JPH0481745A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obviate the generation of an adverse influence on photographic performance in spite of preservation at and under high temp. and high-humidity conditions by incorporating an emulsion layer contg. specific flat plate silver halide particles into emulsion layer and incorporating a specific silver halide emulsion stabilizing material in a solid state into silver halide emulsion layers and/or hydrophilic colloidal layers. CONSTITUTION:The emulsion contg. the flat plate silver halide particles having the particle diameter of >=3 times the thickness of the particles is incorporated into at least one layer of the photosensitive silver halide emulsion layers. These particles occupy at least 50% of the total projection area of the silver halide particles existing in the same layer. In addition, such silver halide emulsion stabilizing material which has the solubility in water at 9.5 pH of >=3 times the solubility in water of 6.0 pH is incorporated in the solid state into at least layer of the silver halide emulsion layers and/or hydrophilic colloidal layers. The degradation in the photographic performance is obviated in this way in spite of preservation under the high-temp. and high-humidity conditions.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a silver halide photographic light-sensitive material, and more particularly, it relates to a silver halide emulsion stabilizer that can be used without deteriorating other photographic properties. The present invention relates to a silver halide photographic material with sufficient effects.

(Prior Art) Generally, the image sharpness of a photographic light-sensitive material decreases as the thickness of the emulsion layer increases due to light scattering of silver halide emulsion grains. In particular, in a multilayer color light-sensitive material having red-sensitive, green-sensitive and blue-sensitive emulsion layers, light scattering accumulates due to the multilayer structure, and the sharpness of the underlying emulsion layer is greatly reduced.

U.S. Pat. No. 3,402,046 discloses that a blue-sensitive emulsion layer, which is the uppermost emulsion layer of a multilayer color light-sensitive material, has a grain size of 0.
A method is described in which the sharpness is improved by using coarse particles of 7 microns or more that cause less light scattering.

However, these methods have the disadvantage that the graininess of the blue-sensitive emulsion layer deteriorates because coarse grains having a particle size larger than that required as blue-sensitive emulsion grains are used.

U.S. Pat. No. 4,439,520 discloses that at least one of a green-sensitive emulsion layer and a red-sensitive emulsion layer has a thickness of less than 0.3 microns and a diameter of at least 0.3 microns. 6 microns, diameter/thickness ratio of 8
A color photographic light-sensitive material is described in which sharpness, sensitivity, and graininess are improved by using tabular silver halide emulsion grains having a particle size of 1 or more.

On the other hand, various silver halide emulsion stabilizers are added to photosensitive silver halide emulsions.

For example, U.S. Pat.
No. 88,132 and No. 4,740.454 disclose mercaptothiadiazole compounds as compounds that expand the interimage effect.

Additionally, Research Disclosure 18716 (RDI
8716) page 649 discloses various antifoggants.

Additionally, as a bleach accelerator, U.S. Pat. No. 3,893.85
Specification No. 8, German Patent No. 1,290°812, British Patent No. 1,138,842, Japanese Unexamined Patent Publication No. 1983
-95630 and Research Disclosure No. 17129 (July 1978 issue) disclose compounds having a mercapto group or a disulfide group.

These compounds are generally adsorbed to silver halide grains and exhibit their respective effects during development processing.

According to research conducted by the present inventors, the adsorption of sensitizing dyes to tabular silver halide grains is generally weak, and when the above-mentioned stabilizing substances are added to tabular silver halide grains, adsorption of sensitizing dyes is insufficient, resulting in sensitivity cause a decline.

In addition, if the amount of sensitizing dye added is increased in order to sufficiently adsorb the sensitizing dye, the sensitizing dye may not flow out or decolorize sufficiently during development, resulting in so-called residual color, where the sensitizing dye remains on the developed photographic material. This brings about the problem.

A method has been invented in which antifoggants are released during development without being substantially adsorbed to silver halide grains in photographic materials before development.

That is, the antifoggant is linked to another matrix to deactivate its action, and the antifoggant is chemically released during development.

Examples of such a linking group include those described in JP-A-54-145135 (UK Patent Publication No. 2.010.818A),
U.S. Pat. No. 4,248,962, U.S. Pat. No. 4,409,32
No. 3, which releases an antifoggant by an intramolecular ring-opening reaction as described in British Patent No. 2,096°783, and British Patent No. 2. 072. No. 363, JP-A-57-154, 2
Those that release antifoggants by intramolecular electron transfer as described in Specification No. 34, etc., those that release antifoggants with desorption of carbon dioxide gas as described in JP-A-57-179,842, etc. Alternatively, there may be mentioned linking groups such as those described in JP-A-59-93422 that are released upon elimination of formalin.

However, when these compounds are stored under high temperature and high humidity conditions, chemical reactions that should occur during development occur, releasing antifoggants and desorbing sensitizing dyes.
On the contrary, the above chemical reaction causes the problem of increased fog.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to develop a method for producing a large interimage effect with little decrease in sensitivity in a light-sensitive material containing tabular silver decagenide grains. A second object of the present invention is to provide a method for increasing the desilvering rate with less decrease in sensitivity in a light-sensitive material containing tabular silver halide grains.

A third object of the present invention is to provide a method for reducing fog in a light-sensitive material containing tabular silver halide grains with less deterioration in sensitivity.

A fourth object of the present invention is to provide a photographic material containing tabular silver halide grains, which can be stored as a silver halide emulsion without adversely affecting photographic performance even when the photographic material is stored under high temperature Toriya conditions. The object of the present invention is to provide a method for expressing the effect as a stabilizer.

(Means for Solving the Problems) The above object of the present invention is to provide a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support. One layer contains an emulsion containing tabular silver halide grains with a grain diameter of three times or more the grain thickness, and the grains occupy at least 50% of the total projected area of the silver halide grains present in the same layer. and in at least one silver halide emulsion layer and/or hydrophilic colloid layer, pH=9.
．． 1. A silver halide photographic material comprising a silver halide emulsion stabilizing substance in a solid state whose solubility in water at pH=6.0 is three times or more than that at pH=6.0.

(2) In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, at least one layer of the light-sensitive silver halide emulsion layer has grains having a grain diameter of three times or more the grain thickness. containing an emulsion containing tabular silver halide grains, the grains occupying at least 50% of the total projected area of the silver halide grains present in the same layer, and at least one silver halide emulsion layer and/or , a silver halide emulsion stabilizing substance whose solubility in water at pH=9.5 is three times or more than the solubility in water at pH=6.0 is adsorbed in the hydrophilic colloid layer. This was achieved by a silver halide photographic material, which contains silver halide in a state in which it is adsorbed on non-photosensitive fine particles having a surface that allows the silver halide to be absorbed.

The silver halide emulsion stabilizing substance used in the present invention includes known photographic reagents.

The above-mentioned solid state means a fixed state in which the material cannot substantially diffuse in the hydrophilic colloid layer, and a state in which a diffraction pattern can be obtained by X-ray or electron beam diffraction.

Photographic reagents include reagents usefully used in silver halide photosensitive materials, such as development inhibitors, antifoggants,
Represents a desilvering accelerator, an image stabilizer, a processing dependency improving agent, etc.

Since these photographically useful reagents often overlap in terms of their usefulness, representative examples are described below.
ees) and T. H. James (T, H,
James) [The Theory of the Photographic Process]
hePhotographic Process) J
3rd edition, 1966, Macmillan
) Publishing, pp. 344-346.

Specifically, mercaptotetrazoles, mercaptotriazoles, mercaptoimidazoles, mercaptopyrimidines, mercaptobenzimidazoles, mercaptobenzthiazoles, mercaptobenzoxazoles, mercaptothianazoles, benztriazoles, benzimidazoles, and indazoles. , adenines, guanines, triazaindenes, tetraazaindenes, pentaazaindenes, and the like.

Among these compounds, those having a pKa of 4 to 11 are more preferable, especially those having a pKa of 6 to 11.
The following can be mentioned.

Representative examples of silver halide emulsion stabilizing substances of the present invention include:
It is represented by the following general formula (I) or (n).

General Formula (I) In the formula, Ml represents a hydrogen atom, a cation or a protecting group for a mercapto group that is cleaved with an alkali, and Z represents an atomic group required to form a 5- to 6-membered heterocycle. This heterocycle may have a substituent or be fused. To explain in more detail, M is a hydrogen atom,
Cations (e.g. sodium ions, potassium ions,
(e.g. ammonium ion) or alkali-cleavable mercapto group protecting groups (e.g. -COR'C0OR'
-CH2CH2COR' etc. However, R' is a hydrogen atom,
represents an alkyl group, an aralkyl group, an aryl group, etc.).

X' represents an atomic group necessary to form a 5- to 6-membered heterocycle. This heterocycle contains a sulfur atom, selenium atom, nitrogen atom, oxygen atom, etc. as a heteroatom, and may be fused.

5- or 6-membered heterocycles include tetrazole, triazole, imidazole, oxazole, thiadiazole,
Examples include pyridine, pyrimidine, triazine, azabenzimidazole, purine, tetraazaindene, doria)indene, pentaazaindene, benztriazole, benzimidazole, benzoxazole, benzthiazole, benzselenazole, and naphthimidazole.

R is a linear or branched alkylene group, a linear or branched alkenylene group, a linear or branched aralkylene group,
or represents an arylene group, and Z represents a polar substituent. Y is -s---.

R,OR2RIOR.

II N--C-N--N-C--3OIN R5000 11II ll NSO2--CO--0C--C R60R,R,SR.

-N-C-N--N-C-N- or R,0O -N-C-0-, R1, R2, R3, R4, R
5, R=, R1, R=, Re and Rto each represent a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group, alkenyl group, or aralkyl group. R'
represents a hydrogen atom or a group capable of substituting it. n is O
or 1, and m represents 0, ■ or 2.

More specifically, R is a linear or branched alkylene group,
It represents a straight-chain or branched alkenylene group, a straight-chain or branched aralkylene group, or an arylene group.

