclic Ch
"emistry" Imidazole and Der
ivatives part I, pages 336-9, Chemical Abstracts (Chemical Abst)
ract), 58, 7921 (1963), 394.
Page, E. Hogarth, "Journal of the Chemical Society" (E. Hoggarth "Journal"
of Chemical Society ") 1160
~ 7 (1949) and S.S. R. Saudler, W.A. Caro, "Organic Functional Group Preparation," Academic Press, Inc. (SR
Saudler, W.C. karo “Organic Fan
partial Group Preparation
n "Academic Press, pages 312-5 (1)
968), M.A. Shamdon et al. (M. Chamdon, e
t al. ,), Bulletin de la Societe Simique de France (Bulletin de la S)
ociete Chimique de Franc
e), 723 (1954), D.E. A. Shirley, D.M.
W. Alley, Journal of the American Chemical Society (DA Shirley, DW.
Alley, J. Amer. Chem. Soc. ), 7
9, 4922 (1954), A.S. Ball, W. Marchwald Berichte (A. Wohl, W. Marchwa
ld, Ber. ) (German Chemical Society), 22 volumes, 568
Page (1889), Journal of American Chemical Society (J. Amer. Chem. So
c. ), 44, 1502-10, U.S. Pat. No. 3,01.
7,270, British Patent No. 940,169, Japanese Patent Publication No. 4
9-8334, JP-A-55-59463, Advanced in Heterocyclic Chemistry (Adv.
anched in Heterocyclic Che
, 165-209 (1968), West German Patent No. 2,716,707, The Chemistry of Heterocyclic Compounds, Imidazole and Derivatives (The Chemistr).
y of Heterocyclic Compound
ds Imidazole and Derivati
ves), Vol. 1, 384, Organic Synthesis (Org. Synth.) IV. , 569 (19
63), Berichte (Bre.), 9, 465 (197).
6), Journal of American Chemical Society (J. Amer. Chem. Soc.), 45,
2390 (1923), JP-A-50-89034, JP-A-53-28426, JP-A-55-21007, and JP-A-4.
0-28496.

Further, these nitrogen-containing heterocyclic compounds can be used in silver halide emulsion layers, hydrophilic colloid layers (eg, intermediate layers,
It is contained in a surface protective layer, a yellow filter layer, an antihalation layer), but is preferably contained in a silver halide emulsion layer or a layer adjacent thereto.

The addition amount is 1 × 10 ⁻⁷ to 1 × 10.
^-3 mol / m ² , preferably 5 × 10 ^-7 to 1 × 10 ^-4
mol / m ² , more preferably 1 × 10 ^{-6 to} 3 × 10 ^-5 mol /
m ² .

The silver halide emulsion prepared according to the present invention can be used in both color photographic light-sensitive materials and black-and-white photographic light-sensitive materials. Examples of the color photographic light-sensitive material include color paper, color photographic film, color reversal film, and black-and-white light-sensitive material include X-ray film, general photographic film, and print light-sensitive film. Particularly, it can be preferably used for a color photographic light-sensitive material, and in this case, a blue-sensitive layer on the support,
When at least one of the silver halide emulsion layers of the green-sensitive layer and the red-sensitive layer is provided, the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer are not particularly limited. 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 a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light,
In the multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in the order of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer from the support side. But,
Depending on the purpose, the order of installation may be reversed, 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-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-113438.
No. 59-113440, No. 61-20037, No. 61-20038, a coupler as described in the specification, a DIR compound, etc., may be contained, and a color mixing inhibitor as commonly used is included. You can leave. A plurality of silver halide emulsion layers constituting each unit photosensitive layer is a high-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045,
A two-layer structure of a low-sensitivity emulsion layer 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
-112751, 62-200350, 62-206541, 62-206
A low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support as described in JP-A No. 543. 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), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL
/ RL / RH can be installed in this order. See also
As described in JP-A 5-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, the layers can be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. . Further, 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 sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and the layer is composed of three layers having different sensitivities in which the sensitivities are gradually lowered toward the support. Even when it is composed of three layers having different sensitivities, the method of
As described in JP-A-59-202464, the medium-speed emulsion layer /
It may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer.
In addition, high sensitivity emulsion layer / low sensitivity emulsion layer / medium sensitivity emulsion layer,
Alternatively, they may be arranged in the order of low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four or more layers, the arrangement may be changed as described above. In order to improve color reproducibility, U.S. Pat.Nos. 4,663,271 and 4,705,744
No. 4,707,436, JP-A-62-160448, 63-89.
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of a main photosensitive layer such as BL, GL and RL described in the specification of No. 850, adjacent to or in proximity to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

A preferred silver halide contained in a photographic emulsion layer other than the light-sensitive silver halide emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide containing about 30 mol% or less of silver iodide. , Silver iodochloride, or silver iodochlorobromide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, 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) No. 17643 (December 1978).
Mon), pp. 22-23, "I. Emulsion preparation
and types) ”and ibid. No. 18716 (November 1979), 64
Page 8, No. 307105 (November 1989), pages 863-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Glafkides, Chemie et Phisique Photographiqu).
e, PaulMontel, 1967), "Photographic Emulsion Chemistry" by Duffin,
Published by Focal Press (GF Duffin, Photographic Emu
lsion Chemistry (Focal Press, 1966)), "Production and Coating of Photographic Emulsions" by Zelikman et al., VL Zelikman et al., Making and Coating Photogr.
aphic Emulsion, Focal Press, 1964) and the like.

Monodispersed 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 by Gatov, Photographic Science and Engineering (Gutoff, PhotographicScience
and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,0
It can be easily prepared by the method described in 48, 4,439,520 and British Patent 2,112,157. The crystal structure may be uniform, may have a different halogen composition between the inside and the outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, 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 emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. 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.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. 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. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion,
It can be used by mixing in the same layer. US Patent No.
No. 4,082,553, the surface of which is covered with a silver halide grain, U.S. Pat. It can be preferably used for the silver emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. 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.
It is described in No. 9-214852. 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. There is no particular limitation on the grain size of these fogged silver halide grains, but as the average grain size,
0.01 to 0.75 μm, particularly 0.05 to 0.6 μm is preferable. Also,
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 number of silver halide grains are within ± 40% of the average grain size) (Having a particle size of 1).

