JPH06202262A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable change of performance due to storing conditions to be reduced while maintaining high sensitivity by sensitizing a silver halide emulsion with a selenium compound and incorporating a specified compound in a silver halide emulsion layer or a hydrophilic colloidal layer. CONSTITUTION:The silver halide photographic sensitive material has at least one silver halide emulsion layer containing the sensitized silver halide emulsion on a support and in at least one of silver halide emulsion layers or the hydrophilic colloidal layers at least one of the compounds represented by the formula in which each of R1-R4 is an alkyl, aryl, or heterocyclic group, and each of R1-R2, R3-R4, R1-R3, and R2-R4 may combine with each other to form a ring but not an aromatic ring, any carbon atom directly combining with the N atom of the hydrazine group is not substituted by an oxo group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material which has high sensitivity and shows little change in performance due to storage conditions before and after exposure. is there.

[0002]

2. Description of the Related Art In recent years, demands for silver halide photographic light-sensitive materials have become more and more strict. In particular, it is strongly desired to realize stable performance under various storage conditions before and after exposure as well as high sensitivity and high image quality as the number of shooting opportunities increases. By the way, various chemical sensitization methods have hitherto been studied for higher sensitivity and higher image quality. Among them, the selenium sensitization method is described, for example, in U.S. Patent Nos. 1,574,444 and 1,602,592.
1,623,499, 3,297,447, JP-A-59-180536, JP-A-59-192241,
59-185329, JP-B-44-15748,
No. 43-13489, Japanese Patent Application Nos. 2-130976 and 2-229300, etc. The selenium-sensitized emulsion achieves high sensitivity and high image quality, but is still at a desired level of improvement in stability of performance depending on storage conditions before and after exposure.

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, if the dye desensitization decreases,
The sensitivity (that is, spectral sensitization) in the light absorption region by the sensitizing dye is also increased accordingly. 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 are C.I. E. K. Mees, “The Theory of the Photographic Process (Th
e Theory of the Photograph
Hic Process) ”pages 1067-1069 (published by Macmillan Inc. 1942).

As a method for reducing dye desensitization and increasing sensitivity, JP-A-47-28916 and JP-A-49-4673 are known.
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-ba showing a gentle sensitizing maximum such as dicarbocyanine, tricarbocyanine, rhodocyanine and merocyanine.
The dye is limited to the nd sensitizing dye and has the maximum sensitization in a relatively long wavelength region.

In US Pat. No. 3,695,888, it is possible to obtain a sensitization in the infrared region by combining a specific tricarbocyanine with ascorbic acid, 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.

[0006] However, in the above-mentioned conventional techniques, there are few cases in which the sensitizing effect of the dye is sufficiently satisfactory, and those having a high sensitizing effect tend to increase fog.

Attempts have been made to add hydrazines to silver halide light-sensitive materials or developing solutions for various purposes.

US Pat. No. 2,419,975, JP-A-6
In JP-A 3-261362 and JP-B-51-15745, hydrazines are added to a developer and used.

In Japanese Patent Publication Nos. 58-9410 and 58-9411, acylhydrazines are added to a light-sensitive material in order to obtain a high-contrast silver halide light-sensitive material.

Addition of this hydrazine has a small sensitizing effect but increases fog.

JP-A-63-95444, 63-431
In No. 45, the stability of the dye image against heat and light is improved by using a magenta coupler in combination with a specific hydrazine compound.

JP-A-63-220142, 63-25
In 6951 and 63-229455, photobleaching is prevented by using an organic coloring substance and a specific hydrazine compound in combination.

However, no example of using hydrazines as in the present invention is known.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material which has a high sensitivity and has a small change in performance due to storage conditions before and after exposure.

[0015]

As a result of various studies, the present inventor has found that the above object can be achieved by the following means.

(1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one silver halide emulsion contained in the silver halide emulsion layer is selenium-enhanced. A silver halide photographic light-sensitive material characterized by containing at least one compound represented by the following general formula (I) in at least one of a silver halide emulsion layer or a hydrophilic colloid layer.

General formula (I)

[0018]

[Chemical 5] 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 photographic light-sensitive material as described in (1) above, which is spectrally sensitized with a sensitizing dye.

(3) The above-mentioned (1) or (2), wherein the compound represented by the general formula (I) is a compound selected from the following general formulas (II), (III) and (IV). ) A silver halide photographic light-sensitive material as described in any of the above.

General formula (II)

[0023]

[Chemical 6] General formula (III)

[0024]

[Chemical 7] General formula (IV)

[0025]

[Chemical 8] In the formula, R ₅ , R ₆ , R ₇ and R ₈ are each an alkyl group,
It represents 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 represent a methine group.

However, R ₅ , R ₆ , R ₇ , R ₈ , Z ₁ ,
Of Z ₄ and Z _5, the carbon atom directly bonded to the nitrogen atom of hydrazine is not substituted with an oxo group.

(4) At least one kind of silver halide emulsion contained in the silver halide emulsion layer is chemically sensitized by both selenium sensitization and sulfur sensitization (1) to (3).
The silver halide photographic light-sensitive material as described in any one of 1.

The present invention will be described in detail below.

In the present invention, at least one silver halide emulsion is selenium sensitized.

Regarding the selenium sensitization method, US Pat.
No. 74944, No. 1602592, No. 16234
No. 99, No. 3297446, No. 3297447
No. 3320069, No. 3408196, No. 3408197, No. 3442653, No. 34.
No. 20670, No. 3591385, French Patent No. 2693038, No. 2093209, Japanese Patent Publication No. 52
-34491, 52-34492, and 53-29.
5, 57-22090, and JP-A-59-18053.
No. 6, No. 59-185330, No. 59-181337.
No. 59-187338 and No. 59-192241.
Issue No. 60-150046, Issue No. 60-151637
No. 61-246738, JP-A-3-42221,
Japanese Patent Application Nos. 1-287380, 1-250950, 1-254441, 2-334090 and 2-11
No. 0558, No. 2-130976, No. 2-13918
No. 3, No. 2-229300, and British Patent No. 2558.
46, No. 861984, and H.M. E. Specc
er et al., Jourlan of Photograph
hic Science magazine, Vol. 31, pp. 158-169 (1983).

These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, or in Japanese Patent Application Nos. 2-264447 and 2-26.
It is added at the time of chemical sensitization in the form described in No. 4448.
It is preferably added before the start of chemical sensitization. The selenium sensitizer used is not limited to one type, and two or more types of the above selenium sensitizers can be used in combination. The unstable selenium compound and the non-unstable selenium compound may be used in combination.

The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the kind and size of silver halide, the temperature and time of ripening, etc.
It is preferably 1 × 10 ⁻⁸ mol or more per mol of silver halide. More preferably 1 × 10 ⁻⁷ mol or more and 1 × 10
^-4 mol or less. The temperature of chemical ripening when a selenium sensitizer is used is preferably 45 ° C. or higher. It is more preferably 50 ° C. or higher and 80 ° C. or lower. pAg and pH are arbitrary. For example, the effects of the present invention can be obtained in a wide range of pH from 4 to 9.

The selenium sensitization is more effective when carried out in the presence of a silver halide solvent.

The silver halide solvent that can be used in the present invention is, for example, US Pat. No. 3,271,157.
No. 3,531,289, No. 3,574,62
No. 8, JP-A Nos. 54-1019 and 54-158917.
(A) Organic thioethers described in JP-A No. 1993-54,
No. 3-82408, No. 55-77737, No. 55-2
982, etc., (b) thiourea derivative, and (c) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, described in JP-A-53-144319. (D) imidazoles, (e) sulfites described in JP-A-54-100717,
(F) Thiocyanate and the like.

Particularly preferred solvents are thiocyanate and tetramethylthiourea. Although the amount of the solvent used varies depending on the kind, in the case of thiocyanate, the preferable amount is 1 per mol of silver halide.
It is not less than × 10 ^-4 mol and not more than 1 × 10 ^-2 mol.

The silver halide photographic emulsion of the present invention can achieve higher sensitivity and lower fog by combined use of sulfur sensitization and / or gold sensitization in chemical sensitization.

The sulfur sensitization is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time.

The gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time.

For sulfur sensitization, known sulfur sensitizers can be used. For example thiosulfate,
Thioureas, allyl isothiocyanate, cystine, p
-Toluenethiosulfonate, Rhodanine and the like. Other U.S. Pat. Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668, 3,501,313,
No. 3,656,955, German patents 1,4
No. 22,869, Japanese Patent Publication No. 56-24937, Japanese Patent Laid-Open No. 5
Sulfur sensitizers described in JP-A-5-45016 can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains, but it is 1 × 10 ⁻⁷ mol or more per 5 mol of silver halide and 5 × 10 ^−4. It is preferably not more than mol.

