JPH07209813A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To stably obtain a wide exposure latitude and excellent gradation reproduction performance by forming a specified silver halide photosensitive unit and a magnetic recording layer and incorporating a solid dye dispersion. CONSTITUTION:The photosensitive unit comprising photosensitive layers different in silver halide grain diameter by >=1.2 times and the magnetic recording layer, and the slid dye dispersion is provided on a support. The magnetic recording layer may be a transparent magnetic layer, or a striped magnetic layer, or magnetic particles may be added to the support. This magnetic layer may contain a fatty acid, especially preferably, myristic acid, oleic acid, and stearic acid, and when the magnetic layer contain an aliphatic acid ester, its friction coefficient is lowered and its traveling performance and durability are enhanced, and it is preferred to use butyl stearate and butyl palmitate.

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 capable of stably obtaining a wide exposure latitude and excellent gradation reproducibility. The present invention relates to a silver halide photographic light-sensitive material in which information at the time of production can be used, and a wide exposure latitude and excellent gradation reproducibility can be stably obtained without changing with time.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials, particularly silver halide color photographic light-sensitive materials, are widely used today because of their high sensitivity and excellent gradation. However, the development processing of a silver halide color photographic light-sensitive material is a so-called wet processing, and it takes time to prepare a processing solution, it becomes dirty, a waste solution containing various chemicals is discharged, a dark room is required, and after the operation is started. There were drawbacks such as the long time it took to obtain the first print. In order to make up for these drawbacks and make full use of the advantages of the silver halide color photographic light-sensitive material described above, a system in which a skilled engineer concentrates from the development of color negatives to the production of color prints in a few large development laboratories. Has been taken.

However, although the essence of wet processing has not changed in recent years, improvements in equipment such as printers and automatic processors, improvements in developing solutions, improvements in silver halide color photographic light-sensitive materials and their packaging forms have been accumulated. As a result, so-called mini laboratories that can consistently perform color negative development to color print production in a small space such as at a photo shop are rapidly becoming widespread, and the time taken to finish a photograph has been shortened all at once. ing.

Under these circumstances, it has been strongly demanded to develop a color negative and produce a color print in a short time even in a large developing room, and the delivery time has been shortened.
In order to reliably shorten the delivery time, it is necessary to spend time in all processes from color negative development in the laboratory, exposure of color paper, development to sort of color print for each customer, work such as bag packing. Shortening is requested. In addition, if you get a poor quality color print,
Since it takes a long time to redo the production of color prints again, from the standpoint of producing color prints, there has been a demand for efficient work in the production process of color prints and improvement in yield.

In recent years, in order to more efficiently and highly accurately perform development processing after photography of a silver halide color photographic light-sensitive material and printing on color paper, information on photography conditions is recorded in the silver halide color photographic light-sensitive material. There is a proposal to use it effectively.

US Pat. No. 4,947,196 and International Patent Publication 90 /
No. 04254 discloses a photographing camera having a roll-shaped film having a magnetic layer containing magnetic particles capable of magnetic recording on the back surface of a photographic film and a magnetic head. According to the above-mentioned improved technology, the magnetic layer is provided with identification information such as the type and manufacturer of the light-sensitive material, information related to the conditions at the time of shooting, information about the customer, information related to the print conditions, and information related to the print reprint conditions on the film. By magnetically inputting and outputting with, it is possible to improve the print quality, improve the efficiency of printing work, and improve the efficiency of laboratory paperwork.

However, when a silver halide photographic film having a magnetic layer is packed in a cartridge and stored, the fog density increases (Dmax decreases in the case of a reversal sensitive material) and the linearity of the characteristic curve deteriorates with time. A phenomenon was found. When the linearity of the characteristic curve is deteriorated, the density change in a part of the image becomes small, or conversely becomes large. If the area where these changes occur is on the skin part of a portrait, a pseudo contour will appear, even if the linearity is not significantly deteriorated, and the image quality will be significantly impaired. In addition, when the linearity is significantly deteriorated, the variation in the finished quality of the print becomes large, which causes a large decrease in the yield.
In particular, this was a serious problem when one photosensitive unit contained silver halide photographic emulsions having different average grain sizes of 1.2 times or more.

[0008] By the way, it is known that a silver halide photographic light-sensitive material is provided with a light absorption filter and a filter layer which absorbs light in a specific wavelength region for the purpose of preventing halation or adjusting sensitivity. In a color photographic light-sensitive material, a yellow filter layer is provided at a position closer to the support than the blue-sensitive silver halide layer and farther from the support than other color-sensitive layers, and the green and red photosensitive layers feel blue light. Generally, a method for preventing the above is used, or a method for providing an antihalation layer for preventing unnecessary light scattering on the side closer to the support than the photosensitive emulsion layer is used.

For such a filter layer, fine yellow or black colloidal silver is used because of the problem of residual color. However, it has been known that such colloidal silver causes a problem of desilvering failure by causing fog in an adjacent silver halide emulsion layer or increasing a desilvering load.

In order to improve these drawbacks, it is known to allow a dye to be present in a hydrophilic colloid layer together with a mordant such as a cationic polymer. JP-A-50-65230, US Pat. Nos. 2,548,564, 3,625,694 Issue 4,124,386,
Etc. Further, a technique relating to a silver halide photographic light-sensitive material containing a dye having a specific structure as an oil or a polymer latex composition is disclosed in JP-A-4-362634.
No., etc. However, with this method, although the fog that occurs when the silver halide photographic light-sensitive material having a magnetic recording layer is packed and stored in a cartridge, only a slight improvement is recognized with respect to the problem of the linearity of the characteristic curve. There wasn't.

[0011]

SUMMARY OF THE INVENTION The main object of the present invention is to provide a color photographic light-sensitive material for photographing, which can stably obtain a wide exposure latitude and excellent gradation reproducibility. An object of the present invention is to provide a silver halide photographic light-sensitive material having a magnetic recording layer and capable of stably obtaining a wide exposure latitude and excellent gradation reproducibility.

[0012]

DISCLOSURE OF THE INVENTION The inventors of the present invention have diligently studied silver halide photographic light-sensitive materials having a magnetic recording layer, and found that different halogens having a difference in average grain size of 1.2 times or more on a support. The present invention has been completed by a silver halide photographic light-sensitive material having a silver halide light-sensitive unit containing a silver halide photographic emulsion and a magnetic recording layer, and containing a solid dispersion of a dye. It is a thing.

The magnetic recording layer according to the present invention means a magnetic recording layer disclosed in Japanese Patent Laid-Open No.
-109604, Japanese Examined Patent Publication No. 57-6576, Japanese Patent Laid-Open No. 60-45248, U.S. Pat. No. 4,947,196, International Publication No. 90/04254, 91/1175.
No. 0, No. 91/11816, No. 92/08165, No. 92/08227, and the like, or a transparent magnetic layer as described in JP-A-4-124642.
No. 4,124,645 and the like may be stripe-shaped magnetic layers. Further, magnetic particles may be contained in the support.

When the magnetic layer is a transparent layer, the optical density is preferably 1.0 or less, more preferably 0.75 or less, and particularly preferably 0.02 to 0.30.

In the magnetic recording layer according to the present invention, the coating amount of the ferromagnetic powder is 1 m ^{2 of the} silver halide color light-sensitive material.
The amount of iron per unit is preferably 5 g or less, preferably 2
g or less, particularly preferably 0.01 to 0.5 g.