Examples of the polar substituent represented by Z include substituted or unsubstituted amino groups (including salt forms), quaternary ammoniamyl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, heterocyclic oxy groups, Heterocyclic thio group, sulfonyl group, carbamoyl group, sulfamoyl group, carbonamide group, sulfonamide group, acyloxy group, ureido group, acyl group, aryloxycarbonyl group, thioureido group, sulfonyloxy group, heterocyclic group, hydroxy group can give.

R,,R2,R3,R,,Rs,R,,R,,R,,
R and RIG represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aralkyl group.

In addition, R" represents a hydrogen atom or a group that can be substituted for this, and examples of the substitutable group include a halogen atom (e.g., fluorine, chloro, bromine), a substituted or unsubstituted alkyl having 1 to 6 carbon atoms, group, substituted or unsubstituted aryl group having 6 to 12 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms, 1 to 12 carbon atoms Sulfonyl group with 1 to 12 carbon atoms, sulfonamide group with 1 to 12 carbon atoms,
12 sulfamoyl groups, carbamoyl groups having 1 to 12 carbon atoms, amide groups having 2 to 12 carbon atoms, ureido groups having 1 to 12 carbon atoms, aryl or alkoxycarbonyl groups having 2 to 12 carbon atoms, Examples include an aryl or alkoxycarbonylamino group and a cyano group.

In general formula (I), preferably R is substituted or R2 is an unsubstituted alkylene group, Y is -C-N-R3 (■ 10 N N C-or atom, Z is a substituted or unsubstituted amino group or a salt thereof, This is the case for heterocyclic groups.

(■ Below, general formula (I) The compound represented by Chi, Preferred specific examples are shown below.

(I-1) 02NH2 (I-13) H (I-14) (I-15) (■ (I-11) In the formula, the ring formed by Q2 is triazole, tetrazole, imidazole, oxazole, thiadiazole. , pyridine, pyrimidine, triazine, azabenzimidazole, purine, tetraazaindene, triazaindene, pentaazaindene, benztriazole, benzimidazole, benzoxazole, benzthiazole, benzselenazole, indazole, naphthimidazole and the like.

These rings may further include alkyl groups (e.g. methyl, ethyl, n-hexyl, hydroquinethyl, carboxyethyl), alkenyl groups (e.g. allyl), aralkyl groups (e.g. hensyl, phenethyl), aryl groups (e.g. phenyl). , naphthyl, p-acetamidophenyl,
p-carboxyphenyl, m-hydroxyphenyl, p
-sulfamoylphenyl, p-acetylphenyl, ○
Methoxyphenyl, 2,4-diethylaminophenyl,
2,4-dichlorophenyl), alkylthio groups (e.g. methylthio, ethylthio, n-butylthio), arylthio groups (e.g. phenylthio, naphthylthio), aralkylthio (e.g. benzylthio), etc.

Furthermore, in addition to the above-mentioned substituents, a nitro group, an amino group, a halogen atom, a carboxyl group, a sulfo group, etc. may be substituted on the condensed ring.

The compounds represented by the general formula (II) of the present invention are all known and can be easily obtained or synthesized.

Among the compounds represented by the general formula (II), preferred specific examples are shown below, but the invention is not limited thereto.

(II-5) (I[-6) (II-7) (II-3) (n-4) (n-8) (n-9) Hs (n-10) If) (n-12) ( II-13) (II-14) (■ (■ ■) The pKa values of typical compounds represented by the general formula (I) or (n) of the present invention are shown.

C1(.

The pKa value was measured by the following method.

Add excess sodium hydroxide to the sample and finally
An aqueous solution with a concentration of 0-' mol/l was prepared.

This solution was titrated with a 0.2N aqueous hydrochloric acid solution at 25° C. under nitrogen bubbling using a titration apparatus equipped with a glass electrode and a silver/silver chloride reference electrode.

For pKa, the pH value at which 1/2 of the total number of moles of the sample was dissociated was read.

Next, the non-photosensitive fine particles that provide a surface on which the substance of the present invention can be adsorbed form a discontinuous solid phase different from the hydrophilic colloid (hereinafter referred to as binder) continuous phase, and are mixed and dispersed in the binder. means what you are doing.

In order to mix and disperse the fine particles, it is sufficient to make the surface of the fine particles (the surface that comes into contact with the binder) hydrophilic, and this requires a means to make the chemical structure of the powder on the surface have a hydrophilic part and a surface active part. It is preferable to use either one of the methods of using powder whose surface has been treated with a micelle layer using an agent, or to use both methods in combination.

Examples of the chemical structure composition having a hydrophilic moiety include cases where the chemical structure composition atoms include at least one type of Lewis acid atom such as an oxygen atom, a sulfur atom, or a halogen atom; It is particularly preferable if it has a carboxylic acid group, a hydroxyl group, a sulfonic acid group, a phosphoric acid group, etc.

Examples of surfactants used as dispersion aids for powder when surface-treating with a micelle layer using a surfactant include alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfonates, alkyl sulfates, and alkyl phosphates. Anionic surfactants such as esters, sulfosuccinates and sulfoalkyl polyoxyethylene alkylphenyl ethers; nonionic surfactants such as steroidal saponins, alkylene oxide derivatives and glycidol derivatives; diamino acids, aminoalkyl It is preferred to use amphoteric surfactants such as sulfonic acids and alkylhetaines; and cationic surfactants such as quaternary ammonium salts. Specific examples of these surfactants can be found in the "Handbook of Oral Surfactants" (Sangyo Tosho, 1966)
and "Emulsifier/Emulsifier Research/Technical Data Collection" (Kagakupanronsha, 1978).

Furthermore, the surface may be activated by compounds themselves that can serve as binders, such as polyvinyl alcohol derivatives, seratin, or celluloses.

Furthermore, the chemical composition of the microparticles used in the present invention may be a single substance or a mixture of two or more types of compounds, and the chemical composition of one particle may be uniform within, outside, or on the surface. It may be a mixture of two or more chemical compositions.

Next, as specific examples, Cu, Zn, Ti, Sn, In
, Mo, W, Fe, A1, Si, Co, Zr.

Examples include metals such as Ni, Pd, Cd, Ru, Rh, and Ir, and oxides of these metals.

In addition, specific examples that are easily available as commercially available microparticles include colloidal silica, colloidal alumina, and mixtures of both.
1. Du Pont de Nemours Co.

(USA) to LudoxAM, LudoxAS, L
udoxLS, LudoxTM.

With product names such as Ludox H3, 8 San Kagaku ■ sells Snowtex 20, Snowtex C1, Snowtex N,
MOnSantOCo with product names such as Ten-Tex 0
(USA) 5ytonC-30,5yton 2
With product names such as 00, Na1co Chem, Co
, (USA) is Nalcoagl 030, N
Examples include those commercially available under trade names such as Alcoag 1060 and Nalcoag ID 21-64.

The microparticles used in the present invention contain an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, etc. or an organic base such as tetramethyl-ammonium ion as a stabilizer. It's okay.

Sodium hydroxide, potassium hydroxide, and ammonium hydroxide are particularly preferred as stabilizers because the higher the pH, the more stable the solution, and the lower the ionic strength, the more stable the stabilizer.

Colloidal silica, colloidal alumina, and colloidal silica alumina are particularly preferred as the microparticles used in the present invention.

The fine grains of the present invention may be silver halide fine grains having substantially no sensitivity.

Also included are crushed and classified products of organic polymer compounds such as polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate, and starch.

Alternatively, a polymer compound synthesized by a suspension polymerization method, a polymer compound made into a spherical shape by a spray try method or a dispersion method, or an inorganic compound can also be used.

The present invention also includes JP-A-62-14647 and JP-A-62-14647.
Fine particles containing fluorine atoms or silicon atoms such as those described in No. 17744 and No. 62-17743 may also be used.

The size of the fine particles of the present invention is 2 μm or less, 0.001 μm
Above, preferably 1 μm or less and 0.005 μm or more, particularly 0.5 μm or more and 0.005 μm or more.

The solid dispersed silver halide emulsion stabilizing substance of the present invention can be prepared, for example, as described below, but is not limited to the method described below.

■ Mechanical dispersion method, for example, by mixing water, a surfactant, and a silver emulsion stabilizing substance solid, and applying mechanical abrasion stress with glass beads or zirconia beads, such as in a ball mill. A method typified by various types of dispersing mills. Of course, you can also use the Polytron, Manton Galarin, automatic breast needle, daysilver, etc.

■ Precipitation and dispersion method by adjusting the pH A typical method is to adjust the pH to a level where the silver halide emulsion stabilizing substance dissolves to form an alkaline aqueous solution, and then lower the pH to obtain a fine solid precipitate. Preferably, it is prepared in the presence of colloids. The solid dispersion must be prepared not only in the presence of gelatin, etc., but also in the coexistence of a silver halide emulsion, emulsion, polymer latex, or other compounds necessary for the production of silver halide photographic light-sensitive materials. I can do it.

Furthermore, when lowering the pH to obtain a fine solid precipitate, mechanical stress may be applied using a ball mill, Polytron, Manton Galarin, automatic milk needle, DeSilver, or the like.

■ Precipitation dispersion method using poor solvent.

That is, after dissolving a silver halide emulsion stabilizing substance in a suitable solvent, a dispersed solid is prepared by adding a poor solvent for the stabilizing substance or adding it to a poor solvent for the stabilizing substance and precipitating it. How to get it.

At this time as well, mechanical stress may be applied as in (2). or,
It may also be prepared in the presence of a protective colloid such as gelatin. Further, it is preferable to remove excess salt and solvent from the dispersed solid prepared in (1) or (2) by a Tadel water washing method, an ultrafiltration method, or the like.

Two or more types of silver halide emulsion stabilizing substances may be mixed to form a dispersed solid.

Regardless of the presence or absence of fine particles, it is preferable to use gelatin or a surfactant as a dispersant depending on the purpose. The amount of the silver halide emulsion stabilizing substance used in the present invention is preferably 1 o -6 mol or more and less than 10 -1 mol, particularly 1 o -5 mol or more and less than 10 mol per mol of silver halide.

The silver halide emulsion stabilizing substance of the present invention is added to at least one photosensitive silver halide emulsion layer and/or a hydrophilic colloid layer, and includes a layer containing tabular silver halide grains and/or an adjacent hydrophilic colloid layer. Particular preference is given to adding it to the layer.

