JPH0764233A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity, to lower fog, and to obtain superior latent image stability and storage stability with the lapse of time and low illumination- reciprocity law failure characteristics by incorporating a specified compound and silver halide grains undergoing grain formation and/or chemical sensitization in the presence of this specified compound. CONSTITUTION:The silver halide grains contains the compound represented by formula I and they have been grown and/or chemically sensitized in the presence of the compound represented by formula II or the like, and in formulae I and II, each of R1-R4 is H, alkyl, alkenyl, alkynyl, aryl, or the like; each of R5-R8 is a substituent; each of L1 and L2 is a methine group; Z1 is O, S, Se, Te, or the like; each of R9-R11 is H, alkyl, alkenyl, alkynyl, or the like; each of R1 and R2, R3 and R4, R5 and R6, R7 and R8, and R9 and R10 may combine with each other to form a ring; R12 is alkyl, alkenyl, alkynyl, or the like; and M is a cation.

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 emulsion used in a silver halide photographic light-sensitive material, and more specifically, it has high sensitivity and low fog and has latent image stability, stability over time and reciprocity law failure characteristics. The present invention relates to a silver halide photographic emulsion used in an improved silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, the demand for silver halide emulsions for photography has become more and more severe, and for example, high standards have been made for photographic performance such as high sensitivity and excellent graininess, high sharpness, high optical density and low fog. There is. These challenges are high sensitivity,
It is often solved by a low fog silver halide emulsion manufacturing technique.

Conventionally, silver halide photographic light-sensitive materials tend to cause fog due to the presence of nuclei that can be developed even if they are not exposed to light. In particular, fog is generated during storage with a decrease in sensitivity or gradation. In many cases, this will cause deterioration.

Further, stability in the period from exposure to development, that is, latent image stability is also an important characteristic. Silver halide forms a latent image when exposed to light, but when the latent image is unstable, it regresses or is intensified over time or due to heat or the like. This phenomenon appears as a decrease or increase in sensitivity in terms of photographic performance.

Latent image stability is determined by the method and structure of silver halide, surface treatment, chemical and spectral sensitization methods, binder properties such as gelatin, type of hardener, pH of coating solution and silver ion. It is greatly affected by the concentration.

Various methods have been proposed for increasing the latent image stability. For example, a method using a benzothiazolium described in JP-A No. 50-94918 and a Schiff base described in JP-A No. 57-100425 is disclosed.

However, even if these techniques are used, the latent image stability is not sufficiently improved, the sensitivity is lowered, and the fog is increased, so that the development of a further improved technique has been desired.

In order to reduce such an unfavorable phenomenon as much as possible, a compound conventionally known as an antifoggant or stabilizer, for example, US Pat. No. 2,406,927.
1-phenyl-5-mercaptotetrazole or 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, etc. described in JP No. 3,804,633, JP-B-39-2825, etc. The technique of adding to a silver halide emulsion is used in combination with the technique of improving latent image stability.

[0009] However, the combination of these materials alone has not been a technique for solving the problem of storage stability over time.

Further, Japanese Patent Laid-Open No. 2-108038 and Japanese Patent Laid-Open No. 3-19
Japanese Patent Publication No. 4540 discloses that aging stability is improved by using an oxidizing agent for silver such as thiosulfonate. However, although these techniques certainly suppress the increase in fog over time, they have the drawbacks that the effect of improving latent image regression is insufficient and that the low-illuminance reciprocity law failure characteristic deteriorates.

[0011]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity, low fog, latent image stability, storability with time, and low illuminance failure characteristics. To provide photographic emulsion.

[0012]

The above object of the present invention is to provide a compound containing a compound represented by the following general formula (I) and represented by any one of the following general formulas (II) to (IV). In a silver halide photographic emulsion characterized by containing grain-forming and / or chemically sensitizing silver halide grains.

[0013]

[Chemical 3]

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₅ , R ₆ , R ₇ and Each R ₈ represents a substituent. L ₁ and L ₂ each represent a methine group,
Z ₁ is an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom,
It represents -C (R ₉ ) (R ₁₀ )-or -N (R ₁₁ )-. R ₉ , R ₁₀ and R ₁₁ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Also, R ₁
And R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , R ₇ and R ₈ , R ₉ and R ₁₀ ,
Each may be bonded to form a ring.

