JPS63257745A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the processing stability and the controllability with respect to the developing effect by specifying the average aspect ratio of nonphotosensitive silver halide particles and the diameter of the particles expressed in terms of spheres so as to enhance the function per one particle. CONSTITUTION:This sensitive material has a photosensitive silver halide emulsion layer on the supporting body and contains nonphotosensitive silver halide particles as flat platy hyperfine particles in an emulsion layer. The amt. of the hyperfine particles accounts for >=50%, preferably >=90% of the total projection area of all the particles contained in the emulsion layer. The average aspect ratio of the hyperfine particles is >=2, preferably >=7 and the diameter of the particles expressed in terms of spheres is <=0.2mum, preferably <=0.07mum. The hyperfine silver halide particles inhibit the outflow of halogen, especially iodine from the sensitive material to a processing soln. and also inhibit the outflow of a development retarding substance other than halogen produced in the sensitive material during development.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a photographic material with excellent processing stability and development effect controllability.

(Prior art) When developing a photographic material, if development inhibitors eluted from the material accumulate in the processing solution, it will cause fluctuations in photographic properties, and it is well known in the art that this is undesirable. In order to solve this problem, in addition to replenishing the developer according to the processing amount and keeping the composition of the processing solution at a constant equilibrium value, there is also a method that suppresses development or prevents it from easily flowing into the processing solution. A method of providing a non-light-sensitive emulsion layer containing ultrafine grain silver halide having the ability to trap development inhibitors near the surface of a photosensitive material is commonly used. No. 3,737,317, special 'Kaikai 50-2
No. 3228, No. 50-55332, No. 61-3904
It is presented in issue 3, etc.

On the other hand, in order to control the development speed of photosensitive silver halide grains or to control the interimage effect between photosensitive emulsion layers, ultrafine silver halide grains are added to the photosensitive emulsion layer or the non-photosensitive emulsion layer. A method of incorporating is also widely used in the industry, for example,
-3,728°121 and the same No. 4.082,553, etc., the method is described.

However, such ultrafine silver halide grains having various functions are so-called Lippmann emulsions, and their shape has not been studied in the past.

In recent years, various studies have been conducted on the shape of photosensitive silver halide grains, and in particular, the usefulness of grains with an extremely high aspect ratio (diameter/thickness ratio), as represented by US-4,434,426, has been investigated. being chanted. The above patent relates to particles with a thickness of 0.3 μm or less, a particle diameter of 0.6 μm or more, and an aspect ratio of 8 or more.
Of course, it is possible to prepare tabular grains in the fine grain range that is not included in the above size range, but the usefulness of this is described in Japanese Patent Laid-Open No. 6
No. 2-18555 was investigated as a photosensitive emulsion, but there has been no investigation as a non-photosensitive emulsion.

The present inventors have attempted to improve the functionality of each ultrafine silver halide grain of 0.2 μm or less and to reduce the amount of silver contained in the light-sensitive material.

(Problems to be Solved by the Invention) An object of the present invention is to improve processing stability by increasing the functionality per particle of ultrafine silver halide grains that are substantially non-photosensitive and contained in light-sensitive materials. An object of the present invention is to provide a photographic material with excellent controllability of development effects.

(Means for Solving the Problems) The object of the present invention is to provide a silver halide photographic photosensitive material comprising at least one photosensitive silver halide emulsion layer on a support and further containing non-photosensitive silver halide grains. In materials,
Of the non-photosensitive silver halide grains, 50% of the total projected area
This was achieved by a silver halide photographic material characterized in that the average aspect ratio of grains accounting for 2.0% or more and a sphere equivalent diameter of 0.2 μm or less.

The contents of the present invention will be explained in detail below.

There are many roles for the ultrafine grained silver halide used near the surface of the photosensitive material, but the main ones are: first, to suppress the outflow of halogen, especially iodine, from the photosensitive material into the processing solution; The second purpose is to suppress the outflow of development inhibitors other than halogen (for example, leaving groups from DIR couplers) generated in the sensitive material during the development process. The former is thought to be able to fulfill the above role by replacing the halogen in the ultrafine particles with a halogen that easily forms a less soluble silver salt, and the latter by adsorbing development inhibitors on the surface of the ultrafine particles. It is being In either case, the effect is largely controlled by the surface area of the ultrafine particles.

When ultrafine-grained silver halide is used in a non-photosensitive layer located between a light-sensitive silver halide emulsion layer and a support in a sensitive material, the suppressor produced is usually suppressed by the development product. The purpose of the trap is to adjust the development speed of adjacent layers and the development effect between layers. Further, colloidal silver may be used in advance in the same layer as development nuclei to form a filter layer of colloidal silver between emulsion layers having different color sensitivities during development.

Even in such cases, the effects of ultrafine particles will be greatly influenced by their shape.