When preparing the solid dispersion of the silver halide emulsion stabilizing substance of the present invention, it does not substantially dissolve in an aqueous solution with a pH of 6 or less,
Surfactants that are water-soluble at pH 8 or higher can be preferably used.

Insoluble in water at a pH of 7 or less means that the solubility of the surfactant in water at 25° C. is 0.1% by weight or less, more preferably 0.05% by weight or less. Also, soluble in water at pH 8 or higher means that the solubility in water at 25° C. is 0.5% by weight or higher.

Such a surfactant is preferably one represented by the following general formula (W).

General formula (W) (R+.+D).

In the formula, R represents a substituted or unsubstituted alkyl group, alkenyl group, allyl group, or hydrogen group having 1 to 12 carbon atoms, and the total number of carbon atoms is 5 to 25, and D is COOHl-0-P+0H.
)2, represents -0-P-OM0 0H. Also, m and n represent an integer from 1 to 3.

As a preferable example of R, the alkyl group has 1 carbon number.
~12 straight-chain or branched alkyl groups (e.g. methyl,
ethyl, propyl, butyl, hexyl, heptyl, nonyl, decyl, dodecyl, etc.), alkenyl groups (aryl groups, etc.), aryl groups (such as phenyl, methoxyphenyl, chlorophenyl, hexylphenol, 2,4
- dibutylphenol, etc.).

These surfactants are insoluble in water and do not show surface activity when the pH is below 7, but they dissolve in water and show surface activity when the pH is above 8. In that case, the surface activity at 1% by weight in water is 50 dynes/cm or less, preferably 45 dynes/cm or less.

Specific compound examples are shown below.

-IC,H. , COOH C. H. , COOH C. , H2. COOH C,H. , CH=CH+CH. +, COOHC. H. O
COCH2C. H. OCC)-CH CH2-COOH C. H. , OCOCH2CH2COOHC. H. C.H.C.
H20CO-CH=CH-COOHC2H.

C. H. , OCO (CH2+.COOHI CIIH870P-ONa H) Next, the tabular silver 10-genide grains used in the present invention will be described.

The "tabular silver halogenide grains" used in the present invention have a diameter/thickness ratio of 3 times or more.

The diameter of a silver halide grain herein refers to the diameter of a circle having an area equal to the projected area of the grain. In the present invention, the diameter of the tabular silver halide grains is 0.4 to 5.0μ, preferably 0.0μ.
．． It is 8 to 4.0μ.

In general, tabular silver halide grains are tabular with two parallel surfaces, and therefore "thickness" in the present invention refers to the distance between the two parallel surfaces constituting the tabular silver halide grains. expressed.

The silver halide composition of the tabular silver halide grains is as follows:
Any of silver bromide, silver iodide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, and silver chloride may be used, but silver bromide and silver iodobromide are preferable, especially silver bromide. Silver iodide content is 0-30 mol%
Silver iodobromide is preferred.

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

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

For example, pBrl. Form seed crystals containing 40% or more of tabular grains by weight in an atmosphere with a relatively low pBr value of 3 or less, and grow the seed crystals while simultaneously adding silver and halogen solutions while keeping the pBr value at the same level. It can be obtained by

During this grain growth process, no new crystal nuclei are generated.
It is desirable to add the silver and halogen solution accordingly.

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

When producing the tabular silver halide grains of the present invention, by using a silver halide solvent as necessary, grain size, grain shape (diameter/thickness ratio, etc.), grain size distribution,
The growth rate of particles can be controlled. The amount of solvent used is 10-3 to 1.0% by weight of the reaction solution, especially IO-2
~10-1% by weight is preferred.

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

Often used silver halide solvents include ammonia, thioethers and thioureas. Regarding thioethers, U.S. Pat. No. 3,271,1
No. 57, No. 3,790,387, No. 3,574,
628 etc. can be referred to.

These silver halide solvents are added in order to accelerate grain growth during the production of tabular silver halide grains of the present invention.

Addition rate and amount of silver salt solution (e.g. A g N O + aqueous solution) and halide solution (e.g. KBr aqueous solution),
A method of increasing the concentration of addition is preferably used.

These methods are described, for example, in British Patent No. 1°335.
No. 925, U.S. Patent No. 3. 672. No. 900, No. 3,650,757, No. 4,242.445, JP-A No. 55-142329, No. 55-158124,
Reference may be made to the descriptions in No. 58-113927, No. 58-113928, No. 58-111934, No. 58-111936, etc.

The tabular silver halide grains of the present invention can be chemically sensitized if necessary.

Chemical sensitization methods include so-called gold sensitization methods using gold compounds (for example, U.S. Pat. Nos. 2,448,060 and 3,32).
No. 0,069) or sensitization methods using metals such as iridium, platinum, rhodium, palladium (for example, U.S. Pat. No. 2.4)
No. 48,060, No. 2.566.245, No. 2,56
6.263) or a sulfur sensitization method using a sulfur-containing compound (for example, U.S. Pat. No. 2,222,264), or a reduction sensitization method using tin salts, polyamines, etc. (for example, U.S. Pat. No. 2,487,850). , No. 2.518.698, No. 2.s21,925), or a combination of two or more of these can be used.

Particularly from the viewpoint of high sensitivity, the tabular silver halide grains of the present invention are preferably gold sensitized, sulfur sensitized, or a combination thereof.

In the layer containing the tabular silver halide grains of the present invention,
It is necessary that tabular grains having a diameter/thickness ratio (aspect ratio) of 3 or more account for 50% or more of the total projected area of the silver halide grains present in the layer, and preferably,
Tabular grains with a diameter/thickness ratio of 4 or more account for 50% or more of the total projected area of silver halide grains included in the layer, and more preferably tabular grains with a diameter/thickness ratio of 5 or more in the layer. This is the case when the silver halide grains are present in an amount of 50% or more of the total projected area of the silver halide grains contained therein.

The thickness of the layer containing tabular silver halide grains is from 0.3 to
It is preferably 6.0μ, particularly 0.5 to 4.0μ.

Further, the coating amount of tabular silver halide grains is 0.1 to 6 g.
/rd, particularly preferably 0.3 to 3 g/n-r.

When the present invention is applied to a multilayer color photographic light-sensitive material, it has at least one layer each of red-sensitive, green-sensitive, and blue-sensitive emulsion layers, but the order of these light-sensitive layers is not particularly limited.
It is determined according to the purpose.

Furthermore, as will be described later, the silver halide color photographic light-sensitive material of the present invention may contain dye-forming couplers.
Usually, a cyan dye-forming coupler is used in the red-sensitive layer, a magenta dye-forming coupler is used in the green-sensitive layer, and a yellow dye-forming coupler is used in the blue-sensitive layer, but different combinations can be used depending on the purpose.

The tabular 710 silver generator emulsion used in the present invention may be used in any of the above-mentioned red-sensitive, green-sensitive and blue-sensitive layers. When these color-sensitive layers consist of two or more light-sensitive layers, they may be used in any layer. A typical example where at least one silver halide emulsion layer of the silver halide emulsion layer and the red color sensitive layer is provided, and there is no particular restriction on the number of stones and the order of the layers of the silver halide emulsion layer and the non-photosensitive layer. is a silver halide photographic light-sensitive material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity; The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light, and in multilayer silver halide color photographic light-sensitive materials, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are installed in this order from the body side. However, depending on the purpose, the above-mentioned order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-chromic layer.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in German Patent No. 1,121,470 or British Patent No. 923.045. A two-layer configuration can be preferably used.

Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.
No. 112751, No. 62200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close 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 (B) / high sensitivity green photosensitive layer (GH) / low sensitivity green photosensitive layer (GL)/
High sensitivity red photosensitive layer (R11) / low sensitivity blue photosensitive layer (R
L) or Bll/BL/GL/Gll/IIH
/RL order, or BH/BL/GH/GL/RL/R
They can be installed in the order of H, etc.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/R
) They can also be arranged in the order of I/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH can be arranged in this order from the side farthest from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, the medium-sensitivity emulsion layer/high-sensitivity emulsion N/low-irradiation emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer,
Alternatively, they may be arranged in a single layer such as a low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer.

Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic photosensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. be. Particularly preferred are silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 10 mole percent silver iodide.

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

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

Examples of silver halide photographic emulsions that can be used in the present invention include Research Disclosure (RD) N.

17643 (December 1978), pp. 22-23, “
1. Emulsion preparation
on and types)” and the same Ni1187
16 (November 1979), p. 648, Nα3
07105 (November 1989), pp. 863-865,
and “Physics and Chemistry of Photography” by Glafkides, published by Beaumontel (P., Glafkides, Che+wie).
et Ph1sique Photography
ue, Paul Montel, 1967), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G.
F. Duffin.

Photographic Emulsion Che
mistry (Focal Press1966)>
, “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L, Zelikmanetal)
,, Making and Coating
Photographic emulsion,
Focal Press, 1964).

U.S. Patent Nos. 3,574.628 and 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. They may also be bonded with compounds other than silver halide, such as silver rhodan or lead oxide, and mixtures of particles of various crystal forms may be used.

The above-mentioned emulsions may be of the surface latent image type that forms latent images primarily on the surface, of the internal latent image type that forms inside the grains, or of the type that has latent images both on the surface and inside the grains, but negative-tone emulsions It is necessary that Among the internal latent image type emulsions, a core/shell type internal latent image type emulsion described in JP-A-63-264740 may be used. A 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, etc., but is preferably 3 to 40 nm, and preferably 5 to 20 nm.

The silver halide emulsion used is usually one that has been physically ripened, chemically matured, and spectrally sensitized. Additives used in such processes are subject to research disclosure restrictions17.
643, identification 18716 and same no.

307105, and the relevant parts are summarized in the table below.

The photosensitive material of the present invention includes grain size, grain size distribution, halogen composition, grain shape,
Two or more types of emulsions differing in at least one characteristic of sensitivity can be mixed and used in the same layer.