[0015]

[Chemical 4]

In the formula, R ₁₂ , R ₁₃ and R ₁₄ each represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and M represents a cation. Q represents a divalent linking group, and m is 0 or 1. Also, R ₁₂ , R ₁₃ , R ₁₄ ,
Qs may combine with each other to form a ring.

The compounds of the general formulas (II) to (IV) are
It may be a polymer containing a divalent group derived from the structure represented by (II) to (IV) as a repeating unit.

More preferably, when the compound represented by the general formula (I) is a compound in which R ₃ and R ₄ are bonded to each other to form a ring, the effect is further enhanced.

The present invention will be described in more detail below.

First, the compounds represented by the above general formulas (I) to (IV) will be described.

In the general formulas (I) to (IV), R ₁ ,
Examples of the alkyl group represented by R ₂ , R ₃ , R ₄ , R ₁₂ , R ₁₃ and R ₁₄ include methyl, ethyl, propyl, i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl and cyclohexyl. , Octyl, dodecyl and the like. These alkyl groups further include halogen atoms (eg chlorine, bromine, fluorine etc.), alkoxy groups (eg methoxy, ethoxy, 1,1-dimethylethoxy, hexyloxy, dodecyloxy etc.), aryloxy groups (eg phenoxy, naphthyl). Oxy, etc.), aryl groups (eg phenyl, naphthyl etc.), alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, 2-ethylhexylcarbonyl etc.),
Aryloxycarbonyl group (eg phenoxycarbonyl, naphthyloxycarbonyl etc.), alkenyl group (eg vinyl, allyl etc.), heterocyclic group (eg 2-pyridyl, 3-pyridyl, 4-pyridyl, morpholyl, piperidyl, piperazyl, pyrimidyl, Pyrazolyl, furyl etc.), alkynyl group (eg propargyl), amino group (eg amino, N, N-dimethylamino, anilino etc.),
It may be substituted with a cyano group, a sulfonamide group (eg, methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, phenylsulfonylamino, etc.).

R ₁ , R ₂ , R ₃ , R ₄ , R ₁₂ , R ₁₃ and R ₁₄
Examples of the alkenyl group represented by are vinyl, allyl and the like.

R ₁ , R ₂ , R ₃ , R ₄ , R ₁₂ , R ₁₃ and R ₁₄
Examples of the alkynyl group represented by include propargyl.

R ₁ , R ₂ , R ₃ , R ₄ , R ₁₂ , R ₁₃ and R ₁₄
Examples of the aryl group represented by include phenyl, naphthyl and the like.

R ₁ , R ₂ , R ₃ , R ₄ , R ₁₂ , R ₁₃ and R ₁₄
The heterocyclic group represented by, for example, pyridyl group (for example, 2-pyridyl, 3-pyridyl, 4-pyridyl, etc.), thiazolyl group, oxazolyl group, imidazolyl group, furyl group, thienyl group, pyrrolyl group, pyrazinyl group, Examples thereof include a pyrimidinyl group, a pyridazinyl group, a selenazolyl group, a sulforanyl group, a piperidinyl group, a pyrazolyl group and a tetrazolyl group.

The above alkenyl group, alkynyl group, aryl group and heterocyclic group are all R ₁ , R ₂ , R ₃ , R ₄ and
The alkyl group represented by R ₁₂ , R ₁₃ and R ₁₄ and a group similar to the group shown as the substituent of the alkyl group can be substituted.

The substituent represented by R ₅ , R ₆ , R ₇ and R ₈ is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group or an alkoxy group. Carbonyl group, aryloxycarbonyl group, sulfonamide group, sulfamoyl group, ureido group, acyl group, carbamoyl group, amide group, sulfonyl group, amino group, cyano group, nitro group, mercapto group, alkylthio group, arylthio group, alkenylthio group Represents a group, a heterocyclic thio group, a hydrogen atom and the like. These groups may be substituted with the same groups as the alkyl groups represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₁₂ , R ₁₃ and R ₁₄ and the groups shown as the substituents of the alkyl groups. it can.

