JPH1090828A - Silver halide photographic sensitive material and photographic element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent interlayer movement of dyes and the like added to upper and lower layers during storage by incorporating a swellable inorganic laminar compound in one of photographic element constituent layers. SOLUTION: This photosensitive material has at least one photosensitive emulsion layer and at least one nonphotosensitive layer on a support, and at least one of the nonphotosensitive layers contains the swellable inorganic laminar compound, such as swellable clay minerals like bentonite, hectonite, and monmorillonite, swellable synthetic mica, and swellable synthetic smectite. These compounds have an aspect ration of >=100, preferably, >=200, especially, >=500. A binder to be used for the swellable inorganic laminar compounds is, preferably, >=500 and it is added in amount of, for example, 1-2000 pts.wt., preferably, 10-2000 pts.wt., especially, 20-500 pts.wt. 100 pts.wt. of the swellable inorganic laminar compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to photographic elements, and more particularly to photographic elements with controlled diffusion of photographically useful compounds in photographic elements and / or photographic elements with improved storage stability.

[0002]

2. Description of the Related Art In the field of silver halide photography, various photographic useful compounds are introduced into a hydrophilic colloid layer in order to realize various photographic functions to construct photographic elements such as photosensitive materials and image receiving materials. ing. As a method for introducing the photographically useful compound into the hydrophilic colloid layer of the photographic element, when the photographically useful substance is soluble in water, a method of dissolving them and directly adding it to the coating solution is used. In the case of being insoluble in water, (1) dissolved in a water-miscible organic solvent and added directly to the coating solution, (2) dissolved in a water-immiscible organic solvent and emulsified in a protective colloid solution (3) Disperse and add to the coating solution (emulsification dispersion method); (3) Finely disperse in water or a protective colloid solution in a solid state with a mill or the like and add to the coating solution as a solid dispersion (solid dispersion method) ) A method of adding to a coating liquid as latex or impregnating latex is employed.

The photographically useful compounds which are added to each layer of the photographic element in various ways as described above are usually used fixed in the layers. However, various problems occur due to interlayer diffusion during raw storage or during storage after processing. For example, there are the following problems. (1) Color mixing occurs when a coloring material added and fixed as an emulsion to an emulsion layer or a coloring material layer diffuses into an adjacent layer that develops another color. In order to prevent this, usually, measures such as reducing the oil / binder ratio of the additional layer, increasing the thickness of the intermediate layer, and polymerizing the coloring material or the oil in which the coloring material is dissolved are taken. However, all of these countermeasures cause adverse effects such as lowering the color developability, suppressing the diffusion of the dye in the case of the diffusion transfer system, and deteriorating the curl due to the increase in the film thickness. (2) Additives that affect photographic properties, such as development inhibitors, development accelerators, reducing agents or dyes, diffuse into adjacent layers depending on storage conditions, and often cause deterioration of photographic properties. In order to prevent this, measures such as increasing the molecular weight of the additive, introducing a hydrophobic group, and increasing the thickness of the intermediate layer are taken. However, these countermeasures are accompanied by an adverse effect that the effect of the additive is reduced or the curl is deteriorated due to an increase in the film thickness. (3) In particular, during storage under high humidity, a powder blowing failure occurs due to the additive diffusing in the layer and depositing on the surface. In order to solve this, a binder is usually selected or its amount is increased. However, these countermeasures are not sufficient, and an adverse effect that the curl is deteriorated due to the increase in the film thickness occurs.

Further, the above-mentioned problem due to the interlayer diffusion of the additive compound itself does not occur. Occurs. (4) The compound contained is oxidized by oxygen and deteriorates, or light is irradiated in the presence of oxygen to promote photobleaching. In order to prevent this, an antioxidant or an ultraviolet absorber is added, or a protective layer or an intermediate layer of a polymer having a low oxygen permeability is provided, but the effect is not always sufficient and curling is also deteriorated. (5) The added compound is altered under high humidity. (6) A trace amount of nitrogen oxides or sulfur oxides in the air diffuses into the film and reacts with the compounds in the photographic element to color,
Causes problems such as discoloration and deterioration.

[0005]

Accordingly, it is an object of the present invention, as described above, to provide various additives added to a photographic element, interlayer diffusion of a photographically useful compound, or various gases contained in the atmosphere. (Oxygen, water vapor, carbon dioxide, nitrogen oxides, sulfur oxides, etc.) by diffusing into the photographic element layer, etc. without changing the structure of the additive itself, It is an object of the present invention to provide a method for solving the problem without changing the composition or without increasing the thickness of the intermediate layer to deteriorate curl and the like.

[0006]

The above objects of the present invention have been attained by the following silver halide light-sensitive materials or photographic elements (1) to (6). (1) A silver halide photographic material having a layer containing a swellable inorganic layered compound. (2) A silver halide photosensitive material having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive layer on a support, wherein at least one of the non-photosensitive layers has a swellable inorganic material. The silver halide photographic light-sensitive material according to (1), which comprises a layered compound. (3) A photographic element comprising a light-sensitive element having at least one light-sensitive silver halide emulsion layer on a support and a receiving element for receiving a silver image or a dye image formed in the light-sensitive element, A photographic element, characterized in that at least one of the layers contains a swellable inorganic layered compound. (4) The photographic element according to (3), wherein the non-photosensitive layer of the photographic element contains a swellable inorganic layered compound. (5) A photosensitive element having at least one photosensitive silver halide emulsion layer on a support, a function of bringing the photosensitive element into close contact with the photosensitive element during processing, and supplying components necessary for development to the photosensitive element. A photographic element comprising a processing element having a function of removing unnecessary components or both of them, wherein the swellable inorganic layered compound is contained in at least one layer of the photographic element. (6) The photographic element according to (5), wherein the non-photosensitive layer of the photographic element contains a swellable inorganic layered compound.

The details of the present invention will be described below. Examples of the swellable inorganic layered compound used in the present invention include swellable clay minerals such as bentonite, hectonite, and montmorillonite, swellable synthetic mica, and swellable synthetic smectite. These swellable inorganic layered compounds are 10 to 15
It has a laminated structure consisting of unit crystal lattice layers of angstrom thickness, and the substitution of metal atoms in the lattice is significantly larger than other clay minerals. As a result, the lattice layer has a shortage of positive charges, and cations such as Na ⁺ , Ca ²⁺ , and Mg ²⁺ are adsorbed between the layers to compensate for the shortage. The cations interposed between these layers are called exchangeable cations and exchange with various cations. In particular, when the cations between the layers are Li ⁺ and Na ⁺ , the bond between the layered crystal lattices is weak because the ionic radius is small, and the swells greatly with water. When shear is applied in this state, it is easily cleaved and forms a stable sol in water.
Bentonite and swellable synthetic mica have a strong tendency and are preferred for the purpose of the present invention. In particular, swellable synthetic mica is preferably used. As the swellable synthetic mica used in the present invention,
Na tetrathick mica NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ , Na or Li teniolite (NaLi) Mg ₂ Li (Si ₄ O ₁₀ ) F ₂ , Na or Li hextry (NaLi) ₁ / 3Mg ₂ / 3Li _1/3 (Si ₄ O ₁₀ ) F _{2 and the} like. The swellable synthetic mica preferably used in the present invention has a thickness of 1 to 50 nm and a plane size of 1 to 20 μm. For diffusion control, the thinner the better, the better the flatness is, and the better the planar size is, as long as the smoothness and transparency of the coated surface are not deteriorated. Therefore, the aspect ratio is 100
The number is preferably at least 200, particularly preferably at least 500.

The amount of the swellable inorganic layered compound used in the present invention is preferably 50 to 500 mg / m ² , and more preferably 100 to 500 mg / m ^{2 in} order to control the diffusion using the intermediate layer or the protective layer.
３００300 mg / m ² . 5-500 to improve film quality
It can be arbitrarily selected within the range of 0 mg / m ² according to the purpose. Since the surface of the swellable inorganic layered compound used in the present invention is negatively charged, it is not preferable to add a polymer having a cation site and a cationic surfactant to the same layer. As the binder used in the layer containing the swellable inorganic layered compound used in the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl Various kinds of synthetic hydrophilic high-molecular substances such as a single or copolymer such as alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, and polyacrylamide can be used.

As the gelatin, besides lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolyzate and gelatin enzyme dispersion can also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, epoxy compounds and the like are added to gelatin. What is obtained by reacting is used. Since the refractive index of the swellable synthetic mica used in the present invention is about 1.53, the binder used in combination is preferably a polymer having the same refractive index. The refractive index of gelatin is 1.53 ~
Since it is 1.54, it is particularly preferable as a swellable synthetic mica dispersion polymer or binder. The binder amount of the swellable inorganic layered compound-added layer used in the present invention is 1 to 2,000 parts by weight, preferably 10 to 1,000 parts by weight, particularly preferably 20 to 500 parts by weight, based on 100 parts by weight of the swellable inorganic layered compound. It is.

Next, a method for dispersing the swellable inorganic layered compound used in the present invention will be described. To 100 parts by weight of water, 5 to 10 parts by weight of a swellable inorganic layered compound are added, and the mixture is sufficiently blended with water.
After swelling, it is dispersed in a disperser. Examples of the dispersing machine used for carrying out the present invention include various milling methods in which a direct mechanical force is applied to disperse, a high-speed stirring type dispersing machine having a large shearing force, and a dispersing machine for applying high-intensity ultrasonic energy. and so on. Specifically, a ball mill, a sand grinder mill, a biscomil, a colloid mill, a homogenizer, a dissolver, a polytron, a homomixer, a homoblender, a kedi mill, a jet agitator,
There are a capillary type emulsifying device, a liquid siren, an electromagnetic strain type ultrasonic generator, an emulsifying device having a Paulman whistle, and the like. The dispersion of 5 to 10% by weight dispersed by the above method has a high viscosity or a gel state, and has extremely good storage stability. When it is added to the coating solution, it is diluted with water and stirred sufficiently before adding.

Since the surface of the swellable inorganic layered compound used in the present invention is negatively charged, the surface becomes hydrophobic when a cationic surfactant or the like is adsorbed on the surface. When using a swellable inorganic layered compound whose surface has been hydrophobized in this way, after swelling with a solvent having a sufficient affinity for the hydrophobic part of the surfactant adsorbed on the surface, disperse the binder solution. Can be added to prepare a coating solution.

The layer incorporating the swellable inorganic layered compound used in the present invention is not particularly limited as long as it is at least one layer of a photographic element. For example, a surface protective layer, an emulsion layer, an intermediate layer, an undercoat layer,
Although a back layer and other auxiliary layers can be mentioned, a non-photosensitive layer, particularly a surface protective layer and an intermediate layer, are preferred.

The photographically useful compounds which can be used in the present invention include dye image forming couplers, dye image donating redox compounds, stain inhibitors, antifoggants, ultraviolet absorbers, fading inhibitors, color mixing inhibitors, nucleating agents, Physical development nuclei, silver halide solvents, bleaching accelerators, dyes for filters and their precursors, dyes, pigments, sensitizers, hardeners, brighteners, desensitizers, developers, antistatic agents, oxidation Inhibitors, developer scavengers, latex, dye capture agents (such as mordants), development accelerators, development inhibitors, bases or base precursors, thermal solvents, color adjusting agents, and dispersing oils used as media for dispersing these. (Oil), silver halide, organic silver salts, and the like. Examples of these compounds include Research Disclosure (RD) No. 17
No. 643, No. 18716 and No. 18716. No. 307105 and the like. Hereinafter, a part thereof will be described.

A) Dye-Image-Forming Coupler A compound that forms a colored or non-colored dye by coupling with the oxidation product of an aromatic primary amine developing agent is called a coupler. As couplers, yellow, magenta, cyan and black couplers are useful.

As a typical example of the yellow coupler that can be used in the present invention, an oil-protected acylacetamide coupler can be mentioned. Specific examples thereof are described in US Patent Nos. 2,407,210 and 2,407.
Nos. 875,057 and 3,265,506. US Pat. Nos. 3,408,194 and 3,447,92 describe two equivalent yellow couplers.
No. 8, No. 3,933,501 and No. 4,02
No. 2,620 or the like, or a yellow coupler of an oxygen atom-elimination type or JP-B-58-10739, U.S. Pat. Nos. 4,401,752 and 4,326,024.
No., R. D. No. 18053 (April 1979), U.S. Patent No. 1,425,020, West German Application Publication No. 2,219,
No. 917, No. 2,261, 361, No. 2, 32
A typical example is a nitrogen atom-elimination type yellow coupler described in JP-A Nos. 9,587 and 2,433,812. α-pivaloylacetanilide-based couplers are excellent in the fastness of color-forming dyes, especially in light fastness, while α-benzoylacetoanilide-based couplers can provide high color-forming density. Of these, for example, U.S. Pat. Nos. 3,933,501 and 4,022,620,
Nos. 4,326,024 and 4,401,752
No. 4,248,961, JP-B-58-1073
9, UK Patent Nos. 1,425,020 and 1,47
No. 6,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649 and EP 249,473A are preferred.

Examples of the magenta coupler which can be used in the present invention include oil-protected couplers of the indazolone type or cyanoacetol type (preferably 5-pyrazolone type and pyrazoloazole type such as pyrazolotriazoles). 5-pyrazolone-based capillar is 3-
It is preferable that the coupler is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the color forming dye.
No. 1,082, No. 2,343,703, No. 2,6
No. 00,788, No. 2,908,573, No. 3,
Nos. 062,653, 3,152,896 and 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone coupler, a nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or an arylthio group described in U.S. Pat. No. 4,351,897 is preferable. Further, in the case of a 5-pyrazolone coupler having a ballast group described in EP 73,636, a high color density can be obtained.