As the gold sensitizer for the above-mentioned gold sensitization, the oxidation number of gold may be +1 valence or +3 valence, and a gold compound usually used as a gold sensitizer can be used. Representative examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold and the like.

The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is 1 × 10 ^-7 per mol of silver halide.
It is preferably not less than 5 and not more than 5 × 10 ⁻⁴ mol.

In chemical ripening, there are no particular restrictions on the timing and order of addition of a silver halide solvent and a selenium sensitizer or a sulfur sensitizer and / or a gold sensitizer which can be used in combination with a selenium sensitizer. There is no need to provide it,
For example, the above compounds can be added at the same time as the initial (preferably) chemical ripening or during the progress of chemical ripening, or at different addition points. In addition, upon addition, the above compound may be dissolved in water or an organic solvent capable of mixing with water, for example, a single liquid or a mixed liquid of methanol, ethanol, and acetone, and then added.

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. Usually, an unstable selenium compound and / or a non-unstable selenium compound is added at high temperature,
Sensitization is preferably performed by stirring the emulsion at 40 ° C. or higher for a certain period of time. Examples of unstable selenium compounds include Japanese Examined Patent Publication Nos. 44-15748 and 43-13489.
No. 2, Japanese Patent Application No. 2-130976, Japanese Patent Application No. 2-22930
It is preferable to use the compounds described in No. 0 and the like. Specific examples of the unstable selenium sensitizer include, for example, isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example, 2 -Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides,
Examples include colloidal metal selenium.

Preferred types of labile selenium compounds have been mentioned above, but are not limiting. Stable selenium compounds as sensitizers for photographic emulsions are known to those skilled in the art, as long as selenium is unstable, the structure of the compounds is not so important, and organic compounds of selenium sensitizer molecules are not important. It is generally understood that the moieties carry selenium and have no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used.

As the non-labile selenium compound used in the present invention, Japanese Patent Publication Nos. 46-4553 and 52-34.
The compounds described in JP-B No. 492 and JP-B-52-34491 are used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinethione and derivatives thereof.

Of these selenium compounds, the following general formulas (V) and (VI) are preferable.

General formula (V)

[0053]

[Chemical 9] In the formula, Z ₁ and Z ₂ may be the same or different and each represents an alkyl group (eg, methyl group, ethyl group, t
-Butyl group, adamantyl group, t-octyl group), alkenyl group (for example, vinyl group, propenyl group), aralkyl group (for example, benzyl group, phenethyl group), aryl group (for example, phenyl group, pentafluorophenyl group, 4-chlorophenyl group, 3-nitrophenyl group, 4
-Octylsulfamoylphenyl group, α-naphthyl group), heterocyclic group (for example, pyridyl group, thienyl group, furyl group, imidazolyl group), -NR ₁ (R ₂ ), -OR
It represents ₃ or -SR _4.

R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. As the alkyl group, aralkyl group, aryl group or heterocyclic group, Z ₁
An example similar to is given.

However, R ₁ and R ₂ are hydrogen atoms or acyl groups (for example, acetyl group, propanoyl group, benzoyl group, heptafluorobutanoyl group, difluoroacetyl group, 4-nitrobenzoyl group, α-naphthoyl group, 4 -Trifluoromethylbenzoyl group).

In formula (V), Z ₁ preferably represents an alkyl group, an aryl group or —NR ₁ (R ₂ ), and Z ₂
Represents -NR ₅ (R ₆ ). R ₁ , R ₂ , R ₅ and R
₆ may be the same or different, a hydrogen atom,
It represents an alkyl group, an aryl group, or an acyl group.

In the general formula (V), more preferably N, N-
Dialkylselenourea, N, N, N'-trialkyl-
N'-acyl selenoureas, tetraalkyl selenoureas,
Represents N, N-dialkyl-arylselenoamide, N-alkyl-N-aryl-arylselenoamide.

General formula (VI)

[0059]

[Chemical 10] In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each is an aliphatic group, an aromatic group, a heterocyclic group or -OR.
_{7, -NR 8 (R 9)} , - SR 10, SeR 11, X, represents a hydrogen atom.

R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or hydrogen. Represents an atom, and X represents a halogen atom.

In the general formula (VI), Z ₃ , Z ₄ ,
The aliphatic group represented by Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (for example, methyl group, ethyl group). Group, n-propyl group, isopropyl group, t-
Butyl group, n-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopentyl group, cyclohexyl group, allyl group, 2-butenyl group, 3-pentenyl group, propargyl group, 3-pentynyl group, Benzyl group,
Phenethyl group).

In the general formula (VI), Z ₃ , Z ₄ ,
The aromatic group represented by Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed aryl group (for example, phenyl group, pentafluorophenyl group, 4-chlorophenyl group, 3 -Sulfophenyl group, α-naphthyl group, 4-methylphenyl group).

In the general formula (VI), Z ₃ , Z ₄ ,
The heterocyclic group represented by Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a saturated or unsaturated 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Represents a heterocyclic group (eg, pyridyl group, thienyl group, furyl group, thiazolyl group, imidazolyl group, benzimidazolyl group).

In the general formula (VI), the cation represented by R ₇ , R ₁₀ and R ₁₁ represents an alkali metal atom or ammonium, and the halogen atom represented by X is, for example, a fluorine atom, a chlorine atom or a bromine atom. Or represents an iodine atom.

In formula (VI), Z ₃ , Z ₄ or Z ₅ preferably represents an aliphatic group, an aromatic group or -OR ₇ ,
R ₇ represents an aliphatic group or an aromatic group.

In formula (VI), trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate is more preferred.

Specific examples of the compounds represented by formulas (V) and (VI) are shown below, but the invention is not limited thereto.

[0068]

[Chemical 11]

[0069]

[Chemical 12]

[0070]

[Chemical 13]

[0071]

[Chemical 14]

[0072]

[Chemical 15]

[0073]

[Chemical 16]

[0074]

[Chemical 17]

[0075]

[Chemical 18] Next, the compounds (I), (II) and (III) used in the present invention
And (IV) will be described.

The general formula (I) will be described in detail below.

R ₁ , R ₂ , R ₃ and R ₄ are, for example, unsubstituted alkyl groups (eg, melty group, ethyl group,
Propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, dodecyl group, octadecyl group, cyclopentyl group, cyclopropyl group, cyclohexyl group), substituted alkyl group (where V is a substituent)
There is no particular limitation on the substituent represented by, for example, a carboxy group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a hydroxy group, an alkoxycarbonyl group (for example, a methoxycarbonyl group). , An ethoxycarbonyl group, a phenoxycarbonyl group, a benzyloxycarbonyl group), an alkoxy group (for example, a methoxy group, an ethoxy group, a benzyloxy group,
Phenethyloxy group), an aryloxy group having 18 or less carbon atoms (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 (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group), aryl group (for example, phenyl group, 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,
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, hydracino group (eg trimethylhydrazino group), ureido group (eg ureido group, N, N-dimethylureido group), imide Group, unsaturated hydrocarbon group (for example, vinyl group, ethynyl group, 1-cyclohexenyl group,
And 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-dimethylaminopropyl 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, etc.} aryl group (eg, phenyl group, α-naphthyl group, β-naphthyl group, eg, phenyl group substituted with the above-mentioned substituent V, naphthyl group), heterocycle (eg, 2-pyridyl group, 2
-Thiazolyl group, 2-pyridyl group substituted with the above-mentioned substituent V) is 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 an oxo group. For example R ₁ ,
R _2, R ₃ and R ₄ are acetyl group, a carboxy group, a benzoyl group, a formyl group, two of malonyl group when they form a ring, succinyl group, glutaryl group, is not an adipoyl group.

Further, among R ₁ , R ₂ , R ₃ and R ₄ , the carbon atom directly bonded to the nitrogen atom of hydrazine is a thioxo group (eg, thioacetyl group, thioaldehyde group, thiocarboxy group, thiobenzoyl group). ) Is preferably not substituted.

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 (which may be substituted (for example, the above-mentioned substituent V)) containing no.

More preferably, R ₁ , R ₂ , R ₃ and R ₄ are those in which the carbon atom directly bonded to the nitrogen atom of hydrazine is an unsubstituted methylene group or an alkyl group (eg methyl group, ethyl group) substituted methylene group. This is the case of the base.
Particularly preferably, an unsubstituted alkyl group (for example, a methyl group,
Ethyl group, propyl group, butyl group), substituted alkyl group {for example, sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-
Sulfobutyl group), carboxyalkyl group (eg carboxymethyl group, 2-carboxyethyl group), hydroxyalkyl group (eg 2-hydroxyethyl 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 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 can be used as long as it is a compound capable of forming a salt with hydrazines, but preferable salts include the following.

