JPH0342454B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic material having a novel filter layer or antihalation layer.

Generally, a silver halide photographic light-sensitive material has a hydrophilic colloid layer including a light-sensitive silver halide emulsion layer on a support, and imagewise exposure is performed to record an image on the light-sensitive silver halide emulsion layer. If you do
It may be necessary to control the spectral composition of light incident on the light-sensitive silver halide emulsion layer. In such cases, the hydrophilic colloid layer, which is located farther from the support than the photosensitive silver halide emulsion layer, usually contains a substance (coloring component) that can absorb light in a wavelength range that is not needed by the silver halide emulsion layer. ) is used to transmit only light in the target wavelength range - a so-called method of providing a filter layer.

Further, the light transmitted through the photosensitive silver halide emulsion layer may be transmitted to the boundary surface of the photosensitive silver halide emulsion layer or
Reflection occurs at the interface between the support and the hydrophilic colloid layer adjacent to the support, which has an undesirable effect on photographic performance. In order to prevent this reflection, a method in which a hydrophilic colloid layer existing on the support side of the silver halide emulsion layer contains a substance (coloring component) capable of absorbing the light that becomes the reflected light - providing a so-called antihalation layer. method is used.

In addition, the photosensitive silver halide emulsion layer contains a substance (coloring component) that can absorb scattered light in order to prevent a decrease in image sharpness due to light scattering in the photosensitive silver halide emulsion layer. Irradiation prevention methods are also used.

The substance capable of absorbing light (hereinafter referred to as dye) described above needs to satisfy the following conditions.

(1) It must have appropriate spectral absorption depending on the purpose of use. (2) It must not have any adverse effect on photographic performance, that is, it must be photochemically inert, such as reducing sensitivity or
No latent image regression, fogging, etc. will occur (3) The color will not be bleached during the photographic processing process or will be eluted out of the system of the light-sensitive material during any processing process and will not have an adverse effect on the photographic performance after the photographic processing. For example, there should be no residual color staining, etc.) Many efforts have been made to find dyes that meet these conditions. For example, British patent no.
No. 506385, an oxonol dye having a pyrazolone nucleus represented by the dye described in U.S. Patent No.
Oxonol dyes having barbituric acid nuclei represented by the dyes described in No. 3247127, U.S. Patent Nos. 2533472 and 3379533, and British Patent No.
Other oxonol dyes such as those described in US Pat. No. 1278621, styryl dyes as described in US Pat. No. 2,298,733, hemioxonol dyes as described in UK Patent No. 584609, merocyanine dyes as described in US Pat. , U.S. Patent No. 2843486
Examples include cyanine dyes listed in this issue.

Examples of dyes that are decolorized during photographic processing include those described in British Patent No. 506,385.

If the colored layer containing the above dye is a filter layer or an antihalation layer placed on the same side of the support as the light-sensitive silver halide emulsion layer, those layers can be selectively colored. is,
It is often necessary to ensure that coloration does not substantially extend to other layers. This is because the coloration spread to other layers not only has harmful spectral effects on the other layers, but also reduces their effectiveness as a filter layer or antihalation layer.

Various techniques have been disclosed in the past as methods for selectively stopping coloring in specific hydrophilic colloid layers, but the most common method is to localize the dye in a predetermined photographic layer using a mordant.

Examples of mordants include ethylenically unsaturated compound polymers having dialkylaminoalkyl ester residues as described in British Patent No. 685,475, reaction products of polyvinyl alkyl ketones and aminoguanidine as described in British Patent No. 850,281, and as described in U.S. Pat. No. 3,445,231. 2
Polymers from -methyl-1-vinylimidazole are known.

When mordanting with a polymer as described above,
Diffusion of dyes from layers containing dyes into other layers is often observed in the wet state. This diffusion may be due to the chemical structure of the mordant, but it is often due to the chemical structure of the dye itself.

