JPH06214340A - Production of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the photosensitive material having a magnetic recording layer which is excellent in optical transparency, is high in its magnetic recording performance (S/N) and good graininess by applying a coating liquid dispersed with a magnetic materials on a base, then drying the coating while passing the base in a magnetic field for orientation. CONSTITUTION:The coating liquid dispersed with the magnetic material is applied on the base and thereafter, the coating is dried while the base is passed in the magnetic field for orientation which arrays the magnetic material in the coating liquid to a specified direction. The timing to start the passage in the magnetic field is preferably at the point where the residual solvent of the magnetic recording layer is <=70% and >=5%. The passage preferably ends after the residual solvent decreases to <=5%. The content of the magnetic material per 1m<2> of the magnetic recording layer is preferably 0.01 to 1g. The magnetic material to be used therein includes fine powder of a ferromagnetic gamma-iron oxide, fine powder of a Co-contg. ferromagnetic gamma-iron oxide, fine powder of ferromagnetic magnetite, fine powder of Co-contg. ferromagnetic magnetite, fine powder of ferromagnetic chromium dioxide, ferromagnetic alloy powder and barium ferrite powder.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a silver halide photographic light-sensitive material having a transparent magnetic recording layer.

[0002]

2. Description of the Related Art In recent years, many studies have been conducted to provide a transparent magnetic recording layer on a silver halide photographic light-sensitive material. For example, by appropriately selecting the amount and size of the magnetic material contained in the magnetic recording layer, a magnetic recording layer having the transparency necessary for the photosensitive material at the time of photographing is provided on the back surface of the photosensitive material having a transparent support. That is, U.S. Pat. Nos. 3,782,947, 42.
No. 79945, No. 4302523, etc. A signal input method to the magnetic recording layer is disclosed in World Publication Nos. 90-4205 and 90-04212.

Starting from these patents, research has been conducted to improve the magnetic recording performance (S / N ratio) of the magnetic recording layer to be obtained, and the particle size of the magnetic substance can be changed by the method of dispersing the magnetic substance. It has been found that a transparent photosensitive material having a high S / N ratio can be obtained by adjusting the size to a desired size. (Patent application 3-
(Described in No. 247807)

However, recently, the transparency that can be realized by the above-mentioned patents is limited, and when it is used for applications such as a reversal film (positive film), the color density due to the magnetic substance of the magnetic recording layer is large. It turned out to be a problem. In addition, since the graininess of the emulsion used for the light-sensitive material has been improved in recent years, the graininess obtained by the method of the aforementioned patent has a new problem that the graininess of the emulsion improved by the magnetic recording layer is deteriorated. Is happening to. In order to obtain a magnetic recording layer that is optically transparent, maintains a high S / N ratio, and has good graininess, a manufacturing method in which the orientation of the magnetic material is increased is required.

[0005]

The object of the present invention is to provide excellent optical transparency and its magnetic recording performance (S / N ratio).
And a method for producing a light-sensitive material having a magnetic recording layer with high graininess.

[0006]

These objects of the present invention are directed to a silver halide having a silver halide emulsion layer on at least one side of a support and at least one optically transparent magnetic recording layer. In the method of manufacturing a photographic light-sensitive material,
This is achieved by a method for producing a photographic light-sensitive material in which a coating solution having a magnetic material dispersed therein is coated on a support, and then the magnetic material in the coating solution is dried while passing through an orientation magnetic field arranged in a certain direction.

The present invention will be described in detail below. First, the orientation magnetic field for orienting the magnetic substance will be described. As a method of generating an orientation magnetic field used in the present invention, either a method using a permanent magnet or a method using a solenoid coil can be used. When using permanent magnets, the magnets to be placed may be only from one side of the support coated with the magnetic substance dispersion liquid, or permanent magnets of the same pole may be combined and placed facing each other, and used from both sides of the support. May be. The latter is preferable from the viewpoint of orientation efficiency. Further, the magnet is not limited to one place on the magnetic material coated support being dried and may be installed at several places or more.

The strength of the permanent magnet used is preferably 2000 Oe or more, and particularly preferably 3000 Oe or more. In addition, when using a solenoid magnet, unlike a permanent magnet, it is easy to create a magnetic field with a long distance.
If it is 0 Oe or more, the effect appears. The magnetic field used in the present invention is preferably installed in a zone for drying the applied magnetic substance dispersion liquid. After applying the magnetic substance liquid, the degree of orientation of the magnetic substance can be increased even if a magnetic field is started without drying at all. However, in this case, agglomeration occurs simultaneously with (or more than) the orientation of the magnetic material, and the resulting granularity of the support tends to deteriorate. Only the orientation does not cause the magnetic substance to aggregate.
For UP, it is important to pass through the magnetic field during drying. As the timing to start passing to the magnetic field,
It is desirable that the residual solvent in the magnetic recording layer be 70% or less to 5% or more. There is no particular limit to the point where the magnetic field is completed,
It is desirable that the residual solvent be less than 5% before it is completely passed, and it may be completely dried in a magnetic field. The definition of the residual solvent in the present invention is calculated on the assumption that the total amount of the solvent in the coating solution applied per unit area at the moment of application to the support is 100%.

Next, the transparent magnetic recording layer used in the present invention will be described. The magnetic material used in the transparent magnetic recording layer of the present invention includes ferromagnetic γ-iron oxide fine powder, Co-containing ferromagnetic γ-iron oxide fine powder, ferromagnetic magnetite fine powder, and Co-containing ferromagnetic magnetite fine powder. , Ferromagnetic chromium dioxide fine powder, ferromagnetic alloy powder, barium ferrite powder and the like. As an example of the ferromagnetic alloy powder, the metal content is 75 wt% or more, and 80 wt% or more of the metal content is at least one ferromagnetic metal or alloy (Fe, Co, Ni, Fe-Co, Fe-Ni, Co). -Ni, Co-
Fe-Ni, etc., and other components (Al, Si, S, Sc, Ti, V, Cr, Mn, Cu, Zn, Y, Mo, Rh, Pd, Ag, Sn, Sb,
B, Ba, Ta, W, Re, Au, Hg, Pb, P, La, Ce, Pr, Nd, Te, Bi, etc.) can be included. Further, the ferromagnetic metal component may contain a small amount of water, hydroxide or oxide. The manufacturing method of these magnetic materials is known, and the magnetic materials used in the present invention can also be manufactured according to known methods. The shape and size of the magnetic material can be widely used without particular limitation, but preferable shapes for the transparent magnetic recording layer are needle-like, rice-like, spherical, cubic, and
Since they are plate-shaped and the effect is remarkable depending on the magnetic field orientation, needle-shaped and rice-shaped grains are particularly preferable. The crystallite size is not particularly limited specific surface area, preferably at least 20 m ² / g in SBET, more 30 m ² / g is particularly preferred in view of graininess. The pH and surface treatment of the magnetic material can be used without particular limitation. In the case of ferromagnetic iron oxide fine powder (which may be surface-treated with a substance containing an element such as titanium, silicon, or aluminum), it should be used without any particular limitation on the ratio of divalent iron / trivalent iron. You can