For example, aryl sulfonates (eg p
-Toluene sulfonate, p-chlorobenzene sulfonate), aryl disulfonate (eg 1,3-benzene disulfonate, 1,5-naphthalene disulfonate, 2,6-naphthalene disulfonate), thiocyanate Acid salts, picrates, carboxylates (eg oxalates, acetates, benzoates, hydrogen oxalates), halogenates (eg hydrochlorides, hydrofluorides, hydrobromides) , Hydroiodide), sulfate, perchlorate, tetrafluoroborate, sulfite, nitrate, phosphate, carbonate, bicarbonate.

Preferred are hydrogen oxalate, oxalate and hydrochlorate.

The general formula (II) will be described in detail below.

R ₅ and R ₆ are synonymous with R ₁ , R ₂ , R ₃ and R _4, and preferred ranges are also the same.

Particularly preferably, a methyl group and R ₅ and R
_{In this case, 6} is 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, and the carbon atom directly bonded to the nitrogen atom of hydrazine may be an unsubstituted methylene group or an alkyl group (for example, methyl group, ethyl group) substituted methylene group. preferable.

Z ₁ is particularly preferably an unsubstituted tetramethylene group.

The general formula (III) will be described in detail below.

R ₇ and R ₈ are synonymous with R ₁ , R ₂ , R ₃ and R _4, and preferred ranges are also the same.

Particularly preferably, a methyl group and R ₇ and R
_{In this case, 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 ethylene group or an ethylene group.

L ₁ and L ₂ represent a methine group or a substituted methine group. As the substituent, for example, the above-mentioned substituent V
And is 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.

These alkylene groups may be unsubstituted or substituted. Examples of the substituent include the above-mentioned substituent V. When the carbon atom directly bonded to the nitrogen atom of hydrazine is an unsubstituted methylene group or an alkyl group (eg, methyl group, ethyl group) substituted methylene group Is preferred.

Z ₄ and Z ₅ are particularly preferably an unsubstituted trimethylene group, an unsubstituted alkyl group or a substituted trimethylene group (eg, 2,2-dimethyltrimethylene group).

The compounds represented by the general formulas (II), (III) and (IV) can be isolated as salts in the same manner as the compounds represented by the general formula (I). As salt,
Examples thereof include those similar to the salt represented by the general formula (I). Preferred are hydrogen oxalate, oxalate and hydrochlorate.

Typical examples of the compounds represented by formulas (I), (II), (III) and (IV) are shown below.
It is not limited to this.

Compounds represented by the general formula (I) (Compounds represented by the general formula (I) are represented by the general formula (II),
It includes compounds represented by (III) and (IV). However, here, examples in which the compounds represented by the general formulas (II), (III), and (IV) are excluded as the compound represented by the general formula (I) will be given. )

[0111]

[Chemical 19]

[0112]

[Chemical 20]

[0113]

[Chemical 21]

[0114]

[Chemical formula 22]

[0115]

[Chemical formula 23] Compound represented by general formula (II)

[0116]

[Chemical formula 24]

[0117]

[Chemical 25]

[0118]

[Chemical formula 26]

[0119]

[Chemical 27] Compound represented by general formula (III)

[0120]

[Chemical 28]

[0121]

[Chemical 29]

[0122]

[Chemical 30]

[0123]

[Chemical 31] Compound represented by general formula (IV)

[0124]

[Chemical 32]

[0125]

[Chemical 33]

[0126]

[Chemical 34] The compound represented by formula (I), (II), (III) or (IV) of the present invention may be added before or after the sensitizing dye. Further, the content in each preferable silver halide emulsion is 1 × 10 ^{−6 to} 5 × 1 per mol of silver halide.
0 ⁻¹ mol, more preferably 1 × 10 ⁻⁵ to 2 × 1
It is 0 ^-2 mol, particularly preferably 10 ^-4 to 2 × 10 ^-6 mol.

When spectrally sensitized, the sensitizing dye and the compound represented by the general formula (I), (II), (III) or (IV) are sensitizing dye / (I), (II), ( III) or (IV)
Is preferably used in a ratio (molar ratio) in the range of 10/1 to 1/1000, and particularly in the range of 1/1 to 1/100.

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

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-
A 5-6 membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus or a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,52
No. 2,052, No. 3,527,641, No. 3,61
7,293, 3,628,964, 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377 and 3,76
9,301, 3,814,609, 3,83
No. 7,862, No. 4,026,707, British Patent Nos. 1,344,281, 1,507,803, Japanese Patent Publication No. 43-4936, No. 53-12,375, and Japanese Unexamined Patent Publication No. 52-375. -110,618 and 52-109,925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

The timing of adding the sensitizing dye to the emulsion may be at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,62.
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A-58-11.
It can be carried out prior to chemical sensitization as described in US Pat. No. 3,928, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. It is also possible to add these said compounds separately, as taught in U.S. Pat. No. 4,225,666, i.e. to add some of these compounds prior to chemical sensitization and the rest to chemical sensitization. It can be added after the sensation, and can be added at any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 4,183,756.

The addition amount is 4 × per mol of silver halide.
It can be used in an amount of 10 ⁻⁶ to 8 × 10 ⁻³ mol.

The silver halide grains used in the present invention are silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
It is silver chloroiodobromide. Other silver salts, such as Rhodan silver,
Silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains. When it is desired to accelerate the development / desilvering (bleaching, fixing and bleach-fixing) steps, silver halide grains having a high silver chloride content are desirable. Further, in the case of suppressing development appropriately, it is preferable to contain silver iodide.
The preferred silver iodide content varies depending on the intended light-sensitive material.
For example, 0.1 to 15 mol% is preferable for the X-ray sensitive material, and 0.1 to 5 mol% is preferable for the graphic arts and the micro sensitive material. In the case of a photographic light-sensitive material represented by color negative, silver halide containing 1 to 30 mol% of silver iodide is preferable, 5 to 20 mol% is more preferable, and 8 to 15 mol% is particularly preferable. is there. It is preferable that the silver iodobromide grains contain silver chloride in order to reduce lattice strain.

The silver halide emulsion of the present invention preferably has a distribution or structure relating to the halogen composition in its grains. A typical example thereof is, for example, Japanese Patent Publication No.
13162, JP-A-61-215540, and JP-A-6-215540
No. 0-222845, JP-A-60-143331, and JP-A-61-75337. Core-shell type or double structure type grains having a halogen composition in which the inside and the surface of the grains are different. is there. Further, it is not a simple double structure but a triple structure as disclosed in JP-A-60-222844 or a multilayer structure having more than that, or a different composition on the surface of the core-shell double structure particles. It is possible to thinly apply a silver halide having.

The internal structure of the particles may be not only the enclosing structure described above but also a so-called junction structure. Examples of these are, for example, JP-A-59-133540, JP-A-58-108526, and European Patent 199,290A2.
Japanese Patent Publication No. 58-24772, Japanese Patent Laid-Open No. 59-1625.
No. 4 and the like. The crystal to be bonded can be generated by bonding to the edge, corner, or face of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal has a uniform halogen composition or has a core-shell type structure.

In the case of a joint structure, it is naturally possible to combine silver halides with each other, but silver salt compounds such as rhodan silver and silver carbonate which do not have a rock salt structure can also be combined with silver halide to form a joint structure. In addition, a non-silver salt compound such as lead oxide may be used as long as a joint structure is possible.

In the case of grains such as silver iodobromide having these structures, it is a preferable embodiment that the silver iodide content of the core portion is higher than that of the shell portion. On the contrary, in some cases, grains having a low silver iodide content in the core portion and a high shell portion are preferable. Similarly, with respect to the grains having a junction structure, the grains having a high silver iodide content in the host crystal and having a relatively low silver iodide content in the junction crystal may be used, or vice versa. Further, the boundary portion having different halogen compositions of the particles having these structures may be a clear boundary or an unclear boundary. In addition, a positive embodiment in which the composition is positively and continuously changed is also a preferred embodiment.

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

It is important to control the halogen composition near the surface of the grain. Increase the content of silver iodide near the surface,
Alternatively, by increasing the silver chloride content, the adsorbability of the dye and the developing rate are changed, so that the halogen composition can be selected according to the purpose. When changing the halogen composition in the vicinity of the surface, it is possible to select either a structure that encloses the entire grain or a structure that adheres only to a part of the grain. For example, it is a case where the halogen composition of only one side of the tetrahedral grain composed of the (100) plane and the (111) plane is changed or the halogen composition of one of the main plane and the side surface of the tabular grain is changed.

