JPH0617996B2 - Silver halide photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material having an improved inter-image effect and improved sharpness and graininess.

(Prior Art) By color-developing a silver halide color photographic material, an oxidized aromatic primary amine type color developing agent and a coupler react to react with indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine. It is known that dyes of the same kind and the like can be formed to form a color image. In this method, a subtractive color method is usually used for color reproduction, and a yellow, magenta, and cyan color image forming agents that have a complementary color relationship with a silver halide emulsion that is selectively exposed to blue, green, and red, respectively. Is used. To form a yellow color image, for example, an acylacetanilide or a dibenzoylmethane-based coupler is used, and for forming a magenta color image, mainly pyrazolone, pyrazolobenzimidazole, pyrazolopyrazole, pyrazolotriazole, cyano are used. Acetophenone or indazolone couplers are used, and phenolic or naphtholic compounds are mainly used for forming a cyan image.

By the way, the dyes produced from these couplers are not ideal spectral absorption spectra, and particularly magenta and cyan dyes have broad absorption spectra or have sub-absorption in the short wavelength region, which makes them suitable for color photographic materials. Not desirable for color reproduction.

In particular, the secondary absorption in the short wavelength region tends to cause a decrease in saturation. As a means for improving this, it can be improved to some extent by expressing an inter-image effect.

Regarding the inter-image effect, for example, Hanson (H
anson) et al., “Journal of the Optical.
Society Bob America (Journal of the Optical
Society of Ameica) ", Vol. 42, pp. 663-669.
Page and A. Thiels, “Zeitschrift fr Wissenschaftliche Photographie, P.
hotophysique und Photo-chemie), Volume 47, Volume 106
Pp.-118 and 246-255.

U.S. Pat. No. 3,536,486 discloses the incorporation of diffusible 4-thiazoline-2-thiones into exposed color reversal photographic elements and also U.S. Pat. No. 3,536,4.
No. 87 describes the introduction of diffusible 4-thiazoline-2-thiones into unexposed color reversal photographic elements to obtain the desired interimage effect.

Further, in Japanese Patent Publication No. 48-34169, when a color photographic light-sensitive material is developed to reduce silver halide to silver, the presence of an N-substituted 4-thiazoline-2-thione compound causes a remarkable interimage effect. It is described that appears.

It is also possible to provide a colloidal silver-containing layer between the cyan layer and the magenta layer of a color reversal photographic element to obtain a preferable inter-image effect by Research Disclosure (R
esearch Disclosure), NO. 131, Item 13116 (1)
975).

Further, U.S. Pat. No. 4,082,553 discloses a color reversal light-sensitive material having a layer arrangement capable of moving iodide ions during development, in which one layer contains latent image-forming silver haloiodide grains. , Another layer with latent image forming silver halide grains,
A method for obtaining a good inter-image effect by including silver halide grains whose surfaces have been fogged so as to be developed independently of image exposure is described.

However, in the above method, the inter-image effect is insufficient, the use of a colloidal silver-containing layer, the introduction of fogged silver halide grains, and the like cause a large decrease in color density in a color reversal light-sensitive material. It has drawbacks.

In addition to the above, for example, a coupler (DIR coupler) capable of releasing a development-inhibiting substance such as a benzotriazole derivative or a mercapto compound at the time of a coupling reaction with an oxidized product of a color developing agent in a color development processing step is used. Alternatively, it is also known that an inter-image effect can be produced by using a hydroquinone compound or the like that can release a development-inhibiting substance such as an iodine ion or a mercapto compound during development, but if these compounds are used, Their use has been limited because of marked desensitization and a decrease in color density.

(Object of the Invention) An object of the present invention is, firstly, to provide a multilayer color photographic light-sensitive material having a large inter-image effect without impairing other photographic characteristics.

The second object of the present invention is to provide a silver halide photographic light-sensitive material excellent in sharpness.

The third object of the present invention is to provide a silver halide photographic light-sensitive material having high sharpness and good graininess.

(Structure of the Invention) The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, and the content of silver iodide in the whole light-sensitive silver halide emulsion. Has an average value of 1.0 to 5.0 mol% and at least 1
The light-sensitive silver halide emulsion layer of the layer or its adjacent layer,
This is achieved by a silver halide photographic light-sensitive material characterized by containing at least one compound represented by the following general formula [I], [II], [III] or [IV].

General formula [I] General formula (II) General formula (III) General formula (IV) In the formula, R represents a linear or branched alkylene group, a linear or branched alkenylene group, a linear or branched aralkylene group, or an arylene group, and R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, It represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group.
Z represents a polar substituent, and X represents a hydrogen atom, a cation for neutralizing the molecule, or a precursor. n represents 0 or 1.

More specifically, R is a linear or branched alkylene group (eg, methylene group, ethylene group, propylene group, butylene group, hexylene group, 1-methylethylene group,
Etc.), a linear or branched alkenylene group (for example, a vinylene group, a 1-methylvinylene group, etc.), a linear or branched aralkylene group (for example, a benzylidene group, etc.), an arylene group (for example, phenylene, naphthylene, Etc.).

R ₁ is a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, propyl group, 2-dimethylaminoethyl group, etc.), a substituted or unsubstituted aryl group (eg, 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.).

