JPH06235997A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide emulsion capable of attaining the stability of a latent image after exposure and improving the aging preservation property, particularly regression of the latent image, by adding a new compound to a silver halide photosensitive material. CONSTITUTION:A silver halide photosensitive material contains a compound expressed by the formula, where R1, R2 indicate hydrogen atom, the alkyl group, alkenyl group, alkinyl group, allyl group, and heterocyclic group, R3, R4, R5, R6 indicate hydrogen atom or a substituent, Z indicates a group of nonmetal atoms for forming a 5-6-membered ring, and R1, R2 may form a ring. Any silver halide of silver bromide, silver bromide iodide, silver bromide chloride iodide, silver bromide chloride, and silver chloride may be used for the photographic emulsion layer of the photosensitive material. Silver bromide iodide, silver bromide, or silver bromide chloride containing silver iodide of 30mol.% is preferably used for the silver halide. Various couplers may be used in this photosensitive material in response to the color to be generated in each photosensitive layer.

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 storability is improved by a novel compound. .

[0002]

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

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

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

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

Therefore, the latent image has the property of being easily attenuated or subjected to an intensifying force with the lapse of time from exposure to development.

This attenuation of the latent image is called "latent image regression" in the art, and the latter is called latent image assisting force.

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

The simplest method for solving the problems due to latent image regression or latent image intensification is to perform development processing immediately after photographing exposure, and the next simple method is the period until development processing after photographing exposure. The method is to cool the photographed light-sensitive material and store it at a low temperature.

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

From the viewpoint of actual usage conditions and usage patterns, there are cases where the film is left for several months between the photographic exposure and the development processing.

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

As a method of preventing latent image intensification, Japanese Patent Publication No.
-9109, a method of using a hardening agent that releases an acid in an emulsion film to lower the pH, and JP-A-48-6725 discloses a method of adding a rhodium compound and an iridium compound when emulsifying a silver halide, JP-B-57-23250 is a method of adding a mercapto heterocyclic compound to a silver halide emulsion prepared by using a rhodium compound, and JP-A-53-127714 is a silver halide emulsion prepared by using a rhodium compound. There has been proposed a method of adding a hydroxyazaindolizine compound and a nitrogen-containing heterocyclic compound having a mercapto group therein.

However, the silver halide emulsion was unsatisfactory because it had a specific preparation method, had to be spectrally sensitized with a specific sensitizing dye, and the effect was not sufficient.

[0015]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide emulsion having improved storability with time, especially latent image degradation.

[0016]

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

[0017]

[Chemical 2]

In the formula, R1 and R2 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group, and R3, R4, R5 and R6 represent a hydrogen atom or a substituent. Z represents a nonmetallic atom group for forming a 5- or 6-membered heterocycle. R1 and R2 may combine to form a ring.

In the general formula [I], the alkyl group represented by R1 and R2 is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group or a tert-group.
Examples thereof include a butyl group, an n-pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group and an n-dodecyl group. These alkyl groups further include a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.),
Alkoxy group (eg methoxy group, ethoxy group, 1,1-dimethylethoxy group, n-hexyloxy group, n-dodecyloxy group etc.), aryloxy group (eg 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 (eg, 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, etc., alkynyl group (eg, propargyl group, etc.), amino group (eg, amino) Group, N, N-dimethylamino group, anilino group, etc.), hydroxy group, cyano group, sulfo group, carboxyl group, sulfonamide group (for example, methylsulfonylamino group, ethylsulfonylamino group, n-butylsulfonylamino group,
n-octylsulfonylamino group, 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 with an alkyl group represented by R1 and R2, and a group similar to the group shown as the substituent of the alkyl group.

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

The heterocyclic group represented by R1 and R2 includes
For example, pyridyl group (eg, 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 , A sulforanyl group, a piperidinyl group, a pyrazolyl group,
Examples thereof include a tetrazolyl group. These groups are R1,
It can be substituted by the alkyl group represented by R2 and the same groups as those shown as the substituent of the alkyl group.