Next, the meaning of transparency in the present invention will be described. The term “transparent” in the present invention specifically means a case where the maximum value Dmax of the optical density of the magnetic recording layer is 0.3 or less. The optical densities in the present invention refer to the optical densities D ^B , D ^G , and D ^R measured through the filters B, G, and R using the X light densitometer status A mode. The maximum of these is defined as Dmax. The maximum value Dmax of the optical density of the magnetic recording layer in the present invention is 0.
It may be 3 or less, but it is preferably small in consideration of the influence on the photographic image, and preferably 0.10 or less, particularly preferably 0.05 or less in consideration of application to a reversal film.

The content of the magnetic material per 1 square meter of the transparent magnetic recording layer in the present invention is preferably 0.01 g to 1 g, but it does not matter as long as the above-mentioned optical transparency can be maintained, and the S / N ratio is not limited. It is preferable that the amount is as high as possible in order to increase the height.

Next, the binder of the magnetic recording layer used in the present invention will be described. As the binder of the magnetic recording layer used in the present invention, a known thermoplastic resin, thermosetting resin, radiation curable resin, reactive resin or a mixture thereof which has been conventionally used as a binder for a magnetic recording medium may be used. You can Examples of the thermoplastic resin include vinyl chloride / vinyl acetate copolymers, vinyl chloride, copolymers of vinyl acetate and vinyl alcohol, maleic acid and / or acrylic acid, vinyl chloride / vinylidene chloride copolymers, vinyl chloride / vinyl chloride. Acrylonitrile copolymer, vinyl-based copolymer such as ethylene / vinyl acetate copolymer, nitrocellulose, diacetyl cellulose, triacetyl cellulose, cellulose acetate propionate, cellulose derivative such as cellulose acetate butyrate resin, acrylic resin, polyvinyl Acetal resin, polyvinyl butyral resin, polyester polyurethane resin,
Examples thereof include rubber resins such as polyether polyurethane, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene butadiene resin, and butadiene acrylonitrile resin, silicone resins, and fluorine resins.

The hydrophilic binders are described in Research Disclosure No. 17643, page 26, and No. 18716, page 651, and include water-soluble polymers, cellulose esters, latex polymers, water-soluble polyesters and the like. Can be mentioned. Water-soluble polymers include gelatin, gelatin derivatives, casein,
Examples thereof include agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, and maleic anhydride copolymer, and examples of cellulose ester include carboxymethyl cellulose and hydroxyethyl cellulose. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene anhydride-containing copolymers, acrylate ester-containing copolymers, vinyl acetate-containing copolymers, butadiene-containing copolymers and the like. Of these, gelatin is the most preferable. Further, a gelatin derivative or the like may be used in combination with gelatin. As the gelatin, so-called lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives, modified gelatin and the like can be used, and among them, lime-processed gelatin and acid-processed gelatin are preferably used. The magnetic recording layer containing gelatin is preferably hardened. Examples of the hardener that can be used in the magnetic recording layer include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), 2-hydroxy-4, 6-
Dichloro-1,3,5-triazine and others are described in U.S. Pat. Nos. 3,288,775, 2,732,303, British Patents 974,723, 1,167,207 and the like. Reactive halogen-containing compounds, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, and other U.S. Pat. Nos. 3,635,718 and 3,232.
763, N-hydroxymethylphthalimide, compounds having reactive olefins described in British Patent No. 994,869, etc., and US Pat. No. 2,73.
N-methylol compounds described in, for example, US Pat. No. 3,103,2,316 and 2,586,168.
Isocyanates described in U.S. Pat. No. 437, etc., aziridine compounds described in U.S. Pat. Nos. 3,017,280 and 2,983,611, U.S. Pat.
No. 725,294, 2,725,295, etc., acid derivatives, epoxy compounds, US Pat. No. 3,091,537, halogen carboxaldehydes such as mucochloric acid. Can be mentioned. Alternatively, as an inorganic compound hardener, chrome alum, zirconium sulfate, JP-B-56-12853, JP-A-58-32699, Belgium Patent 825,726,
JP-A-60-225148 and 51-126125.
Japanese Patent Publication No. 58-50699, JP-A No. 52-5442.
No. 7, U.S. Pat. No. 3,321,313 and the like can be exemplified by a carboxyl group-activating type hardener.

The amount of the hardener used is usually 0.01 to 30% by weight, preferably 0.05 to 20% by weight based on dry gelatin.
% By weight. The mixing ratio of the magnetic substance and the binder in the magnetic recording layer in the present invention is preferably 100 to 3000 parts by weight of the binder with respect to 100 parts by weight of the magnetic substance. When the amount of the binder is small, the dispersibility and durability are poor, and when the amount of the binder is too large, the filling degree of the magnetic layer decreases, which is not preferable. The magnetic recording layer of the present invention may further contain a conventionally known lubricant, abrasive, matting agent and antistatic agent. In the present invention, any of the above binders can be used, but diacetyl cellulose, triacetyl cellulose and gelatin are preferred from the viewpoint of dispersibility and transparency.

The thickness of the magnetic recording layer in the present invention is 0.1.
-10 μm, preferably 0.2-5 μm, and more preferably 0.3-3 μm. The magnetic recording layer of the present invention may be provided on the same surface as the silver halide emulsion layer of the light-sensitive material,
It may be provided on the opposite surface. It is preferably provided on the surface opposite to the silver halide emulsion layer.