Silver halide grains coated with grain surfaces as described in U.S. Pat. No. 4,082,553, U.S. Pat. No. 4,626,4
Silver halide grains and colloidal silver with covered grain interiors described in No. 98 and JP-A No. 59-214852 are preferably used in a photosensitive silver halide emulsion layer and/or a substantially non-photosensitive hydrophilic colloid layer. Can be used.

Silver halide grains with a puffed interior or surface are defined as
refers to silver halide grains that can be developed (non-imagewise). A method for preparing silver halide grains with a fogging inside or on the surface of the grains is described in US Pat.

The silver halides forming the inner core of the core/shell type silver halide grains whose interiors are fogged may have the same halogen composition or may have different halogen compositions. As the silver halide coated inside or on the surface of the grain, any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used. Although there is no particular limitation on the grain size of these diffused silver halide grains,
The average particle size is preferably 0.05 to 0.75 μm, particularly 0.05 to 0.6 μm. In addition, there are no particular limitations on the particle shape, and regular particles may be used.
It may be a polydisperse emulsion, but it may be a monodisperse emulsion (at least 95% of the weight or number of silver halide grains is ±4 of the average grain size).
0% or less) is preferable.

In the present invention, it is preferred to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is a fine silver halide grain that is not exposed to light during imagewise exposure to obtain a dye image and is not substantially developed during the development process. preferable.

The fine grain silver halide has a silver bromide content of 0 to 100 mol %, and may contain silver chloride and/or silver iodide as necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter equivalent to a circle of projected area) of 0.01 to 0.5 μm, and preferably 0.01 to 0.5 μm.
02 to 0.2 μ- is more preferable.

Fine-grain silver halide can be prepared in the same manner as ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically enhanced, nor is there any need for spectral sensitization. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, hendithiaprylam-based, or mercapto-based compound, or a zinc compound. This layer containing fine silver halide grains can preferably contain colloidal silver.

The amount of coated silver in the light-sensitive material of the present invention is preferably 6.0 g/% or less, most preferably 4.5 g/rd or less.

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

Tomoe's wife = d city 〆 or; c; c:
c; -w% City: In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde, as described in No. 411.987 and No. 4,435,503.

The photosensitive material of the present invention includes U.S. Pat. No. 4,740,454, U.S. Pat.
It is preferable to contain a mercapto compound described in JP-A No. 1283551.

The photosensitive material of the present invention releases a fogging agent, a development accelerator, a) λ silver halide solvent, or a precursor thereof, regardless of the amount of developed silver produced during the development process, as described in JP-A-1-106052. It is preferable to contain a compound that

The dye dispersed in the photosensitive material of the present invention by the method described in International Publication No. 088104794, Japanese Patent Publication No. 11-502912, or EP 317.308A, US Pat.
, 420,555 and JP-A-1-259358.

Various color couplers can be used in the light-sensitive material of the present invention, specific examples of which are disclosed in Research Disclosure No. 117643, ■-C-G, and No.
No. 307105, ■-〇-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401,752, No. 4,
248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, British Patent No. 1,476.760, U.S. Patent No. 3,973,968, British Patent No. 4.314,
No. 023, No. 4,511,649, European Patent No. 24
9.473A, etc. are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
No. 0,619, No. 4.35L897, European Patent No. 7
No. 3,636, U.S. Patent No. 3,061,432, U.S. Pat.
No. 552, Research Disclosure Nα2423
0 (June 1984), Japanese Patent Publication No. 60-43659,
No. 61-72238, No. 60-35730, No. 55
-118034, US Patent No. 60-185951, US Patent No. 4.500,630, US Pat.
No. 4, 556, 630, International Publication-08810
Particularly preferred are those described in No. 4795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052.212.
No. 4,146,396, No. 4,228.23
No. 3, No. 4,296.200, No. 2,369.9
No. 29, No. 2,801.171, No. 2,772.
No. 162, No. 2.895,826, No. 3,772
, No. 002, No. 3,758,308, No. 4,33
4.011, 4,327.173, West German Patent Publication No. 3329.729, European Patent No. 121,365A
No. 249°453A, U.S. Patent No. 3,446,
No. 622, No. 4,333,999, No. 4.775
, No. 616, No. 4. ．． No. 451,559, No. 4,4
No. 27.767, No. 4,690,889, No. 4.
No. 254212, No. 4,296.199, Japanese Unexamined Patent Publication No. 6
1-42658 and the like are preferred. moreover,
JP-A-64-553, JP-A-64-554, JP-A-64-5
Pyrazoloazole couplers described in US Pat. No. 55, No. 64-556 and imidazole couplers described in U.S. Pat.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4.576910, British Patent No. 2.102.1
No. 37, European Patent No. 341188A, etc.

Couplers that allow coloring dyes to develop appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
, No. 570, European Patent No. 96.570, and German Patent Publication No. 3,234,533 are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure No. 17643.
-G term, ■-G term of 307105, U.S. Patent No. 4,
163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929, U.S. Pat. A coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released during coupling described in U.S. Pat. No. 4,774.181, and U.S. Pat. No. 4,777
．． It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye as described in No. 120.

Compounds that release photographically useful residues upon coupling can also be preferably used in the present invention.

DIR couplers that release development inhibitors are the aforementioned RD
17643, ■-F section and Doso 307105, ■-F
Patents described in Sections, JP-A No. 57-151944, JP-A No. 57-154234, JP-A No. 60-184248, JP-A No. 6
No. 3-37346, No. 63-37350, U.S. Patent 4
, 248,962 and 4.782.012 are preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
Those described in JP-A No. 2.13L188, JP-A-59-157638, and JP-A-59-170840 are preferred. Also, JP-A-50-107029, JP-A No. 60-25234
Compounds that release fogging agents, development accelerators, silver halide solvents, etc. through redox reactions with oxidized developing agents described in JP-A No. 0, JP-A-144940, and JP-A-1-45687 are also preferred.

Other compounds that can be used in the light-sensitive material of the present invention include the competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , long equivalent couplers described in JP-A-60-185950, etc.,
DIR redox compound releasing couplers, DIR coupler releasing couplers, DI described in JP-A-6224252 etc.
R coupler-releasing redox compounds or DIR redox-releasing redox compounds No. 302A, No. 313. No. 3084, a coupler releasing a dye that recolors after separation, as described in R. D. k 114
49, No. 24241, bleaching accelerator releasing coupler described in JP-A No. 61-201247, etc., U.S. Pat. No. 4,555
, No. 477, etc.;
Couplers that emit leuco dyes described in US Pat. No. 4,774,181 and couplers that emit fluorescent dyes are mentioned.

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

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

The boiling point at normal pressure used in the oil-in-water dispersion method is 175"
Specific examples of high boiling point organic solvents of C or higher include phthalic acid esters (dibutyl phthalate, synchrohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-amyl phenyl) phthalate, bis(2,4-di-amyl phenyl) phthalate, (2.4-di-amylphenyl) isophthalate, bis(1.1-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate,
-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate,
di-2-ethylhexylphenylphosphonate, etc.),
Benzoic acid esters (2-ethylhexylhenshade, dodecylbenzoate, 2-ethylhexyl-p-hydroxyhenzoate, etc.), amide il (N,N-
diethyldodecaneamide, NN diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2.4
-tar t-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives ( N,N-dibutyl2
-butoxy-5-tert-octylaniline, etc.),
Examples include hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.).

Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30"C or higher, preferably 50"C or higher and about 160"C or lower can be used. Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, and cyclohexanone. , 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of latex dispersion processes, effects, and latex for impregnation are described in U.S. Patent No. 4,199,363, OLS No. 2,54L274
.

541, No. 230, etc.

The color photosensitive material of the present invention contains phenethyl alcohol and JP-A-63-257747, JP-A-62-272248
1,2-benzisothiazolin-3-one, n-butyl p-hydroxyhenzoate, phenol, 4-chloro-3.5 described in JP-A-1-80941.
-dimethylphenol, 2-phenoxyethanol, 2
- It is preferable to add various preservatives or antifungal agents such as (4-thiazolyl)benzimidazole.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D. Nil 17643, page 28, Nα1871
6, page 647 right column to page 648 left column, and 307
105, page 879.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side where the emulsion layer exists is preferably 28 μm or less, more preferably 23 μm or less, still more preferably 18 μm or less, and particularly 16 μm or less. Preferred and membrane swelling rate TI/! is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness was measured at 25°C and 55% relative humidity (2
The membrane swelling rate TI/□ means the membrane thickness measured in days).
It can be measured according to techniques known in the art. For example, Knee Green (A, Green)
Photographic Science and Engineering (Photogr, Sci, Eng,)
It can be measured by using a swellometer (swelling membrane) of the type described in Vol. The saturated film thickness is defined as 90% of the maximum swollen film thickness, and is defined as the time until the saturated film thickness reaches 172.

The membrane swelling rate TI/□ can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the conditions mentioned above, using the formula: (maximum swollen film thickness -
It can be calculated according to (film thickness)/film thickness.

The photosensitive material of the present invention has a hydrophilic colloid layer (with a total dry film thickness of 2 μm to 20 μm) on the side opposite to the side having the emulsion layer.
It is preferable to provide a layer (referred to as a hack layer). This layer contains the aforementioned light absorbers, filter dyes, ultraviolet absorbers, anti-static agents, hardeners, binders, plasticizers,
It is preferable to contain a lubricant, a coating aid, a surface active agent, etc. The swelling ratio of this back layer is preferably 150 to 500%.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl -4-amino-N-ethyl-N-
β-hydroquine ethylaniline, 3-methyl-4-amino-N-ethyl-Nβ-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and sulfates thereof, Examples include hydrochloride and toluenesulfonate. Among these, 3-methyl-4-amino-N-ethyl-
Nβ-hydroxyethylaniline sulfate is preferred. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts,
It is common to include development inhibitors or antifoggants such as iodide salts, benzimidazoles, hendithiazoles or mercapto compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, and catechol sulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity Imparting agent, aminopolycarboxylic acid, aminopolyphosphonic acid,
Various calcinants such as alkylphosphonic acids and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1 , 1-diphosphonic acid, nitrilo-N,N,l1l-)rimethylenephosphonic acid, ethylenediamine-N,N,N,N tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid) and their salts. This can be cited as a representative example.