The silver halide grains used in the present invention, even if they are normal crystals not containing twin planes, are edited by The Photographic Society of Japan, Fundamentals of The Photographic Industry, Silver Salt Photographs (Corona Publishing Co.), P.P. 163, eg, single twin containing one twin plane, parallel multiple twin containing two or more parallel twin planes, non-parallel containing two or more non-parallel twin planes. It can be selected and used from multiple twins and the like according to the purpose. An example of mixing particles having different shapes is disclosed in U.S. Pat. No. 4,865,964, but this method can be selected if necessary.
In the case of normal crystal, a cube consisting of (100) plane, (11
An octahedron composed of 1) planes is disclosed in JP-B-55-42737 and JP-A-60-222842 (110).
A dodecahedral grain composed of planes can be used. In addition, the Journal of Imaging Scene
30: p. 247 (h11) plane particles typified by (211), (hh1) plane particles typified by (331), (21) as reported in 1986.
The (hk0) plane particles typified by the (0) plane and the (hk1) plane particles typified by the (321) plane may be selected and used according to the purpose although some preparation methods are required. A tetrahedral grain in which the (100) plane and the (111) plane coexist in one grain,
Depending on the purpose, particles having two planes or many planes, such as particles having (100) planes and (110) planes coexisting, or particles having (111) planes coexisting with (110) planes, may be selected and used. You can

The value obtained by dividing the circle-equivalent diameter of the projected area by the grain thickness is called the aspect ratio, and defines the shape of tabular grains. Tabular grains having an aspect ratio of greater than 1 can be used in the present invention. Tabular grains are described, for example, in Cleeve, "The Theory and Practice of Photography" (Cleve, Photography).
Theory and Practice (193
0)), p. 131; Gatov, Photographic Science and Engineering (Gutoff, P.
photographic Science and E
14: 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, 4,439,520 and British Patent No. 2,112,1
It can be prepared by the method described in No. 57, etc.
When the tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitizing efficiency by the sensitizing dye, which are described in detail in the above-cited US Pat. No. 4,434,226. . The average aspect ratio of 80% or more of the total projected area of the grains is preferably 1 or more and less than 100. It is more preferably 2 or more and less than 20, and particularly preferably 3 or more and less than 10. The shape of tabular grains can be selected from triangles, hexagons, circles, and the like. US Patent No. 4,7
A regular hexagon having six sides of approximately the same length as described in Japanese Patent No. 97,354 is a preferred form.

Although the diameter of the circle equivalent to the projected area is often used as the grain size of tabular grains, US Pat.
The average diameter as described in No. 8,106 is 0.6
Particles of micron or smaller are preferable for improving image quality. It is preferable to limit the grain thickness of the tabular grains to 0.5 μm or less, more preferably 0.3 μm or less, in order to improve the sharpness. Furthermore, the coefficient of variation of particle thickness is 3
Emulsions with high thickness uniformity of 0% or less are also preferable. Further, grains described in JP-A-63-163451, in which the grain thickness and the interplanar distance between twin planes are defined, are also preferable.

In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select particles containing no dislocation lines, particles containing several dislocations or particles containing many dislocations according to the purpose. It is also possible to select dislocations or curved dislocations introduced linearly with respect to a specific direction of the crystal orientation of the particles, or to introduce the dislocations throughout the particles, or to only a specific portion of the particles, for example, the particles. Introducing dislocation lines such as introducing dislocations introduced only in the fringe portion is preferable not only in the case of tabular grains but also in the case of amorphous grains typified by regular crystal grains or potato grains. Also in this case, it is a preferable form to limit to a specific part such as a vertex or a ridge of the particle.

The silver halide emulsion used in the present invention is a treatment for rounding grains as disclosed in, for example, European Patent Nos. 96,727B1 and 64412B1, or West German Patent No. 2,306,447C2. The surface may be modified as disclosed in JP-A-60-221320.

A structure in which the particle surface is flat is generally used.
It is sometimes preferable to intentionally form the unevenness.
JP-A-58-106532, JP-A-60-22132
Part of the crystals described in US Pat. No. 0, for example, a method of drilling holes in the centers of vertices or planes, or US Pat.
Raffle particles described in 643,966 are examples.

The grain size of the emulsion used in the present invention depends on the circle equivalent diameter of the projected area using an electron microscope, the sphere equivalent diameter of the grain volume calculated from the projected area and grain thickness, or the sphere equivalent diameter of the volume by the Coulter counter method. Can be evaluated. It can be used by selecting from ultrafine particles having a sphere-equivalent diameter of 0.05 micron or less, and coarse particles having a sphere-equivalent diameter of more than 10 microns. It is preferable to use grains having a size of 0.1 micron or more and 3 microns as the photosensitive silver halide grains.

The emulsion used in the present invention may be a so-called polydisperse emulsion having a wide grain size distribution or a monodisperse emulsion having a narrow size distribution, and can be selected and used according to the purpose. As a scale representing the size distribution, the variation coefficient of the projected area circle diameter of particles or the sphere equivalent diameter of volume may be used. When using a monodisperse emulsion, the coefficient of variation is 25% or less,
It is preferable to use an emulsion having a size distribution of 20% or less, and more preferably 15% or less.

In terms of the number of grains or weight, a monodisperse emulsion may be defined as a grain size distribution such that 80% or more of all grains fall within ± 30% of the average grain size. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in an emulsion layer having substantially the same color sensitivity are mixed in the same layer or different layers. Can be applied in multiple layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The photographic emulsion used in the present invention is described, for example, in "Physics and Chemistry of Photography" by Grafkid, published by P. Grafkides, Chimie et Ph.
ysique Photographie Pau
L Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.F. Duffi).
n, Photographic Emulsion C
chemistry (Focal Press, 196)
6)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al, Making and Coating Ph
otographic Emulsion, Foca
1, Press, 1964) and the like. That is, for example, the acidic method,
Either the neutral method or the ammonia method may be used, and the method of reacting the soluble silver salt and the soluble halogen salt may be, for example, a one-sided mixing method, a simultaneous mixing method, or a combination thereof. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used.
As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

The method of adding pre-precipitated silver halide grains to a reaction vessel for emulsion preparation is described in US Pat. Nos. 4,334,012, 4,301,241 and 4,150,994. Is more preferable. These can be used as seed crystals, and are effectively supplied as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size, and the addition method may be selected from total addition at once, addition in plural times or continuous addition. It is also effective in some cases to add particles having various halogen compositions in order to modify the surface.

A method for converting most or only a part of the halogen composition of silver halide grains by a halogen conversion method is described in US Pat. Nos. 3,477,852 and 4,14.
2,900, European Patents 273,429, 273.
No. 430 and West German Laid-Open Patent No. 3,819,241 and the like, which is an effective particle forming method. A solution of soluble halogen or silver halide grains can be added to convert it to a more sparingly soluble silver salt. It is possible to select from a method such as conversion at once, conversion by dividing into plural times, or continuous conversion.

In addition to the method of adding soluble silver salt and halogen salt at a constant concentration and a constant flow rate for grain growth, British Patent No. 1,
469,480, U.S. Pat. No. 3,650,757,
A particle forming method in which the concentration is changed or the flow rate is changed as described in U.S. Pat. No. 4,242,445 is also a preferable method. By increasing the concentration or increasing the flow rate, the amount of silver halide supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied if necessary. Furthermore, when adding a plurality of soluble silver salts having different solution compositions, or when adding a plurality of soluble halogen salts having different solution compositions, an addition method in which one is increased and the other is decreased is also an effective method. Is.

A mixer for reacting a solution of a soluble silver salt and a soluble halogen salt is described in US Pat. No. 2,996,287.
Issue 3, Issue 3,342,605, Issue 3,415,650
No. 3,785,777, West German Published Patent No. 2,55
It can be selected and used from the methods described in 6,885 and 2,555,364.

A silver halide solvent is useful for the purpose of promoting ripening. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. Other ripening agents can also be used. All of these ripening agents can be added to the dispersion medium in the reactor before adding the silver and halide salts,
It is also possible to add halide salts, silver salts or peptizers and to introduce them into the reactor. As another variant, the ripening agent can be introduced independently at the halide salt and silver salt addition stages.

Ammonia, thiocyanate (Rhodan potassium, Rhodan ammonium, etc.), organic thioether compound (for example, US Pat. Nos. 3,574,628 and 3,0).
No. 21,215, No. 3,057,724, No. 3,03
8,805, 4,276,374, 4,29
7,439, 3,704,130, 4,78
2,013, compounds described in JP-A-57-104926 and the like. ), A thione compound (for example, JP-A-53-82).
408, 55-77737, U.S. Pat. No. 4,22.
Growth of tetra-substituted thioureas described in 1,863, etc., compounds described in JP-A-53-144319), and silver halide grains described in JP-A-57-202531. Examples thereof include mercapto compounds, amine compounds (for example, JP-A No. 54-100717, etc.), etc. that can accelerate the reaction.

