JP3240530B2 - Silver halide photographic materials - Google Patents

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 using an emulsion composed of silver halide grains whose storage stability has been improved by a novel compound. .

[0002]

2. Description of the Related Art In recent photosensitive materials, there is a strong demand for high sensitivity and low fog, and furthermore, it has been important to improve the storability in order to maintain their performance for a longer time.

In order to form an image on a silver halide photographic light-sensitive material, a photographic exposure process for forming a latent image and a developing process for converting the generated latent image into a silver image or a dye image are performed. It is well known that two processes are required.

[0004] Regarding this process, for example, James
There is a detailed description in The Theory of the photographic process.

The formation of a latent image by photographic exposure is chemically a microscopic state change of a silver halide crystal.
The latent image itself has inherently unstable properties.

Accordingly, the latent image has a property of being easily attenuated or intensified with the passage of time from exposure to development.

This latent image attenuation is referred to in the art as latent image regression, and the latter is referred to as latent image intensification.

The behavior of these latent images generally depends on the storage conditions of the exposed photosensitive material. For example, latent image regression at high-temperature storage or latent image regression at low-temperature storage when the latent image intensification is extremely low is almost impossible. Does not occur.

The simplest method for solving the problems caused by latent image regression or latent image intensification is to carry out development processing immediately after photographic exposure, and the next simple method is to carry out development processing after photographic exposure until development processing is performed. This is a method in which the photographed photosensitive material is cooled and stored at a low temperature.

Although these methods are the simplest and simplest methods from a chemical point of view, they are not solutions that are pleasing to users.

[0011] In view of actual use conditions and use form, there is a case where the apparatus is left for several months from the photographing exposure to the development processing.

When the latent image regression or the latent image intensification is particularly different in the behavior of each layer in a multilayer color photographic light-sensitive material, the color balance is lost and color reproduction is deteriorated.

As a method for preventing latent image intensification, Japanese Patent Publication No. Sho 51
No. -9109, a method of using a hardener to release the acid in the emulsion film to lower the pH, JP-A-48-6725 discloses a method of adding a rhodium compound and an iridium compound during the emulsification of silver halide, Japanese Patent Publication No. 57-23250 discloses a method of adding a mercapto heterocyclic compound to a silver halide emulsion prepared using a rhodium compound, and JP-A-53-127714 discloses a silver halide emulsion prepared using a rhodium compound. A method of adding a hydroxyazaindolizine compound and a nitrogen-containing heterocyclic compound having a mercapto group therein has been proposed.

However, the silver halide emulsion was not satisfactory because of a specific preparation method, a need to be spectrally sensitized with a specific sensitizing dye, and an insufficient effect.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide emulsion having improved storage stability over time, particularly, regression of a latent image.

[0016]

The object of the present invention has been attained by a silver halide photographic material characterized by containing a compound represented by the following general formula [I].

[0017]

Embedded image

In the formula, R1 and R2 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and Z1 represents an oxygen atom, a selenium atom, a sulfur atom,
Represents a tellurium atom, -N (R7)-, -C (R8) (R9)-. R1 and R2 may combine to form a ring. R
7, R8 and R9 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. R
3, R4, R5 and R6 represent a hydrogen atom or a substituent. Z2 represents a non-metallic atomic group for forming a 5- to 6-membered heterocyclic ring, and L1 and L2 represent a methine group.

In the general formula (I), examples of the alkyl group represented by R1 and R2 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and a tert-
Butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-octyl, n-dodecyl and the like. These alkyl groups further include a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.),
An alkoxy group (for example, methoxy group, ethoxy group, 1,1-dimethylethoxy group, n-hexyloxy group, n-dodecyloxy group, etc.), an aryloxy group (for example, phenoxy group,
Naphthyloxy group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, n
-Butoxycarbonyl group, 2-ethylhexylcarbonyl group, etc.), aryloxycarbonyl group (for example, phenoxycarbonyl group, naphthyloxycarbonyl group, etc.),
Alkenyl group (eg, vinyl group, allyl group, etc.), heterocyclic group (eg, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, morpholyl group, piperidyl group, piperazyl group, pyrimidyl group, pyrazolyl group, furyl) Group), alkynyl group (eg, propargyl group), amino group (eg, amino group, N, N-dimethylamino group, anilino group, etc.), hydroxy group, cyano group, sulfo group, carboxyl group, sulfonamide group (Eg, a methylsulfonylamino group, an ethylsulfonylamino group, an n-butylsulfonylamino group, an n-octylsulfonylamino group, a phenylsulfonylamino group, etc.) and the like.