Next, processing solutions for color reversal light-sensitive materials other than color developing solutions and processing steps will be explained.

Among the processing steps of the color reversal photosensitive material, the steps from black development to color development are as follows.

1) Black and white development - water washing, reversal, one color development 2) Black and white development - water washing, light reversal, one color development 3)! The white development-water washing one-color development steps 1) to 3) are all performed according to U.S. Patent No. 4.8.
By replacing the rinsing step described in No. 04.616, it is possible to simplify the process and reduce waste liquid.

Next, the steps after color development will be explained.

4) Color development - Adjustment - Bleach - Fixed - Wash - Stable 5) Color development - Wash - Wash - Bleach - Fixed - Wash - Stable 6) Color development - Adjustment - Bleach - Wash with water - Fixed - Wash - Stable 7) Color development - Wash with water 1) Bleaching 1) Washing with water 1) Stable 8) Color development - Bleaching 1) Washing with water 1) Stable 9) Color development -
Bleach - Bleach-fixing - Washing - Stable 10) Color development - Bleach - Bleach fixing - Constant fixing - Washing - Stable 11) Color development - Bleach - Washing - Constant fixing - Washing - Stable 12)
Color development - Adjustment - Bleach fixing - Washing - Stable 13) Color development - Washing - Bleach fixing - Washing - Stable 14) Color development - Bleach fixing - Washing - Stable 15) Color development - Adjustment - Bleach fixing - Washing - Stable 4) In the treatment steps 1) to 15), the water washing step immediately before the stabilization step may be removed, or conversely, the final stabilization step may not be performed.
) and any one of the steps 4) to 15) are connected to form a color reversal step.

A known developing agent can be used in the black and white developer used in the present invention. As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone),
Aminophenols (e.g. N-methyl-p-aminophenol), 1-phenyl-3-pyrazolines, ascorbic acid and the 1,2,3,4-tetrahydroquinoline ring described in U.S. Pat. No. 4,067,872. Heterocyclic compounds such as a condensation of and an intrene ring can be used alone or in combination.

In addition, the black and white developer used in the present invention may include preservatives (e.g., sulfites, bisulfites, etc.), buffers (e.g., carbonates, boric acid, borates, alkanolamines),
alkaline agents (e.g. hydroxides, carbonates), dissolving tablets (
(e.g., polyethylene glycols, esters thereof), pHJ adjusters (e.g., organic acids such as acetic acid), sensitizers (e.g., quaternary ammonium salts), development accelerators, surfactants, antifoaming agents, hardening films. A viscosity-imparting agent, a viscosity-imparting agent, and the like can be contained.

The black and white developer used in the present invention needs to contain a compound that acts as a silver halide solvent, but normally the sulfite added as the preservative mentioned above plays this role. Other usable silver halide solvents include KSCN.

Na5CN, KzSO3, NazSOi, KzSzO
s, N a z S z O s , K z S z O
z , N a z S z Os, and the like.

The pH value of the developer thus adjusted is selected to be sufficient to provide the desired density and contrast, but is in the range of about 8.5 to about 11.5.

In order to carry out sensitization using such a black and white developer, it is usually sufficient to extend the time up to about three times as long as the standard processing. If the treatment temperature is raised at this time, the extended time for exacerbation treatment can be shortened.

These color developing solutions and black and white developing solutions generally have a pn of 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic material to be processed, but is generally less than 32% per square meter of photosensitive material, and by reducing the bromide ion concentration in the replenishing solution, it can be increased to 500% or less.
It can also be less than d. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, Capacity of treatment liquid (cmff) The above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, it is better to provide a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, as described in Japanese Patent Application Laid-Open No. 1-82.
Method using a movable lid described in No. 033, JP-A-63
The slit development processing method described in Japanese Patent No. 216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it to all steps such as bleaching, bleach-fixing, fixing, washing with water, and stabilization. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The reversal bath used after black and white development can contain a known fogging agent. That is, stannous ion-organophosphate salt (U.S. Pat. No. 3,617,282), No. 1
Tin ion organic phosphonocarboxylic acid complex salt (Special Publication No. 1983-
32616) stannous ion complex salts such as stannous ion-aminopolycarboxylic acid complex salts (U.S. Pat. No. 1,209,050), borohydride compounds (U.S. Pat. No. 2,984,567) , boron compounds such as heterocyclic amine borane compounds (UK Patent No. 1,011,000), and the like. The pH of this fogging bath (reversal bath) ranges over a wide range from acidic to alkaline, with pH ranging from 2 to 12, preferably from 2.5 to 10,
Particularly preferably, it is in the range of 3 to 9. In place of the reversal bath, a light reversal process may be performed by re-exposure, and the reversal step can also be omitted by adding the above-mentioned fogging agent to the color developing solution.

The silver halide color photographic material of the present invention is subjected to a bleaching treatment or a bleach-fixing treatment after color development. These treatments may be performed immediately without going through the color developing agent processing step, or in order to prevent unnecessary post-development and air fog, and to reduce the carry-over of the color developer into the desilvering process. In addition, in order to wash out and detoxify the sensitive material parts such as sensitizing dyes and dyes contained in the photographic light-sensitive material and the color developing agent impregnated in the photographic photosensitive material, after the color development process, stopping, adjustment, and washing are carried out. After passing through the following processing steps, the material may be subjected to a bleaching treatment or a bleach-fixing treatment.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (I[[), peracids, quinones, nitro compounds, etc.9 Typical bleaching agents include organic complex salts of iron (I[[), e.g. Aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, malic acid, etc. Can be used. Among these, aminopolycarboxylic acid iron (I[[) complex salts, including ethylenediaminetetraacetic acid iron(III) complex salt and 1,3-diaminopropanetetraacetic acid iron (I[[) complex salt] are used for quick processing and prevention of environmental pollution. It is preferable from the viewpoint of iron aminopolycarboxylate (I
[I) Complex salts are particularly useful in both bleach and bleach-fix solutions. These aminopolycarboxylic acid iron (I
[[) The pl+ of the bleaching solution or bleach-fixing solution using a complex salt is usually 4.0 to 8, but it is also possible to process at a lower pH for speeding up the processing.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290.812, No. 2,059,988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group described in JP-A-53-124424, JP-A-53-141623, JP-A-53-28426, Research Disclosure No. k17129 (July 1978), etc.; JP-A-50-140129 Thiazolidine derivatives described in Japanese Patent Publication Nos. 45-8506, 52-20832, 53-32735, and U.S. Pat. No. 3,706,561; West German Patent No. 1,127 ,71
No. 5, iodide salts described in JP-A-58-16,235;
Polyoxyethylene compounds described in West German Patent No. 966.410 and West German Patent No. 2,748.430;
Polyamine compounds described in No. 836; other JP-A-49-
No. 40,943, No. 49-59,644, No. 53-9
No. 4.927, No. 54-35.727, No. 55-26
．． No. 506, compounds described in Nos. 58 to 163.940;
Bromide ion etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred, as described in U.S. Pat.
Compounds described in No. 630 are preferred. Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the light-sensitive material, and are particularly effective when bleach-fixing color light-sensitive materials for photography.

In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferable 8! The acid is a compound having an acid dissociation constant (pKa) of 2 to 5, and specifically, acetic acid, propionic acid, hydroxyacetic acid, etc. are preferable.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. Further, a combination of thiosulfate, thiocyanate, thioether compound, thiourea, etc. is also preferred. As the preservative for the fixer and bleach-fixer, sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds described in European Patent No. 294,769A are preferred. Furthermore, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

The total time of the desilvering process is preferably as short as possible without causing desilvering defects. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C to 5°C.
0°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step, it is preferable that stirring be as strong as possible. Specific methods for strengthening agitation include the method of impinging a jet of processing liquid on the emulsion surface of the photosensitive material described in JP-A-62-183460, and the method described in JP-A-62-183.
No. 461, a method of increasing the stirring effect using a rotating means, and further improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. Examples include a method of increasing the W1 recirculation amount of the entire processing liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleaching agent and fixing agent into the emulsion film, and as a result increases the desilvering rate. Further, the above-mentioned stirring improving means includes:
It is more effective when a bleach accelerator is used, and the accelerating effect can be significantly increased and the fixing inhibiting effect caused by the bleach accelerator can be eliminated.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable to have the photosensitive material conveying means described in Japanese Patent Application No. 191259. As described in the above-mentioned Japanese Patent Application Laid-Open No. 60491257, such a conveying means can significantly reduce the amount of processing liquid brought into the post bath from the front bath, and is highly effective in preventing deterioration of the performance of the processing 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 water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urnal of the 5ociety
of Motion Picture and
It can be determined by the method described in Televisron Engineers Vol. 64, P, 248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to this problem,
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288.838 can be used very effectively. Also, JP-A-57-8,542
Chlorine-based disinfectants such as inchiazolone compounds, cyabendazoles, chlorinated sodium isocyanurate, and other benzotriazoles described in the issue, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing, Hygiene Complete technical volume: "Sterilization, sterilization, and anti-mildew technology of microorganisms" (1982), Society of Industrial Engineers of Japan, Japan Anti-bacterial and Anti-Mildew Society, "Encyclopedia of anti-bacterial and anti-mildew agents" (1982)
The fungicides described in 1985) can also be used.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. A range is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out. For example, a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials for shadows, may be further carried out. can be mentioned. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

It is also possible to add various botanical agents and antifungal agents to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration by adding water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. and No. 15.159, aldol compounds described in No. 13,924, U.S. Patent No. 3
, 719,492, JP-A-53-1
Examples include urethane compounds described in No. 35628.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-
Pyrazolidones may also be incorporated.

Typical compounds are JP-A-56-64339 and JP-A No. 57-
144547, Oyohi 1m58-115438, etc.

The various processing solutions used in the present invention are used at a temperature of 10'C to 50'C.6 Usually, the standard temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time. Conversely, by lowering the temperature, it is possible to improve the image quality and the stability of the processing solution.

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

A solid dispersion of the silver halide stabilizing substance of the present invention, the surfactant Triton .0g was added to this solution.