The magnitude of the change in surface area due to flattening can be understood by comparing it with cubic grains, for example. The surface area of a disk that has the same volume as a cube and has an aspect ratio of 8 is 3 x 7 T, or about 1.54 times as large as that of a cube. Therefore, for phenomena dominated by surface area, this tabular grain is expected to have approximately 1.54 times the ability.

In the present invention, the aspect ratio of a tabular ultrafine grain refers to the diameter/thickness ratio of the grain, the diameter of a silver halide grain refers to the diameter of a circle with an area equal to the projected area of the grain, and the thickness refers to the diameter/thickness ratio of the grain. It refers to the distance between two parallel planes forming a silver halide grain.

The average aspect ratio of the tabular ultrafine particles used in the present invention is 2 or more, preferably 5 or more, and more preferably 7 or more. Also, its diameter is 0.2μm when converted to a sphere.
or less, preferably 0.1 μm or less, and 0.07 μm or less
It is more preferable that it is less than m.

The proportion of the ultrafine tabular silver halide grains in the emulsion layer containing the ultrafine tabular silver halide grains used in the present invention is preferably 50% or more, and 70% of the total projected area. It is more preferably at least 90%, most preferably at least 90%.

These tabular silver halide grains are manufactured by Japanese Patent Publication No. 47-11386.
As described in et al., it is also possible to use monodispersed silver halide grains in terms of grain size and/or thickness.

Here, the monodispersity of tabular silver halide grains means that 95% of the grains are within ±60% of the number average grain size.
Preferably, it refers to a dispersion system whose size falls within ±40%. Here, the number average grain size is the number average diameter of the projected area diameter of silver halide grains.

The halogen composition of the tabular grains includes silver chloride, silver bromide,
Silver iodobromide, silver chlorobromide, silver iodochloride, and silver chloroiodobromide are preferred.

When selecting the halogen composition, it is preferable to select a silver halide having higher solubility than the silver halide used in the light-sensitive emulsion layer.

The tabular ultrafine particles may have a uniform halogen composition or may consist of two or more phases having different halogen compositions.

Furthermore, the tabular ultrafine particles can be selected from those formed from a (111) plane, a (100) plane, or a mixture of (111) planes and (100) planes.

The ultrafine tabular silver halide grains used in the present invention can be used by fogging the surface and/or inside of the grains with a conventional chemical sensitization method, a reducing agent, or light, depending on the intended use.

In the present invention, the layer to which non-photosensitive tabular silver halide grains is added can be selected depending on the purpose. For example, U
No. S-3,728,121, No. 3,737,317, JP-A No. 50-23228, No. 50-55332,
It may be added to a non-photosensitive layer as in US Pat. No. 61-39043, or it may be added to a photosensitive emulsion layer as in US Pat. No. 4,082,553.

The thickness of the layer containing ultrafine tabular silver halide grains is 0.
It is preferably 1 to 6.0 μ, preferably 0.2 to 3.0, more preferably 0.5 to 2.0 μ.

Further, the coating silver amount of the tabular silver halide ultrafine grains is 0.1~
2 g/M, especially O, 1-1 g/rd is preferred.

Next, a method for producing tabular silver halide grains will be described.

The tabular silver halide grains can be produced by appropriately combining methods known in the art.

For example, seed crystals containing 40% or more of tabular grains by weight are formed in an atmosphere with a relatively low pBr value of pBrl, 3 or less, and silver and halogen solutions are simultaneously added while keeping the pBr value at the same level. Obtained by growing crystals.

During this grain growth process, it is desirable to add a silver and halogen solution to prevent the generation of new crystal nuclei.

The size of the tabular silver halide grains can be adjusted by controlling the temperature, selection of the type and amount of solvent, the silver salt used during grain growth, the addition rate of halide, etc.

When producing the tabular silver halide grains of the present invention, halogenation is carried out as necessary! I! By using a solvent, the particle size, particle shape (diameter/thickness ratio, etc.), particle size distribution, and particle growth rate can be controlled.

For example, as the amount of solvent used increases, the particle size distribution can be made monodisperse and the growth rate can be accelerated. On the other hand, there is also a tendency for the thickness of the particles to increase with the amount of solvent used.

Halogenation often used! ! Examples of the solvent include ammonia, thioethers, and thioureas.

These silver halide solvents are added to accelerate grain growth during the production of tabular silver halide grains of the present invention.
A method of increasing the addition rate, amount, and concentration of the m-salt solution (for example, AgN0. aqueous solution) and the halide solution (for example, KBr aqueous solution) is preferably used.