Examples of the pyrazoloazole-based coupler include pyrazolobenzimidazoles described in US Pat. No. 3,369,879 and pyrazolo [5,1-c] [US Pat. No. 3,725,067]. 1,2,4] triazoles; D. No. 24220 (June 1984). European Patent No. 11 is used in view of the low yellow side absorption and the light fastness of the coloring dye.
Preference is given to imidazo [1,2-b] pyrazoles described in US Pat. No. 9,741 and pyrazolo [1,5-b] [1,2,4] triazole described in EP 119,860. Of these, US Pat. No. 4,310,619
No. 4,351,897 and European Patent No. 73,63.
No. 6, U.S. Pat. Nos. 3,061,432 and 3,72
No. 5,067, R.C. D. No. 24220 (June 1984
Mon.), JP-A-60-33552, R.A. D. No. 242
30 (June 1984), JP-A-60-43659, ibid.
No. 1-72238, No. 60-35730, No. 55-1
Nos. 18034, 60-185951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, International Publication WO 88/0479.
Those described in No. 5, etc. are preferred.

Cyan couplers usable in the present invention include oil-protected naphthol couplers and phenol couplers, and are described in US Pat. No. 2,474,293.
No. 4,052,212, 4,146,396;
Nos. 4,228,233 and 4,296,20
A typical example is an oxygen atom-elimination type double-equivalent naphthol coupler described in No. 0. Further, specific examples of phenol couplers are described in US Pat. No. 2,369,929.
No. 2,801,171, No. 2,772,16
No. 2, No. 2,895,826 and the like. Cyan couplers which are robust against humidity and temperature are preferably used in the present invention, and typical examples thereof include alkyl groups having an ethyl group or more at the meta-position of the phenol nucleus described in U.S. Pat. No. 3,772,002. Phenolic cyan coupler having a group, U.S. Pat. No. 2,772,162
No. 3,758,308, No. 4,126,39
No. 6, No. 4,334,011, No. 4,327,1
No. 73, West German Patent Publication No. 3,329,729 and JP-A-59-166956, and the like, and 2,5-diacylamino-substituted phenolic couplers described in U.S. Pat. , 333,999,
Nos. 4,451,559 and 4,427,76
Phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position described in No. 7, etc.

JP-A-60-237448, JP-A-61-1
No. 53640, No. 61-14557 and the like.
The naphthol coupler substituted at the − position with a sulfonamide group, an amide group, etc. is particularly excellent in the robustness of a color image,
It is preferred. Further, Japanese Patent Application Laid-Open No. 64-553,
No. 64-554, No. 64-555, No. 64-556
And the imidazole couplers described in US Pat. No. 4,818,672 can also be used.

Of these, US Pat. No. 4,052,2
No. 12, No. 4,146,396, No. 4,228,
No. 233, No. 4,296,200, No. 2,36
9,929, 2,801,171, 2,7
No. 72,162, No. 2,895,826, No. 3,
No. 772,002, No. 3,758,308, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 12
Nos. 1,365A, 249,453A, U.S. Pat. Nos. 3,446,622, 4,333,999, 4,775,616, and 4,451,559.
No. 4,427,767 and No. 4,690,889
Nos. 4,254,212 and 4,296,19
No. 9 and JP-A-61-42658 are particularly preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat.
No. 0,211, No. 4,367,282, No. 4,4
Nos. 09,320, 4,576,910, British Patent 2,102,137, and European Patent No. 341,188A. U.S. Pat. No. 4,366,237 discloses a coupler in which a coloring dye has an appropriate diffusibility.
British Patent 2,125,570, European Patent 96,5
No. 70 and West German Patent (Publication) No. 3,234,533 are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in R.C. D. VII-G of No. 17643
No., the same No. No. 307105, paragraphs VII-G; U.S. Pat.
163,670, JP-B-57-39413, U.S. Pat. Nos. 4,004,929 and 4,138,258.
And those described in British Patent No. 1,146,368 are preferred. Further, a coupler described in U.S. Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling, and U.S. Pat.
It is also preferable to use a coupler having a dye precursor group capable of forming a dye by reacting with a developing agent described in No. 7,120 as a leaving group. Compounds that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are:
The aforementioned R.I. D. No. Nos. 17643, VII-F and No.
No. 307105, the patent described in section VII-F,
Nos. 7-151944, 57-154234, 60
184248, 63-346, 63-3
No. 7,350, U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred. In addition, R. D. No. No. 11449, ibid. The bleaching accelerator releasing couplers described in JP-A-24241 and JP-A-61-201247 are effective for shortening the processing time having a bleaching ability. When added to the material, the effect is great.
Examples of 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-A-59-157538.
And No. 59-170840 are preferred.
Also, JP-A-60-107029 and JP-A-60-2523
Compounds which release a fogging agent, a development accelerator, a silver halide solvent, and the like by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A No. 40, JP-A-1-44940 and JP-A-1-45687 are also preferable.

Other couplers that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,42.
No. 7,283, etc .; U.S. Pat.
No. 472, No. 4,338,393, No. 4,31
No. 0,618, etc.
No. 185950, JP-A-62-24252, etc., DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, European Patent Nos. 173,302A and 313,308A No. 4,555,477, a coupler releasing a ligand described in U.S. Pat. No. 4,555,477, a coupler releasing a leuco dye described in JP-A-63-75747, Couplers that emit a fluorescent dye described in U.S. Pat. No. 4,774,181 are exemplified.
The above couplers and the like can be used in combination of two or more in the same layer in order to satisfy the characteristics required for the light-sensitive material.

B) Dye image-donating redox compound Another water-insoluble compound that can be used in the present invention is a dye image-donating redox compound used in a color diffusion transfer photosensitive material (for wet development and thermal development). . Specifically, it is a compound represented by the following general formula [LI]. General formula [LI] (Dye-Y) n-Z Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a mere bond or a linking group,
May cause a difference in the diffusivity of the compound represented by (Dye-Y) n-Z corresponding to or opposite to a photosensitive silver salt having an image-like latent image, or release Dye and release Done D
ye and (Dye-Y) n-Z represent a group having a property that causes a difference in diffusivity, and n represents 1 or 2, and when n is 2, two (Dye-Y) ) May be the same or different.

Specific examples of the dye donating compound represented by the general formula [LI] include the following compounds (i) to (v). The following (i) to (iii) are for forming a diffusible dye image (positive dye image) in reverse correspondence to the development of silver halide, and (iv) and (v) are for silver halide. Is formed to form a diffusible dye image (negative dye image) corresponding to the development.

(I) US Pat. Nos. 3,134,764, 3,362,819 and 3,597,200;
No. 3,544,545, No. 3,482,972, etc., a dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when reacted with silver halide. (ii) As described in U.S. Pat. No. 4,503,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can also be used. . Examples include U.S. Pat.
Compounds which release a diffusible dye by an intramolecular nucleophilic substitution reaction described in U.S. Pat.
Compounds which release a diffusible dye by an intramolecular reversal reaction of an isoxazolone ring described in JP-A No. 354 or the like.

(Iii) US Pat. No. 4,559,290;
EP 220,746 A2, U.S. Pat.
No. 3,396, JP-A-87-6199, and the like, a non-diffusible compound that reacts with a reducing agent remaining without being oxidized by development to release a diffusible dye can also be used. Examples include U.S. Pat. No. 4,139,389.
No. 4,139,379, JP-A-59-1853.
No. 33, 57-84453, etc., compounds which release a diffusible dye by a nucleophilic substitution reaction in the molecule after being reduced, U.S. Pat. No. 4,232,107; No. 101649, No. 61-88257,
R. D. No. 24025 (1984) and the like, compounds which release a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 3,008,588A,
JP-A-56-142530, U.S. Pat.
Compounds disclosed in US Patent Nos. 4,450,223 and the like, which release a diffusible dye by the cleavage of a single bond after reduction described in US Patent Nos. 4,450,223 and the like. Examples include nitro compounds that release a diffusible dye after accepting, and compounds that release a diffusible dye after accepting electrons described in U.S. Pat. No. 4,609,610.

More preferred are EP 220,746 A2, JP-A-87-6199, US Pat. No. 4,783,396, and JP-A-63-2016.
Compounds having an NX bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule described in JP-A Nos. 53-63-201654.
No. 42, a compound having an SO ₂ —X (X is as defined above) and an electron-withdrawing group in one molecule.
No. 71344 describes that a PO-X bond (X
Has the same meaning as described above) and a compound having an electron-withdrawing group, C-X 'in one molecule described in JP-A-63-271341.
Compounds having a bond (X 'has the same meaning as X or represents -SO2-) and an electron-withdrawing group can be mentioned. Further, compounds described in JP-A-1-161237 and JP-A-1-161342, in which a single bond is cleaved after reduction by a π bond conjugated to an electron-accepting group to release a diffusible dye, can also be used. Among them, a compound having an NX bond and an electron-withdrawing group in one molecule is particularly preferable. Examples thereof are EP 220,746 A2 or US Pat. No. 4,783,39.
Compounds (1) to (3), (7) to (10), (1
2), (13), (15), (23)-(26), (31), (32), (35), (3
6), (40), (41), (44), (53) to (59), (64), (70), compounds (11) to (23) described in Published Technical Report 87-6199, etc. It is.

(Iv) A compound having a diffusible dye as a leaving group and capable of releasing a diffusible dye by reacting with an oxidized reducing agent (DDR coupler). Specifically, British Patent No. 1,330,524, JP-B-48-39165,
U.S. Pat. Nos. 3,443,940 and 4,474,8
No. 67, No. 4,483,914 and the like. (v) reducible to silver halide or organic silver salt,
A compound that releases a diffusible dye when the partner is reduced (DR
R compound). Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidized decomposition products of the reducing agent. A representative example is U.S. Pat.
Nos. 8,312, 4,053,312, 4,0
Nos. 55,428 and 4,336,322;
Nos. 9-65839, 59-69839, 53-3
No. 819, No. 51-104343, RD17465
Nos. 3,725,062 and 3,72
No. 8,113, No. 3,443,939, JP-A-58-1983.
No. 116537, No. 57-179840 and U.S. Pat. No. 4,500,626. Specific examples of the DRR compound include the aforementioned US Pat. No. 4,500,6.
Compounds described in Columns 22 to 44 of No. 26 can be mentioned, and among them, compounds (1) to
(3), (10)-(13), (16)-(19), (28)-(30), (33)-(3
5), (38) to (40), and (42) to (64) are preferred. Compounds described in U.S. Pat. No. 4,639,408, columns 37 to 39 are also useful.

C) Organic or inorganic dyes and pigments The dyes and pigments used in the present invention include azo, azomethine, oxonol, cyanine, phthalocyanine, quinacridone, anthraquinone, dioxazine, and indigo. And organic dyes or inorganic dyes such as perinone / perylene type, titanium oxide, cadmium type, iron oxide type, chromium oxide, and carbon black. Can also be used. These dyes and pigments in the present invention can be used in any state such as an aqueous paste state or a powder state immediately after production. U.S. Pat. No. 4,420,555, JP-A-61-204630.
And oil-soluble dyes described in JP-A-61-205934 and the like are also useful. Useful dyes for use in the present invention may be any of a variety of well-known dyes. The structures of these dyes include arylidene compounds, heterocyclic arylidene compounds, anthraquinones, triarylmethanes, azomethine dyes, azo dyes, cyanines, merocyanines, oxonols, styryl dyes, phthalocyanines, indigo and others.

The arylidene compound is a compound in which an acidic nucleus and an aryl group are linked by one or more methine groups. Examples of the acidic nucleus include 2-pyrazolin-5-one, 2-isoxazolin-5-one, barbituric acid, 2-thiobarbituric acid, benzoylacetonitrile, cyanoacetamide, cyanoacetanilide, cyanoacetate, malonic ester, and malon. Dianilide, dimedone,
Benzoylacetoanilide, pivaloylacetoanilide, malononitrile, 1,2-dihydro-6-hydroxypyridin-2-one, pyrazolidine-3,5-dione, pyrazolo [3,4-b] pyridine-3,6-dione, indane -1,3-dione, hydantoin, thiohydantoin, 2,5-dihydro-furan-2-one and the like. The aryl group includes a phenyl group, which is preferably substituted with an electron-donating group such as an alkoxy group, a hydroxy group, or an amino group.

The heterocyclic arylidene compound is a compound in which an acidic nucleus and a heteroaromatic ring are linked by one or more methine groups. Examples of the acidic nucleus include those described above. Heteroaromatic rings include pyrrole, indole, furan, thiophene, pyrazole coumarin and the like.

Anthraquinones are those obtained by substituting anthraquinone with an electron donating group or an electron withdrawing group. Triarylmethanes represent compounds in which three substituted aryl groups (which may be the same or different) are bonded to one methine group. An example is phenolphthalein.

The azomethine dye represents a dye in which an acidic nucleus and an aryl group are linked by an unsaturated nitrogen linking group (azomethine group). Acidic nuclei include those known as photographic couplers in addition to those described above. Indoanilines also belong to the azomethine dye. An azo dye represents one in which an aryl group or a heteroaromatic ring group is linked by an azo group.