Examples of the ferromagnetic powder include γ-Fe ₂
O ₃ powder, Co deposited γ-Fe ₂ O ₃ powder, Co deposited Fe ₃ O ₄ powder, Co deposited FeO _x (4/3 <x <3/2) powder, other Co-containing iron oxide, Examples of other ferrites, such as hexagonal ferrites, include M-type and W-type hexagonal Ba ferrites, Sr ferrites, lead ferrites, Ca ferrites, or
These solid solutions or ion substitutes are mentioned.

As the hexagonal ferrite magnetic powder, at least one of Fe atoms, which is a constituent element of these uniaxially anisotropic hexagonal ferrite crystals, is selected from divalent metals and Nb, Sb and Ta. Species of pentavalent metal and 0.05-per chemical formula
Those substituted with Sn atoms in the range of 0.5 are used. Two
As the valent metal, elements such as Mn, Cu, and Mg that relatively well replace the Fe atoms in the ferrite are preferable. Divalent metal (M ^II )
And the appropriate substitution amount of pentavalent metal (M ^v ) depends on the combination of M ^II and M ^v , but it is roughly per one chemical formula of M ^II.
0.5 to 1.2 is preferable.

The coercive force (Hc) of the ferromagnetic powder is usually 200.
~ 2,000 Oersted, preferably 300-2,000 Oersted.

The size of the magnetic powder in the major axis direction is preferably 0.3 μm or less, more preferably 0.2 μm or less.

The specific surface area of the ferromagnetic powder by the BET method is
Usually 20 m ² / g or more, preferably 25~80m ² / g.

The shape of the ferromagnetic powder is not particularly limited, and for example, any shape such as needle, spherical or ellipsoidal shape can be used.

The magnetic layer of the present invention may contain a fatty acid, and myristic acid, oleic acid and stearic acid are particularly preferable.

If the magnetic layer contains a fatty acid ester, the friction coefficient of the magnetic layer is lowered and the running property and durability of the silver halide photographic light-sensitive material of the present invention are improved. Butyl stearate and butyl palmitate are preferred.

The magnetic layer of the present invention may contain other lubricant.

As the binder, a transparent one such as cellulose ester or gelatin is used.

As the organic solvent used in the dispersion, kneading and coating of the particles, acetone, methyl ethyl ketone, cyclohexanone or the like ketone-based solvent; propanol, butanol, isobutyl alcohol or the like alcohol-based solvent; ethyl acetate, butyl acetate An ester system such as isopropyl acetate; an ether system such as glycol dimethyl ether; a tar system (aromatic hydrocarbon) such as xylene; a chlorinated hydrocarbon system such as methylene chloride and ethylene chloride.

Prior to coating, the support may be subjected to corona discharge treatment, plasma treatment, undercoating treatment, heat treatment, dust removal treatment, metal vapor deposition treatment and alkali treatment. Regarding these supports, for example, West German Patent No. 3,338,854A, JP-A-5959
-116926, U.S. Pat. No. 4,388,368, Yukio Mitsuishi, "Fiber and Industry", Volume 31, p50-55, 1975.

In the present invention, when the magnetic particles are contained in the support, it is preferable to concentrate them on the side of the support opposite to the side where the photographic constituent layers are coated. As a method of concentrating on one surface side of the support, after casting a dope containing a support polymer and magnetic particles, the magnetic particles are concentrated on one surface side of the support by gravity, magnetic force, etc. As shown in JP-B-30-986 and International Patent No. 91/11750, there is a method of simultaneously casting a dope containing magnetic particles and a dope not containing magnetic particles to concentrate them on one surface side of the support. It is preferable that the production is faster.

The thickness of the support is preferably 50 to 150 μm,
More preferably 60-130 μm, particularly preferably 70-120 μm
Is. If the thickness is smaller than this, the accuracy of writing and reading by the magnetic head deteriorates at the high coating speed of the silver halide photosensitive material when magnetically recording information during manufacturing, which is not preferable. On the other hand, if it is thicker than this, the suitability for exposure / developing equipment as a silver halide photosensitive material is deteriorated.

When the magnetic particles are contained in the support, the thickness of the layer in which the magnetic particles are present is preferably 2 μm or less, more preferably 1.5 μm or less, particularly preferably 1 μm or less 0.1 μm.
It is more than m. The coating amount of magnetic particles is 10 to 1000 mg / m ² , preferably 15 to 300 mg / m ² , and particularly preferably 20 to 100 mg / m ^2.
Is. In this case, iron oxide having a small amount of aluminum, calcium or silicon doped therein is preferably used as the magnetic particles. The acicular ratio of the magnetic particles is preferably 1-7.

In the process of casting a dope containing magnetic particles and drying it to form a magnetic layer, the magnetic particles may be regularly oriented by facing magnets, or a random magnetic field may be applied to obtain a so-called randomize. It is also effective to apply a treatment.

The polymer forming the support is preferably polyethylene terephthalate produced by the coextrusion method. Further, cellulose triacetate can also be used. In the case of polyethylene terephthalate, JP-A 1-244446, 1-291248, 1-298350,
2-89045, 2-93641, 2-81749, 2-214852
It is preferable to use polyethylene terephthalate having a high water content, as disclosed in Japanese Patent Application No. 2-291135 and Japanese Patent Application No. 2-291135, because the dispersion stability of magnetic particles is improved.

It is preferable to add a small amount of a known dye or pigment to the support to prevent halation, irradiation and light piping.

By adding an inorganic or organic matting agent to the dope containing the magnetic particles, or by matting the surface after forming the magnetic layer, the surface roughness is set to a certain region. The efficiency of writing and reading by the head can be improved.

By adjusting the viscosity balance, changing the solvent composition, adjusting the surface tension, and changing the plasticizer content of the dope containing magnetic particles and the dope not containing magnetic particles, Physical properties can be adjusted.

After the support is formed, an undercoat layer or a backing layer can be applied online to simplify the process.

In the present invention, in addition to recording the information on the photographing conditions on the magnetic recording layer, it is also possible to record the information on the outside of the photographing screen of the silver halide color photographic light-sensitive material together with the information. The aspect ratio of the photographing screen of the silver halide photographic light-sensitive material of the present invention is 1: 1 of the conventional 135 standard.
5, High definition type 1: 1.8, Panorama type 1: 3, etc. can be set arbitrarily.

In the present invention, the photosensitive unit refers to an assembly of photosensitive layers having substantially the same color sensitivity, and the photosensitive unit may be composed of a single photosensitive layer or a plurality of photosensitive layers. It may consist of a photosensitive layer. The silver halide photographic light-sensitive material of the present invention is characterized in that at least one light-sensitive unit contains different silver halide photographic emulsions having an average grain size difference of 1.2 times or more. The silver halide photographic emulsions having different grain sizes may be mixed in one layer, or may be in different layers to form a photosensitive unit with a plurality of layers.

The silver halide photographic emulsions having different average grain sizes may be used in any amount ratio, but a smaller amount of emulsion is 1 for all silver halide photographic emulsions of the same photosensitive unit.
When it is at least mol%, the effect of the present invention is effectively exhibited, which is preferable. More preferably, it is 5 mol% or more.

Each light-sensitive unit contains a silver halide photographic emulsion. Usually, a red light-sensitive unit contains a cyan coupler, a green light-sensitive unit contains a magenta coupler, and a blue light-sensitive unit contains a yellow coupler. However, this combination can be changed according to the purpose.