More specifically, regarding the tabular silver halide grains used in the present invention and the silver halide emulsion containing them, including the manufacturing method, for example, U.S. Pat. , No. 4,414,310,
Same No. 4. 425. No. 425, same No. 4,399,21
No. 5, No. 4,435.501, No. 4.386,1
No. 56, No. 4,400,463, No. 4. 414
．． 306, 4,425,426, European Patent No. 84.637A2. It is described in JP-A No. 59-99433, Research Disclosure Magneto 22534 (January 1983), and JP-A No. 62-18555.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide containing from about 1 mole percent to about 25 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin crystal shapes. It may have crystal defects such as, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention are, for example, Research Disclosure (RD), Volume 17643 (
December 1978), pp. 22-23, ″■, Emulsion Manufacturing (
Ea+ulsion preparation and
types)”, and 11h18716 (1
(November 979), p. 648, "Physics and Chemistry of Photography J" by Glafkide, published by Paul Montell (P.
des.

Chemic et Ph1sique Photog
raphique paul montel.

1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F. Duffin, I'hot
graphicEmulsion Chemistry
y (Focal Press+ 1966) )
"Production and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L, Zelik+man et al.
al, Makingand Coating, P
photographic E++ulsion+
Focal Press.

Kudzu can be prepared using the method described in (1964) and others.

U.S. Patent Nos. 3,574,628 and 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413.748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Cutoff, Photographic Sci.
ence and )! ngineering), 1st
4, 248A+257 (1970); U.S. Patent Nos. 4,434°226, 4,414,310, 4
, 433.048, 4,439,520 and British Patent No. 2,112.157.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, it may have a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure 11h.
17643 and 18716, and the relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Additive type RD17643 RD18716
1 Chemical sensitizer Page 23 Page 648 Right column 2 Sensitivity increasing agent
Same as above 4 Whitening agent page 24 Ultraviolet absorber 8 Dye image stabilizer page 25 9 Hardener page 26 Page 651 left column 10
Binder page 26 Same as above 11 Plasticizer, lubricant page 27 650 Right column Various color couplers can be used in the present invention, specific examples of which can be found in the aforementioned Research Disclosure (RD).
) Magneto 17643, described in the patent described in ■-C-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26.024, No. 4.401゜752, Special Publication No. 5
No. 8-10739, British Patent No. 1.425,020,
Same 1st. 476, 760, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
0,619, European Patent No. 4.351°897, European Patent No. 73,636, U.S. Patent No. 3,061,432, European Patent No. 3,725.067, Research Disclosure 11h24220 (June 1984) ), Japanese Patent Application Publication No. 1983-
No. 33552, Research Disclosure m242
30 (June 1984), JP-A No. 60-43659,
U.S. Patent No. 4,500,630, U.S. Patent No. 4,540.6
Particularly preferred are those described in No. 54 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. 4°0.52,21.
No. 2, No. 4.146,396, No. 4,228.2
No. 33, same No. 4. 296. 200, No. 2,369
, No. 929, No. 2.801゜171, No. 2,772
, No. 162, No. 2゜895.826, No. 3,77
No. 2,002, No. 3,758,308, No. 4.
334. No. 011, No. 4.327.173, West German Patent Publication No. 3.32'9.729, European Patent No. 121
No. 365A, U.S. Patent No. 3,446,622, U.S. Patent No. 4,333,999, U.S. Patent No. 4. 451. 559, European Patent No. 4,427,767, European Patent No. 161.62
Those described in No. 6A etc. are preferred.

Colored couplers to correct unnecessary absorption of coloring dyes are described in Research Disclosure No. 17643.
- Section G, U.S. Patent No. 4,163゜670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4.004,929, U.S. Patent No. 4,138,258, British Patent No. 1.146.36
The one described in No. 8 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
, 570, European Patent No. 96,570, and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820; U.S. Pat.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
Preferred are those described in No. 57-154234, No. 60-184248, and U.S. Pat.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097.140;
No. 2,131,188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , a multi-equivalent coupler described in JP-A No. 4,310,618, a DIR redox compound releasing coupler described in JP-A-60-185950, etc., and a dye that exhibits a color after separation described in European Patent No. 173,302A. Examples include couplers that emit light.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in U.S. Pat. No. 2,322.027 and the like.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. It is described in No. 230, etc.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of Na17643, and pages 647, right column to page 648, left column of Douben 18716.

