JPH11271909A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve influences on the storage stability in fog and sensitivity due to chlorine ions contained in gelatin by specifying the chlorine ion content in the silver halide photo-graphic sensitive material. SOLUTION: A binder for forming at least one of silver halide emulsion layers is composed essentially of the gelatin containing chlorine ions reduced to 500 ppm, preferably, 300 ppm, especially, 100 ppm. The content of chlorine ions is reduced by the usual ion exchange method and an effect on the storage stability is similar as far as the absolute amount of the chlorine ions is reduced. As the hydrophilic binder, the gelatin is used as a main component, and it is preferred to reduce an amount of calcium ions, too, to <=50 ppm, preferably, to <=10 ppm in addition to the chlorine ions.

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 having improved storage stability.

[0002]

2. Description of the Related Art Ordinary photographic gelatin contains many raw materials and many inorganic ions mixed during production. Since the inorganic ions have various effects on the photographic performance, many gelatin production processes are provided with a deionization process. Particularly, since the influence of calcium ions is large, for example, JP-A-64-73337,
JP-A-62-168132, JP-A-1-179141,
Japanese Patent Application Laid-Open No. 1-211754 discloses a technique in which the calcium content is defined and its influence is reduced as much as possible. However, the influence of calcium was originally attracted much attention due to the large content of calcium. However, as the calcium content became smaller and the effect became smaller, the effects of other ions became not negligible. In particular, chloride ions act directly on silver halide,
It has been found that the silver halide photographic material has a bad influence on the storage stability.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material in which the influence of the above-mentioned chloride ion on the preservability is improved.

[0004]

The above object of the present invention is achieved by the following constitution.

[0005] 1. In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide photographic light-sensitive material has a chloride ion of 500 or more.
A silver halide photographic light-sensitive material characterized by being at most ppm.

[0006] 2. In a silver halide photographic material having at least one silver halide emulsion layer on a support, a binder forming at least one of the silver halide emulsion layers is mainly composed of gelatin, and chloride ions of the gelatin are A silver halide photographic light-sensitive material characterized by being at most 500 ppm.

[0007] 3. A method for producing a silver halide photographic light-sensitive material, comprising using gelatin in which chlorine ions are reduced to 500 ppm or less by deionization.

[0008] 4. 3. The silver halide photographic material according to 1 or 2, wherein the silver halide photographic material is hardened with a vinyl sulfone hardener having a molecular weight of 350 or less.

[0009] 5. 5. The silver halide photographic light-sensitive material according to 1, 2, or 4, wherein the silver halide emulsion layer contains tabular silver halide grains having an aspect ratio of at least 3.

[0010] 6. 6. The silver halide photographic material according to 1, 2, 4 or 5, wherein the vinyl sulfone hardener having a molecular weight of 350 or less is represented by the following general formula (1).

[0011]

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[In the formula, A represents a linking group having at least one ether bond, hydroxyl group, or amide bond, or an alkylene chain having 1 to 6 carbon atoms. n is 2 or 3
Represents ] 7. 7. The silver halide photographic light-sensitive material according to 6, wherein A of the vinyl sulfone hardener represented by the general formula (1) is a group selected from the following groups.

[0013]

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8. The calcium content of gelatin obtained by deionizing the chloride ion to 500 ppm or less is 50 ppm.
8. The silver halide photographic light-sensitive material according to any one of items 1, 2, 4 to 7, wherein

9. (1) the deionized gelatin is lime-treated in the presence of at least one selected from primary amine compounds and secondary amine compounds;
9. The silver halide photographic light-sensitive material according to any one of 2, 4 to 8.

10. In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the gelatin in at least one silver halide emulsion layer contains 50 ppm or less of calcium ions and 50 ppm or less. A silver halide photographic material characterized in that calcium is added to the extent possible.

Hereinafter, the present invention will be described in detail.

In the silver halide photographic light-sensitive material of the present invention (hereinafter also referred to as a light-sensitive material), a binder forming at least one layer of a silver halide emulsion layer contains gelatin as a main component, and the gelatin contains 500 ppm of chloride ions.
It is characterized by containing deionized gelatin, preferably 300 ppm or less, more preferably 100 ppm or less. In order to reduce the amount of chloride ions, a method using an ion exchange method is usually employed, but the effect on storage stability is the same in any method as long as the absolute amount of chloride ions is reduced.

The hydrophilic binder of the silver halide photographic light-sensitive material of the present invention contains gelatin as a main component, and as a hardener for hardening the gelatin, the pH of the film surface of the silver halide photographic light-sensitive material varies. A vinyl sulfone-based material is preferable because it is not allowed to be used. In particular, a hardening agent having a molecular weight of 350 or less is preferable from the viewpoint of high diffusivity, uniformity of the hardening degree of each layer, and stabilization of storage stability. Molecular weight 35
0 or less of a vinyl sulfone hardener is represented by the following general formula (1)
Is preferably represented by

[0020]

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[In the formula, A represents a linking group having at least one ether bond, hydroxyl group, or amide bond, or an alkylene chain having 1 to 6 carbon atoms. n is 2 or 3
Represents A of the vinyl sulfone hardener represented by the general formula (1) is preferably selected from the following.

[0022]

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Hereinafter, specific examples of the vinyl sulfone-based hardener represented by the general formula (1) of the present invention will be shown, but the invention is not limited thereto.

[0024]

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These hardeners represented by the general formula (1) are used in an amount of 1 to 50 with respect to 1 g of gelatin as a binder.
mg, preferably in the range of 5 to 40 mg. As the hardener, other carboxy active hardeners, epoxy hardeners and acrylic hardeners may be used in combination.

It is preferable that the gelatin of the present invention not only has a reduced amount of chloride ions but also has a reduced amount of calcium ions. The content is 50 ppm or less, preferably 10 ppm or less. In order to improve the storage stability of the silver halide photographic light-sensitive material, it is more preferable to add calcium in an amount of 50 ppm or less to the deionized gelatin. Calcium originally contained in gelatin and calcium added later have different effects, and the effect is greater when calcium is added again to deionized gelatin. This was a surprising finding.

The light-sensitive material of the present invention has at least one layer of a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer on a support. This is a silver halide color photographic light-sensitive material in which one color-sensitive layer is composed of three or more layers.

The order of applying the red-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer and the blue-sensitive silver halide emulsion layer is not particularly limited, but the red-sensitive silver halide emulsion layer, the green It is preferably a light-sensitive silver halide emulsion layer or a blue-sensitive silver halide emulsion layer.

In the present invention, at least one color-sensitive layer may be composed of three or more layers, and preferably, two or more color-sensitive layers are composed of three or more layers.

In the present invention, at least one color-sensitive layer comprises three or more layers containing a silver halide emulsion, and these layers have a difference in sensitivity. The sensitivity referred to here is determined according to the sensitivity evaluation method of the embodiment described later. (However, in the case of a green-sensitive layer and a red-sensitive layer, a Toshiba glass filter Y-48 is used at the time of exposure.) The sensitivity difference of each layer is not particularly limited, but the sensitivity is expressed by a logarithm of an exposure amount that gives a certain density. In this case, the sensitivity difference is 0.
It is preferably from 1 to 1.0.

