JPS59113434A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having a filter layer, etc. not causing any adverse effect on photographic performance due to decoloration and elution during photographic processing by using a hydrophilic colloidal layer having microcapsules consisting of the core material of a dye and a substance soluble in an alkaline soln., as a shell material. CONSTITUTION:A silver halide photosensitive material has at least one hydrophilic collodial layer on a support, and this layer contains microcapsules consisting of a dye as the core material and an alkaline soln. -soluble substance, such as methacrylic acid methacrylate copolymer, as the shell material. A photosensitive material having a filter layer and/or an antihalation or irradiation preventing layer is obtained. It does not cause any adverse effect on photographic performance due to single decoloration or elution during photographic processing.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a 710 silver germide photographic material having a novel filter layer or /S lation prevention layer.

Generally, silver halide photographic light-sensitive materials have a hydrophilic colloid layer including a light-sensitive silver halide emulsion layer on a support, and an image is recorded on the light-sensitive silver halide emulsion layer. When imagewise exposure is carried out for the purpose of achieving this, it may be necessary to control the spectral composition of the light incident on the light-sensitive silver halide emulsion layer. In such cases, a hydrophilic colloid layer that is located farther from the support than the photosensitive silver halide emulsion layer is usually filled with a substance (colored A method is used in which a so-called filter layer is provided (method □) in which only light in the target wavelength range is transmitted.

In addition, the light transmitted through the photosensitive silver halide emulsion layer is reflected at the interface between the photosensitive silver halide emulsion layer or the interface between the support and a hydrophilic colloid layer adjacent to the support, resulting in photographic performance. This will have an undesirable effect on the person. 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 reflected light □Providing a so-called antihalation layer Method □ is used.

In addition, the light-sensitive silver halide emulsion layer contains a substance (coloring component) that can absorb scattered light to prevent light scattering in the light-sensitive silver halide emulsion layer and prevent a decrease in image sharpness. Methods to prevent irradiation are also used.

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

(2) It must have an 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, and (+1) it must have a negative effect on photographic performance, such as decreased sensitivity, latent image regression, etc. (3) The generation of capri, etc. should not occur (3) The color should not be bleached during the photographic processing process or be eluted out of the system of the photosensitive material during any of the processing steps and have an adverse effect on the photographic performance after the photographic processing (in other words, no residual Many efforts have been made to find dyes that meet these conditions.For example, oxonol dyes having a pyrazolone nucleus, typified by the dye described in British Patent No. 506.385; Oxonol dyes having a barbylic acid nucleus represented by the dyes described in U.S. Patent No. 3,247.127, U.S. Patent Nos. 2,533.472 and 3,379,533, British Patent No. 1, 278,62
Other oxonol dyes such as those described in U.S. Pat. No. 1, styryl dyes as described in U.S. Pat. 493.747, U.S. Patent No. 2,843,48
Examples include cyanine dyes described in No. 6.

Examples of dyes that are bleached during photographic processing include those described in British Patent No. 506.385.

If the colored layer containing the above dye is a single filter layer or an antihalation layer placed on the same side of the support as the light-sensitive silver halide emulsion layer, those layers are selectively colored. There is no need for coloring to substantially extend to other layers. This is because coloration in the pond layer not only has harmful spectral effects on other layers, but also reduces its 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. 685.47'5, reaction products of polyvinyl alkyl ketones and aminoguanidine as described in British Patent No. 850.281, and U.S. Pat. Polymers from 2-methyl-1-vinylimidazole are known, as described in Patent No. 3445.231.

When mordanting with polymers as described above is carried out, diffusion of the dye from the dye-containing layer to the pond layer in the wet state is often observed. This diffusion may be due to the chemical structure of the mordant, but it also depends on the chemical structure of the dye itself. It is often based on

1) When a polymer mordant such as the one described above is used, after photographic processing, particularly in the case of rapid processing, residual color due to the dye is likely to occur on the photographic material. The reason for this is that the bonding force between the mordant and the dye is considerably reduced in an alkaline liquid such as a liquid, but some bonding force remains, which may cause the dye to remain in the photographic layer or cause difficult color restoration. This is thought to be because a decolorizing product is generated in the layer.