The color photographic light-sensitive material according to the present invention is described in the aforementioned RD, Magnetics 17643, pages 28-29, and 6th volume of the same issue 18716.
It can be developed by the usual methods described in 51 left column to right column.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization step after desilvering treatment such as fixing or bleach-fixing.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal on the Society on Motion Picture and Television Engineers (Jo
urnal or the 5ociety of M
tion Picture and Televisi
on Engineers) Volume 64, P, 248-2
58 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be greatly reduced, but the increased residence time of water in the tank causes bacteria to propagate and the generated suspended matter to adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, the method for reducing calcium and magnesium described in Japanese Patent Application No. 131632/1988 can be used very effectively as a solution to such problems. can. In addition, chlorine-based disinfectants such as inthiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A No. 57-8542, "Chemistry of Antibacterial and Antifungal Agents" by Hiroshi Horiguchi It is also possible to use the disinfectants described in ``Sterilization, sterilization, and anti-mildew technology of microorganisms'', Hygiene Technology Extra Section, and ``Encyclopedia of Antibacterial and Antifungal Agents'', Japan Antibacterial and Anti-Mold Science Extra Section.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can also be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
a at 15-45°C for 20 seconds-10 minutes, preferably 2
A range of 30 seconds to 5 minutes at 5-40°C is selected.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8543 and 58-1483
No. 4, No. 59-184343, No. 60-220345,
No. 60-238832, No. 60-239784, 60-
No. 239749, No. 61-4054, No. 61-118'1
All known methods described in No. 49 and the like can be used. In particular, a stabilizing bath containing -hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2-methyl-4-isothiazolin-3-one, a bismuth compound, an ammonium compound, etc. is preferably used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

(Examples) The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.

Example 1 A total of 10 types of fogged silver iodobromide emulsions (iodine content: 0.5 mol %) as shown in Table 1 were prepared.

Here, emulsions E to J were prepared in a manner similar to that described in JP-A-62-18555.

Table 1 An emulsion layer having the composition shown below was coated on an undercoated cellulose triacetate film support, and silver iodobromide A-H shown in Table 1 was applied to each layer of No. 3.8.13 (sequentially). Add,
Samples 101 to 150 were created (Table 2).

1st N: Antihalation layer black colloidal silver 0.25 g/r
rl Ultraviolet absorber U-10, 1g/r+ (Ultraviolet absorber U-20, 1g/i High boiling point m solvent Oi 1 1 0.1cc/rr!
Gelatin 1.9 g/n?
2714th intermediate layer-1 Cpd-D 10■/d High boiling point organic solvent 0f1-340■/d Gelatin
0.4 g/td 3rd layer: Intermediate layer-2 Silver iodobromide emulsion (emulsion name and coated silver amount are listed in Table 2) Gelatin 0.4 g/nr 4th layer: 1st red-glare emulsion layer increase Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (monodisperse cubic with average grain size 0.3μ and Agl content 5 mol%) Silver amount 0.4 g/rd Coupler C-10 ,2g#c-20,05g/n(High boiling point organic solvent Oi 1-1 0.1cc/rd
Gelatin 0.8 g/rr
r Fifth layer: Second red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (monodisperse cubic emulsion with an average grain size of 0.5 μm and an Agl content of 4 mol%) ) Silver @ 0.4 g/rd coupler C-10,2g/n? c-30,2g/n1 C-20,05g/n? High boiling point Ia solvent Ot l -10,1 cc/nf gelatin 0.8 g/I 6th layer: 3rd red light emulsion layer Silver iodobromide spectrally sensitized with sensitizing dyes S-1 and S-2 Emulsion (monodispersed cubes with average grain size 0.6μ and Agl content 2 mol%) Silver amount 0.4 g/rrt Coupler c-30,7 g/rrr Gelatin 1.1 g/ffr 7th layer: Intermediate layer-3 Dye D-10.02g/rrr Gelatin 0.6g/rd
8th layer: Intermediate layer-4 Silver iodobromide emulsion (emulsion name and coated silver amount are listed in Table 2 ia) Compound Cp d-A 0.2 g/g Gelatin 1.0 g/rri 9th N = 1st green emulsion Emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (monodispersed cubic with average grain size 0.3 μm and Agl content 5 mol%) Silver amount 0.5 g/rrr Coupler C -4-0,3g/rJ Compound Cpd-80,03g/rrr gelatin
0.5 g/g 10th layer: 2nd green-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-3 and S-4 (
Monodispersed cubes with average particle size of 0.5μ and Agl content of 5 mol%) iAmount 0.4 g/rrr coupler C-
40.3g/n? Compound Cpd-80,03g/n? Gelatin 0.6g/lrr 1st
Layer 1: Third green-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-3 and S-4 (
Tabular emulsion with an average grain size of 0.6 μm and an aspect ratio of 5 and an Agl content of 2 mol %) Silver content 0.5 g/g Coupler C-40.8 g/rd Compound Cpd-80.08 g/m Gelatin 1.0 g/m rrr 1st
2nd layer: Intermediate layer-5 Dye D-20.05g/rrf Gelatin 0.6g/cd
13th layer: yellow filter, more yellow colloid w10.1g/rrr Compound Cp d-A 0.01g/rd
Gelatin 1.1 g / 1st
4th layer: 1st blue emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-S and S-6 (
Monodisperse cubic emulsion with average grain size 0.3μ and Agl content 3 mol%) Silver amount 0.6g/n? Coupler C-50,6g/m Gelatin 0.8g/rt
r 15th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion containing enhancing dyes S-7 and S-8 (
(Tabular emulsion with average grain size 0.5 μ, aspect ratio 7, Agl content 2 mol %) I amount Q, 4 g/m Coupler C-50, 3 g/rd C-60, 3 g/rd Gelatin 0.9 g/rrr 1st
6th layer: 3rd blue emulsion layer Silver iodobromide emulsion containing enhancing dyes S-7 and S-8 (
Contains AgT with an average particle size of 1.0μ and an aspect ratio of 7! T2 mol% tabular emulsion) 11 Amount 0.4 g/% Coupler C-60,7 g/n? Gelatin 1.2 g/n (
17th layer: 1st protective layer UV absorber U-10,04g/rrlU-30,0
3g/rr? U-40,03g/nf U-50,05g/rd U-60,05,g/n? Compound Cpd-CQ, 3g/rr? Dye D-30,05g/ryf Gelatin 0.7 g / r
d 18th layer: 2nd protective layer Silver iodobromide emulsion (emulsion name and coated silver amount are listed in Table 2) Polymethyl methacrylate (average grain size 1.5 μ) 0.1 g/rrr
426 copolymer of methyl methacrylate and acrylic acid (average particle size 1.5μ) 0.1g/rrr
Silicone oil 0.03 g/1
Fluorine-containing surfactant W-13g/rrl gelatin
0.8 g/rrl In addition to the above composition, gelatin hardener H-1 and surfactant were added to each layer.