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 bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above-mentioned three Research Disclosures, and the related 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, page 23 to 24, page 648, right column 866 to 868 Color sensitizer: page 649, right column 4. Brightening agent: page 24, page 647, right column 868, fogging prevention 24: 25, page 649, right column 868: 870, stabilizer: light absorber, 25: Page 26 Page 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7. Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image Page 25 650 Page Left column 872 Stabilizer 9. Hardener 26 pages 651 left column 874 to 875 10. Binder 26 pages 651 left column 873 to 874 11. Plasticizer, page 27 650 pages right column 876 Lubricants 12. Coating aids , Pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. static, page 27, page 650, right column, pages 876 to 877, inhibitor 14. matting agent, pages 878 to 879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add to the light-sensitive material a compound capable of reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. . In the light-sensitive material of the present invention, U.S. Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-28
It is preferable to contain the mercapto compound described in No. 3551. A compound which, in the light-sensitive material of the present invention, releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. In the light-sensitive material of the present invention, a dye dispersed by the method described in International Publication WO88 / 04794 or JP-A-1-502912 or
EP 317,308A, U.S. Pat.No. 4,420,555, JP 1-2593
It is preferable to include the dye described in No. 58. Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 1764 mentioned above.
3, VII-CG, and No. 307105, VII-CG
Are described in the patents listed in. Yellow couplers include, for example, U.S. Patents 3,933,501 and 4,02.
No. 2,620, No. 4,326,024, No. 4,401,752, No.
4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,
No. 020, No. 1,476,760, U.S. Patent No. 3,973,968,
No. 4,314,023, No. 4,511,649, European Patent No. 24
Those described in No. 9,473A, 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, U.S. Pat.Nos. 3,061,432 and 3,725,067,
Research Disclosure No. 24220 (June 1984
Month), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A 61-7.
No. 2238, No. 60-35730, No. 55-118034, No. 60-185951
U.S. Pat.Nos. 4,500,630, 4,540,654, and
Those described in 4,556,630 and International Publication WO88 / 04795 are particularly preferable. Examples of cyan couplers include phenol-based and naphthol-based couplers, and US Pat.
52,212, 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 described in US Pat.
3,451,820, 4,080,211 and 4,367,282,
No. 4,409,320, No. 4,576,910, British patent 2,1
No. 02,137 and European Patent No. 341,188A.

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 described in Research Disclosure No. 17643, Item VII-G, No. 307.
105 VII-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57
-39413, U.S. Pat.Nos. 4,004,929, 4,138,258
And those described in British Patent No. 1,146,368 are preferred.
Further, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181, and a dye capable of reacting with a developing agent described in U.S. Pat. It is also preferable to use a coupler having a precursor group as a leaving group.
Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are described in RD 17643, VII-F above.
And Patent Nos. 307105 and VII-F, JP-A-57-151944, 57-154234, 60-184248,
63-37346, 63-37350, U.S. Patent 4,248,962,
Those described in JP-A-4,782,012 are preferable. RD No.1
The bleaching accelerator releasing couplers described in 1449, 24241 and JP-A-61-201247 are effective for shortening the processing time having a bleaching ability, and in particular, the above-mentioned tabular silver halide grains. The effect is great when it is added to the photosensitive material using. As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,097,1
No. 40, No. 2,131,188, JP-A Nos. 59-157638 and 59-1.
Those described in No. 70840 are preferable. In addition, JP-A-60-10
7029, 60-252340, JP-A-1-44940, 1-456
Compounds which release 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 No. 87 are also preferable.

Other compounds which 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 light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling 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, bis phthalate. (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), 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-Ethylhexylphenylphosphonate, etc., Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecaneamide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctylazese) Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate, etc., aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
Organic solvents above 160 ° C can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

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. The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.
Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D. No.17643, page 28, No.18716, page 647 From right column 648
It is described on the left column of the page and on page 879 of the same No. 307105. 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, particularly preferably 16 μm or less. Also, the film swelling speed T
_1/2 is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, A. Green et al., Photographic Science and Engineering (Photog
r.Sci.Eng.), No. 19, No. 2, pages 124 to 129 can be measured by using a swellometer (swelling meter) of the type described, and T _1/2 is 30 ° C. in a color developer. , 90% of the maximum swollen film thickness reached after treatment for 3 minutes and 15 seconds is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness. Membrane swelling speed T
_1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling 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 light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
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 150-500
% Is preferred.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28 to 29, No. 18716, 651 left column to right column, and No. 307105, pages 880 to 881 can be developed by a usual method. The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As this color developing agent,
Aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof are 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-hydroxy Pentyl) 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, N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates and hydrochlorides Alternatively, p-toluenesulfonate may be used.
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-toluenesulfonate or sulfuric acid Salt is preferred. Two or more of these compounds can be used in combination depending on the purpose. Color developers include alkaline metal carbonates, borates or phosphates.
It is common to include a pH buffer, a chloride salt, a bromide salt, an iodide salt, a development inhibitor such as a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agent, aminopolycarboxylic acid,
Aminopolyphosphonic acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1- Hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and them Can be mentioned as a representative example.

When the reversal processing is carried out, black and white development is usually carried out and then color development is carried out. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developers depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and is 500 ml or less by reducing the bromide ion concentration in the replenisher. You can also 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 represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. Is. 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 color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a color developing agent at a high concentration.

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. Typical bleaching agents include organic complex salts of iron (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. . Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these 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. Particularly preferred organic acid has an acid dissociation constant (pKa) of 2
A compound of -5, specifically acetic acid, propionic acid,
Hydroxyacetic acid and the like are preferred. Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used. In particular, ammonium thiosulfate can be used most widely. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or European Patent No. 294
The sulfinic acid compounds described in No. 769A are preferable. Furthermore,
For the purpose of stabilizing the solution, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution. In the present invention, the fixer or the bleach-fixer has a pH of
For adjustment, a compound having a pKa of 6.0 to 9.0, preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole.
It is preferable to add 1 to 10 mol / l.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The 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.
As a specific method for strengthening stirring, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461 Method to increase the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution to further improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. 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 processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
No. 60-191258 and No. 60-191259. The above-mentioned JP-A-6
As described in No. 0-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide 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 as follows.
nd Tele-vision Engineers Volume 64, P. 248 ~ 253 (195
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, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" (1986)
Sankyo Publishing, Sanitary Technology Society, "Microbial sterilization, sterilization, antifungal technology" (1982), Industrial Technology Association, Japan Antibacterial and Antifungal Society edited, "Antibacterial and Antifungal Encyclopedia" (1986) Can also be used. PH of washing water in the processing of the light-sensitive material of the present invention
Is 4-9, preferably 5-8. The washing water temperature and 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 further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. be able to. As a dye stabilizer,
Aldehydes such as formalin and glutaraldehyde,
Examples thereof include 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, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat.No. 3,342,597, No. 3,342,599, Schiff base type compounds described in Research Disclosure Nos. 14,850 and No. 15,159, aldol compounds described in No. 13,924, U.S. Pat.No. 3,719,492. Metal salt complexes described, JP-A-53-135
The urethane compound described in No. 628 can be mentioned.
The silver halide color light-sensitive material of the present invention contains various 1-phenyl-3-methyl-3-phenyl-3-(-3-phenyl) -3-phenyl-3- (phenyl-3-phenyl) -3- (phenyl-3-phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3-(-3-phenyl-3-phenyl-3- (cyclohexyl) -3- (phenyl-3-phenyl-3-methyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3- (3-phenyl-3-phenyl-3- (3-phenyl-3- (phenyl-phenyl--3-one-
You may incorporate pyrazolidones. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, JP-A-58-115438 and the like. Various treatment liquids in the present invention are 10 ℃
Used at ~ 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.

The silver halide color photographic light-sensitive material of the present invention is more likely to exhibit the effect when applied to the lens-fitted film unit described in JP-B-2-32615, JP-B-3-39784 and the like. It is valid.

[0225]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto.