Examples of the alkenyl group represented by R1 and R2 include a vinyl group and an allyl group. These groups can be substituted by an alkyl group represented by R1 and R2, and a group similar to the group shown as a substituent of the alkyl group.

The alkynyl groups represented by R1 and R2 include, for example, a propargyl group. These groups can be substituted by an alkyl group represented by R1 and R2, and a group similar to the group shown as a substituent of the alkyl group.

Examples of the aryl group represented by R1 and R2 include a phenyl group and a naphthyl group.
These groups can be substituted by an alkyl group represented by R1 and R2, and a group similar to the group shown as a substituent of the alkyl group.

The heterocyclic groups represented by R1 and R2 include:
For example, pyridyl group (for example, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, etc.), thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group , Sulfolanyl group, piperidinyl group, pyrazolyl group,
And a tetrazolyl group. These groups are represented by R1,
It can be substituted by an alkyl group represented by R2 and a group similar to the group shown as a substituent of the alkyl group.

As the substituent represented by R3, R4, R5 and R6, an alkyl group (for example, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-
-Pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-dodecyl group, etc., alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, propargyl group, etc.), Aryl group (for example, phenyl group, naphthyl group, etc.), heterocyclic group (for example,
Pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc., halogen atom (for example, chlorine) Atom, bromine atom,
Iodine atom, fluorine atom, etc.), alkoxy group (for example,
Methoxy group, ethoxy group, propyloxy group, n-pentyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-octyloxy group,
n-dodecyloxy group, etc.), aryloxy group (for example,
Phenoxy group, naphthyloxy group, etc.), alkoxycarbonyl group (for example, methyloxycarbonyl group, ethyloxycarbonyl group, n-butyloxycarbonyl group, n-
Octyloxycarbonyl group, n-dodecyloxycarbonyl group, etc., aryloxycarbonyl group (for example, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfonamide group (for example, methylsulfonylamino group, ethylsulfonylamino group, n- Butylsulfonylamino group, n-hexylsulfonylamino group, cyclohexylsulfonylamino group, n-octylsulfonylamino group, n-dodecylsulfonylamino group, phenylsulfonylamino group, etc., sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl) Group, dimethylaminosulfonyl group, n-butylaminosulfonyl group, n-hexylaminosulfonyl group, cyclohexylaminosulfonyl group, n-octylaminosulfonyl group, n-dodecylaminosulfonyl group, Nylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), ureide group (for example, methylureide group, ethylureide group, pentylureide group, cyclohexylureide group, n-octylureide group, n-dodecylureide group) Phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group,
n-pentylcarbonyl group, cyclohexylcarbonyl group, n-octylcarbonyl group, 2-ethylhexylcarbonyl group, n-dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc., carbamoyl group (for example, aminocarbonyl group) ,
Methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, n-pentylaminocarbonyl group, cyclohexylaminocarbonyl group, n-octylaminocarbonyl group, 2-ethylhexylaminocarbamoyl group, n-dodecylaminocarbonyl group, phenylamino Carbonyl group, naphthylaminocarbonyl group,
2-pyridylaminocarbonyl group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, propylcarbonylamino group, n-pentylcarbonylamino group, cyclohexylcarbonylamino group,
Ethylhexylcarbonylamino group, n-octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc., sulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, n-butylsulfonyl group, cyclohexylsulfonyl) Group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, n-butylamino group, Cyclopentylamino group, 2-ethylhexylamino group, n-dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group), cyano group, nitro group, carboxyl group, hydroxyl group, hydrogen atom and the like. These groups can be substituted by an alkyl group represented by R1 and groups similar to the groups shown as substituents of the alkyl group.

