JPS6311929A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a large inter-image effect by incorporating monodisperse silver halide particles into a silver halide emulsion layer and incorporating a specific compd. into the silver halide emulsion layer and/or non-photosensitive layer. CONSTITUTION:The silver halide emulsion layer of a silver halide photographic sensitive material having at least one silver halide emulsion layer on a base contains the monodisperse silver halide particles and contains at least one kind of the compd. expressed by the formula I in the silver halide emulsion layer and/or the non-photosensitive layer. In the formula, R denotes a straight chain or branched alkylene group, alkenylene group, aralkylene group or arylene group, Z denotes a hydrogen atom or polar substituent, Y denotes the compd. expressed by the formula II. R1-R8 respectively independently denote a hydrogen atom or substd. or unsubstd. alkyl group, aryl group, alkenyl group or aralkyl group, X is a hydrogen atom, alkali metal atom, ammonium group or the group to be cloven under alkaline conditions, n denotes 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic material with improved interimage effect and improved sharpness and graininess.

(Prior art) By color-developing a silver halide color photographic light-sensitive material, the oxidized aromatic-amine color developing agent and coupler react to produce indophenol, indoaniline, indamine, azomethine, and phenoxazine. , phenazine and similar dyes are known to form color images. In this system, subtractive color reproduction is usually used for color reproduction, with silver halide emulsions selectively sensitive to blue, green, and red, and yellow, magenta, and cyan color image-forming agents, which are complementary colors, respectively. is used. To form a yellow image, for example, acylacetanilide or dibenzoylmethane couplers are used, and to form a magenta image, pyrazolone, pyrazolobenzimidazole, pyrazolopyrazole, pyrazolotriazole, cyano Acetophenone or indacylon couplers are used, and phenolic or naphthol couplers are primarily used to form cyan images.

By the way, the dyes produced from these couplers do not have ideal spectral absorption spectra; magenta and cyan dyes in particular have broad absorption spectra or have sub-absorption in the short wavelength region, making it difficult for color photographic materials to be used. Unfavorable for color reproduction.

In particular, sub-absorption in the short wavelength region tends to cause a decrease in chroma. As a means of improving this, it is possible to improve it to some extent by creating an interimage effect.

Regarding the interimage effect, 1For example, Hanson (
Hanson et al., 'Journal of the Optical Society of America
of the 0ptical 5ociety o
f America)”, Vol. 42, pp. 663-66
Page 9 and A. Th1els
Author: Zeitsschrift fj
ir VissenschaftlichePhoto
graphie, photophysique un
d Photo-chemie) Vol. 47, pages 106 to 11g and pages 246 to 255.

U.S. Pat. No. 3,536,486 discloses that by introducing diffusible 4-thiazoline-2-thione into exposed color reversal photographic elements, U.S. Pat.
No. 87 describes a method for introducing diffusible 4-thiazoline-2-thione into unexposed color reversal photographic elements to obtain desirable interimage effects.

In addition, Japanese Patent Publication No. 34169/1983 discloses that when developing a color photographic light-sensitive material to reduce silver halide to silver, the presence of an N-substituted-4-thiazoline-2-thione compound produces a remarkable interimage effect. It is stated that the effect appears.

Research Disclosure (
Research Disclosure), Oni 131
, Section 13116 (1975).

Furthermore, U.S. Pat. No. 4,082,553 discloses a color reversal photosensitive material having a layer arrangement that allows movement of iodide ions during development, in which one layer contains latent image-forming silver haloiodide grains. , latent image-forming silver halide grains in another layer;
A method is described for obtaining good interimage effects by including silver halide grains whose surfaces are fogged so that they can be developed independently of imagewise exposure.

However, in the above method, the interimage effect is insufficient, the use of a colloidal silver-containing layer, the introduction of fogged silver halide grains, etc. cause a decrease in the density of one color in color reversal light-sensitive materials. It has its drawbacks.

In addition to the above, couplers (DIR couplers) that can release development-inhibiting substances such as benzotriazole derivatives and mercapto compounds during a coupling reaction with an oxidized form of a color developing agent in one color development process, for example.
It is known that interimage effects can be avoided by using hydroquinone compounds that can release development-inhibiting substances such as iodide ions and mercapto compounds during development. The use of these compounds has been limited because they are associated with significant desensitization and a decrease in color density.According to the inventors' many years of research, polydispersity It has become clear that when a compound that improves the interimage effect is used in a light-sensitive silver halide emulsion, the gradation in high-exposed areas becomes significantly softer when exposed to white light, and this has a significant negative effect on tone reproduction in high-exposed areas. Ta.

(Objective of the Invention) The object of the present invention is, firstly, to
An object of the present invention is to provide a multilayer color photographic material having a large interimage effect.

A second object of the present invention is to provide a multilayer color silver halide photographic material with excellent sharpness.

A third object of the present invention is to provide a black and white silver halide photographic material having high sharpness and good graininess.

(Structure of the Invention) The 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, in which the silver halide emulsion layer has monodisperse halogenated By a silver halide photographic light-sensitive material containing silver grains, and containing at least one compound represented by general formula (1) in the silver halide emulsion layer and/or non-photosensitive layer. achieved.

General formula (1) where R represents a linear or branched alkylene group, alkenylene group, aralkylene group, or arylene group,
Z is a hydrogen atom or a polar substituent R3, R4, R,, R
, R7 and R8 each independently represent a hydrogen atom, or a substituted or unsubstituted alkyl group, aryl group, alkenyl group, or aralkyl group, X is a hydrogen atom, an alkali metal atom, an ammoniamyl group, or under alkaline conditions n represents a group cleaved below; n represents O or 1;

More specifically, R is a linear or branched alkylene group (
For example, methylene group, ethylene group, propylene group, butylene group, hexylene group, 1-methylethylene group, etc.),
Straight-chain or branched alkenylene groups (e.g., vinylene, 1-methylvinylene, etc.), straight-chain or branched aralkylene groups (e.g., benzylidene, etc.), arylene groups (e.g., phenylene, naphthylene, etc.) represent.

Examples of the polar substituent represented by 2 include substituted or unsubstituted amino groups (including salt forms, such as amino groups, hydrochloride of amino groups, methylamino groups, dimethylamino groups, hydrochloric acid of dimethylamino groups) salt, dibutylamino group,
Dipropylamino group, N-dimethylaminoethyl-N-
methylamino group, etc.).

Quaternary ammoniayl groups (e.g., trimethylammonylamyl chloride group, dimethylbenzylammonyl chloride group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, 2-methoxyethoxy group, etc.), aryloxy groups (e.g., phenoxy Base.

), alkylthio groups (e.g., methylthio group, butylthio group, etc.), arylthio groups (e.g., phenylthio group, etc.), heterocyclic oxy groups (e.g., 2-pyridyloxy group, 2-imidazolyloxy group, etc.), Heterocyclic thio groups (e.g., 2-benzthiazolylthio group, 4-birazolylthio group, etc.), sulfonyl groups (e.g., methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl groups (e.g., unsubstituted carbamoyl group, methylcarbamoyl group, etc.), sulfamoyl group (e.g., unsubstituted sulfamoyl group, methylsulfamoyl group 1, etc.), carbonamide group (e.g., acetamide group, benzamide group 1, etc.), sulfonamide group (
For example, methanesulfonamide group, benzenesulfonamide group, etc.), acyloxy group (e.g., acetyloxy group, benzoyloxy group, etc.), ureido group (e.g., unsubstituted ureido group, methylureido group, ethylureido group, etc.), acyl groups (e.g., acetyl group, benzoyl group, etc.), aryloxycarbonyl groups (e.g.,
phenoxycarbonyl group, etc.), thioureido group (e.g., unsubstituted thioureido group, methylthioureido group 1
etc.), sulfonyloxy groups (e.g., methanesulfonyloxy group, p-toluenesulfonyloxy group, etc.).