Example 1 An aqueous solution of 30 g of inert gelatin, 6 g of potassium bromide and 1 liter of distilled water was stirred at 75 ° C., and 35 cc of an aqueous solution of 5.0 g of silver nitrate and potassium bromide were added thereto. A seed emulsion was prepared by adding 35 g of an aqueous solution containing 2 g and 0.98 g of potassium iodide at a flow rate of 70 cc / min for 30 seconds each and then increasing the pAg to 10 and ripening for 30 minutes.

Subsequently, a predetermined amount of 1 liter of an aqueous solution containing 145 g of silver nitrate and an aqueous solution of a mixture of potassium bromide and potassium iodide are added in equimolar amounts at a predetermined temperature and a predetermined pAg at a rate close to the critical growth rate. It was added at a rate to prepare a tabular core emulsion. Furthermore, the remaining silver nitrate aqueous solution and an aqueous solution of a mixture of potassium bromide and potassium iodide having a different composition from the preparation of the core emulsion were added in equimolar amounts at an addition rate close to the critical growth rate to coat the core. By doing so, core / shell type silver iodobromide tabular emulsions 1 to 5 were prepared.

Aspect ratio control was obtained by selecting the pAg during core and shell preparation. The results are shown in Table 1.
Shown in.

[0229]

[Table 1]

Using the emulsions 1 to 5 prepared above, the following samples were prepared. Sample 1 which is a multi-layer color light-sensitive material was obtained by coating each layer of the composition shown below in multiple layers on an undercoated cellulose triacetate film support.
01-108 were produced. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Hardening agent The numeral corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, the sensitizing dye and the compounds (I) to (I
For V), the coating amount per mol of silver halide in the same layer is shown in mol.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

Second Layer (Intermediate Layer) Emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 (XI-1) 6.9 × 10 ⁻⁵ (XIV −15) 1.8 × 10 ⁻⁵ (XIV −7) 3.1 × 10 ^-4 Compounds I to IV (Table 2) 3.0 x 10 ^-3 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.10 gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.70 (XI-1) 3.5 × 10 ⁻⁴ (XIV −15) 1.6 × 10 ⁻⁵ (XIV −7) 5.1 × 10 ⁻⁴ Compound I ~ IV (Tables 3, 4) 3.0 x 10 ^-3 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth Layer (High Sensitivity Red Sensitive Emulsion Layer) Emulsion 1 Silver 1.40 (XI-1) 2.4 × 10 ⁻⁴ (XIV −15) 1.0 × 10 ⁻⁴ (XIV −7) 3.4 × 10 ⁻⁴ Compound I ~ IV (Tables 3,4) 3.0 x 10 ^-3 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 AB-18 1.3 x 10 ^-5 mol HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

Sixth Layer (Intermediate Layer) Cpd-1 0.10 HBS-1 0.50 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion C Silver 0.35 (B-6) 3.0 × 10 ^-5 (B-9) 2.1 × 10 ^-4 (A-12) 8.0 × 10 ^-4 ExM- 1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion D Silver 0.80 (B-6) 3.2 × 10 ^-5 (B-9) 2.2 × 10 ^-4 (A-12) 8.4 × 10 ^-4 ExM- 2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

Ninth Layer (High Sensitivity Green Sensitive Emulsion Layer) Emulsions 1 to 5 (Tables 3 and 4) Silver 1.25 (B-6) 3.7 × 10 ⁻⁵ (B-9) 8.1 × 10 ⁻⁵ (B-12) ) 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 AB-32 1.2 × 10 ^-5 mol HBS-1 0.25 HBS-2 0.10 Gelatin 1.44

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60

Eleventh Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Emulsion C Silver 0.18 (A-3) 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 HBS-1 0.28 Gelatin 1.10

Twelfth layer (medium-speed blue-sensitive emulsion layer) Emulsion D Silver 0.40 (A-3) 7.4 × 10 ⁻⁴ ExC-6 7.0 × 10 ⁻³ ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78

Thirteenth Layer (High Sensitivity Blue Sensitive Emulsion Layer) Emulsion F Silver 1.00 (A-3) 4.0 × 10 ⁻⁴ ExY-2 0.10 ExY-3 0.10 AB-37 1.4 × 10 ⁻⁵ mol HBS-1 0.070 Gelatin 0.86

Fourteenth layer (first protective layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

Fifteenth layer (second protective layer) H-1 0.44 B-1 (diameter about 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter about 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B are appropriately added. -6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt and rhodium salt.

[0247]

[Table 2]

In Table 2, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Has been done.

[0249]

[Chemical 69]

[0250]

[Chemical 70]

[0251]

[Chemical 71]

[0252]

[Chemical 72]

[0253]

[Chemical formula 73]

[0254]

[Chemical 74]

[0255]

[Chemical 75]

[0256]

[Chemical 76]

[0257]

[Chemical 77]

[0258]

[Chemical 78]

[0259]

[Chemical 79]

[0260]

[Chemical 80]

[0261]

[Chemical 81]

[0262]

[Chemical formula 82]

Subsequently, the following samples were prepared. Sample 101
~ 108, the emulsion of the fifth layer was changed to Emulsion 2 and XI
-1, XIV-15 and XIV-7 were added in amounts of 1.1
Doubled samples 109-116 were made. Further, the emulsion of the fifth layer of Samples 101 to 108 was changed to Emulsion 3, and XI-
Samples 117 to 124 were prepared in which the amounts of 1, XIV-15 and XIV-7 added were 1.2 times each. Furthermore, sample 1
The emulsion of the fifth layer of 01 to 108 was changed to emulsion 4, and XI-
Samples 125 to 132 were prepared in which the amounts of 1, XIV-15 and XIV-7 added were 1.4 times each. Furthermore, sample 1
The emulsion of the fifth layer of 01 to 108 was changed to emulsion 5, and XI-
Samples 133 to 140 having 1.8 times the addition amounts of 1, XIV-15 and XIV-7 were prepared. Samples 101 to 1
White light (color temperature of light source 4800 ° K) for each of 40
The density of each sample is measured by measuring the cyan density of each sample, which is obtained by the development process, and the sensitivity of each sample is defined by the reciprocal of the exposure amount that gives the minimum density + 0.2. Is the relative value when the value of sample 101 is 100
The results are shown in Tables and 4. In addition, each sample was tested at 50 ° C and relative humidity of 7
After leaving it under 0% condition for 3 days, it was exposed and developed in the same manner, and the sensitivity and fog were determined. Sensitivity was expressed as relative values when the sensitivity of Sample 101, which was not left under conditions of 50 ° C. and 70% relative humidity for 3 days, was 100.

The obtained results are summarized in Tables 3 and 4.
The color development processing steps and processing liquid compositions used for investigating the above performance are shown below.