Zirconium oxide (ZrO) beads (40-12rM
1 diameter) was added and ground in a ball mill for 48 hours. After this, 2.5 g of gelatin was added as a powder, dissolved at 40°C, and the ZrO beads were removed by filtration, followed by heating at 7°C.
It was cooled to When adding to the emulsion layer during coating, the temperature was raised to 408C to dissolve and add.

Table 1 Example 1 Preparation of Sample 101 A multilayer color photosensitive material consisting of each layer having the following composition was prepared on a cellulose triacetate film support having a thickness of 205 μm and undercoated on both sides of the film. did.

The coating amount of each composition is the value per 1rrl' of sample.

Regarding silver halide and colloidal silver, the weights are shown in terms of equivalent silver.

1st layer: Antihalation layer black colloidal silver 0.25g gelatin
1.9g UV absorber U-10,
04g Ultraviolet absorber U-20.1g Ultraviolet absorber U-30.1g Ultraviolet absorber U~4 0.1g Ultraviolet absorber U-60.1g Additive P-10.1g Additive F-100.2g High boiling point Organic solvent 0il-10.1g 2nd layer: Intermediate layer Seratin compound Cpd-D Dye D-4 High boiling point organic solvent 0i1-3 Dye D-6 3rd layer/intermediate layer Non-photosensitive fine grain silver iodobromide emulsion (average Particle size 0.1, czm
, Agr content 1 mol%) Silver amount 0.15g Fine grain silver iodobromide emulsion with surface and interior covered (average grain size 0.06
μm, coefficient of variation 18%, Agl content 1 mol%) Silver amount
0.05g Additive M-10.05g Gelatin 0.4g 4th layer: Low sensitivity red emulsion layer Emulsion A Emulsion B Gelatin compound cpd- and coupler C-1 g g g 5g 5g 0.40g 1 O■ 0, 4■ 40■ 0, 1g Coupler C-2 Coupler C-9 Coupler C-10 Compound Cpd-D Additive F-2 High boiling point organic solvent Oi1-2 Additive F-12 5th layer: Medium-sensitivity red-sensitive emulsion layer Emulsion B Silver amount Emulsion C Silver amount Gelatin additive F-13 Coupler C-1 Coupler C-2 Coupler C-3 Additive F-2 High boiling point organic solvent Oi1-2 6th layer: High sensitivity red-sensitive emulsion layer Emulsion D Silver amount Gelatin 0.05g 0.05g 0.10g 10■ 0, 1■ 0.10g 0, 5■ g g g 05■ g 5g g 1■ g 0゜l.

g g Coupler C-30.7g Coupler C-10.3g Additive P-10.1g Additive F-20.1■ 7th layer: Intermediate layer Ceratin 0.6g Color mixing inhibitor C
pd-L O, 05g Additive F-11, 5■ Additive Cpd-N O, 02g Additive M
-10,3g Color mixture prevention agent Cpd-K O,05g Ultraviolet absorber U-10,1g Ultraviolet absorber U-60,1g Dye D-10,02g Dye Dye 6 0. 05g 8th layer:
Silver iodobromide emulsion with a puffed surface and interior of the intermediate layer (average grain size 0)
．． 06 μm, coefficient of variation 16%, Ag content 0.3 mol%
) Silver amount 0.02g gelatin
1.0g additive P-I Q, 2
g Color mixture prevention agent Cpd-J O, Ig Color mixture prevention agent Cpd-M O, 05g Color mixture prevention agent Cpd
-A O, Ig 9th layer: low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (average grain size 0.1μ
m,Ag! Content 0. 1 mol%) Silver amount 0.05g Silver amount 0.3g Silver amount 0.1g Silver amount 0.1g 0.5g 0.20g 0.10g 0.10g 0.10g 0.03g 0.02g 0.02g 0. 02g Emulsion E Emulsion F Emulsion G Gelatin coupler C-4 Coupler C-7 Cobra-C-8 Coupler C-11 Compound Cpd-B Compound Cpd-E Compound Cpd-F Compound Cpd-G Compound Cpd-HO,02g Compound Cpd- D 10■High boiling point organic solvent 0i1-20.2g 10th layer: medium-sensitivity green-sensitive emulsion layer Emulsion G Silver amount emulsion H Silver amount gelatin g g g g g g 5g 3g 2g 2g 5g 5g 1g Coupler C-4 Coupler C -7 Coupler C-8 Coupler C-11 Compound Cpd-B Compound Cpd-E Compound Cpd-F Compound cpa-c Compound Cpd-H High-boiling organic solvent Oi1-2 11th layer: High-sensitivity green-sensitive emulsion layer Emulsion layer Silver Amount 0.5g gelatin
1.1g Coupler C-4 Coupler C-7 Coupler C-8 Coupler C-12 Coupler C-9 Compound Cpd-B Compound Cpd-E Compound Cpd-F Compound Cpd-G Compound Cpd-H Additive F-2 High boiling point Organic solvent Oi1-2 Additive F-13 12th layer: Intermediate layer gelatin additive F-1 Dye D-1 Dye D-3 Dye D-8 Dye D-2 g g g g 5g 8g 2g 2g 2g 2g 3■ 4g 05■ g O■ g 7g 3g 5g 13th layer: Yellow filter layer Yellow colloidal silver Silver amount Ceratin Dye D-5 Color mixing inhibitor Cpd-A High boiling point organic solvent Oi1-1 Dye D-7 Additive M-2 No. 14th layer/intermediate layer Ceratin dye D-9 15th layer: Low sensitivity blue-sensitive emulsion layer Emulsion J Silver amount emulsion K Silver amount emulsion L Silver amount gelatin coupler C-13 Coupler C-5 Additive F-2 16th layer: Medium-speed blue-sensitive emulsion layer g g 5g 1g 1g 3g 1g 0, 6g 0, 02g Emulsion L Silver amount Gelatin Coupler C-13 Coupler C-5 Coupler C-6 Additive F-2 17th layer: High-speed blue-sensitive emulsion Layer emulsion M Silver amount emulsion N Silver amount Gelatin coupler C-6 Coupler C-14 Additive F-2 Additive F-9 18th layer: 1st protective layer gelatin Ultraviolet absorber U-1 Ultraviolet absorber U-2 Ultraviolet Absorber U-3 Ultraviolet absorber U-4 g g g g g g 04■ 0, 2g o. 4g 1.4g 0, 5g 0, 2g 0, 4■ 1■ g 4g 1g 3g 3g Ultraviolet absorber U-5 Ultraviolet absorber U-6 High boiling point organic solvent Oi1-1 Formalin scavenger,, Cp d -C pd-I Ethyl acrylate latex dispersion dye D-3 Additive Cpd-J Additive F-1 Additive CI) d-N Additive F-6 Additive M-2 19th layer: 2nd protective layer colloid Silver Fine grain silver iodobromide emulsion (average grain size 0°AgI content 1 mol%) Silver content Gelatin 20th layer: Third protective layer 0.05g 0.05g 0.02g 0°0°g g 5g 5g 2g O■ 1g O■ 5g 0, 1■ 06μm1 0,1g 0,7g Gelatin 0.7g polymethyl methacrylate (average particle size 1.5μm)
0.1g 420 copolymer of methyl methacrylate and acrylic acid (average particle size 1.5μm) 0.1g Silicone oil 0.03g Surfactant W-13.0■ Surfactant W-20.03g 21st layer (back layer) Gelatin UV absorber U-1 UV absorber U-2 High boiling point organic solvent 0i1-1 22nd layer (back protective layer) Gelatin 5g Polymethyl methacrylate (average particle size 1.5μm)
0.03 g 4:6 copolymer of methyl methacrylate and acrylic acid (average particle size 1.
5 μm) 10g 0.05g 0.02g 0.01g 0.1g Surfactant w-i1mg Surfactant W-210■ Additive F-1 was added to each silver halide emulsion layer.

In addition to the above composition, each layer also contained gelatin hardening agent H-1.
Then, coating surfactants W-3 and W-4 and emulsifying surfactant W-5 were added.

Furthermore, phenol 1,2-benzisothiazolin-3-one, 2-phenoxyethanol,
Phenyl isothiocyanate and phenethyl alcohol were added.

COOCJy(iso) 5L; 11tLthL; UtJl’1 C-10 0H dibutyl phthalate tricresyl phosphate pd-A H H3 Hs H3 I H3 pd-D H H pd-E Js 0 C3H Cpd Cpd-H CH.

Jn ([)shi4119 Cpd-J CH CH Cpd-to CH CH CH Cpd-M CH (CHz)<5(Le C2H4 (CHHz)asOae (CHz)ssOaeHN(CJs)sS-4 C211゜ 2H5 (CH2)4SOIe C,H 3O+eHN(CJ5)3 SO3eHN(C2H5)1 O3e SO, Na SO,K OOH +CH2 CH÷ (-CH2-CH-) COOC, H.

0OH x/y=1/ ■ HNO3 ■ CH2=CH3O, CH2C0NHCH2H2 CH3O□CH2C0NHCH.

CH3 CsFl, 502NH(CHz)30(CHri2N-
CH3CH2 C,F, 5O2NCH2COOK C,H.

CH2COOCR1CI (C!Hs)C4H@aOs
S CHCOOCHz CH (CJs) C4H1150, ~
a CH2CH=CH2CH.

Shiguchi 113 2115 -N H Monodisperse tetradecahedral particles 0.35 Monodisperse cubic internal latent particles 0.45 l0 5.0 Monodisperse tetradecahedral particles 0.60 4.0 Monodisperse cubic particles 0.35 4.0 Sample 10 The silver iodobromide emulsion used in ■ is as follows. It is.

Monodispersed tetradecahedral particles 0.65 3.5 Monodispersed octahedral particles 0.80 4.0 11++3 ma
Among the silver halide grains in the layer, the 15th layer, and the 17th layer, the tabular silver halide grains whose grain diameter is three times the grain thickness (aspect ratio 3) or more are the total projected area of the silver halide grains in each layer. The percentages are 85%, 70%, 73%, respectively.
They were 85%, 82%, and 90%.