As the protective colloid used in the preparation of the emulsion of the present invention and as the binder of the other hydrophilic colloid layers, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives. A variety of synthetic hydrophilic polymer substances such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers; Can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Ph
oto. Japan. No. 16. P30 (1966)
You may use the enzyme-treated gelatin as described in,
Further, a hydrolyzate or an enzymatic hydrolyzate of gelatin can also be used.

The emulsion of the present invention is preferably washed with water for desalting and then dispersed in a newly prepared protective colloid. The temperature of washing with water can be selected according to the purpose, but it is preferably selected in the range of 5 to 50 ° C. The pH at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 2 and 10. More preferably, it is in the range of 3-8. The pAg at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 5 and 10. As a method of washing with water, a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugation method, a coagulation sedimentation method, or an ion exchange method can be selected and used. In the case of the coagulation sedimentation method, it can be selected from a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like.

During preparation of the emulsion of the present invention, for example, during grain formation,
The presence of a metal ion salt during the desalting step, chemical sensitization, or before coating is preferable depending on the purpose. When the grains are doped, they are preferably added at the time of grain formation, when the grains are modified, or when used as a chemical sensitizer, after grain formation and before the end of chemical sensitization. When doping the entire grain, a method of doping only the core portion of the grain, only the shell portion, only the epitaxial portion, or only the base grain can be selected. Specifically, for example, Mg, C
a, Sr, Ba, Al, Sc, Y, La, Cr, Mn,
Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, P
d, Re, Os, Ir, Pt, Au, Cd, Hg, T
l, In, Sn, Pb, Bi or the like can be used. These metals include ammonium salts, acetate salts, nitrate salts,
It can be added in the form of a salt that can be dissolved at the time of grain formation, such as a sulfate, a phosphate, a hydroxide or a hexacoordinated complex salt and a tetracoordinated complex salt. For example, CdBr ₂ , CdCl ₂ , Cd
(NO ₃ ) ₂ , Pb (NO ₃ ) ₂ , Pb (CH ₃ CO
O) ₂ , K ₃ [Fe (CN) ₆ ], (NH ₄ ) ₄ [Fe
(CN) ₆ ], K ₃ IrCl ₆ , (NH ₄ ) ₃ RhCl
₆ , K ₄ Ru (CN) _{6 and the} like. The ligand of the coordination compound can be selected from halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one type of metal compound, or may use two or more types in combination.

The metal compound is preferably added after being dissolved in water or a suitable solvent such as methanol or acetone.
In order to stabilize the solution, a method of adding a hydrogen halide aqueous solution (eg, HCl, HBr, etc.) or an alkali halide (eg, KCl, NaCl, KBr, NaBr, etc.) can be used. If necessary, acid
You may add alkali etc. The metal compound may be added to the reaction vessel before grain formation or during grain formation. In addition, a water-soluble silver salt (eg AgNO ₃ ) or an aqueous alkali halide solution (eg NaCl, KBr,
KI) and continuously added during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and the alkali halide may be prepared and continuously added at an appropriate time during grain formation. It is also preferable to combine various addition methods.

The method of adding a chalcogenide compound as described in US Pat. No. 3,772,031 during preparation of an emulsion may be useful in some cases. In addition to S, Se, and Te, cyanates, thiocyanates, selenocyanates, carbonates,
Phosphate and acetate may be present.

During grain formation of the silver halide emulsion of the present invention,
It is preferable to carry out reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization.

Here, the reduction sensitization is a method of adding a reduction sensitizer to a silver halide emulsion, pAg1 called silver ripening.
No. 7, a method of growing or aging in a low pAg atmosphere, or a method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

Known reduction sensitizers are stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, or two or more kinds of compounds can be used in combination. As reduction sensitizers, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but the range of 10 ^-7 to 10 ^-3 mol is suitable per mol of silver halide.

The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during grain growth. It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time during grain growth. Further, a reduction sensitizer may be added in advance to the water solubility of the water-soluble silver salt or the water-soluble alkali halide, and the silver halide grains may be precipitated using these aqueous solutions. Further, it is also a preferable method to add the solution of the reduction sensitizer in several times as the grains grow, or to continuously add the solution for a long time.

During the process of producing the emulsion of the present invention, acid for silver is used.
It is preferable to use an agent. What is an oxidizing agent for silver?
Has the effect of acting on metallic silver and converting it to silver ions
Refers to a compound. Especially the formation process of silver halide grains and
Very small silver particles by-produced during the chemical sensitization process
Compounds that can convert the above into silver ions are effective. here
The silver ions generated in are silver halide, silver sulfide, and selenium.
It may form a sparingly soluble silver salt such as silver halide, or silver nitrate.
A silver salt which is easily soluble in water may be formed. Oxidation for silver
The agent may be an inorganic substance or an organic substance. inorganic
Oxidizing agents include ozone, hydrogen peroxide and its addition
Thing (eg NaBO₂・ H₂O₂・ 3H₂O, 2Na
CO₃・ 3H₂O₂, Na_FourP₂O₇・ 2H₂O₂Two
Na₂SO_Four・ H₂O₂・ 2H₂O), peroxy acid salt
(Eg K₂S₂O₈, K₂C₂O ₆, K₂P
₂O₈), A peroxy complex compound (for example, K₂[Ti
(O₂) C₂O_Four] ・ 3H₂O, 4K₂SO_Four・ Ti
(O₂) OH / SO_Four・ 2H₂O, Na₃[VO
(O₂) (C₂H_Four)₂] ・ 6H₂O), permanganate
Salt (eg KMnO_Four), Chromates (eg, K₂
Cr₂O₇) Such as oxygenates, halogens such as iodine and bromine
Element, perhalogenate (eg potassium periodate) high
Valency metal salts (eg potassium hexacyanoferrate)
Um) and thiosulfonate.

Examples of the organic oxidant include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide and chloramine T). , Chloramine B).

Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents such as thiosulfonates, and organic oxidizing agents such as quinones. It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. It can be selected from the method of using an oxidant and then the reduction sensitization, the reverse method thereof, or the method of coexisting both. These methods can be selectively used in the grain forming step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, thiazoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, for example tria Theindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,
Many compounds known as antifoggants or stabilizers such as 3,3a, 7) tetraazaindenes), pentaazaindenes, etc. can be added. For example, U.S. Pat. Nos. 3,954,474 and 3,982,9
No. 47 and Japanese Patent Publication No. 52-28660 can be used. Japanese Patent Application Sho 6
There are compounds described in 2-47225. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to adding the effect of preventing fog and stabilizing during the preparation of the emulsion, the crystal wall of the grain is controlled, the grain size is reduced, the solubility of the grain is reduced, and the chemical sensitization is controlled. It can be used for various purposes such as controlling the arrangement of dyes.

When the present invention is used as a color light-sensitive material, at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer is provided on a support. Well, there is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed 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, and in a multilayer silver halide color photographic light-sensitive material, it is generally a unit photosensitive layer. The arrangement is such that the red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

A non-photosensitive layer such as an intermediate layer of each layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer may be formed, for example, in JP-A-61-437.
No. 48, No. 59-113438, No. 59-11344.
No. 0, No. 61-20037 and No. 61-20038 may contain a coupler and a DIR compound, and may contain a color mixing inhibitor which is usually used.

A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers 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. Also,
For example, JP-A-57-112751, JP-A-62-2003.
No. 50, No. 62-206541, No. 62-206543
As described in the publications, etc., a low-sensitivity emulsion layer may be provided on the side remote from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

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 (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
Can be installed in order.

Further, as described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange 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, a silver halide emulsion layer having the highest photosensitivity in the upper layer, a silver halide emulsion layer having a lower photosensitivity in the upper layer, and a lower layer than the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order.

In addition, for example, high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order.

Also, in the case of four or more layers, the arrangement may be changed as described above.

The light-sensitive material of the present invention contains the grain size, grain size distribution, halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498,
It is described in JP-A-59-214852.

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

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

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

Fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized,
Also, spectral sensitization is not necessary. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer.

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

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

Types of Additives RD17643 RD18716 RD307105 (December 1978) (November 1979) (November 1989) 1. Chemical sensitizer Page 23 Page 648 Right column Page 866 2. Sensitivity enhancer Page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer, page 649, right column, 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Fogging prevention page 24 to 25 page 649 right column 868 to 870 page agents and stabilizers 6. Light absorbers, pages 25 to 26, page 649, right column, page 873, filter dyes, to page 650, left column, ultraviolet absorbers 7. Stain page 25 right column page 650 left column page 872 Inhibitor to right column 8. Dye image Page 25 Page 650 Left column Page 872 Stabilizer 9. Hardener 26 pages 651 pages left column 874-875 pages 10. Binder page 26 page 651 left column 873 to page 874 11. Plasticizers, lubricants Page 27 Page 650 Right column Page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Static page 27 page 650 right column 876 to 877 inhibitor 14. Matting agent pp. 878-879 Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, fixing is performed by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound capable of being converted into a light-sensitive material.