[0265]

[Table 3]

[0266]

[Table 4]

(Treatment Method) Process Treatment time Treatment temperature Color development 3 minutes 15 seconds 38 ° C. Bleach 3 minutes 00 seconds 38 ° C. Water wash 30 seconds 24 ° C. Settling 3 minutes 00 seconds 38 ° C. Water wash (1) 30 seconds 24 ℃ Wash with water (2) 30 seconds 24 ℃ Stability 30 seconds 38 ℃ Dry 4 minutes 20 seconds 55 ℃

Next, the composition of the processing liquid will be described. (Color developer) (Unit g) 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-hydroxyethylamino] -2-me 4.5 chillaniline sulfate Water was added to 1.0 liter pH 10.05

(Bleach) (Unit: g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 10.0 3-Mercapto-1,2,4-triazole 0.08 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Water was added to 1.0 liter pH 6.0

(Fixing Solution) (Unit: g) Ethylenediaminetetraacetic acid disodium salt 0.5 Ammonium sulfite 20.0 Ammonium thiosulfate aqueous solution (700 g / liter) 290.0 ml Water was added to 1.0 liter pH 6.7

(Stabilizing Solution) (Unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5 Tables 3 and 4 of the present invention By using the compounds represented by formulas (I) to (IV) and using a silver halide emulsion composed of tabular grains having an aspect ratio of 2 or more, a silver halide photographic light-sensitive material having high sensitivity and high storage stability can be obtained. It turns out that the material can be obtained.

Example 2 Each treatment of the sample of Example 1 was carried out as follows using an automatic processor FP-560B manufactured by Fuji Photo Film Co., Ltd. The treatment process and the treatment liquid composition are shown below.

(Processing process) Process processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 600 ml 17 liters Bleach 50 seconds 38.0 ° C 140 ml 5 liters Bleach fixing 50 seconds 38.0 ° C-5 liters Fixed 50 seconds 38.0 ℃ 420 ml 5 liters Water wash 30 seconds 38.0 ℃ 980 ml 3.5 liters Stability (1) 20 seconds 38.0 ℃ −3 liters Stability (2) 20 seconds 38.0 ℃ 560 mls 3 liters Dry 1 minute 30 seconds 60 ℃ * Replenishment amount per 1 m ² of light-sensitive material The stabilizing solution is a countercurrent system from (2) to (1), and the overflow solution of washing water is all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank so that all of the overflow solution generated by supplying the replenishing solution to the bleaching tank and the fixing tank is added to the bleach-fixing bath. I was allowed to flow in. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the washing process were each per 1 m ² of the light-sensitive material. They were 65 ml, 50 ml, 50 ml and 50 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step.

The composition of the treatment liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphospho 3.3 3.3 Acid sodium sulfite 3.9 5.1 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.0 Water was added to 1.0 liter 1.0 liter pH 10.05 10.15

(Bleaching solution) Tank solution (g) Replenishing solution (g) 1,3-diaminopropane tetraacetate ferric iron amo 130 195 ammonium monohydrate ammonium bromide 70 105 ammonium nitrate 14 21 hydroxyacetic acid 50 75 acetic acid 40 60 1.0 liter by adding water 1.0 liter pH [Prepared with ammonia water] 4.4 4.4

(Bleaching Fixing Tank Solution) A 15:85 (volume ratio) mixture of the above bleaching tank solution and the following fixing tank solution. (P
H7.0)

(Fixer) Tank solution (g) Replenisher (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution 280 ml 840 ml (700 g / liter) Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 1.0 liter 1.0 liter pH with water added [Prepared with ammonia water and acetic acid] 7.4 7.45

(Washing Water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
/ Liter or less, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

(Stabilizer) Common to tank liquid and replenisher (unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization 10) Disodium ethylenediaminetetraacetate Salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

The sensitivity of each sample thus obtained,
The fog and storability gave the same results as in Example 1.

Example 3 Emulsion 6 (for use in the present invention) In 1 liter of a 0.7% by weight gelatin solution containing 0.04 M potassium bromide, 2 M silver nitrate aqueous solution containing gelatin and 2 M containing gelatin were added. 25 cc of each potassium bromide aqueous solution of 1 minute with vigorous stirring at 30 ° C.
Were mixed simultaneously. After this, the temperature is raised to 75 ° C., and 10% by weight
300 cc of gelatin solution was added. Next, 30 cc of a 1 M silver nitrate aqueous solution was added over 5 minutes, and then 10 cc of 25 wt% ammonia water was added, followed by aging at 75 ° C. After completion of the ripening, the ammonia was neutralized, and then 1M silver nitrate aqueous solution and 1M potassium bromide aqueous solution were added to give pBr of 2.
Simultaneous mixing was performed at an accelerated flow rate (the flow rate at the end was 5 times that at the start) while being kept at 3. The amount of silver nitrate aqueous solution used at this time was 600 cc. This emulsion was washed with water by a conventional flocculation method, and further dispersed gelatin was added to obtain 800 g of a hexagonal tabular silver halide emulsion (seed emulsion-A). This seed emulsion-A has an average projected area circle-equivalent diameter (grain size) of 1.0 μm and an average thickness of 0.
It was a monodisperse hexagonal tabular grain having a coefficient of variation of 11% at 18 μm. Next, 250 g of this seed emulsion-A was taken, 800 cc of distilled water, 30 g of gelatin, and 6.5 g of potassium bromide.
g, heated to 75 ° C., and stirred. In it 1M
Aqueous silver nitrate solution and 1M aqueous alkali halide solution (10 mol% potassium iodide to 90 mol% potassium bromide)
Were mixed together at an accelerated flow rate (the flow rate at the end was 3 times that at the start) while keeping pBr at 1.6. The amount of silver nitrate aqueous solution used at this time was 600 cc. Further, the 1 M silver nitrate aqueous solution and the 1 M potassium bromide aqueous solution were simultaneously mixed at an accelerated flow rate (the flow rate at the end was 1.5 times that at the start) while keeping pBr at 1.6 at the same time. The amount of silver nitrate aqueous solution used here is 200
It was cc. This emulsion was washed with water by the method described above and dispersed gelatin was added to obtain a monodispersed hexagonal tabular silver halide emulsion (emulsion 6). The resulting emulsion 6 had a total projected area of 9
Hexagonal tabular grains account for 2%, the hexagonal tabular grains have an average grain size of 1.75 μm, an average thickness of 0.29 μm, an average aspect ratio of 6: 1 and a coefficient of variation of 16%. there were.

Emulsion 7 (for use in the present invention) Seed emulsion B was prepared in the same manner as Emulsion 6 (however, the amount of the second 1M silver nitrate aqueous solution was 20 cc and the amount of ammonia water was 8 cc). . Next, this seed emulsion-B was grown in the same manner as emulsion 6. However, the growth pBr was kept at 1.5. The obtained emulsion has 90% of the total projected area.
Of hexagonal tabular grains have an average size of 2.1 μm and an average thickness of 0.2 μm.
1 μm, average aspect ratio 10: 1 and coefficient of variation 19
%Met.

Emulsion 8 (for use in the present invention) In the method for preparing Emulsion 6, the amount of the 1M silver nitrate aqueous solution for the second time was changed from 30 cc to 10 cc, ammonia water was not added, and the pBr for the third time was adjusted to 2 3 to 1.
Seed Emulsion-C was obtained by changing to 7. Next, this seed emulsion-C was grown in the same manner as emulsion 6 to obtain emulsion 8.

62% of the total projected area of the resulting emulsion 8 was occupied by hexagonal tabular grains. The hexagonal tabular grains had an average size of 2.0 μm and an average thickness of 0.17.
μm, average aspect ratio 12: 1 and coefficient of variation 37%
Met.