The polar substituent represented by Z includes, for example, a substituted or unsubstituted amino group (including a salt form, for example, amino group, hydrochloride of amino group, methylamino group, dimethylamino group, hydrochloric acid of dimethylamino group). Salt, dibutylamino group,
Dipropylamino group, N-dimethylaminoethyl-N-
Methylamino group, etc.), quaternary ammoniumyl group (eg, trimethylammonium milk chloride group, dimethylbenzylammonium milk chloride group, etc.), alkoxy group (eg, methoxy group, ethoxy group, 2-hydroxyethoxy group, etc.) , An aryloxy group (eg, phenoxy group, etc.), an alkylthio group (eg, methylthio group,
Butylthio group, etc.), arylthio group (eg, phenylthio group, etc.), heterocyclic oxy group (eg, 2-pyridyloxy group, 2-imidazolyloxy group, etc.), heterocyclic thio group (eg, 2-benzthia) Zolylthio group, 4
-Pyrazolylthio group, etc.), sulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl group (eg, unsubstituted carbamoyl group, methylcarbamoyl group, etc.), sulfamoyl group ( For example, an unsubstituted flufamoyl group, a methylsulfamoyl group, etc.), a carbonamide group (for example,
Acetamide group, benzamide group, etc.), sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.), acyloxy group (eg, acetyloxy group, benzoyloxy group, etc.), ureido group (eg, no Substituted ureido group, methylureido group, ethylureido group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), thioureido group (eg, none) Substituted thioureido group, methylthioureido group, etc.), sulfonyloxy group (eg, methanesulfonyloxy group, p-toluenesulfonyloxy group, etc.), heterocyclic group (eg, 1-morpholino group, 1
-Piperidino group, 2-pyridyl group, 4-pyridyl group, 2
-Thienyl group, 1-pyrazolyl group, 2-imidazolyl group, 2-tetrahydrofuryl group, 2-tetrahydrothienyl group, etc.) and cyano group. Where Z is
Sulfonic acid group, carboxylic acid group, hydroxy group, and
It is not an alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.).

Further, in the general formula [I] or [II], Z is not a substituted or unsubstituted amino group.

X is a hydrogen atom, a cation necessary for neutralizing the molecule (for example, sodium ion, potassium ion,
Zinc ion, nickel ion, magnesium ion, calcium ion, ammonium ion, etc.) or a precursor (a group which can be X = H or an alkali metal ion under alkaline conditions, for example, an acetyl group,
Cyanoethyl group, methanesulfonylethyl group, etc.).

Of the general formulas [I], [II], [III], and [IV], the case of being represented by the general formulas [I] and [III] is preferable, and more preferable is the general formula [I]. And in [III], R represents a linear or branched alkylene group. More preferred is the general formula [III]
In the case where Z is a substituted or unsubstituted amino group or a salt thereof.

Specific examples of the compounds represented by the general formulas [I], [II], [III] and [IV] are shown below, but the compounds of the present invention are not limited thereto.

(1) Reference example (2) (3) Reference example (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) Reference example (14) Reference example (15) Reference example (16) Reference example (17) Reference example (18) Reference example (19) Reference example (20) Reference example (21) Reference example (22) Reference example (23) (24) (25) (26) (27) (28) (29) (30) Reference example (31) (32) Reference example (33) (34) (35) (36) (37) (38) (39) (40) (41) Reference example (42) Reference example (43) Reference example (44) (45) (46) (47) (48) (49) Reference example (50) (51) The compounds represented by the general formulas [I] to [IV] used in the present invention are "advances in heterocyclic
Chemistry (Advances in Heterocyclic Chemistr
y) ”, Vol. 9, pp. 165-209 (1968), and can synthesize.

A typical synthesis example is shown below.