Examples of the ring formed by R ₁ and R ₂ include benzene, naphthalene, thiophene, pyridine, furan, pyrimidine, cyclohexene, pyran, pyrrole,
Examples include rings such as pyrazine and indole.

R ₃ and R ₄ preferably form a ring, and examples of the ring that can be formed include rings such as piperidine, pyrrolidine, morpholine, pyrrole, pyrazole, piperazine and the like.

The ring formed by R ₅ and R ₆ and R ₇ and R ₈ is, for example, benzene, naphthalene, thiophene, pyridine, furan, pyrimidine, cyclohexene, pyran,
Examples include rings such as pyrrole, pyrazine, and indole.

The above rings are R ₁ , R ₂ , R ₃ , R ₄ , R ₁₂ ,
The alkyl group represented by R ₁₃ and R ₁₄ and a group similar to the group mentioned as the substituent of the alkyl group can be substituted.

The methine group represented by L ₁ and L ₂ may have a substituent, and examples of the substituent include an alkyl group, an aryl group, a halogen atom, an alkoxy group, an aryloxy group,
Examples thereof include an alkoxycarbonyl group and an aryloxycarbonyl group. These groups further include R ₁ , R ₂ , R ₃ ,
The alkyl group represented by R ₄ , R ₁₂ , R ₁₃ and R ₁₄ and a group similar to the groups mentioned as the substituent of the alkyl group can be substituted.

The group represented by M is preferably a metal ion or an organic cation. Examples of the metal ion include lithium ion, sodium ion, potassium ion and the like, and examples of the organic cation include ammonium ion (ammonium, tetramethylammonium,
Tetrabutylammonium, etc.), phosphonium ion (tetraphenylphosphonium), guanidyl and the like.

The general formula (I) used in the present invention is described below.
Specific examples of the compound represented by (IV) (hereinafter referred to as the compound of the present invention) will be given, but the present invention is not limited thereto.

[0035]

[Chemical 5]

[0036]

[Chemical 6]

[0037]

[Chemical 7]

[0038]

[Chemical 8]

[0039]

[Chemical 9]

[0040]

[Chemical 10]

[0041]

[Chemical 11]

[0042]

[Chemical 12]

[0043]

[Chemical 13]

[0044]

[Chemical 14]

[0045]

[Chemical 15]

[0046]

[Chemical 16]

[0047]

[Chemical 17]

[0048]

[Chemical 18]

[0049]

[Chemical 19]

Specific synthetic examples of the compound represented by formula (I) of the present invention are shown below, but other compounds can be easily synthesized by the same method.

Synthesis Example 1 (Synthesis of Exemplified Compound I-4) 14.9 g of 2-methylbenzothiazole, 17.7 g of p-diethylaminobenzaldehyde and sodium hydride (hard oil 60
%) 6 g and dimethylformamide 60 cc were added, and the mixture was stirred at room temperature
Reaction was carried out for a minute. The reaction solution was poured into water and the precipitated solid was filtered. The solid was dried and then recrystallized from methanol to obtain the desired product. Yield 19.4g (63%).

Synthesis Example 2 (Synthesis of Exemplified Compound I-21) 2,5-Dimethylbenzoxazole 147.2 g, 4-morpholinobenzaldehyde 191.2 g, dimethylformamide 4
After adding 40 ml and dissolving, sodium methoxy powder at room temperature
59.4g was added in small portions. After the addition was completed, the mixture was stirred for 2 hours at room temperature, and then 300 ml of tap water was added to stop the reaction. The precipitated solid was filtered and dried, and then heat-washed with 300 ml of toluene, filtered, and dried to obtain the desired product. Yield 25
6.7 g (80%) The amount of the compound represented by formula (I) used in the present invention is preferably 2 × 10 ⁻⁷ to 1 × 10 ⁻² mol, and more preferably 2 × 10 ⁻⁷ mol, per mol of silver halide. It is preferably from 10 ^{-7 to} 5 10 ^-3 mol.