The substituents represented by R3, R4, R5 and R6 include alkyl groups (eg, 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 (eg, phenyl group, naphthyl group, etc.), heterocyclic group (eg,
Pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulforanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc., halogen atom (for example, chlorine Atom, bromine atom,
Iodine atom, fluorine atom, etc., alkoxy group (eg,
Methoxy group, ethoxy group, propyloxy group, n-pentyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-octyloxy group,
n-dodecyloxy group, etc.), an aryloxy group (eg,
Phenoxy group, naphthyloxy group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, n-butyloxycarbonyl group, n-
Octyloxycarbonyl group, n-dodecyloxycarbonyl group and the like), aryloxycarbonyl group (for example, phenyloxycarbonyl group, naphthyloxycarbonyl group and the like), 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) Group, dimethylaminosulfonyl group, n-butylaminosulfonyl group, n-hexylaminosulfonyl group, cyclohexylaminosulfonyl group, n-octylaminosulfonyl group, n-dodecylaminosulfonyl group, fluorine Nylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), ureido group (eg, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, n-octylureido group, n-dodecylureido 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, 2-
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, etc.), cyano group, nitro group, carboxyl group, hydroxyl group, hydrogen atom and the like. These groups can be substituted with an alkyl group represented by R1 and a group similar to the group shown as the substituent of the alkyl group.

Examples of the ring formed by combining R1 and R2 include a morpholine ring, a piperidine ring, a piperazine ring and a pyrrolidine ring. These rings are R1
It can be substituted with the alkyl group represented by and a group similar to the group shown as the substituent of the alkyl group.

The 5- or 6-membered ring represented by Z is 5
Or a 6-membered monocycle and a polycyclic condensed ring condensed with those rings, for example, cyclopentane ring, cyclohexane ring, benzene ring, naphthalene ring, thiophene ring, pyridine ring, furan ring, pyrimidine ring, pyran ring, Examples thereof include a pyrrole ring, a pyrazine ring, a thiazole ring, an oxazole ring, an imidazole ring, a selenazole ring, an indole ring, a morpholine ring, a piperidine ring, a piperazine ring, a pyrrolidine ring, a benzothiazole ring, a benzoxazole ring, and a benzimidazole ring. These rings can be substituted with an alkyl group represented by R1 or R2, and a group similar to the group shown as the substituent for the alkyl group.

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

[0028]

[Chemical 3]

[0029]

[Chemical 4]

[0030]

[Chemical 5]

[0031]

[Chemical 6]

[0032]

[Chemical 7]

[0033]

[Chemical 8]

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

Synthesis Example 1. (Synthesis of Compound Example 1) 9.3 g of aniline, p-dimethylaminobenzaldehyde 14.
9 g and 5 ml of concentrated hydrochloric acid were added, and the mixture was heated at 100 ° C. for 15 hours. After completion of the reaction, the mixture was neutralized with 10% aqueous sodium hydroxide solution and the precipitated solid was collected by filtration. The obtained crude crystal was dried and then recrystallized from toluene to obtain the desired product. Yield 17.5g,
The yield was 78%.

The silver halide of any one of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride is used in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. Good. Preferred silver halides are silver iodobromide, silver bromide and 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 crystal bodies such as cubes, octahedra and tetradecahedrons, and irregular crystal shapes such as spherical grains. It may have a crystal defect such as a crystal possession, a crystal plane such as a twin plane, or a combination thereof.

In the case of constituting 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 which are optionally used are generally preferably subjected to physical ripening or chemical ripening, In general, spectral sensitization is used depending on the photosensitive layer of each color used. Additives that can be used in such a process are Research Disclosure No. 17643, no. 18716, and No. 308119
(Respectively, RD17643, RD18716 and RD308119
Abbreviated).

The places described below are shown.

Item RD308119 Page / Item RD17643 Page RD18716 Page Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-A-A, B, 23-24 648-9 C, D, H , I, J item Supersensitizer 996 IV-AE, J item 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 In the practice of the present invention, Known photographic additives that can be used are also exemplified in the above Research Disclosure. Shown below are the relevant locations.

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 Whitening agent 998 V24 Ultraviolet absorber 1003 VIIIC, 25- 26 XIIIC Item Light absorber 1003 VIII 25 to 26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25 to 26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plastic 1006 XII 27 650 Moisture Lubricants 1006 XII 27 650 Activators / Coating aids 1005 XI 26 to 27 650 Agents Matting agents 1007 XVI Image agents 1011 XXB (Contained in light-sensitive material) The light-sensitive material of the present invention is colored in each color light-sensitive layer. Various couplers can be used depending on the desired color, specific examples of which are illustrated in Research Disclosure above. Shown below are the relevant locations.