The ring formed by R1 and R2 includes, for example, a benzene ring, a naphthalene ring, a thiophene ring, a pyridine ring, a furan ring, a pyrimidine ring, a cyclohexene ring, a pyran ring, a pyrrole ring, a pyrazine ring and an indole ring. Can be These rings include an alkyl group represented by R1,
And a group similar to the group shown as the substituent of the alkyl group.

The methine groups represented by L1 and L2 can have a substituent, for example, an alkyl group (eg, a methyl group, an ethyl group, a propyl group), an aryl group (eg, a phenyl group). And an alkoxy group (for example, methoxy group, ethoxy group, etc.), an aryloxy group (for example, phenoxy group, etc.), a halogen atom (for example, chlorine atom, bromine atom, etc.).

The 5- to 6-membered heterocyclic ring formed by Z2 includes, for example, a morpholine ring, a piperidine ring, a piperazine ring, a pyrrolidine ring and the like. These rings are R1,
It can be substituted by an alkyl group represented by R2 and a group similar to the group shown as a substituent of the alkyl group.

Specific examples of the compound of the present invention are shown below.
The present invention is not limited to this.

[0029]

Embedded image

[0030]

Embedded image

[0031]

Embedded image

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

Specific examples of the synthesis of the compound of the present invention are shown below. Other compounds can be easily synthesized in the same manner.

Synthesis Example 1 (Synthesis of Compound Example 39) 2,5-Dimethylbenzoxazole 5 g, p-morpholinobenzaldehyde 6.5 g, sodium hydride (hard oil 60%)
1.5 g and 15 ml of dimethylformamide were added, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the reaction solution was added to 200 ml of water,
The precipitated solid is filtered off. The solid was dried and then recrystallized from ethyl acetate to obtain the desired product. Yield 5.7
g, yield was 52%.

Synthesis Example 2 (Synthesis of Compound Example 40) 6.1 g of 2-methyl-6-methoxybenzthiazole, 6.5 g of p-morpholinobenzaldehyde, sodium hydride (hard oil 6
0%) 1.5 g and dimethylformamide 20 ml were added at room temperature.
Stirred for hours. After completion of the reaction, the reaction solution is added to 200 ml of water, and the precipitated solid is separated by filtration. The solid was dried and then recrystallized from ethyl acetate to obtain the desired product. Yield 7.
The yield was 2 g and the yield was 60%.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any one of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride is used. Is also good. Preferred silver halide is silver iodobromide, silver bromide or silver chlorobromide containing 30 mol% or less of silver iodide.

The silver halide grains in the photographic emulsion may be so-called regular grains having regular crystals such as cubic, octahedral, and tetradecahedral, or may have irregular crystal forms such as spherical. It may have a crystal defect, a crystal defect such as a twin plane, or a composite form thereof.

In constructing the light-sensitive material of the present invention, the emulsion of the present invention to be used and other silver halide emulsions other than the emulsion of the present invention used as necessary are generally preferably subjected to physical ripening and chemical ripening. In general, those which have been subjected to spectral sensitization in accordance with the respective light-sensitive layers to be used are used. Additives that can be used in such a process are described in Research Disclosure No. 17643, no. No. 18716, and No. 308119
(Hereinafter referred to as RD17643, RD18716 and RD308119, respectively)
Abbreviated as ").

The following shows the places to be described.

Item RD308119 page / Item RD17643 Page RD18716 Item Chemical sensitizer 996 III-A Item 23648 Spectral sensitizer 996 IV-AA, B, 23-24 648-9C, D, H , I, J Section Supersensitizer 996 IV-AE, J Section 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Known photographic additives that can be used are also exemplified in the above-mentioned Research Disclosure. The relevant places are shown below.

Item RD308119 page / Item RD17643 Page RD18716 Page Color turbidity inhibitor 1002 VII-I Item 25 650 Dye image stabilizer 1002 VII-J Item 25 Brightener 998 V24 Ultraviolet absorber 1003 VIIIC, 25- 26 XIIIC Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Static inhibitor 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticity 1006 XII 27 650 Moisture Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26-27 650 Agent Matting agent 1007 XVI Image agent 1011 XXB (Contained in photosensitive material) The photosensitive material of the present invention is colored in the photosensitive layer of each color. A variety of couplers can be used depending on the color desired, examples of which are illustrated in Research Disclosure, supra. The relevant places are shown below.