Cyanine represents two basic nuclei linked by one or more methine groups. Oxazole, benzoxazole, thiazole,
There are quaternary salts such as benzothiazole, benzimidazole, quinoline, pyridine, indolenine, benzoindolenine, benzoselenazole, imidazoquinoxaline and pyrylium.

The merocyanine dye represents a dye in which the above-mentioned basic nucleus and acidic nucleus are linked by a double bond or linked by one or more methine groups. Oxonol dyes are those in which two of the above acidic nuclei are linked by one or more odd number of methine groups. The styryl dye represents the above-mentioned basic nucleus and an aryl group linked by two or four methine groups. The phthalocyanine may or may not be coordinated to the metal. Indigo may be unsubstituted or substituted indigo, including thioindigo.

When an oil-soluble dye is used as a filter dye or an antihalation dye, any effective amount can be used, but the optical density is 0.05 to 3.5.
It is preferable to use it so that it may be within the range. The timing of addition may be any step before coating. Although the specific amount of the dye varies depending on the dye, the dispersing polymer, the dispersing method, and the like, it is generally 10 ⁻³ g / m ^{2 to} 3.0 g / m ² , particularly 10 ⁻³ g.
/ M ² in the range of to 1.0 g / m ² can be found in desired amounts.

D) Oil for Dispersion As a high-boiling organic substance (oil for dispersion), which is used to suppress crystallization when a water-insoluble photographically useful compound is finely dispersed in an aqueous medium, water is actually used. Those which are insoluble at the top and have a boiling point of 190 ° C. or more at normal pressure are preferred. It is also required to contain an emulsified dispersion of a high-boiling organic substance (dispersion oil) for various purposes such as adjustment of the elastic modulus of the film constituting the photographic element, capture of oil-soluble substances, and adjustment of adhesion or adhesion. May be done. Examples of this type of organic substance include carboxylic acid esters, phosphoric acid esters, carboxylic acid amides, ethers, phenols, anilines, substituted hydrocarbons, and surface-inactive hydrophobic organic polymers. You can choose. Specific examples thereof include di-n-butyl phthalate, diisooctyl phthalate, dicyclohexyl phthalate, dimethoxyethyl phthalate, and di-n-adipate.
Butyl, diisooctyl azelenate, tri-n citrate
-Butyl, butyl laurate, di-n-butyl sebacate, tricyclohexyl phosphate, tri-n-butyl phosphate, triisooctyl phosphate, N, N-diethylcaprylic amide, N, N-dimethylpalmitic acid Amide, n
-Butyl- (m-pentadecyl) phenyl ether, ethyl- (2,4-di-tert-butyl) phenyl ether, 2,5-di-tert-amylphenol, 2-n-butoxy-5-tert-octylaniline , Paraffin chloride, poly (methyl methacrylate), poly (ethyl methacrylate), poly (ethyl acrylate), poly (cyclohexyl methacrylate), poly (N-tert-butylacrylamide), poly (N-tert-octylacrylamide), etc. .

The above-mentioned oil for dispersion contains a low-boiling organic solvent that is immiscible with water (having a boiling point of 130 ° C. or less at 1 atm),
Or you may use together with a water-miscible organic solvent. In order to increase the stability of the obtained dispersion, the water-immiscible or water-miscible organic solvent used to bring the photographically useful substance into a solution state is distilled, more preferably, vacuum distillation or ultrafiltration, and the like. It may be removed by a known method. Examples of such organic solvents include propylene carbonate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, ethyl propionate, sec-butyl alcohol, methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone, dimethylformamide, Metrusulfoxide is mentioned as an example. The preferred amount of the organic solvent used is 0.1% by weight of the water-insoluble photographically useful compound dispersed.
The amount is 1 to 100 times.

E) Latex The monomers constituting the polymer latex that can be used in the present invention include, for example, acrylic esters, methacrylic esters, crotonic esters, vinyl esters, maleic diesters, fumaric diesters, Examples include itaconic acid diester, acrylamides, methacrylamides, vinyl ethers, styrenes, and the like.

Specific examples of these monomers will be described below. As acrylates, methyl acrylate, ethyl acrylate, n-propyl acrylate,
Isopropyl acrylate, n-butyl acrylate,
Isobutyl acrylate, tert-butyl acrylate,
Hexyl acrylate, 2-ethylhexyl acrylate, acetoxyethyl acrylate, phenyl acrylate, 2-methoxy acrylate, 2-ethoxy acrylate, 2- (2-methoxy ethoxy) ethyl acrylate, and the like. As methacrylic acid esters,
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, te
Examples thereof include rt-butyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, and 2-ethoxyethyl methacrylate. Examples of the crotonic acid ester include butyl crotonate and hexyl crotonate. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, and vinyl benzoate. Examples of the maleic acid diester include diethyl maleate, dimethyl maleate, dibutyl maleate and the like. Examples of the fumaric acid diester include diethyl fumarate, dimethyl fumarate, dibutyl fumarate and the like. Examples of the itaconic acid diester include diethyl itaconate, dimethyl itaconate, and dibutyl itaconate.

The acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, n-butylacrylamide, te
rt-butylacrylamide, cyclohexylacrylamide, 2-methoxyethylacrylamide, dimethylacrylamide, diethylacrylamide, phenylacrylamide and the like. Examples of the methacrylamides include methyl methacrylamide, ethyl methacrylamide, n-butyl methacrylamide, tert-butyl methacrylamide, 2-methoxy methacrylamide, dimethyl methacrylamide, diethyl methacrylamide and the like. Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, and the like. As styrenes, styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, chloromethyl styrene, methoxy styrene, butoxy styrene, acetoxy styrene,
Chlorostyrene, dichlorostyrene, bromostyrene,
Examples thereof include methyl vinyl benzoate and 2-methylstyrene.

The polymer composed of these monomers may be a homopolymer or a copolymer. Acrylic esters, methacrylic esters, styrenes, binary or terpolymers of acrylic acid, methacrylic acid; copolymers of styrenes and butadiene; polyvinylidene chlorides are preferably used.

In photographic elements of the type in which the mobile dye released by development is transferred to an image receiving element, a dye capture agent is incorporated into the photographic element in the following manner. (1) It is incorporated as a dye fixing agent (mordanting agent) into the dye element. (2) For the purpose of lowering Dmin (density of a white background), it is contained in an intermediate layer or a protective layer in the photosensitive element. (3) For the purpose of preventing post-transfer of a dye in a processing solution (in a pod) for a diffusion transfer type color instant photographic element (in particular,
Secondary amine type polymer latex). As the dye-capturing agent used in these applications, a water-soluble polymer mordant, an oil-soluble polymer mordant, and a latex mordant are used. In particular, the polymer latex mordant is preferably used in the above applications (2) and (3).

Here, the polymer mordant includes a polymer having a tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety,
And polymers containing these quaternary cationic groups. Further, a polymer mordant containing a group of imidazole or a derivative thereof has high light fastness and is preferably used.

For a polymer containing a vinyl monomer unit having a tertiary amine group, see JP-A-60-60643.
And specific examples of the polymer containing a vinyl monomer unit having a tertiary imidazole group are described in JP-A-60-118834 and JP-A-60-57836.
No. 60-122941, Japanese Patent Application No. 61-87180,
No. 61-87181, U.S. Pat. No. 4,282,305
No. 4,115,124 and 3,148,06
No. 1 and the like.

Specific examples of the polymer containing a vinyl monomer unit having a quaternary imidazolium salt include British Patent Nos. 2,056,101, 2,093,041, 1,594,961, and US Pat. Patent No. 4,124,38
No. 6, No. 4,115,124, No. 4,273,8
No. 53, No. 4,450,224, JP-A-48-2
8,225 and the like.

Other specific examples of the polymer containing a vinyl monomer unit having a quaternary ammonium salt include US Pat. Nos. 3,709,690 and 3,898,088.
No. 3,958,995, JP-A-60-5783.
No. 6, No. 60-60643, No. 60-122940
No. 60-122942 and No. 60-23513
No. 4, etc.

Free radical polymerization of ethylenically unsaturated solid monomers can be achieved by thermal decomposition of chemical initiators or by the action of reducing agents on redox compounds (redox initiators) or by physical action, such as ultraviolet light or other high energy It is initiated by the addition of free radicals formed by radiation, radio frequency, etc., to the monomer molecules.

The main chemical initiators include persulfate (ammonium and potassium persulfate), hydrogen peroxide, 4,4'-azobis (4-cyanovaleric acid) and the like (these are water-soluble), There are butyronitrile, benzoyl peroxide, chlorobenzoyl peroxide and other compounds, which are insoluble in water. A common redox initiator is hydrogen peroxide-
Iron (II) salt, potassium persulfate-potassium bisulfate, cerium salt alcohol and the like. Examples of initiators and their effects are described in FA
Bovey, Emulsion Polymerization, Interscience P
ublishes Inc. New York, 1955, pp. 59-93.

As the emulsifier, a compound having surface activity is used, and preferably, soap, sulfonate and sulfate, cationic compound, amphoteric compound and polymer protective colloid are used. Examples of these groups and their effects can be found in Belgische Chemische Industrie Vol. 28, 16-16.
It is described on page 0 (1963).

Specific examples of the polymer latex which can be used in the present invention are described below, but the present invention is not limited to these.

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F) Silver halide and organic silver salt The silver halide which can be used in the present invention includes silver chloride, silver bromide,
Any of silver bromoiodide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide may be used. The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion.
The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Further, a so-called core-shell emulsion having a different phase between the inside of the grain and the grain surface layer may be used. The silver halide emulsion may be monodispersed or polydispersed, or a mixture of monodispersed emulsions may be used. The particle size is preferably from 0.1 to 2 μm, particularly preferably from 0.2 to 1.5 μm.
The crystal habit of silver halide grains is cubic, octahedral, tetrahedral,
It may have a flat shape with a high aspect ratio or any other shape. Specifically, U.S. Pat. No. 4,500,626, column 50,
No. 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) 17029 (1978)
) And any of the silver halide emulsions described in JP-A-62-253159 can be used.

Use the silver halide emulsion as it is
Usually, it is used after chemical sensitization. Normal type photosensitive material
Sensitization, reduction sensitization, and noble metal sensitization for emulsions
And selenium sensitization, etc., alone or in combination
be able to. These chemically sensitized nitrogen-containing heterocyclic compounds
(JP-A-62-25315).
No. 9). Photosensitive silver halide used in the present invention
The coating amount of silver is 1 mg / m ^TwoTo 10 g / m^Twoof
Range.

The silver halide which can be used in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide. The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Further, a so-called core-shell emulsion having a different phase between the inside of the grain and the grain surface layer may be used. The silver halide emulsion may be monodispersed or polydispersed, or a mixture of monodispersed emulsions may be used. The particle size is preferably from 0.1 to 2 μm, particularly preferably from 0.2 to 1.5 μm. The crystal habit of silver halide grains is cubic, octahedral,
It may be a tetradecahedron, a flat plate with a high aspect ratio, or any other. Specifically, U.S. Pat. Nos. 4,500,626, column 50, 4,628,021, and Research Disclosure Magazine (hereinafter abbreviated as RD) 17029 (1)
978), and any of the silver halide emulsions described in JP-A-62-253159 can be used.

The silver halide used in the present invention may be spectrally sensitized with methine dyes or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Specifically, U.S. Pat. No. 4,617,257, and JP-A-59-180550.
No. 60-140335, RD17029 (197
8 years), sensitizing dyes described on pages 12 to 13 and the like.
These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, a dye which has no spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. , 615, 641, and JP-A-63-23145). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after nucleation of silver halide grains. Good. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

When the photosensitive element of the present invention is processed by thermal development, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, an organic silver salt is particularly preferably used. Organic compounds that can be used to form the above-described organic silver salt oxidizing agents include U.S. Pat. No. 4,500,626 Nos. 52-5.
There are benzotriazoles, fatty acids and other compounds described in column 3 and the like. Also useful are silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in JP-A-60-113235 and acetylene silver described in JP-A-61-249044. Two or more organic silver salts may be used in combination. The above organic silver salts can be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of the photosensitive silver halide. The total coating amount of the photosensitive silver halide and the organic silver salt is 50 m in terms of silver.
g / m ² to 10 g / m ² is suitable. g) Reducing agent Another photographically useful compound that can be used in the present invention is a reducing agent. As the reducing agent, those known in the art can be used. Further, the above-described dye-donating compound having a reducing property is also included (in this case, another reducing agent may be used in combination). Further, a reducing agent precursor which does not itself have a reducing property but expresses a reducing property by the action of a nucleophilic reagent or heat during the development process can be used. Examples of the reducing agent used in the present invention are described in U.S. Pat. No. 4,500,626, columns 49 to 50, and 4,4,50.
No. 83,914, columns 30-31, 4,330,61
No. 7,4,590,152, JP-A-60-1403
No. 35, pages (17) to (18), and 57-40245
Nos. 56-138736 and 59-178458
No. 59-53831, No. 59-182449,
No. 59-182450, No. 60-119555, No. 60-128436 to No. 60-128439, No. 60-198540, No. 60-181742
No. 61-259253, No. 62-244444
No. 62-131256 to No. 62-131256
No. 78-9 of EP 220,746 A2.
There are reducing agents and reducing agent precursors described on page 6 and the like. Various combinations of reducing agents, such as those disclosed in U.S. Pat. No. 3,039,869, can also be used.