The light-sensitive material of the present invention can be incorporated into US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention can be incorporated into Japanese Patent Laid-Open No. 1-1060.
It is preferable to include a compound described in No. 52, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing.

International Publication WO88 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912 or EP317,308A,
U.S. Pat. No. 4,420,555, Japanese Patent Laid-Open No. 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 are described in Research Disclosure No. 17643, VII-CG, and No. 17643. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
Those described in European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone type compounds and pyrazoloazole type compounds are preferable, for example, US Pat. Nos. 4,310,619 and 4,351,8.
97, European Patent 73,636, US Patent 3,0.
61,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238 and 60.
-35730, 55-118034, 60-1
Those described in US Pat. No. 8,5951, US Pat. Nos. 4,500,630, 4,540,654, 4,556,630 and International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A, U.S. Patents 3,446,622, 4,333,999.
Issue No. 4,775,616, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,08.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. Of 307105
Item VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258, British Patent No. 1,14.
Those described in 6,368 are preferable. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,774,181 and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

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 RD1 above.
7643, Item VII-F and No. 307105, VII
-Patents described in paragraph F or JP-A-57-151
944, 57-154234, 60-1842.
No. 48, No. 63-37346, No. 63-37350.
U.S. Pat. Nos. 4,248,962 and 4,782.
Those described in No. 012 are preferable.

A coupler capable of releasing a nucleating agent or a development accelerator imagewise during development is described in British Patent 2,093.
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Compounds releasing a fog 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 JP-A-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Competitive couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. , RD. No.
11449, 24241, JP-A-61-201247.
Bleach accelerator releasing couplers described in U.S. Pat.
Examples thereof include ligand releasing couplers described in U.S. Pat. No. 555,477, couplers releasing a leuco dye described in JP-A-63-75747, and couplers releasing a fluorescent dye described in U.S. Pat. No. 4,774,181. .

The coupler used in the present invention can be introduced into the photographic 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 point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate,
Decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or Esters of phosphonic acid (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-) Diethyl dodecane amide, N, N-diethyl lauryl amide, N-tetradecyl pyrrolidone, etc.),
Alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate) , Trioctyl citrate, etc.), aniline derivatives (N, N
-Dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-257747 are used.
272248, and 1,2-benzisothiazolin-3-one, n-butyl, p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol described in JP-A No. 1-80941. It is preferable to add various antiseptics or antifungal agents such as 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

Suitable supports which can be used in the present invention are described in, for example, RD. No. 17643, page 28, ibid.
No. 18716, page 647, right column to page 648, left column, and ibid. 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T
_1/2 can be measured according to a method known in the art. For example, A Green (A. Gre
en) et al. in Photographic Science and Engineering (Photogr. Sci. En.
g. ), Vol. 19, No. 2, by using the type of Swellometer described (swelling meter) pp 124-129, can be measured, T _1/2 is 30 ° C. in a color developing solution, 3 minutes 15 seconds processing 90% of the maximum swollen film thickness reached when
It is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150.
~ 500% is preferred.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, ibid.
18716, page 651, left column to right column, and the same No. Thirty
The development can be carried out by a usual method described in 7105, pages 880 to 881.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-.
N, N-diethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-
Examples thereof include N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, especially 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole compound, a benzothiazole compound or a mercapto compound. It is common to include such development inhibitors or antifoggants. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acid, 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 agents. Agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclo Hexane diamine tetraacetic 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 salts thereof can be mentioned as representative examples.

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.

PH of these color developing solution and black and white developing solution
Is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and 500 ml or less by reducing the bromide ion concentration in the replenishing solution. 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 the 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-mentioned aperture ratio is preferably 0.1 or less, more preferably 0.1. It is 001-0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-82 is available.
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps,
For example, it is preferably applied in all steps of bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. 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 within a range of 2 to 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. it can.

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, for example, iron (III) organic complex salts 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 bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. Compounds having a mercapto group or a disulfide group described in 17129 (July 1978) and the like;
Thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5.
Thiourea derivatives described in No. 61; West German Patent No. 1,12
7,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410 and 2,748,
No. 430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40,943, 49-59,644, 53-94,927, and 54-35, 727, 5
Compounds described in JP-A Nos. 5-26,506 and 58-163,940; bromide ion and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of having a large accelerating effect, and in particular, US Pat. No. 3,893,
858, West German Patent 1,290,812, JP-A-5
The compounds described in 3-95,630 are preferred. Furthermore,
The compounds described in US Pat. No. 4,552,834 are also preferred. 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 preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, and specifically, acetic acid and propionic acid are preferable.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. It is commonly used, especially ammonium thiosulfate being the most widely used. Also,
Thiosulfates and thiocyanates, thioether compounds,
A combined use of thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, or 2 for adjusting the pH. -It is preferable to add 0.1 to 10 mol / liter of imidazoles such as methylimidazole.

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 processing 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 step, it is preferable that the stirring is strengthened as much as possible. As a specific method for strengthening the stirring, a method of causing a jet of a processing solution to collide with 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 stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator.

The automatic developing machine used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, 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.
Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage counterflow method is described in the Journal of the Societ.
y of Motion Picture and T
Evolution Engineers Volume 64,
P. 248 to 253 (May 1955 issue).

According to the multistage countercurrent system described in the above-mentioned document,
Although the amount of water to be washed can be significantly reduced, the increase in the residence time of water in the tank causes problems such as bacteria breeding and the resulting suspended matter adhering to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. In addition, JP-A-57
No. 8,542, isothiazolone compounds, siabendazoles, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, edited by Hygiene Technology Society, "Microbial sterilization, sterilization, and antifungal technology" (1982)
It is also possible to use the fungicides described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal Society (1986).

The 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 set variously depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes,
A range of 30 seconds to 5 minutes at 25 to 40 ° C is preferably 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 stabilizing treatment, JP-A-57-8543 and 58-58 are used.
All known methods described in Nos. 14834 and 60-220345 can be used.

In addition, the washing treatment may be followed by a further stabilizing treatment. As an example of the stabilizing treatment, a stabilizing agent containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing, is used. You can mention the bath. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

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

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

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, US Pat.
Indoaniline compounds described in No. 342,597, No. 3,342,599, Research Disclosure No. 14, 850 and the same No. Examples of the Schiff base type compounds described in JP-A No. 15,159, 15, aldol compounds described in JP-A No. 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A No. 53-135628. be able to.

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64339 and JP-A-57-14.
Nos. 4547 and 58-115438.

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

The silver halide light-sensitive material of the present invention comprises
For example, U.S. Pat. No. 4,500,626, JP-A-60-
No. 133449, No. 59-218443, No. 61-2
It can also be applied to the photothermographic materials described in 38056 and EP 210,660A2.

The silver halide light-sensitive material of the present invention, when applied to a film unit with a lens described in JP-B-2-32615 and JP-B-3-39784,
It is more effective and more effective.

[0243]

【Example】

Example 1 1 kg of gelatin and 18 g of potassium bromide were dissolved in 25 liters of water, pH was adjusted to 5 and temperature was adjusted to 60 ° C. To this, 3.80 liters of an aqueous solution containing 380 g of silver nitrate,
An aqueous solution containing 260 g of potassium bromide and 11 g of potassium iodide in 3.80 liters was added over 5 minutes while controlling pAg at 6.8 (first stage). Continuing,
10.6 liter of an aqueous solution containing 2120 g of silver nitrate was added to 1
An aqueous solution containing 1440 g of potassium bromide and 63 g of potassium iodide in 0.6 liter was added over 10 minutes while controlling pAg to 6.8 (second step).

Next, washing with water was carried out twice by coagulation sedimentation method using a water-soluble polymer while adjusting pAg to 7.5 at 35 ° C. Add 1 kg of gelatin, pAg 8.0,
Redispersion was carried out under the condition of pH 6.5. Thus, a cubic emulsion having a sphere equivalent diameter of 0.15 μm was obtained. This is Emulsion A.