Furthermore, when the above-mentioned polymer mordant is used, after photographic processing, particularly in the case of rapid processing, residual color due to the dye is likely to occur in the photographic material. The reason for this is that in an alkaline solution such as a developer, the bonding force between the mordant and the dye is considerably reduced, but some bonding force still remains, which may cause the dye to remain in the photographic layer or to form poorly soluble recolorable decolorizers. This is thought to be because substances are generated in the layer. These disadvantages also depend on the chemical structure of the mordant and
In particular, this is largely due to the chemical structure of the dye itself.

The present invention is intended to improve the problems in the above-mentioned technology, and therefore, an object of the present invention is to provide a filter that does not undergo non-reactive bleaching or elution during photographic processing, and does not have an adverse effect on photographic performance. An object of the present invention is to provide a photographic material having a layer and/or an antihalation (irradiation) layer.

The purpose is to provide a silver halide photographic material having at least one hydrophilic colloid layer on a support, in which the hydrophilic colloid layer acts as a core material and is removed during the development process of the silver halide photographic material. Achieved by a silver halide photographic light-sensitive material containing a material to be decolorized or bleached, and containing microcapsules (hereinafter referred to as the microcapsules of the present invention) formed from a substance that can be dissolved in an aqueous alkaline solution as a wall material. I found out that it can be done.

The dyes according to the present invention are typically cyanine-based, merocyanine-based, styryl-based, benzylidene-based, cinnamyridine-based, oxanol-based, azo-based, anthraquinone-based, and trimethanol-based, and these are disclosed in British Patent No. 506385. , same No. 1521083
No., U.S. Patent No. 2409612, U.S. Patent No. 2527583, U.S. Patent No.
No. 2538009, No. 2865752, No. 2956879, No. 3016306, No. 3148187, No. 3247127,
Same No. 3260601, Same No. 3282699, Same No. 3384487,
Same No. 3423207, Same No. 3637676, Same No. 4187225,
Special Publication No. 39-22069, No. 43-13168, Japanese Patent Publication No. 48-1973
No. 68623, No. 48-85130, No. 49-114420, No. 50
-91627, No. 51-3623, No. 51-77327, etc.

For example, pyrazolone oxonol dyes typified by the dyes described in U.S. Pat. No. 2,274,782, oxonol dyes with a barbiturate nucleus typified by the dyes described in U.S. Pat. No. 3,247,127, U.S. Pat. No. 3379533, British Patent No.
Other oxonol dyes such as those described in U.S. Pat.
2298733, 3423207, and 3384487; the merocyanine dyes described in U.S. Pat. No. 2,527,583; cyanine dyes typified by the dyes described in US Pat. No. 2,843,486.

Next, examples of dyes according to the present invention will be shown.

■■■ Tortoise shell [0256] ■■■ ■■■ Tortoise shell [0257] ■■■ ■■■ Tortoise shell [0258] ■■■ ■■■ Tortoise shell [0259] ■■■ ■■■ Tortoise shell [0260] ■■■ ■■■ Tortoise shell [0261] ■■■ ■■■ Tortoise shell [0262] ■■■ ■■■ Tortoise shell [0263] ■■■ ■■■ Tortoise shell [0264] ■■■ ■■■ Tortoise shell [0265] ■■■ ■■■ Tortoise shell [0266] ■■■ ■■■ Tortoise shell [0267] ■■■ ■■■ Tortoise shell [0268] ■■■ ■■■ Tortoise shell [0269] ■■■ ■■■ Tortoise shell [0270] ■■■ ■■■ Turtle shell [0271] ■■■ The dyes contained in these microcapsules of the present invention can be easily removed by flowing out into a normal color processing solution, or simply by processing with an alkaline aqueous solution at any time. will be removed. Also, some of these dyes can be decolorized or bleached during processing so that it is not necessary to completely remove them.

As the wall material of the microcapsules of the present invention, a polymer that dissolves at a pH of 7 or higher, preferably 8 or higher is preferably used.

Such a wall film of an alkali-soluble polymer may be dissolved and eluted from the silver halide photographic material during the development process, or it may not be eluted. Preferably, it is eluted.