The magnetic recording layer of the present invention can be provided by any of coating, printing, vapor deposition, heat fusion, thermal transfer and tape bonding methods. Further, a support having a magnetic recording layer may be prepared by co-casting a polymer solution in which a magnetic material is dispersed and a polymer solution for preparing a support. In this case, the polymer in which the magnetic substance is dispersed is preferably substantially the same as the polymer for preparing the support. Further, when providing the magnetic recording layer, it is preferable to carry out a known magnetic field orientation treatment. As a method for applying the magnetic recording layer by coating, a general coating method, specifically, doctor coating, extrusion coating, slide coating, roller coating, gravure coating or the like can be used. Further, methods for preparing a magnetic substance dispersion liquid are already known, and the magnetic recording layer of the present invention can also be produced by using the dispersion liquid prepared by these methods.

The support of the light-sensitive material in the present invention is not particularly limited, but various plastic films can be used, and preferred are cellulose derivatives (for example, diacetyl-, triacetyl-, propionyl-,
Butanoyl-, acetylpropionyl-acetate, etc.), polyamides, polycarbonates described in U.S. Pat. No. 3,023,101, polyesters (especially polyethylene terephthalate, poly-1,4-cyclohexanediene) described in Japanese Patent Publication No. 48-40414. Methylene terephthalate, polyethylene 1,2-diphenoxyethane-
4,4'-dicarboxylate, polybutylene terephthalate, polyethylene naphthalate), polystyrene,
Polypropylene, polyethylene, polymethyl bentene,
Polysulfone, polyether sulfone, polyarylate, polyetherimide and the like, particularly preferably triacetyl cellulose, polyethylene terephthalate,
Polyethylene naphthalate. A plasticizer may be added to these supports for the purpose of imparting flexibility and the like. Particularly for cellulose esters, plasticizer-containing substances such as triphenyl phosphate, biphenyl diphenyl phosphate, and dimethyl ethyl phosphate are usually used.

Although these supports differ depending on the type of polymer, the thickness is about 1 mm from a sheet to a thin film of about 20 μm, and the thickness is usually 50 μm to 300 μm. The support has a neutral base color, prevents light piping,
A dye may be contained for the purpose of preventing halation.

In order to firmly adhere a photographic layer (eg, a photosensitive silver halide emulsion layer, an intermediate layer, a filter layer, a magnetic recording layer, a conductive layer) to these supports, chemical treatment,
Mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment,
After surface activation treatment such as high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc., a photographic emulsion may be directly applied to obtain the adhesive strength. An undercoat layer may be provided after the treatment or without surface treatment, and the photographic emulsion layer may be coated thereon. As the gelatin hardening agent, the above-mentioned hardener can be used. The undercoat liquid may contain various additives, if necessary. For example, surfactants, antistatic agents, antihalation agents, coloring dyes,
Examples include pigments, coating aids, antifoggants and the like. When the undercoating liquid of the present invention is used, an etching agent such as resorcin, chloral hydrate, chlorophenol and the like can be contained in the undercoating liquid. The undercoating liquid relating to the present invention is generally well-known coating method, for example, dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, or US Pat. No. 2,681. It can be applied by an extrusion coating method using a hopper described in Japanese Patent No. 294,294. As required, US Pat. Nos. 2,761,791, 3,508,947, 2,
941,898 and 3,526,528,
Two or more layers can be coated simultaneously by the method described in Yuji Harazaki, “Coating Engineering”, page 253 (published by Asakura Shoten in 1973).

The photographic material of the present invention comprises a silver halide emulsion layer, a magnetic recording layer, a back layer, a protective layer, an intermediate layer, an antihalation layer and the like, and these are mainly hydrophilic colloid layers. Used. Examples of the binder for the hydrophilic colloid layer in that case include proteins such as gelatin, colloidal albumin and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; sugar derivatives such as agar, sodium alginate, and starch derivatives: synthetic hydrophilic colloids. Examples thereof include polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or derivatives and partial hydrolysates thereof, dextran, polyvinyl acetate, polyacrylic acid ester, rosin and the like.
Mixtures of two or more of these colloids may be used if desired. The most used of these is gelatin or its derivatives, and the gelatin referred to here is so-called lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin.

The silver halide emulsion layer and other hydrophilic colloid layers in the photographic light-sensitive material of the present invention can be hardened with various organic or inorganic hardeners (single or in combination).

Color reversal films and color negative films can be mentioned as typical examples of silver halide color photographic light-sensitive materials which are particularly preferred in the present invention. Less than,
A general color reversal film will be used for explanation.

The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light. In a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-113.
No. 438, No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound, and the like, and a color mixing inhibitor may be used as usual. May be included. The plural silver halide emulsion layers constituting each unit light-sensitive layer preferably have a two-layer constitution of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. be able to. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition,
57-112751, 62-200350, 62-206541, 62-2
As described in No. 06543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / Low sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / RH / RL order, or BH / BL / GH /
It can be installed in the order of GL / RL / RH. In addition,
As described in JP-A-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. In addition, JP-A-56-25738 and 62-63
As described in Japanese Patent No. 936, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support. Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and the layer is composed of three layers having different sensitivities in which the sensitivities are gradually lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side distant from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, 4
In the case of more than one layer, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat.
No. 663,271, No. 4,705,744, No. 4,707,436, and JP-A Nos. 62-160448 and 63-89850.
It is preferable to arrange a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, or RL, adjacent to or in proximity to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material. The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about
It may be fine particles of 0.2 microns or less or large size grains having a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is described in, for example, Research Disclosure (RD) No. 17643 (December 1978), pp. 22-23, I. Emulsion preparation and types ", and
No.18716 (November, 1979), p.648, ibid., No.307105 (1989)
November), pp.863-865, and "Graphide's Physics and Chemistry", published by Paul Montel (P.Glafkides, Chemie).
et Phisique Photographique, PaulMontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.
F. Duffin, Photographic Emulsion Chemistry (Focal P
ress, 1966)), "Manufacturing and coating of photographic emulsions" by Zelikman et al., published by Focal Press (VL Zelikman et al., M
aking and Coating Photographic Emulsion, Focal Pre
ss, 1964) and the like. Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and E.
14: 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048,
It can be easily prepared by the method described in U.S. Pat. No. 4,439,520 and British Patent No. 2,112,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure,
Further, silver halides having different compositions may be joined by epitaxial joining, and, for example, silver rhodan,
It may be bonded to a compound other than silver halide such as lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain, or a type which has a latent image on both the surface and the inside.
It must be a negative emulsion. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm. As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such processes are Research Disclosure N
No. 17643, No. 18716, and No. 307105, and the relevant parts are summarized in the table below.