il ■ 0■ H +Cl1t C1l,
Cl1z C1l +. ,.

C-5 0i1-1 Diptyl phthalate ○i l-2 Tricresyl phosphate pdA υII pdB pdD il -I S-4 SOsHN(1;xHsJs CHz-CHSOzCH*CONHCHtCl(z=c
HsOicHtcON)IC)ItHI Method 1 of evaluating processing stability in color inversion processing
One method is to examine changes in photographic properties due to changes in the amount of replenishment. When the amount of replenishment of the black and white developer changes, the most significant change in photographic properties is due to the accompanying change in bromide ion concentration. Therefore, samples 101~
Among 150, 101 to 115.150 were used to give an exposure of 20 CMS using an optical wedge, and the concentration of potassium bromide in the JQ white developer solution was varied according to the following steps.

For processed sample 101, the exposure amount that would give a yellow image color density of 1.0 was determined when the potassium bromide concentration in the black and white developer was 2.5 g/l. Next, when sample 101 was processed by changing the potassium bromide concentration in the black and white developer,
The color density when the above exposure amount was applied was investigated.

Similar tests were conducted on samples 102-115.150. By the above method, samples 101 to 115.1
For No. 50, changes in color density with respect to changes in potassium bromide concentration in the black and white developer were investigated. The treatment steps are shown below, and the results are shown in Table 3.

Processing process Time Temperature First development 6 minutes 38℃ First water washing 45 seconds 38〃 Reversal 45〃38〃 Color development 6 minutes 38〃 Bleach 2 〃 38〃 Bleach-fixing
4〃38〃 Second water wash full 1// 38〃Second water wash +2
1 1 #38 Stable 1 25 The composition of each treatment liquid was as follows.

Nitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt 2.0g Sodium sulfite 30g Hydroquinone potassium monosulfonate 20g Potassium carbonate 33g 1-phenyl-4-
Methyl-4-hydroxymethyl-3-pyrazolidone 2.0g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide
2.0 ■ Add water 100
0100O9,60 pH was adjusted with hydrochloric acid or potassium hydroxide.

42 water permeability mother liquor Ethylenediaminetetramethylenephosphonic acid 2.0g Disodium phosphate 5.0g 1゜ Add water 1000dl) H7,
00 pH was adjusted with hydrochloric acid or sodium hydroxide.

,) HvA unregulated inversion layer nitrilo-N,N,N-)rimethylenephosphonic acid 5.sodium salt 3.0g stannous chloride dihydrate 1. Ogp-aminophenol 0.1g Sodium hydroxide
8g glacial acetic acid 151
Add R1 water and 100ON! pH
6,00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Nitrilo-N,N,N-1-rimethylenephosphonic acid, pentasodium salt 2.0g Sodium sulfite 7.0g Trisodium phosphate
12 hydrate salt 36g
Potassium bromide 1.0g Potassium iodide 90% Sodium hydroxide
3.0g citradinic acid
1.5 g N-ethyl-N-(β-methanesulfonamidoethyl) = 3-methyl-4-amine aniline sulfate 11 g 3.6-cythiaoctane-1°8-diol 1.0 g Add water
10100O! par
1! , 80 pH was adjusted with hydrochloric acid or potassium hydroxide.

Ethylenediaminetetraacetic acid, 2-sodium salt, dihydrate 10.0gEthylenediaminetetraacetic acid, Fe ([11) ・Ammonium, dihydrate 120gAmmonium bromide 100gAmmonium nitrate
10g bleach accelerator o
, add oos mole water 1000
dpH6.30 The pH was adjusted with hydrochloric acid or aqueous ammonia.