In the present invention, the polymers contained and advantageously used as the wall material of microcapsules include:
Polymer compounds such as vinyl polymers and condensed polymer compounds that have carboxyl groups, sulfonic acid groups, etc. in their side chains; for example, vinyl polymers have carboxyl groups in their side chains, such as methacrylic acid, acrylic acid, vinyl sulfonic acid, etc. , a monomer having a sulfonic acid group and a monomer such as acrylic esters such as methyl methacrylate and ethyl methacrylate, styrenes such as styrene and α-methylstyrene, and vinyl ketones such as vinyl methyl ketone. Examples include copolymers (the composition ratio of the monomer having a carboxyl group or sulfonic acid group in the side chain and other monomers is preferably 40:60 to 70:30 (weight ratio)),
In addition, as condensation polymer compounds, lysine and terephthaloyl chloride, adivic acid chloride,
Examples include condensates with polyvalent carboxylic acid chlorides such as sebacyl chloride. In addition to these, examples include carboxyl group-containing cellulose derivatives having a carboxyl group in the molecule.

In the present invention, the polymer contained and used as the wall material of the microcapsules is more specifically a vinyl polymer methacrylic acid (MAA)-methyl methacrylate (MMA) copolymer (MAA/MMA=40 /60-70/30 (wt%)), methyl acrylate (MA)-ethyl methacrylate (MAE) copolymer (MA/MAE = 40/
Copolymers of acrylic acid or methacrylic acid and acrylic esters or methacrylic esters, such as 60 to 70/30 (wt%), and carboxyl groups or sulfonate copolymers such as vinyl sulfonic acid-methacrylic ester copolymers. vinyl polymers having carboxyl groups or their salts, condensation polymers of lysine and acid chlorides such as terephthaloyl chloride, which have carboxyl groups in the molecule, and cellulose derivatives that have carboxyl groups in the molecule. It is mentioned as one that can be used advantageously.

The thickness of the wall material of the microcapsule according to the present invention can be freely changed depending on the solubility of the wall material and the purpose. For example, the film thickness can be arbitrarily selected from the viewpoint of preventing damage to photographic performance during storage and preventing dye from remaining after processing. Furthermore, in order to control the time during which the dye in the core material non-repairs or flows out during the treatment process, the thickness of the wall material can be changed depending on the purpose, such as changing the thickness of the wall material.

Moreover, the decolorization or outflow of these core material materials can be controlled not only by the wall material film thickness but also by selecting and using polymers with different dissolution rates.

The shape of the microcapsules according to the present invention may be spherical, cubic, columnar, acicular, flat, or blocky, but preferably uniform spherical.

The average particle size of the microcapsules according to the present invention is
The thickness is preferably 10 μm or less. More preferably, it is 5 μm or less, more preferably 1 μm or less, and most preferably 0.5 μm or less.

Next, a method for manufacturing microcapsules used in the present invention will be explained.

Methods for producing microcapsule particles can be roughly divided into two. One is interfacial polymerization using emulsification such as electroemulsification, and the other is so-called micelle polymerization, in which polymerization is performed after forming micelles. It is not possible to use both methods for all core materials when encapsulating the core material. That is, in the interfacial polymerization method, for example, it is impossible to use a core material that easily reacts with acid chlorides, and in the micelle polymerization method, a core material that prevents radical reactions cannot be used.

The method for producing microcapsules is described by G.
Birrenback, PPSpeiser, Journal of
Pharmaceutical Sciences, 65(12) p1763-1766 (1976
), P. Tulkens, M. Roland, A. Trouet,
P.Speiser, FEBS Letters, 84(2) p.323 (1977)
Micelle polymerization method by P.Speiser et al. described in P.Courreur, A.Watanabe, K.Higashitsuji, K.
Nishizawa, Journal of Colloid and
Interface Science, (Journal of Colloid and Interface Science) 64(2)
p.278 (1978), M.Arakawa, T.Kondo,
Canadian Journal of Physiology and
Pharmacolo-gy, (Canadian Journal of Physiology and Pharmacology) 58(2)
An interfacial polymerization method using electroemulsification as described on p. 186 (1980) is advantageously used.