Item RD308119 / Item RD17643 / Yellow coupler 1001 VII-D VII CG-G Magenta coupler 1001 VII-D VII CG-G Cyan coupler 1001 VII-D VII CG-G Coupler 1002 VII-G Section VII G Section DIR Coupler 1001 VII-F Section VIIF Section BAR Coupler 1002 VII-F Section Release of Other Useful Residues 1001 VII-F Section Coupler Alkali-Soluble Coupler 1001 VII-E Section of the Present Invention When various additives are used in the light-sensitive material, they can be added by a dispersion method described in RD308119XIV.

In the present invention, 28 of RD17643 described above is used.
RD18716, pages 647-8, and RD308119 XVII
The support described in (1) can be used.

The light-sensitive material of the present invention includes the aforementioned RD308119
An auxiliary layer such as a filter layer or an intermediate layer described in the section VII-K can be provided.

The light-sensitive material of the present invention uses the RD308119VI described above.
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in the section I-K can be adopted.

The present invention can be applied to various color photographic materials represented by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. it can.

The light-sensitive material of the present invention can be prepared according to RD17643 28-29
RD18716, page 615, and RD308119, section XIX.

[0051]

Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 First, a method for preparing the emulsion EmA-1 used in this example will be described.

[Preparation of Emulsion EmA-1] Emulsion EmA-1
The method for preparing is described.

The following aqueous solutions (a-1) to (a-4) were used.

Aqueous solution (a-1) Gelatin 51.93 g 28% aqueous ammonia 1056 ml 56% acetic acid 10590 ml Water is added to make 11827 ml.

Aqueous solution (a-2) Silver nitrate 1587 g 28% aqueous ammonia 1294 ml Add water to make 2669 ml.

Aqueous solution (a-3) Gelatin 34.93 g Potassium bromide 1454.7 g Add water to make 3493 ml.

Emulsion solution containing silver iodide fine particles (average particle size 0.06 μm) (a-4) Silver iodide fine particle stock solution (finished to 1467 ml containing 45.6 g of gelatin per mole of AgI) 1239 ml 4-hydroxy -6-Methyl-1,3,3a, 7-tetrazaindene 5.22 g Add water to make 2294 ml.

An aqueous solution (a-1) of the above composition, which was vigorously stirred at a temperature of 60 ° C., was equivalent to 0.407 mol of a monodisperse silver iodobromide emulsion containing 2 mol% silver iodide and having an average grain size of 0.27 μm. Was added as seed particles, and pH and pAg were prepared using acetic acid and an aqueous potassium bromide solution.

Thereafter, while controlling the pH and pAg as shown in Table 1, at the flow rates shown in Tables 2 and 3, each of (a-2), (a-3) and (a-4) was obtained. The aqueous solution was added by a double jet method. Table 1 shows the grain growth conditions of EmA-1.

[0061]

[Table 1]

Table 2 shows the flow rates of the aqueous solutions (a-2) and (a-3), and Table 3 shows the flow rates of the aqueous solution (a-4).

[0063] Next, a phenylcarbamyl gelatin solution was added to the solution obtained above, and the pH of the solution was adjusted to precipitate and aggregate the particles, followed by desalting and washing with water.

Thus, a monodispersed emulsion EmA-1 having an average grain size of 0.8 μm and an average silver iodide content of 8.0 mol% was obtained.

This EmA-1 was adjusted to pAg 8.0, 2.0 × 10 ⁻⁶ mol / mol AgX sodium thiosulfate was added at a temperature of 55 ° C. and a pH of 5.8, and the mixture was aged for 60 minutes. A mixed solution of 4.4 × 10 ⁻⁷ mol / mol AgX and ammonium thiocyanate was added, and the mixture was further aged for 60 minutes.

Thereafter, the compound of the present invention and Comparative Compounds 1 to 5 shown in Table 4 were added to the emulsion in an amount of 1/10 mol of the total amount of the sensitizing dye. -A, SD-B, and SD-C were used in combination for adsorption and spectral sensitization. Further, magenta couplers MA, M-
B, MC were added.