Synthesis Example 1 Synthesis method of compound (1) 2,5-dimercapto-1,3,4-thiadiazole 7.5 g, 2-aminoethyl chloride hydrochloride 5.8
g and 4 g of pyridine were added to 60 ml 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 methanol / water. Yield 7.1g Melting point 2
28 to 229 ° C. (dec) Synthesis example 2 Synthesis method of compound (14) 2,5-dimercapto-1,3,4-thiadiazole 7.5 g, 2-dimethylaminoethyl chloride hydrochloride 7.3 g, pyridine 4 g -Add 60 ml of butanol and heat to reflux for 2 hours. The reaction solution was ice-cooled and the precipitated crystals were collected by filtration and recrystallized from ethanol. Yield 7.9 g Melting point 161 to 163 ° C. Synthesis example 3 Synthesis method of compound (13) 2,5-dimercapto-1,3,4-thiadiazole 7.5 g, 2-diethylaminoethyl chloride hydrochloride 8.6 g, pyridine 4 g The mixture was added to 60 ml 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 / 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, 3-dimethylaminopropyl chloride hydrochloride 7.9 g, pyridine 4 g n- It was added to 60 ml of 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 11 g Melting point 149-152 ° C Synthesis example 5 Synthesis method of compounds (42) and (43) Synthesis method of 2- [N, N-bis (2-methoxycarbonylethyl) amino] ethyl chloride hydrochloride 2-Aminoethanol 6 0.1 g was added to 75 ml of methanol, and 20 ml of methyl acrylate was added dropwise under ice cooling. After the dropping, the mixture was stirred under ice cooling for 2 hours and further at room temperature for 20 hours. 100 ml of chloroform was added to the oil (23 g) obtained by distilling off the reaction solution under reduced pressure, 8.7 ml of thionyl chloride was added dropwise under ice cooling, and then the mixture was heated under reflux for 1 hour. The reaction solution was evaporated under reduced pressure and the obtained residue was recrystallized from isopropanol / n-hexane. Yield 21 g, melting point 103-104 ° C. Method for synthesizing compound (42) 2,5-dimercaptothiadiazole 7.5 g, 2-
14.4 g of [N, N-bis (2-methoxycarbonylethyl) amino] ethyl chloride and 8.1 g of pyridine were added to 80 ml of dioisan, and the mixture was heated under reflux for 2 hours. The compound (42) was obtained as a syrup by purifying the residue obtained by distilling the reaction solution under reduced pressure by column chromatography (stationary phase alumina, developing solvent methanol / ethyl acetate). Yield 8.4 g Method for synthesizing compound (43) 7.3 g of compound (42) was added to 20 ml of 20% aqueous sodium hydroxide solution, and the mixture was stirred at 50 ° C. for 2 hours. The reaction solution was ice-cooled, neutralized with 35% hydrochloric acid, and the resulting precipitate was collected by filtration and recrystallized from DMF / ethanol to obtain compound (43). Yield 3.2 g Melting point 188-189 ° C. Synthesis example 6 Synthesis method of compound (4) 2,5-dimercapto-1,3,4-thiadiazole 1
5.0 g and 20 ml of 28% sodium methoxide solution were added to 100 ml of ethyl alcohol, dissolved by heating, and 13.5 g of 2-chloroethylurea was added dropwise. After the dropping, the mixture was heated under reflux for 4 hours. After the reaction, the reaction solution was poured into 700 ml of ice water, and the precipitated crystals were collected by filtration and recrystallized from methanol. Yield 1
6.4 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 ml of acetone, and then 22 ml of sodium methoxide 28% solution, 12 g of β-chloropropionamide was added. Further, 15 g of sodium iodide was added to this reaction liquid, and the mixture was heated under reflux for 20 hours. After cooling, the obtained crystals were collected by filtration and washed with water. The crystals were recrystallized from a mixed solvent of dimethylformamide-methanol to obtain compound (2). Yield 12.0 g Melting point 175 to 177 ° C. The general formula [I], [II], [III], or [I] of the present invention.
It has been found by the study of the present inventors that the compound represented by the formula [V] greatly inhibits the development of silver halide due to the interaction with iodine ions.

In the layer that receives the inter-image effect (hereinafter referred to as the receiving layer) or the intermediate layer adjacent to the layer, the general formula [I] [I
I] If at least one of the compounds represented by [III] or [IV] is contained, it is released by the development of a layer giving an interimage effect (hereinafter referred to as an imparting layer) and further released to the receiving layer. The interaction between the diffused iodine ions and the compound represented by the general formula [I], [II], [III], or [IV] greatly suppresses the development of the receptor layer. It can be said that the greater the difference in development inhibition of the receiving layer when the imparting layer is exposed and developed and when it is not exposed, the greater the inter-image effect.
It has been found that the compound represented by the general formula [I], [II], [III], or [IV] greatly enhances the interimage effect.

However, the interimage effect of the compound represented by the general formula [I], [II], [III], or [IV] is closely related to the silver iodide content of the silver halide emulsion of the receiving layer or the imparting layer. I have a relationship. If the average silver iodide content of the light-sensitive silver halide emulsion is too low, the iodine ions diffusing from the providing layer to the receiving layer in the case of developing the developing layer and in the case of not developing are represented by the general formula [I], [II], [III],
Alternatively, the development inhibition due to the interaction with the compound represented by [IV] is too small, and a large interimage effect cannot be obtained. On the contrary, when the silver iodide content of the light-sensitive silver halide emulsion is too high, a large amount of iodine ions are released in the development due to the fog unrelated to the exposure of the imparting layer and the receptive layer, and the iodine diffused into the receptive layer is increased. The number of ions increases, and the general formulas [I], [II], [II
The development of the receptor layer is greatly suppressed by the interaction between the compound represented by I] or [IV] and its iodine ion.
Therefore, even if the imparting layer is exposed and developed, and iodine ions diffuse into the receiving layer, a large interimage effect cannot be obtained.

The average content of silver iodide in all the light-sensitive silver halide emulsions in the present invention is 1.0 to 5.0 mol%, and
2 to 4.8 mol% is preferable, and 1.5 to 4.5 mol% is particularly preferable.

When the compounds represented by the general formulas [I], [II], [III] and [IV] of the present invention are used in a multilayer color photographic light-sensitive material, a silver halide emulsion layer or a yellow filter layer adjacent to the emulsion layer It is contained in at least one layer such as a halation layer, an intermediate layer or a protective layer, but it is most preferably contained in a silver halide emulsion layer.