Heterocyclic groups (e.g., 1-morpholino group, 1-piperidino group, 2-pyridyl group, 4-pyridyl group, 2-chenyl group, 1-pyrazolyl group, 2-imidazolyl group, 2-tetrahydrofuryl group, 2-tetrahydro chenyl group, etc.)
, a cyano group, a sulfonic acid group or a salt thereof, a carbonyl acid group or a salt thereof, a hydroxy group, and an alkoxycarbonyl group (eg, a methoxycarbonyl group, an ethoxycarbonyl group, etc.).

or -N-3O□-, R1, R,, R3
, R.

Rs, R7 and R each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group (e.g., methyl group, ethyl group, propyl group, 2-dimethylaminoethyl group, etc.), a substituted or unsubstituted alkyl group, Aryl groups (e.g. phenyl group, 2-methylphenyl group).

etc.), a substituted or unsubstituted alkenyl group (eg, propenyl group, 1-methylvinyl group, etc.), or a substituted or unsubstituted aralkyl group (eg, benzyl group, phenethyl group, etc.).

X is a hydrogen atom, an alkali metal atom (for example.

sodium atom, potassium atom 9, etc.), an ammonylamyl group (e.g., trimethylammonylamyl chloride group, dimethylbenzylammonylamyl chloride group, etc.), or a group that cleaves under alkaline conditions (under alkaline conditions,
=H or a group that can be an alkali metal, such as an acetyl group, a cyanoethyl group, a methanesulfonylethyl group, etc.

In general formula (13), preferably R is an alkylene group, Y is -5-1, and n=1.

Specific examples of the compound represented by the general formula (1) are shown below, but the compounds of the present invention are not limited thereto.

CH.

(1 of ShiH5 (TI) CQ” CH.

CH.

CH, CH, C00H CH.

CH3 CH.

Qe H3 The compound represented by the general formula [I] used in the present invention is
'Advances in Heterocyclic Chemistry
icChemistry)”, Volume 9, Pages 165-2
09 pages (1968), “Journal of Pharmaceutical Society Japan (Journ
al of Pharmaceutical 5ocie
ty Japan)”, Vol. 71, pp. 1481-14
It can be synthesized with reference to US Pat. No. 2,823,208, p. 84 (1951). In addition, when Y represents a ureido group or a thiourido group, 2-amino-5-mercapto-1,3,4-thiadiazole is reacted with isocyanates or isothiocyanates, or
2-Mercapto-5-phenoxyluponylamino-1
, 3,4-thiadiazole with amines.

Typical synthesis examples are shown below.

Synthesis Example 1 Synthesis method of compound (1) 2.5-dimercapto-1,3,4-thiadiazole 7
．． 5g, 2-aminoethyl chloride hydrochloride 5.8g,
4 g of pyridine was added to 60 mQ of n-butanol, and the mixture was heated under reflux for 2 hours. The reaction solution was cooled with water, and the precipitated crystals were collected by filtration and recrystallized from methanol/water. Yield 7.1 g, melting point 228-229°C (decomposition) Synthesis Example 2 Synthesis method of compound (14) 2.5-dimercapto-1,3,4-thiadiazole 1
．． 5g.

7.3 g of 2-dimethylaminoethyl chloride hydrochloride,
4 g of pyridine was added to 60 mQ of n-butanol and heated under reflux for 2 hours. The reaction solution was ice-cooled, and the precipitated crystals were collected by filtration and recrystallized from ethanol. Yield 7.9g, melting point 16
1 to 163°C Synthesis Example 3 Synthesis method of compound (13) 2.5-dimercapto-1,3,4-thiadiazole 7
．． 5g, 2-diethylaminoethyl chloride hydrochloride 8
．． 6 g of pyridine and 4 g of pyridine were added to 60 mQ of n-butanol, and the mixture was heated under reflux for 2 hours. The reaction solution was ice-cooled, and the precipitated crystals were collected by filtration and recrystallized from methanol/water. Yield 10.1
g, melting point 184-186°C Synthesis Example 4 Synthesis method of compound (3) 2.5-dimercapto-1,3,4-thiadiazole 7
．． 5 g of 3-dimethylaminopropyl chloride hydrochloride, 7.9 g of pyridine, and 4 g of pyridine were added to 60 mQ of n-butanol and heated under reflux for 2 hours. The reaction solution was ice-cooled, and the precipitated crystals were collected by filtration and recrystallized from ethanol. Yield 11g,
Melting point 149-152°C Synthesis Example 5 Synthesis method of compounds (42) and (43) ■ 2
- Synthesis method of (N,N-bis(2-methoxycarbonylethyl)aminocoethyl chloride hydrochloride) 6.1 g of 2-aminoethanol was added to 75 mQ of methanol, and 20 mM of methyl acrylate was added dropwise under water cooling.After the dropwise addition, 20 mM of methyl acrylate was added under water cooling. The reaction mixture was stirred for 20 hours and further stirred at room temperature for 20 hours. The reaction solution was distilled off under reduced pressure. To the resulting oil (23 g) was added 100 mM of chloroform, and 8.7+ wfi of thionyl chloride was added dropwise under water cooling. Then, the mixture was heated under reflux for 1 hour. The reaction solution was distilled off under reduced pressure, and the resulting residue was recrystallized from isopropanol/n-hexane. Yield: 21 g, melting point: 103-104°C. ■ Synthesis of compound (42) 2.5-dimercaptothiadiazole 7. 5g, 2-
[14.4 g of N,N-bis(2-methoxycarbonylethyl)aminocoethyl chloride and 8.1 g of pyridine were added to dioxane 80n+Q, heated under reflux for 2 hours, and the resulting residue was distilled off under reduced pressure. Compound (42) was obtained as a syrup by purification by column chromatography (stationary phase alumina, developing solvent methanol/ethyl acetate). Yield: 8.4 g (1) Synthesis of Compound (43) 7.3 g of Compound (42) was added to 20+ am of a 20% aqueous sodium hydroxide solution and stirred at 50°C for 2 hours. The reaction solution was neutralized with 35% hydrochloric acid while cooling on ice, and the resulting precipitate was collected by filtration and recrystallized from DMF/ethanol to obtain compound (43). Yield 3.2g, melting point 188-18
9°C Synthesis Example 6 Synthesis method of compound (4) 2.5-dimercapto-1,3,4-thiadiazole 1
5.0g.

20 mQ of a 28% sodium methoxide solution was added to ethyl alcohol loOmR, dissolved by heating, and 13.5 g of 2-chloroethyl urea was added dropwise. After the dropwise addition, the reaction solution was heated under reflux for 4 hours, and the reaction solution was poured into 700 mfi of ice water, and the precipitated crystals were collected by filtration and recrystallized from methanol.