The light-sensitive material of the present invention comprises a photosensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer. US Pat. It can be preferably used for a photosensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface is a silver halide grain that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,4.
98, JP-A-59-214852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged,
Any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is preferably 0.01 to 0.75 μm, particularly preferably 0.05 to 0.6 μm. The particle shape is not particularly limited,
Regular grains may be used, or a polydisperse emulsion may be used.
Monodispersion (wherein at least 95% of the weight or number of silver halide grains has a grain size within ± 40% of the average grain size) is preferred. In the present invention, it is preferable to use non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that it is not fogged in advance. .

The fine grain silver halide has a silver bromide content of
It is 0 to 100 mol%, and may contain silver chloride and / or silver iodide, if necessary. Preferably silver iodide is 0.5
~ 10 mol% is contained. Fine grain silver halide has an average grain size (average diameter of circles equivalent to the projected area) of 0.01
.About.0.5 .mu.m is preferable, and 0.02 to 0.2 .mu.m is more preferable. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred. Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table.

Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 Page 868 Supersensitizer ~ page 649 Right column 4. Whitening agent page 24 647 Page right column 868 page 5. Fogging prevention 24 ~ 25 page 649 Page right column 868 ~ 870 Agent, stabilizer 6. Light absorber , Pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dyes, ultraviolet absorbers, 7. stain, page 25, right column, page 650, left column, page 872, inhibitor, right column 8. dye image, page 25, page 650, left Column 872 Stabilizer 9. Hardener page 26 651 page left column 874 to 875 page 10. Binder page 26 page 651 page left column 873 to 874 page 11. Plasticizer, page 27 650 right column page 876 lubricant 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surface active agent, 13. static, page 27, page 650, right column, pages 876 to 877, inhibitor, matting agent, pages 878 to 879

In order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add to the light-sensitive material a compound capable of reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. . In the light-sensitive material of the present invention, U.S. Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-28
It is preferable to contain the mercapto compound described in No. 3551. A compound which, in the light-sensitive material of the present invention, releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. In the light-sensitive material of the present invention, a dye dispersed by the method described in International Publication WO88 / 04794 or JP-A-1-502912 or
EP 317,308A, U.S. Pat.No. 4,420,555, JP 1-2593
It is preferable to include the dye described in No. 58. Various color couplers can be used in the light-sensitive material of the present invention. Specific examples thereof include Research Disclosure No. 17643, VII-C to G, and No. 307105, VII.
-C-G. Examples of yellow couplers include U.S. Pat.Nos. 3,933,501, 4,022,620, 4,326,024, and 4,401,752.
No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020, No. 1,476,760, and U.S. Patent No. 3,97.
Those described in 3,968, 4,314,023, 4,511,649, European Patent 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,63 are preferred.
6, U.S. Pat.Nos. 3,061,432, 3,725,067,
Research Disclosure No. 24220 (June 1984
Month), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A 61-7.
No. 2238, No. 60-35730, No. 55-118034, No. 60-185951
U.S. Pat.Nos. 4,500,630, 4,540,654, and
Those described in 4,556,630 and International Publication WO88 / 04795 are particularly preferable. Examples of cyan couplers include phenol-based and naphthol-based couplers, and US Pat.
52,212, 4,146,396, 4,228,233, and
4,296,200, 2,369,929, 2,801,171,
No. 2,772,162, No. 2,895,826, No. 3,772,002
No. 3, No. 3,758,308, No. 4,334,011, No. 4,32
7,173, West German Patent Publication 3,329,729, European Patent 12
1,365A, 249,453A, U.S. Pat.No. 3,446,622
No. 4, No. 4,333,999, No. 4,775,616, No. 4,45
1,559, 4,427,767, 4,690,889, and
Those described in 4,254,212, 4,296,199 and JP-A-61-42658 are preferable. Furthermore, JP-A-64-553,
Pyrazoloazole couplers described in JP-A Nos. 64-554, 64-555 and 64-556 and imidazole couplers described in US Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in US Pat.
3,451,820, 4,080,211 and 4,367,282,
No. 4,409,320, No. 4,576,910, British patent 2,1
No. 02,137 and European Patent No. 341,188A.
As couplers in which the colored dye has an appropriate diffusibility, those described in U.S. Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570 and West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unwanted absorption of coloring dyes are Research Disclosure No. 1
7643, VII-G, No. 307105, VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat.
Those described in 4,929, 4,138,258 and British Patent 1,146,368 are preferable. Also, U.S. Pat.
And a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.
It is also preferable to use a coupler having a dye precursor group as a leaving group capable of reacting with a developing agent to form a dye as described in 4,777,120. Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are
RD17643, Item VII-F and No. 307105, VII-
Patents described in paragraph F, JP-A-57-151944 and JP-A-57-1542
No. 34, No. 60-184248, No. 63-37346, No. 63-37350
Nos. 4,248,962 and 4,782,012 are preferable. RD No. 11449, 24241, JP-A-61
-The bleach accelerator releasing couplers described in 201247 etc. are effective in shortening the time of the processing step having a bleaching ability,
In particular, the effect is great when added to the light-sensitive material using the above-mentioned tabular silver halide grains. As couplers that release a nucleating agent or a development accelerator imagewise during development, those described in British Patents 2,097,140 and 2,131,188 and JP-A-59-157638 and 59-170840 are preferable. Further, by a redox reaction with an oxidant of the developing agent described in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and 1-45687, a fogging agent and a development accelerator. ,
A compound that releases a silver halide solvent or the like is also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,3.
38,393, 4,310,618 and the like, multi-equivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds described in JP-A-60-185950 and JP-A-62-24252. Alternatively, DIR redox-releasing redox compounds, couplers that release dyes that undergo color restoration after separation described in European Patents 173,302A and 313,308A, ligand-releasing couplers described in U.S. Pat. -75747 couplers releasing leuco dyes, U.S. Pat.
Examples thereof include couplers that release the fluorescent dye described in No. 181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate. (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di
-2-Ethylhexylphenylphosphonate, etc., Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecane amide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters bis (2-ethylhexyl) sebacate, dioctyl azelate , Glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.),
Hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like can be mentioned. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably about 50 ° C or higher.
An organic solvent at 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat.
LS) No. 2,541,274 and No. 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-272248,
And 1,2-benzisothiazolin-3-one described in JP-A-1-80941, n-butyl p-hydroxybenzoate,
It is preferable to add various preservatives or antifungal agents such as phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole. Suitable supports that can be used in the present invention are described, for example, in RD. No. 17643, page 28, No. 18716, page 647, right column to page 648, left column, and No. 307105, page 879. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, particularly preferably 16 μm or less. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness is 25 ° C and 55% relative humidity (2 days)
The film swelling speed T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering by A. Green et al.
(Photogr.), 19 Certificates, No. 2, by using a 124 type described on pages to 129 Swellometer (swelling meter) can be measured, T _1/2 in color developer 30 The saturated film thickness is defined as 90% of the maximum swollen film thickness reached when the film is treated at ℃ for 3 minutes and 15 seconds.
The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing aging conditions after coating. The swelling rate is 1
50 to 400% is preferable. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness)
/ Can be calculated according to the film thickness. The light-sensitive material of the present invention has a total dry film thickness of 2 μm to 20 on the side opposite to the side having the emulsion layer.
It is preferable to provide a hydrophilic colloid layer (referred to as a back layer) having a thickness of μm. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is preferably 150 to 500%.