The order of coating is not particularly limited, but is preferably a layer having the lowest sensitivity, a layer having an intermediate sensitivity, and a layer having the highest sensitivity from the support side. These three or more layers may be immediately adjacent to each other, or a hydrophilic colloid layer containing no silver halide emulsion may be used.
May be present.

The image forming coupler according to the present invention may be any coupler as long as it forms a color image.

Examples of the yellow coupler include those described in US Pat. Nos. 3,933,051, 4,022,620, 4,326,024, 4,401,752, and 4,248,961. JP-B-58-10739, British Patent Nos. 1,425,020 and 4,314,023
No. 4,511,649, European Patent 249,473
Those described in No. A or the like are preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Pat. Nos. 3,061,432, 3,725,067, 4,310,619, and 4,351. , 897, EP 73,636, Research Disclosure (hereinafter referred to as RD) 24220, 24230 (June 1984), JP-A-55-118034, and JP-A-60-335.
No. 52, No. 60-35730, No. 60-43659
No. 60-185951, No. 61-72238,
U.S. Pat. Nos. 4,500,630 and 4,540,654
No. 4,556,630, International Publication WO88 / 04
No. 795.

Examples of the cyan coupler include known phenol couplers and naphthol couplers. For example, US Pat. Nos. 4,228,233, 4,296,200, 2,369,929, and 2,810, Nos. 171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011, 4,327,173 No. 3,329,729, European Patent 121,36.
Nos. 5A and 249,453A; U.S. Pat.
No. 622, No. 4,333,999, No. 4,775,6
No. 16, 4,451, 559, 4,427,76
No. 7, 4,690,889, 4,254,212
No. 4,296,199, JP-A-61-42658.
No. 1 are preferred.

Further, a coupler having the following functions and structures may be used.

For the purpose of correcting unnecessary absorption of a coloring dye, a coupler described in US Pat. No. 4,744,181 for correcting unnecessary absorption of a coloring dye by using a fluorescent dye released at the time of coupling, and US Pat. , No. 120, it is also preferable to use a coupler having a dye precursor group capable of forming a dye by reacting with a developing agent as a leaving group.

US Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, West German Patent (published) 3,234, and the like are examples of couplers in which a coloring dye has an appropriate diffusivity. No. 533 is preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820, 4,080,
No. 211, No. 4,367,282, No. 4,409,3
20 and 4,576,910, British Patent 2,10
2,173.

Couplers which release a photographically useful residue upon coupling can also be preferably used in the present invention. A DIR coupler releasing a development inhibitor is disclosed in
Nos. 7-151944, 57-154234, 60
Nos. 184248, 63-37346, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred.

As a coupler which releases a nucleating agent or a development accelerator in an image form during development, British Patent 2,097,1 discloses a coupler.
Nos. 40 and 2,131,188, JP-A-59-157.
Nos. 638 and 59-170840 are preferred.

Other couplers that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
No. 4,283,472.
No. 4,338,393, and 4,310,618, multi-equivalent couplers described in JP-A-60-185950.
Compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound, or DIR redox compound described in JP-A-62-24252.
IR redox releasing redox compounds, EP 17
No. 3,302A, couplers capable of releasing a dye which becomes bicolor after release, RD11449, JP-A-24241, JP-A-61-61
Bleaching accelerator releasing couplers described in
Examples thereof include a ligand releasing coupler described in U.S. Pat. No. 4,553,477 and a leuco dye releasing coupler described in JP-A-63-75747.

Further, various couplers can be used in the present invention, and specific examples thereof are RD17643 described above.
VII-CF and RD308119, 1001-2
Page VII-DF.

The additive used in the present invention is RD3081
19, XIV, etc. can be added.

The coupling reactivity of the coupler is described in J. Org. Te
xter's method (J. Texter, J. Photog)
r. Sci. , 36, 14 (1988)), i.e., a competitive reaction using a water-soluble external coupler citrazic acid.

The couplers which are the object of the present invention are the image forming couplers which have the same color sensitivity and are added to each of the plurality of layers in the largest number of moles.

In the present invention, it is preferable that the same color-sensitive layer has at least three layers, and that the medium-sensitive layer contains a coupler having a slower reaction than the couplers contained in the high-sensitive layer and the low-sensitive layer.

The silver halide grain of the present invention has two parallel main planes in that the influence of chloride ions is small and the storage stability is hardly affected, and the equivalent circle diameter of the main plane (the same projection as the main plane) It is preferable that the tabular grains have a ratio of the diameter of a circle having an area) to the distance between the main planes (ie, the thickness of the grains), that is, the aspect ratio of 3 or more. Further, it is preferable that 50% or more of the total projected area of all grains is tabular grains having an aspect ratio of 5 or more.

The diameter of the tabular grains of the present invention is from 0.3 to 10
μm, preferably 0.5 to 5.0 μm, more preferably 0.5 to 2.0 μm. The particle thickness is preferably from 0.05 to 0.8 μm.

The measurement of the grain diameter and the grain thickness of the tabular grains can be obtained by the method described in US Pat. No. 4,434,226.

The size distribution of the tabular grains of the present invention is obtained by calculating the coefficient of variation of the circle-converted diameter of the main plane (the diameter of a circle having the same projected area as the main plane) (the standard deviation of the diameter distribution divided by the average diameter). Is preferably 30% or less, and more preferably 20% or less.

The halogen composition of the tabular grains of the present invention is preferably silver iodobromide or silver chloroiodobromide.
The silver iodide content is preferably from 1 to 15 mol%,
More preferably, it is 3 to 12 mol%.

The intergranular distribution of the silver iodide content of the tabular grains of the present invention is calculated by dividing the coefficient of variation of the silver iodide content (the standard deviation of the silver iodide content intergranular distribution by the average silver iodide content). Stuff) is 3
It is preferably at most 0%, more preferably at most 20%.

The tabular grains of the present invention preferably have at least two or more phases having different halogen compositions inside the grains, but the silver iodide content of the phase having the largest silver iodide content excluding the outermost layer Is preferably less than 10 mol%, more preferably less than 5 to 10 mol%, even more preferably less than 5 to 8 mol%. The volume fraction of the phase in the particles is preferably 30% or more and 90% or less, more preferably 30% or more and 60% or less. The outermost layer refers to a layer having a thickness of 100 ° on the grain surface, and the inside of the tabular grain of the present invention where the maximum silver iodide-containing layer is present refers to the inside of the outermost layer.

The structure related to the halogen composition in the silver halide grains can be examined by an X-ray diffraction method, a composition analysis method using EPMA, or the like.

The maximum silver iodide-containing phase in the grain as referred to in the present invention does not include a highly iodine-localized territory castle formed by the operation described below for forming dislocation lines.