The stacking order of the photosensitive units is not particularly limited, and various stacking orders can be adopted according to the purpose. For example, a blue photosensitive unit, a green photosensitive unit, and a red photosensitive unit can be laminated in this order from the support side.

Further, the photosensitive layers having different color sensitivities may be sandwiched between two photosensitive layers having the same color sensitivities. Also, for the purpose of improving color reproducibility, a red photosensitive unit, a green photosensitive unit and a blue photosensitive unit are used.
In addition to one photosensitive unit, it is also possible to use a photosensitive unit having a fourth or higher color sensitivity. In this case, the layer structure is described in JP-A-61-34541 and JP-A-61-201245.
It is described in No. 61-198236 and No. 62-160448, which can be referred to. In this case, the fourth or more color-sensitive photosensitive units may be arranged at any stacking position. Further, the fourth or higher color-sensitive photosensitive unit may be composed of a single layer or a plurality of layers.

Various non-photosensitive layers may be provided between the layers constituting the photosensitive unit and as the uppermost layer and the lowermost layer.

For these non-photosensitive layers, JP-A-61-43748 is used.
Issue 59-113438, Issue 59-113440, Issue 61-20037, Issue
The coupler as described in 61-20038, the DIR compound, etc. may be contained, and the color mixture inhibitor may be contained as is usually used. These non-photosensitive layers are used in Research Disclosure Magazine (hereinafter abbreviated as RD).
No. 308119 Page 1002 It may be an auxiliary layer of the filter layer or the intermediate layer described in Section VII-K.

Examples of the layer structure that can be used in the silver halide photographic light-sensitive material of the present invention include the normal layer, the reverse layer and the unit structure described in RD No. 308119 page 1002, item VII-K.

As the silver halide photographic emulsion used in the silver halide photographic light-sensitive material of the present invention, a monodispersed silver halide photographic emulsion is preferable for adjusting photographic gradation. A monodisperse silver halide emulsion having a coefficient of variation of 0.20 or less, more preferably 0.15 or less is preferred. Here, the coefficient of variation is a coefficient representing the breadth of the particle size distribution and is defined by the following equation.

Coefficient of variation = S / dm (where S is the standard deviation of the particle size distribution.) Here, the average particle size dm is the frequency ni of particles having the particle size di.
Is defined as follows: dm = Σdini / Σni The grain size referred to here is a diameter when a projected image of a silver halide grain is converted into a circular image having the same area.

The average grain size of the silver halide photographic emulsion according to the present invention is preferably 0.1 to 10.0 μm, more preferably 0.2 to 5.0 μm, and particularly preferably 0.3 to 3.0 μm.

The silver halide grains used in the present invention may have any shape. It may be a normal crystal such as a cube, an octahedron, a tetradecahedron, an icosahedron, or a twin crystal such as a tabular crystal.

In the case of a tabular twin, the ratio of the value converted to the diameter of a circle having the same area as the projected area of the grain and the grain thickness is 1 to 2
0 is preferably 60% or more of the projected area,
Further, it is preferably 1.2 to 8.0, and particularly preferably 1.5 to 5.0.

Monodisperse normal crystal emulsions are disclosed, for example, in JP-A-59-1.
77535, 60-138538, 59-52238, 60-143331
No. 60-35726, No. 60-258536, No. 61-14636 and the like.

Monodisperse twinned emulsions are disclosed, for example, in JP-A-61-146.
It can be produced by referring to the method for growing a spherical seed emulsion disclosed in No. 36.

The silver halide photographic light-sensitive material according to the present invention is characterized by containing a solid dispersion of a dye in at least one layer thereof. As the dye used in the present invention,
The compounds of the general formula [I] (formula 1) to the general formula [IX] (formula 9) are preferably used.

Specific examples of the compounds that can be preferably used in the silver halide photographic light-sensitive material of the present invention are shown below, but the present invention is not limited thereto.

[0055]

[Chemical 10]

[0056]

[Chemical 11]

[0057]

[Chemical 12]

[0058]

[Chemical 13]

[0059]

[Chemical 14]

[0060]

[Chemical 15]

[0061]

[Chemical 16]

[0062]

[Chemical 17]

[0063]

[Chemical 18]

[0064]

[Chemical 19]

[0065]

[Chemical 20]

[0066]

[Chemical 21]

[0067]

[Chemical formula 22]

[0068]

[Chemical formula 23]

[0069]

[Chemical formula 24]

[0070]

[Chemical 25]

[0071]

[Chemical formula 26]

[0072]

[Chemical 27]

[0073]

[Chemical 28]

[0074]

[Chemical 29]

[0075]

[Chemical 30]

[0076]

[Chemical 31]

The dye compound used in the present invention is in the form of a solid fine particle dispersion obtained by a method of making fine particles with a ball mill, a sand mill or the like, or a method of dissolving it in an organic solvent and dispersing it in a gelatin solution. When it is present in gelatin or a polymer binder, it can be incorporated in any photosensitive emulsion layer or non-photosensitive hydrophilic colloid layer in the photographic constituent layers.

The solid dispersion of the dye used in the present invention is
Although it is water-insoluble and stable in the color photographic light-sensitive material, it is treated with a developer (preferably pH ≧ 9) after exposure, so that the hydrophilic group in the dye compound is dissociated and becomes water-soluble. Most of the color photographic light-sensitive material disappears due to the removal or decolorization. For this purpose, an organic compound having a carboxyl group, a sulfamoyl group or a sulfonamide group in the molecule is preferably used.

A solid dispersion of two or more dyes may be used in the silver halide photographic light-sensitive material of the present invention, or a water-soluble dye may be partially used in combination as long as the effect of the present invention is not impaired. Good.

The amount of the dye used in the present invention varies depending on the purpose of use and is not particularly limited, but generally 1 mg /
It is used so as to be m ² or more, preferably 50 mg / m ² or more and 2 g / m ² or less, preferably 0.5 g / m ² or less.

Additives used in the method and process for producing a silver halide photographic emulsion as described above are RD No. 1
7643, No. 18716, and No. 308119 (respectively RD1
7643, RD18716 and RD308119).

The silver halide photographic emulsion used in the present invention can be subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are RD17643, R
It is described in D18716 and RD308119.

Known photographic additives that can be used in the present invention are also described in the above-mentioned Research Disclosure.

Various couplers can be used in the present invention, and specific examples thereof are also described in the above RD.

Additives that can be used in the silver halide photographic emulsion according to the present invention can be added by the dispersion method described in RD308119 1007, page XIV.

The silver halide photographic light-sensitive material according to the present invention can be applied to a color photographic light-sensitive material represented by a color negative film for general use or movies, a color film for slides and the like.

In order to obtain a dye image using the silver halide photographic light-sensitive material of the present invention, a commonly known color development process can be carried out after exposure. Examples of such a developing method include RD17643, pages 28 to 29 and RD18716.
Mention may be made of the method described on page 647 and RD308119 XIX.

If necessary, the surface of the transparent support of the present invention on which the photographic constituent layer is formed is subjected to a surface activation treatment such as corona discharge and / or an undercoat layer prior to the formation of the photographic constituent layer. I can do things.

As the undercoat layer, for example, JP-A-59 is used.
-19941, 59-77439, 59-224841 and Japanese Patent Sho 58-
The undercoat layer described in No. 53029 can be mentioned as a suitable example. The undercoat layer provided on the surface of the transparent support opposite to the photographic constituent layer is also referred to as a back layer.