Ethylenediaminetetraacetic acid・Fe (Iff)・Ammonium・dihydrate sogEthylenediaminetetraacetic acid・2sodium・dihydrate 5.0gSodium thiosulfate aogSodium sulfite
Add 12.0g water
1000adpH6.60 pH was adjusted with hydrochloric acid or aqueous ammonia.

The tap water was passed through a hotbed column packed with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400). The calcium and magnesium ion concentrations were reduced to below 3.71 kg, and then 20 g/l of sodium isocyanurate dichloride and 1.5 g/l of sodium sulfate were added. The pH of this solution is 6.5~
It is in the range of 7.5.

Formalin (37%) 5. 0IR
1 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Add 0.5 d of water to 1000 dpHill. There is little change in photographic properties (yellow color density) even if the potassium bromide content changes, and the black and white developer is much more stable than the comparative photosensitive material in which ordinary silver iodobromide grains are added to the 18th layer. It was revealed that this is a photosensitive material whose photographic properties are stable against changes in composition. As a result, processing stability equivalent to that of the comparative light-sensitive material can be obtained even if the non-light-sensitive silver halide emulsion coating (2) in the light-sensitive material of the present invention is lowered.

Example 2 Among the samples 101 to 150 released in Example 1, sample 1
01116 to 129.150 were exposed as described below and processed in the processing steps of Example 1, and the interimage effect from the green sensitive layer to the red sensitive layer was compared. The exposure method was to first expose the magenta image (green-sensitive layer) with green monochromatic light in steps so that the color density of the magenta image (green-sensitive layer) became the minimum density and the maximum density. Next, the entire sample was uniformly exposed to red monochromatic light so that the color density of the cyan image (red-sensitive layer) was 1.0 at the maximum density part of the magenta image.

After processing these samples, the cyan image density (D = 1.0) at the magenta maximum density area was measured, and the cyan image density at the magenta minimum density area was measured, and the change from the green sensitive layer to the red sensitive layer was measured. The interimage effect (development of the red-sensitive layer is suppressed or promoted depending on the degree of development of the green-sensitive layer) was investigated. The results are shown in Table 4. This result means that the present invention can greatly increase the interimage effect from, for example, a green-sensitive layer to a red-sensitive layer without increasing the amount of coated silver.

Next, for Samples 101.130 to 150, the interimage effect from the red sensitive layer to the green sensitive layer was compared in the same manner as above. As shown in Table 5, the present invention means that, for example, the interimage effect from the red-sensitive layer to the green-sensitive layer can be greatly increased without increasing the amount of coated silver.

Example 3 A total of two types of non-fogging silver bromide emulsions as shown in Table 6 were prepared. Here, the emulsion is JP-A-62-18555.
It was prepared using a method similar to that described in . Using these, the practical samples and comparative samples of the present invention shown in Table 7 were created.

Table 6 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) Coating amounts are expressed in units of g/rtr of silver for silver halide and colloidal silver, and amounts expressed in g/rrr for couplers, additives and gelatin.
The sensitizing dyes are expressed in moles per liter of silver halide in the same layer.