In the light-sensitive material of the present invention, the microcapsules include a hydrophilic colloid layer containing a photosensitive silver halide emulsion layer on the same side as the photosensitive silver halide emulsion layer on the support, and a photosensitive silver halide emulsion layer on the same side as the photosensitive silver halide emulsion layer on the support. At least one of the hydrophilic colloid layers opposite the emulsion layer
Contained in the layer. That is, the layers containing the microcapsules are a photosensitive silver halide emulsion layer, a non-photosensitive hydrophilic colloid layer such as a protective layer, an intermediate layer, a subbing layer, etc. It may be optionally included in the non-photosensitive hydrophilic colloid layer furthest from the body or in the non-photosensitive hydrophilic colloid layers on both sides of the photosensitive silver halide emulsion. When it is contained in a non-photosensitive hydrophilic colloid layer, the layer is preferably a non-photosensitive hydrophilic colloid layer adjacent to a photosensitive silver halide emulsion layer.

In the present invention, in order to incorporate microcapsules into a hydrophilic colloid layer, the produced microcapsules may be added to a coating composition for the hydrophilic colloid layer, uniformly dispersed, and applied. The amount of microcapsules added at this time can be changed as appropriate depending on the purpose, taking into consideration optical density and the like.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains conventional halides such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Any of those used in silver photographic emulsions are included and prepared by known methods.

A silver halide photographic emulsion in which the above-mentioned silver halide grains are dispersed in a binder liquid can be sensitized with a chemical sensitizer. Chemical sensitizers that can be advantageously used in combination in the present invention are roughly classified into four types: noble metal sensitizers, sulfur sensitizers, selenium sensitizers, and reduction sensitizers.

As the noble metal sensitizer, gold compounds and compounds such as ruthenium, rhodium, palladium, iridium, and platinum can be used.

In addition, when using a gold compound, ammonium thiocyanate and sodium thiocyanate can be used in combination.

As the sulfur sensitizer, in addition to activated gelatin, sulfur compounds can be used.

As selenium sensitizers, active and inactive selenium compounds can be used.

As the reduction sensitizer, monovalent tin salts, polyamines, bisalkylaminosulfides, silane compounds, isinoaminomethanesulfinic acid, hydrazinium salts, and hydrazine derivatives can be used.

Various sensitizing dyes can be used, and methine dyes and styryl dyes such as cyanine, merocyanine, hemicyanine, rhodacyanine, oxonol, and hemioxonol, which are known as sensitizing dyes, are advantageously used in the present invention. Can be mentioned. These sensitizing dyes can be used singly or in combination of two or more.

The optimal concentration of sensitizing dye used in the present invention can be determined according to methods known to those skilled in the art.

The amount of sensitizing dye to obtain supersensitization in the present invention is not particularly limited, but is about 2 ml per mole of silver halide.
Advantageously, a range of sensitizing dyes from x10 ^-6 moles to about 1 x10 ^-3 moles is used. Particularly advantageous are 5
The range is from ×10 ^-6 mol to 1 × 10 ^-5 mol.

In the present invention, stabilizers commonly used in the silver halide emulsion layer, such as 4-hydroxy-6
-Methyl-1,3,3a,7-tetrazaindene and 4-hydroxy-cyclopentano[f]-1,3,3a,7-tetradeindene, 5-phenyl-1-mercapto as described in U.S. Pat. No. 2,444,607 Tetrazole, 2-mercaptobenzothiazole, etc. can be contained.

Furthermore, the silver halide emulsion contains development accelerators such as polyalkylene oxide and its derivatives,
Quaternary ammonium salt compounds, 1,4-thiazine derivatives, pyrrolidine derivatives, urethanes, urea compounds, thiourea compounds, imidazole or imidazoline derivatives, phosphorus or sulfur onium salts described in U.S. Pat. No. 2,288,226, etc. can be used. can.

The hydrophilic colloid layer (including the photographic emulsion layer) of the silver halide photographic light-sensitive material of the present invention may contain a surfactant alone or in combination.