These disadvantages are largely due to the chemical structure of the mordant and, in particular, 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-restorative bleaching or elution during photographic processing, and does not have an adverse effect on photographic performance. and/or to provide a photographic material having an antihalation (irradiation) layer.

The object is to provide a silver halide photographic material having at least one hydrophilic colloid layer on a support, wherein the hydrophilic colloid layer has a dye as a core material and is soluble in an alkaline solution as a wall material. It has been found that this can be achieved by a silver halide photographic material containing microcapsules (hereinafter referred to as microcapsules of the present invention) formed from a substance.

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. 3
No. 85, No. 1,521,083, U.S. Patent No. 2.4
09, No. 61.2, No. 2, 527.

No. 583, No. 2,538,009, No. 2,865
, No. 752, No. 2,956,879, No. 3,01
No. 6,306, No. 3,148,187, No. 3,2
No. 47,127, No. 3,260.601, No. 3,
No. 282,699, same No. 3. ．． No. 384,487, No. 3,423,207, No. 3,637,676, No. 4,187,225, Special Publication No. 39-22069,
No. 43-131.68, JP-A No. 48-68623,
No. 48-85130, No. 49-114420, No. 5
No. 0-91627, No. 51-3623, No. 51-77
It is described in No. 327, etc.

For example, pyrazolone oxonol dyes represented by the dyes described in U.S. Pat. No. 2,274,782, oxonol dyes having barbyl nuclei represented by the dyes described in U.S. Pat. No. 3,247,127, The pond oxonol dyes as described in U.S. Pat. No. 2,533,472, U.S. Pat.
Diallylazo dyes typified by the dyes described in U.S. Patent Nos. 2,298.733 and 3,423,20
No. 7, 3.384.487, merocyanine dyes as described in U.S. Pat. No. 2,527.583, British Patent No. 384.609, Hemioxonol dyes represented by dyes such as U.S. Pat. No. 2,843,48
Examples include cyanine dyes typified by the dyes described in No. 6.

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

Exemplary dye Yellow dye -1 -2 03Na -3 -4 75 -6 Magenta dye -1 So3K So, Ni -2 M-3 -4 b IJ 3 m -5 -5 1-1 Cyan dye -1 bsu35 d
U35-2 -3 -4 The dyes contained in these microcapsules of the present invention can be easily removed by flowing out into a common color processing solution, or simply by treating with an alkaline aqueous solution at any time. will be removed. However, some of these dyes can be decolored or bleached during processing, so it is not necessary to completely remove them.

The wall material of the microcapsules of the present invention has a pH of 7.
As mentioned above, polymers that dissolve at pH 8 or higher are preferably used.

The wall film of such alkali-converting polymer may or may not be eluted from the silver halogenide photographic light-sensitive material by hexalysis during the development process.

Preferably, it is flanged.

In the present invention, polymers contained and advantageously used as the wall material of microcapsules include polymeric compounds such as vinyl polymers and condensed polymeric compounds having carboxyl groups, sulfonic acid groups, etc. in side chains, such as vinyl polymers. As a combination, monomers having a carboxyl group or sulfonic acid group in the side chain such as methacrylic acid, acrylic acid, and vinyl sulfonic acid, acrylic acid esters such as methyl methacrylate and ethyl methacrylate, styrene, and α-methyl Examples include copolymers with monomers such as styrenes such as styrene and vinyl ketones such as vinyl methyl ketone (monomers with a carboxyl group or sulfonic acid group in the side chain, and copolymers with other monomers). The composition ratio is 40:60 to 70:30
(weight ratio) is preferable. ), and condensation polymer compounds include condensates of lysine and polyvalent carboxylic acid chlorides such as terephthaloyl chloride, adipic acid chloride, and sepatic acid chloride. Examples of these 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 methacrylic acid (MAA)-methyl methacrylate (MMA) copolymer (MAA/MMA), which is a vinyl polymer.
= 40/60 to 70/30 (wt%)), methyl acrylate (MA) - ethyl methacrylate (M
AE) copolymer (MA, / MAFi = 40
/ 60 to 70 / 30 (weight ratio)), a copolymer of acrylic acid or methacrylic acid and an acrylic ester or methacrylic ester, a carboxyl group such as a vinyl sulfonic acid-methacrylic ester copolymer, or Vinyl polymers that have sulfo groups or their salts, condensation polymers of lysine and acid chloride such as terephthaloyl chloride that have carboxyl groups in their molecules, and cellulose that has carboxyl groups in their molecules. Derivatives and the like are mentioned as those which are advantageously used.