The compound of the present invention represented by the general formula [I], [II], [III], or [IV] varies depending on the properties and purpose of the silver halide photographic light-sensitive material to be applied, or the development processing method. The amount is 10 ⁻¹ to 10 ⁻⁵ mol, and preferably 3 × 10 ^{−2 to} 3 × 10 ⁻⁴ mol, relative to 1 mol of silver halide present in one layer or an adjacent layer.

The general formula [I], [II], [III], or [I] of the present invention
V] is introduced into the light-sensitive material,
It is dissolved in a solvent usually used in photographic light-sensitive materials such as water, methanol, ethanol, propanol or fluorinated alcohol and then added to the hydrophilic colloid.
When a silver halide emulsion layer is contained, it may be any of during grain formation of the silver halide emulsion, during physical ripening, immediately before chemical sensitization, during chemical sensitization, after chemical sensitization, or during preparation of a coating solution, It is selected according to the purpose.

Photosensitive materials to which the present invention is applied include, for example, color negative films, color reversal films (inner and outer), color papers, color positive films, color reversal papers,
Any color photographic light-sensitive material such as a color diffusion transfer process or a die transfer process may be used. Further, any black-and-white photographic light-sensitive material such as black-and-white negative film, black-and-white photographic paper, roentgen film and squirrel film may be used.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, in addition to tabular silver halide, any halide of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride can be used. You may use together silver. A preferred silver halide is silver iodobromide or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is about 0.5 mol% to about 10 mol%
It is a silver iodobromide containing up to silver iodide. These silver halide grains may be so-called regular grains having regular crystal bodies such as cubes, octahedra and tetradecahedrons, and those having irregular crystal shapes such as spheres and twin crystals. It may have a crystal defect such as a plane or a composite form thereof. Also, a mixture of particles having various crystal forms may be used.

The grain size of silver halide that can be used in combination with tabular silver halide may be fine grains of about 0.1 micron or less or large grains with a projected area diameter of up to about 10 microns, and a monodisperse emulsion having a narrow distribution. Alternatively, it may be a polydisperse emulsion having a wide distribution.

The silver halide photographic emulsion which can be used in the present invention can be produced by a known method, for example, Research Disclosure,
176, NO.17643 (December 1978), 22
Pp. 23, "I. Emulsion Preparation and
Types) ”and ibid., 187, No. 18716 (197).
No. 9, pp. 648, can be followed.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphide, published by P.Glafkides, Chimi.
e et Physique Photographique Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.
F. Duffin, Photographic Emulsion Chemistry (Focal Pre
ss, 1966), "Manufacturing and coating of photographic emulsion" by Zelikmann et al.,
Published by Focal Press (VL Zeilkman et al, Making and
Coating Photographic Emulsion, Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Known silver halide solvents (for example, ammonia, rhodancal or U.S. Pat. No. 3,271,157, JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-53-144319, JP-A-53-144319, SHO 54-100717
Physical aging in the presence of thioethers and thione compounds described in JP-A No. 54-155828. Also by this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size distribution can be obtained.

The silver halide emulsion consisting of the above-mentioned regular grains can be obtained by controlling the pAg and pH during grain formation.
For details, see, for example, Photographic Science and Engineering.
neering) Volume 6, 159-165 (1962); Journal of Photographic Science (Journal)
of Photographic Science), Volume 12, 242-251
Page (1964), U.S. Pat. No. 3,655,394 and British Patent No. 1,413,748.

The monodisperse emulsion comprises silver halide grains having an average grain diameter of greater than about 0.1 micron, at least 9
Emulsions such that 5% by weight are within ± 40% of the average grain diameter are typical. The average grain diameter is 0.25 to 2 microns and at least 95% by weight or (number of grains) at least 95% of the silver halide grains have an average grain diameter of ± 2.
Emulsions such as within 0% can be used in the present invention.
A method for producing such an emulsion is described in US Pat. No. 3,574,6.
28, 3,655,394 and British Patent 1,413,748. In addition, JP-A-4
8-8600, 51-39027, 51-83
097, 53-137133, and 54-4852.
1, No. 54-99419, No. 58-37635,
Monodisperse emulsions such as those described in JP-A-58-49938 can also be preferably used in the present invention.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are described in British Patent 1,027,1
46, U.S. Pat. Nos. 3,505,068 and 4,44
No. 4,877 and Japanese Patent Application No. 58-248469. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halide such as silver rhodanide and lead oxide. These emulsion grains are described in U.S. Pat. Nos. 4,094,684, 4,142,900,
No. 4,459,353, British Patent No. 2,038,79.
No. 2, U.S. Pat. Nos. 4,349,622 and 4,39.
5,478, 4,433,501, 4,46
No. 3,087, No. 3,656,962, No. 3,85
2,067, JP-A-59-162540 and the like.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may coexist.

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 the soluble silver salt from the emulsion before and after physical ripening, Nudel water washing, flocculation sedimentation method or ultrafiltration method is used.

The emulsion used in the present invention is usually one that has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643 (December 1978) and No. 1 mentioned above.
8716 (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 described in the above two Research Disclosures, and the locations described in the table below are shown.