When a diffusion-resistant reducing agent is used, an electron transfer agent and / or an electron-transferring agent may be used, if necessary, in order to promote electron transfer between the diffusion-resistant reducing agent and the developable silver halide.
Alternatively, an electron transfer agent precursor can be used in combination. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. It is desirable that the electron transfer agent or its precursor has a higher mobility than the diffusion-resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any one that does not substantially move in the layer of the photosensitive element among the reducing agents described above, and is preferably a hydroquinone, Examples thereof include sulfonamidophenols, sulfonamidonaphthols, compounds described as electron donors in JP-A-53-110827, and the above-mentioned dye-donating compounds having diffusion resistance and reducing property. The addition amount of the reducing agent is 0.001 to 20 mol, particularly preferably 0.01 to 10 mol, per 1 mol of silver.

The reducing agent may be incorporated in the photosensitive element, or may be supplied to the photosensitive element (and the dye fixing element) during processing as one component of the processing composition contained in a rupturable container. The former mode is preferable when processing is performed by thermal development, and the latter mode is preferably used when processing is performed by a so-called color diffusion transfer method in which processing is performed at room temperature.

H) Other photographically useful compounds Other photographically useful compounds that can be used in the present invention include:
For example, antifoggants and development inhibitors represented by mercaptotetrazole, mercaptotriazoles, mercaptopyrimidines, mercaptobenzimidazoles, mercaptothiadiazoles, benzotriazoles, imidazoles, etc .; p-phenylenediamines, hydroquinones, developing agents such as p-aminophenols; auxiliary developing agents represented by pyrazolidones; nucleating agents such as hydrazines and hydrazides; silver halide solvents such as hypo;
Bleaching accelerators such as aminoalkylthiols; and dyes such as azo dyes and azomethine dyes. or,
In addition to the precursor of the above-mentioned photographically useful compound, or a compound further having a redox function of releasing the above-mentioned photographically useful compound with the progress of development, for example, the above-mentioned dye material for a color diffusion transfer photosensitive element, DIR- Or D
AR-hydroquinones can also be mentioned as good photographically useful compounds. The above-mentioned photographically useful compounds may be bonded via a timing group, and such a timing group releases a photographically useful compound by an intramolecular ring closure reaction described in JP-A-54-145135. , British Patent No. 2,072,363, JP-A-5
No. 7,154,234, which release a photographically useful compound by intramolecular electron transfer.
No. 79842, which releases a photographically useful compound with the elimination of carbon dioxide gas, or JP-A-59-1984.
No. 93442, which release a photographically useful compound with release of formalin.

As a method for dispersing the water-insoluble photographically useful compound in the above photographically useful compound, typically, an oil-in-water dispersion method using a high boiling point solvent in the presence of a dispersant can be mentioned. Specifically, a water-insoluble photographically useful compound kept in a solution state by any of the following methods is mixed with water or a hydrophilic colloid aqueous solution in the presence of a dispersant,
Can be prepared. If necessary, the following dispersing machine can be used to further reduce the size of the dispersion particles.

Examples of the disperser include a high-speed stirring type disperser having a large shearing force, and a disperser for applying high-intensity ultrasonic energy. Specific examples include a colloid mill, a homogenizer, a capillary emulsifier, a liquid siren, an electromagnetic strain type ultrasonic generator, and an emulsifier having a Paulman whistle. A high-speed stirring type dispersing machine preferable for use in the present invention is a disperser, a polytron, a homomixer, a homoblender, a Keddy mill, a jet agitator, or the like, in which a main part having a dispersing action is rotated at high speed in a liquid (500 to 15,000 rp).
m, preferably 2,000 to 4,000 rpm). The high-speed stirring type disperser used in the present invention is also called a dissolver or a high-speed impeller disperser. As described in JP-A-55-129136, a saw-toothed blade is alternately arranged on a shaft rotating at high speed. A preferred example is a device in which an impeller bent in the vertical direction is attached to the device.

In order to obtain a finely emulsified dispersion of a water-insoluble photographically useful compound, as described in WO 93/3420, after increasing the amount of a surfactant and finely dispersing the same, an excess of surfactant is obtained by washing with water. A method for removing the agent (because it is not preferable in terms of photographic properties, physical properties, and manufacturing suitability) is also effective. However, in this case, when the above-mentioned dispersion is added to the coating solution or when the added coating solution is dissolved and aged over time, in order to prevent aggregation and precipitation of the water-insoluble photographically useful compound from occurring, a special method is required. It is extremely effective to add the terminal hydrophobic group-modified polyvinyl alcohol described in Japanese Patent Application No. 6-216712 or a modified product thereof to the dispersion. The co-solvent or surfactant can be removed by known methods, for example, U.S. Pat. Nos. 2,322,027 and 2,801,171;
No. 2946360, No. 3396027, No. 4233
No. 397.

Further, a water-insoluble photographically useful compound is dissolved in an acid, an alkali, a water-miscible organic solvent or a mixture thereof, and then the terminal hydrophobic group-modified polyvinyl alcohol described in Japanese Patent Application No. 6-216712 or a modified product thereof is used. For example, by neutralizing in the presence of a polymer dispersant such as the above, or by mixing with water, precipitation and dispersion can be performed. As a representative example of the dispersion method by this method, British Patent No. 1,193,3
No. 49, U.S. Pat. Nos. 4,957,857 and 4,9
Nos. 33,270 and the like describe a case where the invention is applied to a color coupler for photography, and JP-A-4-163453 describes a case where the invention is applied to other water-insoluble photograph useful compounds.

When the water-insoluble photographically useful compound is a solid, a fine solid dispersion can be directly obtained by dispersing in a medium in the presence of water and a dispersant. A typical example is a solid dispersion of a dye as described in WO 88/04794. In addition, application to pigments such as carbon black and titanium oxide is also effective.
As the medium dispersion, a method of mechanically dispersing by a ball mill, a sand grinder mill, a colloid mill or the like is general.

A water-insoluble photographically useful compound can be filled in an aqueous polymer latex and incorporated into a photographic light-sensitive element. Methods for dispersing using polymer latex are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,54.
1, 230 and the like.

As the hydrophilic colloid in the hydrophilic colloid composition used in the present invention, a binder or a protective colloid usually used in a silver halide photographic light-sensitive element is used. Gelatin is advantageously used as a binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl Alcohol, polyvinyl alcohol partial acetal, poly-N-
Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used.

As gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolysates and gelatin enzyme dispersions can also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, epoxy compounds and the like are added to gelatin. What is obtained by reacting is used.

The swellable inorganic layered compound of the present invention can be used in a photographic material using silver halide as an optical sensor or in various photographic elements used in combination therewith. For example, silver halide black-and-white or color light-sensitive materials that are wet-processed, silver halide black-and-white or color light-sensitive materials that are heat-processed, silver halide black-and-white or color light-sensitive materials that are wet-processed using diffusion transfer technology, diffusion transfer Silver halide black-and-white or color light-sensitive materials that are heat-developed using technology, photographic elements used in combination with these light-sensitive materials (for example, the function of supplying necessary processing elements to the light-sensitive materials and / or unnecessary in processing) A processing sheet having a function of removing the components which have become a photosensitive material, and a receiving element (image receiving element or dye diffusion transfer method) for receiving an image forming substance such as silver ion or dye diffused imagewise from the photosensitive material. In this case, the technique of the present invention can be applied to a dye-fixing element, etc. The form of the photographic element can be a roll or a sheet. Stated in another good. Applications,
Black and white light-sensitive materials, X-ray light-sensitive materials, squirrel light-sensitive materials, dry silver light-sensitive materials, color negatives, color reversal, color print light-sensitive materials, color and black-and-white instant light-sensitive materials, color and black-and-white heat-developable light-sensitive materials, and the like. .

The silver halide emulsion and other materials (additives and the like) and the photographic constituent layers (layer arrangement and the like) applied to the photographic element according to the present invention, and the photographic element applied for processing the photographic element As the processing method and the processing additive, the following patent gazettes, in particular, European Patent EP 355660A2 (Japanese Unexamined Patent Publication No.
No. 9544) Those described in the specification are preferably used.

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In a system for forming an image by diffusion transfer of a dye, a dye fixing element (image receiving material) is used together with a photosensitive element. The dye-fixing element may be coated separately on a support separate from the photosensitive element, or may be coated on the same support as the photosensitive element. As for the relationship between the photosensitive element and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of U.S. Pat. No. 4,500,626 can be applied to the present invention. The dye-fixing element can be provided with auxiliary layers such as a protective layer, a release layer, a neutralizing layer, a timing layer, and an anti-curl layer, if necessary. It is particularly useful to provide a protective layer. The swellable inorganic layered compound used in the present invention can be added to any of the above layers, but it is particularly effective to include it in the protective layer, the release layer and the anti-curl layer. In the case of processing by thermal development, since a very high pH value is not required, it is not necessary to provide a neutralizing layer and a timing layer on the photosensitive element and the dye fixing element.

In the constituent layers of the light-sensitive element and the dye-fixing element, a plasticizer, a slipping agent, or a high-boiling organic solvent can be used as an agent for improving the releasability between the light-sensitive material and the dye-fixing element. Specific examples include (2) of JP-A-62-253159.
5), pages 62-245253 and the like. Further, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used. Examples thereof include various modified silicone oils described in Technical Data P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X).
-22-3710) are effective. In addition, JP
Silicone oils described in JP-A-2155953 and JP-A-63-46449 are also effective.

An anti-fading agent may be used in the photosensitive element and the dye fixing element. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.
Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective. Examples of ultraviolet absorbers include benzotriazole-based compounds (such as U.S. Pat. No. 3,533,794), 4-thiazolidone-based compounds (such as U.S. Pat. No. 3,352,681),
Benzophenone compounds (JP-A-46-2784, etc.), and JP-A-54-48535, 62-13
Nos. 6641 and 61-88256. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective. Examples of metal complexes include U.S. Pat. Nos. 4,241,155, 4,245,018, columns 3 to 36, 4,254,195, columns 3 to 8, JP-A-62-174741, and JP-A-62-174741. 61-88256 (2
7) to (29), JP-A-63-199248,
-75568 and 1-74272. Examples of useful anti-fading agents are disclosed in
No. 215272, pages (125) to (137).

A fluorescent whitening agent may be used in the photosensitive element and the dye fixing element. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing element or to supply it from outside such as a photosensitive element. As an example, K.K. Veenkataraman
Hen "The Chemistry of Synthe
tic Dyes ", Volume V, Chapter 8, JP-A-61-143
No. 752 and the like. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given. The fluorescent whitening agent can be used in combination with an anti-fading agent.

As hardeners used in the constituent layers of the photosensitive element and the dye fixing element, US Pat. No. 4,678,739 No. 4
Column 1, JP-A-59-116655, JP-A-62-2452
No. 61, No. 61-18942 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-
Bis (vinylsulfonylacetamide) ethane, etc.), N
-Methylol-based hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157).

In the constituent layers of the light-sensitive element and the dye-fixing element, various surfactants can be used for the purpose of coating aid, improving releasability, improving slipperiness, preventing static charge, accelerating development and the like. Specific examples of the surfactant are described in JP-A-62-173463.
And No. 62-183457. The constituent layers of the light-sensitive element and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, and improving releasability. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8-17, and JP-A-61-20.
No. 944, No. 62-135826 or the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as fluorine oil or a solid fluorine compound resin such as ethylene tetrafluoride resin. No.

A matting agent can be used for the photosensitive element and the dye fixing element. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
JP-A-63-274944 such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads in addition to the compounds described on page 1-88256 (29).
And No. 63-274952. In addition, the constituent layers of the photosensitive element and the dye-fixing element may contain a heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-8.
No. 8256, pages (26) to (32).

An image formation accelerator can be used in the light-sensitive element and / or the dye-fixing element. It is particularly preferred to use an image formation accelerator when processing by heat development. The image formation accelerators promote the oxidation-reduction reaction between the silver salt oxidizing agent and the reducing agent, the formation of dyes from dye-donating compounds, the decomposition of dyes or the release of diffusible dyes, and the promotion of reactions such as It has the function of promoting the transfer of the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling point organic solvent (oil), a thermal solvent, a surfactant, silver or It is classified into compounds that interact with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. Details of these are described in U.S. Pat. No. 4,678,739, columns 38-40.

In a system in which thermal development and transfer of a dye are carried out simultaneously in the presence of a small amount of water, it is preferable to include a base and / or a base precursor in a dye-fixing element from the viewpoint of enhancing the storage stability of the photosensitive element. Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by an intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement, and the like. Specific examples thereof are described in U.S. Pat. No. 4,511,493 and JP-A-62-26503.
No. 8, etc. In addition to the above, European Patent Publication 2
No. 10,660, U.S. Pat. No. 4,740,445, a combination of a hardly soluble metal compound and a compound capable of forming a complex with a metal ion constituting the hardly soluble metal compound (referred to as a complex forming compound); JP-A-61-23
Compounds that generate a base by electrolysis described in No. 2451 can also be used as the base precursor. In particular, the former method is effective. The sparingly soluble metal compound and the complex forming compound are advantageously added separately to the light-sensitive element and the dye-fixing element.

In the present invention, various development stoppers can be used in the photosensitive element and / or the dye-fixing element for the purpose of always obtaining a constant image with respect to fluctuations in processing temperature and processing time during development. As used herein, the term "development terminator" refers to a compound that neutralizes a base or reacts with a base immediately after appropriate development to reduce the base concentration in the film and to stop development by interacting with a compound or silver and silver salt to suppress development. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For further details, see JP-A-62-25
No. 3159, pages (31) to (32).