Preparation of Sample 102 Emulsion D, Emulsion E, Emulsion G, Emulsion ■, Emulsion J of Sample 101
, Emulsion K, Emulsion M, and Emulsion N, respectively, are polydisperse spherical grains, monodisperse tetradecahedral grains, monodisperse tetradecahedral grains, and polydisperse twinned grains (grains whose grain diameter is three times or more the grain thickness have a total projected area of sample 101 and all samples except for changing to monodisperse cubic particles, polydisperse spherical particles, monodisperse octahedral particles, and polydisperse spherical particles
2 was produced.

The average grain size, coefficient of variation, and AgI content of the above emulsions were adjusted to be the same as those of emulsions D, E, G, I, J, L, M, and N, respectively.

Preparation of Samples 103 to 107 Compounds I-L l-15, I-9,
Samples 103 to 107 were prepared in exactly the same manner as sample 101, except that ll-11 and -16 were dissolved in methanol and added in 5 x 10-' mol each per 1 mol of silver halide.
was created.

Preparation of Samples 108 to 112 Compounds I-1, ■=15, I-9,
Samples 108 to 112 were prepared in exactly the same manner as sample 102, except that ll-11 and -16 were dissolved in methanol and added in an amount of 5X10-' mol each per 1 mol of silver halide.
was created.

Preparation of Samples 113 to 117 Sample 102 (7) Solid dispersion of silver halide stabilizing substance in the 6th layer, 9th layer, 10th layer, 11th layer, 15th layer, and 17th layer ■ to [F] Samples 113 to 117 were prepared in exactly the same manner as Sample 102, except that 5xio-'' moles of each of these were added to 1 mole of silver halide.

Preparation of Samples 118 to 122 Solid dispersions of silver halide stabilizing substances ■ to [F] are added to the 6th layer, 9th layer, 10th layer, 11th layer, 15th layer, and 17th layer of Sample 101. 5 each for 1 mole of silveride
Samples 118 to 122 were prepared in exactly the same manner as sample 101 except that 10 -3 mol of X was added.

Samples 101 and 102 prepared in this manner had each density of cyan, macenta, and yellow of 1.0, and 20 cycles/
The value of MTF in mm was determined.

The results are shown in Table 1.

Table 1 It is clear that the sharpness is significantly higher than that of .

Samples 101 to 122 were exposed through a light wedge and subjected to the following development process to obtain a density of 1 each for cyan, magenta, and yellow.
．． The relative sensitivity at 0 and the maximum image density (Dmax) were determined. In the case of color reversal photosensitive materials, it can be said that the larger the value of Dmax, the less fog. The results are shown in Table 2.

Incidentally, the development treatment at this time was carried out in the following manner.

As shown in the results in Table 1, sample 101 using tabular emulsion
The following is clearer from the results of Sample 102 in Table 2 in which no tabular emulsion was used.

When a stabilizer is added as a methanol solution to a tabular emulsion-containing layer, it causes a decrease in sensitivity, but when a stabilizer is added as a solid dispersion of the present invention, there is almost no decrease in sensitivity. , Dmax can be made high, that is, fog can be kept low.

Next, sample 101~105.108~110°113~
The interimage effect on the red-sensitive emulsion layer, green-sensitive emulsion layer, and blue-sensitive emulsion layer was determined for samples 115.118 to 120.

The interimage effects on the red-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the blue-sensitive silver halide emulsion layer were determined as follows.

The samples were exposed to red light through a light wedge and developed as described below. Next, the sample was exposed to white light (red light, green light, and blue light) and developed, and the three colors of light were adjusted so that the sample turned gray. did. Note that the exposure amounts of red light during red light exposure and red light during white light exposure were the same.

The density of the developed sample was measured, and the density was measured when exposed to red light.
Cyan density when exposed to white light is 1. 0 exposure difference △,
5ogE (R) was determined as an interimage effect on the red-sensitive silver halide emulsion layer.

In the same manner, the interimage effect on the green-sensitive silver halide emulsion layer and the blue-sensitive silver halide emulsion layer was determined.

The results are shown in Table 3.

From the results in Table 3, the following can be said. When an interimage effect-producing compound is added as a methanol solution to the tabular emulsion-containing layer, it causes a decrease in sensitivity, but when the above compound is added as a solid dispersion of the present invention, there is almost no decrease in sensitivity and a large interference is caused. An image effect is produced.

Samples 101-103.105.106.108.110
．． 111.113.115.116.118.120.
Regarding No. 121, changes in photographic performance when stored for a long period of time under high temperature conditions were determined. The sample was incubated at 40° C. and 55% RH for one month, exposed through a light wedge, developed, and measured for cyan, magenta, and yellow densities. The sensitivity and Dmax of a sample exposed and developed before incubation and a sample after incubation were compared.

That is, the increase in sensitivity at a concentration of 1°0 due to incubation is expressed as Δj2ogE', and the decrease in Dmax is expressed as ΔDmax, as shown in Table 4.

From the results in Table 4, the following can be said. When a stabilizer is added as a methanol solution to suppress changes in photographic performance when stored in a flat emulsion under high temperature conditions, sensitivity decreases, but when the stabilizer is added as a solid dispersion of the present invention. , changes in photographic performance when stored under high-temperature conditions can be suppressed without causing almost any decrease in sensitivity.

Samples 101-103.107.108.113.117
．． 118 and 122 were exposed through a light wedge and subjected to the following development process.

At this time, the bleaching time was changed in units of 10 seconds, and the amount of remaining silver was 5 μg.
/c+ (The bleaching time for desilvering was determined below.

[Processing process]

Processing process Time Temperature Tank capacity Replenishment amount Black and white development 6 minutes 38°C 1212, 21/1 - Water washing 211
38” 4” 7.5” Reverse 2”
38" 41/1.1 〃Color development 6〃38
"12112.2"Adjustment 2
3811 4 1.1 Bleaching
611 3811 12 0.22 Fixed
Arrival 4〃38〃811 1. l 〃
Second water wash 41138” 8117.5”
Fixed 111251/ 211 1.1 〃
The composition of each treatment liquid was as follows.

Kuro Wataru Ei Mother liquor Replenisher Nitrilo-N, N, N -trimethylenephos Honic acid 5 sodium mu salt sodium sulfite hydroquinone mono 2.0g 2.0g 30g 30g potassium sulfonate potassium carbonate 1-phenyl-4-meth chill-4-hydroxy dimethyl-3-pyra Zolidon potassium bromide potassium thiocyanate potassium iodide 0g 0g 3g 3g 2.0g’2, Og 2.5g 1.4g 1.2g 1.2g 2.0■ pH9,609,60 pH was adjusted with hydrochloric acid or potassium hydroxide.

Kyouten Taka mother liquor Replenishment liquid Nitrilo-N, N, N Same as mother liquor-
Trimethylenephosphonic acid pentasodium salt 3.0g stannous chloride
Dihydrate salt 1. Og p-aminophenol 0.1g Sodium hydroxide 8g Glacial acetic acid 15J pH6.00 The pH was adjusted with hydrochloric acid or sodium hydroxide.

Main Negative Star Ecoffin Mother liquor Replenisher Nitrilo-N, N, N -trimethylenephos Honic acid 5 sodium mu salt sodium sulfite Trisodium phosphate 12 hydrate salt potassium bromide potassium iodide Sodium hydroxide Citrazic acid N-ethyl-(β-methyl) Tansulfonamide 2.0g 7.0g 2.0g 7.0g 6g 1.0g 90■ 3.0g 3.0g 1.5g 6g 1.5g ethyl)-3-methy -4-amineani phosphorus sulfate 3.6-Schier 1° 8-Octanedio- le 1g 1.0g 1g 1.Og pH 11,801,2,00 pH was adjusted with hydrochloric acid or potassium hydroxide.

Ethylenediaminetetravinegar Acid/disodium salt ・Dihydrate salt sodium sulfite 1-thioglycerin Sorbitan ester* pH 8.0g 2g 0.4- 0.1g 6.20 Same as mother liquor pH was adjusted with hydrochloric acid or sodium hydroxide.

engineered blood deer Mother liquor replenisher ethylenediamine 4 vinegar Acid/disodium salt ・Dihydrate salt ethylenediamine 4 vinegar Acid・Fe(I[[)・A Ammonium dihydrate salt potassium bromide ammonium nitrate 2.0g 4.0g 120g 240g 100g200g 10g 20g pH5,705,50 pH was adjusted with hydrochloric acid or sodium hydroxide.

Emperor Isho ammonium thiosulfate sodium sulfite sodium bisulfite Mother liquor Replenisher Same as 8.0g mother liquor 5.0g 5.0g Genko Deer Polyoxyethylene- p-monononylphe nyl ether (average Degree of polymerization 10) Sorbitan ester* 0.5d p H6,60 The pH was adjusted with hydrochloric acid or aqueous ammonia.

Example 2 The performance of Samples 101 to 122 was compared in exactly the same manner as in Actual Flow Side 1 except that the development process in Example 1 was carried out as described below, and almost the same results as in Example 1 were obtained.

Processing process Time Temperature h'l capacity black and white development 6 minutes 38° CI2J First water washing 2113811411 Reversal 2〃3811411 Color development 6〃381/1211 Adjustment 2〃381141 bleach-fixing 61
138111211 Second water wash (1) 21138/141 Second water wash (2) 2/138/141/ Stable 2〃 38〃 4〃7゜5 〃 Replenishment amount 2.2n/bore, 511 1, l〃 2. 2 ll 1, l〃 1.3〃 1.1 〃 The overflow liquid of the second water washing (2) was led to the second water washing (1) bath.

The composition of each treatment liquid was as follows.

Hoshiwari Image Solution Replenisher Nitrilo-N, N, N Trimethylenephosphonic Acid Pentasodium Salt Diethylenetriamine Pentaacetic Acid Pentasodium Salt Potassium Sulfite Hydroquinone Monosulfonate Potassium Carbonate L-Phenyl-4-Methyl-4-Hydroxy Methyl-3-pyrazolidone Potassium bromide Potassium thiocyanate Potassium iodide 2.0 g 2.0 g 3.0 g 3.0 g 30.0 g 30.0 g 20.0 g 20.0 g 33.0 g 33.0 g 2.0 g 2.5g 1.2g 2.0■ 2.0g 1.4g 1.2g 2.0■ pH (25℃) 9.60 9.70
pH was adjusted with hydrochloric acid or potassium hydroxide.