1st layer (antihalation layer) Black colloid! ! ! 0.2 Gelatin 1.3ExM-9
0,06 UV-10,03 UV-20,06 UV-30,06 Solv-10,15 Solv-20,15 Solv-30,05 2nd layer (middle layer) Gelatin 1. 0UV-1
0,03 ExC-40,02 ExF-10,004 Solv-10,l 5olv-20,1 3rd layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag14 mol%, uniform-Agl type, spherical Equivalent diameter 0.5μ, coefficient of variation of equivalent sphere diameter 20%, plate-shaped particles, diameter/thickness ratio 3.0) Coated silver amount 1. 2 Silver iodobromide emulsion (Ag 13 mol%, uniform Agl type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter 15%, spherical grains, diameter/thickness ratio 1.0) Coating 11ffi '0.6 Gelatin 1.0ExS-1
4xto-'ExS-25X10-' ExC-10,05 ExC-2,0,50 ExC-30,03 ExC-40,12 ExC-50,01 4th layer (high sensitivity red-sensitive emulsion layer) Silver iodobromide Emulsion (Ag 16 mol%, internal high AgI type with core-shell ratio 1:1, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 5.0) Coated silver amount 0. 7 Gelatin 1.0ExS-1
3xlO-' ExS-22,3X 10-' ExC-60.11 ExC-70,05 ExC-40,05 Solv-10,05 Solv-30,05 5th layer (middle layer) Gelatin 0. 5Cpd-
10,l 5olv-10,05 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag 14 mol%, surface cylinder AgT type with core-shell ratio 1:1, equivalent sphere diameter 0.5μ, equivalent sphere diameter Coated silver N 0135 Silver iodobromide emulsion (Ag 13 mol%, uniform Agl type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grain, diameter/thickness ratio 4.0) 25%, spherical particles, diameter/thickness ratio 1.0) Coating iJI amount 0.20 Gelatin 1. 0ExS-
35xxo-'ExS-43X10-'ExS-5xxio-' ExM-80,4 ExM-90,07 ExM-100,02 ExY-110,03 Solv-10,3 Solv-4'0. 05 7th layer (high sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag+4 mol%, internal high Agl type with core-shell ratio l:3, equivalent sphere diameter 0.7.c+, coefficient of variation of equivalent sphere diameter 20%) , plate-like particles, diameter/thickness ratio 5.0) Coated silver amount 0. 8 Gelatin 0. 5ExS-
35xto-'ExS-43X10-' ・ExS-51X 1 0-' ExM-80,I ExM-90,02 ExY -110,03 ExC-20,03 ExM-140,OL Solv-10,2 Solv-40, Of 8th layer (middle layer) Gelatin 0. 5cpd-
1o, 05 Solv-10, 02 9th layer (donor layer for multilayer effect on red-sensitive layer) Silver iodobromide emulsion (Ag 12 mol%, core shell ratio 2:1 internal height A)
GL type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 15%
, plate-shaped grains, diameter/thickness ratio 6.0) Coated silver amount 0.35 Silver iodobromide emulsion (Ag 12 mol %, internal high Agl type with core-shell ratio 1:1, equivalent sphere diameter 0.4 μ, equivalent sphere diameter Coefficient of variation 20%, plate-like particles, diameter/thickness ratio 6.0) Coated silver amount 0.20 Gelatin 0. 5ExS-
3axto-' ExY-130,11 ExM-120,03 ExM-140,10 Solv-10,20 1st O layer (yellow filter single layer) Yellow colloidal silver 0.05 Gelatin 0. 5Cpd-20,1
3 Cpd-10,10 11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (A gr 4.5 mol%, uniform Agl type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 15 %, plate-shaped particles, diameter/thickness ratio 7.0) Coated silver amount 0. 3 Silver iodobromide emulsion (Ag 13 mol%, uniform Agl type, equivalent sphere diameter 0.3μ, coefficient of variation of equivalent sphere diameter 25%, spherical grains, diameter/thickness ratio 7.0) Coating amount II 0.15 Gelatin 1.6ExS-6
2X10-' ExC-160,05 ExC-20,10 ExC-30,02 ExY-130,07 ExY-151,0 ExC-170,3 Solv-10,20 12th N (high sensitivity blue emulsion II) Silver bromide emulsion (Ag 110 mol%, internal high Agl type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25%, multiple twinned plate-like grains, diameter/thickness ratio 2.0) Coated silver amount 0. 5 Gelatin 0. 5ExS-
61xto-' ExY -150,20 ExY -130,01 Solv-! 0.
10 13th layer (1st protective layer) Gelatin 0.8UV-40
, l UV-50,15 Solv-10,01 Solv-20,01 14N (second protective layer) Gelatin 0.45 polymethyl methacrylate particles Diameter 1.5μ 0. 2H-10
,4 Cpd-5o,5 Cpd,-60,5 In addition to the above components, each layer contains an emulsion stabilizer Cpd-3
(0,04g/rrf) surfactant Cpd-4(0,
02 g/rrr) was added as a coating aid. Other following compounds Cpd-5 (0.5g/rrr) ~Cpd
-6 (0.5 g/rrr) was added.

UV-1 IV-2 UV-3 eC UV-5 Solv-1 tricresyl phosphate 3o1v-2 diptyl phthalate 0IV-3 o1v-4 Cpd-1 Cpd-3Cpd 4 xC-1 I (n) c, u.

ExC-2 CoExC-3 II ExC-4 1'll+ ExC-5 II C11゜ExC-6 H C11□ C(CIls)t ExC-7 xM-8 C2 ExY-11 lh I ExY-13 C1h CH
sj xM-14 f ExY-15 xC-16 0 ■ Day lh ExY-17 ExS-1 ExS-2 ExS-3 u;X2)zsO2" (C1li)as
OJaxS-4 X5-5 ExS-6 (CIlg) as(he(C1lz) asOsNa
CL=CHSow CHz' C0NHCtl□C
Hz”CHSon CHz C0N)I C1h
xF-1 Ct It s Cz 11 s
Samples 301 to 305 were created as described above. First, sample 301 was imagewise exposed and processed continuously according to the following processing steps until the cumulative replenishment amount of the color developer reached three times the tank capacity. Sample 301 subjected to IOCMS exposure was processed using an optical web after continuous processing. Next, the wedge-exposed sample 301 was processed in the same manner as in the continuous process, with the amount of replenishment of the color developing solution set to 1/2 of that in the processing steps described below.