Next, 2-hydroxy-4 was used as a hardening agent.
After uniformly adding an appropriate amount of 6-dichlorotriazidisodium, each emulsion was coated and dried on a triacetate support which had been coated so that the coated silver amount was 2.0 g / m ² , to obtain a light-sensitive material. .

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

Each of these samples was subjected to wedge exposure using a green light in a usual manner, color-developed in accordance with the following color processing steps, and photographic performance was comparatively evaluated. Table 4 shows the results. Note that the green light sensitivity in Table 4 was expressed as a relative sensitivity with the sensitivity of Sample 1 (comparative) set to 100.

Processing Step Processing Temperature Processing Time Color Development 38 ° C 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 3 minutes 15 seconds Fixed 6 minutes 30 seconds Rinse 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry each The composition of the processing solution used in the processing step is as follows.

(Color developing solution) 4-amino-3-methyl-N-ethyl-N-β-hydroxyethyl aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid / trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to 1000 ml, and adjust to pH 10.6 with sodium hydroxide.

(Bleaching Solution) Ammonium iron (III) ethylenediaminetetraacetate 100.0 g Diammonium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to 1000 ml, and the pH was adjusted to 6.0 using aqueous ammonia. Adjust to

(Fixing solution) Ammonium thiosulfate 175.0 g Sodium sulfite anhydrous 8.6 g Sodium metasulfite 2.3 g Water was added to make 1000 ml, and the pH was adjusted to 6.0 with acetic acid. (Stabilizing solution) Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica Corporation) 7.5 ml Make up to 1000 ml with water.

[0076]

[Table 4]

[0077]

[Table 5]

[0078]

[Table 6]

The sensitivity is defined by the reciprocal of the exposure amount giving a density of fog density + 0.1. It was expressed as a relative sensitivity when the green light sensitivity of the day 1 was 100. The higher the number, the higher the sensitivity of the sample.

It can be seen that the compound of the present invention has a superior latent image regression preventing ability as compared with the comparative compound.

Example 2 The following emulsion was prepared to prepare a multilayer photosensitive material 101.

Em-1 Average grain size 0.8 μm, average silver iodide content 8.0 mol%, monodispersed surface low silver iodide content emulsion Em-2 Average grain size 0.38 μm, average silver iodide content 8 mol %, Monodispersion type, surface low silver iodide-containing emulsion Em-3 Average grain size: 0.65 μm, average silver iodide content: 8 mol%, monodispersion type, surface low silver iodide-containing emulsion Em-4: average grain size Em-5 having a diameter of 0.85 μm, an average silver iodide content of 8 mol%, a monodispersed emulsion, and a surface low silver iodide-containing emulsion Em-5 having an average grain size of 1.20 μm, an average silver iodide content of 6 mol%, and a monodispersed emulsion. Surface-low silver iodide-containing emulsion Em-6 Average grain size 0.70 μm, average silver iodide content 8 mol%, monodispersed emulsion, surface low silver iodide-containing emulsion Em-7 Average grain size 1.40 μm, average iodine Emulsion having a silver iodide content of 8 mol%, monodispersion type, surface low silver iodide content type Em-8 Average grain size 0.08 μm, average silver iodide content of 4 mol%, monodispersion type, surface low silver iodide content type Emulsion [EmB-1] Em-2 described in Japanese Patent Application No. 2-39004.
The same emulsion as described above is prepared as follows.

[Preparation of Silver Iodide Fine Particles] An aqueous solution containing 5% by weight of ossein gelatin was added to a reaction vessel, and while stirring at 40 ° C., a 3.5N silver nitrate aqueous solution and a 3.5N potassium iodide aqueous solution were each 1 mol 30 minutes. Was added at a constant rate.

The pAg during the addition is controlled by a conventional pAg control means.
Kept at 13.5. The formed silver iodide has an average grain size of 0.06 μm β
-AgI and a mixture of γ-AgI.

This emulsion is called a silver iodide fine grain emulsion.

[Preparation of Spherical Twin Seed Emulsion] A monodisperse spherical seed emulsion was prepared by the following method.