As a surfactant, it can be used as a coating aid, an emulsifier, a permeability improver for processing liquids, an antifoaming agent, an antistatic agent, an anti-adhesive agent, and a material for improving photographic properties or controlling physical properties. Natural products such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glycidal, higher alkylamines, pyridine and other heterocycles, quaternary nitrogen onium salts, and cationic interfaces such as phosphonium or sulfonium. activator,
Various active agents can be used, such as anionic surfactants containing acidic groups such as carboxylic acid, sulfonic acid, phosphoric acid, sulfuric acid ester groups, and phosphoric acid ester groups, and amphoteric surfactants such as amino acids and aminosulfonic acids.

The hardening treatment of the hydrophilic colloid layer can be carried out according to a conventional method. Hardeners used include conventional photographic hardeners, such as aldehyde compounds such as formaldehyde, glyoxal, and glutaraldehyde, and derivative compounds thereof such as acetals or sodium bisulfite adducts;
Metasulfonic acid ester compounds, mucochloric acid or mucohalogen acid compounds, epoxy compounds, aziridine compounds, active halogen compounds, maleic acid imide compounds, active vinyl compounds, carbodiimide compounds, isoxazole compounds, N- Examples include inorganic hardeners such as methylol compounds, isocyanate compounds, chromium alum, and zirconium sulfate.

In addition to these, the hydrophilic colloid layer also contains a plasticizer,
It can contain additives having various functions for improving the quality of photographic materials, such as antistatic agents, ultraviolet absorbers, and antioxidants.

When the silver halide photosensitive material of the present invention is used for color use, a commonly used coupler can be incorporated into the photosensitive material. That is, examples of diffusion-resistant magenta couplers include compounds such as pyrazolotriazole, pyrazolinobenzimidazole, indazolone, and pyrazolone. As pyrazolone magenta couplers, U.S. Patent No. 2600788, U.S. Patent No. 3062653, and U.S. Patent No. 3127269
No. 3311476, No. 3419391, No.
No. 3519429, No. 3558318, No. 3684514, No. 3888680, JP-A-49-29639, JP-A-49-
No. 111631, JP-A-49-129538, JP-A-50-
No. 13041, patent application No. 1983-24690, patent application No. 134470
Examples include compounds described in Japanese Patent Application No. 50-156327. Pyrazolotriazole magenta couplers include compounds described in British Patent No. 1247493 and Belgian Patent No. 792525; pyrazolinobenzimidazole magenta couplers include U.S. Patent No. 3061432 and West German Patent No. 2156111.
Compounds described in Japanese Patent Publication No. 46-60479,
Furthermore, as an indazolone magenta coupler,
The compounds described in Belgian patent no. 769116 are used.

Examples of diffusion-resistant yellow couplers include known open-chain ketomethylene compounds, such as benzoylacetanilide type yellow couplers and pivaloylacetanilide type yellow couplers. More preferred are two-equivalent type yellow couplers in which the carbon atom at the coupling position is substituted with a substituent that can leave during the coupling reaction. Examples of these are U.S. Pat. No. 2,875,057;
No. 3265506, No. 3664841, No. 3408194, No. 3447928, No. 3277155, No. 3415652,
JP-A-49-13576, JP-A-48-29432, JP-A-Sho
No. 48-66834, JP-A-49-10736, JP-A-49-
No. 122335, Japanese Patent Application Publication No. 1983-28834, Japanese Patent Application Publication No. 1973-
It is described in issues such as No. 132926.

Phenol or nitol derivatives are generally used as diffusion-resistant cyan couplers. Examples include U.S. Patent Nos. 2423730 and 2474293.
No. 2801171, No. 2895826, No. 2895826, No. 2801171, No. 2895826, No.
3476563, 3737316, 3758308, 3839044, JP-A-47-37425, JP-A-50-
No. 10135, JP-A-50-25228, JP-A-50-112038
No., JP-A-50-117422, JP-A-50-130441,
U.S. Patent No. 2369929, U.S. Patent No. 2474293, U.S. Patent No.
No. 3591383, No. 2895826, No. 3458315, No. 3311476, No. 3419390, No. 3476563,
3253924 and UK Patent No. 1201110, US Patent No. 3034892, US Patent No. 3386301 and US Patent No.
It is described in No. 2434272, etc.