The thickness of the wall material of the microcapsule according to the present invention can be freely changed depending on the atrial nature of the wall material and the purpose. Shi0
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. In addition, the thickness of the wall material can be changed depending on the purpose, such as changing the thickness of the wall material, in order to control the time during which the dye in the core material flows out in a non-restorative manner. .

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

The shape of the microcapsules according to the present invention may be spherical, cubic, columnar, acicular, flat, or lump-like, but
Preferably, it has a uniform spherical shape.

The average particle size of the microcapsules according to the present invention is preferably 10 μm or less. More preferably, the sail length is 5 μm or less, more preferably 1 μm or less, and most preferably 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 by electric 7L conversion, and the other is so-called micelle polymerization in which polymerization is performed after micelle formation. 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, a core material that easily reacts with acid chlorides cannot be used, 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. Birrenba.
ck.

P, P, 5peiser, Journal of P
pharmaceutical science, s,
(Pharmaceutical Science) 65 (12)
p 1763-1766 (1976), P, Tu
lkens, M., Roland, A. Trouet
, P, 5peiser.

F, E, B, S, Letters, (F.E.
Be Nis Letters) 84 (2) p. 323 (
1,977) p, 5p described in P, Courreur
Micelle polymerization method by Eiser et al., A. Watan
abe, K., Higashitsuji, K., Ni
N15hiza.

Journal of Co11oid and Engineering
erface 5science.

(Journal of Colloid and Interface Science) 64 (2) P, 278 (1978), M
, Arakawa, T., Kondo, C! anad
ian's journey of Physiology
An interfacial polymerization method using electroemulsification as described in Canadian Journal of Pharmacolo-gy, 58 (2) p. 183 (1980) is advantageously used.

In the photosensitive forest 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, It is contained in at least one hydrophilic colloid layer on the opposite side to the photosensitive silver halide emulsion layer. That is, the layer containing the microcapsules is a photosensitive silver halide emulsion layer,
A non-photosensitive hydrophilic colloid layer ψ is a protective layer, an intermediate layer,
A non-photosensitive colloid layer, such as a subbing layer, which is closest to the support, a non-photosensitive hydrophilic colloid layer farthest from the support, or a non-photosensitive hydrophilic colloid on both sides of a photosensitive silver halide emulsion. It is optional to include it in the layer.

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 manufactured 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 halogenated silver 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.

For reduction sensitizers, 111. IiI tin salt, polyamine,
Bisalkylaminosulfide, silane compounds, isinoaminomethanesulfinic acid, hydrazinium salts, and hydrazine derivatives can be used.

Various sensitizing dyes can be used, and known sensitizing dyes advantageously used in the present invention include cyanine, merocyanine, hemicyanine, rhodacyanine,
Examples include methine dyes and styryl dyes such as oxonol, hemioki, and sonol. These sensitizing dyes are 1
Each species can be used individually or two or more species can be used in combination.

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 approximately 2X 1.0- per mole of silver halide.
It is advantageous to use a sensitizing dye in the range from 'molar to about I x 10-s molar. Particularly advantageous is 5X i
It ranges from ff' moles to IX 10-5 moles.

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 U.S. Pat.
4-hydroxy-cyclopentano[f]-1,3,3a, 7-tetrazaindene, 5-
Phenyl-1-mercaptotetrazole, 2-mercaptobenzothiazole, etc. can be contained.

Furthermore, the silver halide emulsion contains a development accelerator such as polyalkylene oxide and its derivatives, quaternary ammonium salt compounds, 1,4-thiazine derivatives, pyrrolidine derivatives, urethane, urea compounds, thiourea compounds, and imidazole. or imidacillin derivatives, US Pat. No. 2.2
Onium salts of phosphorus or sulfur described in 88.226 can be used.

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.