[0090]

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

Example 1 (Production of Support) 100 parts of cellulose triacetate having an acetylation degree of 61.4% and 15 parts of triphenyl phosphate were completely dissolved in 738 parts of a mixed solvent of methylene chloride-methyl alcohol to obtain a dope.

On the other hand, a cellulose triacetate dope containing magnetic particles was prepared as follows.

Co-adhered γ-Fe ₂ O ₃ 100 parts by weight (coercive force: 610 Oe BET surface area 35 m ² / g, major axis length 0.23 μm, needle ratio 7) Cellulose triacetate 210 parts by weight Methylene chloride 2100 parts by weight Methyl ethyl ketone 1000 parts by weight The above components were mixed together with a dissolver and then dispersed with a sand grinder to obtain a dispersion liquid. The viscosity was measured with a Brookfield viscometer and was 8.8 poise.

20 parts by weight of the above dispersion was taken and thoroughly mixed with a dope having the following composition by a dissolver.

Cellulose triacetate 13.8 parts by weight Methylene chloride 163.1 parts by weight Cyclohexanone 55 parts by weight Ethanol 3.1 parts by weight Next, each dope was filtered and kept at 27 ° C., and two castings were provided on a rotating 6 m endless stainless steel band. The cellulose triacetate base containing magnetic particles and having a thickness of 85 μm was obtained by uniformly casting from the mouth, evaporating the solvent until peeling was possible, peeling from the stainless steel band, and further drying.

The cellulose triacetate dope containing magnetic particles was dried so that the dry film thickness was 1 μm, and after casting, it was dried while carrying out an orientation treatment with a facing magnet. The coating amount of magnetic particles was 50 mg / m ² .

The coercive force of the support was 670 Oe. or,
The optical transmission density was 0.10.

On the surface of the above base, gelatin 20 g, water 40
g, salicylic acid 20 g, methanol 600 g, acetone 1200
and 200 g of methylene chloride were applied and dried.

On the opposite side of the triacetyl cellulose film support from the magnetic particle-containing layer side, layers having the following compositions were sequentially formed from the support side.

First layer Aluminasol AS-100 (aluminum oxide) 0.8 g (manufactured by Nissan Chemical Industries, Ltd.) Second layer Diacetyl cellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle size 0.2 μm) 50 mg (silver halide color photosensitive material) Preparation) Each layer having the following composition was provided on the above transparent support to prepare a silver halide photographic light-sensitive material, Sample 101.

[0102] The coating amount (Composition of photosensitive layer) The silver halide and colloidal silver, the amount expressed in terms of metallic silver in the unit of g / m ^2, also, the coupler, the additive g / m ² The amount expressed in units is also shown for the sensitizing dye in terms of the number of moles per mole of silver halide in the same layer.

First layer: antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (OIL-1) 0.16 Gelatin 1.60 Second layer: Intermediate layer Compound (SC-1) 0.14 High boiling point solvent (OIL-2) 0.17 Gelatin 0.80 Third layer: silver halide emulsion layer Silver halide emulsion 0.15 Sensitizing dye (SD-1) 2.0 × 10-4 Sensitizing dye (SD-2) 1.4 × 10-4 Sensitizing Dye (SD-3) 1.4 × 10-5 Sensitizing dye (SD-4) 0.7 × 10-4 Cyan coupler (C-1) 0.53 High boiling point solvent (OIL-3) 0.48 Gelatin 1.09 4th layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0.15 High boiling point solvent (OIL-2) 0.19 Gelatin 1.10 Fifth layer: First protective layer Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1.0 Mol%) 0.40 UV absorber (UV-1) 0.065 High boiling point solvent (OIL-1) 0.07 High boiling point solvent (OIL-3) 0.07 Gelatin 0.65 Sixth layer: Second protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, coating aid Su-1, dispersion aid Su
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, antifoggant AF-1, two kinds of AF-2 having an average molecular weight of 10,000 and an average molecular weight of 1,100,000, and preservative DI-1 were added.

[0103]

[Chemical 32]

[0104]

[Chemical 33]

[0105]

[Chemical 34]

[0106]

[Chemical 35]

The emulsion used in the above sample was prepared by mixing emulsions having different grain sizes prepared as described below at a ratio of 1: 1. The average particle diameter is represented by the diameter of a circle having the same projected area. Further, each emulsion was optimally subjected to gold / sulfur sensitization.

(Preparation method of silver halide emulsion) Average grain size
A silver iodobromide emulsion was prepared by the double jet method using 0.33 μm monodisperse silver iodobromide grains (silver iodide content 2 mol%) as seed crystals.

The solution (G-1) was heated to 70 ° C., pAg = 7.8 and pH.
= 7.0, and while stirring well, a seed emulsion corresponding to 0.34 mol was added.

(Formation of Internal High Iodine Phase-Core Phase) After that, the solution (H-1) and the solution (S-1) were kept at a flow rate ratio of 1: 1 and accelerated (flow rate at the end). (3.6 times the initial flow rate) was added over 86 minutes.

(Formation of External Low Iodine Phase-Shell Phase) Subsequently, while maintaining pAg = 10.1 and pH = 6.0, the solution (H-
2) and the solution (S-2) were added at a flow rate of 1: 1 at an accelerated flow rate (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes. The pAg and pH during grain formation were controlled using an aqueous potassium bromide solution and a 56% aqueous acetic acid solution.

(G-1) Ocein gelatin 100.0 g Compound-I (10% methanol solution) 25.0 ml 28% aqueous ammonia solution 440 ml 56% acetic acid aqueous solution 660 ml Finish with water to 5 liters.

(H-1) Ocein gelatin 82.4 g Potassium bromide 151.6 g Potassium iodide 90.6 g Water was added to 1030.5 ml.

(S-1) Silver Nitrate 309.2 g 28% Aqueous Aqueous Solution Equivalent Finish with water to 1030.5 ml.

(H-2) Oscein gelatin 302.1 g Potassium bromide 770.0 g Potassium iodide 33.2 g Water was added to 3776.8 ml.

(S-2) Silver nitrate 1133.0 g 28% aqueous ammonia solution Equivalent to 3376.8 ml with water.

[0117]

[Chemical 36]

After the particles were formed, they were washed with water by a conventional flocculation method, and then gelatin was added and redispersed, and the pH and pAg were adjusted to 5.8 and 8.06 at 40 ° C., respectively.

The obtained emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a variation coefficient of grain size distribution of 0.12 and a silver iodide content of 8.5 mol%.

Similarly, the average grain size of seed crystals, temperature, pA
Silver halide emulsions having different average grain sizes were prepared by changing g, pH, flow rate and addition time. In each case, the grain size distribution was a core / shell type monodisperse emulsion having a variation coefficient of 0.2 or less. Each emulsion was subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to obtain a sensitizing dye, a stabilizer (ST-1), an antifoggant (A
F-1) was added.

A sample 111 was obtained in the same manner as the sample 101 except that the magnetic particles (Co-coated γ-Fe ₂ O ₃ ) were removed from the cellulose triacetate base containing the magnetic particles.

Silver halide photographic light-sensitive materials, Samples 102 to 104 and 112 to 114, were prepared in the same manner as in Samples 101 and 111 except that the silver halide photographic emulsion was changed.

Then, in the preparation of Samples 101 to 104 and 111 to 114, the yellow colloidal silver of the fourth layer was used as the dye exemplified compound (IX-1).
And samples 105 to 108 and 115 to 118 were prepared in the same manner except that the coating amount was changed to 0.35 g / m ² . A solid dispersion of dye was prepared as follows.