Sensitizing dyes for Emulsions 6, 7, 8 and 1
A mixture of (XI-1), (XIV-15) and (XIV-7) at a molar ratio of 5: 2: 7 was added in an amount of 70% of the saturated adsorption amount in each emulsion. After holding this at 60 ° C for 20 minutes,
Each was optimally chemically sensitized with sodium thiosulfate, chloroauric acid and potassium thiocyanate at 0 ° C. and pH 6.5. Thus, Emulsion 6-1 and Emulsion 7- shown in Table 5 were obtained.
1, emulsion 8-1 and emulsion 1-1 were obtained.

[0286]

[Table 5]

The fifth layer emulsion of Example 1 was prepared as Emulsions 1-1 and 6
-1, 7-1 and 8-1 (the ninth layer is emulsion 1), and the sensitizing dyes (XI-1) and (XIV-1
5) and (XIV-7) were removed, and samples 301 to 301 shown in Table 6 were removed.
20 was produced. The compounds of the present invention used here were modified as shown in Table 6. After exposing Samples 301 to 320 in the same manner as in Example 1, the development processing described below was performed. Further, the sample stored in the same manner as in Example 1 was exposed and developed. The development was carried out using an automatic processor by the method described below until the cumulative replenishment amount of the developing solution became 3 times the tank capacity, and then the sample for performance evaluation was processed. (Treatment method) Process Treatment time Treatment temperature Replenishment amount Tank capacity Color development 2 minutes 00 seconds 40 ° C 3.5 ml 10 liters Bleach 3 minutes 00 seconds 40 ° C 25 ml 20 liters Water washing 30 seconds 24 ° C 1200 ml 10 liters Fixed 3 Min 00 sec 40 ℃ 25 ml 20 liter Water wash (1) 30 s 24 ℃ 10 liter from (2) to (1) Countercurrent piping system Water wash (2) 30 s 24 ℃ 1200 ml 10 liter Stability 30 s 40 ℃ 25 ml 10 liter Dry 4 min 20 sec 55 ℃ Replenishment amount is 35 mm width 1 m per length

Next, the composition of the processing liquid will be described. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-3.0 3.2 Diphosphonic acid Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 6.0-Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N- (4-hydroxybutylamino)]-2-methylaniline sulfate 6.0 15.0 Water was added to 1.0 liter 1.0 liter pH 10.05 10.15

(Bleaching solution) Tank solution (g) Replenishing solution (g) Sodium ferric ethylenediaminetetraacetate 100.0 120.0 Trihydrate Ethylenediaminetetraacetic acid disodium salt 10.0 11.0 3-Mercapto-1,2,4-triazole 0.08 0.09 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5 ml 4.0 ml Add water 1.0 liter 1.0 liter pH 6.0 5.7

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ethylenediaminetetraacetic acid disodium salt 0.5 0.7 Ammonium sulfite 20.0 22.0 Ammonium thiosulfate aqueous solution (700 g / l) 290.0 ml 320.0 ml Water 1.0 liter 1.0 liter pH 6.7 7.0

(Stabilizer) Common tank / replenisher (g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2 , 4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

[0292]

[Table 6]

After the development processing, the cyan density was measured, and the sensitivity was defined from the characteristic curve by the reciprocal of the exposure amount that gives the density of the minimum density + 0.2.
It was expressed as a relative value when 00 was set. Table 6 shows a result list of fogging and sensitivity. From the results in Table 6, high sensitivity can be achieved by using particles having a high aspect ratio. Furthermore, it can be seen that by using the compound of the present invention, a significantly greater effect than that expected with particles having a low aspect ratio can be obtained, and a high sensitivity that cannot be achieved by the conventional techniques can be achieved. At this time, storage resistance is also greatly improved. As described above, according to the present invention, a photosensitive material having high sensitivity and excellent storage stability can be obtained.

Example 4 Preparation of Emulsion While stirring well an aqueous solution prepared by dissolving 6 g of potassium bromide and 23 g of inert gelatin in 3.7 liters of distilled water,
A 14% aqueous solution of potassium bromide and a 20% aqueous solution of silver nitrate were added thereto by a double jet method at a constant flow rate for 1 minute under the conditions of 45 ° C. and pAg of 9.6 (this addition (I) was the total). 2.40% of the silver amount was consumed).
Next, add an aqueous gelatin solution (17%, 3300 cc) and stir at 45 ° C., then add a 20% silver nitrate aqueous solution to pAg.
Was added at a constant flow rate to reach 8.40 (this addition (II) consumed 5.0% of the total silver). 75 ℃
And add 35 μl of 25% NH ₃ aqueous solution,
After maintaining for 5 minutes, 510 μl of 1N H ₂ SO ₄ was added to neutralize. Further, a 20% potassium bromide solution containing potassium iodide and a 33% silver nitrate aqueous solution were added by a double jet method so that 8.3 g of potassium iodide was added.
It was added over 0 minutes (with this addition (III), the total silver amount was 9
2.6% consumed). During this time, the temperature was 75 ° C, pAg
Was held at 8.10. The amount of silver nitrate used in this emulsion was 425 g, and after desalting by an ordinary flocculation method, gold and sulfur were added in the presence of sensitizing dyes S-5 and S-6 (addition amount will be described later). A tabular AgBrI (AgI = 2.0 mol%) emulsion-1-2 was sensitized optimally.
Was prepared. Emulsion -2-2 was obtained by removing potassium iodide from the halogen solution used in the addition (III) in the preparation procedure of Emulsion 1-2, and 830 ml of a 1% potassium iodide aqueous solution.
During the addition (III), when 60% of the total amount of silver was consumed, the addition of the solution of silver nitrate and potassium bromide was stopped, and
Add over a period of 0 seconds and adjust the flow rate of the remaining addition (III) to 3
Prepared by the same method except doubling.

Emulsion -3-2 was prepared in the same manner as in the above-mentioned procedure for preparing emulsion -2-2, except that the aqueous potassium bromide solution was added immediately before the addition of the aqueous potassium iodide solution and the pAg was adjusted to 9.0. Prepared by

Emulsion-4-2 was prepared by the same method as in the above-mentioned procedure for preparing emulsion-2-2, except that the temperature was changed to 30 ° C. immediately before the addition of the potassium iodide aqueous solution. The addition of potassium bromide and silver nitrate aqueous solution after the addition of potassium iodide aqueous solution was carried out at 30 ° C., pAg of 8.
It was conducted under the condition of 1.

Emulsions prepared as described above-1-2 to 4-2
The sphere-equivalent diameters of all were equivalent to 0.7 μm, and the average particle diameter / particle thickness ratio was in the range of 6.5 to 7.0.

Regarding Emulsions 1-2 to 4-2, Japanese Patent Application Laid-Open No.
According to the method described in Example 1- (2) of 3-220238, direct dislocations were observed using a transmission electron microscope. As a result, dislocation was not observed in Emulsion-1-2. Emulsion -2-2-4-2, 50%
Ten or more dislocation lines were observed in the number of grains or more. Further, the emulsions -3-2 and 4-2 are different from the emulsion -2-2.
Dislocation lines tended to be observed uniformly among the grains.

Further, regarding Emulsions 1-2 to 4-2,
The interparticle iodine distribution was determined according to the method described in EP 147868A. The results are shown in Table 7.