As a method for producing tabular grains, methods known in the art can be appropriately combined. For example, JP-A Nos. 61-6643, 61-146305 and 62
-157024, 62-18556, 63-9
No. 2942, No. 63-151618, No. 63-163
No. 451, No. 63-220238, No. 63-3112
A known method such as No. 44 can be referred to. For example, p in a liquid phase in which silver halide is formed, which is one type of a double jet method, a double jet method, and a double jet method, is used.
A so-called control double jet method in which Ag is kept constant and a triple jet method in which soluble silver halides having different compositions are independently added can also be used. A forward mixing method can be used, and a method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. If necessary, a silver halide solvent can be used. Silver halide solvents often used include ammonia, thioethers and thioureas. Regarding thioethers, U.S. Pat.
271,157, 3,790,387 and 3,574,628. The mixing method is not particularly limited, and a neutral method using no ammonia, an ammonia method, an acidic method, or the like can be used. However, from the viewpoint of reducing fogging of silver halide grains, it is preferable to use pH (hydrogen). The logarithmic value of the reciprocal of the ion concentration) is 5.5 or less, more preferably 4.5 or less.

The tabular grains of the present invention contain iodide ions. In this case, the method of adding iodide ions in grain growth is not particularly limited, and they may be added as an ion solution such as potassium iodide. For example, it may be added as fine silver iodide particles.

The tabular grains of the present invention are preferably formed at least in part by using silver halide fine grains, since the halogen composition distribution among grains becomes more uniform and the non-uniformity of photosensitive quantum efficiency is reduced. It is more preferable to use silver halide fine grains throughout the grain growth. However, in the present invention, "growing using silver halide fine grains over the whole grains" means:
When seed particles are used, the seed particles are not included.

The grain formation using the silver halide fine grains is as follows.
Grains may be grown using only silver halide fine grains as in the grains disclosed in JP-A-1-183417, JP-A-1-183644, JP-A-1-183645 and the like.
It is sufficient that at least one of the halogen atoms is supplied by silver halide fine particles. In this case, the iodide ions are preferably supplied by silver halide fine particles. As claimed in Japanese Patent Application No. 3-218608, there are two or more kinds of silver halide fine grains used for grain growth, at least one of which is composed of only one kind of halogen atom. Is also good.

As in the claims described in JP-A-2-16737, it is desirable to use silver halide grains having a lower solubility than the growing silver halide grains. It is particularly desirable to use silver iodide as the grains.

The position of the dislocation of the tabular grains of the present invention does not necessarily have to be at a specific position, but preferably exists at the fringe portion of the tabular grains. It is also preferred that the compound be present both in the particle fringe portion and in the particle.

In the present invention, the fringe portion of a tabular grain refers to the outer periphery of the tabular grain. More specifically, the perpendicular to the vertical line dropped from the center of gravity of the tabular grain projection surface to each side of the grain as viewed from the principal plane side. Means a region outside 50% of the length (side), preferably outside 70%, and more preferably outside 80%.

The dislocation lines inside the grains as referred to in the present invention indicate dislocation lines existing in regions other than the above-mentioned fringe portion.

Regarding the number of dislocation lines in the tabular grains of the present invention, the number of dislocation lines containing 5 or more dislocation lines is preferably 50% or more of the total projected area of silver halide grains in the emulsion.
More preferably, it is 0% or more. Further, the number of dislocation lines is more preferably 10 or more.

When dislocation lines are present in the inside of the grain and the fringe portion, it is preferable that five or more dislocation lines exist inside the grain, and it is more preferable that there are five or more dislocation lines both inside the fringe portion and inside the grain.

The method for introducing dislocation lines in the tabular grains of the present invention is not particularly limited, but is a method in which an aqueous solution of an iodide ion such as potassium iodide and a water-soluble silver salt solution are added by double jet at the position where the dislocation is to be introduced. Or a method of adding silver iodide fine grains, a method of adding only an iodine ion solution, a method using an iodide ion releasing agent as described in JP-A-6-11781, and the like.
In particular, a method in which an aqueous iodide ion solution and a water-soluble silver salt solution are added by a double jet, a method in which silver iodide fine particles are added, and a method in which an iodide ion releasing agent is used are preferable, and a method in which silver iodide fine particles are used is more preferable. The aqueous solution of iodide ions is preferably an aqueous solution of an alkali iodide, and the aqueous solution of a water-soluble silver salt is preferably an aqueous solution of silver nitrate.

The dislocation is preferably introduced after the formation of the maximum silver iodide-containing phase inside the grain, and more preferably after the formation of the phase and before the formation of the adjacent phase.

In relation to the position of the entire grain, it is preferable that the silver is introduced in an amount corresponding to 50 to 95% of the silver amount of the entire grain, and more preferably 60 to 80%.

The silver halide emulsion of the present invention can be subjected to reduction sensitization. Reduction sensitization is performed by adding a reducing agent to a silver halide emulsion or a mixed solution for grain growth. Alternatively, a silver halide emulsion or a mixed solution for grain growth is prepared under a low pAg of pAg7 or less,
Alternatively, it is carried out by ripening or growing particles under high pH conditions of pH 7 or more. These methods may be combined. Also, JP-A-7-219093,
As described in JP-A-7-225438, reduction sensitization may be performed before or after the chemical sensitization step.

Preferred reducing agents include thiourea dioxide, ascorbic acid and its derivatives, and stannous salts. Other suitable reducing agents include borane compounds,
Examples include hydrazine derivatives, formamidinesulfinic acid, silane compounds, amines and polyamines, and sulfites. The addition amount is 10 ^-2 per mol of silver halide.
Preferred is from 10 to 10 ^-8 mol.

For low pAg ripening, a silver salt can be added, but a water-soluble silver salt is preferred. Silver nitrate is preferred as the water-soluble silver salt. The pAg at the time of aging is suitably 7 or less, preferably 6 or less, and more preferably 1 to 1.
3 (where pAg = -log [Ag ⁺ ]).

High pH ripening is carried out, for example, by adding an alkaline compound to a silver halide emulsion or a mixed solution for grain growth. As the alkaline compound,
For example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and the like can be used. In the method of adding ammoniacal silver nitrate to silver halide formation, an alkaline compound other than ammonia is preferably used because the effect of ammonia is reduced.

In the silver halide emulsion of the present invention, an oxidizing agent for silver may be added during the production process. The oxidizing agent for silver refers to a compound having an effect of acting on metallic silver to convert it into silver ions. In particular, a compound which converts silver atoms by-produced in the process of forming silver halide grains into silver ions is effective. Here, the generated silver ion may form a water-insoluble silver salt such as silver halide, silver sulfide, or silver selenide, or may form a water-soluble silver salt such as silver nitrate. You may.

The silver halide emulsion used in the present invention is preferably subjected to selenium sensitization in addition to sulfur sensitization and gold sensitization.

As the selenium sensitizer used in the present invention, selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Examples of unstable selenium compounds include, for example, JP-B-44-15748 and JP-B-43-134.
No. 89, Japanese Patent Application No. 2-130976, 2-22930
It is preferable to use the compound described in No. 0. Specific examples of unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids (for example, 2
-Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (eg, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium. No.