The page-item RD17643 items RD308119 th page yellow coupler 1001 VII-D section VII C~G term magenta coupler 1001 VII-D section VII C~G Cyan coupler 1001 VII-D section VII C~G Colored Coupler 1002 VII-G term VII G term DIR coupler 1001 VII-F term VII F term BAR coupler 1002 VII-F term Other useful residue release 1001 VII-F term coupler Alkali-soluble coupler 1001 VII-E term of the present invention When various additives are used in the light-sensitive material, these can be added by the dispersion method described in RD308119XIV.

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

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

The present invention can be applied to various color light-sensitive materials typified 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 is RD17643 28-29.
Pages, RD18716, page 615, and RD308119, section XIX.

[0048]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto.

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

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

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

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

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

Aqueous solution (a-3) Gelatin 34.93 g Potassium bromide 1454.7 g Water is added 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 (Containing 45.6 g of gelatin per 1 mol of AgI and finishing to 1467 ml) 1239 ml 4-hydroxy -6-Methyl-1,3,3a, 7-tetrazaindene 5.22 g Add water to make 2294 ml.

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

Thereafter, while controlling the pH and pAg as shown in Table 1, each of (a-2), (a-3) and (a-4) was carried out at the flow rates shown in Tables 2 and 3. The aqueous solution was added by the double-mix method.

Table 1 shows the particle growth conditions of EmA-1.

[0059]

[Table 1]

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

[0061]

[Table 2]

[0062]

[Table 3]

Then, a phenylcarbamyl gelatin solution was added to the solution obtained above to adjust the pH of the solution to precipitate and agglomerate the particles, followed by desalting and washing with water.

Thus, a monodisperse 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 aged for 60 minutes.

Thereafter, the compounds of the present invention and comparative compounds 1 to 5 shown in Table 4 were each added to this emulsion in an amount of 1/10 mol of the total addition amount of the sensitizing dye, and thereafter the sensitizing dye SD shown below was added. -A, SD-B, and SD-C were used together for adsorption and spectral sensitization was performed. Furthermore, magenta couplers M-A and M-
B and MC were added.

Next, after uniformly adding an appropriate amount of 2-hydroxy-4,6-dichlorotriazidium as a hardening agent,
Each emulsion was coated and dried on an undercoated triacetate support so that the coated silver amount was 2.0 g / m ² , to obtain a light-sensitive material.

[0068]

[Chemical 9]

[0069]

[Chemical 10]

[0070]

[Chemical 11]

Each of these samples was subjected to wedge exposure by a usual method using green light, color-developed according to the following color processing steps, and photographic performances were compared and evaluated. The results are shown in Table 4. The green light sensitivities in Table 4 are shown as relative sensitivities when the sensitivity of Sample 1 (comparative) is 100.

Treatment process Treatment temperature Treatment time Color development 38 ° C. 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water wash 3 minutes 15 seconds Fixation 6 minutes 30 seconds Water wash 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry The composition of the processing solution used in each processing step is as follows.

(Color developer) 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 make 1000 ml, and adjust to pH 10.6 with sodium hydroxide.

(Bleach) Ethylenediaminetetraacetic acid iron (III) ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1000 ml, and pH was adjusted to 6.0 with ammonia water. Adjust to.

(Fixer) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.6 g Sodium metasulfite 2.3 g Water was added to make 1000 ml, and pH was adjusted to 6.0 with acetic acid. (Stabilizing liquid) Formalin (37% aqueous solution) 1.5 ml Conidax (Konica Corp.) 7.5 ml Add water to make 1000 ml.

[0076]

[Table 4]

Sensitivity is defined as the reciprocal of the exposure amount that gives a density of fog +0.1, and the same day green light sensitivity of sample No. 1 is 1
It was expressed as relative sensitivity when set to 00. The higher the number, the higher the sensitivity of the sample.

It can be seen that the compounds of the present invention are superior in latent image regression preventing blue feeling performance to the comparative compounds.

Example 2 A multilayer photosensitive material 101 was prepared by adjusting the following emulsions.