Yield 16.4 g, melting point 174-176°C Synthesis Example 7 Synthesis method of compound (2) 15 g of 2,5-dimercapto-1,3,4-thiadiazole was added to 300 mM acetone, and then 22 mM
of sodium methoxide and 12 g of β-
Chlorpropionamide was added.

Furthermore, 15 g of sodium iodide was added to this reaction solution, and 2
The mixture was heated under reflux for 0 hours. After cooling, the obtained crystals were collected by filtration and washed with water. The crystals were recrystallized from a mixed solvent of dimethylformamide and methanol to obtain compound (2).

Yield 12.0 g, melting point 175-177°C Synthesis Example 8 Synthesis method of compound (44) 2.5-dimercapto-1,3,4-thiadiazole 1
5.0 g, 20.0 g of 1-(2-chloroethyl)imidazole hydrochloride, and 9.5 g of pyridine in 10 g of acetonitrile.
The mixture was added to 0 mQ and heated under reflux for 4 hours. After the reaction, the reaction solution was cooled, the precipitated crystals were collected by filtration, and recrystallized from a mixed solvent of dimethylformamide and methanol to obtain compound (44).
I got it.

Yield 11.2g, melting point 226-228°C Synthesis Example 9 Synthesis method of compound (45) 2-Mercapto-5-phenoxycarbonylamino = 1
．． 200 mg of acetonitrile was added to 12.7 g of 3.4-thiadiazole, and 6.2 g of 3-N,N-dimethylaminopropylamine was added dropwise at room temperature. 1. At 50°C after dropping.
The mixture was heated and stirred for 5 hours, and the precipitated crystals were collected by filtration and recrystallized from a mixed solvent of methanol and concentrated hydrochloric acid to obtain compound (45).

Yield 10.7g% Melting point 228-230℃ Synthesis Example 10
Synthesis method of compound (46) 2-amino-5-mercapto-
13.3 g of 1,3,4-thiadiazole was dissolved in 100 mM of acetonitrile and 40 mQ of dimethylacetamide, and 15.9 g of 3-(N,N-dimethylamino)propyl isothiocyanate was added dropwise at room temperature.

After the dropwise addition, the mixture was heated and stirred at 50° C. for 2 hours, and the precipitated crystals were collected by filtration and recrystallized from a mixed solvent of methanol and concentrated hydrochloric acid to obtain compound (46).

Yield 12.6g, melting point 146-148℃ Synthesis Example 11
Synthesis method of compound (50) 2-mercapto-5-phenoxycarbonylamino-1,3,4-thiadiazole 12
．． 100 g of ethyl alcohol was added to 7 g, and 8.7 g of 3-morpholinopropylamine was added dropwise at room temperature. After the addition, the mixture was stirred at room temperature for 5 hours, and the precipitated crystals were collected by filtration and recrystallized from a mixed solvent of methanol and salt i4 to obtain compound (50).

Yield: 10.9 g, melting point: 255 DEG -257 DEG C. Monodisperse silver halide grains in the present invention have a grain size distribution defined by the following formula. That is, when the standard deviation S of the particle size distribution is divided by the average particle size F, the value is 0.20 or less.

In the case of spherical silver halide grains, the average grain size referred to here refers to the average diameter of the grains, and in the case of grains with shapes other than cubic or spherical, the projected image is converted to a circular image of the same area. f is defined by the following formula, where the individual grain diameter is ri and the number of grains is ni.

The above particle size can be measured by various methods commonly used in the technical field for the above purpose.A representative method is Loveland's "Particle Size Analysis". Law J A, S
, T.M., Symposium on Ride Microscopy, 1955, pp. 94-122 or.

"The Theory of Photographic Processes" by J Mies and James,
It is described in Chapter 2 of the 3rd edition, published by Macmillan (1966). The particle size can be measured using the projected area of the particle or an approximate diameter value.

The silver halide grains used in the silver halide emulsion layer according to the present invention preferably contain the above-mentioned monodisperse silver halide grains in an amount of 70% or more of the total grains in the same silver halide emulsion layer, particularly It is preferable that all the grains are monodisperse silver halide grains.

The monodisperse silver halide grains used in the present invention may be used alone, or two or more types of monodisperse silver halide grains having different average particle diameters may be arbitrarily mixed and preferably used. Can be done.

The shape of the silver halide grains according to the present invention may be, for example, hexahedral, octahedral, dodecahedral, plate-like, spherical, etc., or may be a mixture of these various shapes.

To produce monodisperse silver halide grains, grains of a desired size can be obtained by a double jet method while keeping ρAg constant. Monodisperse silver halide grains can also be produced by a double jet method in the presence of a silver halide solvent such as ammonia, thioether or thiourea.

Examples of the silver halide solvent used in the present invention include U.S. Pat. No. 3,271,157, U.S. Pat. No. 3,531,289, U.S. Pat.
Organic thioethers described in JP-A-53-82408 and JP-A-55-777, etc.
Thiourea derivatives described in No. 37, No. 55-2982, etc., and halogenated compounds having an oxygen or thiocarbonyl group sandwiched between a sulfur atom and a nitrogen atom described in JP-A No. 53-144319. Silver solvent, JP-A-54-1007
Examples include imidazoles, sulfites, and thiocyanates described in No. 17.

The method for producing monodisperse silver halide emulsions is described in U.S. Patent No. 3,
No. 574,628, No. 3,655,394 and British Patent No. 1,413,748. Also, JP-A-48-8600, JP-A No. 51-39027, JP-A No. 5
No. 1-83097, No. 53-137133, No. 54-
No. 48521, 54-! No. 119419, 58-3
Monodisperse emulsions such as those described in No. 7635 and No. 58-49938 can also be preferably used in the present invention.

In the process of producing silver halide grains according to the present invention,
For example, an iridium salt, a cadmium salt, a zinc salt, a lead salt, a thallium salt, a rhodium salt, or a complex salt thereof may be present.

The monodisperse silver halide emulsion according to the present invention may be a surface latent image type emulsion that forms a latent image on the grain surface or an internal latent image type emulsion that forms a latent image inside the grain. .

The latent image of the internal latent image type emulsion referred to here is 30 mm from the grain surface.
It is preferable to exist at a distance of 500 people, and particularly preferably to exist at a distance of 50 to 400 people.

This internal latent image type emulsion can be produced by depositing silver halide on a silver halide emulsion whose grain surfaces have been chemically sensitized. Silver halide deposition methods include, for example, adding silver nitrate aqueous solution and alkali halide aqueous solution to a silver halide emulsion in which the surface of each grain has been chemically sensitized while controlling p and Ag; A method may also be employed in which fine grain unsensitized silver halide is added to a chemically sensitized silver halide emulsion and Ostwald ripening is performed.

These methods are described in US Pat.
No. 3,966,476, et al.

When a polydisperse light-sensitive silver halide emulsion is used in the layer receiving the interimage effect (hereinafter referred to as the "receiving layer") and the compound that improves the interimage effect of the present invention is further used, white light exposure is possible. The layer that gives an interimage effect (hereinafter referred to as the "imparting layer") in the highly exposed areas when exposed to light is developed and released, and the iodide ions diffused into the receiving layer cause polydispersity of the photosensitive silver halide in the receiving layer. Among the emulsions, the fine grain emulsion was particularly inhibited in development, and the gradation in highly exposed areas became significantly softer, resulting in a significant loss of tone reproduction in highly exposed areas.