In the present invention, a tellurium sensitizer can be used in combination.

These selenium sensitizers and tellurium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent.
No. 38, No. 4-140742, No. 5-11381,
It can be added at the time of chemical sensitization in the form described in JP-A-5-11385 or JP-A-5-11388. Preferably, it is added before the start of chemical sensitization. The selenium sensitizer and the tellurium sensitizer used are not limited to one kind, and two or more of the above-described selenium sensitizer and tellurium sensitizer can be used in combination. An unstable selenium compound and a non-unstable selenium compound may be used in combination. Further, at least one of each of the selenium sensitizer and the tellurium sensitizer may be used in combination. The addition amount of the selenium sensitizer and tellurium sensitizer used in the present invention depends on the activity of the selenium sensitizer and tellurium sensitizer used, the type and size of silver halide, the ripening temperature and time, and the like. Different, but preferably 1 ×, per mole of silver halide.
It is at least 10 ^-8 mol. More preferably, it is 1 × 10 ⁻⁷ mol or more and 3 × 10 ⁻⁵ mol or less. The temperature of chemical ripening when using a selenium sensitizer and a tellurium sensitizer is preferably 45 ° C. or higher. More preferably 50 ° C or higher, 80 ° C
It is as follows. pAg and pH are arbitrary. For example, p
The effect of the present invention can be obtained in a wide range of H from 4 to 9. It is more effective to perform selenium sensitization and tellurium sensitization in the presence of a silver halide solvent.

Examples of the silver halide solvent which can be used in the present invention include US Pat. Nos. 3,271,157, 3,531,289 and 3,574,628; (A) Organic thioethers described in JP-A Nos. 1019 and 54-158917;
(B) thiourea derivatives described in JP-A Nos. 408, 55-77737 and 55-2982;
(C) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, (d) imidazoles described in JP-A-54-100717, e) sulfites, and (f) thiocyanate. Particularly preferred solvents include thiocyanate and tetramethylthiourea. Although the amount of the solvent used varies depending on the kind, for example, in the case of thiocyanate, the preferable amount is 1 × 10 ⁻⁴ mol to 1 × 10 ⁻² mol per mol of silver halide.

The silver halide photographic emulsion of the present invention can achieve higher sensitivity and lower fog by using sulfur sensitization and / or gold sensitization in chemical sensitization. Sulfur sensitization is usually performed by adding a sulfur sensitizer,
This is carried out by stirring the emulsion at a high temperature, preferably at 40 ° C. or higher, for a certain time. Gold sensitization is usually performed by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Known sulfur sensitizers can be used for the sulfur sensitization. For example, thiosulfates, thioureas, allylisothiocyanate, cystine, p-toluenethiosulfonate,
And rhodanine. Other US Patents 1,5
No. 74,944, No. 2,410,689, No. 2,
278,947, 2,728,668, 3,501,313, 3,656,955, German Patent 1,422,868, JP-B-56-2493.
No. 7, JP-A-55-45016 and the like can also be used. The addition amount of the sulfur sensitizer may be an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, silver halide grain size, etc., but is not less than 1.times.10.sup.- ⁷ mol per mol of silver halide.
× 10 ^-4 mol or less is preferred.

As the gold sensitizer for gold sensitization, the oxidation number of gold may be +1 or +3, and gold compounds usually used as gold sensitizers can be used. Representative examples include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric acidide, ammonium aurothiocyanate, pyridyl trichlorogold and the like. Although the amount of the gold sensitizer to be added varies depending on various conditions, it is preferably 1 × 10 ⁻⁷ mol to 5 × 10 ⁻⁴ mol per mol of silver halide.

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

In the present invention, reduction sensitization can be further used in combination. Specifically, for example, hydrazine derivatives, stannous chloride, aminoiminomethanesulfinic acid,
Examples include borane compounds and polyamine compounds.

In the present invention, the silver halide emulsion is prepared by using Research Disclosure 308119 (hereinafter referred to as RD308).
119) can also be used in combination. The places to be described are shown below.

[Item] [Page of RD308119] Iodine composition 993 IA Section Production method 993 IA and 994 E Crystal habit (normal crystal) 993 IA Crystal habit (twin crystal) 993 IA Item Epitaxial 993 IA Item Halogen composition (uniform) 993 IB Item Halogen composition (not uniform) 999 IB Item Halogen conversion 994 IC Item Halogen substitution 994 IC Item Metal-containing 994 ID Item Monodispersion 995 I-F Solvent addition 995 I-F Latent image forming position (surface) 995 I-G Latent image forming position (internal) 995 I-G Applicable photosensitive material (negative) 995 I-H Applicable light-sensitive material (positive) Section 995 IH Use the emulsion as a mixture Section 995 IJ Desalting Section 995 II-A The silver halide emulsion of the present invention has physical ripening, chemical ripening and spectral sensitization. It is possible to use what was done. Additives used in such a process are described in Research Disclosure No. 17643, no. 18716 and no.
308119 (hereinafter referred to as RD17643, RD1
8716 and RD308119).

The following shows the places to be described.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A section 23 648 Spectral sensitizer 996 IV-AA, B, 23 to 24 648 to 9C, D , H, I, J Section Supersensitizer 996 IV-AE, J Section 23-24 648-9 Antifoggant 998 IV 24-25 649 Stabilizer 998 IV 24-25 649 Known methods usable in the present invention Are also described in the above-mentioned Research Disclosure. The relevant sections are shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Anti-turbidity agent 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Brightener 998 V 24 UV absorber 1003 VIII- C, XIIIC section 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII binder 1003 IX 26 651 Static inhibitor 1006 XIII 27 650 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator Coating aid 1005 XI 26 to 27 650 Matting agent 1007 XVI developer (contained in the light-sensitive material) 1011 XXB Various couplers can be used in the present invention as long as the effects of the present invention are not impaired. A specific example is the above research disclosure. It is described in. The relevant locations are shown below.

[Item] [Page of RD308119] [RD17643] Colored coupler 1002 VII-G VIIG DIR coupler 1001 VII-F VIIF BAR coupler 1002 VII-F Other useful residues Emission coupler 1001 VII-F Item Alkali-soluble coupler 1001 Item VII-E The additives used in the present invention can be added by a dispersion method described in RD308119XIV.

In the present invention, the aforementioned RD17643
28 pages, RD18716 pages 647-8 and RD308
The support described in XIX 119 can be used.

The light-sensitive material of the present invention is obtained by using the above-mentioned RD30811
An auxiliary layer such as a filter layer or an intermediate layer described in section 9VII-K can be provided.

The light-sensitive material of the present invention can be obtained by using the above-mentioned RD30811.
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in section 9VII-K can be employed.

The present invention can be applied to various color light-sensitive 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. .