A ₃ Ossein gelatin 150 g Potassium bromide 53.1 g Potassium iodide 24 g 7.2 L with water B ₃ Silver nitrate 1.8 kg 6 L with water C ₃ Potassium bromide 1327 g 1-Phenyl-5-mercaptotetrazole (dissolved in methanol) 0.3 g 3 liters of water D ₃ ammonia water (28%) 705 ml The B ₃ solution and the C ₃ solution were added to the A ₃ solution stirred vigorously at 40 ° C. in 30 seconds by the double jet method to generate nuclei. Was.
The pBr at this time was 1.09 to 1.15.

[0088] After 1 minute 30 seconds, it was added in 5 minutes aging at C ₃ solution for 20 seconds. During ripening, the KBr concentration was 0.071 mol / l and the ammonia concentration was 0.63 mol / l.

Thereafter, the pH was adjusted to 6.0, and immediately desalination was performed.
Washing was performed. When this seed emulsion was observed with an electron microscope, it was a monodisperse spherical emulsion having an average particle size of 0.36 μm and a distribution of 18%. This emulsion is called a seed emulsion.

Next, an emulsion having an average grain size of 1.25 μm according to the present invention was prepared using the following three kinds of aqueous solutions, an emulsion solution containing a silver iodide fine grain emulsion and a seed emulsion.

Aqueous solution A ₂ gelatin 231.9 g HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] ₁₇ (CH ₂ CH ₂ O) _n H 10% methanol solution (average molecular weight about 1300) 30.0 ml 28% ammonia water 1056ml Add water to make 11827ml.

[0092] by adding an aqueous solution B ₂ Silver nitrate 1587g 28% aqueous ammonia 1295ml water to 2669ml.

Aqueous solution C ₂ Potassium bromide 1572 g Water is added to make 3774 ml.

[0094] silver iodide fine emulsion containing solution D ₂ silver iodide fine grain emulsion 1499.3G 4-hydroxy-6-methyl-1,3,3a, 7- tetrazaindene 5.2 g 10% aqueous potassium hydroxide solution 14.75ml Add water to make 1373 ml.

At a temperature of 60 ° C., 0.407 mol of a seed emulsion was added to an aqueous solution A ₂ of the above composition which was vigorously stirred.
The pH and pAg were adjusted using acetic acid and aqueous potassium bromide solution.

Thereafter, while controlling the pH and the pAg as shown in Table 5, the aqueous solutions B ₂ and C ₂ and the emulsion solution D ₂ containing silver iodide fine particles were added to Tables 7 and 8, respectively.
And by the triple jet method at a flow rate as shown in Table 9.

After the addition was completed, an aqueous solution of phenylcarbamyl gelatin was added, and the pH of the mixed solution was adjusted to precipitate and aggregate the particles, followed by desalting and washing with water.

Then, the pH was adjusted to 5.80 and the pAg to 8.06 at 40 ° C.

Thus, a monodispersed silver iodobromide emulsion having an average grain size of 1.25 μm, an average silver iodide content of 8.0 mol% and a grain size distribution of 13.2% was obtained.

This emulsion is designated as EmB-1.

Table 10 shows the particle structure in the formulation of EmB-1 and the volume ratio of each phase.

[0102]

[Table 7]

Table 7 shows the grain growth conditions of EmB-1.

Table 8 shows the addition pattern of B ₂ , Table 9 shows the addition pattern of C ₂ , and Table 10 shows the addition pattern of D ₂ .

[0105]

[0106]

[Table 11]

This EmB-1 has the following characteristics.

Average grain size 1.25 μm Monodispersity (width of distribution) 14.0% Average silver iodide content 8.0% Silver iodide content deviation at outer periphery of grain 0.0 mol% Silver iodide content relative standard deviation 9.0% Surface Silver iodide content 0.0 mol% Average aspect ratio 3.3 After adjusting the pAg of the emulsion Em to 8.5, pH 5.8 and a temperature of 55 ° C., the sensitizing dyes S-7, S-6, S-5 and S-8 were added. In addition, the sensitizing dye was adsorbed for an additional 30 minutes. Thereafter, 1.0 × 10 ⁻⁶ mol / mol AgX sodium thiosulfate was added, and 10 minutes later, a mixed solution of chloroauric acid 2.2 × 10 ⁻⁷ mol / mol AgX and ammonium thiocyanate was added, followed by aging for 60 minutes.