[0300]

[Table 7]

Samples shown in Tables 8 and 9 were prepared using the prepared emulsions 1-2 to 4-2. On a 205 μm thick cellulose triacetate film support, which was undercoated on both sides of the film, a multi-layer color light-sensitive material comprising layers of the following compositions was prepared. The coating amount of each composition is 1 m ^{2 of} sample
The relevant value was shown. 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 Ultraviolet absorber U-1 0.2 g Ultraviolet absorber U-3 0.1 g Ultraviolet absorber U-4 0.2 g High boiling organic solvent Oil-1 0.1 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 Fine grain silver iodobromide emulsion with surface and internal fog ( Average particle 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 organic solvent Oil-3 40 mg

Fourth Layer: Low Sensitivity Red Sensitive Emulsion Layer Emulsion A Silver amount 0.3 g Emulsion B Silver amount 0.4 g Gelatin 0.8 g Coupler C-1 0.12 g Coupler C-3 0.02 g Coupler C-10 0.02 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-sensitive red-sensitive emulsion layer Emulsion B Silver amount 0.2 g Emulsion (Tables 8 and 9) Silver amount 0.3 g Compounds (I) to (IV) (Tables 8 and 9) 0.0015 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 High boiling point organic solvent Oil-3 0.05 g Ethyl acrylate latex dispersion 0.05 g

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion (Tables 8 and 9) Silver amount 0.4 g Compounds (I) to (IV) (Tables 8 and 9) 0.0015 g Gelatin 1.1 g Coupler C-1 0.4 g Coupler C-3 0.1 g Additive P-1 0.02 g High boiling point organic solvent Oil-3 0.1 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 0.05 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 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

Ninth layer: low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion with fogged grains (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

Layer 10: Medium-speed 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 0.02 g coupler C-12 0.20 g compound Cpd-B 0.03 g compound Cpd-E 0.02 g compound Cpd-F 0.02 g compound Cpd-G 0.05 g compound Cpd-H 0.05 g additive F-5 0.08 mg high boiling organic solvent Oil -0.01 g

Layer 11: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion with fogged grains (average grain size 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-8 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 0.02 g High boiling point organic solvent Oil-2 0.04 g

Twelfth 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

Thirteenth 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 dispersion of dye E-2 0.05 g

14th layer: intermediate layer 0.6 g of gelatin

Fifteenth Layer: Low-Sensitivity Blue-Sensitive Emulsion Layer Silver iodobromide emulsion with fogged grain 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: Medium sensitivity 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 0.02 g Coupler C-6 0.002 g Coupler C-11 0.02 g

Seventeenth 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 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: 2nd protective layer Colloidal silver Silver amount 0.05 mg Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI content 1 mol%) Silver amount 0.05 g Gelatin 0.3 g

20th layer: 3rd protective layer Colloidal silver Silver amount 0.05 mg Fine grain silver iodobromide emulsion (average grain size 0.07 μm, AgI content 1 mol%) Silver amount 0.05 g Gelatin 0.4 g Polymethylmethacrylate (average grain Diameter 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

Additives F-1 to F-9 were added to each silver halide emulsion layer and the intermediate layer. Further, in each layer, in addition to the above composition, a gelatin hardening agent H-1 and coating surfactants W-3, W-4 and W-5, and an emulsifying surfactant W are included.
-6 was added. Furthermore, phenol as an antiseptic / antifungal agent,
1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenyl isothiocyanate, and phenethyl alcohol were added.

[0323]

[Chemical 83]

[0324]

[Chemical 84]

[0325]

[Chemical 85]

[0326]

[Chemical 86]

[0327]

[Chemical 87]

[0328]

[Chemical 88]

[0329]

[Chemical 89]

[0330]

[Chemical 90]

[0331]

[Chemical Formula 91]

[0332]

[Chemical Formula 92]

[0333]

[Chemical formula 93]

[0334]

[Chemical 94]

[0335]

[Chemical 95]

[0336]

[Chemical 96]

The silver iodobromide emulsions used in the samples are as follows. Emulsion name Grain characteristics Mean sphere equivalent variation coefficient AgI content (μm) (%) (%) A Monodisperse tetradecahedral grain 0.35 16 4.0 B Monodisperse cubic internal latent image type grain 0.45 10 2.0 C Polydisperse twin grain 0.70 20 6.0 (Internal high iodine core / shell particles, average aspect ratio 1.5) D polydispersed twin particles, average aspect ratio 0.5 0.90 25 6.0 E polydispersed twin particles 0.30 18 6.5 F polydispersed twin particles 0.40 23 5.5 G Monodisperse cubic internal latent image type grains 0.50 11 4.5 H Monodisperse tetradecahedral grains 0.80 15 5.0 I Polydisperse twin grains, 1.00 25 6.5 Average aspect ratio 1.5 J Polydisperse twin grains, 0.60 20 3.5 Average aspect ratio 1.5 K monodisperse tetrahedral particles 0.70 15 5.0 L monodisperse octahedral particles 0.80 14 5.0 M monodisperse octahedral particles 1.00 18 5.0 N polydisperse twin particles 1.20 25 7.5 (internal high iodine core / shell particles) average Aspect ratio 1.5

Spectral sensitization of Emulsions A to H Emulsion name Sensitizing dye added Amount (g) added per mol of silver halide A XIV-6 0.15 XIV-23 0.02 XIV-5 0.15 B XIV -6 0.15 XIV-23 0.04 XIV-5 0.20 C XIV-6 0.15 XIV-23 0.02 XIV-5 0.05 D XIV-6 0.08 XIV-23 0.01 XIV -5 0.02 E A-11 0.5 B-18 0.08 B-11 0.02 B-19 0.05 F A-11 0.3 B-18 0.07 B-11 0.03 G A-11 0.25 B-18 0.08 H A-11 0.2 B-18 0.03 B-11 0.03 B-19 0.1

Spectral sensitization of Emulsions I to N Emulsion name Sensitizing dye added Amount (g) added per mol of silver halide I A-11 0.3 XIV-23 0.02 B-11 0.02 A- 20 0.1 B-19 0.05 J A-7 0.2 A-6 0.05 K A-7 0.2 A-6 0.05 L A-7 0.22 A-6 0.06 M A-7 0.15 A-6 0.04 N A-7 0.22 A-6 0.06

Samples 401 to 430 were exposed to white light through a continuous wedge, subjected to the developing treatment shown below, and then the cyan density was measured. The sensitivity is defined as the reciprocal of the exposure amount required for the optical density to reach 1.5, and the value of the sample 401 is 10
The relative value was set to 0 and shown in Tables 8 and 9. After storing the samples 401 to 430 under the same conditions as in Example 1,
After exposure and development under the conditions of this embodiment, the cyan density was measured. Tables 8 and 9 show the obtained sensitivity and the decrease ΔDmax in the maximum color density when the sample without storage was used as a reference. The sensitivity was expressed as a relative value with the value of the sample 401 without storage set to 100. The development processing step and processing solution composition are shown below.

The processing of the sample for examining the above performance was carried out by using an automatic processor after processing the sample separately imagewise exposed until the cumulative replenishing amount of the color developing solution became three times the tank volume.