The light-sensitive material of the present invention includes, for example, the type / serial number, manufacturer name, emulsion No. Various information on photographic materials such as, for example, shooting date and time,
Aperture, exposure time, lighting conditions, filters used, weather,
Various information when shooting the camera, such as the size of the shooting frame, the model of the camera, the use of anamorphic lenses, etc., such as the number of prints, selection of filters, customer's color preference, the size of the trimming frame, etc. In order to input various information necessary at the time, for example, the same various information obtained at the time of printing, such as the number of prints, selection of a filter, preference of a customer's color, size of a trimming frame, and other customer information,
A magnetic recording layer may be provided.

In the present invention, the magnetic recording layer is preferably coated on the side opposite to the photographic component layer with respect to the support, and the undercoat layer, the antistatic layer (conductive layer), It is preferable that a recording layer and a slip layer are formed.

As the magnetic fine powder used for the magnetic recording layer, metal magnetic powder, iron oxide magnetic powder, Co-doped iron oxide magnetic powder, chromium dioxide magnetic powder, barium ferrite magnetic powder and the like can be used. . Methods for producing these magnetic powders are known, and they can be produced according to known methods.

The optical density of the magnetic recording layer is preferably small considering the influence on the photographic image, and is 1.5 or less, more preferably 0.2 or less, and particularly preferably 0.1 or less. The optical density is measured by using a Sakura densitometer PDA-65 manufactured by Konica Corporation, using a filter that transmits blue light, causing light having a wavelength of 436 nm to be perpendicularly incident on the coating film, Depends on the method of calculating the absorption.

The amount of magnetization of the magnetic recording layer per 1 m ² of the photosensitive material is preferably at least 3 × 10 ^-2 emu. The amount of magnetization was measured by using an external magnetic field of 1000 in a coating direction of a coating film having a fixed volume using a sample vibration magnetometer (VSM-3) manufactured by Toei Industry.
The magnetic flux density (residual magnetic flux density) when the external magnetic field is reduced to 0 after saturation with Oe once is measured, and this is converted into the volume of the transparent magnetic layer contained per 1 m ² of the photographic light-sensitive material. You can ask. If the amount of magnetization per unit area of the transparent magnetic layer is smaller than 3 × 10 ⁻² emu, input / output of magnetic recording is hindered.

The thickness of the magnetic recording layer is 0.01 to 20 μm
It is preferably from 0.05 to 15 μm, more preferably from 0.1 to 10 μm.

As the binder constituting the magnetic recording layer, vinyl resins, cellulose ester resins, urethane resins, polyester resins and the like are preferably used. It is also preferable to form a binder by aqueous coating using an aqueous emulsion resin without using an organic solvent. Further, it is necessary to adjust physical properties of the binder by curing with a curing agent, heat curing, electron beam curing, or the like. In particular, curing by adding a polyisocyanate-type curing agent is preferable.

It is necessary to add an abrasive to the magnetic recording layer in order to prevent clogging of the magnetic head, and it is preferable to add nonmagnetic metal oxide particles, particularly alumina fine particles.

Examples of the support for the photosensitive material include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), cellulose triacetate film, cellulose diacetate film, polycarbonate film, polystyrene film, and polyolefin film. it can.
In particular, JP-A-1-244446 and JP-A-1-291248.
No. 1-298350 No. 2-89045 No. 2
-93641, 2-181749, 2-214
When a polyester having a high water content as shown in JP-A Nos. 852 and 2-291135 is used, even if the support is thinned, the curl recovery property after the development processing is excellent.

In the present invention, the supports preferably used are cellulose triacetate, PET and PEN. When these are used, the thickness is preferably 50 to 100 μm, particularly preferably 60 to 90 μm.

The light-sensitive material of the present invention comprises ZnO, V ₂ O ₅ , T
iO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , Mg
It may have a conductive layer containing metal oxide particles such as O, BaO and MoO ₃ . As the metal oxide particles, those containing oxygen vacancies and those containing a small amount of heteroatoms forming a donor with respect to the metal oxide used are generally preferred because of high conductivity. It is preferable because no fog is given to the silver emulsion.

As the binder for the conductive layer or the undercoat layer, the same binder as that for the magnetic recording layer can be used.

Further, it is preferable to coat a higher fatty acid ester, a higher fatty acid amide, a polyorganosiloxane, a liquid paraffin, a wax, etc. on the magnetic recording layer as a sliding layer.

When the light-sensitive material of the present invention is used as a roll-shaped color light-sensitive material, not only can the size of the camera and the cartridge be reduced, but also resources can be saved, and the storage space for the developed negative film can be saved. , The film width is about 20 to 35 mm, preferably 20 to 35 mm.
３０30 mm. Shooting screen area is also 300-700mm
If it is in the range of about ² and preferably in the range of 400 to 600 mm ^2, the small format can be realized without deteriorating the image quality of the final photographic print, and the size of the patrone and the size of the camera can be reduced more than before. In addition, the aspect ratio of the shooting screen is not limited, and is not limited to the conventional 12 aspect ratio.
6 size 1: 1, half size 1: 1.4,135
It can be used for various types such as (standard) size 1: 1.5, high-vision type 1: 1.8, panorama type 1: 3.

When the light-sensitive material of the present invention is used in the form of a roll, it is preferable that the light-sensitive material is housed in a cartridge. The most common cartridge is the current 135 format patrone. In addition, JP-A-58-67329, JP-A-58-195236, JP-A-58-181535, JP-A-58-182634,
U.S. Pat. No. 4,221,479, JP-A-1-23104
No. 5, 2-170156, 2-199451,
2-124564, 2-201441, 2-
No. 205843, No. 2-210346, No. 2-211
No. 443, No. 2-214853, No. 2-264248
Nos. 3-37645 and 3-37646; U.S. Pat. Nos. 4,846,418 and 4,848,693;
The cartridges proposed in JP-A-4,832,275 and the like can also be used. Further, the present invention can be applied to "Small photographic roll film cartridge and film camera" in JP-A-5-210201.

The light-sensitive material of the present invention is the same as RD17643 described above.
Pages 28-29, RD18716 647 and RD30
The development can be performed by the usual method described in XIX of No. 8119.

[0110]

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

Example 1 Preparation of Seed Emulsion-1 A seed crystal emulsion was prepared as follows.

JP-B-58-58288, 58-58
No. 289, a silver nitrate aqueous solution (1.161 mol) was added to the following solution A1 adjusted to 35 ° C.
And a mixed aqueous solution of potassium bromide and potassium iodide (potassium iodide 2 mol%) while maintaining the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV. For 2 minutes to form nuclei. Subsequently, the temperature of the solution was raised to 60 ° C. over a period of 60 minutes, the pH was adjusted to 5.0 with an aqueous solution of sodium carbonate, and then an aqueous solution of silver nitrate (5.902 mol), potassium bromide and iodide were added. A mixed aqueous solution of potassium (2 mol% of potassium iodide) was added over 42 minutes by a double jet method while keeping the silver potential at 9 mV. After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing were immediately performed using a normal flocculation method.

The resulting seed crystal emulsion had an average sphere-equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and 90% or more of the total projected area of the silver halide grains had a maximum side ratio of 1.0%.
~ 2.0 hexagonal tabular grains. This emulsion is referred to as seed emulsion-1.