Various color couplers can be used in the present invention, specific examples of which are mentioned above in Research Disclosure.
It is described in the patents described in No. 17643, VII-C to G. As the dye-forming coupler, a coupler which gives the three primary colors (that is, yellow, magenta and cyan) of the subtractive color method by color development is important, and specific examples of the diffusion-resistant hydrophobic 4-equivalent or 2-equivalent coupler are described above. Research Disclosure No.17643, VII-C
In addition to the couplers described in the patents described in paragraphs D and D, the following can be preferably used in the present invention.

A typical 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 Pat. No. 2,
No. 407,210, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat. Nos. 3,408,194 and 3,447,928 are preferred.
No. 3,933,501 and No. 4,022.
No. 620 and other yellow couplers of oxygen atom elimination type or Japanese Patent Publication No. 58-10739, U.S. Pat. Nos. 4,401,752, 4,326,024, R
D18053 (April 1979), British Patent No. 1,42
No. 5,020, West German Application Publication No. 2,219,917,
Typical examples thereof include nitrogen atom releasing yellow couplers described in Nos. 2,261,361, 2,329,587 and 2,433,812. The α-pivaloyl acetanilide type coupler is excellent in the fastness of the color forming dye, especially the light fastness, while
The benzoylacetanilide coupler provides high color density.

Examples of magenta couplers that can be used in the present invention include hydrophobic indazolone or cyanoacetyl, preferably 5-pyrazolone and pyrazoloazole couplers having a ballast group. The 5-pyrazolone-based 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 color forming dye, and a representative example thereof is US Pat.
311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896 and No. 3,936,015.
As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is particularly preferable. European Patent No. 7
The 5-pyrazolone-based coupler having a ballast group described in JP-A No. 3,636 provides high color density. As a pyrazoloazole coupler, US Pat. No. 3,061,43
2 pyrazolobenzimidazoles, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in US Pat. No. 3,725,067, Research Disclosure No. 24220 ( 1984 6
And the disclosure of pyrazolotetrazole and research disclosure described in JP-A-60-33552.
No. 24230 (June 1984) and JP-A-60-
The pyrazolopyrazoles described in 43659 are mentioned. The imidazo [1,2-b] pyrazoles described in U.S. Pat. No. 4,500,630 are preferable in view of low yellow sub-absorption of a color forming dye and light fastness, and are described in European Patent 119,860A. Pyrazolo [1,5-b]
[1,2,4] triazole is particularly preferred.

The cyan couplers that can be used in the present invention include hydrophobic and diffusion resistant naphthol-based and phenol-based couplers. The naphthol-based couplers described in US Pat. No. 2,474,293, preferably US Pat. No. 4,052. , 2
No. 12, No. 4,146, 396, No. 4,228,
Representative examples thereof include oxygen atom desorption type two-equivalent naphthol couplers described in JP-A Nos. 233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Pat. Nos. 2,369,929 and 2,80.
1,171, 2,772,162, 2,8
95,826, JP-A-60-55340 and the like.

Cyan couplers which are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include an alkyl group having an ethyl group or higher at the meta-position of the phenol nucleus described in US Pat. No. 3,772,002. A phenolic cyan coupler having a group, US Pat. No. 2,772,162,
No. 3,758,308, No. 4,126,396
No. 4,334,011, No. 4,327,17
3, 2,5-diacylamino-substituted phenol-based couplers described in West German Patent Publication No. 3,329,729 and European Patent 121,365, and US Pat. Nos. 3,446,622 and 4 , 333, 999, 4,451, 559 and 4,427, 767.
And the like, which have a phenylureido group at the 2-position and an acylamino group at the 5-position.

In order to correct the unnecessary absorption of the color-forming dye, it is preferable to mask a color negative photosensitive material for photographing with a colored coupler. Yellow colored magenta couplers described in U.S. Pat. No. 4,163,670 and Japanese Patent Publication No. 57-39413 or U.S. Pat. No. 4,004,92.
No. 9, No. 4,138,258 and British Patent No. 1,
Typical examples are magenta colored cyan couplers described in JP-A-146368. Other colored couplers are Research Disclosure, No. 1 mentioned above.
7643, VII-G.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such couplers are
U.S. Pat. No. 4,366,237 and British Patent No. 2,
Specific examples of magenta couplers are disclosed in 125,570, European Patent No. 96,570 and West German Patent Application Publication No. 3,2.
No. 34,533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are found in US Pat. No. 3,451,82.
0 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and US Patent No. 4,367,
282.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. As the DIR coupler releasing a development inhibitor, the couplers of the patents described in the above-mentioned Research Disclosure, No. 17643, VII to F are useful.

A preferred combination with the present invention is JP-A-57-15.
Developer deactivation type represented by 1944; US Pat. No. 4,
248,962 and JP-A-57-154234; timing-type represented by JP-A-59-39653; particularly preferable are JP-A-57-151944 and JP-A-57-151944. -217932, Japanese Patent Application Nos. 59-75474, 59-82214, 59
No. 82214 and No. 59-90438, and developer deactivating DIR couplers and Japanese Patent Application No. 59-3.
It is a reactive DIR coupler described in 9653 and the like.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods, for example, a solid dispersion method, a calcaly dispersion method, preferably a latex dispersion method, more preferably an oil-in-water dispersion method, etc. are typical examples. be able to. In the oil-in-water dispersion method, after dissolving in either a single liquid of a high boiling organic solvent having a boiling point of 175 ° C. or higher and a so-called auxiliary solvent having a low boiling point or a mixed liquid of both, water or gelatin is added in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous solution. Examples of high boiling organic solvents are US Pat. No. 2,32
2, 027 and the like. The dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, rinsing with water, ultrafiltration or the like before being used for coating.