In the present invention, examples of the support of the photosensitive element and the dye-fixing element include paper and synthetic polymers (films). Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or a film containing pigment such as titanium oxide in these films, and polypropylene. For example, a mixed paper made from synthetic resin pulp such as polyethylene, a synthetic resin pulp such as polyethylene, and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass and the like are used. These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In addition, JP-A-62-253159 (29) to (3)
1) The support described on page can be used. A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black, or another antistatic agent may be applied to the surface of these supports. The photosensitive element and / or the dye fixing element may have a form having a conductive heating element layer as a heating means for diffusion transfer by heat development or heating of the dye. In this case, as the transparent or opaque heating element, those described in JP-A-61-145544 can be used. Note that these conductive layers also function as antistatic layers.

The diffusion transfer photographic material of the present invention may be processed by a so-called color diffusion transfer method of forming an image using an alkaline processing composition at around normal temperature, or may be processed by heat development. As the color diffusion transfer method, various known methods can be adopted. Hereinafter, the case of processing by heat development will be described in detail. The heating temperature in the heat development step can be developed at about 50 ° C. to about 250 ° C.,
Especially about 80 ° C to about 180 ° C is useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step. In the latter case, the heating temperature in the transfer step can be transferred within the range from the temperature in the heat development step to room temperature, but is more preferably from 50 ° C. or higher to about 10 ° C. lower than the temperature in the heat development step.

Although the transfer of the dye is caused only by heat,
Solvents may be used to promote dye transfer. Also,
As described in detail in JP-A-59-218443 and JP-A-61-238056, a method in which development and transfer are carried out simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water) is also useful. is there. In this method, the heating temperature is preferably 50 ° C. or higher and the boiling point of the solvent or lower. For example, when the solvent is water, the heating temperature is preferably 50 ° C. or higher and 100 ° C. or lower. Examples of the solvent used for promoting development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases include Those described in the section of formation accelerator are used)
Can be mentioned. In addition, a low-boiling solvent or a mixed solution of a low-boiling solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex forming compound may be contained in the solvent.

These solvents can be used in such a manner that they are applied to the dye fixing element, the photosensitive element, or both.
The amount used may be as small as not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film (especially not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film). As a method for imparting a solvent to the photosensitive layer or the dye fixing layer, for example, JP-A-61-147244 (2)
6) There is a method described on page. Further, the solvent can be used by being incorporated in a photosensitive element or a dye-fixing element or both in advance in a form such as enclosing a solvent in a microcapsule.

In order to promote dye transfer, a system in which a hydrophilic heat solvent which is solid at normal temperature and dissolves at high temperature is incorporated in the photosensitive element or the dye fixing element can be adopted. The hydrophilic thermal solvent may be incorporated in either the photosensitive element or the dye fixing element, or may be incorporated in both. The layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer and a dye-fixing layer, but is preferably incorporated in the dye-fixing layer and / or an adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles. Further, in order to promote dye transfer, a high boiling organic solvent may be contained in the photosensitive element and / or the dye fixing material.

As a heating method in the developing and / or transferring step, a heating block or a plate is brought into contact, or a hot plate, a hot presser, a heating roller, a halogen lamp heater, an infrared or far infrared lamp heater, or the like is contacted. Or passing through a high temperature atmosphere. A pressure condition and a method of applying pressure when the photosensitive element and the dye fixing element are overlapped and brought into close contact with each other are described in JP-A-61-1.
No. 47244 (page 27) can be applied.

For processing the photographic element of the present invention, any of various heat developing apparatuses can be used. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181
No. 353, No. 60-18951, Shokai 62-259
An apparatus described in No. 44 or the like is preferably used.

Examples of a method of exposing and recording an image on a photosensitive element include a method of directly photographing a landscape or a person using a camera or the like, a method of exposing through a reversal film or a negative film using a printer or a enlarger, Using a copier exposure device or the like, a method of scanning and exposing an original image through a slit or the like, a method of exposing image information by emitting a light emitting diode, various lasers, and the like via an electric signal, a method of exposing image information to a CRT, a liquid crystal display, There is a method of outputting an image to an image display device such as an electroluminescence display or a plasma display and exposing the image directly or via an optical system.

As a light source for recording an image on a photosensitive element,
As described above, light sources described in U.S. Pat. No. 4,500,626, column 56, such as natural light, tungsten lamps, light emitting diodes, laser light sources, and CRT light sources, can be used. Also, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the nonlinear optical material is
It is a material that can express nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is given,
Lithium niobate, potassium dihydrogen phosphate (KDP),
Inorganic compounds typified by lithium iodate, BaB ₂ O _{4 and the} like, urea derivatives, nitroaniline derivatives such as 3
-Methyl-4-nitropyridine-N-oxide (PO
Nitropyridine-N-oxide derivatives such as M) and the compounds described in JP-A Nos. 61-53462 and 62-210432 are preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. The image information includes an image signal obtained from a video camera, an electronic still camera, a television signal represented by the Nippon Television Signal Standards (NTSC), and an image obtained by dividing an original image into a number of pixels such as a scanner. An image signal generated using a computer represented by a signal, CG, or CAD can be used.

[0099]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 On a polyethylene terephthalate film support having an undercoat, each layer having the following composition was applied in multiple layers.
A model multilayer light-sensitive material 100 for observing oil movement between layers was prepared. The number corresponding to each component indicates the coating amount in g / m ² , and the silver halide indicates the coating amount in terms of silver.

(Photosensitive Material 100) First Layer (Oil Emulsion Layer) Oil-A 2.00 Gelatin 2.00 Surfactant-A 0.05 Second Layer (Intermediate Layer: Diffusion Control Layer) Gelatin 1.00 Surfactant-A 0.02 Third Layer (emulsion layer; color-forming layer) Silver iodobromide emulsion Silver 2.50 Yellow colored magenta coupler A 1.00 Gelatin 1.50 Surfactant-A 0.05 Fourth layer (protective layer) Gelatin 0.70 Surfactant-A 0.10 H-1 0.22

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In the light-sensitive material 100, the second layer (intermediate layer) has a swellable synthetic mica somasif ME1 as shown in Table 6 below.
Light-sensitive materials 101 to 110 were produced in the same manner as in the light-sensitive material 100 except that 00 (manufactured by Corp Chemical Co.) was added.

The light-sensitive materials 100 to 100
110 was stored under an environment of 80 ° C. and 70% RH for 2 days, and then sufficiently covered with a fresh light-sensitive material by white light exposure, followed by standard development of color negative development (CN-16).

In the light-sensitive materials 100 to 110, if the oil does not coexist in the same layer, the yellow colored magenta coupler does not cause a color-forming reaction due to the development processing.
During storage, particularly when stored under high-temperature and high-humidity conditions, if the oil permeates through the intermediate layer and diffuses into the emulsion layer, the yellow colored magenta coupler undergoes a color-forming reaction due to development processing, and the color of the film is reduced. Changes from yellow to magenta. Thus, by measuring the green light density, it is possible to estimate the degree of interlayer movement of oil in the photosensitive material. Therefore, the photosensitive materials 100 to 110
Was measured for green light transmission density, and the results are shown in Table 6.
The photosensitive materials 100 to 107 are further shown in FIG.

[0106]

[Table 6]

As is clear from the results shown in Table 6 and FIG. 1, it is found that the interlayer movement of the oil can be completely prevented by containing at least 0.05 g / m ² or more of the inorganic layer compound in the intermediate layer.

Example 2 On a polyethylene terephthalate film support having an undercoat, each layer having the following composition was applied in multiple layers.
Photosensitive material 200 was produced. The number corresponding to each component is
The coating amount is expressed in g / m ² , and for silver halide, the coating amount is expressed in terms of silver.

(Photosensitive Material 200) First Layer (Emulsion Layer; Coloring Layer) Silver Iodobromide Emulsion Silver 2.50 Yellow Colored Magenta Coupler A 1.00 Oil-A 2.00 Gelatin 2.00 Surfactant-A 0.05 Second Layer (Intermediate Layer: Diffusion control layer) Gelatin 1.00 Surfactant-A 0.02 Third layer (protective layer) Gelatin 0.70 Surfactant-A 0.10 H-1 0.15

In the light-sensitive material 200, the second layer (intermediate layer) was formed as an intermediate layer of the light-sensitive material 105, which is one of the light-sensitive materials in which the suppression of interlayer diffusion of oil in the dry film in Example 1 was perfect. A light-sensitive material 201 was prepared in the same manner as the light-sensitive material 105 except that the above-mentioned was changed.

After the photosensitive materials 200 and 201 thus produced were sufficiently covered with white light exposure, the development time was 1 minute and 45 seconds in color negative development (CN-16).
The development progress was observed by changing to minutes 15 seconds, 2 minutes 45 seconds, 3 minutes 15 seconds, and 3 minutes 45 seconds. By observing the progress of development of the photosensitive materials 200 and 201, it can be determined whether or not the intermediate layer containing the inorganic layered compound suppresses the diffusion of a processing solution such as a developing agent during the development processing. Photosensitive material 20 processed as described above
The results of measuring the green light transmission densities of 0 and 201 are shown in Table 7.

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[Table 7]

From the results, it is clear that the intermediate layer containing the inorganic layered compound of the present invention slightly suppresses the development at the early stage of development during the development process, but does not suppress it at all around the standard development time of 3 minutes and 45 seconds, but rather accelerates it. You can see that.

Example 3 A photosensitive element having the structure shown in Table E below was prepared and used as a photosensitive element 301.

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[Table 8]

[0116]

[Table 9]

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[0119]

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[0121] In the light-sensitive element 301, instead of gelatin 0.79 g / m ² of the second layer, the gelatin and the 0.25 g / m ² and Somashif ME100 in the same manner as the light-sensitive element 301 except for using 0.12 g / m ² photosensitive elements 302 was produced.

A dye-fixing element was prepared by coating a support having the composition shown in Table G below and the physical properties shown in Table H below with the layer composition shown in Table F below. The optical brightener (1) in the second layer was introduced into the same layer by an oil protection method using the high-boiling organic solvent (1), ethyl acetate and sodium dodecylsulfonate in the same layer. . This was designated as dye fixing element R300.

[0123]

[Table 10]

[0124]

[Table 11]

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[Table 12]

Water-soluble polymer (1) Sumikagel L5-H
(Manufactured by Sumitomo Chemical Co., Ltd.) Water-soluble polymer (2) Copper-carrageenan (manufactured by Taito Corporation) Water-soluble polymer (3) Dextran (molecular weight 300,000) Fluorescent brightener (1) 2,5-bis (5 -t-benzoxazole
(2)) Thiophene High-boiling organic solvent (1) Empara 40 (manufactured by Ajinomoto Co., Inc.)

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The photosensitive elements 301 and 302 and the dye-fixing element 300 produced in this way are described in JP-A-2-84634.
The processing was performed using the image device described in the item No. That is, an original image (a test chart in which yellow, magenta, and cyan wedges having continuously changing density are recorded) was scanned and exposed through a slit, and this photosensitive material was immersed in water maintained at 40 ° C. for 5 seconds. Thereafter, it was squeezed with a roller, and then immediately overlaid so that the present dye-fixing element and the film surface were in contact with each other, and heated for 15 seconds using a heat roller prepared so that the water-absorbed film surface reached 83 ° C. Next, when the dye fixing element was peeled off, a color image corresponding to the original image was obtained on the dye fixing element.

In the image produced using the photosensitive element 301, magenta was mixed with the cyan image, and cyan was mixed with the magenta image. In particular, the color mixture of the former was large. However, in the photosensitive element 302 of the present invention, almost no color mixing occurred despite the small amount of gelatin applied.

Example 4 On an undercoated cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to produce a multilayer color photosensitive material 401. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² unit, and the silver halide coating amount indicates the coating amount.
However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Photosensitive Material 401) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 HBS-1 0.15 HBS-2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M silver 0.065 ExC-2 0.04 polyethyl acrylate latex 0.20 gelatin 1.04

Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.25 silver iodobromide emulsion B silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Speed Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E silver 0.15 silver iodobromide emulsion F silver 0.10 silver iodobromide emulsion G silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Speed Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver silver 0.030 Cpd-1 0.16 HBS-1 0.60 gelatin 0.60

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J silver 0.09 silver iodobromide emulsion K silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

Twelfth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

13th layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 Gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion M silver 0.10 H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70 In addition, storability, processability, pressure resistance, antifungal
To improve antibacterial, antistatic and coating properties
1 to W-3, B-4 to B-6, F-1 to F
-17 and iron salts, lead salts, gold salts, platinum salts, palladium salts, iridium salts, and rhodium salts.

[0145]

[Table 13]

In Table J, (1) Emulsions J to L were prepared according to the examples in JP-A-2-19938.
Reduction sensitization was performed using thiourea dioxide and thiosulfonic acid during the preparation of the particles. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope. (5) Emulsion L is a double-structured grain containing an internal high iodine core described in JP-A-60-143331.

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By changing the sixth layer (intermediate layer) in the photosensitive material 401 as described below, the photosensitive material 402
And 403 were produced.