[Solution A1] Ossein gelatin 24.2 g Potassium bromide 10.8 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) (10% ethanol solution) 6.78 ml 10% nitric acid 114 ml H ₂ O 9657 ml Preparation of silver iodide fine grain emulsion SMC-1 6.0% by weight gelatin aqueous solution containing 0.06 mol of potassium iodide While stirring 5 liters vigorously, 7.06
2 liters of an aqueous silver nitrate solution and 2 liters of a 7.06 mol aqueous potassium iodide solution were added over 10 minutes. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles are prepared, the pH is adjusted using an aqueous sodium carbonate solution.
Was adjusted to 5.0. The average particle size of the obtained silver iodide fine particles was 0.05 μm. This emulsion is designated as SMC-1.

Preparation of Emulsion Em-1 0.178 moles of seed crystal emulsion-1 and HO (CH ₂ CH ₂
O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n
H (m + n = 9.77) in 10% ethanol solution 0.5
4.5% by weight of an aqueous inert gelatin solution 70
Keep 0 ml at 75 ° C., pAg 9.6, pH 5.0.
Then, particles were formed by the simultaneous mixing method with vigorous stirring by the following procedure.

1) 0.692 mol of silver nitrate aqueous solution and 0.1 mol
297 moles of SMC-1 and potassium bromide aqueous solution
The pAg was added while maintaining the pH at 9.6 and the pH at 5.0.

2) Subsequently, an aqueous solution of 2.295 mol of silver nitrate, 0.071 mol of SMC-1 and an aqueous solution of potassium bromide were added while maintaining the pAg at 9.6 and the pH at 5.0.

Each solution was added at an optimum rate throughout the particle formation so as to prevent formation of new nuclei and Ostwald ripening between particles. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The obtained emulsion had a particle size (cubic 1 of the same volume).
The emulsion was a tabular grain having a side composition of 1.00 μm and an average aspect ratio of 5.7 and having a halogen composition shown in Table 1 below. Observation of this emulsion with an electron microscope revealed that there were no grains having dislocation lines.

Preparation of Emulsion Em-2 0.178 mol of seed crystal Emulsion-1 and HO (CH ₂ CH ₂
O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n
H (m + n = 9.77) in 10% ethanol solution 0.5
4.5% by weight of an aqueous inert gelatin solution 70
0 ml at 75 ° C., pAg 8.3, pH 5.0.
Then, particles were formed by the simultaneous mixing method with vigorous stirring by the following procedure.

1) 2.1 mol of silver nitrate aqueous solution and 0.19
5 mol of SMC-1 and an aqueous solution of potassium bromide were added to pA
g while maintaining the pH at 8.9 and the pH at 5.0 (formation of host particles).

2) Subsequently, the temperature of the solution was lowered to 60 ° C., and pAg
Was adjusted to 9.8. Then, 0.071 mol of SMC
-1 was added and aging was performed for 2 minutes (introduction of dislocation lines).

3) 0.92 mol of silver nitrate aqueous solution and 0.0
69 mol of SMC-1 and an aqueous solution of potassium bromide were added to p
Ag was added while keeping the pH at 9.8 and the pH at 5.0 (shelling of host particles).

Each solution was added at an optimum rate throughout the particle formation so that the formation of new nuclei and the Ostwald ripening between particles did not proceed. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The obtained emulsion had a particle size (cubic 1 of the same volume).
Table 1 of 1.00 μm, average aspect ratio, 7.0
This was an emulsion comprising tabular grains having the halogen composition shown in Table 1. When this emulsion was observed with an electron microscope, five or more dislocation lines were observed in both the fringe portion and the inside of the grains in 60% or more of the total projected area of the grains in the emulsion.

Preparation of Emulsion Em-3 0.178 mol of seed crystal emulsion-1 and polyisoprene-
4.5% by weight containing 0.5 ml of a 10% solution of polyethylene oxy-disuccinate sodium salt in ethanol
Of inert gelatin aqueous solution at 75 ° C.
After adjusting the Ag to 8.9 and the pH to 5.0, particles were formed by the simultaneous mixing method with vigorous stirring by the following procedure.

1) 0.692 mol of silver nitrate aqueous solution
297 moles of SMC-1 and potassium bromide aqueous solution
The pAg was added while keeping the pH at 8.9 and the pH at 5.0.

2) Subsequently, an aqueous solution of 2.295 mol of silver nitrate, 0.071 mol of SMC-1 and an aqueous solution of potassium bromide were added while keeping the pAg at 8.9 and the pH at 5.0.

3) After completion of the step 2), 0.004 mol of SCM-1 was added and the mixture was aged for 15 minutes.

Each solution was added at an optimum rate throughout the particle formation so as to prevent formation of new nuclei and Ostwald ripening between particles. After the above step 3), after performing a water washing treatment at 40 ° C. using a normal flocculation method,
Gelatin was added for redispersion, and the pAg was adjusted to 8.1 and the pH was adjusted to 5.8.

The obtained emulsion had a particle size (cubic 1 of the same volume).
The emulsion was a tabular grain having a halogen composition shown in Table 1 having a side length of 0.65 μm and an average aspect ratio of 4.3. Observation of this emulsion with an electron microscope revealed that there were no grains having dislocation lines. The surface silver iodide content is 1
2.0 mol%.

Preparation of Emulsion Em-4 0.178 moles of seed crystal emulsion-1 and HO (CH ₂ CH ₂
O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n
H (m + n = 9.77) in 10% ethanol solution 0.5
4.5% by weight of an aqueous inert gelatin solution 70
0 ml at 75 ° C., pAg 8.9, pH 5.0.
Then, particles were formed by the simultaneous mixing method with vigorous stirring by the following procedure.

1) 2.1 mol of silver nitrate aqueous solution and 0.19
5 mol of SMC-1 and an aqueous solution of potassium bromide were added to pA
g was maintained at 8.9 and the pH was maintained at 5.0.

2) Subsequently, the solution was cooled to 60 ° C.
Was adjusted to 9.8. Then, 0.071 mol of SMC
-1 was added and aging was performed for 2 minutes (introduction of dislocation lines).

3) 0.959 mol silver nitrate aqueous solution and 0.1 mol
030 mol of SMC-1 and an aqueous solution of potassium bromide,
The pAg was added while maintaining the pH at 9.8 and the pH at 5.0.

Each solution was added at an optimum rate throughout the particle formation so as to prevent the formation of new nuclei and the Ostwald ripening between particles from proceeding. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The obtained emulsion had a particle size (cubic 1 of the same volume).
The emulsion was a tabular grain having a halogen composition shown in Table 1 having a side length of 0.65 μm and an average aspect ratio of 7.0. When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 6.7 mol%.

Table 1 below shows the AgI composition, aspect ratio, and the presence or absence of a transition line in each layer of the silver halide grains of the emulsions Em-1 to Em-4.

[0139]

[Table 1]

Emulsions A-1 to A-7, B
-1 to B-7 were produced.