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 %, Monodisperse type, surface low silver iodide containing emulsion Em-3 average grain size 0.65 μm, average silver iodide content 8 mol%, monodisperse type, surface low silver iodide containing emulsion Em-4 average grain Diameter 0.85 μm, average silver iodide content 8 mol%, monodisperse type, surface low silver iodide content type emulsion Em-5 average grain size 1.20 μm, average silver iodide content 6 mol%, monodisperse type, surface Low silver iodide-containing emulsion Em-6 average grain size 0.70 µm, average silver iodide content 8 mol%, monodisperse type, surface low silver iodide-containing emulsion Em-7 average grain size 1.40 µm, average iodide Silver content 8 mol%, monodisperse type, surface low silver iodide content type emulsion Em-8 average grain size 0.08 μm, average silver iodide content 4 mol%, monodispersion type, surface low silver iodide Yes emulsion [EmB-1] Em-2 of Japanese Patent Application No. Hei 2-39004 specification, wherein
The same emulsion 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., 3.5N silver nitrate aqueous solution and 3.5N potassium iodide aqueous solution, 1 mol each for 30 minutes. Was added at a constant rate.

The pAg during addition is determined by a conventional pAg control means.
I kept it at 13.5. The produced silver iodide is β with an average grain size of 0.06 μm.
It was a mixture of -AgI and γ-AgI.

This emulsion is called a silver iodide fine grain emulsion.

[Preparation of Spherical Twinning 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 Water 7.2 liters B ₃ Silver nitrate 1.8 kg Water 6 liters C ₃ Potassium bromide 1327 g 1-phenyl-5-mercaptotetrazole (dissolved in methanol) 0.3g water with 3 liters D ₃ of aqueous ammonia (28%) to a vigorously stirred a ₃ solution with 705 ml 40 ° C., was added B ₃ solution and C ₃ solution by a double jet method at 30 seconds, subjected to generation of nuclei It was
At this time, pBr was 1.09 to 1.15.

After 1 minute and 30 seconds, C ₃ solution was added in 20 seconds and aging was carried out for 5 minutes. The KBr concentration during aging was 0.071 mol / liter, and the ammonia concentration was 0.63 mol / liter.

After that, the pH was adjusted to 6.0 and immediately desalted,
It was washed with water. When the seed emulsion was observed with an electron microscope, it was a monodisperse spherical emulsion having an average grain 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 types 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 in 10% methanol (average molecular weight about 1300) 30.0 ml 28% ammonia water 1056 ml Add water to make 11827 ml.

Aqueous solution B ₂ Silver nitrate 1587 g 28% ammonia water 1295 ml Water is added to make 2669 ml.

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

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

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

Thereafter, while controlling the pH and pAg as shown in Table 5, the aqueous solutions B ₂ and C ₂ and the emulsion solution D ₂ containing the silver iodide fine particles were added to Table 6 and Table 7, respectively.
And the triple jet method at the flow rates shown in Table 8.

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

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

Thus, a monodisperse 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 9 shows the particle structure of EmB-1 on the formulation and the volume ratio of each phase.

Table 5 shows EmB-1 grain growth conditions.

[0101]

[Table 5]

Table 6 shows the B ₂ addition pattern, Table 7 shows the C ₂ addition pattern, and Table 8 shows the D ₂ addition pattern.

[0103]

[Table 6]

[0104]

[Table 7]

[0105]

[Table 8]

[0106]

[Table 9]

This EmB-1 has the following characteristics.

Average grain size 1.25 μm Monodispersity (broad distribution) 14.0% Average silver iodide content 8.0% Peripheral silver iodide content deviation 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 emulsion Em to 8.5, pH 5.8 and temperature 55 ° C., sensitizing dyes S-7, S-6, S-5 and S-8 were added. In addition, the sensitizing dye was further adsorbed for 30 minutes. After that, 1.0 × 10 ⁻⁶ mol / mol AgX of sodium thiosulfate was added, and after 10 minutes, a mixed solution of 2.2 × 10 ⁻⁷ mol / mol AgX of chloroauric acid and ammonium thiocyanate was added and further aged for 60 minutes.

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

In all the following descriptions, the amount of the compound added to the light-sensitive material is the number of grams per 1 m ² unless otherwise specified.