Examples of surfactants include coating aids, emulsifiers, permeability improvers for processing liquids, antifoaming agents, antistatic agents, anti-adhesive agents,
Natural products such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glycidal, higher alkylamines, and heterocycles such as pyridine are used as base materials for improving photographic properties or controlling physical properties. cationic surfactants such as quaternary nitrogen onium salts, phosphonium or sulfoniums, anionic surfactants containing acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfuric ester groups, phosphoric ester groups, amino acids, amino acids, etc. Various active agents can be used, including amphoteric surfactants such as sulfonic acids.

The hardening treatment of the hydrophilic colloid layer can be carried out according to a conventional method. Hardeners used include common photographic hardeners, such as aldehyde compounds such as formaldehyde, cryoxal, and glutaraldehyde, derivative compounds thereof such as their acetals or sodium bisulfite adducts, and methanesulfonic acid ester compounds. , mucochloric acid or mucohalogen acid compounds, epoxy compounds, aziridine needles, active halogen compounds, maleic acid imide compounds, active vinyl compounds, carbodiimide compounds, inoxazole compounds, N''''-
Examples include inorganic hardeners such as methylol compounds, isocyanate thread compounds, chrome bright bread, and zirconium sulfate.

The hydrophilic colloid layer can contain additives having various functions for improving the quality of the photographic material, such as plasticizers, 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, pyrazolinopenzimidazole, indacylon, and pyrazolone. As a pyrazolone magenta coupler, US Patent No. 2, . No. 600,788, No. 3,062,6
No. 53, No. 3.127,269, No. 3,311,
No. 476, No. 3, '419.391, No. 3.51
No. 9,429, No. 3.558,318, No. 3. ．．
No. 684,514, No. 3, . 888.680, JP-A-49-29639, JP-A-49-111631,
% Publication No. 49-129538, Japanese Patent Publication No. 13041-1972
No., %Gan Sho 50-24690, %Gan Sho 50-1.34
No. 470 and Japanese Patent Application No. 156327/1980. British Patent No. 1,247,493 as pyrazolotriazole magenta caglar;
The compound pyrazolinopenzimidazole magenta coupler described in Belgian Patent No. 792,525 includes US Pat. 60479
In addition, as the indacylon magenta coupler, the compound described in Belgian Patent No. 769,116 is used.

Diffusion-resistant yellow couplers include well-known open chain ketomethylene compounds such as benzoylacetanilide type yellow couplers and pivaloylacetanilide type yellow couplers. More preferred are two-equivalent yellow couplers in which the carbon atom at the coupling position is substituted with a substituent that can be removed during the coupling reaction.

These columns are from U.S. Patent No. 2,875,057;
．． No. 265,506, No. 3,664.841, No. 3.408,194, No. 3.447.928, No. 3.277.155, No. 3,415,652,
JP-A-49-13576, JP-A-48-29432, JP-A-48-66834, JP-A-49-10736
No., Japanese Patent Publication No. 49-122335, % Publication No. 50-288
No. 34, JP-A-50-132926, etc.

Phenol or nithol derivatives are generally used as diffusion-resistant cyan couplers. For example, U.S. Pat. Nos. 2,423,730 and 2.474,2
No. 93, No. 2,801,171, No. 2.895'
, No. 826, No. 3,476.563, No. 3.73
No. 7,316, No. 3,758.308, No. 3.8
No. 39.044, JP-A-47-37425, JP-A-5
0-10135, JP 50-25228, JP 50-112'038, JP 50-117422, JP 50-130441, U.S. Patent No. 2,369
, No. 929, No. 2,474,293, No. 3,59
No. 1,383, No. 2,895,826, No. 3, 4
No. 58,315, No. 3,311,476, No. 3,
No. 419,390, No. 3.476.563, No. 3
, 253.924 and British Patent No. 1,201,11
No. 0, U.S. Patent No. 3,034,892, U.S. Patent No. 3,38
No. 6,301 and No. 2.434,272, etc.

The usage of each of the above-mentioned diffusion-resistant couplers is generally from p 2 x 10-' moles to 5 x:1. O-1 mol, preferably I
10-'' mole to 5×10-1 mole.

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

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

General formula (1) A=T1M B, Z In the formula, A is a component that can react with the oxidized form of the color developing agent,
Any component may be used as long as it can react with the oxidized color developing agent to release the TIME-2 group.

TIME is a timing group, and 2 is a component that suppresses the phenomenon by being released from the timing group.