"Preparation of Emulsions A-1 and A-2" For each of Em-1 and Em-2 shown in Table 1, SD-1 (structure will be described later) 3.0 × 10 3 per mol of silver at 55 ° C. ^-5 mol, S
D-2 (structure is described later) 1.5 × 10 ⁻⁴ mol, SD-3
(Structure will be described later) 3.0 × 10 ⁻⁴ mol is added, then 6.0 × 10 ⁻⁶ mol of sodium thiosulfate, 1.7 × 10 ⁻⁶ mol of chloroauric acid, and 3.1 × potassium thiocyanate.
10 ^-4 mol was added, and aging was performed for an optimum time.

After ripening, 4-hydroxy-6-methyl (1,3,3a, 7) tetrazaindene was added as a stabilizer to prepare emulsions A-1 and A-2, respectively.

"Preparation of Emulsion A-3" Em-2 described in Table 1
In addition, SD-1 3.0 × 1 per mol of silver at 55 ° C.
0 ^-5 mol, SD-2 1.5 × 10 ^-4 mol, SD-
3 3.0 × 10 ⁻⁴ mol were added, then 6.0 × 10 ⁻⁶ mol of sodium thiosulfate and a Se sensitizer (S below)
e-21) in an amount of 1.0 × 10 ⁻⁶ mol, chloroauric acid 1.7 ×
10 ^-6 mol, potassium thiocyanate 3.1 × 10 ^-4 m
ol, and after aging for an optimal time,
Emulsion A-3 was prepared by adding hydroxy-6-methyl (1,3,3a, 7) tetrazaindene as a stabilizer.

[0144]

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[Preparation of Emulsions A-4 and A-6] Each of Em-3 and Em-4 shown in Table 1 was charged at 55 ° C. with SD-15.0 × 10 ⁻⁵ mol per mol of silver and SD-2 at 55 ° C. 2.0 ×
10 ⁻⁴ mol and 3.0 × 10 ⁻⁴ mol of SD-3 are added, and then sodium thiosulfate is added to 8.0 × 10 ⁻⁶ mol.
1, 2.0 × 10 ⁻⁶ mol of chloroauric acid and 3.1 × 10 ⁻⁴ mol of potassium thiocyanate were added, and the mixture was aged for an optimal time.

After ripening, 4-hydroxy-6-methyl (1,3,3a, 7) tetrazaindene was added as a stabilizer to prepare Emulsions A-4 and A-6.

[0147] to Em-3, Em-4 each of "Emulsion A-5, Preparation of A-7" shown in Table 1, per silver 1mol at 55 ℃, SD-1 5.0 × 10 -5 mol, SD -2 2.
0 × 10 ⁻⁴ mol and 3.0 × 10 ⁻⁴ mol of SD-3 were added, and then sodium thiosulfate was added to 8.0 × 10 ⁻⁶ m.
ol, Se sensitizer (Se-21) was added at 1.0 × 10 ⁻⁶ mo
1, 2.0 × 10 ⁻⁶ mol of chloroauric acid and 3.1 × 10 ⁻⁴ mol of potassium thiocyanate were added, and the mixture was aged for an optimal time.

After ripening, 4-hydroxy-6-methyl (1,3,3a, 7) tetrazaindene was added as a stabilizer to prepare emulsions A-5 and A-7.

"Preparation of Emulsions B-1 to B-3" Emulsion A-1
To A-3, SD-1, SD-2, SD
Instead of -3, SD-6 (the structure is described later) 4.0 × 10
^-4 mol, SD-7 (the structure is described later) 8.010 ^-5 mo
1, SD-8 (the structure is described later) of 5.0 × 10 ⁻⁵ mol was added to prepare Emulsions B-1 to B-3.

"Preparation of Emulsions B-4 to B-7" Emulsion A-4
To A-7, SD-1, SD-2, SD
SD-6 5.0 × 10 ^-4 mol instead of -3, SD
-7 1.0 × 10 ^-4 mol, SD-8 6.0 × 10
Emulsions B-4 to B-7 were prepared by adding ^-5 mol.

Table 2 shows the contents of the emulsions A-1 to A-7 and B-1 to B-7.

[0152]

[Table 2]

<< Preparation of Multilayer Color Photographic Material >> On a triacetylcellulose film support provided with an undercoat layer, each layer having the following composition is formed in order from the support side by one application to form a multilayer color photographic material. A photosensitive material / sample 100 was prepared.

The amount of addition is expressed in grams per m ² .
However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes (indicated by SD) were shown in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV-1 0.3 CM-1 0.044 OIL-1 0.044 Gelatin 1.33 Second Layer (Intermediate Layer) AS-10 .160 OIL-1 0.20 Gelatin 1.40 Third layer (low-sensitivity red-sensitive layer) Silver iodobromide a 0.12 Silver iodobromide b 0.50 SD-1 3.0 × 10 ^-5 SD-2 1.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 SD-4 3.0 × 10 ^-6 C-1 0.51 CC-1 0.047 OIL-2 0.45 AS- 2 0.005 Gelatin 1.40 Fourth layer (Medium-speed red-sensitive layer) Emulsion A-4 0.64 C-1 0.22 CC-1 0.028 DI-1 0.002 OIL-20 21 AS-3 0.006 Gelatin 0.87 Fifth layer (high-sensitivity red-sensitive layer) Emulsion A-1 1.20 C-1 .17 CC-1 0.029 DI-1 0.027 OIL-2 0.23 AS-3 0.013 gelatin 1.23 6th layer (intermediate layer) OIL-1 0.29 AS-1 0.23 gelatin 1.00 7th layer (low-sensitivity green color-sensitive layer) Silver iodobromide a 0.245 Silver iodobromide b 0.105 SD-4 5.0 × 10 ^-4 SD-5 5.0 × 10 ^{− 4} M-1 0.21 CM-2 0.039 OIL-1 0.25 AS-2 0.003 AS-4 0.063 Gelatin 0.98 8th layer (intermediate layer) M-1 0.03 CM- 2 0.005 OIL-1 0.16 AS-1 0.11 Gelatin 0.80 Ninth layer (medium-speed green-sensitive layer) Emulsion B-4 0.87 M-1 0.17 CM-20 048 CM-3 0.059 DI-2 0.012 OIL-1 0.29 AS-4 0.05 AS- 0.005 Gelatin 1.43 10th layer (high-sensitivity green color-sensitive layer) Emulsion B-1 1.19 M-1 0.09 CM-3 0.020 DI-3 0.005 OIL-1 0.11 AS-4 0.026 AS-5 0.014 AS-6 0.006 Gelatin 0.78 11th layer (yellow filter layer) Yellow colloidal silver 0.05 OIL-1 0.18 AS-7 0.16 Gelatin 1 0.000 12th layer (low-sensitivity blue-sensitive layer) Silver iodobromide g 0.29 Silver iodobromide h 0.19 SD-9 8.0 × 10 ^-4 SD-10 3.1 × 10 ^-4 Y-1 0.91 DI-4 0.022 OIL-1 0.37 AS-2 0.002 Gelatin 1.29 13th layer (high-sensitivity blue-sensitive layer) Silver iodobromide h 0.13 Iodine odor Silver halide i 1.00 SD-9 4.4 × 10 ^-4 SD-10 1.5 × 10 ^-4 Y-1 48 DI-4 0.019 OIL-1 0.21 AS-2 0.004 Gelatin 1.55 Fourteenth layer (first protective layer) Silver iodobromide j 0.30 UV-1 0.055 UV-20 .110 OIL-2 0.63 gelatin 1.32 15th layer (second protective layer) PM-1 0.15 PM-2 0.04 WAX-1 0.02 D-1 0.001 gelatin 0.55 hard Filming agent H-0 (Amount shown in Table 3) The characteristics of the silver iodobromide are shown below (the average particle size is one side length of a cube having the same volume).