The basic structure of the multilayer sample 101 is shown below.

[0110] In all of the following description, the addition amount of the compound to the photosensitive material in particular shows the number of grams per 1 m ² unless otherwise noted.

Further, silver halide and colloidal silver are shown in terms of silver, and the amount of sensitizing dye added is shown as the number of moles per mole of AgX in the same layer.

Sample-101 First Layer: Anti-Harlation Layer Black Colloidal Silver 0.18 g Gelatin 1.57 g Ultraviolet Absorber (UV-1) 0.17 g High Boiling Solvent (Oil-1) 0.14 g Second Layer: First Intermediate Layer Gelatin 1.00 g Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (Em-2) 0.66 g Silver iodobromide emulsion (Em-3) 0.29 g Gelatin 1.29 g Sensitizing dye (S-1) 3.21 × 10 ^-4 mol Sensitizing dye (S-2) 2.71 × 10 ^-4 mol Sensitizing dye (S-3) 3.45 × 10 ^-5 mol Coupler (C-1) 0.96 g Colored coupler (CC-1) 0.07 g High Boiling point solvent (Oil-1) 0.52 g Fourth layer: second intermediate layer Gelatin 0.75 g Fifth layer: first green-sensitive emulsion layer Silver iodobromide emulsion (Em-2) 0.66 g Silver iodobromide emulsion (Em- 3) 0.29 g gelatin 1.08 g sensitizing dye (S-7) 2.67 × 10 ^-4 mol sensitizing dye (S-6) 2.23 × 10 ^-4 mol sensitizing dye (S-5) 4.48 × 10 ^-5 mol Sensitizing dye (S-8) 7.04 × 10 ^-6 mol Coupler (M-4) 0.13 g Coupler (M-2) 0.29 g Colored coupler (CM-2) 0.082 g High boiling solvent (Oil) -3) 0.51 g Sixth layer: second green-sensitive emulsion layer Silver iodobromide emulsion (Em-4) 0.76 g Gelatin 0.80 g Sensitizing dye (S-7) 1.45 × 10 ^-4 mol Sensitizing dye (S- 6) 1.21 × 10 ^-4 mol sensitizing dye (S-5) 2.43 × 10 ^-5 mol Sensitizing dye (S-8) 3.82 × 10 ^-6 mol Coupler (M-4) 0.036 g Coupler (M-2) 0.077 g Colored coupler (CM-1) 0.035 g High boiling solvent (Oil-3) 0.15 g Seventh layer: Third intermediate layer Gelatin 0.55 g SC-1 0.032 g Eighth layer: First blue-sensitive emulsion layer Iodobromide silver halide emulsion (Em-3) 0.76g gelatin 1.16g sensitizing dye (S-11) 2.88 × 10 -4 mol sensitizing dye (S-9) 7.19 × 10 -5 mol coupler (Y-1) 0.40g high-boiling Solvent (Oil-3) 0.16 g Ninth layer: fourth intermediate layer Gelatin 0.75 g SC-1 0.044 g Tenth layer: second red-sensitive emulsion layer Silver iodobromide emulsion (Em-1) 0.95 g Gelatin 0.93 g increase Sensitizing dye (S-1) 1.74 × 10 ^-4 mol Sensitizing dye (S-2) 1.47 × 10 ^-5 mol Sensitizing dye (S-3) 1.87 × 10 ^-5 mol Coupler (C-1) 0.33 g high Boiling point solvent (Oil-1) 0.33 g Eleventh layer: Third red-sensitive emulsion layer Silver iodobromide emulsion (Em-5) 2.30 g Gelatin 1.49 g Sensitizing dye (S-1) 1.16 × 10 ^-4 mol Sensitization Dye (S-2) 9.80 × 10 ^-5 mol Sensitizing dye (S-3) 1.25 × 10 ^-5 mol Coupler (C-2) 0.19 g SC-1 0.027 g High boiling solvent (Oil-1) 0.43 g 12th layer: 5th intermediate layer Gelatin 0.75 g SC-1 0.044 g 13th layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion (EmB-1) 1.82 g Gelatin 0.62 g Sensitizing dye (S-7) 9.62 × 10 ^-5 mol sensitized Containing (S-6) 8.00 × 10 -5 mol sensitizing dye (S-5) 1.61 × 10 -5 mol sensitizing dye (S-8) 2.53 × 10 -6 mol Coupler (M-3) 0.06 g Coupler ( M-2) 0.13 g Colored coupler (CM-2) 0.01 g High boiling solvent (Oil-1) 0.35 g 14th layer: 6th intermediate layer Gelatin 0.75 g SC-1 0.044 g 15th layer: 2nd blue-sensitive emulsion Layer Silver iodobromide emulsion (Em-6) 1.06 g Gelatin 0.925 g Sensitizing dye (S-11) 2.17 × 10 ^-4 mol Sensitizing dye (S-9) 1.12 × 10 ^-5 mol Coupler (Y-1) 0.31 g High boiling solvent (Oil-3) 0.13 g Sixteenth layer: Third blue-sensitive emulsion layer Silver iodobromide emulsion (Em-7) 1.84 g Gelatin 1.10 g Sensitizing dye (S-11) 1.44 × 10 ^-4 Molar sensitizing dye (S-9) 5.65 × 10 ^-5 mol Coupler (Y-1) 0.52 g High boiling solvent (Oil-3) 0.21 g 17th layer: 1st protective layer Silver iodobromide emulsion (Em-8) ) 0.10g gelatin 1.52 g UV absorber (UV-1) 0.006 g UV absorber (UV-2) 0.099 g High boiling solvent (Oil-1) 0.0065 g High boiling solvent (Oil-4) 0.0065 g 18th layer: 2nd protective layer Gelatin 0.55 g Alkali-soluble matting agent (average particle size 2 μm silica) 0.12 g Polymethyl methacrylate (average particle size 3 μm) 0.02 g Sliding agent (WAX-1) 0.04 g Agent (Su-
1), dispersing aids (Su-2, Su-3), gelatin hardeners (HI, H-2), stabilizers (Stab-1), antifoggants (AF-1, AF-2) and Preservative (DI-1)
Was added.