Photosensitive material 402: Gelatin 0.25 polyethyl acrylate latex 0.15 Photosensitive material 403: Gelatin 0.25 Somasif ME100 0.12

The light-sensitive materials 401 to 401 thus prepared
After storing 403 for 1 week in an environment of 50 ° C. and 80% RH, the color negative development (CN-
16) Standard development was performed. The fog density (particularly the green-sensitive layer and the blue-sensitive layer) of each photosensitive material was measured. Further, using the photosensitive materials 401 to 405 after the above processing, color photographic paper manufactured by Fuji Film Co., Ltd. was exposed and developed. As a result, the photosensitive material 401 was a wet-preserved product, and the photosensitive material 402 was a mixture of magenta in a place where cyan was to be developed and cyan in a place where magenta was to be developed, in both the fresh sensitive material and the wet-preserved product. However, in the photosensitive element 403 of the present invention, the above-mentioned color mixing did not occur in both the fresh photographic material and the wet preserved product.

Example 5 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further applied. A multilayer color photographic paper 500 having the following layer configuration was produced.

(Preparation of Photosensitive Material 500) Various photographic constituent layers were applied on the above-mentioned reflective support to prepare a multilayer color photographic paper 500 having the following waste constitution. The coating solution was prepared as follows.

Preparation of Coating Solution for First Layer 122.0 g of yellow coupler (ExY), color image stabilizer (Cpd-1) 1
5.4 g, 7.5 g of color image stabilizer (Cpd-2), 1 of color image stabilizer (Cpd-3)
6.7 g was dissolved in 44 g of a solvent (Solv-1) and 180 ml of ethyl acetate, and this solution was emulsified and dispersed in 1000 g of a 10% aqueous gelatin solution containing 86 ml of 10% sodium dodecylbenzenesulfonate to prepare Emulsion A. On the other hand, silver chlorobromide emulsion A (cubic, large-sized emulsion A with an average grain size of 0.88 μm and 0.70 μm)
3: 7 mixture with μm small size emulsion A (silver molar ratio).
The variation coefficients of the particle size distribution are 0.08 and 0.10, respectively. In each size emulsion, 0.3 mol% of silver bromide was locally contained on a part of the surface of a silver chloride-based grain). In this emulsion, the blue-sensitive sensitizing dyes A, B and C shown below each contained 8.0 × 10
^-5 moles and 1.0 for small size emulsion A, respectively.
× 10 ^-4 mol is added. The emulsion was chemically ripened by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer so as to have the following composition. The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Cpd-11, Cpd-12, Cpd-
The total amount of each of 13 and Cpd-14 was 15.0 mg / m ² and 60.0 mg / m ² , respectively.
m ² , 5.0 mg / m ² and 10.0 mg / m ² .
The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

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(For a large-sized emulsion per mol of silver halide, sensitizing dyes A, B, and C were added in an amount of 1.4 × 10 4
^-4 mol or 1.7 × 10 for small size emulsion
^-4 mol was added. Green sensitive emulsion layer

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(The sensitizing dye D was used in an amount of 3.0 × 10 ^-4 mol for a large-size emulsion and 3.6 × 10 ^-4 mol for a small-size emulsion per mol of silver halide. Pigment
E per mole of silver halide of 4.0 × 10 ^-4 for large emulsions and 7.0 × 10 ^-4 for small emulsions
Moles of sensitizing dye F per mole of silver halide,
2.0 × 10 ^-4 mol was added to the large size emulsion, and 2.8 × 10 ^-4 mol was added to the small size emulsion. ) Red-sensitive emulsion layer

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(Per mol of silver halide, 5.0 × 10 ^-4 mol of sensitizing dyes G and H were used for the large-size emulsion, and 8.0 × 10 ^-4 mol was used for each small-size emulsion.
^-4 mol was added. ) Further, the following compounds are added in an amount of 2.0 mol per mol of silver halide.
× 10 ^-4 mol was added.

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Further, 1- (5-methylureidophenyl) -5 was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer.
-Mercaptotetrazole was added to 3.3 × 10 ^-4 mol, 1.0 × 10 ^-3 mol and 5.9 × 10 mol per mol of silver halide, respectively.
^-4 mol was added. Furthermore, the second layer, the fourth layer, the sixth layer and each 0.2 mg / m ² in the seventh ^{layer, 0.2mg / m 2, 0.6mg /} m 2, 0.1
mg / m ² was added. For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added per mole of silver halide.
1 × 10 ^-4 mol and 2 × 10 ^-4 mol were added.

The following compounds were added to the sixth layer as irradiation prevention water-soluble dyes.

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. [; Including (content 15 wt% Ti0 ₂₎ and a bluish dye (ultramarine) a white pigment in a polyethylene of the first layer side] Polyethylene laminated paper: support

First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A Silver 0.25 Gelatin 1.38 Yellow coupler (ExY) 0.60 Color image stabilizer (Cpd -1) 0.08 Color image stabilization Agent (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Color image stabilizer (Cpd-5) 0.02 Solvent (Solv-1) 0.22 Second layer (color mixture prevention layer) Gelatin 1.01 Color mixing inhibitor (Cpd-4) 0.13 Solvent (Solv-1) 0.07 Solvent (Solv-2) 0.20 Solvent (Solv-3) 0.15 Solvent (Solv-7) 12 Color image stabilizer (Cpd-7) 0.10 Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion 0.13 (cubic, large-size emulsion B having an average grain size of 0.55 µm)
1: 3 mixture (silver molar ratio) with 0.39 μm small size emulsion B. The coefficient of variation of the particle size distribution is 0.10 and 0.0, respectively.
8. In each size emulsion, 0.8 mol% of silver bromide was locally contained on a part of the surface of the grain having silver chloride as a substrate. 1.) Gelatin 1.45 Magenta Kabler (ExM) 0.13 Ultraviolet absorber (UV-A) 0.12 Color image stabilizer (Cpd-2) 0.01 Color image stabilizer (Cpd-5) 0.02 Color image Stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-7) 0.08 Color image stabilizer (Cpd-8) 0.03 Color image stabilizer (Cpd-9) 0.01 Solvent (Solv-) 4) 0.22 Solvent (Solv-5) 0.11 Solvent (Solv-8) 0.15 Fourth layer (color mixture prevention layer) Gelatin 0.73 Color mixture inhibitor (Cpd-4) 0.10 Solvent (Solv-5) 1) 0.05 solvent (Solv-2) 0.15 solvent (Solv-3) 0.12 solvent (Solv-7) 0.09 color image stabilizer (Cpd-7) 0.07 fifth layer (red sensitivity) Emulsion layer) Silver chlorobromide emulsion 0.19 silver (cubic, large size emulsion with average grain size 0.50μm,
1: 4 mixture (silver molar ratio) with a small size emulsion of 0.41 μm. The coefficient of variation of the particle size distribution is 0.09 and 0,0 respectively.
11. In each size emulsion, 0.8 mol% of silver bromide was locally contained on a part of the surface of the grain having silver chloride as a substrate. ) Gelatin 0.74 Cyan coupler (ExC) 0.24 Ultraviolet absorber (UV-B) 0.21 Color image stabilizer (Cpd-1) 0.20 Color image stabilizer (Cpd-6) 0.011 color image Stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Solvent (Solv-1) 0.01 Solvent (Solv-6) 0 .20 6th layer (UV absorbing layer) Gelatin 0.73 UV absorbing agent (UV-C) 0.34 Color image stabilizer (Cpd-7) 0.05 Solvent (Solv-9) 0.40 7th layer ( Protective layer) Gelatin 1.01 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Paraffin run 0.02 Surfactant (Cpd-11) 0.01

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[0181]

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[0185]

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[0188]

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The light-sensitive material 500 prepared as described above was replaced with gelatin 0.6 g / m ² instead of the fourth color mixture prevention layer.
The same light-sensitive material 501 as that of the light-sensitive material 500 was prepared in the same manner except that the intermediate layer was provided, and an undercoat layer having the same composition as the intermediate layer was further provided under the first layer. Further, the photosensitive material 50
The same photosensitive material 50 as the photosensitive material 500 except that an intermediate layer having the following composition is provided instead of the intermediate layer of the fourth layer, and an undercoat layer having the following composition is further provided below the first layer.
2 was created. Intermediate layer and undercoat layer composition Gelatin 0.40 Somasif ME100 0.20

The light-sensitive materials 500, 501 and 502 were subjected to BGR three-color separation exposure, and were continuously processed in the following processing steps using a paper processor.

Processing process Temperature Time Replenishment amount Tank capacity Color development 38.5 ° C 45 seconds 73ml 500ml Bleaching and fixing 30-35 ° C 45 seconds 60ml 500ml Rinse (1) 30-35 ° C 20 seconds 500ml Rinse (2) 30-35 ° C 20 seconds 500ml rinse (3) 30 to 35 ° C. 20 seconds 370M1 500ml drying 70 to 80 ° C. 60 seconds * replenishment rate is per photosensitive material 1 m ² (rinse was (1) → (3) 3 tank countercurrent system f) the The composition of the treatment liquid is as follows. Color developer Tank solution Replenisher Water 700ml 700ml Sodium triisopropylene (β) sulfonate 0.1g 0.1g Ethylenediaminetetraacetic acid 3.0g 3.0g 1,2-Dihydroxybenzene-4,6-disulfonic acid disodium salt 0.5g 0.5g Triethanolamine 12.0 g 12.0 g Potassium chloride 6.5 g Potassium bromide 0.03 g Potassium carbonate 27.0 g 27.0 g Optical brightener (WHITEX4, manufactured by Sumitomo Chemical) 1.0 g 3.0 g Sodium sulfite 0.1 g 0.1 g Disodium-N, N- Bis (sulfonatoethyl) hydroxylamine 10.0 g 13.0 g N-ethyl-N- (β-methanesulfonamidoethyl) 3-methyl-4-aminoaniline sulfate 5.0 g 11.5 g Add water 1000 ml 1000 ml pH (25 ° C ) 10.0 11.0

Bleach-fix solution (same as tank solution and replenisher) Water 600 ml Ammonium thiosulfate (700 g / liter) 100 ml Ammonium sulfite 40 g Iron (III) ammonium ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Nitric acid (67 %) Add 30g water and 1000ml pH (25 ℃) (with acetic acid and ammonia water) 4.8

Rinse solution (tank solution and replenisher are the same) Deionized water (calcium and magnesium are each 3 ppm or less)

The light-sensitive material 501 should be colored cyan and magenta, but magenta and cyan were mixed respectively. However, in the light-sensitive material 502 of the present invention, no color mixing occurred even though the color mixing inhibitor was not contained. Next, each of the processed samples of the photosensitive materials 500 to 502 was subjected to a light fastness test using a 200,000 lux xenon light weatherometer. 1 at reflection density 1.0
The residual dye rate after irradiation for 0 weeks was measured. Table 1 shows the results.
The results are shown in FIG. As is clear from the results, the photosensitive materials 500 and 501 of the comparative examples are significantly faded in magenta and yellow, whereas the photosensitive material 502 of the present invention is slightly faded, and thus has a remarkable prevention of fading. It turns out that there is an effect. On the other hand, among the three colors, the light fastness of the cyan layer located at the uppermost layer was almost the same in all three samples. It is said that the cyan dye formed by the above color development is faded by a photoreduction mechanism, and it has been found that the light fastness is rather deteriorated by blocking oxygen. However, as in the present invention, only the layer whose oxygen is to be blocked is sandwiched by the mica-containing layer, so that oxygen can be blocked for each layer. Thereby, the light fastness of magenta and yellow could be remarkably improved without deteriorating the light fastness of the cyan image.

[0195]

[Table 14]

Example 6 A dye fixing element 600 and a photosensitive element 600 were produced in the same manner as in the dye fixing element 300 and the photosensitive element 301 in Example 3. In the dye fixing element 600, 0.125 g / m ² and Somashif ME 100 0.125 g / m ² of a water-soluble polymer 0.25 g / m ² of water-soluble polymer protective layer of the fourth layer (1) (1)
A dye-fixing element 601 was produced in the same manner as described above.
The thus-prepared photosensitive element 600 and dye fixing elements 600 and 601 were processed using an image apparatus described in JP-A-2-84634 to prepare a solid black sample. This sample was stored in an environment of 0 ° C. and 25 ° C. alternately every day for one month, and the state of the surface was observed. Dye fixing element 600
Although powdery precipitates appeared on the surface of the dye fixing element 601 of the present invention, such precipitates were not detected at all.

Example 7 <Preparation of photosensitive silver halide emulsion> A method for preparing a blue photosensitive silver halide emulsion (1) is described below. Average molecular weight 12
0.96 g gelatin and 0.9 kg potassium bromide
g of distilled water containing 1 g in a reaction vessel.
The temperature was raised to ° C. Silver nitrate was added to this solution with vigorous stirring.
10.5 ml of an aqueous solution (A) containing 5 g and 10 ml of an aqueous solution (B) containing 0.35 g of potassium bromide were added over 150 seconds. Thirty seconds after the completion of the addition, 12 ml of a 10% aqueous solution of potassium bromide was added, and 30 seconds later, the temperature of the reaction solution was raised to 75 ° C. After adding 35.0 g of lime-processed gelatin together with 250 ml of distilled water, 39 ml of an aqueous solution (C) containing 10.0 g of silver nitrate and 30 ml of an aqueous solution (D) containing 6.7 g of potassium bromide were added while increasing the addition flow rate.
Minutes over 15 seconds. Then silver nitrate 96.7
g of an aqueous solution (E) containing potassium iodide and an aqueous solution (F) containing potassium iodide at a molar ratio of 7:93 to potassium bromide (potassium bromide concentration: 26%), while increasing the flow rate.
And the silver potential of the reaction solution is -20 with respect to the saturated calomel electrode.
It was added over 20 minutes to reach mV. Silver nitrate 2
97 ml of an aqueous solution (G) containing 4.1 g and a 21.9% aqueous solution of potassium bromide (H) were added over 3 minutes so that the silver potential of the reaction solution became 25 mV with respect to the saturated calomel electrode. After maintaining the temperature at 75 ° C. for 1 minute after the completion of the addition, the temperature of the reaction solution was lowered to 55 ° C. Then, 15 ml of 1N sodium hydroxide was added. Two minutes later, 100 ml of an aqueous solution (I) containing 5 g of silver nitrate and 200.5 ml of an aqueous solution (J) containing 4.7 g of potassium iodide were added over 5 minutes. After completion of the addition, 7.11 g of potassium bromide was added, and the mixture was kept at 55 ° C. for 1 minute. Then, 248 ml of an aqueous solution (K) containing 62 g of silver nitrate and 231 ml of an aqueous solution (L) containing 48.1 g of potassium bromide were added for 8 minutes. Was added. Thirty seconds later, an aqueous solution containing 0.03 g of sodium ethylthiosulfonate was added.
The temperature was lowered, and the emulsion particles were coagulated and settled using Kao's Demol to desalinate. Dispersion was performed by adding sodium benzenethiosulfonate, phenoxyethanol, water-soluble polymer (10), and lime-processed gelatin.