The specific sequence of TIME is based on an intramolecular nucleophilic substitution reaction as described in JP-A-5.4-145135, or by electron transfer along a conjugated chain as described in JP-A-56-114946. In short, any compound may be used as long as it first releases TIME-2 when the A-T In bond is broken, and then releases TIME-2 when the TIME-Z bond is broken. 2 contains a development inhibiting component as described in Research Disclosure, A 17643 (1978), preferably mercaptotetrazole, selenotetranol, mercaptobenzothiazole, selenobenzothiazole, mercaptobenzoxazole, seleno. Included are benzoxazole, mercaptobenzimidazole, selenobenzimidazole, benzotriazole, benzodiazole, and derivatives thereof.

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

General formula (2) B -Y In the formula, BI'i 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 release Y (development inhibiting component). . As Y, a development inhibiting component represented by general formula (1) can be used.

The DIR compound in which the component capable of reacting with the oxidized form of the color developing agent has a direct inhibitory component is disclosed in U.S. Patent No. 3,958.
, No. 993, No. 3. '961,959, same No. 3,9
No. 38,996, JP-A No. 5O-i47716, No. 50
-152731, 51-105819, 51-
No. 6724, No. 52-46817, U.S. Patent No. 3.9
No. 28,041, No. 3,227.554, No. 3.
Examples include those described in No. 773,201, No. 3,632.345, British Patent No. 2,010,818, and Japanese Patent Application Laid-open No. 52-49030.

A in the above-mentioned general formula (1) and B in the general formula (2) include those that react with the oxidant of the landlord system and those that do not form a pigment.

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. It can be appropriately selected depending on the chemical structure, etc., but the latex dispersion method and the oil-in-water emulsion dispersion method are particularly effective. These dispersion methods are well known, and the latex dispersion method and its effects are described in Japanese Patent Application Laid-open Nos. 49-74538 and 51-599.
No. 43, No. 54 32552 and Research Disclosure.
e), August 1976, A 14850.77-79
It is described in the section.

When the present invention is applied to a multilayer color photographic material, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer, which are commonly used in silver halide photographic materials, are used. The desired photosensitivity of each emulsion layer can be obtained by using sensitizing dyes, filter layers, etc. in a manner known in the art. Each silver halide emulsion layer is
A desired spectral wavelength sensitivity can be achieved by using a filter layer containing the 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 the silver halide photographic material of the present invention, auxiliary layers such as a protective layer, an intermediate layer, and a back layer may be provided as appropriate in addition to the silver halide emulsion layer, the filter layer, the antihalation layer, and the like.

As the support, a conventionally known support such as a plastic film may be appropriately selected depending on f:lfl.

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 any processing method such as the known black-and-white development method, color development method, etc., which usually involves a processing step at pH 7 or higher, 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 stagnation and fixing are performed separately after color development. , further washing with water and stabilizing treatment as necessary: or pre-hardening, neutralization, color development, stop-fixing, washing with water, bleaching, fixing, washing with water, post-hardening,
A method of performing color development in the order of washing with water, a method of performing color development, washing with water, supplementary color development, stopping, bleaching, fixing, washing with water, and stabilization, a method in which the developed silver produced by color development is bleached, and then color is developed again. Any method can be used, such as a development method that increases the color grade produced by increasing the color density, or a method that treats a low-silver photosensitive material using an amblifier agent such as a peroxide or a co/(rut complex salt). May be processed.

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 1 g of Exemplary Dye Y-3 was dissolved in 5% gelatin water core bath solution 00 TLl containing 0.3 g of sodium triisopropylnaphthalene sulfonate, and applied to a dry film thickness of 1.0 μm. -1 was created.

Sample-2 12, OF sulfosuccinic acid bis-2-ethylhexyl ester sodium salt and 6.0 g of polyoxyethylene-4-lauryl ether were added to 80 Jul of n-
Dissolve in hexane. Then, 4f) slowly add 2 g of Exemplary Dye Y-3 to mA' of distilled water,
Stir thoroughly.