Also, among the polydisperse photosensitive silver halide emulsions of the receiving layer,
Coarse grain emulsions are less susceptible to interimage effects.

On the other hand, when the monodisperse photosensitive silver halide emulsion of the present invention is used in the receiving layer, and a compound that improves the interimage effect of the present invention is further used, in the highly exposed area when exposed to white light, , development is not significantly inhibited by iodide ions diffused into the receiving layer after the imparting layer is developed. Therefore, the tone in the highly exposed area is less softened, and the tone reproduction in the highly exposed area is not impaired.Moreover, the interimage effect can be improved even when a polydisperse silver halide emulsion is used in the receiving layer. It was expressed more than in comparison.

When the compound represented by the general formula of the present invention is used in a multilayer color photographic light-sensitive material, a silver halide emulsion layer containing a monodisperse silver halide emulsion and/or a non-photosensitive layer 1, for example, a yellow filter. It is contained in at least one layer such as an antihalation layer, an intermediate layer, or a protective layer, but is preferably contained in a silver halide emulsion layer containing a monodisperse silver halide emulsion or a layer adjacent thereto. Furthermore, it is most preferable to include it in a silver halide emulsion layer containing a monodisperse silver halide emulsion.

Furthermore, when applying the present invention to black and white photographic materials,
A compound represented by the general formula [I] is contained in a silver halide emulsion layer containing a monodisperse silver halide emulsion and/or a protective layer.

The compound of the present invention represented by general formula (1) varies depending on the nature, purpose, or development method of the silver halide photographic material to which it is applied, but generally the compound of the present invention is added to 1 mole of silver halide present in the same layer or an adjacent layer. On the other hand, 10-1 to 10-
5 moles, preferably 3×10−” to 3×10
- moles.

In order to introduce the compound represented by the general formula (1) of the present invention into a light-sensitive material, it is dissolved in a solvent commonly used in photographic light-sensitive materials such as water, methanol, ethanol, propatool, or fluorinated alcohol, and then Add to hydrophilic colloids. (2) When it is contained in the silver halide emulsion layer, it may be present at the time of grain formation of the silver halide emulsion, at the time of physical ripening, immediately before chemical sensitization, during chemical sensitization, after chemical sensitization, or at the time of coating solution preparation. Either one may be used and is selected depending on the purpose.

The photosensitive materials to which the present invention is applied include, for example, color negative films, color reversal films (inner and outer molds), color papers, and color positive films.

Color reversal paper, color diffusion transfer process and die
Color photographic materials such as transfer process, black and white negative film, and black and white photographic paper.

Any black and white photographic material such as X-ray film or lithographic film may be used.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. The preferred silver halide is silver iodobromide or silver iodochlorobromide containing up to about 30 mole percent silver iodide. Particularly preferred is silver iodobromide containing from about 0.5 mole percent to about 10 mole percent silver iodide.

The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof. Also, mixtures of particles of various crystal forms may be used.

The grain size of silver halide is approximately 0. It may be fine particles of 1 micron or less or large particles with a projected area diameter of about 10 microns.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, such as Research Disclosure,
Volume 176, No. 17643 (December 1978),
Pages 22-23, 1■, Emulsion production (Emulsion P
187, No. 18716 (November 1979)
May), 648, the method described above can be followed.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Paul Montell (P.

Glafkides, Chimia et Phys
ique Photo6raphique.

Paul Montel, 1967), ``Photographic Emulsion Chemistry'' by Duffin, published by Focal Press (G, F
, Duffin.

Photographic! 2mulsion Ch
emistry, Focal Press.

1966), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al.
, Published by Focal Press (V, L, Zelikn+
anet al, Makingand Coatin
5 PhotoEraphic Emul-sion+
Focal Press+ 1964). In other words.

Any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, a method in which pAε in a liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

In addition, known silver halide solvents (for example, ammonia, Rodankali or U.S. Pat.
No. 144319, No. 54-100717 or No. 5
Physical ripening can also be carried out in the presence of thioethers and thione compounds described in No. 4-155828 and the like.

By this method as well, a silver halide emulsion with a regular crystal shape and a nearly uniform grain size distribution can be obtained.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling I'Ag and pH during grain formation. For more information, please see Photographic Science
and Engineering (Photographic
5science and engineering
), Volume 6, pp. 159-165 (1962); Journal of Photographic Science (Jour
nal ofPhotographic 5cienc
e L Vol. 12, pp. 242-251 (1964), U.S. Patent No. 3. 655. No. 394 and British Patent No. 1
, No. 413.748.

Further, tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering (
Gutoff, Photographic 5ci-
ence and IF Hineering) + 14th
Vol. 248-257 (1970); U.S. Patent No. 4.
434. No. 226, No. 4,414,310, No. 4
, 433°048, 4,439,520 and British Patent No. 2,112.15'7. The use of tabular grains has advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes, which are detailed in the above-cited U.S. Pat. No. 4,434,226. .

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1,027,1
46, U.S. Patent No. 3.505.068, 4,4
44,877 and Japanese Patent Application No. 58-248469.

Further, silver halides having different compositions may be joined by epitaxial joining, and for example, silver halides, rhodan silver,
It may be bonded with a compound other than silver halide, such as lead oxide. These emulsion grains are described in U.S. Patent No. 4,094.
, No. 684, No. 4,142.900 1. 4,459
, 353, British Patent No. 2,038,792, U.S. Patent No. 4.349.622, U.S. Patent No. 4,395,4781
．． 4゜433.501, 4,463,087,
It is disclosed in 3.656,962, 3,852,067, JP-A-59-162540, etc.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains.

In order to remove soluble root salts from the emulsion before and after physical ripening, Nudel water washing, flocculation sedimentation method, ultraleakage method, etc. are used.

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization.

The additives used in such processes are based on the research and research mentioned above.
Disclosure+-NO, 17643 (December 1978
) and No. 18716 (November 1979), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

Additive type RD17643 RD187
161 Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity enhancers Same as above 3 Spectral sensitizers, Pages 23-24 Page 648 Right column - Super sensitizers 649 True right column 4 Brighteners
Page 24 5 Antifoggant Pages 24-25 Page 649 Right column and Stabilizer 6 Light absorber, Fi Page 25-26 Page 649 Right column ~
Luther dye, page 650 left column ultraviolet absorber 7 stain inhibitor page 25 right column page 650 left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column 10
Binder 26 pages Same as above 11
Plasticizer, lubricant Page 27 Page 650 Right column 12
Coating aid, pages 26-27 Same as above Surfactant Various color couplers can be used in the present invention, specific examples of which are described in Research Disclosure No. 17643, ■-〇, G mentioned above. described in the patent issued by As dye-forming couplers, couplers that provide the three primary colors (i.e., yellow, magenta, and cyan) in subtractive color development are important; Hydrophobic, diffusion resistant.

Specific examples of 4-equivalent or 2-equivalent couplers include the couplers described in the aforementioned Research Disclosure No. 17643, Sections 1-C and D, as well as 4. The following can be preferably used in the present invention.