Chemical sensitization was performed at 60 ° C. After adding the sensitizing dye (12) as a gelatin dispersion before chemical sensitization, a mixed solution of potassium thiocyanate and chloroauric acid was added, and then sodium thiosulfate and a selenium sensitizer were added. The termination of sensitization was performed with a mercapto compound,
The amounts of the sensitizing dye, chemical sensitizer and mercapto compound were optimized for sensitivity and fog. The grains in the resulting emulsion were tabular grains accounting for more than 99% of the total projected area of all grains, had an average equivalent sphere diameter of 1.07 μm, and an average thickness of 0.3
The average equivalent circular diameter was 1.47 μm, and the average aspect ratio was 3.9.

[0199]

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[0200]

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The method for preparing the blue-sensitive silver halide emulsion (2) is described below. Gelatin having an average molecular weight of 12,000
Distilled water 119 containing 96 g and 0.9 g of potassium bromide
1 ml was placed in a reaction vessel and heated to 40 ° C. To this solution, 37.5 ml of an aqueous solution (A) containing 1.5 g of silver nitrate and 37.5 ml of an aqueous solution (B) containing 1.051 g of potassium bromide were added over 90 seconds with vigorous stirring. 30 seconds after completion of the addition, 12 ml of a 10% aqueous solution of potassium bromide
Was added, and after 30 seconds, the temperature of the reaction solution was raised to 75 ° C. 35.0 g of lime-processed gelatin was added to 250 m of distilled water.
Then, 116 ml of an aqueous solution (C) containing 29.0 g of silver nitrate and 91 ml of an aqueous solution (D) containing 20 g of potassium bromide were added for 11 minutes 35 while accelerating the addition flow rate.
Added over seconds. Next, 302 ml of an aqueous solution (E) containing 96.7 g of silver nitrate and an aqueous solution (F) containing potassium iodide at a molar ratio of 3.3: 96.7 to potassium bromide (potassium bromide concentration: 26%) were added. While the silver potential of the reaction solution is 2 with respect to the saturated calomel electrode.
It was added over 20 minutes to reach mV. Silver nitrate 2
97 ml of an aqueous solution (G) containing 4.1 g and a 21.9% aqueous solution of potassium bromide (H) were added over 3 minutes so that the silver potential of the reaction solution became 0 mV with respect to the saturated calomel electrode. After maintaining at 75 ° C. for 1 minute after completion of the addition,
The temperature of the reaction was lowered to 55 ° C. Then, 15 ml of 1N sodium hydroxide was added. Two minutes later, 153 ml of an aqueous solution (I) containing 10.4 g of silver nitrate and 414.5 ml of an aqueous solution (J) containing 9.35 g of potassium iodide were added over 5 minutes. After the addition was completed, 7.11 g of potassium bromide was added, and the mixture was kept at 55 ° C. for 1 minute. Then, 228 ml of an aqueous solution (K) containing 57.1 g of silver nitrate and 201 ml of an aqueous solution (L) containing 43.9 g of potassium bromide were added.
Added over minutes. Thirty seconds later, an aqueous solution containing 0.04 g of sodium ethylthiosulfonate was added. The temperature was lowered, and desalting and dispersion were carried out in the same manner as in the blue-sensitive silver halide emulsion (1). Chemical sensitization was performed in the same manner except that the blue-sensitive silver halide emulsion (1) and the selenium sensitizer were not added. The sensitizing dye and the mercapto compound whose chemical sensitization was stopped were substantially proportional to the surface area of the emulsion grains. The grains in the obtained emulsion were tabular grains accounting for more than 99% of the total projected area of all grains, and the average equivalent spherical diameter was 0.6%.
6 μm, average thickness 0.17 μm, average equivalent circular diameter 1.
The average aspect ratio was 6.3 μm.

The method for preparing the blue-sensitive silver halide emulsion (3) is described below. 1345 ml of distilled water containing 17.8 g of lime-processed gelatin, 6.2 g of potassium bromide and 0.46 g of potassium iodide was placed in a reaction vessel, and the temperature was raised to 45 ° C. To this solution, 70 ml (A) of an aqueous solution containing 11.8 g of silver nitrate and 70 ml (B) of an aqueous solution containing 3.8 g of potassium bromide were added over 45 seconds with vigorous stirring. After maintaining at 45 ° C. for 4 minutes, the temperature of the reaction solution was raised to 63 ° C. After adding 24 g of lime-processed gelatin together with 185 ml of distilled water, 208 ml of an aqueous solution containing 73 g of silver nitrate (C)
And a 24.8% aqueous solution of potassium bromide (D) were added over a period of 13 minutes while accelerating the addition flow rate so that the silver potential of the reaction solution became 0 mV with respect to the saturated calomel electrode. After maintaining at 63 ° C. for 2 minutes after completion of the addition, the temperature of the reaction solution was lowered to 45 ° C. Then, 15 ml of 1N sodium hydroxide was added. Two minutes later, 8.4 silver nitrate
g of an aqueous solution containing 60 g (E) and 8.3 g of potassium iodide
And 461 ml of an aqueous solution containing (F) were added over 5 minutes. Further, an aqueous solution 496 containing 148.8 g of silver nitrate
ml (G) and a 25% aqueous solution of potassium bromide (H) were added over 47 minutes so that the silver potential of the reaction solution became 90 mV with respect to the saturated calomel electrode. 30 seconds after completion of the addition, an aqueous solution containing 2 g of potassium bromide and 0.06 g of sodium ethylthiosulfonate was added. The temperature was lowered, and in the same manner as in the blue-sensitive silver halide emulsion (2),
Desalting, dispersion and chemical sensitization were performed. The grains in the obtained emulsion had an average grain size of 0.44 expressed by a diameter equivalent to a sphere.
μm, average thickness 0.2μm, average equivalent circular diameter 0.53μ
m, and hexagonal tabular grains having an average aspect ratio of 2.6.

The method for preparing the green photosensitive silver halide emulsion (4) is described below. Gelatin having an average molecular weight of 12,000
Distilled water 119 containing 96 g and 0.9 g of potassium bromide
1 ml was placed in a reaction vessel and heated to 40 ° C. To this solution, 17.5 ml of an aqueous solution (A) containing 0.7 g of silver nitrate and 17.5 ml of an aqueous solution (B) containing 1.051 g of potassium bromide were added over 120 seconds with vigorous stirring.
30 seconds after the completion of the addition, 12 m
After 30 seconds, the temperature of the reaction solution was raised to 75 ° C. 35.0 g of lime-processed gelatin is added to 250 parts of distilled water.
Then, 56 ml of an aqueous solution (C) containing 19.0 g of silver nitrate and 461 ml of an aqueous solution (D) containing 10 g of potassium bromide were added for 7 minutes 35 while increasing the addition flow rate.
Added over seconds. Next, 302 ml of an aqueous solution (E) containing 96.7 g of silver nitrate and an aqueous solution (F) (potassium bromide concentration: 26%) containing potassium iodide at a molar ratio of 3.3: 96.7 to potassium bromide were added. While the silver potential of the reaction solution is 0 with respect to the saturated calomel electrode.
It was added over 20 minutes to reach mV. Silver nitrate 2
97 ml of an aqueous solution (G) containing 4.1 g and a 21.9% aqueous solution of potassium bromide (H) were added over 3 minutes so that the silver potential of the reaction solution became 0 mV with respect to the saturated calomel electrode. After maintaining at 75 ° C. for 1 minute after completion of the addition,
The temperature of the reaction was lowered to 55 ° C. Next, 122 ml of an aqueous solution (I) containing 8.3 g of silver nitrate and 332 ml of an aqueous solution (J) containing 7.48 g of potassium iodide were added over 5 minutes. After completion of addition, 7.11 g of potassium bromide
And kept at 55 ° C. for 1 minute.
228 ml of an aqueous solution (K) containing 8 g and potassium bromide 4
201 ml of an aqueous solution (L) containing 8.3 g was added over 8 minutes. The temperature was lowered, and desalting and dispersion were carried out in the same manner as in the blue-sensitive silver halide emulsion (1). Chemical sensitization is also performed by using a sensitizing dye (13) instead of the sensitizing dye (12),
Except that a gelatin dispersion of the mixture of (14) and (15) was added, the same procedure was carried out as for the blue-sensitive silver halide emulsion (1). The sensitizing dyes (13), (14), (1)
The mixing ratio of 5) is 12: 2: 1 (molar ratio). The grains in the emulsion thus obtained were tabular grains accounting for more than 99% of the total projected area of all grains, and had an average equivalent spherical diameter of 0.85.
μm, average thickness 0.26 μm, average equivalent circular diameter 1.2
The average aspect ratio was 5 μm and the average aspect ratio was 4.8.

[0204]

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The method for preparing the green photosensitive silver halide emulsion (5) is described below. Except that sodium hydroxide and sodium ethylthiosulfonate are not added during grain formation, grains are formed, desalted and dispersed in the same manner as in the blue-sensitive silver halide emulsion. An emulsion was prepared in the same manner as in the silver halide emulsion (4). The grains in the resulting emulsion were tabular grains having a total projected area of 99% of all grains.
% And the average equivalent spherical diameter is 0.66 μm
With an average thickness of 0.17 μm and an average equivalent circular diameter of 1.05 μm
m, and the average aspect ratio was 6.3.

The preparation method of the green photosensitive silver halide emulsion (6) is described below. Grain formation, desalting and dispersion were carried out in the same manner as for the blue-sensitive silver halide emulsion (3) except that sodium ethylthiosulfonate was changed to 4 mg without adding sodium hydroxide during grain formation. An emulsion was prepared in the same manner as in the green light-sensitive silver halide emulsion (4) except that no selenium sensitizer was added in the chemical sensitization.
The grains in the obtained emulsion were hexagonal tabular grains having an average grain size of 0.44 μm, an average thickness of 0.2 μm, an average equivalent circular diameter of 0.53 μm, and an average aspect ratio of 2.6, expressed in terms of sphere equivalent diameter. .

The method for preparing the red-sensitive silver halide emulsion (7) is described below. The sensitizing dye at the time of chemical sensitization is replaced with a sensitizing dye (1
6) Gelatin dispersion and sensitizing dyes (17) and (18)
An emulsion was prepared in the same manner as in the green light-sensitive silver halide emulsion (4), except that the mixture was added as a gelatin dispersion. The sensitizing dyes (16), (17) and (18)
Is 40: 2: 58 (molar ratio). The resulting grains had tabular grains of 99% of the total projected area of all grains.
Occupies a ratio exceeding 0.85 μm in average sphere equivalent diameter
With an average thickness of 0.26 μm and an average equivalent circular diameter of 1.25 μm
m, and the average aspect ratio was 4.8.

[0208]

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The preparation method of the red-sensitive silver halide emulsion (8) is shown below. The sensitizing dye at the time of chemical sensitization is replaced with a sensitizing dye (1
6) Gelatin dispersion and sensitizing dyes (17) and (18)
An emulsion was prepared in the same manner as in the green light-sensitive silver halide emulsion (5) except that the mixture was added as a gelatin dispersion. The sensitizing dyes (16), (17) and (18)
Is 40: 2: 58 (molar ratio). The grains in the obtained emulsion were tabular grains accounting for more than 99% of the total projected area of all grains, and had an average equivalent spherical diameter of 0.66.
μm, average thickness 0.17 μm, average equivalent circular diameter 1.0
5 μm and an average aspect ratio of 6.3.

The preparation method of the red-sensitive silver halide emulsion (9) is shown below. The sensitizing dye at the time of chemical sensitization is replaced with a sensitizing dye (1
An emulsion was prepared in the same manner as the green light-sensitive silver halide emulsion (6), except that the gelatin dispersion of 6) and the gelatin dispersion of a mixture of the sensitizing dyes (17) and (18) were added. The grains in the obtained emulsion were hexagonal tabular grains having an average grain size of 0.44 μm, an average thickness of 0.2 μm, an average equivalent circular diameter of 0.53 μm, and an average aspect ratio of 2.6, expressed in terms of sphere equivalent diameter. .

<Preparation of Zinc Hydroxide Dispersion> 31 g of zinc hydroxide powder having a primary particle size of 0.2 μm, 1.6 g of carboxymethyl cellulose and 0.4 g of sodium polyacrylate as a dispersant, lime-treated ossein 8.5 g of gelatin and 158.5 ml of water were mixed, and this mixture was dispersed in a mill using glass beads for 1 hour. After dispersion
The glass beads were separated by filtration to obtain 188 g of a dispersion of zinc hydroxide.