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

Sample-101 First layer: anti-halation layer Black colloidal silver 0.18 g Gelatin 1.57 g Ultraviolet absorber (UV-1) 0.17 g High boiling point 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) 0.077g Colored coupler (CM-1) 0.035g High boiling point solvent (Oil-3) 0.15g 7th layer: 3rd intermediate layer gelatin 0.55g SC-1 0.032g 8th layer: 1st 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 Point 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 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 11th 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 Increase Sensitizing 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 point 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 sensitizing dye (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) 0.06g Coupler (M-2) 0.13g Colored coupler (CM-2) 0.01g High boiling solvent (Oil-1) 0.35g 14th layer: 6th intermediate layer Gelatin 0.75g SC-1 0.044g 15th layer : Second 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 point solvent (Oil-3) 0.13 g 16th layer: 3rd blue sensitive emulsion layer Silver iodobromide emulsion (Em-7) 1.84 g Gelatin 1.10 g Sensitizing dye (S-11) ) 1.44 × 10 ^-4 mol Sensitizing dye (S-9) 5.65 × 10 ^-5 mol Coupler (Y-1) 0.52 g High boiling point solvent (Oil-3) 0.21 g 17th layer: 1st protective layer Iodobromide Silver emulsion (Em-8) 0.10g Gelatin 1.52g Ultraviolet absorber (UV-1) 0.006g Ultraviolet absorber (UV-2) 0.099g High boiling point solvent (Oil-1) 0.0065g High boiling point solvent (Oil-4) 0.0065g Eighteenth layer: Second protective layer Gelatin 0.55g Alkali-soluble matting agent (average particle size 2μm silica) 0.12g Polymethylmethacrylate (average particle size 3μm) 0.02g Sliding agent (WAX-1) 0.04g For each layer In addition to the above composition, is a coating aid (Su-
1), dispersion aids (Su-2, Su-3), gelatin hardening agents (HI, H-2), stabilizers (Stab-1), antifoggants (AF-1, AF-2) and Preservative (DI-1)
Was added.

[0113]

[Chemical 12]

[0114]

[Chemical 13]

[0115]

[Chemical 14]

[0116]

[Chemical 15]

[0117]

[Chemical 16]

[0118]

[Chemical 17]

[0119]

[Chemical 18]

[0120]

[Chemical 19]

[0121]

[Chemical 20]

[0122]

[Chemical 21]

The above sample was subjected to wedge exposure through a yellow filter and then subjected to the following developing treatment.

Treatment process (38 ° C.) Color development Standard 2 minutes 45 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Settling 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying each The composition of the processing solution used in the processing step 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 10 and 11.

Sensitivity was defined as in Example 1, and sample 101
It was expressed as a relative sensitivity with 100 being the sensitivity for 1 day of natural standing.

[0127]

[Table 10]

[0128]

[Table 11]

The sensitivity is represented by the reciprocal of the exposure amount that gives a density of fog + 0.1, and is represented by a relative value with the blue sensitivity on the same day as 100. It can be seen that the compounds of the present invention of Sample Nos. 6 to 49 have smaller latent image regression width after exposure than the samples of Sample Nos. 1 to 5 to which the comparative compound is added.

[0130]

INDUSTRIAL APPLICABILITY The present invention achieves stabilization of a latent image after exposure by adding a novel compound to a silver halide photographic light-sensitive material.

[0131]

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[Procedure amendment]

[Submission date] January 28, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1] [Wherein R 1 and R 2 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R 1
3, R4, R5 and R6 represent a hydrogen atom or a substituent. Z represents a nonmetallic atomic group for forming a 5- or 6-membered ring. R1 and R2 may form a ring. ]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

In the formula, R1 and R2 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group, and R3, R4, R5 and R6 represent a hydrogen atom or a substituent. Z represents a nonmetallic atomic group for forming a 5- or 6-membered ring. R1 and R2 may combine to form a ring.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material containing a compound represented by the following general formula [I]. [Chemical 1] [Wherein R 1 and R 2 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R 1
3, R4, R5 and R6 represent a hydrogen atom or a substituent. Z represents a nonmetallic atom group for forming a 5- or 6-membered heterocycle. R1 and R2 may form a ring. ]