A representative example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. A specific example is US Patent No. 2.
No. 407,210 1. It is described in No. 2,875.057 and No. 3,265.506 of the same. The use of two-equivalent yellow couplers is preferred for the present invention; U.S. Pat. 3゜933.501 and 4,022,62
The oxygen atom separation type yellow coupler described in No. No. 10739, U.S. Patent No. 4
, No. 401, 752, 4. 326. No. 024, R
D18053 (April 1979), UK Patent 1,42
No. 5,020, West German Application No. 2゜219.917,
2,261,361, 2,329,587 and 2. 433. A typical example thereof is the nitrogen atom separation type yellow coupler described in No. 812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include hydrophobic indacylon- or cyanoacetyl-based couplers, preferably 5-pyrazolone- and pyrazoloazole-based couplers, which have a ballast group. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye.
311.082, 2,343.703, 2゜6
No. 00.788, No. 2,908.573, No. 3.06
No. 2,653 1. No. 3,152,896 and No. 3,
No. 936,015, etc. 5- of Nitokei
As a leaving group for pyrazolone couplers, US Pat.
Particularly preferred are the nitrogen atom leaving groups described in US Pat. No. 310.619 or the arylthio groups described in US Pat. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73,636 provides high color density. As a pyrazoloazole coupler, US Patent No. 3. 061. 432, preferably pyrazolo[5,1
-c] [1,2,4] Triazoles, Research Disclosure No. 24220 (June 1984) and virazolotetrazoles and Research Disclosure No. 33552/1984.

24230 (June 1984) and Japanese Patent Publication No. 1986-43
Examples include pyrazolopyrazoles described in No. 659.

U.S. Pat. 500. The imidazo[1,2-b]pyrazoles described in EP 119.860A are preferred, as are the pyrazolo[1,5-b][
1,2,4]) Riazole is particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol and phenolic couplers, as described in US Pat. 474°293, preferably the naphthol couplers described in U.S. Pat. No. 4,052.
, No. 212, No. 4,146.396, No. 4,228,
Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 233 and No. 4,296,200. Specific examples of phenolic couplers include U.S. Pat. No. 2,369.929 and U.S. Pat.
No. 71, No. 2,772.162, No. 2.895,82
It is stated in issue 6 etc.

Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is the one described in U.S. Pat. Phenolic cyan coupler having U.S. Pat. No. 2,772,162;
No. 3,758°308, No. 4,126,396, No. 4,334.011, No. 4,327,173, West German Patent Publication No. 3,329,729 and European Patent No. 12
1.365, etc., and U.S. Pat. No. 3.446.
, No. 622, 4. 333. No. 999, 4,45
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in No. 1,559 and No. 4,427.767.

In order to correct unnecessary absorption of color pigments, it is preferable to use a colored coupler in combination with a color negative sensitive material for photographing to perform masking. Yellow colored magenta couplers described in U.S. Pat. No. 4,163.670 and Japanese Patent Publication No. 57-39413, etc. or U.S. Pat.
No. 9, No. 4,138.258 and British Patent No. 1.
146. Typical examples include the magenta-colored cyan coupler described in No. 368. Other colored couplers are from the aforementioned Research Disclosure.

No. 17643, described in section ■-G.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
U.S. Patent No. 4,366.237 and British Patent No. 2.
No. 125,570 contains a specific example of a magenta coupler in 4. Also, European Patent No. 96,570 and West German Application No. 3,
No. 234,533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451,82.
No. 0 and No. 4. 080. It is described in No. 211. Specific examples of polymerized magenta couplers are described in British Patent No. 2. 102. No. 173 and U.S. Patent No. 4.36
7.282.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. As the DIR coupler that releases the development control agent, the patented coupler described in the aforementioned Research Disclosure, No. 17643, Section 1-F is useful.

Preferred in combination with the present invention is JP-A-57-
Phenomenal method deactivated type represented by No. 151944; U.S. Pat.
Timing type represented by No. 1987-39653
Particularly preferred are JP-A-57-151944, JP-A-5B-217932,
Phenomenological deactivation type DIR couplers described in Japanese Patent Application No. 59-75474, No. 59-82214, No. 59-82214, No. 59-90438, etc. and Japanese Patent Application No. 1983
This is a reactive DIR coupler described in No.-39653 and the like.

The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods, such as a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. be able to. In the oil-in-water dispersion method, a high-boiling organic solvent with a boiling point of 175°C or higher and a so-called auxiliary solvent with a low boiling point are dissolved in a liquid solution or a mixture of the two, and then water or a mixture of the two is dissolved in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous gelatin solution. Examples of high boiling point organic solvents are U.S. Pat.
．． It is described in No. 027, etc.

Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

Specific examples of the latex dispersion process, effects, and latex for impregnation include U.S. Pat. It is described in.

The photosensitive material produced using the present invention contains a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, and the like. It may also contain sulfonamide phenol derivatives and the like.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
6-Hydroxychroman[,5-hydroxycoumarans 1. Spirochroman'f4, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzenes,
Representative examples include aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The arrangement of these layers can be arbitrarily selected as required. The preferred order of layer arrangement is red sensitivity, green sensitivity, and blue sensitivity from the support side, or blue sensitivity, red sensitivity, and green sensitivity from the support side. Furthermore, each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may exist between two or more emulsion layers having the same malignancy.
1. Cyan-forming coupler in the red-sensitive emulsion layer. Usually, the green-sensitive emulsion layer contains a magenta-forming coupler and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
It is preferable to appropriately provide auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an anti-hesion layer, and a backing layer.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic materials. be done. Useful flexible supports include cellulose, i-forms (W cellulose, cellulose acetate, cellulose acetate butyrate, etc.), films made of synthetic polymers (polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc.), and baryta. It is paper coated or laminated with a layer or an α-first nofin polymer (for example, polyethylene, polypropylene ethylene, butene copolymer).

The support may be colored using a dye or pigment, or may be black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion to photographic emulsion layers and the like.

The surface of the support is subjected to glow discharge, corona discharge, ultraviolet irradiation 1. before or after undercoating treatment. Perform flame treatment, etc.

It's okay.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods can be used, such as dip coating, roller coating, curtain coating, and extrusion coating. U.S. Pat. No. 2,681,2 as appropriate.
No. 94, No. 2,761゜791, No. 3,526,52
8, No. 3.508.947, etc. by the coating method described in 1. Multiple layers may be applied simultaneously.

The color photographic material according to the present invention is described in the aforementioned Research Disclosure, No. 17643, 28-29.
Development processing can be carried out by the usual method described in the left column to the right column of page 651 of the same publication, No. 18716. The color photographic material of the present invention is usually subjected to a water washing treatment or a stabilization treatment after development, bleach-fixing or fixing treatment.

In the washing process, two or more tanks are generally used for countercurrent washing to save water. A representative example of the stabilization treatment is a multistage countercurrent stabilization treatment as described in JP-A-57-8543 instead of the water washing step. In the case of this process, 2 to 9
A countercurrent bath in the tank is required. Various compounds are added to the wood stabilizing bath for the purpose of stabilizing the image. various buffering agents (e.g. borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia) to adjust membrane pH (e.g. pH 3-8); ,
Representative examples include monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and formalin. In addition, water softeners (
Inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, amine, noboliphosphonic acid, phosphonocarboxylic acid, etc.) 1.
Various additives such as disinfectants (benzisothiazolinones, birithiazolones, 4-thiazolinebenzimidazoles, halogenated phenols, etc.), surfactants, optical brighteners, hardeners, etc. may be used. 1. Two or more of the same or different target compounds may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

(Margins below) (Example) The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.
- Sample 101 was created by applying the twelfth layer.