<Preparation of Emulsified Dispersion of Color Developing Agent and Coupler> Table 15 below shows the cyan emulsion used in the second layer, the magenta emulsion used in the sixth layer, and the tenth emulsion in Table 3 below.
The composition of the yellow emulsion used in the layer is shown.

[0213]

[Table 15]

[0214]

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[0215]

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The oil phase component and the water phase component having the compositions shown in Table 15 are each dissolved to form a uniform solution at 60 ° C. The oil phase component and the aqueous phase component were combined and dispersed in a 1-liter stainless steel container at 10,000 rpm for 20 minutes using a dissolver with a 5 cm diameter disperser. To this, warm water of the amount shown in Table 1 was added as post-hydration, and 2000 rpm
For 10 minutes. In this way, cyan (second
, Magenta (sixth layer) and yellow (tenth layer) to prepare an emulsified dispersion of couplers of three colors. The emulsions of the other layers were prepared in the same manner.

<Preparation of Dye Composition for Yellow Filter and Antihalation Layer> The dye composition was prepared and added as an emulsified dispersion as follows. The leuco dye, the developer and, if necessary, the high-boiling organic solvent are weighed, ethyl acetate is added thereto, and the mixture is heated and dissolved at about 60 ° C. to form a uniform solution. For 100 cc of this solution, 1 surfactant (7) is added. 0.0 g,
190 cc of a 6.6% aqueous solution of lime-processed gelatin heated to about 60 ° C. is added, and the mixture is homogenized with a homogenizer for 10,000 minutes.
The mixture was dispersed at rpm to produce two kinds of dye dispersions shown in Table 16 below.

[0218]

[Table 16]

[0219]

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<Preparation of Support> A support used in the present invention was prepared by the following method. Polyethylene-
100 weight units of 2,6-naphthalate (PEN) polymer and Tinuvin P. 326 (manufactured by Ciba-Geigy) was dried, melted at 300 ° C., extruded from a T-die, stretched 3.3 times at 140 ° C., and then stretched at 130 ° C. to 3.times. The film is stretched three times in the transverse direction, and further heat-set at 250 ° C. for 6 seconds to form a P having a thickness of 92 μm.
An EN film was obtained. The PEN film has a blue dye, a magenta dye, and a yellow dye (Publication Technical Report: I-1, I-4, I-6, described in Official Technique No. 94-6023).
I-24, I-26, I-27, II-5) were converted to yellow density 0.01, magenta density 0.08, and cyan density 0.0.
9 was added. Further, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 113 ° C. and 30 hours, thereby providing a support that was not easily curled.

<Coating of Undercoat Layer> The support was subjected to a corona discharge treatment, a UV irradiation treatment, and a glow discharge treatment on both surfaces, and then gelatin (0.1 g / m 2) was applied to each surface.
² ), sodium α-sulfodi-2-ethylhexyl succinate (0.01 g / m ² ), salicylic acid (0.02
5 g / m ² ), PQ-1 (0.005 g / m ² ), PQ
-2 (0.006 g / m ² ) was applied (10 cc / m ² , using a bar coater) to provide an undercoat layer on the high temperature side during stretching. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were set at 115 ° C.).

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<Coating of Back Layer> 1) Coating of antistatic layer Tin oxide-antimony oxide composite having an average particle size of 0.005 μm
Dispersion of fine particle powder with a specific resistance of 5Ω · cm (secondary
Coagulated particle diameter: about 0.08 μm; 0.027 g / m ^Two), Ze
Latin (0.03 g / m^Two), (CH_Two= CHSO_TwoC
H_TwoCH_TwoNHCO)_TwoCH_Two(0.02 g / m^Two),
Poly (degree of polymerization 10) oxyethylene-p-nonylpheno
(0.005g / m^Two), PQ-3 (0.008 g)
/ M^Two) And resorcinol were applied.

2) Coating of Magnetic Recording Layer Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g) , Major axis 0.1
4 μm, short axis 0.03 μm, saturation magnetization 89 emu / g,
Fe ^{+ 2} / Fe ^{+ 3} = 6/94, the surface of which has been treated with silicon oxide aluminum oxide at 2% by weight of iron oxide) 0.06 g / m ² of diacetyl cellulose 1.15 g / m ² (of iron oxide Dispersion was carried out using an open kneader and a sand mill), PQ-4 (0.075 g / m ² ) and PQ-5 (0.00
4 g / m ² ) was applied with a bar coater using acetone, methyl ethyl ketone, cyclohexanone, and dibutyl phthalate as solvents to obtain a 1.2 μm-thick magnetic recording layer. C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (50 g
/ M ² ), silica particles as a matting agent (average particle size 1.0 μm)
m) and abrasive aluminum oxide (Reynolds Metal Reynolds)
Metal ERC-DBM; average particle size 0.44 μm)
It was added in an amount of 5 mg / m ² and 15 mg / m ^2, respectively. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.). Saturation magnetization moment of the X- light (blue filter) The increase of the color density of about 0.1 D ^B of the magnetic recording layer in, also the magnetic recording layer is 4.2 emu / g, coercive force was 7.3 × 10 ⁴ A / m, and the squareness ratio was 65%.

3) Coating of sliding layer Hydroxyethyl cellulose (25 mg / m ² ), PQ-
6 (7.5 mg / m ² ), PQ-7 (1.5 mg / m ² ),
Polydimethylsiloxane (1.5 mg / m ² ) was applied. This mixture was melted at 105 ° C. in xylene / propylene glycol monomethyl ether (1/1), and propylene monomethyl ether (10-fold amount) was added at room temperature.
And then dispersed in acetone (average particle size: 0.01 μm) and then added. 115 for drying
For 6 minutes (115 ° C. for all rollers and conveyors in the drying zone). The sliding layer has a dynamic friction coefficient of 0.10 (5 m
Stainless steel ball of mφ, load 100g, speed 6cm
/ Min), a coefficient of static friction of 0.09 (clip method), and a coefficient of kinetic friction between an emulsion surface and a sliding layer described later, which were 0.18, were also excellent characteristics.

Using the above materials and supports, the following Table 1
All of the layers 7 to 21 were simultaneously coated in a multi-layer manner to prepare a multi-layered photosensitive material 701 as a color negative film.

[0227]

[Table 17]

[0228]

[Table 18]

[0229]

[Table 19]

[0230]

[Table 20]

[0231]

[Table 21]

[0232]

Embedded image

The total amount of potassium ions contained in the produced light-sensitive material was 2.2 × 10
^-4 .

Further, a processing member R-1 having the contents shown in Tables 22 and 23 below was prepared.

[0235]

[Table 22]

[0236]

[Table 23]

[0237]

Embedded image

The light-sensitive material 701 manufactured as described above
In contrast, the light-sensitive material 702 was prepared by replacing 500 mg / m ² of the lime-processed gelatin in the first, fifth and ninth layers with 100 mg / m ² of the swellable synthetic mica of the present invention (Somasif ME100: manufactured by Corp Chemical). Produced. As a comparative sample, a light-sensitive material 703 to which the compound of the present invention was not added was also prepared.

The following evaluation was performed using the obtained photosensitive material. (Evaluation of curl) Photosensitive materials 701 to 703 were heated at 25 ° C 10
It was stored at% RH for 5 hours, and relative evaluation of curl was performed. Curling was observed in the photosensitive material 701, and after storage under the above-mentioned dry conditions, the photosensitive material 701 was rounded into a cylindrical shape. Photosensitive material 703
Curl was observed on the coating surface side. The curling of the photosensitive material 702 was hardly observed. (Evaluation of color mixing in storage under high humidity)
703 was stored at 50 ° C. and 80% RH for 1 week, and then subjected to imagewise exposure with green light and red light.
² (corresponding to 45% of the amount of water at the time of maximum swelling of the light-sensitive material), and then overlapped with the processing member R-1 and heated from the back surface of the light-sensitive material for 18 seconds with a heat drum at 83 ° C. Thereafter, the photosensitive material was peeled off from the processing member R-1. Photosensitive material 70
In No. 1, color mixing was observed. The photosensitive material 703 showed a very large color mixture. No color mixing was observed in the photosensitive material 702 of the present invention.

Example 8 0.9 g / m ² of gelatin for the surface protective layer of Coating Sample 4 of Example 1 of JP-A-9-80666 was replaced with 0.5 g / m ² of gelatin and 0.25 g / m ² of Somasif ME100. The coating sample A was prepared in the same manner except that the sample was changed to. Apply sample A 5
After storing for 1 week in an environment of 0 ° C. and 80% RH, exposure and development of Example 1 of the same issue were performed together with a fresh coating sample A. As a result, even if it was a wet preservation product, no decrease in sensitivity or the like due to preservation was observed.

Example 9 In the samples 401 to 403 of Example 4, the cellulose triacetate film as the support was replaced with US Pat.
No. 682, a support used for the sample 104 in Example 1, that is, an undercoat layer and a back layer were provided by the method described in column 21, line 54 to column 23, line 29 of the same specification,
Samples 401-401 except using a heat treated PEN support
Samples 901 to 903 were manufactured in the same manner as 403. When photographic properties were evaluated in the same manner as in Example 4, similar results were obtained.

Example 10 A sample 1001 was prepared by changing the eighth layer (intermediate layer) of the sample 201 of Example 2 starting from the paragraph number 0090 of JP-A-9-5912 as follows. Gelatin 0.30 g Somasif ME100 0.15 g Sample 1001 was stored for 1 week in an environment of 50 ° C. and 80% RH, and then subjected to a color reversal process described in paragraphs 0080 and thereafter of JP-A-9-5912 together with a fresh photosensitive material. However, almost no color mixing was observed in both the fresh photographic material and the wet-processed preserved product.

[0243]

According to the present invention, at least one layer (particularly, a protective layer, an intermediate layer, etc.) constituting a photographic element contains a swellable inorganic layered compound, thereby obtaining various photographic useful compounds, or oxygen, carbon dioxide in the atmosphere, It is possible to prevent or control the diffusion of gases such as sulfur oxides and nitrogen oxides which adversely affect photographic performance in the layer. Specifically, the following excellent effects are exhibited. (1) When used as an intermediate layer of a color material layer, a remarkable effect is exhibited in preventing interlayer movement during storage of a color material and the like added to the upper and lower layers, that is, in preventing color mixing. (2) Color mixing due to diffusion of an oxidized color developing agent to an adjacent layer is prevented by using the intermediate layer of each emulsion layer of a color light-sensitive material. (3) The layer containing the swellable inorganic layered compound can cut off oxygen by layer. By sandwiching only layers containing compounds that are susceptible to (photo) oxidation, it is possible to improve the storability of the photographic element without affecting compounds that are degraded by oxygen barrier (eg, color paper Has a remarkable effect on improving the light fastness). (4) Under high humidity, deterioration of additives due to diffusion (moisture absorption) of water into a coating film of a photographic element is suppressed, and storage stability is improved. (5) While the photographic element is being stored, the compound in the coated film is prevented from diffusing to the film surface and causing powder dust to break down. (6) A trace amount of nitrogen oxides or sulfur oxides in the air diffuses into the film and reacts with the compounds in the photographic element to color,
Prevents problems such as discoloration and deterioration.

[Brief description of the drawings]

FIG. 1 is a graph showing the results of Example 1, wherein the vertical axis represents the optical density and the horizontal axis represents the amount of the compound of the present invention added to the photosensitive material.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI G03C 8/52 G03C 8/52

Claims (10)

[Claims] 1. A silver halide photographic light-sensitive material comprising a layer containing a swellable inorganic layered compound. 2. A silver halide photosensitive material having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive layer on a support, wherein at least one of the non-photosensitive layers swells. 2. The silver halide photographic light-sensitive material according to claim 1, comprising a hydrophilic inorganic layered compound. 3. A photographic element comprising a light-sensitive element having at least one light-sensitive silver halide emulsion layer on a support, and a receiving element for receiving a silver image or a dye image formed in the light-sensitive element, A photographic element characterized in that at least one layer of the photographic element contains a swellable inorganic layered compound. 4. The photographic element according to claim 3, wherein the non-photosensitive layer of the photographic element contains a swellable inorganic layered compound. 5. A photosensitive element having at least one photosensitive silver halide emulsion layer on a support, a function of bringing the photosensitive element into close contact with the photosensitive element during processing and supplying the photosensitive element with components necessary for development. A photographic element comprising a processing element having a function of removing components unnecessary by development or a function of both, wherein at least one layer of the photographic element contains the swellable inorganic layered compound. . 6. The photographic element according to claim 5, wherein the non-photosensitive layer of the photographic element contains a swellable inorganic layered compound. 7. The layer containing the swellable inorganic layered compound, wherein the weight ratio of the swellable inorganic layered compound to the binder is 1/10 to 1: 1.
The silver halide light-sensitive material or photographic element according to any one of claims 1 to 6, wherein the ratio is 0/1. 8. The silver halide light-sensitive material or photographic element according to claim 1, wherein the swellable inorganic layered compound has an aspect ratio of 100 or more. 9. The silver halide light-sensitive material or photographic element according to claim 1, wherein said swellable inorganic layered compound is a swellable synthetic mica. 10. The silver halide light-sensitive material or photographic element according to claim 1, wherein said swellable inorganic layer compound is bentonite.