(Preparation Method of Solid Dispersion of Dye) Dye (IX-1) 0.15 g 2% Gelatin 80 ml Surfactant (10% solution) 3 ml The above mixed solution was put in an alumina ball mill pot having a volume of 360 ml, and alumina 400 g of balls (mixture having a diameter of 3 mm to 10 mm) were added and the mixture was rotated for 5 days for dispersion.

Each of these samples was made into a standard 135 size 2
Two pieces were cut into a standard of 4 shots and stored in a film cartridge, and light wedge exposure was performed by a conventional method to evaluate the linearity of the characteristic curve. One of the samples was immediately exposed and developed, and the other was stored under conditions of 55 ° C and 40% RH for 7 days.
It was exposed and developed. The cyan density image of each sample was measured for R density with a PDA-65 densitometer (manufactured by Konica Corporation), and the change in fog and the maximum density (Dmax) and minimum density (Dmi) of the characteristic curve were measured.
n), Dmax-0.15 x (Dmax-Dmin), Dmin +
Exposure amount (logH) between two points of 0.15 x (Dmax-Dmin)
Was equally divided to obtain 6-point data, and the deviation from the straight line obtained by the method of least squares was obtained by the following formula. This value does not become 0 because the characteristic curve is not a perfect straight line, but this value increases as the linearity deteriorates due to performance fluctuations due to storage, so it was used as a quantity indicating the goodness of linearity.

[0126]

[Equation 1]

The development processing was carried out under the following conditions.

[0128] The replenishment amount is a value per 1 m ² of the photographic light-sensitive material.

The color developing solution, the bleaching solution, the fixing solution, the stabilizing solution and the replenishing solution thereof were prepared as follows.

<Color developer> 4-amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) 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 Water was added to make 1 liter, and the pH was adjusted to 10.1.

<Bleach> Ethylenediaminetetraacetic acid iron (III) ammonium salt 100 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150 g Glacial acetic acid 10 ml Add water to make 1 liter, and adjust to pH 6.0 with ammonia water. did.

<Fixer> Ammonium thiosulfate 175 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to make 1 liter, and pH was adjusted to 6.0 with acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corporation) 7.5 ml Water was added to make 1 liter.

<Color development replenisher> Water 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxy Ethyl) aniline sulfate 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Water was added to make 1 liter, and the pH was adjusted to 10.18 with potassium hydroxide or 20% sulfuric acid.

<Bleach Replenisher> Water 700 ml 1,3-Diaminopropanetetraacetate Iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g Ammonia water or glacial acetic acid is used to adjust the pH to 4.0. After adjustment, water was added to make 1 liter.

<Fixing Replenisher> Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 using aqueous ammonia or glacial acetic acid, water was added to make 1 liter.

<Stable Replenisher> Same as the stabilizer.

The results are shown in Table 1 below.

[0139]

[Table 1]

In order to realize a wide exposure latitude, it is necessary to mix and use silver halide photographic emulsions having different grain sizes, and to combine silver halide photographic emulsions having an average grain size difference of 1.2 times or more. Sample 10 in which a silver halide emulsion layer is provided on a support having a magnetic recording layer.
In Nos. 1 to 104, the linearity deterioration after storage increased as the particle size difference increased, and the deterioration became particularly remarkable when the average particle size difference was 1.2 times or more. This behavior is similarly observed in Samples 111 to 114 that do not have a magnetic recording layer, but it can be seen that the presence of the magnetic recording layer causes remarkable deterioration. However, use of the solid disperse dye according to the present invention remarkably improves these drawbacks.

Example 2 In the preparation of 107 to 108 of Example 1, the following dyes were used as comparative dyes A and B and exemplified compounds (I-1), (I-3), (I-9) and (II-
2), (III-4), (IV-1), (V-5), (V-7), (VI-6), (VII-
9), (VIII-1), (IX-5)
1-212 were prepared.

The comparative dyes A and B are dyes by weight in the conventional manner.
It was dissolved in 0.7 times the amount of (OIL-2) and ethyl acetate, and was emulsified and dispersed in the presence of an appropriate amount of a surfactant and added.

[0143]

[Chemical 37]

These samples were evaluated in the same manner as in Example 1. However, since the sensitivity greatly changes depending on the dye and particle size, the exposure illuminance was appropriately changed as the exposure condition. The results are shown in Table 2 below.

[0145]

[Table 2]

With the comparative dyes A and B, although the increase in fog was considerably suppressed as compared with the case of colloidal silver, it was still at a high level as compared with the silver halide photographic light-sensitive material of the present invention, and the straight line of the characteristic curve was obtained. There was only a slight improvement in sex. On the other hand, it was confirmed that the solid dispersions of the dyes used in the present invention all have the effects of the present invention. Among them, the general formulas [I], [V],
The compound represented by [IX] has a large effect and is preferable. Example 3 Sample 30 was prepared in the same manner as in Example 1 except that the support was changed to the polyester support described below.
1 to 308 were produced.

(Preparation of Polyester Support) The following first undercoat layer and second undercoat layer were coated on both sides of a film of polyethylene terephthalate having a thickness of 80 μm, and then a magnetic recording layer was coated on one surface. did.

(First Undercoat Layer) 100 parts by weight of a resin solution for an undercoat layer obtained by emulsion polymerization of the following composition, 0.2 part by weight of the following surfactant (SU-3), hexamethylene-1,6 -A coating liquid for undercoat layer consisting of 0.3 part by weight of bis (ethylene urea) and 900 parts by weight of water was applied so as to have a wet film thickness of 20 μm, and then dried.

<First subbing layer composition> 2-hydroxyethyl methacrylate 75 parts Butyl acrylate 90 parts t-Butyl acrylate 75 parts Styrene 60 parts Sodium dodecylbenzene sulfonate 6 parts Ammonium persulfate 1 part Water 700 parts (second bottom) Draw layer) 10 parts by weight gelatin, 0.2 saponin
An undercoat layer coating solution consisting of 1 part by weight of water and 1000 parts by weight of water was applied to give a wet film thickness of 20 μm, and then dried.

(Magnetic Recording Layer) The following magnetic layer was provided on one side of the above support coated with the first and second undercoat layers.

<Magnetic Layer Composition> γ-Fe ₂ O ₃ (Coercive force: 330 Oe, specific surface area 32 m ² / g) 200 mg / m ² Gelatin 3.0 g / m ² Di- (2-ethylhexyl) sodium sulfosuccinate 200 mg / m ² bisvinylsulfonylmethane 30 mg / m ² WAX-1 60 mg / m ²

[0152]

[Chemical 38]

Next, samples 311 to 318 were prepared in the same manner except that the magnetic recording layer on the back surface was not provided.

Using this sample, evaluation was performed in the same manner as in Example 1. The results are shown in Table 3 below.

[0155]

[Table 3]

The silver halide photographic light-sensitive material prepared in Example 1 was halogenated in the same manner except that the support was changed to polyester and that the magnetic layer was coated on the support instead of being kneaded. When a silver photographic light-sensitive material was prepared, the deterioration of the linearity of the characteristic curve during storage tended to be larger in Samples 301 to 308 than in Samples 101 to 108. However, it was found that the silver halide photographic light-sensitive material according to the present invention maintained the linearity of the characteristic curve and suppressed the increase of fog as in Example 1.