The steps of latex dispersion method, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230. It is described in.

The light-sensitive material produced by using the present invention, as a color antifoggant or color mixing inhibitor, is a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamidephenol. You may contain a derivative etc.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Hydroquinones as organic anti-fading agents,
6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Typical are hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Take as an example. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

The present 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 at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. These layer arrangements can be arbitrarily selected as needed. The preferred order of layer arrangement is red-sensitive, green-sensitive, blue-sensitive from the support side or blue-sensitive, red-sensitive and green-sensitive from the support side. Each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity. Usually, a cyan-forming coupler is contained in the red-sensitive emulsion layer, a magenta-forming coupler is contained in the green-sensitive emulsion layer, and a yellow-forming coupler is contained in the blue-sensitive emulsion layer, but different combinations can be used depending on circumstances.

The light-sensitive material according to the present invention, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to appropriately provide an auxiliary layer such as a back layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as a plastic film, paper or cloth usually used for a photographic light-sensitive material or a rigid support such as glass, pottery or metal. To be done. Useful as flexible supports are cellulose derivatives (cellulose nitrate,
Films made of cellulose acetate, cellulose acetate butyrate, etc.), synthetic polymers (polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc.), baryta layers or α-olefin polymers (eg polyethylene, polypropylene, ethylene / butene copolymers), etc. It is a paper or the like coated or laminated with. The support may be colored with a dye or pigment. It may be black for the purpose of shading. The surface of these supports is generally
It is subjected to a subbing treatment to improve the adhesion with the photographic emulsion layer and the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoat treatment.

For coating the photographic emulsion layer and other hydrophilic colloid layers, for example, dip coating method, roller coating method, curtain coating method,
Various known coating methods such as extrusion coating method can be used. US Pat. No. 2,681,294 as required
No. 276179, No. 3526528, No. 3508947 and the like may be used to simultaneously coat multiple layers.

The color photographic light-sensitive material according to the present invention is processed by the conventional method described in Research Disclosure, No. 17643, pages 28 to 29 and No. 18716, page 651, left column to right column. be able to.
The color photographic light-sensitive material of the present invention is usually subjected to washing treatment or stabilizing treatment after development, bleach-fixing or fixing treatment.

In the water washing step, it is general to carry out countercurrent water washing of two or more tanks to save water. A typical example of the stabilizing treatment is a multistage countercurrent stabilizing treatment as described in JP-A-57-8543 instead of the water washing step. 2-9 in the case of this step
A countercurrent bath in the bath is required. Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, various buffers (eg borate, etaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia mono) for adjusting the membrane pH (eg pH 3 to 8). Representative examples thereof include carboxylic acid, dicarboxylic acid, polycarboxylic acid and the like) and formalin. In addition, water softener (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericide (benzisothiazolinones, irithiazolones, 4-thiazoline) as required. Various additives such as benzimidazoles, halogenated phenols, etc.), surfactants, fluorescent brighteners, and hardeners may be used, and two or more of the same or different target compounds may be used in combination. Good.

In addition, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjuster after the treatment.

(Examples) Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto.

Example 1 First on the following order on a triacetate film base.
~ Sample No. 101 was prepared by applying the twelfth layer.

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

Second layer: gelatin intermediate layer 2,5-di-t-octylhydroquinone is dissolved in 100 cc of dibutyl phthalate and 100 cc of ethyl acetate,
10 kg of 1% aqueous solution of 10% gelatin and 2 kg of emulsion obtained by high-speed stirring together with 1 kg of non-chemically sensitized fine grain emulsion (grain size 0.06μ, 1 mol% silver iodobromide emulsion)
% Gelatin was mixed and coated so that the dry film thickness would be 2 μm (silver amount 0.4 g / m ² ).

Third layer; low-sensitivity red-sensitive emulsion layer 100 g of 2- (heptafluorobutylamide) -5- {2 '-(2 ", 4" -di-t-aminophenoxy) butylamide} -phenol which is a cyan coupler, 100cc of tricresyl phosphate and 100cc of ethyl acetate
500 g of an emulsion obtained by dissolving in 1 kg of a 10% gelatin aqueous solution at high speed and 1 g of a red-sensitive monodispersed silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin, and having an iodine content of 3.5 mol%). , An average particle size of 0.3 μ, and a coefficient of variation of particle size of 19%), and applied so that the dry film thickness was 1 μ. (Silver amount: 0.5 g / m ² ) Fourth layer: High-sensitivity red-sensitive emulsion layer 2- (heptafluorobutyramide) -5- {2 ′-(2 ″, 4 ″ -di-t-, which is a cyan coupler. Aminophenoxy) butyramide} -phenol (100 g) was added to tricresyl phosphate (100 cc) and ethyl acetate (100 cc).
1000 g of an emulsion obtained by dissolving in a 1% aqueous solution of 10% gelatin and stirring at high speed was added to 1 kg of a red-sensitive silver iodobromide emulsion.
(It contains 70 g of silver and 60 g of gelatin, and the iodine content is 3.
5 mol and an average particle size of 0.6 μ) were mixed, and a dry film thickness of 2.5 μ was applied. (Amount of silver: 0.8 g / m ² ) Fifth layer; Intermediate layer 2,5-di-t-octylhydroquinone is dissolved in 100 cc of dibutyl phthalate and 100 cc of ethyl acetate,
1 kg of an emulsion obtained by high-speed stirring with 1 kg of an aqueous solution in 10% gelatin was mixed with 1 kg of 10% gelatin to obtain a dry film thickness of 1
It was applied so as to have a thickness of μ.