First layer; antihalation layer (gelatin layer containing black colloidal silver).

Second layer; gelatin middle layer.

2.5-di-t-octylhydroquinone was dissolved in 100 cc of dibutyl phthalate and 100 cc of ethyl acetate, and 2 kg of the emulsion obtained by stirring at high speed with 1 kg of an aqueous solution of 10% gelatin was made into a fine grain emulsion (without chemical sensitization). (
(grain size 0.06 μm, 1 mol% silver iodobromide emulsion) was mixed with 1.5 kg of 10% gelatin and coated to a dry film thickness of 2 μm (silver amount 0.4 g/rrr)
.

3rd layer; low-sensitivity red-sensitive emulsion layer 100 g of 2-(heptafluorobutyramide)-5-(2'-(2',4'-di-t-aminophenoxy)butyramide)-phenol, which is a cyan coupler, 100 cc of tricresyl phosphate and 100 cc of ethyl acetate
cc and stirred at high speed with 1 kg of a 10% aqueous gelatin solution, 500 g of the emulsion obtained was mixed with 1 kg of red-sensitive polydisperse silver iodobromide emulsion (A) (containing 70 g of silver and 60 g of gelatin, and containing iodine content is 4 mol%, average particle size 0.4μ
m, -knee = 0.35) and coated to a dry film thickness of 1 μm. (Amount of silver: 0.5 g/a) Fourth layer: Highly sensitive red-sensitive emulsion layer containing cyan coupler 2-(heptafluorobutyramide)-5-(2'-(2',4'-di-t- 100 g of aminophenoxy)butyramide)-phenol was mixed with 100 cc of tricresyl phosphate and 100 ml of ethyl acetate.
cc and stirred at high speed with 1 kg of a 10% aqueous gelatin solution, 1000 g of the emulsion obtained was mixed with 1 kg of red-sensitive silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin, with an iodine content of 2.5 mol%). , average particle size of 0.55 μm) and coated to give a dry film thickness of 2.5 μm. (
Silver amount 0.7g/rr? ) Fifth layer: Intermediate layer 2.5-di-t-octylhydroquinone was dissolved in 100 cc of dibutyl phthalate and 100 cc of ethyl acetate.

1 kg of a 10% gelatin aqueous solution and 1 kg of an emulsion obtained by stirring at high speed were mixed with 1 kg of 10% gelatin and applied to a dry film thickness of 1 μm.

6th layer; Low green-sensitive emulsion layer 1-(, which is a magenta coupler instead of a cyan coupler)
2,4,6-trichlorophenyl)-3-(3-(2,
300 g of an emulsion obtained in the same manner as the emulsion for the third layer except that 4-di-t-amylphenoxyacetamido)benzamide)-5-pyrazolone was used was mixed with 1 kg of a green-sensitive silver iodobromide emulsion ( The mixture contained 70 g of silver and 60 g of gelatin, had an iodine content of 3 mol %, and had an average particle size of 0.35 μm, and was coated to a dry film thickness of 1.3 μm. (Amount of silver 0
．． 7g/resistant) 7th layer; Highly sensitive green-sensitive emulsion layer 1-(
2,4,6-trichlorophenyl)-3-(3-(2,
1000 g of an emulsion obtained in the same manner as the emulsion of the third layer except that 4-di-t-amylphenoxyacetamido)benzamide)-5-pyrazolone was used was mixed into a green-sensitive silver iodobromide emulsion. 1 kg (contains 70 g of silver and 60 g of gelatin, iodine content is 2.5 mol%, average particle size is 0.60 μm)
) and applied to a dry film thickness of 3.5 μm.

(Amount of silver: 0.8 g/rrr) 8th layer: Yellow filter An emulsion containing yellow colloidal silver was coated to give a dry film thickness of 1 μm.

9th layer: Low-sensitivity blue-sensitivity emulsion layer α-(
pivaloyl)-α-(1-benzyl-5-ethoxy-3
1000 g of an emulsion obtained in the same manner as the emulsion of the third layer except that 2-chloro-5-dodecyloxycarbonylacetanilide (hydantoinyl)-2-chloro-5-dodecyloxycarbonylacetanilide was used was mixed with 1 kg of blue-sensitive silver iodobromide emulsion (70 g of silver). , containing 60 g of gelatin, iodine content of 2.5 mol%, average particle size of 0.50
μm) and coated to a dry film thickness of 1.5 μm. (Amount of silver: 0.6 g/rrf) 10th layer: Highly sensitive blue-sensitive emulsion layer α-(
pivaloyl)-α-(1-benzyl-5-ethoxy-3
-Hydantoinyl)-2-chloro-5-dodecyloxycarbonylacetanilide was used, but 1000 g of an emulsion obtained in the same manner as the emulsion of the third layer was mixed with 1 kg of blue-sensitive silver iodobromide emulsion (70 g of silver, gelatin Contains 60g, iodine content is 2.5 mol%, average particle size 1.0μ = 1
) and coated to a dry film thickness of 3 μm. (
Silver amount: 1.1 g/rd) Eleventh layer: Second protective layer 1 kg of an emulsion of an ultraviolet absorber was mixed with 10% gelatin 1-, and coated to a dry film thickness of 2 μI.

12th layer: Fine grain emulsion covered with the surface of the first protective layer (grain size 0.06 μm)
A 10% aqueous gelatin solution containing 1 mol % silver iodobromide emulsion) was coated to give a silver coating amount of 0.1 g/r& and a dry film thickness of 0.8 μm.

A gelatin hardener and a surfactant were added to each layer, respectively.

Preparation of Sample 102 Instead of the polydisperse red-sensitive silver halide emulsion used in the third layer of sample 101, a monodisperse surface latent image type red-sensitive silver halide emulsion (B) (70 g of silver, 60g gelaten
Sample 102 was prepared in exactly the same manner as Sample 101, except that the iodine content was 4 mol %, the average particle size S was 0.4 μm, and 7=0.15).

Preparation of Sample 103 Instead of the polydisperse red-sensitive silver halide emulsion used in the third layer of sample 101, a monodisperse internal latent image type red-sensitive silver halide emulsion (C) (70 g of silver, ze = o, is)
Sample 10 was prepared in exactly the same manner as sample 101 except that .
3 was produced.

Preparation of sample 104.105.110.111 Sample 101
Samples 104, 105, 110, and 111 were prepared in exactly the same manner as Sample 101, except that the compounds shown in Table 1 were added in the amounts shown in Table 1 to the third layer of the sample.

Preparation of samples 106, 107, 112 to 117 Sample 102
Samples 106, 107, and 112 to 117 were prepared in exactly the same manner as Sample 102, except that the compounds shown in Table 1 were added to the third layer in the amounts shown in Table 1.

Preparation of samples 108, 109, 118 to 120 Sample 103
Sample 1 was prepared in exactly the same manner as Sample 103, except that the compounds shown in Table 1 were added to the third layer in the amounts shown in Table 1.
08.109.118-120 were produced.

For these samples 101-120, a portion of each was exposed to red light through a continuous wedge, and another portion was exposed to white light (red + green + blue light) through a continuous wedge.

The red exposure amount during white light exposure and the exposure amount during red light exposure were equivalent. These exposed samples were subjected to the following development treatment.