Emulsion A was divided into two equal parts and subjected to the following sulfur sensitization and selenium / sulfur sensitization, respectively. <Sulfur Sensitization> Sensitizing dye I shown below was used as silver halide 1
1.3 × 10 ⁻³ mol per mol was added, and the mixture was aged at 65 ° C. for 10 minutes. Sensitizing dye I

[0246]

[Chemical 35] Subsequently, chloroauric acid, potassium thiocyanate and sodium thiosulfate were each added per mol of silver halide,
4.0 x 10 ^-5 mol, 4.0 x 10 ^-3 mol, 4.0 x 1
Add 0 ^-3 moles, 6.0 × 10 ^-5 moles, and add 1/1 at 65 ° C.
It was aged only for the time when the sensitivity at the time of 00 second exposure was maximized. <Sulfur / Selenium Sensitization> Under the above sulfur sensitization conditions, chloroauric acid, potassium thiocyanate and sodium thiosulfate were added, and at the same time, the compound Se-40 in the specific example of the selenium sensitizer was 1.0 ×. Add 10 ^-5 mol and add 1 at 65 ° C
/ 100 sec. Aging was performed for a time such that the sensitivity at the time of exposure becomes maximum.

The emulsion prepared as described above, to which the hydrazine compound of the present invention was added at the ratio shown in Table 1, was coated on a cellulose triacetate support under the following coating conditions to prepare Sample 1
01-118 were created. Emulsion coating conditions <Emulsion layer> -Emulsion ... Chemically sensitized emulsion shown in Table 1 0.5 g / m ² -Amount of hydrazine compound of the present invention shown in Table 1-Coupler 1.0 g / m ²

[0248]

[Chemical 36] ・ Tricresyl phosphate 0.8 g / m ²・ Gelatin 2.5 g / m ² <Protective layer> ・ Gelatin 3.0 g / m ²・ Hardener 0.30 g / m ²

[0249]

[Chemical 37] 14 these samples under the conditions of 40 ℃, 70% relative humidity
After standing for a period of time, the film was exposed for 1/100 second through a SC-52 filter manufactured by Fuji Film and a continuous wedge, and the following color development processing was performed.

Treatment Step Temperature (° C.) Time 1. Pre-bath 27 ± 1 10 seconds 2. Backing removal 27-385 seconds and spray water washing 3. Color development image 41.1 ± 0.1 3 minutes 4. Stop 27-38 30 seconds 5. Bleach promotion 27 ± 1 30 seconds 6. Bleach 38 ± 1 3 minutes 7. Washing with water 27-38 1 minute 8. Stationary 38 ± 12 2 minutes 9. Washing with water 27-38 2 minutes 10. Stability 27-38 10 seconds Prescription of each treatment liquid (1) Pre-bath Prescription value Water at 27-38 ° C 800 ml Borax (10-hydrate) 20.0 g Sodium sulfate (anhydrous) 100 g Sodium hydroxide 1.0 g Water In addition, 1.00 liter pH (27 ° C.) 9.25 (3) Color developer Water having a prescribed value of 21 to 38 ° C. 850 ml Kodak anti-calcium No. 4 2.0 ml sodium sulfite (anhydrous) 2.0 g Toastman Antifog No. 9 0.22 g Sodium bromide (anhydrous) 1.20 g Sodium carbonate (anhydrous) 25.6 g Sodium bicarbonate 2.7 g Color developing agent; 4-Amino-3-methyl 4.0 g -N-ethyl-N- (β -Methanesulphonamidoethyl) -aniline 1.00 liter by adding water pH (27 ° C) 10.20 (4) Stop water with prescription value 21-38 ° C 900 ml 7.0N sulfuric acid 50 ml Water by adding 1.00 liter pH (27 ° C) 0.9 (5) Bleach accelerating solution Prescription value Water 900 ml Sodium metabisulfite (anhydrous) 10.0 g Glacial acetic acid 25.0 ml Sodium acetate 10.0 g EDTA-4Na 0.7 g PBA 5.5 g Water In addition 1.0 liter pH (27 ° C.) 3.8 ± 0.2 PBA stands for 2-dimethylaminoethylisothiourea dihydrochloride. (6) Bleaching solution Prescription value Water at 24-38 ° C 800 ml Gelatin 0.5 g Sodium persulfate 33.0 g Sodium chloride 15.0 g Sodium monophosphate (anhydrous) 9.0 g Phosphoric acid (85%) 2.5 ml Water 1.0 liter pH (27 ° C.) 2.3 ± 0.2 (8) Fixing Prescription value Water at 20 to 38 ° C. 700 ml Kodak anti-calcium No. 4 2.0 ml 58% ammonium thiosulfate solution 185 ml Sodium sulfite (anhydrous) 10.0 g Sodium bisulfite (anhydrous) 8.4 g Water was added to 1.0 liter pH (27 ° C) 6.5 (10) Stable prescription value 21 -38 ° C. Water 1.0 liter Kodak Stabilizer Additive 0.14 ml Formalinde (37.5% solution) 1.50 ml The concentration of each treated sample was measured with a green filter. The sensitivity and fog value of each sample were determined from the measurement results. The sensitivity was represented by the relative value of the reciprocal of the exposure amount that gives a density of fog + 0.2.

After exposure, a sample that was left under conditions of 50 ° C. and 60% relative humidity for 7 days and a sample that had been similarly stored in a freezer after exposure were simultaneously developed and their sensitivities were compared. The product stored at 50 ° C and 60% was less sensitive than the product stored in the freezer. This phenomenon is called latent image regression.

The magnitude of latent image regression is the ratio of the sensitivity values (50) defined by the reciprocal of the exposure amount that gives a density of fog + 0.2.
The sensitivity is shown in Table 1 in terms of the sensitivity of the product stored at 60 ° C./the sensitivity of the product stored in the freezer).

Further, the sample left at 40 ° C. and 70% relative humidity for 14 hours was continuously examined.
The sample that had been left for a day and the sample that had been stored in the freezer instead of being left at 50 ° C. and 60% were simultaneously exposed and developed, and their sensitivities were compared. The product stored at 50 ° C and 60% was more sensitized than the product stored in the freezer.

The magnitude of the sensitization is the ratio of the sensitivity values defined by the reciprocal of the exposure amount giving a density of fog + 0.2 (50 ° C., 6
It is expressed in Table 1 as (sensitivity of 0% preserved product / definition of preserved freezer product).

The results are shown in Table 1. It can be seen from Table 1 that the samples of the present invention have high sensitivity and the change in performance due to storage conditions before and after exposure is extremely small.

The sample of the present invention suppresses an increase in fogging with a minimum and achieves an increase in sensitivity. The sensitivity of the sample of the present invention was significantly higher than the sensitivity expected from the effect of selenium sensitization and the effect of the hydrazine compound in Comparative Example.

In the samples of the present invention, the magnitude of the change in performance with respect to the storage conditions before and after exposure was smaller than that expected from the effect of selenium sensitization and the effect of the hydrazine compound in Comparative Examples, and expected from Comparative Examples. Achieving stability that cannot be achieved.

[0258]

[Table 1] Example 2 Using the emulsion prepared in Example 1, multi-layer color light-sensitive materials 201 to 210 each having layers having the following compositions were prepared on a triacetyl cellulose support.

The coating amount of each component is the amount of silver expressed in units of g / m ² for silver halide and colloidal silver.
The amounts of couplers, additives and gelatin are shown in units of g / m ² , and the sensitizing dyes are shown in the number of moles per mole of silver halide in the same layer.