The amount of each diffusion-resistant coupler mentioned above is generally 2x per mole of silver in the light-sensitive silver halide emulsion layer.
10 ⁻³ mol to 5×10 ⁻¹ mol, preferably 1×
The amount is 10 ^-2 mol to 5×10 ^-1 mol.

When applying the present invention to color negative film,
It is preferable for color reproduction to contain a DIR compound.

DIR compounds can be divided into those in which the component capable of reacting with the oxidized form of a color developing agent has a development inhibiting component directly, and those in which the component capable of reacting with the oxidized form of a color developing agent has a development inhibiting component via a timing group. Here, the latter DIR compound is preferably represented by the following general formula (1).

General formula (1) A-TIME-Z In the formula, A is a component that can react with the oxidized form of the color developing agent, and reacts with the oxidized form of the color developing agent to produce TIME.
Any component may be used as long as it can release the -Z group.

TIME is a timing group, and Z is a component that suppresses development by being released from the timing group. Specific examples of TIME include intramolecular nucleophilic substitution reactions as described in JP-A No. 54-145135, and electron transfer along a conjugated chain as described in JP-A-56-114946. Well, in short, first the A-TIME bond is broken and TIME-Z is released, and then the TIME-Z bond is broken and Z is released.
Any compound that releases can be used. Z contains a development inhibiting component as described in Research Disclosure, No. 17643 (1978), preferably mercaptotetrazole, selenotetrazole,
Included are mercaptobenzothiazole, selenobenzothiazole, mercaptobenzoxazole, selenobenzoxazole, mercaptobenzimidazole, selenobenzimidazole, benzotriazole, benzodiazole, and derivatives thereof.

On the other hand, a preferred DIR compound in which the component capable of reacting with the oxidized form of a color developing agent has a direct inhibitory component is represented by the following general formula (2).

General formula (2) B-Y In the formula, B is a component that can react with the oxidized form of the color developing agent, and releases Y (development inhibiting component) by reacting with the oxidized form of the color developing agent. As Y, a development inhibiting component represented by general formula (1) can be used.

DIR compounds in which the component capable of reacting with the oxidized form of the color developing agent has a direct inhibitory component are disclosed in U.S. Patent Nos. 3958993, 3961959, and 3938996;
JP-A-50-147716, JP-A No. 50-152731, JP-A No. 51-
105819, US Patent No. 51-6724, US Patent No. 52-46817, US Patent No. 3928041, US Patent No. 3227554, US Patent No. 3773201
No. 3632345, British Patent No. 2010818, and Japanese Patent Application Laid-open No. 52-49030.

A in the above general formula (1) and B in the general formula (2) include those that react with the oxidized product of the color developing agent to form a dye and those that do not.

Various methods can be used to disperse the diffusion-resistant coupler and DIR compound, such as the so-called alkaline aqueous dispersion method, solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. The dispersion method can be appropriately selected depending on the chemical structure, etc., and the latex dispersion method and the oil-in-water emulsion dispersion method are particularly effective. These dispersion methods have been well known, and the latex dispersion method and its effects have been described in Japanese Patent Application Laid-open Nos. 49-74538, 51-59943, and
54-32552, Research Disclosure, August 1976, No. 14850,
Described in paragraphs 77-79.

When the present invention is applied to a multilayer color photographic material, the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer used in the silver halide photographic material are Each desired photosensitivity can be obtained by using a sensitizing dye, a filter layer, etc. in a conventionally known manner. Each silver halide emulsion layer can be made to have a desired spectral wavelength sensitivity by using a filter layer containing microcapsules according to the present invention on the spectral sensitized emulsion layer. Further, each silver halide emulsion layer can contain microcapsules according to the present invention.

In addition to the silver halide emulsion layer, filter layer, and antihalation layer, the silver halide photographic material of the present invention may optionally be provided with auxiliary layers such as a protective layer, an intermediate layer, and a back layer.

As the support, conventionally known supports such as plastic film may be selected as appropriate depending on the purpose. These supports are generally subjected to a subbing process to enhance adhesion with the photographic emulsion layer.