As a method for adding the compound represented by the general formula (I) of the present invention to a silver halide emulsion, a method well known in the art can be used. For example, the compound can be dispersed directly in the emulsion, or dissolved in a water-soluble solvent such as pyridine, methanol, ethanol, methyl cellosolve, acetone, fluorinated alcohols, dimethylformamide, or mixtures thereof, or water. Can be diluted with or dissolved in water and added to the emulsion in the form of a solution. Ultrasonic vibration can also be used during the dissolution process.

Further, the compound represented by the general formula (I) of the present invention is dissolved in a volatile organic solvent as described in US Pat. No. 3,469,987, and this solution is dispersed in a hydrophilic colloid to give a dispersion. There is also used a method of adding to an emulsion, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it and adding this dispersion to the emulsion as described in JP-B-46-24185.

Further, the compound represented by the general formula (I) of the present invention can be added to the emulsion in the form of a dispersion prepared by an acid dissolution dispersion method.

Compound of the Invention The compound represented by the general formula (I) may be added at any time during the period from the formation of silver halide grains to the coating, but it is particularly added before the completion of chemical sensitization. Preferably.

The compounds represented by the general formulas (II) to (IV) of the present invention are described in JP-A No. 54-1019, J. Org. Chem .; 53 , 396 (19).
88), Chem. Abst. 59 , 9776e.

The compounds represented by the general formulas (II) to (IV) of the present invention are 1 × 10 ^-7 to 1 × 10 ⁷ per mol of silver halide.
^-2 mol is preferably used, more preferably 1 x 10 ^{-6 to} 5 x 10
^-3 mol is preferred.

The compounds represented by the general formulas (II) to (IV) of the present invention may be used in combination of two or more kinds, or may be added at two or more times. As a method for adding these compounds to the silver halide emulsion, a method well known in the art can be used. For example, the water-soluble compound is an aqueous solution having a suitable concentration, and the water-insoluble or sparingly-soluble compound is a suitable organic solvent miscible with water, for example, alcohols, glycols, ketones, esters,
Among amides and the like, it can be dissolved in a solvent that does not adversely affect the photographic characteristics and added as a solution of those solvents.

In the present invention, a sulfur sensitizer, a selenium sensitizer and a tellurium sensitizer can be used in combination as the chemical sensitizer.

In the chemical sensitization of the present invention, the sensitivity can be further increased by using gold sensitization together. Examples of useful gold sensitizers include chloroauric acid, gold thiosulfate, gold thiocyanate, and the like, U.S. Patent Nos. 2,597,856, 5,049,484, and 5,
049,485, JP-B-44-15748, JP-A-1-147537, 4
Examples include gold complexes of organic compounds disclosed in No. 70650 and the like.

The above-mentioned various sensitizers may be added by adding them by dissolving them in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent depending on the properties of the compound used, or by adding gelatin. A method of mixing with a solution in advance and adding it may be a method disclosed in JP-A-4-140739, that is, a method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent.

In the present invention, when the chemical sensitization is performed in the presence of a silver halide adsorbing compound, the effect of the present invention is further enhanced. The silver halide-adsorptive compound is a sensitizing dye,
Antifoggants and stabilizers can be used.

As the sensitizing dyes, polymethine dyes containing cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes, oxonols, merostyryl and streptocyanines are used. Can be mentioned.

Examples of the antifoggants and stabilizers include tetrazaindenes and azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, promobenzimidazoles and mercaptothiazoles. , Mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), and mercaptopyrimidines, mercaptotriazines, such as thioketo such as oxazolithion. Compounds, further benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfonic acid amide, hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbi Mention may be made of the acid derivatives.

In the present invention, good results are often obtained by performing sensitization in the presence of a silver halide solvent.

Examples of the silver halide solvent used in the present invention include US Pat. Nos. 3,271,157, 3,531,2891, and 3,5.
(A) Organic thioethyls described in JP-A-74,628, JP-A-54-1019 and JP-A-54-158917, and
53-82408, 55-77737, 55-2982 and the like (b) thiourea derivatives, and (c) an oxygen or sulfur atom described in JP-A-53-144319 Examples thereof include silver halide solvents having a thiocarbonyl group sandwiched between nitrogen atoms, (d) imidazoles described in JP-A-54-100717, (e) sulfite, (f) thiocyanate, and the like.