The emulsions other than the fifth layer are cubic emulsions which have been subjected to normal gold / sulfur sensitization. First layer: Antihalation layer Black colloidal silver 0.20 Gelatin 2.30 Second layer: Intermediate layer Cpd-1 0.10 Gelatin 0.80 Third layer: First red-sensitive emulsion layer Grain size 0.06μ A silver iodobromide cubic emulsion containing 3.5 mol% of silver iodide. Silver 0.19 ExS-4 1.2 × 10 ⁻³ ExC-1 0.29 ExC-2 0.19 ExC-3 0.05 Solv-1 0.10 Solv-2 0.10 Gelatin 2.40 4th Layer: Second red-sensitive emulsion layer A silver iodobromide cubic emulsion having a grain size of 0.11 μm and containing 3.5 mol% of silver iodide. Silver 0.10 ExS-4 5.1 × 10 ^-4 ExC-1 0.12 ExC-2 0.04 Solv-1 0.05 Solv-2 0.05 Gelatin 0.85 Fifth layer: third red sensation Emulsion layer The emulsion prepared in Example 1. The amount of the hydrazine compound of the present invention shown in Table 2 ExC-1 0.085 ExC-2 0.055 Solv-1 0.03 Solv-2 0.03 Gelatin 1.10 6th layer: Intermediate layer Cpd-1 0. 13 Gelatin 0.65 Seventh layer: first green-sensitive emulsion layer A silver iodobromide cubic emulsion having a grain size of 0.06 μm and containing 0.5 mol% of silver iodide. Silver 0.42 ExS-2 1.26 × 10 ⁻³ ExS-3 1.40 × 10 ⁻⁴ ExM-1 0.25 ExM-2 0.10 ExM-3 0.05 Solv-1 0.42 Gelatin 2 .60 Eighth layer: second green emulsion layer A cubic silver iodobromide cubic emulsion having a grain size of 0.11 μm and containing 0.5 mol% of silver iodide. Silver 0.12 ExS-2 8.0 × 10 ^-4 ExS-3 9.0 × 10 ^-5 ExM-1 0.07 ExM-2 0.03 ExM-3 0.015 ExM-4 0.008 Solv- 1 0.15 Gelatin 0.60 Ninth layer: third green emulsion layer A silver iodobromide cubic emulsion having a grain size of 0.16 μm and containing 0.5 mol% of silver iodide. Silver 0.42 ExS-2 7.8 × 10 ^-4 ExS-3 8.8 × 10 ^-5 ExM-1 0.08 ExM-2 0.03 ExM-3 0.02 ExM-4 0.01 Solv- 1 0.14 Gelatin 1.90 10th layer; Yellow filter layer Yellow colloidal silver 0.15 Cpd-1 0.10 Cpd-2 0.05 Gelatin 1.0 11th layer: 1st blue sensitive emulsion layer Grain size Cubic silver iodobromide emulsion containing 0.06 µm and 0.5 mol% of silver iodide. Silver 0.20 ExS-1 2.5 × 10 ⁻³ ExC-1 0.03 ExY-1 0.70 Solv-1 0.25 Gelatin 1.10 12th layer: 2nd blue-sensitive emulsion layer Grain size 0. A silver iodobromide cubic emulsion containing 2.0 mol% of silver iodide at 12 μm. Silver 0.22 ExS-1 2.0 × 10 ⁻³ ExC-1 0.01 ExY-1 0.26 Solv-1 0.09 Gelatin 0.45 13th layer: third blue-sensitive emulsion layer Grain size 0. A cubic silver iodobromide emulsion containing 3.5 mol% of silver iodide at 16 μm. (Aspect ratio) Silver 0.37 ExC-1 0.003 ExY-1 0.07 Solv-1 0.02 Gelatin 0.60 14th layer: 1st protective layer UV-1 0.05 UV-2 0.24 Solv-2 0.12 Gelatin 0.50 Fifteenth layer: Second protective layer B-1 (diameter 1.70μ) 0.01 B-1 (diameter 1.70μ) 0.01 B-3 0.09 H- 10.30 In addition to the above, 1,2-benzisothiazolin-3-one (200 ppm on average for gelatin), n-
Butyl-p-hydroxybenzoate (approx. 1000 p
pm) and 2-phenoxyethanol (approx. 10000)
ppm) was added.

Further, B-4, B-5, W-1, W-2, F
-1 to F-8 and F-9 to F-12 are also added.

The structural formulas of the compounds used to prepare the samples are shown in Chemical Formulas 38 to 48 below.

For the fifth layer (third red-sensitive emulsion layer), Example 1 was used.
The emulsion prepared in 1. and the amount of the hydrazine compound of the present invention shown in Table 2 were used.

These samples were left under conditions of 40 ° C. and 70% relative humidity for 14 hours and then passed through a continuous wedge to 1 /
After exposure for 100 seconds, the same color development process as in Example 1 was performed.

The density of each treated sample was measured with a red filter. The sensitivities of the respective samples were obtained from the measurement results, and the relative values with the value of the sample 201 as 100 are shown in Table 2.

After exposure, a sample left under conditions of 50 ° C. and 60% relative humidity for 7 days and a sample similarly stored in a freezer after exposure were simultaneously developed and their sensitivities were compared. The product stored at 50 ° C and 60% was less sensitive than the product stored in the freezer. This phenomenon is called latent image regression.

The size of latent image regression is the ratio of the sensitivity values (50) defined by the reciprocal of the exposure amount that gives a density of fog + 0.2.
The sensitivity is shown in Table 2.

Further, the sample left at 40 ° C. and 70% relative humidity for 14 hours was continuously examined.
The sample that had been left for a day and the sample that had been stored in the freezer instead of being left at 50 ° C. and 60% were simultaneously exposed and developed, and their sensitivities were compared. The product stored at 50 ° C and 60% was more sensitized than the product stored in the freezer.

The magnitude of the sensitization is the ratio of the sensitivity values defined by the reciprocal of the exposure amount giving a density of fog + 0.2 (50 ° C., 6
It is expressed in Table 2 as follows: sensitivity of 0% preserved product / definition of preserved freezer product).

The results are shown in Table 2.

[0271]

[Table 2] The results can be considered in exactly the same manner as in Example 1, and the usefulness of the present invention will be clear. Example 3 By the method described in U.S. Pat. No. 4,797,354, parallel twin tabular grains having a narrow grain size distribution and mainly hexagonal grains were prepared. After forming a tabular inner core of silver bromide, a first shell of silver iodobromide having a silver iodide content of 11 mol% was grown, and then a silver iodide content of 13 mol% was grown.
A second shell of silver iodobromide was grown. The silver contents of the inner core, the first shell and the second shell are 8%, 59% and 33%.
It became to be%. The average particle size was 0.85 microns and the coefficient of variation of particle size was 19%. The Asbect ratio of the diameter divided by the thickness was 9.5. Observation with a transmission electron microscope confirmed that dislocation lines were mainly contained in the fringe portions of the grains.

The same experiment as in Example 1 was carried out using the obtained emulsion, and the usefulness of the present invention was confirmed even with this emulsion. Example 4 The average iodine content was 5 mol%, the iodine content in the core part was 1 mol%, the iodine content in the shell part surrounding it was 38 mol%, the iodine content in the outermost part was 1 mol%, and the average particle size was average. Is 0.6 μm and the coefficient of variation of particle size distribution is 0.09
A slightly rounded monodisperse triple structure octahedral emulsion was prepared.

The same experiment as in Example 1 was carried out using the obtained emulsion, and the usefulness of the present invention was confirmed even with this emulsion. Example 5 Examples 1 to 4 were carried out by changing only the color development processing step as follows. The results were similar, and the utility of the present invention could be confirmed. (Processing process) Process processing time Processing temperature Color development 2 minutes 45 seconds 38 ℃ Bleaching 3 minutes 00 seconds 38 ℃ Washing with water 30 seconds 24 ℃ Settling 3 minutes 00 seconds 38 ℃ Washing with water (1) 30 seconds 24 ℃ Water Washing (2) 30 seconds 24 ° C Stability 30 seconds 38 ° C Drying 4 minutes 20 seconds 55 ° C Next, the composition of the treatment liquid is 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-methylaniline sulfate 4.5 Add water 1.0 liter pH 10.05 (bleaching solution) (Unit g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 10.0 3-Mercapto-1,2,4-triazole 0.03 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Water was added to 1.0 liter pH (ammonia 6.0 (fixing solution) (unit: g) Disodium salt of ethylenediaminetetraacetic acid 0.5 Ammonium sulfite 20.0 Ammonium thiosulfate aqueous solution (700 g / l) 295.0 ml Add water 1.0 Liter pH 6.7 (Stabilizing liquid) (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

[0274]

[Chemical 38]

[0275]

[Chemical Formula 39]

[0276]

[Chemical 40]

[0277]

[Chemical 41]

[0278]

[Chemical 42]

[0279]

[Chemical 43]

[0280]

[Chemical 44]

[0281]

[Chemical formula 45]

[0282]

[Chemical formula 46]

[0283]

[Chemical 47]

[0284]

[Chemical 48]

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and a hydrophilic colloid layer on a support, and at least one silver halide contained in the silver halide emulsion layer. A silver halide photographic light-sensitive material characterized in that the emulsion is selenium-sensitized and contains at least one compound represented by the following general formula (I) in at least one of the silver halide emulsion layer and the hydrophilic colloid layer. . 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 photographic light-sensitive material according to claim 1, which is spectrally sensitized with a sensitizing dye. 3. The compound represented by the general formula (I) is a compound selected from the following general formulas (II), (III) and (IV), wherein: The silver halide photographic light-sensitive material described in. General formula (II) General formula (III): General formula (IV): In the formula, R ₅ , R ₆ , R ₇ and R ₈ are each an alkyl group,
Represents 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 represent a methine group. However, R ₅ , R ₆ , R ₇ , R ₈ , Z ₁ ,
Of Z ₄ and Z _5, the carbon atom directly bonded to the nitrogen atom of hydrazine is not substituted with an oxo group. 4. At least one silver halide emulsion contained in the silver halide emulsion layer is chemically sensitized by both selenium sensitization and sulfur sensitization. A silver halide photographic light-sensitive material as described in the above item.