Example 4 The following layers were coated on the support used for preparing the samples of Examples 1 and 3 to prepare silver halide photographic light-sensitive materials 401 to 404.
(401: Cellulose triacetate film having magnetic material, 40
2: Cellulose triacetate film without magnetic material, 403:
A polyester film having a magnetic substance, 404: a polyester film having no magnetic substance) was prepared.

First layer Alumina sol AS-100 (aluminum oxide) 0.8 g (manufactured by Nissan Chemical Industries, Ltd.) Second layer Diacetyl cellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle size 0.2 μm) 50 mg (composition of photosensitive layer) For silver halide and colloidal silver, the amount is expressed in g / m ² unit in terms of metallic silver, and for couplers and additives, the amount is expressed in g / m ² unit. Dyes are indicated by the number of moles per mole of silver halide in the same layer.

First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (OIL-1) 0.16 Gelatin 1.60 Second layer: Intermediate layer Compound (SC-1) 0.14 High boiling point solvent (OIL-2) 0.17 gelatin 0.80 third layer: low sensitivity red-sensitive layer Em-41 0.15 Em-42 0.35 sensitizing dye (SD-1) 2.0 × 10 -4 sensitizing dye (SD-2) 1.4 × 10 - ⁴ Sensitizing dye (SD-3) 1.4 × 10 ^-5 Sensitizing dye (SD-4) 0.7 × 10 ^-4 Cyan coupler (C-1) 0.53 Colored cyan coupler (CC-1) 0.04 DIR compound (D-1) ) 0.025 High boiling point solvent (OIL-3) 0.48 Gelatin 1.09 4th layer: Middle red sensitive layer Em-42 0.30 Em-43 0.34 Sensitizing dye (SD-1) 1.7 × 10 ^-4 Sensitizing dye (SD-2) ) 0.86 × 10 ^-4 Sensitizing dye (SD-3) 1.15 × 10 ^-5 Sensitizing dye (SD-4) 0.86 × 10 ^-4 Cyan coupler (C-1) 0.33 Colored cyan coupler (CC-1) 0.013 DIR Compound (D-1) 0.02 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 Fifth layer: High-sensitivity red-sensitive layer Em-44 0.95 Sensitizing dye (SD-1) 1.0 × 10 ^-4 Sensitizing dye (SD-2) 1.0 × 10 ^-4 Sensitizing dye (SD-3) 1.2 × 10 ^-5 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.016 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 6th layer: Intermediate layer compound (SC-1) 0.09 High boiling point solvent ( OIL-2) 0.11 Gelatin 0.80 7th layer: Low sensitivity green sensitive layer Em-41 0.12 Em-42 0.38 Sensitizing dye (SD-4) 4.6 × 10 ^-5 Sensitizing dye (SD-5) 4.1 × 10 ^-4 Magenta coupler (M-1) 0.14 Magenta coupler (M-2) 0.14 Colored magenta coupler (CM-1) 0.06 High boiling point solvent (OIL-4) 0.34 Gelatin 0.70 8th layer: Intermediate layer Gelatin 0.41 9th layer: Medium sensitivity Green-sensitive layer Em-42 0.30 Em-43 0.34 Sensitizing dye (SD-6) 1.2 × 10 ^-4 Sensitizing dye (SD-7) 1.2 × 10 ^-4 Sensitizing dye (SD-8) 1.2 × 10 ^-4 Magenta coupler (M-1) 0.04 Magenta Coupler (M-2) 0.04 Colored magenta coupler (CM-1) 0.017 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point solvent (OIL-4) 0.12 Gelatin 0.50 Layer 10: High sensitivity green Sensitive layer Em-44 0.95 Sensitizing dye (SD-6) 7.1 × 10 ^-5 Sensitizing dye (SD-7) 7.1 × 10 ^-5 Sensitizing dye (SD-8) 7.1 × 10 ^-5 Magenta coupler (M- 1) 0.09 Colored magenta coupler (CM-1) 0.011 High boiling point solvent (OIL-4) 0.11 Gelatin 0.79 11th layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0.15 High boiling point solvent (OIL-2) 0.19 Gelatin 1.10 12th layer: Low sensitivity blue sensitive layer Em-41 0.12 Em-42 0.24 Em-43 0.12 Sensitizing dye (SD-9) 6.3 × 10 ^-5 Sensitizing dye (SD-10) 1.0 × 10 ^-5 Yellow Coupler (Y-1) 0.50 Yellow coupler (Y-2) 0.50 DIR compound (D-4) 0.04 DIR compound (D-5) 0.02 High boiling point solvent (OIL-2) 0.42 Gelatin 1.40 13th layer: high sensitivity blue-sensitive layer Em-43 0.15 Em-45 0.80 Sensitizing dye (SD-9) 8.0 × 10 -5 Sensitizing dye (SD-11) 3.1 × 10 -5 Yellow coupler (Y-1 ) 0.12 High boiling point solvent (OIL-2) 0.05 Gelatin 0.79 14th layer: 1st protective layer Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1 ) 0.065 High boiling point solvent (OIL-1) 0.07 High boiling point solvent (OIL-3) 0.07 Gelatin 0.65 15th layer: 2nd protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethyl methacrylate (average particle size 3 μm) 0.04 Lubricant (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, coating aid Su-1 and dispersion aid Su
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, antifoggant AF-1, two kinds of AF-2 having an average molecular weight of 10,000 and an average molecular weight of 1,100,000, and preservative DI-1 were added.

[0160]

[Chemical Formula 39]

[0161]

[Chemical 40]

[0162]

[Chemical 41]

[0163]

[Chemical 42]

[0164]

[Chemical 43]

As the silver halide emulsion, the following emulsion was prepared and used by a conventional method.

Em-41 Silver iodobromide containing 4.0 mol% silver iodide average grain size 0.30 μm Normal crystal Em-42 Silver iodobromide containing 6.0 mol% silver iodobromide average grain size
0.42 μm Normal crystal Em-43 Silver iodobromide containing 6.0 mol% of silver iodide Average grain size
0.55 μm Normal crystal Em-44 Silver iodobromide containing 6.0 mol% silver iodobromide Average grain size
Twin plate with 0.85 μm diameter-thickness ratio 4.0 Em-45 Silver iodobromide containing 6.0 mol% of silver iodide Average grain size
0.95μm Twin crystal flat plate with diameter-thickness ratio 4.0 Next, the yellow colloidal silver of the 11th layer yellow filter layer was changed to the dye exemplified compound (IX-1), and the coating amount was 0.35 g / m ²
Samples 405 to 408 were prepared in the same manner except that Each of these samples was cut into a standard size of 24 shots of 135 sizes, and two samples stored in a film cartridge were prepared and subjected to optical wedge exposure by a conventional method to evaluate the linearity of the characteristic curve. One of the samples is immediately exposed and developed, the other is
After 7 days of storage at 55 ° C. and 40% RH, exposure and development were performed.
R of each sample is a PDA-65 densitometer (Konica Corporation),
The G and B densities were measured, and the change in fog, the maximum density (Dmax) and the minimum density (Dmin) of the characteristic curve were compared with Dmax-0.15.
X (Dmax-Dmin), Dmin + 0.15 x (Dmax-Dmin)
6 is divided equally between the two points for the exposure dose (log H).
The data of the points were taken, and the deviation from the straight line obtained by the method of least squares was obtained by the above formula. The results are summarized in Table 4.