Known photographic additives that can be used in the construction of a color photographic light-sensitive material using the silver halide photographic emulsion of the present invention are described in Research Disclosure below. Below are the relevant locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I item 25 650 Dye image stabilizer 1001 VII-J item 25 Whitening agent 998 V 24 UV absorber 1003 VIII- C, XIII C Item 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricants 1006 XII 27 650 Activators / coating aids 1005 XI 26 to 27 650 Matte agents 1007 XVI Developer (included in light-sensitive material) Item 1011 XXB Color photographic light-sensitive using the silver halide photographic emulsion of the present invention Various couplers may be used in constructing the material, specific examples of which are described in Research Disclosure below. The relevant locations are shown below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VIIC-G item Magenta coupler 1001 VII-D item VIIC-G item Cyan coupler 1001 VII-G item VIIC-G item Colored coupler 1002 Item VII-G Item VIIG Item DIR coupler 1001 Item VII-F Item VIIF Item BAR coupler 1002 Item VII-F Other useful residues Release coupler 1001 Item VII-F Alkali-soluble coupler 1001 Item VII-E Silver halide photograph of the present invention Additives used in constructing a color photographic light-sensitive material using an emulsion can be added by the dispersion method described in RD308119XIV.

When a silver halide photographic emulsion of the present invention is used to form a color photographic light-sensitive material, the above-mentioned RD17643 28 is used.
The supports described on page RD18716 pp. 647-8 and RD308119 XVII can be used.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention can be provided with auxiliary layers such as the filter layer and the intermediate layer described in the above item RD308119VII-K.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention can have various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the above item RD308119VII-K.

The silver halide photographic emulsion of the present invention is a color negative film for general use or movies, a color reversal film for slides or televisions, a color paper, a color positive film, and various color photographic light-sensitive materials represented by color reversal paper. It can be preferably applied to materials.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention is described in RD17643, pages 28 to 29, RD18716 61.
Development can be carried out by a usual method described on page 5 and XIX of RD308119.

[0076]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

Example 1 Silver iodobromide grains having an average cubic iodine content of 20 mol% and an average cubic equivalent diameter of 0.59 μm and having two parallel twin planes were used as seed crystals, and the core was prepared by a control double jet method in a gelatin aqueous solution. An emulsion was formed of average twinned silver iodobromide grains having a shell ratio of 1: 2 and an iodine content of the shell of 2 mol% and an average cubic equivalent diameter of 0.85 μm.

After grain formation, the emulsion was redispersed at 40 ° C. under the conditions of pHAg 8.9 and pH 6.3 through a usual desilvering water washing process. The emulsion thus prepared is designated as Em-1.

On the other hand, 1 minute before the start of shell formation, the thiosulfonic acid compounds (II-2), (II-9), (III-
3) and (IV-9) were added in an amount of 3 × 10 ⁻⁵ mol per mol of silver to prepare Em-2 to Em-5.

With respect to the emulsions Em-1 to Em-5 thus obtained, the sensitizing dye 5,5'-dichloro-3,3 '-(γ-sulfopropyl) -9-ethyl-thiacarbo was used. Optimum spectral sensitization and chemical sensitization with cyanine hydride, sodium thiosulfate, chloroauric acid, and ammonium thiocyanate, and compound (I) and thiosulfonic acid compounds shown in Table 1 are 3 × 10 per mol of silver
^-5 mol was added. After completion of the aging, 4-hydroxy-7-thymer-1,3,3a, 7-tetrazaindene and 1-phenyl-5-mercaptotetrazole were added and stabilized.

Further, a cyan coupler, 2- {3- (3-cyano-4-)
Chlorophenyl)} ureido-5- {2- (2,5-di-t-amylphenoxy) hexanamide} phenol with ethyl acetate,
A coating solution prepared by dissolving in dioctyl phthalate and dispersing the emulsion in an aqueous solution containing gelatin, and a general photographic additive such as a spreading agent and a hardener, was prepared. Samples 101 to 123 were prepared by coating on a support and drying according to a conventional method.