The mixed bath liquid is transferred to a cylindrical double-walled reaction vessel. Next, while stirring well, 001 g of N,N'-methylenebisacrylamide and 109 g of methacrylic acid are added, and further 1 m9 of sodium riboflavin-5'-phosphate and potassium persulfate are added and dissolved. Then, the mixture is constantly stirred and irradiated with light under a nitrogen atmosphere at a temperature of 35±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 added thereto, the surfactant is removed by ultrafiltration, and the capsules are isolated by centrifugation. The size of the obtained microcapsule particles was 100-300 nm.

Sample 2 was prepared by adding the microcapsule particles to 500 microcapsules of 5% aqueous gelatin solution containing 0.3 g of sodium triisopropylnaphthalene sulfonate and coating the solution to a dry film thickness of 1.0 μm.

Sample-3 Following the same procedure as Sample-2, a gelatin aqueous solution containing microcapsules containing exemplary dye M-1 was added to a dry film thickness of 1.
Sample 3 was prepared by applying the solution to a thickness of 2μ.

Sample-4 Following the same procedure as Sample-2, a gelatin aqueous solution containing microcapsules containing Exemplary Dye 0-4 was added to a dry film thickness of 1.
Sample 4 was prepared by applying the coating to a thickness of 2μ.

These samples were subjected to the following two treatments and the residual rate of the dye was measured. The optical density at the thickest absorption wavelength measured before coating was d1, and the optical density at the thickest absorption wavelength measured after the treatment was d2, and the residual rate was shown in Table 11.

Treatment-1 Each sample is immersed in running water at a temperature of 6.8C and pH 6.8 for 5 minutes.

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

Table 1 As shown in Table 1, the sample of the present invention remains in the coated layer in running water with a pH of 6 or 8, easily flows out of the coated layer in an alkaline solution, and remains in the coated layer. It can be seen that there is no indication of color contamination.

Example 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 containing magenta coupler 1-(2,4
,6-)lichlorophenyl)-3-[3-(α-(2,
4-tert-amylphenoxy)-acetamide)
A dispersion of [penzamide]-5-pyrazolone was added to a green-sensitive silver iodobromide emulsion and coated to give a silver density of 10 to 10 dm<2>.

Layer-2...Protective layer Sodium triingrovir naphthalene sulfonate 0.
A gelatin aqueous solution containing 3 g was applied to give a dry film thickness of 1.0 μm.

Sample-6 Layer-1...Green-sensitive Rogge/Silver Fide Emulsion Layer Sample-
Adjustment coating was carried out in the same manner as Layer 5-1.

Layer-2...Yellow filter single layer The adjustment solution used in sample-1 of row-1 was applied to give a dry film thickness of 1.0 μm.

Sample-7 Layer-1...Green-sensitive silver saponide emulsion layer sample-
Same as Layer 5-1, it is an adjustment coating.

Layer-2: Yellow filter single layer The adjustment solution used in sample-2 of row-1 was applied to a dry film thickness of 1.0 μm.

These samples were passed through a step wedge and applied to interference filters manufactured by Toshiba Chemical Industries, Ltd., respectively.
-54 was used for exposure and the following processing was performed.

Treatment process (38℃) Processing time Color development...3 minutes 15 seconds White...
・・・・・・Rinse with water for 6 minutes and 30 seconds・・・・・・・・・3
Fixing for 15 minutes, 6 minutes, washing with water for 6 minutes, stabilizing for 3 minutes, 15 seconds.
...1 minute 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

Color developing composition: Bleach solution composition: Adjust the instep.

Fixer composition: Stabilizing solution composition: Next, the sensitivity was measured for the color images formed on the sample and comparative sample. When the sensitivity of the second sample-5 was set as 100, the sensitivity of each sample was compared relative to the result.

As shown in the results in Table 2, the t color sensitivity of Sample-6 when exposed to light with the KL-44 filter is only 20 inches lower than that of Sample-5, which is due to the dye contained in the second layer. As a result of the first diffusion, the second layer does not sufficiently play its role as a filter layer. On the other hand, in Sample 7 of the present invention, it is clear that the 21st layer works well as a filter layer and there is no difference in green sensitivity compared to the comparison.

Agent Yoshimi Kuwahara

Claims (1)

[Claims] In a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, the hydrophilic colloid layer has a dye as a core layer and is made of a material that can be dissolved in an alkaline solution as a wall material. A silver halogenide photographic material containing formed microcapsules.