The color developing solution used for developing the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N diethylaniline and 3-methyl. -4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl -β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more of these compounds can be used in combination depending on the purpose. The color developer should have a pH such as alkali metal carbonate, borate or phosphate.
It is common to include a development inhibitor such as a buffer, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, development accelerators such as quaternary ammonium salt amines, dye forming couplers,
Competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, various chelating agents represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, for example , Ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts It can be mentioned as a representative example.

Next, processing solutions and processing steps for the color reversal light-sensitive material of the present invention other than the color developing solution will be described. Among the processing steps of the color reversal light-sensitive material of the present invention, the steps from black development to color development are as follows. 1) Black-white development-water washing-reversal-color development 2) Black-white development-water washing-light reversal-color development 3) Black-white development-water washing-color development Steps 1) to 3) are all performed in US Pat.
In place of the rinse process described in No. 04,616, it is possible to simplify the process and reduce waste liquid. Next, the steps after color development will be described. 4) Color development-adjustment-bleaching-fixing-washing-stable 5) Color development-washing-bleaching-fixing-washing-stable 6) Color development-adjusting-bleaching-washing-fixing-washing-stable 7) Color development-washing -Bleaching-washing-fixing-washing-stable 8) color development-bleaching-fixing-washing-stable 9) color development-bleaching-bleach-fixing-washing-stable 10) color development-bleaching-bleach-fixing-washing-stable 11) Color development-bleaching-washing-fixing-washing-stable 12) Color development-adjusting-bleaching fixing-washing-stable 13) Color development-washing-bleaching fixing-washing-stable 14) Color development-bleaching fixing-washing- Stable 15) Color development-fixing-bleach-fixing-washing-stable 4) to 15), the washing step immediately before the stabilizing step may be eliminated, or conversely the final stabilizing step is not performed. May be. Any one of the above steps 1) to 3) and any one of steps 4) to 15) are connected to form a color reversal step.

Next, the processing liquid of the color reversal processing step of the present invention will be described. Known developing agents can be used in the black and white developing solution used in the present invention. As developing agents, dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-aminophenol), 1-phenyl-3- Use of pyrazolines, ascorbic acid, and heterocyclic compounds such as 1,2,3,4-tetrahydroquinoline ring and indrene ring described in US Pat. No. 4,067,872, alone or in combination. You can In the black and white developer used in the present invention, other preservatives (eg, sulfite, bisulfite, etc.), buffers (eg, carbonate, boric acid, borate, alkanolamine), alkaline agents (eg, Hydroxides, carbonates), dissolution tablets (eg polyethylene glycols, their esters), pH adjusters (eg organic acids such as acetic acid), sensitizers (eg quaternary ammonium salts), development accelerators , A surface active agent, an antifoaming agent, a film hardening agent, a viscosity imparting agent, and the like. The black-and-white developing solution used in the present invention needs to contain a compound acting as a silver halide solvent, and a sulfite salt added as the above preservative usually serves its function. Examples of the sulfite and other silver halide solvents that can be used include KSCN, N
aSCN, K ₂ SO ₃ , Na ₂ SO ₃ , K ₂ S ₂ O ₅ ,
_{Na 2 S 2 O 5, K} 2 S 2 O 3, and the like Na ₂ S ₂ O _3. The pH value of the developer thus adjusted is selected to an extent sufficient to provide the desired density and contrast, but is in the range of about 8.5 to about 11.5. In order to perform a sensitizing process using such a black-and-white developing solution, it is usually necessary to extend the time up to about 3 times that of the standard process. At this time, if the processing temperature is raised, the extension time for the sensitization processing can be shortened.