Sixth layer: low-green emulsion layer Magenta coupler instead of cyan coupler 1-
(2,4,6-Trichlorophenyl) -3- {3-
300 g of an emulsion obtained in the same manner as the emulsion of the third layer except that (2,4-di-t-amylphenoxyacetamide) benzamide} -5-pyrazolone was used, was treated with a green-sensitive iodobromide. 1 kg of a silver emulsion (containing 70 g of silver and 60 g of gelatin, an iodine content of 3.5 mol% and an average particle size of 0.3 μ) was mixed and coated so as to have a dry film thickness of 1.3 μ. (Silver amount: 0.6 g / m ² ) 7th layer: Highly sensitive green emulsion layer A magenta coupler instead of a cyan coupler 1-
(2,4,6-Trichlorophenyl) -3- {3-
1000 g of an emulsion obtained in the same manner as the emulsion of the third layer except that (2,4-di-t-amylphenoxyacetamide) benzamide} -5-pyrazolone was used, was treated with a green-sensitive iodobromide. 1 kg of silver emulsion (including 70 g of silver and 60 g of gelatin,
Iodine content 3.5 mol%, average particle size 0.55
μ), and applied so that the dry film thickness was 3.5 μ. (Amount of silver: 0.8 g / m ² ) Eighth layer: yellow filter layer An emulsion containing yellow colloidal silver was coated so as to have a dry film thickness of 1 μm.

Ninth layer: low-sensitivity blue-sensitive emulsion layer α-which is a yellow coupler instead of the cyan coupler
(Pivaloyl) -α- (1-benzyl-5-ethoxy-
1000 g of an emulsion obtained in the same manner as the emulsion of the third layer except that 3-hydantoinyl) -2-chloro-5-dodecyloxycarbonylacetanilide was used, and 1 kg of a blue-sensitive silver iodobromide emulsion (70 g of silver). , Containing 60 g of gelatin,
Iodine content 3.5 mol%, average particle size 0.45
μ), and applied so that the dry film thickness was 1.5 μ. (Silver amount: 0.6 g / m ² ) 10th layer: high-sensitivity blue-sensitive emulsion layer α- which is a yellow coupler instead of the cyan coupler
(Pivaloyl) -α- (1-benzyl-5-ethoxy-
1000 g of an emulsion obtained in the same manner as the emulsion of the third layer except that 3-hydantoinyl) -2-chloro-5-dodecyloxycarbonylacetanilide was used, and 1 kg of the above spherical silver iodobromide emulsion B (70 g of silver). , 60 g of gelatin, iodine content 3.5 mol%, average particle size 1.1
μ) and applied to give a dry film thickness of 3 μ.
(Amount of silver: 1.1 g / m ² ) Eleventh layer; Second protective layer 1 kg of an emulsion of an ultraviolet absorber was mixed with 1 kg of 10% gelatin and coated so that a dry film thickness was 2 μm.

Twelfth layer: First protective layer Fine grain emulsion with a fogged surface (grain size 0.06 μ,
A 10% aqueous gelatin solution containing 1 mol% silver iodobromide emulsion) was applied so that the silver coating amount was 0.1 g / m ² and the dry film thickness was 0.8 μ.

A gelatin hardening agent and a surfactant were added to each layer.

The average value of the silver iodide content of all the light-sensitive silver halide emulsions of Sample 101 thus prepared is 3.5 mol%.

Preparation of Sample 102 All the iodine contents of the photosensitive silver halide emulsions of the third, fourth, sixth, seventh, ninth and tenth layers of Sample 101 were 5.0.
Sample 1 was prepared in exactly the same manner as Sample 101 except that the content was mol%.
02 was produced. In this case, the average value of silver iodide content of all the photosensitive silver halide emulsions is 5.0 mol%.

Preparation of Sample 103 Same as Sample 101 except that the iodine contents of the photosensitive silver halide emulsions of the third, fourth, sixth, seventh, ninth and tenth layers of Sample 101 were all 6 mol%. Sample 103
Was produced. In this case, the average value of silver iodide content of all the photosensitive silver halide emulsions is 6 mol%.

Preparation of Samples 104 and 105 The iodine contents of the photosensitive silver halide emulsions of the third, fourth, sixth, seventh, ninth and tenth layers of Sample 101 were all 0.5 mol% and 1.5 mol, respectively. Sample 101 except%
Samples 104 and 105 were manufactured in exactly the same manner as in. In this case, the average values of the silver iodide contents of all the light-sensitive silver halide emulsions are 0.5 mol% and 1.5 mol%, respectively.