Processing process Step Time Temperature - Development 6 minutes 38℃ water washing
2 minutes inversion, 2 minutes color development, 6 minutes adjustment, 2 minutes bleaching, 6 minutes fixing, 4 minutes washing, 4 minutes stabilization, 1 minute room temperature axis The composition of the drying solution used is as follows.

Disaster flood
100rnQ Nitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt
3g sodium sulfite
20g hydroquinone monosulfonate
30g Sodium carbonate (monohydrate) 30g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2
g potassium bromide 2
・5g potassium thiocyanate
1.2g potassium iodide (0.1% solution)
2-Water work 10100O
70〇-Nitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt
3g stannous chloride (dihydrate)
IgP-aminophenol
0.1g sodium hydroxide
8g ice vinegar a
Add 15d water
10100O Ashiro Rizuzoku Water
700mj2 Nitrilo N,N,N-trimethylenephosphonic acid pentasodium salt
3g sodium sulfite
7g Sodium phosphate (12 hydrate) 36
g potassium bromide
tg Potassium iodide (0.1% solution) 90- Sodium hydroxide 3
g Citrazic acid 1
．． 5gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate
11g ethylenediamine
Add 3g water
1000mM water adjustment
700mQ Sodium Sulfite
12g Sodium ethylenediaminetetraacetate (dihydrate) 8
gthioglycerin 0
．． 4+a12 glacial acetic acid
Add 3mM water
100 axis Q groove Wataru water
800 g Sodium ethylenediaminetetraacetate (dihydrate) 2
gEthylenediaminetetraacetate iron (m) ammonium (dihydrate) 1
20g potassium bromide
Add 100g water
100100O home base class water
800+d sodium thiosulfate
80.0゜Sodium sulfite
5.0g sodium bisulfite
Add 5.0g water
looomQ Gensei Rensui
80o-formalin (37% by weight)
5. Od Fuji Drywell (Fuji Film (
Surfactant manufactured by Co., Ltd.)
5. Add OmQ water
Compare cyan exposed to 10100O red light and cyan exposed to white light, and find the exposure amount difference Δlo at a density of 1.0.
It can be said that the larger gE is, the larger the interimage effect is.

The gradation (γ) of the highly exposed area during white light exposure is determined by the density = 1.0 point on the characteristic curve and the exposure amount (1og
It is expressed as the slope of the straight line connecting the points on the characteristic curve when the exposure amount is 0.4 more than E).

It can be said that the smaller the value of γ, the softer the gradation in the high exposure area.If the γ value of sample 101 is the best tone reproduction, the smaller the γ value of sample 101, the softer the gradation. It can be said that the reproduction of the condition is poor.

On the other hand, even if the value of γ is larger than that of sample 101, the gradation in the high exposure area is too high and tone reproduction is poor.

The sharpness was determined based on the MTF value.

From these results, it can be seen that, compared to the comparative example, the present invention exhibits a large interimage effect without impairing the gradation of the highly exposed area when exposed to white light.

Example 2 A multilayer color photosensitive material 2 consisting of each layer having the composition shown below was prepared on a cellulose triacetate film support as a sample.
01 was produced.

First layer: antihalation layer black colloidal silver. , l ty/
A second gelatin layer containing -; a third gelatin layer containing an interlayer coupler C-30,172/wr2°; a first red-sensitive emulsion layer 9, OX IU-''mmole-sensitive dye B per mole of silver; te 3, OX 10
-'Mole Sensitizing Dye C 4.2 X 10-'Mole Coupler C-40,093g/rr? per mole of silver coupler
Gelatin layer 4th layer containing C-50,31 g/m coupler C-60,01 gem; Second red-sensitive emulsion layer Silver iodobromide emulsion 1.2 gem (silver iodide 10 mol%, average grain size 1.0 μm ) Sensitizing dye A per mole of silver? , 8 X 10-s
Molar sensitizing dye B 2.2X10 per mole of silver
-' molar sensitizing dye C 3, OX per mole of silver 10 -' molar sensitizing dye D 2.2 X per mole of silver
1O-s-11-/L/Coupler C-40, 1g/rrf Coupler C-50,061g/rrr force, Coupler C-70,046g/rrl' Gelatin layer 5th layer: 3rd red-sensitive emulsion layer Silver iodobromide emulsion 1.5 gem (silver iodide 10 mol%, average grain size 1.5 μm) Sensitizing dye A
8, OX per mole of silver 10-' mole sensitizing dye B 2.4 X per mole of silver
10-' moles Sensitizing Dye C 3.3 x l O-S moles per mole of silver Sensitizing Dye D 2.4 x per mole of silver
10-'molar coupler C-70,32g/lri' coupler C-
Gelatin layer 6th layer containing 170,001 g/distillate; Intermediate gelatin layer 7th layer: 1st green-sensitive emulsion layer Polydisperse silver iodobromide emulsion (F) 0.55 gem
(Iodine content 5 mol%, average particle size 0.5 μm, -=0.36) Sensitizing dye G 3.8 X per 1 mol of silver
10-'Mole Sensitizing Dye E 1.5X per mole of silver
10-' molar coupler C-80,29g/resistance coupler C-30,04g/rn' coupler C-100,055g/m coupler C
8th gelatin layer containing −110,058 g/m; 2nd green-sensitive emulsion layer silver iodobromide emulsion 1.0 g/rrr (
6 mol% silver iodide, spherical grains with an average grain size of 1.2 μm) Sensitizing dye G 2.7 X per mol of silver
10-' mole sensitizing dye E 1 per mole of silver, I
10-' molar coupler 〇-80,25gird coupler C-30,013g/nζ coupler
C-100,009g/m coupler C-110,01
9th layer of gelatin layer containing 1 g/rrr; 3rd green-sensitive emulsion layer Silver iodobromide emulsion 2.0 g/po (8 mol% silver iodide, spherical grains with average grain size 1.8 μm) Coupler C-30 ,008g/rn' coupler C-
Gelatin layer 10th layer containing 120,05g/transparent coupler C-180,001g/rrr; Yellow filter layer 11th gelatin layer containing yellow colloidal silver 0.04g/-; 1st blue-sensitive emulsion layer iodobromide layer Silver emulsion 0.32 g/bo (silver iodide 5 mol%, average grain size 0.4 μm+) Coupler C-130,68 g/bo coupler C-140,03 g/rrr coupler C-
19' Gelatin layer containing 0.015 g/A 12th layer: Second blue-sensitive emulsion layer Silver iodobromide emulsion 0.29 g/A (silver iodide 10 mol%, average grain size 1.0 μm) Coupler C - 13th gelatin layer containing 130.22 g/rri Fine grain emulsion layer Silver iodobromide emulsion 14th gelatin layer containing 0.4 g/resistance (silver iodide 2 mol%, average grain size 0.15 μm) Third blue-sensitive emulsion layer Silver iodobromide emulsion 0.79 g/bo (silver iodide 14 mol%, average grain size 2.3 μm) Coupler C-130, 19 g/rrr Coupler C-150,
Gelatin layer 15th layer containing: In addition to the above composition, a gelatin hardening agent C-16 and a surfactant were added.

The compounds used to prepare the samples are shown below.