4 parts of these samples 101 to 123 were prepared,
The first part (a) was subjected to wedge exposure for (1/100) seconds in accordance with a conventional method, and the other part (b) was subjected to wedge exposure for 8 seconds so that the exposure amount was the same. Another part (c) is 23
Humidify for 4 hours or more in the environment of ℃, 55% RH, and seal it
After being placed in a 65 ° C. environment and left for 2 days, (1/100) second wedge exposure was performed in the same manner as in (a).

The remaining part (d) is (1/10) as in the case of (a).
After performing 0) second wedge exposure, it was left for 3 days under the conditions of 55 ° C. and 30% RH.

The samples (a) to (d) were developed as shown below, and their densities were measured with a red filter. The sensitivity of each sample is represented by the reciprocal of the exposure amount that gives an optical density of red density + fog density +0.15, and is shown as a relative value when the value of sample (a) of sample 101 is 100.

(Processing step) Processing step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780cc Bleach 45 seconds 38 ± 2.0 ° C. 150 ml fixation 1 minute 30 seconds 38 ± 2.0 ° C. 830 ml stability 60 Second 38 ± 5.0 ℃ 830ml Drying 1 minute 55 ± 5.0 ℃ − * Replenishment amount is the value per 1 m ² of light-sensitive material.

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and its replenishing solution were used.

Color developer and color replenisher developer Replenisher Replenisher Water 800cc 800cc Potassium carbonate 30g 35g Sodium hydrogencarbonate 2.5g 3.0g Potassium sulfite 3.0g 5.0g Sodium bromide 1.3g 0.4g Potassium iodide 1.2mg-hydroxylamine sulfate Salt 2.5g 3.1g Sodium chloride 0.6g-4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5g 6.3g Diethylenetriaminepentaacetic acid 3.0g 3.0g Potassium hydroxide 1.2g 2.0 g Add 1 liter of water and adjust the pH of the color developer to pH 10.06 and the replenisher to pH 10.18 using potassium hydroxide or 20% sulfuric acid.

Bleaching solution and bleach replenishing solution Bleaching solution Replenishing solution Water 700cc 700cc 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125g 175g Ethylenediaminetetraacetic acid 2g 2g Sodium nitrate 40g 50g Ammonium bromide 150g 200g Glacial acetic acid 40g 56g Water The pH of the bleaching solution is adjusted to pH 4.4 and the replenisher is adjusted to pH 4.0 using ammonia water or glacial acetic acid.

Fixing Solution and Fixing Replenishing Solution Fixing Solution Replenishing Solution Water 800 cc 800 cc Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g Ammonia water or glacial acetic acid was used as the fixer at pH 6.2, Adjust the pH of the replenisher to 6.5 and add water to make 1 liter.

Stabilizer and stable replenisher water 900 cc p-octylphenol ethylene oxide 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzisothiazolin-3-one 0.1 g siloxane (UCC L-77 ) 0.1g Ammonia water 0.5cc Add water to make 1 liter, then use ammonia water or 50%
Adjust to pH 8.5 with sulfuric acid.

[0091]

[Table 1]

[0092]

[Chemical 20]

[0093]

[Table 2]

As shown in Table 2, the samples using the emulsion of the present invention have high sensitivity, low fog, excellent storage stability with time and latent image stability, and good low illuminance failure characteristics. Further, the sample of the present invention containing a compound represented by the general formula (I) in which R ₃ and R ₄ are bonded to form a ring is
It can be seen that the effect is particularly large.

Example 2 (Preparation of silver halide color light-sensitive material) Sample 201, which is a multilayer color light-sensitive material, was prepared by providing each layer having the composition shown below on a cellulose triacetate film support having an undercoat. .

[0096] The coating amount (Composition of photosensitive layer) The silver halide and colloidal silver, the amount expressed in terms of metallic silver in the unit of g / m ^2, also, the coupler, the additive g / m ² The amount expressed in units is also shown for the sensitizing dye in terms of the number of moles per mole of silver halide in the same layer.