Emulsion No. Average grain size (μm) Average AgI amount (mol%) Diameter / thickness ratio Silver iodobromide a 0.30 2.0 1.0 b 0.40 8.0 1.4 g 0.40 2.0 4. 0h 0.65 8.0 1.4 i 1.00 8.0 2.0 j 0.05 2.0 1.0 In addition to the above composition, coating aids SU-1 and SU-
2, SU-3, dispersing aid SU-4, viscosity modifier V-1,
Stabilizers ST-1, ST-2, antifoggant AF-1, weight average molecular weight: 10,000 and weight average molecular weight: 1,
100,000 two types of polyvinylpyrrolidone (AF-
2) The inhibitors AF-3, AF-4, AF-5 and the preservative Ase-1 were added.

The structures of the compounds used in the above samples are shown below.

The gelatin used was extracted after addition of piperazine during lime treatment.

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[0162]

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[0164]

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[0165]

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[0166]

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[0167]

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As described above, a multilayer color photographic light-sensitive material
Sample 100 was prepared.

With respect to the obtained sample 100, the concentration of chloride ion and the concentration of calcium ion contained in gelatin were changed as shown in Table 3 below. Photosensitive materials and Samples 101 to 115 were prepared in the same manner as Sample 100 except that the preferred vinyl sulfone-based hardener was changed, and their storage qualities were compared. The evaluation of the preservability was performed as follows.

<Evaluation of Storage Property> A sample was prepared at 23 ° C. and 80% R
H for 1 month and at 40 ° C. 55% for 1 week, and the fog concentration and sensitivity before and after storage were measured and compared. The sensitivity is
A wedge exposure using white light was applied, color development processing described later was performed, and the reciprocal of the exposure amount giving a density of minimum density +0.3 from the characteristic curve was defined as sensitivity. The relative sensitivity is shown with the sensitivity of the obtained sample 101 on the same day as 100.

<< Color development processing >> (Processing step) Process Processing time Processing temperature Replenishment amount * Color development 3 minutes and 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 minutes 38 ± 2.0 ° C. 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Drying 60 seconds 55 ± 5.0 ° C.-* The replenishing amount is a value per 1 m ² of the photosensitive material.

<Preparation of Processing Agent> (Composition of Color Developing Solution) Water 800 ml Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxyamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetetraaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Finish to 2.0 liters and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.

(Composition of color developing replenisher) Water 800 ml Potassium carbonate 35 g Sodium bicarbonate 3.0 g Potassium sulfite 5.0 g Sodium bromide 0.4 g Hydroxyamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl -N- (β-hydroxyethyl) aniline sulfate 6.3 g Diethylenetetraamine pentaacetic acid 3.0 g Potassium hydroxide 2.0 g Water was added to make up to 1.0 liter, and potassium hydroxide or 20% sulfuric acid was used. Adjust to pH 10.18.

(Composition of bleaching solution) Water 700 ml 1,3-diaminopropanetetraacetic acid iron (III) ammonium 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g Adjust to pH 4.4 with water or glacial acetic acid.

(Composition of bleach replenisher) Water 700 ml 1,3-diaminopropanetetraacetate ammonium (III) ammonium 175 g ethylenediaminetetraacetic acid 2 g sodium nitrate 50 g ammonium bromide 200 g glacial acetic acid 56 g Adjust to pH 4.4 using aqueous ammonia or glacial acetic acid.

(Fixing solution formulation) Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g Water was added to make up to 1.0 liter, and the pH was adjusted to 6.2 with aqueous ammonia or glacial acetic acid.

(Formulation of Fixing Replenisher) Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Add water to make up to 1.0 liter, and adjust to pH 6.5 with aqueous ammonia or glacial acetic acid. .

(Preparation of Stabilizing Solution and Stabilizing Replenishing Solution) Water 900 ml p-octylphenol / ethylene oxide / 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 ml Add water to make up to 1.0 liter, and adjust to pH 8.5 using ammonia water or 50% sulfuric acid.

Table 3 shows the above progress and results.

[0180]

[Table 3]

As is clear from Table 3, the samples of the present invention have excellent storage stability (fog, sensitivity).

[0182]

According to the present invention, it is possible to provide a silver halide photographic material in which the effect of chloride ions contained in gelatin on the storage stability (fog, sensitivity) of the silver halide photographic material is improved. .

Claims (10)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the chloride ion of the silver halide photographic material is 500 or more.
A silver halide photographic light-sensitive material characterized by being at most ppm. 2. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the binder forming at least one of the silver halide emulsion layers contains gelatin as a main component, and A silver halide photographic light-sensitive material, characterized in that gelatin has a chlorine ion of 500 ppm or less. 3. Chloride ion is reduced to 5 by deionization.
A method for producing a silver halide photographic light-sensitive material, characterized by using gelatin having a concentration of 00 ppm or less. 4. The silver halide photographic material according to claim 1, wherein said silver halide photographic material is hardened with a vinyl sulfone hardener having a molecular weight of 350 or less. 5. A silver halide photographic material according to claim 1, wherein said silver halide emulsion layer contains tabular silver halide grains having an aspect ratio of at least 3. 6. The silver halide photographic material according to claim 1, wherein the vinyl sulfone hardener having a molecular weight of 350 or less is represented by the following general formula (1). . Embedded image [In the formula, A represents a linking group having at least one ether bond, hydroxyl group, or amide bond, or an alkylene chain having 1 to 6 carbon atoms. n represents 2 or 3. ] 7. The silver halide photographic material according to claim 6, wherein A of the vinyl sulfone hardener represented by the general formula (1) is a group selected from the following groups. . Embedded image 8. The silver halide according to claim 1, wherein the calcium content of the gelatin obtained by deionizing the chloride ion to 500 ppm or less is 50 ppm or less. Photosensitive material. 9. The method according to claim 1, wherein the deionized gelatin is lime-treated in the presence of at least one selected from a primary amine compound and a secondary amine compound. A silver halide photographic material according to any one of the preceding claims. 10. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the gelatin of at least one silver halide emulsion layer contains 50 ppm or less of calcium ions. A silver halide photographic light-sensitive material, wherein calcium is added to a concentration of 50 ppm or less.