The surface of the support may be subjected to corona discharge, infrared irradiation, flame treatment, etc. before or after undercoating.

In the silver halide photographic material of the present invention,
The silver halide emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by known coating methods.

As the coating method, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. are used.

The silver halide photographic material of the present invention can be effectively applied to various silver halide photographic materials for X-ray, color, monochrome, transfer, high contrast, and the like.

There are no particular limitations on the processing method for the silver halide photographic material of the present invention, and the processing method used is usually PH7.
Any known processing method including the above-mentioned processing steps, such as a black-and-white development method or a color development method, can be applied.
For example, typical methods include activator treatment, a method in which bleach-fixing is performed after color development, followed by further washing with water and stabilization treatment if necessary, and a method in which bleaching and fixing are performed separately after color development, and as necessary. Depending on the situation, further washing with water and stabilizing treatment may be performed: or a method of pre-hardening, neutralization, color development, stop fixing, washing with water, bleaching, fixing, washing with water, post-hardening, washing with water, color development, washing with water, supplementary color development. developing,
A method in which stopping, bleaching, fixing, washing, and stabilizing are performed in this order; a developing method in which developed silver produced by color development is bleached with halogenation, and then color development is performed again to increase the amount of dye produced; peroxide The processing may be performed using any method, such as a method of processing a low silver content light-sensitive material using an amplifier fire agent such as a cobalt complex salt or a cobalt complex salt.

Next, the silver halide photographic material of the present invention will be specifically explained with reference to Examples.

Example 1 Samples 1, 2, 3 and 4 were prepared by coating a support with a solution containing a dye prepared as described below.

Sample-1 Sample-1 was prepared by dissolving 1 g of Exemplary Dye Y-3 in 500 ml of a 5% aqueous gelatin solution containing 0.3 g of sodium triisopropylnaphthalene sulfonate and applying the solution to a dry film thickness of 1.0 μm.

Sample-2 12.0 g of sulfosuccinic acid bis-2-ethylhexyl ester sodium salt and 6.0 g of polyoxyethylene-4-lauryl ether were added to 80 ml of n
-Soluble in hexane. Then, a solution of 2 g of Exemplary Dye Y-3 dissolved in 40 ml of distilled water was slowly added and stirred thoroughly.

The mixed solution is transferred to a cylindrical double-walled reaction vessel. Next, while stirring well, add 0.1 g of N,N'-methylenebisacrylamide and methacrylic acid.
Add 10 g of sodium riboflavin-5'-phosphate and 1 mg of potassium persulfate and dissolve. and 35± under nitrogen atmosphere with constant stirring.
Light is irradiated at a temperature of 5° C. for 7 to 10 hours until the monomer disappears. N-hexane is distilled off from the resulting microcapsule suspension under reduced pressure, water is then added, the surfactant is removed by ultrafiltration, and the capsules are isolated by centrifugation. The size of the obtained microcapsule particles was 100 to 300 nm. Sample 2 was prepared by adding the microcapsule particles to 500 ml of a 5% aqueous gelatin solution containing 0.3 g of sodium triisopropylnaphthalene sulfonate and applying the solution to a dry film thickness of 1.0 μm.

Sample-3 Sample-3 was prepared by applying an aqueous gelatin solution containing microcapsules containing exemplary dye M-1 to a dry film thickness of 1.2 μm according to the same procedure as Sample-2.

Sample-4 Sample-4 was prepared by applying an aqueous gelatin solution containing microcapsules containing exemplary dye C-4 to a dry film thickness of 1.2 μm according to the same procedure as Sample-2.

These samples were subjected to the following two treatments and the residual rate of the dye was measured. The optical density at the maximum absorption wavelength measured before coating is _d1 , and the optical density at the maximum absorption wavelength measured after treatment is _d2 , and the residual rate is expressed as D= _d2 / _d1 ×100, and the results are shown in Table 1. It was shown to.

Treatment-1 Each sample is immersed in running water at a temperature of 20°C and PH6.8 for 5 minutes.