The pH of these color developing solution and black-and-white developing solution is generally 9 to 12. The replenishment amount of these developers depends on the color photographic light-sensitive material to be processed,
Generally, it is 3 liters or less per 1 square meter of the light-sensitive material, and can be reduced to 500 or less by reducing the bromide ion concentration in the replenisher. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. Is. As a method of reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit development processing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The reversal bath used after black and white development may contain a known fogging agent. That is, stannous ion-organic phosphoric acid complex salt (US Pat. No. 3,617,282), stannous ion organic phosphonocarboxylic acid complex salt (Japanese Patent Publication No. 56-32616), stannous ion-
Aminopolycarboxylic acid complex salt (US Pat. No. 1,209,0
50), stannous ion complex salts, borohydride compounds (US Pat. No. 2,984,567),
Heterocyclic amine borane compounds (UK Patent No. 1,011,0
No. 00 specification) and the like, and the like. The fogging bath (reversal bath) has a wide pH range from the acidic side to the alkaline side, and has a pH of 2 to 12, preferably 2.5 to 10, and particularly preferably 3 to 9.
A light reversal process by re-exposure may be performed instead of the reversal bath, and the reversal step may be omitted by adding the fogging agent to the color developing solution. The silver halide color photographic light-sensitive material of the present invention is bleached or bleach-fixed after color development. These treatments may be carried out immediately after color development without passing through other treatment steps,
In order to prevent unnecessary post-development, air fogging, and to reduce the amount of color developing solution brought into the desilvering process. In order to wash out the impregnated color developing agent and render it harmless, it may be subjected to a bleaching treatment or a bleach-fixing treatment after a processing step such as stopping, adjusting and washing with water after the color developing treatment.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. As a typical bleaching agent, an organic complex salt of iron (III),
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, and other aminopolycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. Etc. can be used. Of these, iron (III) aminopolycarboxylates including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts
Complex salts are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing. If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specification: US Pat.
3,893,858, West German Patent 1,290,812, 2,059,988
No. 53-32736, No. 53-57831, No. 53-37418,
53-72623, 53-95630, 53-95631, 53-104
No. 232, No. 53-124424, No. 53-141623, No. 53-28426
No. 17129 (July 1978) and the like, compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506; Sho 52-20832, same
53-32735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715, iodide salts described in JP-A-58-16,235; West German Patents 966,410, 2,748,43.
No. 0 polyoxyethylene compounds; Japanese Patent Publication No. 45-8
836 Polyamine compounds; Others JP-A-49-40,94
No. 3, No. 49-59,644, No. 53-94,927, No. 54-35,727
Nos. 55-26,506 and 58-163,940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and the compounds described in US Pat. No. 3,893,858, West German Patent 1,290,812 and JP-A-53-95,630 are particularly preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specifically acetic acid, propionic acid, hydroxyacetic acid and the like are preferable.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts, and the use of thiosulfates. Are generally used, and ammonium thiosulfate is most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. The total time of the desilvering process is preferably as short as possible in the range where desilvering failure does not occur. The preferred time is 1 to 3 minutes, more preferably 1 to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to
45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a specific method for strengthening stirring, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461 Method to increase the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution to further improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator. Automatic developing machines used in the light-sensitive material of the present invention are disclosed in JP-A-60-191257, JP-A-60-191258 and JP-A-60-1912.
It is preferable to have a photosensitive material conveying means described in No. 59. As described in JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath and has a high effect of preventing the deterioration of the performance of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture a
nd Television Engineers, Volume 64, P. 248-253 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, such a problem is solved as a solution.
The method of reducing calcium ion and magnesium ion described in 62-288,838 can be used very effectively. Also, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antibacterial and fungicide" (1986) Sankyo Publishing Co., Ltd., Hygiene Engineering Society, "Microbial sterilization, sterilization, and antifungal technology"
(1982) The sterilizing agent described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal can also be used.

Rinsing water in processing the light-sensitive material of the present invention
The pH is 4-9, preferably 5-8. The washing water temperature and the washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but in general, it is 20 seconds to 10 minutes at 15 to 45 ° C., preferably
A range of 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used. In addition, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. be able to. As a dye stabilizer,
Aldehydes such as formalin and glutaraldehyde,
Examples thereof include N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.
Various chelating agents and antifungal agents can also be added to this stabilizing bath. The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example U.S. Pat.
42,597 Indoaniline compounds, 3,342,5
99, Research Disclosure 14,850 and 1
Examples thereof include Schiff base type compounds described in 5,159, aldol compounds described in 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary.
Typical compounds are JP-A-56-64339, JP-A-57-144547,
And No. 58-115438 of the same. The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

[0045]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1

Preparation of Magnetic Coating Material The following magnetic coating composition (formulation 1) was placed in an open kneader and kneaded for 1 hour, and then a shortage of solvent and binder was added to prepare a magnetic coating composition (formulation 2). Dispersed with a mold mill. Then, a coating solution was prepared by further adding a deficient binder / solvent to dilute so as to obtain (Formulation 3). (Formulation 1) Co-containing acicular γ-iron oxide fine powder (SBET 45.0 g / m ² , Hc 800 Oe, σs 70 emu / g) 1000 parts by weight Diacetyl cellulose 20 parts by weight Methyl ethyl ketone 90 parts by weight Cyclohexanone 90 parts by weight (formulation 2) Co-containing acicular γ-iron oxide fine powder (SBET 45.0 g / m ² , Hc 800 Oe, σs 70 emu / g) 10 parts by weight Diacetyl cellulose 10 parts by weight Methyl ethyl ketone 45 parts by weight Cyclohexanone 45 parts by weight (formulation 3) Co-containing acicular γ-iron oxide fine powder (SBET 45.0 g / m ² , Hc 800 Oe, σs 70 emu / g) 1 part by weight diacetyl cellulose 10 parts by weight methyl ethyl ketone 100 parts by weight cyclohexanone 100 parts by weight Coronate L (Nippon Polyurethane Industry Co., Ltd.) Made) 2 parts by weight

Preparation of Base The following undercoat liquid was applied and dried on a polyethylene terephthalate base (90 μm) that had been previously subjected to ultraviolet irradiation treatment, and then the magnetic paint coating liquid prepared in the above was applied and dried. The optical density Dmax of the obtained magnetic recording layer is 0.10.
The coating amount was adjusted so that The thickness of the obtained magnetic recording layer of the base was about 1 μm. In addition, magnetic field orientation treatment was performed in the drying stage. Magnetic field orientation treatment is magnetic force 3000
Gaussian magnets were installed at different positions of residual solvent. The two magnets with the same magnetic force and the same pole were placed so that the base was sandwiched, and the distance from the base was 10 mm. The surface having the magnetic recording layer was used as the back surface. (Undercoating liquid) SnO ₂ / Sb ₂ O ₃ / SiO ₂ (90/10 / 0.5 average particle size 0.15 μm) 0.18 mg / m ² diacetyl cellulose 0.32 g / m ² Aerosil 0.02 〃 polymethyl methacrylate 0.32 〃 poly (methyl methacrylate) / Divinylstyrene) (molar ratio 95: 5) (average particle size 0.2 μm) 0.01〃 dimethyl silicon 0.01〃