N し y i 口〇〇２ 〇Sensitizing dye B Sensitizing dye C Sensitizing dye Sensitizing dye E Sensitizing dye F Sensitizing dye G Preparation of sample 202 Polydisperse emulsion (F )Instead of,
Monodisperse surface latent image type emulsion (G) (iodine content 5 mol%
Sample 202 was prepared in exactly the same manner as Sample 201, except that the average particle size was 0.5 μm, τ=0.18).

Preparation of sample 203 Instead of the polydisperse emulsion (F) of the seventh layer of sample 201,
Monodisperse internal latent image emulsion (H) (iodine content 5 mol%
Sample 20
Sample 203 was prepared in exactly the same manner as in Example 1.

Preparation of sample 204.205.210.211 Sample 201
The compounds shown in Table 2 were added to the seventh layer.

Samples 204, 205, 210, and 211 were prepared in exactly the same manner as sample 201 except that the amounts shown in Table 2 were added.

Preparation of samples 206, 207, 212 to 216 Sample 202
Sample 2 was prepared in exactly the same manner as Sample 202, except that the compounds shown in Table 2 were added to the seventh layer in the amounts shown in Table 2.
06, 207, 212-216 were produced.

Preparation of samples 208, 209, 217 to 219 Sample 203
The compounds shown in Table 2 were added to the seventh layer.

Samples 208, 209, 217 to 219 were prepared in exactly the same manner as sample 203 except that the amounts shown in Table 2 were added.

For these samples 201 to 219, a portion of each sample was exposed to green light through a continuous wedge, and another portion was exposed to white light (red + green + blue light) through a continuous wedge. The green exposure amount during white light exposure and the exposure amount during green light exposure were equivalent. These exposed samples were subjected to color development processing at 38° C. according to the following steps.

Comparing magenta exposed to green light and magenta exposed to white light, it can be said that the greater the difference in exposure amount ΔlogE at 0.9 degrees 'a, the greater the interimage effect.

The gradation γ of the highly exposed area during white exposure is the density on the characteristic curve =
It is expressed by the slope of a straight line connecting the point 1.2 and the point on the characteristic curve when the exposure amount is 1.0 more than the exposure amount (1 ogE) that gives the density. It can be said that the smaller the value of γ, the softer the gradation in the high exposure area.If the γ value of sample 201 is the best tone reproduction, the smaller the γ value of sample 201, the softer the tone. It can be said that the reproduction is poor.

On the other hand, even if the value of γ is larger than that of sample 201, the gradation in the high exposure amount region is too high and tone reproduction is poor.

The sharpness was determined based on the MTF value.

Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing 2 minutes 10 seconds
Arrive 4 minutes 20 seconds Wash with water
Stable for 3 minutes 15 seconds
1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer Diethylenetriaminepentaacetic acid 1.0 gl-Hydroxyethylidene-1,1-cyphosphophone a2.0 g Sodium sulfite 4.0g Potassium carbonate 30.0 g Potassium bromide
1.4g potassium iodide
1.3 ■ Hydroxylamine sulfate 2.4
g Add water 1. Onp)11
0.0 Bleach solution Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Add water
1.0QP86.0 Fixer Sodium sulfite 4.0 g Sodium bisulfite 4.6 g Add water
1.0QP86.6 Stabilized liquid formalin (40%) 2, OmQ
Add water 1.0 Q From these results, it can be seen that the present invention is superior to the comparative example in interimage effect, sharpness, and tone reproduction in high exposure areas.

Example 3 Preparation of sample 301 On the triacetate film base, the following order was applied:
-Sample 301 was created by applying the third layer.

1st layer: Low-sensitivity silver halide emulsion layer Polydisperse silver iodobromide emulsion (1) (coated silver amount 1.0 g
/a) (Iodine content 4 mol%, average particle size 0.35
μ layer τ=0.33) 2nd layer: High sensitivity silver halide emulsion Polydisperse silver iodobromide emulsion (coated silver amount 2.5 g/m) (iodine content 4 mol%, average grain size 0.5 g/m) 7μm, τ=0
．． 35) Third layer: Protective layer gelatin (1.3 g/i) Polymethyl methacrylate particles (diameter 1.5 μm) 0.05 g
In addition to the above composition, each layer contains gelatin hardening agent C-1.
6 Surfactants, thickeners, and sodium polystyrene sulfonate were added.

Preparation of Sample 302 Instead of the polydisperse silver iodobromide emulsion CI) in the first layer of sample 301, the monodisperse silver iodobromide emulsion (J) (containing iodine!
4 mol%, average particle size 0.35 μm, τ=O, L9
) was prepared in exactly the same manner as sample 301 except for using sample 3.
02 was produced.

Preparation of sample 303, 304, 307, 308 Sample 301
Sample 3 was prepared in exactly the same manner as Sample 301, except that the compounds shown in Table 3 were added to the first layer in the amounts shown in Table 3.
03.304.307.308 was created.

Preparation of samples 305, 306, 309 to 317 Sample 302
Sample 3 was prepared in exactly the same manner as Sample 302, except that the compounds shown in Table 3 were added to the first layer in the amounts shown in Table 3.
05.306.309-317 were produced.

These samples were exposed through a continuous wedge. or,
Another part was exposed through a pattern for graininess measurement, and another part was exposed through a pattern for sharpness measurement, and then the following development process was performed.

Developer solution Metol 2g Sodium sulfite 100g Hydroquinone 5g Borax 5H2OL
Add 53g water, Q fixer Ammonium periosulfate 200.0g Sodium sulfite (anhydrous) 20.0g Boric acid
8.0g disodium ethylenediaminetetraacetate 0.1g aluminum sulfate 15.0g sulfuric acid
2.0g glacial acetic acid
Add 22.0 g water
1.0Q (pH adjusted to 4.2) Black and white development was performed at 20° C. for 7 minutes using the above developer. Graininess (RMS granularity) was expressed as a value 1000 times the standard deviation of density fluctuations that occur when scanning with a microdensitometer. Further, the sharpness was measured using the MTF value.

These results are shown in Table 1.

γ is expressed by the slope of a straight line connecting a point on the characteristic curve that gives density=1.0 and a point on the characteristic curve when the exposure amount is 0.5 higher than the current exposure amount (logE).

It can be said that the smaller the value of γ, the softer the gradation in the high exposure amount area.If the γ value of sample 301 is the best tone reproduction, the smaller the γ value of sample 301, the softer the tone.
It can be said that the reproduction of the condition is poor.

On the other hand, when the value of γ is larger than that of sample 301, the gradation in the high exposure amount region is too hard, resulting in poor tone reproduction.

From these results, it can be seen that the present invention is superior to the comparative example in terms of granularity, sharpness, and tone reproduction in high exposure areas.

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, wherein the silver halide emulsion layer contains monodisperse silver halide grains. , and the silver halide emulsion layer and/or non-photosensitive layer contains at least one compound represented by the general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R represents a linear or branched alkylene group, alkenylene group, aralkylene group, or arylene group, and Z represents a hydrogen atom or a polar substituent. represent. Y is -S
−, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas , there are tables, etc. ▼ or ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, R_1, R_2, R_3, R_4
, R_5, R_6, R_7 and R_8 each independently represent a hydrogen atom, or a substituted or unsubstituted alkyl group, aryl group, alkenyl group, or aralkyl group. X represents a hydrogen atom, an alkali metal atom, an ammoniumyl group, or a group that cleaves under alkaline conditions. n represents 0 or 1.