[0113]

Embedded image

[0114]

Embedded image

[0115]

Embedded image

[0116]

Embedded image

[0117]

Embedded image

[0118]

Embedded image

[0119]

Embedded image

[0120]

Embedded image

[0121]

Embedded image

[0122]

Embedded image

The above sample was exposed to a wedge through a yellow filter, and then subjected to the following development processing.

Processing step (38 ° C.) Standard for color development 2 minutes 45 seconds Bleaching 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the processing solution used in the process is exactly the same as that used in Example 1.

The relative sensitivity of each of the obtained samples was measured using green light. The results at that time are shown in Tables 12 to 14.

The sensitivity was defined in the same manner as in Example 1, and
The relative sensitivity was expressed by setting the sensitivity in one day of natural standing of 100 to 100.

[0127]

[Table 12]

[0128]

[Table 13]

[0129]

[Table 14]

The sensitivity was represented by the reciprocal of the exposure amount giving a density of fog + 0.1, and was represented by a relative value with the blue sensitivity on the same day being 100. Sample No. Nos. 6 to 53 of the compounds of the present invention It can be seen that the regression width of the latent image after exposure is smaller than that in the case where the comparative compounds 1 to 5 are added.

[0131]

According to the present invention, the stabilization of a latent image after exposure has been achieved by adding a novel compound to a silver halide photographic material.

Claims (1)

(57) [Claims] 1. A silver halide photographic material comprising a compound represented by the following general formula [I]: [Wherein, R1 and R2 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group;
1 is an oxygen atom, a selenium atom, a sulfur atom, a tellurium atom,
-N (R7)-and -C (R8) (R9)-. R1 and R2 may combine to form a ring. R7, R8 and R
9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. R3, R4, R5 and R6 represent a hydrogen atom or a substituent. Z2 is 5-6
L1 represents a non-metallic atomic group for forming a membered heterocyclic ring;
L2 represents a methine group. ]