Sample 201 First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (OIL-1) 0.16 Gelatin 1.60 Second layer: Intermediate layer Compound (SC-1) 0.14 High Boiling point solvent (OIL-2) 0.17 Gelatin 0.80 Third layer: low-sensitivity red-sensitive layer Silver iodobromide emulsion A 0.15 Silver iodobromide emulsion B 0.35 Sensitizing dye (SD-1) 2.0 × 10 ^-4 Sensitizing dye ( SD-2) 1.4 × 10 ^-4 Sensitizing dye (SD-3) 1.4 × 10 ^-5 Sensitizing dye (SD-4) 0.7 × 10 ^-4 Cyan coupler (C-1) 0.53 Colored cyan coupler (CC-1) ) 0.04 DIR compound (D-1) 0.025 High boiling point solvent (OIL-3) 0.48 Gelatin 1.09 4th layer: Medium sensitivity red sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD- 1) 1.7 × 10 ^-4 sensitizing dye (SD-2) 0.86 × 10 ^-4 sensitizing dye (SD-3) 1.15 × 10 ^-5 sensitizing dye (SD-4) 0.86 × 10 ^-4 cyan coupler (C -1) 0.33 Colored cyan coupler (CC- 1) 0.013 DIR compound (D-1) 0.02 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 Fifth layer: high-sensitivity red sensitive layer Silver iodobromide emulsion (Em-1) 0.95 Sensitizing dye (SD-1) 1.0 × 10 ^-4 Sensitizing dye (SD-2) 1.0 × 10 ^-4 Sensitizing dye (SD-3) 1.2 × 10 ^-5 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.016 High boiling point Solvent (OIL-1) 0.16 Gelatin 0.79 Sixth layer: Intermediate compound (SC-1) 0.09 High boiling point solvent (OIL-2) 0.11 Gelatin 0.80 Seventh layer: Low sensitivity green sensitive layer Silver iodobromide emulsion A 0.12 Iodine Silver bromide Emulsion B 0.38 Sensitizing dye (SD-4) 4.6 × 10 ^-5 Sensitizing dye (SD-5) 4.1 × 10 ^-4 Magenta coupler (M-1) 0.14 Magenta coupler (M-2) 0.14 Colored magenta Coupler (CM-1) 0.03 Colored magenta Coupler (CM-2) 0.03 High boiling point solvent (OIL-4) 0.34 Gelatin 0.70 Eighth layer: Intermediate layer Gelatin 0.41 Ninth layer: Medium green sensitivity Layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD-6) 1.2 × 10 ⁻⁴ Sensitizing dye (SD-7) 1.2 × 10 ⁻⁴ Sensitizing dye (SD-8) 1.2 × 10 ^-4 Magenta coupler (M-1) 0.04 Magenta coupler (M-2) 0.04 Colored magenta coupler (CM-1) 0.008 Colored magenta coupler (CM-2) 0.009 DIR compound (D-2) 0.025 DIR compound (D) -3) 0.002 High boiling point solvent (OIL-4) 0.12 Gelatin 0.50 Layer 10: High sensitivity green sensitive layer Silver iodobromide emulsion (Em-1) 0.95 Sensitizing dye (SD-6) 7.1 × 10 ^-5 Sensitization Dye (SD-7) 7.1 × 10 ^-5 Sensitizing Dye (SD-8) 7.1 × 10 ^-5 Magenta Coupler (M-1) 0.09 Colored Magenta Coupler (CM-1) 0.005 Colored Magenta Coupler (CM-2) 0.006 High boiling point solvent (OIL-4) 0.11 Gelatin 0.79 11th layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0.15 High boiling point solvent (OI) -2) 0.19 Gelatin 1.10 12th layer: low sensitivity blue-sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.24 Silver iodobromide emulsion C 0.12 Sensitizing dye (SD-9) 6.3 × 10 -5 increase Sensitizing dye (SD-10) 1.0 × 10 ^-5 Yellow coupler (Y-1) 0.50 Yellow coupler (Y-2) 0.50 DIR compound (D-4) 0.04 DIR compound (D-5) 0.02 High boiling solvent (OIL- 2) 0.42 Gelatin 1.40 13th layer: High-sensitivity blue-sensitive layer Silver iodobromide emulsion C 0.15 Silver iodobromide emulsion D 0.80 Sensitizing dye (SD-9) 8.0 × 10 ^-5 Sensitizing dye (SD-11) 3.1 × 10 ^-5 Yellow coupler (Y-1) 0.12 High boiling point solvent (OIL-2) 0.05 Gelatin 0.79 14th layer: 1st protective layer Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol) %) 0.40 UV absorber (UV-1) 0.065 High boiling point solvent (OIL-1) 0.07 High boiling point solvent (OIL-3) 0.07 Gelatin 0.65 15th layer: 2nd protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethy Methacrylate (average particle size 3 [mu] m) 0.04 In addition to the sliding agent (WAX-1) 0.04 Gelatin 0.55 In addition the compositions, coating aid Su-1, dispersion aid Su
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, antifoggant AF-1, two kinds of AF-2 having an average molecular weight of 10,000 and an average molecular weight of 1,100,000, and preservative DI-1 were added.