Furthermore, the amount of replenishment of the color developing solution is set to 1/4 of the following step,
Sample 301 was subjected to the same continuous processing and wedge exposed.
processed. Sample 302.303 of the above series of tests
repeated about.

The processing steps are shown below.

Processing process Processing time Processing temperature Replenishment amount Volume color development 3 minutes 15 seconds 38℃ 45 d 7
00 ml bleach 1 minute 00 seconds 38℃ 20
wt1 100d bleach fixing 3 minutes 15 seconds 38℃
30m 1700m water washing (2) 1 minute OO seconds 35℃
30m1 700ad stable 40
seconds 38℃ 20d 70 (ld dry
Drying 1 minute 15 seconds 55°C Refill amount per 351 m width and 1 m length Next, write down the composition of the processing solution.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriamine pentacholic acid 1. '0 1.11-Hydroxyaminethene-1,l-diphosphonic acid 2.0 2.2 Sodium sulfite 4.0 4.9 Potassium carbonate 30.0 42.0 Potassium bromide
1.6-Potassium iodide
2.0■ -Hydroxyamine 2.
4 3.64-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline FafJ1 salt 5.0 7
．． 3 Add water IA INp
H10,0010,05 (Bleach solution) Common to mother liquor and replenisher Ethylenediaminetetraacetic acid ferric ammonium salt 120.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium nitrate 10.0g Ammonium bromide 100.0g Bleach accelerator
5×10″ Add 3M ammonia water pH 6.3 Add water
1.01 (Bleach-fix solution) Mother liquor and replenisher: 50.0 g of ferric ammonium salt of ethylenediaminetetraacetic acid 5.0 g of disodium salt of ethylenediaminetetraacetic acid 12.0 g of sodium sulfite 12.0 g of ammonium thiosulfate aqueous solution (70%) Add 240 d of aqueous ammonia pH 7.3 Add water
B〈Washing water〉 Exchange tap water with H-type strong acid cation ##! Resin (Mitsubishi Kasei■
After passing water through a mixed bed column filled with Diaion 5K-IB) and an OH-type strong basic anion exchange resin (Diaion 5A-1OA) to obtain the following water quality, isocyanate dichloride was added as a disinfectant. Sodium nurate 20a@
/j! was added.

Calcium ion 1.1■/1 Magnesium ion 0.5■/βpH6,9 (Stable solution) Both mother liquor and replenisher are formalin (37%-/v) 2. om
t Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0°05 Add water 11pal
For samples obtained through processing of approximately 6.0 or more, the exposure amount that gives a magenta color density of 1.0 at the start of continuous processing is determined, and the color density when this exposure amount is applied is calculated in the middle and at the end of continuous processing. Checked at 1 point. The results are shown in Table 8.

As is clear from Table 8, when the color light-sensitive material of the present invention was processed, favorable images were obtained in which the color density decreased much less during continuous processing than in the comparative example. This effect became particularly noticeable when the amount of color developer replenishment was reduced.

Example 4 Samples 301, 304, and 305 shown in Table 7 were exposed to IOCMS using an optical wedge, and then processed as shown in Example 3 to compare the sensitivities of the red-sensitive emulsion layers. Compared to sample 301, the anger level of sample 304 increased by about 30%, and the anger level of sample 305 increased by about 50%.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment 1961, Hl 2nd, 31st. , Ya ka de゛゛■,
■, Case Patent Application No. 103 of 1988 2, Name of the invention Silver halide photographic light-sensitive material 3, Person making the amendment Relationship to the case Patent applicant] 4. Subject of amendment ``Details of the invention'' in the specification 5 of ``Explanation'', the statement in the ``Detailed Description of the Invention'' section of the Description of Contents of Amendment is amended as follows.

1) Page 2, line λ “Development inhibitory” "Development inhibitor" and correct it.

2) Page 3! After "high" in the first line, "In order to develop a nine-sensitivity material with excellent processing stability and development effect,"
Or insert ".

3) 7th line of J. "In a non-photosensitive medium" "In the non-photosensitive emulsion layer" and correct it.

4) Page 2g, line μ "S-7 and 5-Jr J “S-! and 5-7J and correct it.

5) Page 2r, line l "S-7 and 5-rJ "S-j and S-6" and correct it.

6) Compound example S-A on page 3 " ” and correct it.

7) Page 33, line 7 from the bottom “/θlU1: "301" and correct it.

Claims (1)

[Claims] In a silver halide photographic light-sensitive material comprising at least one light-sensitive silver halide emulsion layer on a support and further containing non-light-sensitive silver halide grains, the total projected area of the non-light-sensitive silver halide grains is A silver halide photographic material characterized in that grains accounting for 50% or more have an average aspect ratio of 2 or more and a sphere equivalent diameter of 0.2 μm or less.