Preparation of Light-Sensitive Material Each layer having the following composition was coated in multiple layers to prepare a sample as a multi-layer color light-sensitive material. First layer: antihalation layer Black colloidal silver 0.20 g Gelatin 1.9 g UV absorber U-1 0.1 g UV absorber U-3 0.04 g UV absorber U-4 0.1 g High boiling point organic solvent Oil-1 0.1 g Dye E -1 microcrystalline solid dispersion 0.1 g

Second layer: intermediate layer Gelatin 0.40 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 3 mg High boiling organic solvent Oil-3 0.1 g Dye D-4 0.8 mg

Third layer: intermediate layer Fine grained silver iodobromide emulsion (average grain size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) whose surface and inside are fogged
0.05 g gelatin 0.4 g

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.3 g Emulsion B Silver amount 0.2 g Gelatin 0.8 g Coupler C-1 0.15 g Coupler C-2 0.05 g Coupler C-3 0.05 g Coupler C-9 0.05 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g

Fifth layer: Medium-sensitive red-sensitive emulsion layer Emulsion B Silver amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-3 0.2 g High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-2 0.1 g Coupler C-3 0.7 g Additive P-1 0.1 g

7th layer: intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixture inhibitor Cpd-I 2.6 mg Dye D-5 0.02 g Compound Cpd-J 5 mg High boiling organic solvent Oil-1 0.02 g

Eighth layer: intermediate layer A silver iodobromide emulsion whose surface and inside are fogged (average grain size: 0.06)
μm, coefficient of variation 16%, AgI content 0.3 mol%) Silver amount
0.02 g Gelatin 1.0 g Additive P-1 0.2 g Color mixing inhibitor Cpd-A 0.1 g Compound Cpd-C 0.1 g

Layer 9: Low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.1 g Emulsion F Silver amount 0.2 g Emulsion G Silver amount 0.2 g Gelatin 0.5 g Coupler C-4 0.1 g Coupler C-7 0.05 g Coupler C-8 0.20 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.04 g Compound Cpd-J 10 mg Compound Cpd-L 0.02 g High boiling point organic solvent Oil-1 0.1 g High boiling point organic Solvent Oil-2 0.1 g

Layer 10: Medium-speed green-sensitive emulsion layer Emulsion G Silver amount 0.3 g Emulsion H Silver amount 0.1 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-7 0.2 g Coupler C-8 0.1 g Compound Cpd-B 0.03g Compound Cpd-D 0.02g Compound Cpd-E 0.02g Compound Cpd-F 0.05g Compound Cpd-L 0.05g High boiling organic solvent Oil-2 0.01g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.3 g Coupler C-7 0.1 g Coupler C-8 0.1 g Compound Cpd-B 0.08 g Compound Cpd-E 0.02g Compound Cpd-F 0.04g Compound Cpd-K 5 mg Compound Cpd-L 0.02g High boiling organic solvent Oil-1 0.02g High boiling organic solvent Oil-2 0.02g

Twelfth layer: intermediate layer Gelatin 0.6 g Compound Cpd-L 0.05 g High boiling point organic solvent Oil-1 0.05 g

13th layer: Yellow filter layer Yellow colloidal silver Silver amount 0.07 g Gelatin 1.1 g Color mixing inhibitor Cpd-A 0.01 g Compound Cpd-L 0.01 g High boiling organic solvent Oil-1 0.01 g Fine crystals of dye E-2 Solid dispersion 0.05g

14th layer: intermediate layer 0.6 g of gelatin

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.2 g Emulsion K Silver amount 0.3 g Gelatin 0.8 g Coupler C-5 0.2 g Coupler C-6 0.1 g Coupler C-10 0.4 g

Sixteenth layer: Medium sensitivity blue-sensitive emulsion layer Emulsion L Silver amount 0.5 g Gelatin 0.9 g Coupler C-5 0.1 g Coupler C-6 0.1 g Coupler C-10 0.6 g

Layer 17: High-sensitivity blue-sensitive emulsion layer Emulsion M Silver amount 0.2 g Emulsion N Silver amount 0.2 g Gelatin 1.2 g Coupler C-5 0.1 g Coupler C-6 0.1 g Coupler C-10 0.6 g High boiling organic solvent Oil-2 0.1 g

Eighteenth layer: First protective layer Gelatin 0.7 g UV absorber U-1 0.2 g UV absorber U-2 0.05 g UV absorber U-5 0.3 g Formalin scavenger Cpd-H 0.4 g Dye D-1 0.15 g Dye D-2 0.05 g Dye D-3 0.1 g

Layer 19: Second protective layer Colloidal silver Silver amount 0.1 mg Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI content 1
Mol%) Silver amount 0.1 g Gelatin 0.4 g

20th layer: third protective layer Gelatin 0.4 g Polymethylmethacrylate (average particle size 1.5 μ) 0.1 g Methyl methacrylate / acrylic acid 4: 6 copolymer (average particle size 1.5 μ) 0.1 g Silicone oil 0.03g Surfactant W-1 3.0mg Surfactant W-2 0.03g

Additives F-1 to F-8 were added to all emulsion layers in addition to the above composition. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer. Further, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and p-benzoic acid butyl ester were added as antiseptic and antifungal agents.

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

[Table 3]

[0072]

[Chemical 1]

[0073]

[Chemical 2]

[0074]

[Chemical 3]

[0075]

[Chemical 4]

[0076]

[Chemical 5]

[0077]

[Chemical 6]

[0078]

[Chemical 7]

[0079]

[Chemical 8]

[0080]

[Chemical 9]

[0081]

[Chemical 10]

[0082]

[Chemical 11]

[0083]

[Chemical 12]

[0084]

[Chemical 13]

[0085]

[Chemical 14]

Processing of sample The sample was cut into a film having a width of 35 mm and 24 sheets taken. Development of these samples was carried out by Fuji Photo Film Color Reversal Processing CR-56 processing.