[0167]

[Table 4]

In the even-numbered samples having no magnetic recording layer on the support, although the fog rise was small, there was a phenomenon that the linearity of the characteristic curve was greatly deteriorated by storage. On the other hand, in the sample having the magnetic recording layer, the comparative samples 401, 4
As seen in 03, both fogging and deterioration of linearity were extremely large values. On the other hand, in the sample using the solid dispersion of the dye used in the present invention, the fog rise which is the same as that of the comparative sample having no magnetic recording layer is suppressed,
The suppression of the deterioration of linearity was higher than that of the comparative sample.

The effect of the present invention was confirmed even in a light-sensitive material in which such a photosensitive unit was composed of a plurality of emulsions and a plurality of layers.

Further, the same silver halide light-sensitive material was packed in a small cartridge having an internal volume of ⅔, and the same experiment was carried out. As a result, the fog increased and the linearity of the characteristic curve deteriorated. However, it was confirmed that these changes were sufficiently suppressed in the silver halide photographic light-sensitive material of the present invention.

Example 5 In the preparation of Samples 401 to 404 of Example 4, the composition of the photosensitive layer was changed as follows, and silver halide photographic light sensitive materials 501 to 5 were prepared.
04 was prepared. The coating amount of each component is shown in g / m ² . However, for silver halide, the coating amount converted to silver (g
/ M ² ).

(Composition of photosensitive layer) First layer: antihalation layer Black colloidal silver 0.24 Ultraviolet absorber (UV-1) 0.14 Ultraviolet absorber (UV-2) 0.072 High boiling point solvent (OIL-1) 0.31 High boiling point solvent (OIL-3) 0.098 Poly-N-vinylpyrrolidone 0.15 Gelatin 2.02 Second layer: Intermediate layer-1 Gelatin 0.5 Third layer: Intermediate layer-2 Fine grained silver iodobromide emulsion (silver iodide 1.0 mol %, 0.06 μm) 0.05 Gelatin 0.5 Fourth layer: low-sensitivity red-sensitive layer Spectral-sensitized with sensitizing dyes (SD-1) and (SD-15) Em-51 0.6 Cyan coupler (C-3) 0.52 High Boiling point solvent (OIL-3) 0.6 Gelatin 1.3 Fifth layer: High-sensitivity red-sensitive layer Em-52 0.7 Cyan coupler (C-3) spectrally sensitized with sensitizing dyes (SD-1) and (SD-15) 0.78 High boiling point solvent (OIL-3) 1.2 Gelatin 1.8 6th layer: Intermediate layer-3 2,5-di-t-octylhydroquinone 0 .1 High boiling point solvent (OIL-1) 0.2 Gelatin 0.9 Seventh layer: Intermediate layer-4 Fine grained silver iodobromide emulsion with surface fogged (silver iodide 1.0 mol%, 0.06 μm) 0.05 2,5-di- t-octylhydroquinone 0.1 high boiling solvent (OIL-2) 0.25 gelatin 0.9 8th layer: low sensitivity green sensitive layer Em-53 0.55 magenta spectrally sensitized by sensitizing dyes (SD-12) and (SD-13) Coupler (M-3) 0.15 Magenta coupler (M-4) 0.04 High boiling point solvent (OIL-2) 0.25 Gelatin 1.4 9th layer: High sensitivity green sensitive layer By sensitizing dyes (SD-12), (SD-13) Spectral-sensitized Em-52 0.8 Magenta coupler (M-3) 0.56 Magenta coupler (M-4) 0.12 High boiling point solvent (OIL-2) 1.0 Gelatin 1.5 10th layer: Intermediate layer-5,2-di- t-octylhydroquinone 0.1 High boiling point solvent (OIL-1) 0.2 Gelatin 0.9 11th layer: Yellow filter layer Yellow colloidal silver 0.15 2,5-di-t-o Cylhydroquinone 0.1 High boiling point solvent (OIL-1) 0.2 Gelatin 0.9 12th layer: Low sensitivity blue sensitive layer Spectral sensitized by sensitizing dye (SD-14) Em-54 0.6 Yellow coupler (Y-2) 1.4 High Boiling point solvent (OIL-2) 0.6 Gelatin 1.3 13th layer: High sensitivity blue sensitive layer Em-55 0.75 Yellow coupler (Y-2) 3.5 Spectral sensitized with sensitizing dye (SD-14) 3.5 High boiling point solvent (OIL) -2) 1.4 Gelatin 2.1 14th layer: 1st protective layer UV absorber (UV-1) 0.3 UV absorber (UV-2) 0.4 2,5-di-t-octylhydroquinone 0.1 High boiling point solvent (OIL-2) ) 0.6 Gelatin 1.2 15th layer: 2nd protective layer Non-photosensitive fine grain silver halide emulsion made of silver iodobromide containing 0.08 μm average grain size and 1 mol% silver iodide 0.3 Polymethylmethacrylate (diameter 1.5 μm) 0.06 Surfactant (SU-4) 0.004 Gelatin 0.7 In addition to the above composition, each layer contains gelatin hardener H.
1, H-3, surfactant, antifungal agent DI-1 gelatin 1
0.56 mg was added per gram.

The silver halide photographic emulsion used in each light-sensitive layer contains silver iodobromide having an average grain size of 0.30 μm and Em-52 containing 2.5 mol% of Em-52 and silver iodide containing 4.0 mol% of Em-51 silver iodide. Silver iodobromide Average grain size 0.60 μm Em-53 Silver iodobromide containing 3.5 mol% silver iodide Average grain size 0.25 μm Em-54 Silver iodobromide containing 2.5 mol% silver iodide Average grain size 0.35 μm Em-55 Silver iodobromide containing 2.5 mol% of silver iodide has an average grain size of 0.90 μm and was prepared by referring to the method of Example 1 of JP-A-59-178447. All were monodisperse emulsions with a variation coefficient of grain size distribution of 0.2 or less.

Each emulsion was desalted and washed with water, and then appropriately chemically ripened in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to obtain a sensitizing dye and a stabilizer (ST
-1) and an antifoggant (AF-1) were added.

The total dry film thickness of this sample was 20.5 μm.

The structural formulas of the compounds used to prepare the above samples are as follows.

[0177]

[Chemical 44]

[0178]

[Chemical formula 45]

[0179]

[Chemical formula 46]

The development processing steps were as follows.

Processing content Processing time Processing temperature First development 6 minutes 38 ° C Washing with water 2 minutes 38 ° C Inversion 2 minutes 38 ° C Color development 6 minutes 38 ° C adjustment 2 minutes 38 ° C Bleach 6 minutes 38 ° C Fixed 4 minutes 38 ℃ Washing with water 4 minutes 38 ℃ Stability 1 minute Drying at room temperature The composition of the treatment solution used in the above treatment process is as follows.

<First developer> Sodium tetrapolyphosphate 2 g Sodium sulfite 20 g Hydroquinone monosulfonate 30 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Water was added to make 1000 ml (pH = 9.60).

<Inversion Liquid> Nitrilotrimethylenephosphonic acid hexasodium salt 3 g Stannous chloride (dihydrate) 1 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to make 1000 ml (pH = 5.75).

<Color developer> Sodium tetrapolyphosphate 3 g Sodium sulfite 7 g Sodium triphosphate (dihydrate) 36 g Potassium bromide 1 g Potassium iodide (0.1% solution) 90 ml Sodium hydroxide 3 g Citrazic acid 1.5 g N- Ethyl-N- (β-methanesulfonamidoethyl) -4-amino-3-methyl-aniline sulfate 11g 2,2-ethylenedithiodiethanol 1g Water was added to make 1000 ml (pH = 11.70).