Indigo offering Nitrilo-N, N, N -trimethylenephos Honic acid 5 sodium mu salt Tin chloride dihydrate p-aminophenol Sodium hydroxide glacial acetic acid add water pH (25℃) pH is hydrochloric acid or sodium hydroxide Nitrilo-N, N, N -trimethylenephos Honic acid 5 sodium mu salt diethylenetriamine Mother liquor Replenisher Same as mother liquor 3.0g 1.0g 0.1g 8.0g 15.IW 1.01 6.00 Adjusted with ram.

2.0g 2.0g Pentasodium pentaacetic acid Sodium sulfite Tripotassium phosphate 1 dihydrate Potassium bromide Potassium iodide Sodium hydroxide N-ethyl citrazate = (β-methanesulfonamidoethyl)-3-methyl -4-aminoaniline sulfate 3.6-dithiaoctane-1. 8-diol 2.0g 7.0g 36, 0g 1.0g 90.0■ 3.0g 1.5g 10.5g 3.5g 2.0g 7.0g 36, 0g 3.0g 1.5g 10, 5 g 3.5 g pH (25°C) 11.90 12.
05 pH was adjusted with hydrochloric acid or potassium hydroxide.

! ! Hawk mother liquor Replenisher ethylenediamine 6 vinegar Same acid as mother liquor, disodium salt, dihydrate 8.0g Sodium sulfite 12.0g 2-Mercapto-1゜3.4-triazole 0.5g TWEEN
20" 2.〇-Add water
1.01 pH (25°C) 6.20 pH was adjusted with hydrochloric acid or sodium hydroxide.

TWEEN 20”: I CI Ameri
can Inc.

Manufactured surfactant: Mother liquor Replenisher: Ethylenediamine 6 vinegar Mother liquor: Same acid, disodium salt, dihydrate salt 2. Og Ferric ammonium ethylenediaminetetraacetic acid dihydrate 70.0g Ammonium thiosulfate (700g/A) 200.0g Ammonium sulfite 20.0g Add water
1.01 pH (25°C) 6.60 pH was adjusted with acetic acid or aqueous ammonia.

Shijika mother liquor Replenisher ethylenediamine 6 vinegar Add the same acid, disodium salt, dihydrate 1.0g imidazole 1.0g dimethylol urea 8.0g water to the mother liquor
1.0I pH (25°C) 7.50pH was adjusted with acetic acid or aqueous ammonia.

Example 3 The performance of Samples 101 to 122 was compared in exactly the same manner as in Example 1, except that the development process in Example 1 was carried out as described below, and almost the same results as in Example 1 were obtained.

Black and white development 6 minutes 38°C 1212,21,/rd First water wash 2〃38/14117.511 Reversal
2〃 381/ 411 1. l 〃Color development
6〃38/112112.2〃Bleaching 31
1 3871 6/I O, 15 fixed
Arrival 4113811 8/l 2.2 Second wash (1) 2 38114 Second wash (2) 2 38114 7.5 Stable 2 3811 4/l 1.1 Third wash 1 381/4〃1.1〃 The overflow liquid of the second water washing (2) was led to the second water washing (1) bath.

The compositions of the black and white developer to the color developer are the same as in (1).

Bleach solution 1.3-diaminopropanetetraacetic acid ■, 3-diaminopropanetetraacetic acid ferric ammonium monohydrate ammonium bromide ammonium nitrate hydroxyacetic acid acetic acid mother liquor 2.8 g 138.0 g 80, 0 g 20, 0 g 50, 0 g 50.0 g Replenisher 4.0 g 207, 0 g 120, 0 g 30, 0 g T5.0 g 75, 0 g pH (25°C) 3.40 2.80
The pH was adjusted with acetic acid or aqueous ammonia.

Fixed deer mother liquor Replenishment solution Ethylenediamine 6 vinegar Add the same acid di-sodium dihydrate to the mother liquor 1.7 g Sodium benzaldehyde-〇-sulfonate Sodium 20.0 g Sodium bisulfite 15.0 g Ammonium thiosulfate (700 g/Jl 340.0 d Imidazole 28.0 gpH (25°C)
A pH of 4.00 was adjusted with acetic acid or aqueous ammonia.

Replenishment mother liquor Same as ethylenediamine hexaacetic acid, disodium salt, dihydrate Sodium carbonate dimethylol urea 1.0 g 6.0 g 8.0 g pH (25°C) 10.00 pH is acetic acid or sodium hydroxide. It was adjusted.

Third washing solution mother liquor Replenisher ethylenediamine 6 vinegar Same acid as mother liquor, disodium salt, dihydrate 0.2 g Hydroxyethylidene-1,■-diphosphonic acid o, os g Ammonium acetate 2.0 g Sodium dodecylbenzenesulfonate 0. 3g pH (25°C) 4.50pH was adjusted with acetic acid or aqueous ammonia.

Example 4 Comparison of various performances of sample lot 122 was carried out in the same manner as in Example 1 except that the development treatment in Example 1 was carried out as described below, and almost the same results as in Example 1 were obtained.

Except for changing the adjustment solution and stabilizing solution in Example 1 of the development process, as shown below.
The procedure was exactly the same as in Example 1.

! ! Common stock solution/replenisher Ethylenediamine hexaacetic acid, disodium salt, dihydrate 8.0g Sodium sulfite 12.0g Hexamethylenetetramine 3.5g 2-Mercapto-1°3.4-triazole 0.5gTW
EEN 20” Add 2.0d water 1.01pH (25°C)
6.20 pH was adjusted with hydrochloric acid or sodium hydroxide.

TWEEN 20”: I CI Ameri
can Inc.

Surfactant p-monononyl phenyl ether ethylene diamine hexaacetic acid, disodium salt, dihydrate stabilizer 1 0, 2g 1, Og 0.02g pH (25℃) 7.00pH
was adjusted with acetic acid or aqueous ammonia.

1 Stabilizer CHI-CI (2-OH Example 5 A mixed solution of the compounds shown in Table 3 in water and methanol 1:1 was added to 0.05μ colloidal silica, and the mixture was stirred at room temperature for 5 hours. The compounds shown in Table 3 were adsorbed onto colloidal silica.

Polyoxyethylene - Preparation of samples 201 to 202 A methanol solution of compounds I-4 and 11-12 was added to the 6th layer, 9th layer, 10th layer, 11th layer, 15th layer, and 17th layer of sample 101 with halogen Samples 201 to 202 were prepared in exactly the same manner as sample 101, except that 7×10 −' moles of each were added per mole of silveride.

Preparation of Samples 203 to 204 Compounds I-4 and n-12(7) were added to the 6th layer, 9th layer, 10th layer, 11th layer, 15th layer, and 17th layer of sample 102.
7Xl of methanol solution per mole of silver halide
Samples 203 and 204 were prepared in exactly the same manner as sample 102, except that O-'' moles were added.

Preparation of Samples 205 to 206 Compounds ■-4 and I[-
Samples 205 and 206 were prepared in exactly the same manner as Sample 102 except that 12 was adsorbed onto colloidal silica.

Preparation of Samples 207 to 208 Compounds 4 and 12 were added to the 6th layer, 9th layer, 10th layer, 11th layer, 15th layer, and 17th layer of sample 101, respectively.
Samples 207 to 208 were prepared in exactly the same manner as sample 101, except that a substance obtained by adsorbing silica to colloidal silica was added.

In addition, in samples 205 to 208, I-4 and ll-
The amount of 12 added is 7 per mole of silver halide in each layer.
X10-3 mol.

Samples 101, 102, 201 to 208 were exposed to light through a light wedge in the same manner as in Example 1, and developed in the same manner as in Example 1 to give a density of 1. The relative sensitivity at 0 and Dmax were determined.

The results are shown in Table 4.

From the results shown in Table 4, the following is clear. When a stabilizer is added to a flat emulsion-containing layer in the form of a methanol solution, the sensitivity decreases, but when it is added in the form of a stabilizer adsorbed to the colloidal silica of the present invention, the sensitivity is almost reduced. It is possible to increase Dmax (that is, to suppress fog to a low level) without causing a decrease in image quality (Dmax).

Example 6 A sample was prepared in which the Example 3 sensitive material 9 described in JP-A-2-93641 was modified in the same manner as the sample 101 of Example 1 of the present invention. Example 1 of
When similar tests were conducted, results similar to those of the present invention were obtained.

The development process at this time is Example 3 of JP-A-2-93641.
It was performed as described.

(Effects of the Invention) It is known to form silver halide grains into tabular shapes as a means of suppressing light scattering by silver halide grains and improving sharpness.

Various silver halide stabilizers (interimage effect improving compounds, desilvering accelerators, fog inhibitors, etc.) are added to this tabular emulsion.
When added as a conventional solution such as methanol, it causes a large decrease in sensitivity, but when added as a solid dispersion of the present invention, there is almost no decrease in sensitivity. The effect is also fully expressed. These effects are extremely remarkable and have a practical significance.

Claims (2)

[Claims] (1) In a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, at least one of the light-sensitive silver halide emulsion layers has a grain diameter that is three times or more the grain thickness. at least one silver halide emulsion layer and /
or the hydrophilic colloid layer contains in a solid state a silver halide emulsion stabilizing substance whose solubility in water at pH = 9.5 is three times or more the solubility in water at pH = 6.0. A silver halide photographic material characterized by: (2) In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, at least one layer of the light-sensitive silver halide emulsion layer has grains having a grain diameter of three times or more the grain thickness. containing an emulsion containing tabular silver halide grains, the grains occupying at least 50% of the total projected area of the silver halide grains present in the same layer, and at least one silver halide emulsion layer and/or , a silver halide emulsion stabilizing substance whose solubility in water at pH=9.5 is three times or more than the solubility in water at pH=6.0 is adsorbed in the hydrophilic colloid layer. 1. A photographic material containing silver halide in a state of being adsorbed to non-photosensitive fine particles having a surface that allows the silver halide to be oxidized.