Next, the evaluation of these samples will be described. (1) Measurement of optical transparency (X light density) X light densitometer 310TR with status A mode B,
The optical densities (transmission densities) passed through the G and R filters are measured, and the differences between the optical densities of the sample and the reference sample are expressed as D ^B , D ^G , and D ^R , respectively, which are the maximum. Let Dmax be the thing. (2) Evaluation of magnetic recording performance (S / N ratio) Each sample had a track width of 1.5 mm and a head gap of 7μ.
m, with a turnable head of 1000 turns,
A recording density signal of 1000 bpi is recorded at a feed rate of 100 mm / s. Then, the ratio of the output S and the noise N when the signal was reproduced at the same head and the same speed was measured. The values shown are the S / N of the magnetic recording layer obtained in the comparative example.
It is a value when the ratio is 0 dB. The temperature and humidity used for evaluation were 25 ° C. and 60% RH. (3) Saturation magnetic flux density (Bm) and squareness ratio (SQ) The magnetic characteristics at a magnetic field strength (Hm) of 5 kOe were measured using a vibration test magnetometer (VSM) (manufactured by Toei Industry Co., Ltd.). (4) Granularity (RMS) measurement Using specular light as the light source, aperture size 80 μm
Microdensitometry was carried out to determine the RMS value. Table 4 shows the results of the above evaluations performed on the sample prepared in Example 1.

Comparative Example 1 A photosensitive material provided with a magnetic recording layer was obtained in the same manner as in Example 1, except that the magnetic field orientation treatment was not performed when the base was formed.

[0089]

[Table 4]

As can be seen from Table 4, the magnetic recording layer of the present invention not only has a higher S / N ratio than that of a magnetic material having a low degree of orientation at the same optical density but also has improved graininess. The effect was remarkable.

Example 2 A photosensitive layer was applied in the same manner as in Example 1 except that the magnetic paint was prepared and the base was prepared by the method described below.
The samples were processed and subjected to the same evaluation. The evaluation results are shown in Table 5.

A Preparation of Magnetic Dispersion Liquid The following magnetic coating composition (formulation 4) was placed in an open kneader and kneaded for 1 hour, and then a shortage of solvent and binder was added to form a magnetic coating composition (formulation 5). This was dispersed with an annular mill. Next, a binder, a solvent, and a curing agent in a shortage were added to dilute so as to obtain (formulation 6) to obtain a coating liquid. (Formulation 4) Co-containing acicular magnetite fine powder (SBET 48.0 g / m ² , Hc 750 Oe, σs 80 emu / g) 1000 parts by weight Gelatin 30 parts by weight Water 150 parts by weight Sodium dodecylbenzenesulfonate 1 part by weight (formulation 5) Co-containing acicular magnetite fine powder (SBET 48.0 g / m ² , Hc 750 Oe, σs 80 emu / g) 30 parts by weight Gelatin 30 parts by weight Water 150 parts by weight Sodium dodecylbenzene sulfonate 1 part by weight (formulation 6) Co-containing acicular magnetite fine powder (SBET 48.0 g / m ² , Hc 750 Oe, σs 80 emu / g) 1 part by weight Gelatin 10 parts by weight Water 150 parts by weight Sodium dodecylbenzenesulfonate 1 part by weight

Preparation of B Base A polyethylene naphthalate base (85 μm) which had been previously subjected to UV irradiation was coated with the following undercoat liquid and dried, and then the magnetic paint coating liquid prepared in A was applied and dried thereon. The optical density Dmax of the obtained magnetic recording layer is 0.05.
The coating amount was adjusted so that The thickness of the obtained magnetic recording layer of the base was about 1 μm. In addition, magnetic field orientation treatment was performed in the drying stage. Magnetic field orientation treatment is magnetic force 2000
Gaussian solenoid magnets were installed at different positions of residual solvent. The surface having the magnetic recording layer was used as the back surface. (Undercoating liquid) SnO ₂ / Sb ₂ O ₃ / SiO ₂ (90/10 / 0.5 average particle size 0.15 μm) 0.18 mg / m ² diacetyl cellulose 0.32 g / m ² Aerosil 0.02 〃 polymethyl methacrylate 0.32 〃 poly (methyl methacrylate) / Divinylstyrene) (molar ratio 95: 5) (average particle size 0.2 μm) 0.01 〃 dimethyl silicon 0.01 〃 Comparative Example 2 In the same manner as in Example 2, except that the magnetic field orientation treatment was not performed when the base was formed, the magnetic properties were the same. A sensitive material having a recording layer was obtained.

[0094]

[Table 5]

As can be seen from Table 5, the magnetic recording layer of the present invention not only has a higher S / N ratio than that of a magnetic material having a low degree of orientation at the same optical density but also has improved graininess, The effect was remarkable.

[0096]

The magnetic recording layer obtained by the production method of the present invention is optically transparent (having a low transmission density) and has an S /
It has a high N ratio and is excellent in graininess.

Claims (4)

[Claims] 1. A method for producing a silver halide photographic light-sensitive material having a silver halide emulsion layer on at least one side of a support and at least one optically transparent magnetic recording layer, wherein a magnetic substance is dispersed. A method for producing a photographic light-sensitive material, characterized by applying a coating liquid on a support and then drying the magnetic substance in the coating liquid while passing it through an orientation magnetic field arranged in a certain direction. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the residual solvent in the magnetic recording layer is passed through an orientation magnetic field from a point of 70% or less to 5% or more. 3. The magnetic material used in the magnetic recording layer is ferromagnetic γ-iron oxide fine powder, Co-containing ferromagnetic γ-iron oxide fine powder, ferromagnetic magnetite fine powder, Co-containing ferromagnetic magnetite. A silver halide photographic light-sensitive material according to claim 1, which is a fine powder, a fine powder of ferromagnetic chromium dioxide, a ferromagnetic alloy powder, or a barium ferrite powder. 4. The silver halide photographic light-sensitive material according to claim 1, 2 or 3, wherein the shape of the magnetic material used in the magnetic recording layer is acicular or rice granular.