Treatment process time Temperature Tank capacity Replenishment amount First development 6 minutes 38 ° C. 12 liters 2200 ml / m ² First water washing 45 seconds 38 ° C. 2 liters 2200 ml / m ² Reversing 45 seconds 38 ° C. 2 liters 1100 ml / m ² color developing 6 min 38 ° C. 12 liters 2,200 ml / m ² bleaching 2 min 38 ° C. 4 liters 860 ml / m ² bleach-fixing 4 min 38 ° C. 8 1,100 / m ² second water washing (1) 1 minute 38 ℃ 2 liters-second washing (2) 1 minute 38 ℃ 2 liters 1100 ml / m ² stability 1 minute 25 ℃ 2 liters 1100 ml / m ² dry 1 minute 65 ℃ --- Replenishment of the second water washing here In the so-called countercurrent replenishment system, the replenisher was introduced into the second water wash (2) and the overflow solution of the second water wash (2) was introduced into the second water wash (1).

The composition of each treatment liquid was as follows. [First developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid / 5-sodium salt 2.0 g 2.0 g Sodium sulfite 30 g 30 g Hydroquinone / potassium monosulfonate 20 g 20 g Potassium carbonate 33 g 33 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2.0 g 2.0 g Potassium bromide 2.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 g Potassium iodide 2.0 mg-Add water 1000 ml 1000 ml pH 9.60 9.60 The pH was adjusted with hydrochloric acid or potassium hydroxide.

[First Washing Liquid] [Tank Liquid] [Replenishing Liquid] Ethylenediaminetetramethylenephosphonic acid 2.0 g The same disodium phosphate 5.0 g water was added to the tank liquid and 1000 ml pH 7.00 pH was hydrochloric acid or sodium hydroxide. It was adjusted.

[Reversal Solution] [Tank Solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3.0 g Same as tank solution Stannous chloride dihydrate 1.0 g p-amino Phenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide.

[Color developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate dodecahydrate 36 g 36 g Potassium bromide 1.0 g-Potassium iodide 90 mg-Sodium hydroxide 3.0 g 3.0 g Citrazine acid 1.5 g 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino Aniline-3 / 2 sulfuric acid monohydrate 11 g 11 g 3,6-dithiaoctane-1,8-diol 1.0 g 1.0 g Water was added to 1000 ml 1000 ml pH 11.80 12.00 pH was adjusted with hydrochloric acid or potassium hydroxide.

[Bleaching solution] [Tank solution] [Replenisher] Ethylenediaminetetraacetic acid ・ 2 sodium salt ・ dihydrate 10.0g Same as tank solution Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ammonia ・ Dihydrate 120g Bromide potassium 100g Ammonium nitrate 10g bleach accelerator 0.005 mole _{(CH 3) 2 N-CH} 2 -CH 2 -SS-CH 2 -CH 2 -N (CH 3) 2 · 2HCl water to make 1000 ml pH 6.30 pH is hydrochloric acid or It was adjusted with aqueous ammonia.

[Bleach-fixing solution] [Tank solution] [Replenishing solution] Ethylenediaminetetraacetic acid ・ 2 sodium salt ・ dihydrate 5.0 g Same as tank solution Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ammonia ・ Dihydrate 50 g Thio Ammonium sulfate 80 g Sodium sulfite 12.0 g Water was added to 1000 ml pH 6.60 pH was adjusted with hydrochloric acid or aqueous ammonia.

[Second Washing Solution]
[Both tank and replenisher] Mixed bed of tap water filled with 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 the formula column to adjust the concentration of calcium and magnesium ions to 3 mg / liter or less, and then 20 mg / liter of sodium isocyanurate dichloride and 1.5 g / liter of sodium sulfate were added. The pH of this liquid is in the range of 6.5 to 7.5.

[Stabilizer] [Tank solution] [Replenisher] Formalin (37%) 0.5 ml Same as tank solution Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization 10) 0.3 g Triazole 1.7 g Piperazine 6 water Japanese product 0.6 g Add water to 1000 ml without adjusting pH

The results are shown in Tables 8 and 9.

[0352]

[Table 8]

[0353]

[Table 9]

From Tables 8 and 9, the samples according to the present invention are
It can be seen that the sensitivity is remarkably high and the storage stability is also good.

Example 5 Of the samples prepared in Example 1, samples 101-108 were prepared.
Eight types, Japanese Patent Publication No. 2-32615, and Japanese Utility Model 3-397
A film unit with a lens was produced according to the method described in No. 84. These 5 types of film units with lens are used to shoot various subjects under the same conditions, and use the automatic processor FP-5.
Color development processing is performed with 60B AL (Fuji Photo Film Co., Ltd.), and then Fuji Mini Lab Champion, Printer Processor FA-140 (Fuji Photo Film Co., Ltd.) is used to print on Fuji Color Paper, Super FA, Type II. (CP-43FA was used for the color development processing at this time).

The respective patterns obtained by printing through the negatives obtained from these eight types of lens-equipped film units were observed, and Sample 1 having the constitution of the present invention was observed.
It was clearly confirmed that the prints obtained from Nos. 02 to 108 had higher sensitivity than the prints obtained from Comparative Sample 101.

Example 6 Potassium bromide 25.7 g, gelatin 125 g, 5% 3,
An aqueous solution of 6-dithiaoctane-1,8-diol was added to water 2.
Into 5 liters, while stirring well, at 75 ° C, 65 ml of 12.77% aqueous solution of potassium bromide and 65 ml of 17.22% aqueous solution of silver nitrate to which 0.4 g of ammonium nitrate was added were mixed by a double jet method at a constant flow rate for 15 seconds. added. Then, after stirring was continued for 20 minutes as it was, 246.2 g of potassium bromide, 10.5 g of potassium iodide and 3,6
-1.44 liters of an aqueous solution containing 1.7 g of dithiaoctane-1,8-diol and 1.44 liters of a 20.90% silver nitrate aqueous solution containing 9.0 g of ammonium nitrate were added over 90 minutes by the double jet method. (The amount of total silver nitrate added is 375.5 g). Then, the mixture was cooled to 35 ° C., adjusted to pH 4.10, the same precipitating agent as in Preparation Example (1) was added, and the silver halide was washed with precipitated water to obtain gelatin 100.
g, 150 ml of a 5% aqueous phenol solution and 1.4 liters of water were added to adjust pH to 6.8 and pAg to 8.8. The silver halide grains thus obtained have an average diameter of 1.78μ.
m, average thickness 0.12 μm (average diameter / thickness 14.
8), tabular silver halide grains having a diameter of 0.6 μm or more and a thickness of 0.2 μm or less and a diameter / thickness of 10 or more accounted for 97.8% of the total projected area of all grains. Next, this emulsion was ripened at 60 ° C. by adding sodium thiosulfate pentahydrate and potassium tetraaurate. The silver iodobromide emulsions thus prepared were weighed in pots of 1 kg each, and sensitizing dye (XIV-6) 4 × 10 ⁻⁴ mol / kg emulsion, (XIV −2)
3) 1.2 × 10 ^-5 mol kg emulsion and compounds (I) to (IV) of the present invention shown in Table 10 of 7.0 × 10 ^-5 mol kg emulsion were added, and 2,4-dichloro was added. -6-hydroxy-
A 1% by weight aqueous solution of 1,3,5-triazine sodium salt was added and then coated on a polyethylene terephthalate film base so that the dry film thickness was 5 μm, to obtain a photographic light-sensitive material. Tungsten light (5400 ° K) was applied to each of these samples, using a blue filter (bandpass filter that transmits light from 395 nm to 440 nm) and a red filter (filter that transmits light with a wavelength longer than 600 nm). Optical wedge exposure was performed for 1/50 second. After exposure, use a developer with the following composition and
It was developed for a minute, stopped, fixed, and washed with water to obtain strips having a black and white image. The density of the strips was measured using a densitometer manufactured by Fuji Photo Film Co., Ltd., and blue filter sensitivity (SB), red filter sensitivity (SR) and fog were determined. The reference point of the optical density for which the sensitivity was determined was [fog + 0.2]. A sample stored in the same manner as in Example 1 was exposed and developed in the same manner as above. The sensitivities were expressed as relative sensitivities when the sensitivities of the SB and SR samples 601 before storage were 100. Composition of developer Water 700 ml Metol 3.1 g Anhydrous sodium sulfite 45 g Hydroquinone 12 g Sodium carbonate (monohydrate) 79 g Potassium bromide 1.9 g Add water to make 1 liter Add 2 volumes of water to make a working solution. The results obtained are shown in Table 10 as relative values.