The emulsions used for the above samples are as follows. The average particle size is shown as a particle size converted into a cube.
Further, each emulsion was optimally subjected to gold / sulfur sensitization.

[0099]

[Table 3]

[0100]

[Chemical 21]

[0101]

[Chemical formula 22]

[0102]

[Chemical formula 23]

[0103]

[Chemical formula 24]

[0104]

[Chemical 25]

[0105]

[Chemical formula 26]

[0106]

[Chemical 27]

[0107]

[Chemical 28]

[0108]

[Chemical 29]

[0109]

[Chemical 30]

[0110]

[Chemical 31]

<Production of Sample 202 to Sample 223> Sample 20
Sample 201 was prepared in the same manner as in Sample 201, except that the chemically sensitized silver halide emulsion used in the fifth layer of 1 was replaced with the same emulsion as Sample 102 shown in Table 1 of <Example 1>. 202
Was produced. In the same manner, sample 103 to sample 1 in Table 1
Samples 223 to 223 were prepared from multilayer constitution samples 203 using up to 23 emulsions.

Four parts of these samples were prepared in the same manner as in <Example 1>, and after undergoing the above-mentioned treatment steps, the concentration was measured with a red filter. The sensitivity of each sample is expressed as the reciprocal of the exposure dose at which the red density gives an optical density of fogging density +0.15.
It was shown as a relative value when the value of the sample (a) of 1 was 100.

[0113]

[Table 4]

As shown in Table 4, the samples using the emulsion of the present invention have high sensitivity, low fog, excellent storability with time and latent image stability, and good low illuminance failure characteristics. Further, it is understood that the sample of the present invention containing the compound represented by the general formula (I) in which R ₃ and R ₄ are bonded to form a ring is particularly effective.

Further, these effects are obtained by the tenth layer or the thirteenth layer.
When the emulsion used in the layer was replaced with the emulsion of the present invention, it could be confirmed by the same evaluation method.

[0116]

EFFECT OF THE INVENTION High sensitivity and low fog, latent image stability,
A silver halide photographic emulsion for use in a silver halide photographic light-sensitive material having improved stability over time and reciprocity law failure characteristics was obtained.

Claims (2)

[Claims] 1. Particle formation and / or chemical enhancement in the presence of a compound represented by the following general formula (I) and represented by any of the following general formulas (II) to (IV). A silver halide photographic emulsion characterized by containing sensitized silver halide grains. [Chemical 1] In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₅ , R ₆ , R ₇ and R ₈ represent Each represents a substituent. L ₁ and L ₂ each represent a methine group, Z ₁ is an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, —C (R ₉ ) (R ₁₀ ).
- or -N (R ₁₁₎ - represents a. R ₉ , R ₁₀ and R ₁₁ are each
Hydrogen atom, alkyl group, alkenyl group, alkynyl group,
It represents an aryl group or a heterocyclic group. R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ , R ₇ and R ₈ , and R ₉ and R ₁₀ may be bonded to each other to form a ring. [Chemical 2] In the formula, R ₁₂ , R ₁₃ and R ₁₄ each represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and M represents a cation. Q represents a divalent linking group, m
Is 0 or 1. Further, R ₁₂ , R ₁₃ , R ₁₄ and Q may combine with each other to form a ring. The compounds of the general formulas (II) to (IV) may be polymers containing a divalent group derived from the structure represented by (II) to (IV) as a repeating unit. 2. The compound represented by the general formula (I) above,
The silver halide photographic emulsion according to claim 1, which is a compound in which R ₃ and R ₄ are combined to form a ring.