<Preparation Solution (Conditioner)> Sodium sulfite 12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerin 0.4 ml Glacial acetic acid 3 ml Water was added to make 1000 ml (pH = 6.15).

<Bleach> Ethylenediaminetetraacetate sodium (dihydrate) 2 g Ethylenediaminetetraacetate iron (III) ammonium (dihydrate) 120 g Ammonium bromide 100 g Water was added to make 1000 ml (pH = 5.56).

<Fixer> Ammonium thiosulfate 80 g Sodium sulfite 5 g Sodium bisulfite 5 g Water was added to make 1000 ml (pH = 6.60).

<Stabilizer> Formalin (37% aqueous solution) 5 ml Conidax (manufactured by Konica Corp.) 5 ml Water was added to make 1000 ml (pH = 7.00).

Next, Samples 505 to 508 were prepared in the same manner except that the yellow colloidal silver of the 11th yellow filter layer was changed to the dye exemplified compound (IX-1) and the coating amount was 0.70 g / m ^2. did.

Each of these samples was made into a standard 135 size 2
Two pieces were cut into a standard of 4 shots and stored in a film cartridge, and light wedge exposure was performed by a conventional method to evaluate the linearity of the characteristic curve. One of the samples was immediately exposed and developed, and the other was stored under conditions of 55 ° C and 40% RH for 7 days.
It was exposed and developed. Each sample was measured for R, G, and B concentrations with a PDA-65 densitometer (manufactured by Konica Corp.), and changes in Dmax,
For the maximum density (Dmax) and minimum density (Dmin) of the characteristic curve, Dmax-0.15x (Dmax-Dmin), Dmin + 0.15x
The data of 6 points were obtained by equally dividing the exposure dose (log H) between 2 points of (Dmax-Dmin), and the deviation from the straight line obtained by the least square method was obtained by the above formula. The results are summarized in Table 5.

[0191]

[Table 5]

In the even-numbered samples having no magnetic recording layer on the support, the decrease in Dmax is small, but the phenomenon that the linearity of the characteristic curve is greatly deteriorated by storage is observed. On the other hand, in the sample having the magnetic recording layer, the comparative samples 501, 5
As seen in 03, both the Dmax decrease and the linearity deterioration were very large values. On the other hand, in the case of the sample using the solid dispersion of the dye used in the present invention, the Dmax decrease which is the same as that of the comparative sample having no magnetic recording layer was suppressed, and the deterioration of the linearity was suppressed more than that of the comparative sample. there were.

The effects of the present invention could be confirmed also in a silver halide photographic light-sensitive material which undergoes such reversal processing.

Further, the same silver halide light-sensitive material was packed in a small cartridge having an internal volume of ⅔, and the same experiment was carried out. As a result, a decrease in Dmin and a deterioration in the linearity of the characteristic curve were observed. However, it was confirmed that these changes were sufficiently suppressed in the silver halide photographic light-sensitive material of the present invention.

[0195]

EFFECTS OF THE INVENTION According to the present invention, information having a magnetic recording layer at the time of photographing and information at the time of manufacturing can be used, and a wide exposure latitude and excellent gradation reproducibility can be stably obtained without changing with time. It was possible to provide a silver halide photographic light-sensitive material capable of doing so.

Claims (3)

[Claims] 1. A solid dispersion of a dye is provided on a support, which comprises a silver halide photosensitive unit containing different silver halide photographic emulsions having a difference in average grain size of 1.2 times or more and a magnetic recording layer. A silver halide photographic light-sensitive material characterized by containing. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the different silver halide photographic emulsions are monodisperse. 3. A silver halide photographic light-sensitive material according to claim 1, which contains a solid dispersion of a dye selected from compounds represented by the following general formulas [I] to [IX]. . [Chemical 1] In the formula, R ₁ and R ₂ are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, —COOR ₅ , —COR ₅ , or —SO.
₂ R ₅ , -SOR ₅ , -SO ₂ NR ₅ R ₆ , -CONR ₅ R ₆ , -NR ₅ R ₆ , -NR ₅
SO ₂ R ₆ , -NR ₅ COR ₆ , -NR ₅ CONR ₆ R ₇ , -NR ₅ CSNR ₆ R ₇ , -OR
₅ , -SR ₅ or a cyano group is represented, and R ₃ and R ₄ represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R ₅ , R ₆ and R ₇ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and L _{1 to} L ₅ represent a methine chain. n ₁ represents an integer of 0 or 1, and n ₂ represents an integer of 0-2. [Chemical 2] In the formula, R ₁ , R ₃ , L _{1 to} L ₅ , n ₁ and n ₂ each have the same meaning as in formula [I]. E represents the acidic nucleus necessary to form the oxonol dye. [Chemical 3] In the formula, R ₃ , R ₄ , L _{1 to} L ₅ , n ₁ and n ₂ each have the same meaning as in formula [I], and R ₈ and R ₉ have the same meanings as R ₃ and R _4. Represent X ₁ and X ₂ represent an oxygen atom or a sulfur atom. [Chemical 4] In the formula, R ₃ , L ₁ and L ₂ have the same meanings as in the general formula [I], and E has the same meanings as in the general formula [II]. R ₁₀ ,
R ₁₁ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom,
OR ₅ , -SR ₅ , -NR ₅ R ₆ , -NR ₅ SO ₂ R ₆ , -NR ₅ COR ₆ , -COR ₅
Or represents -COOR ₅ . A ring double bond can also be formed by R ₁₀ and R ₁₁ . X ₃ represents an oxygen atom, a sulfur atom, a selenium _{atom, -C (R 12) (R} 13) - or -N (R ₃₎ - _{represents, R 3, R 5, R} 6 are the general formula [I] It has the same meaning. R ₁₂ and R ₁₃ represent a hydrogen atom or an alkyl group. n
₃ represents an integer of 1 to 3. [Chemical 5] In the formula, R ₃ , R ₄ , L ₁ , L ₂ , L ₃ and n ₁ each have the same meaning as in the general formula [I], and E has the same meaning as in the general formula [II]. R ₁₀ and R ₁₁ are each of the general formula [IV]
And has the same meaning as R _10, and R ₁₄ has the same meaning as R ₁₀ . [Chemical 6] In the formula, R ₃ , R ₄ , R ₁₀ , R ₁₁ , L _{1 to} L ₅ , X ₃ , n ₁ and n ₂ each have the same meaning as in the general formula [I], and X ₄
Represents the same meaning as X ₃ and R ₁₅ and R ₁₆ have the same meanings as R ₁₀ . X ⁻ represents a group having an anion. Further, R ₁₀ and R ₁₁ , and R ₁₅ and R ₁₆ can form a ring double bond. [Chemical 7] In the formula, A ₁ represents a pyrrole nucleus, an imidazole nucleus, a pyrazole nucleus, a phenol nucleus, a naphthol nucleus or a condensed heterocyclic nucleus. [Chemical 8] In the formula, Z ₁ , Z ₂ and Z ₃ represent electron withdrawing groups, and A ₂ represents an aryl group or a heterocyclic group. [Chemical 9] In the formula, L _{1 to} L ₃ have the same meanings as in the general formula [I],
Z ₁ has the same meaning as in formula [VIII]. R ₁₇ represents an alkyl group or an aryl group, and R ₁₈ represents an aryl group or an aromatic heterocyclic group. n ₄ represents an integer of 0 to 6.