Treatment-2 Each sample is immersed and stirred in an aqueous solution with a pH of 10.0 and a temperature of 38°C for 3 minutes.

■■■ Tortoise shell [0016] ■■■ As shown in Table 1, the samples of the present invention remain in the coating layer in running water with a pH of 6.8, easily flow out of the coating layer in an alkaline solution, and are difficult to coat. It can be seen that there is no residual color staining in the coated layer.

Example 2 Samples 5, 6 and 7 were prepared by sequentially coating the following layers on a support from the support side.

Sample-5 Layer-1... Green-sensitive silver halide emulsion layer Magenta coupler 1-(2,4,6-trichlorophenyl)-3 in tricresyl phosphate
A dispersion of -[3-{α-(2,4-di-tert-amylphenoxy)-acetamide}benzamide]-5-pyrazolone was added to a green-sensitive silver iodobromide emulsion, and 10 mg/dm ² of silver was added. I applied it to make it look like this.

Layer-2...Protective layer A gelatin aqueous solution containing 0.3g of sodium triisopropylnaphthalene sulfonate is dried to a film thickness of 1.0μ.
It was applied so that

Sample-6 Layer-1... Green-sensitive silver halide emulsion layer Adjustment coating was carried out in the same manner as Layer-1 of Sample-5.

Layer-2...Yellow filter layer The dry film thickness of the adjustment solution used in Sample-1 of Example 1
It was applied to a thickness of 1.0μ.

Sample-7 Layer-1... Green-sensitive silver halide emulsion layer Adjustment coating was carried out in the same manner as Layer-1 of Sample-5.

Layer-2...Yellow filter layer The dry film thickness of the adjustment solution used in Sample-2 of Example 1
It was applied to a thickness of 1.0μ.

A step wedge was passed through each of these samples, and an interference filter KL-44 manufactured by Toshiba Chemical Industries, Ltd. was applied.
and KL-54 for exposure and the following processing.

Processing process (38℃) Processing time Color development...3 minutes 15 seconds Bleaching...6 minutes 30 seconds washing...3 minutes 15 seconds fixation...6 minutes 30 seconds water washing...3 minutes 15 seconds stabilization 1 minute 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

Color developing composition: 4-amino-3-methyl-Nethyl-N(β-
Hydroxyethyl)-aniline sulfate 4.8g Anhydrous sodium sulfite 0.14g Hydroxyamine 1/2 sulfate 1.98g Sulfuric acid 0.74mg Anhydrous potassium carbonate 28.85g Anhydrous potassium bicarbonate 3.46g Anhydrous potassium sulfite 5.10g Potassium bromide 1.16g Chloride Sodium 0.14g Nitrilotriacetic acid trisodium salt (monohydrate)
1.20g Potassium hydroxide 1.48g Add water to make 1.

Bleach composition: Ethylenediaminetetraacetate iron ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt
10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to adjust to 1 and use ammonia water to pH
Adjust to 6.0.

Fixer composition: Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to 1 and adjust to PH6.0 using acetic acid.

Stabilizing liquid composition: Formalin (37% aqueous solution) 1.5ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.)
Add 7.5ml water to make 1.

Next, the sensitivity was measured for the color images formed on the sample and comparative sample. The result is the second
Shown in the table.

■■■ Turtle shell [0017] ■■■ When the sensitivity of sample-5 was set as 100, the sensitivity of each sample was compared relative.

As shown in Table 2, the blue sensitivity of sample 6 when exposed to light with the KL-44 filter is only 20% lower than that of sample 5, which is due to the dye contained in the second layer. Due to the first diffusion, the second layer does not function adequately as a filter layer. On the other hand, in Sample-7 of the present invention, it is clear that the second layer functions sufficiently as a filter layer, and there is no difference in green sensitivity compared to the comparison.

Claims (1)

[Claims] 1 In a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, the hydrophilic colloid layer serves as a core material and is removed and decolorized during the development process of the silver halide photographic light-sensitive material. Alternatively, a silver halide photographic light-sensitive material comprising a bleaching dye and containing microcapsules formed from a substance that can be dissolved in an alkaline aqueous solution as a wall material.