[0358]

[Table 10]

From Table 10, compounds (I) of the present invention
It can be seen that (IV) increases the sensitivity and improves the storage stability.

[0360]

By using the compound represented by formula (I) and the tabular grain silver halide emulsion in which the silver halide grains having an aspect ratio of 2 or more are present in an amount of 50% or more of all the silver halide grains, It is possible to provide a silver halide photographic light-sensitive material having high sensitivity and excellent storage stability. Furthermore, the coefficient of variation of the grain size of the silver halide grains is 0.25.
5 of the total projected area of the following monodisperse grains and silver halide grains
Hexagonal tabular grains and silver halide grains in which 0% or more has two parallel outer surfaces as outer surfaces and the ratio of the length of the side having the maximum length to the length of the side having the minimum length is 2 or less. A silver halide grain having a relative standard deviation of the individual silver iodide content of at least 50% of the grains containing 10 or more dislocations per grain or a silver halide grain having a relative standard deviation of 30% or less. By using the emulsion, it is possible to provide a silver halide color photographic light-sensitive material having the above-mentioned various performances further improved.

[Procedure amendment]

[Submission date] April 7, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0057

[Correction method] Change

[Correction content]

The compound represented by the general formula (III) is, for example, HRSnycler, J
R), JG Michels, Journal of Organic Chemistry (Journal o
f Organic Chemistry) 28, 1144 (1963)
Year), JE Anderson,
JMLehn, Journal of the American Chemical Society (Journal
of The American Chemical Society) Vol. 89, No. 1,
81 (1967), Hermann Steter
Stetter), Peter Woernle Justus Liebig Analen del Hemy (Justus
Liebigs Ammalen der Chemie) No. 724, p. 150 (1969), SF Nelsen
Et al., Tetrahedron, Vol. 42, No. 6, 1
Pp. 769 (1986) and the like, and can be synthesized by referring to them.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0058

[Correction method] Change

[Correction content]

The compound represented by the general formula (IV) can be obtained by, for example, SF Nelsen et al. Journal of the American Chemical Society (J
ournal of The American Chemical Society, Vol. 96, No. 9, p. 2916 (1974), EL Buhle, et al., Journal of the American.
Chemical Society (Journal of The American
Chemical Society), Vol. 65, p. 29 (1943)
, Etc., and can be synthesized by referring to them.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0062

[Correction method] Change

[Correction content]

The oxidation potential was measured by a phase discrimination type second high frequency AC polarography. The details are described below. Acetonitrile (spectral grade) dried in 4A-1 / 16 molecular sieves was used as a solvent, and normal tetrapropylammonium perchlorate (special reagent for polarograph) was used as a supporting electrolyte. The sample solution was prepared by dissolving a sensitizing dye at 10 ⁻³ to 10 ⁻⁵ mol / liter in acetonitrile containing 0.1 M of supporting electrolyte, and a high alkaline aqueous solution of pyrogallol was added to the solution before the measurement, and calcium chloride was passed through the solution. It was deoxygenated with high-purity argon gas (99.999%) for 15 minutes or more. The working electrode was a rotating platinum electrode, the reference electrode was a saturated calomel electrode (SCE), and the counter electrode was platinum. The reference electrode and the sample solution were connected with a Luggin tube filled with acetonitrile containing 0.1 M indicator electrolyte, and Vycor glass was used for the liquid junction. The tip of the Luggin tube and the tip of the rotating platinum electrode were measured at 25 ° C. with a distance of 5 mm to 8 mm. In addition, the measurement of the oxidation potential by the phase discrimination type second harmonic AC voltammetry is described in "Journal
Of Imaging Science "(Journal of Imagi
ng Science), Vol. 30, pp. 27-35 (1986).
It is described in. Under this condition, the dye (XIV-
The oxidation potential of 9) was 0.915 V (vsSCE). The sensitizing dyes satisfying the conditions of the above-mentioned oxidation potential and the maximum spectral sensitivity and represented by the following general formulas (XI), (XII) and (XIII) are particularly preferably used. General formula (XI)

Claims (6)

[Claims] 1. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, wherein the silver halide grains having an aspect ratio of 2 or more are all silver halide grains in the emulsion layer. A silver halide photographic light-sensitive material comprising a silver halide emulsion composed of tabular grains present in an amount of 50% or more and containing a compound represented by the following general formula (I). General formula (I) In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent an alkyl group, an aryl group or a heterocyclic group. R ₁ and R ₂ , R ₃ and R ₄ , R ₁ and R ₃ , and R ₂ and R ₄ may be bonded to each other to form a ring, but they do not form an aromatic ring. However, among R ₁ , R ₂ , R ₃ and R ₄ , the carbon atom directly bonded to the nitrogen atom of hydrazine is not substituted with an oxo group. 2. The silver halide emulsion according to claim 1, wherein the silver halide emulsion is composed of monodisperse grains having a coefficient of variation of the grain size of silver halide grains of 0.25 or less. Silver halide photographic light-sensitive material. 3. A silver halide emulsion having, as an outer surface, two parallel surfaces of which 50% or more of the total projected area of silver halide grains is parallel, and has a maximum length with respect to a side length having a minimum length. 3. The silver halide photographic light-sensitive material according to claim 1 or 2, which is a silver halide emulsion comprising hexagonal tabular grains having a side length ratio of 2 or less. 4. The silver halide emulsion as claimed in claim 1, wherein at least 50% of the number of silver halide grains is composed of grains having 10 or more dislocations per grain. The silver halide photographic light-sensitive material according to claim 3. 5. The silver halide emulsion is a silver halide emulsion composed of silver halide grains having a relative standard deviation of the individual silver iodide contents of the silver halide grains of 30% or less. Item 5. The silver halide photographic light-sensitive material according to Item 1 or 4. 6. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide emulsion is spectrally sensitized with a sensitizing dye.