Production of Samples 106, 107, 110-114 Exactly the same as Sample 101 except that the compounds shown in Table 1 were added to the third, sixth and ninth layers of Sample 101 in the amounts shown in Table 1. Samples 106, 107, 110
114 was produced.

Preparation of Sample 108 Sample 10 except that the compounds shown in Table 1 were added to the third, sixth and ninth layers of Sample 103 in the amounts shown in Table 1, respectively.
Sample 108 was prepared in exactly the same manner as in No. 3.

Preparation of Sample 109 Sample 1 except that the compounds shown in Table 1 were added to the third, sixth and ninth layers of Sample 104 in the amounts shown in Table 1.
Sample 109 was prepared in exactly the same manner as 04.

Preparation of Sample 115 Sample 101 was prepared in the same manner except that compound 3 was added to the second, fifth, and eighth layers of Sample 101 so that the coating amount was 4 × 10 ⁻⁶ mol / m ^2. 116 was produced.

Preparation of Sample 116 Sample 116 was prepared in exactly the same manner as Sample 102, except that the compounds shown in Table 1 were added to the third, sixth and ninth layers of Sample 102 in the amounts shown in Table 1.

Preparation of Sample 117 Sample 117 was prepared in exactly the same manner as Sample 105, except that the compounds shown in Table 1 were added to the third, sixth and ninth layers of Sample 105 in the amounts shown in Table 1.

Each of these samples 101 to 117 was exposed to a red wedge, a green wedge, and a blue wedge at different portions, and a white wedge exposure (red + green + blue light) was applied to the other portion. . The exposure amounts of red light, green light, and blue light during white exposure were the same as those of red exposure, green light exposure, and blue light exposure, respectively.

The exposed samples were subjected to the following development processing.

Treatment process Time Temperature First development 6 minutes 38 ℃ Washing with water 2 minutes 〃 Inversion 2 minutes 〃 Color development 6 minutes 〃 Adjustment 2 minutes 〃 Bleach 6 minutes 38 ℃ Fixing 4 minutes 〃 Water washing 4 minutes 〃 Stable 1 minute Normal temperature drying The following composition is used.

First developer Water 700 ml Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3
g Sodium sulfite 20 g Hydroquinone monosulfonate 30 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4-methyl-4-hydroxymethyl-3pyrazolidone 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide ( 0.1% solution) 2 ml Water is added 1000 ml Inversion solution Water 700 ml Nitro N, N, N-trimethylenephosphonic acid 5 sodium salt 3 g Stannous chloride (dihydrate) 1 g p-aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water added 1000 ml Color developer water 700 ml Nitrilo NNN trimethylenephosphonic acid-5 sodium salt 3 g Sodium sulfite 7 g Sodium triphosphate (12-hydrate) 36 g Odor Potassium iodide 1g Potassium iodide (0.1% solution) 90ml Hydroxyl acid Sodium 3g Citrazic acid 1.5g N.ethyl-N- (β-methanesulfonamidoethyl) -3.methyl-4-aminoaniline / sulfate 11g Ethylenediamine 3g Water added 1000ml Adjusted water 700ml Sodium sulfite 12g Ethylenediamine / Sodium tetraacetate (dihydrate) 8 g Thioglycerin 0.4 ml Glacial acetic acid 3 ml Water is added 1000 ml Bleached water 800 g Ethylenediaminetetraacetate sodium (dihydrate) 2 g Ethylenediaminetetraacetate iron (III) ammonium (dihydrate) 120 g Potassium bromide 100 g Water added 1000 ml Fixer water 800 ml Sodium thiosulfate 80.0 g Sodium sulfite 5.0 g Sodium bisulfite Water added 1000 ml Stabilized water 800 ml Formalin (37% by weight) 5.0 ml FUJI DRYWELL 5.0 ml (Fuji Film Co., Ltd. surfactant) Add water 1000 ml Cyan at the time of red light exposure and cyan at the time of white light exposure are compared, and the difference in exposure amount at a density of 1.0 The log E was measured.

Similarly, in the case of green light exposure and blue light exposure, Δlo
The g E was measured.

These are shown in Table 1.

Compound A Compound B From these results, it can be seen that the present invention has a greater interimage effect and is superior in sharpness than the comparative example.

Example 2 Samples 101 to 117 of Example 1 were exposed to a white wedge and developed in the same manner as in Example 1, and the relative sensitivity when sample 101 was set to 100 was determined for cyan and magenta. Also, the maximum densities (Dmax) of cyan and magenta were obtained. The results are shown in Table 2.

As shown in the above results, the compound of the present invention shows a decrease in relative sensitivity and
There is no decrease in Dmax. Further, as shown in the results of Example 1, when the compound of the present invention is used, the interimage effect is large and the MTF value is also large.

On the other hand, when compound 3 is used as the additive, the sensitivity is greatly reduced and the Dmax is also significantly reduced.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-59-74557 (JP, A) JP-A-57-164734 (JP, A) JP-A-60-6940 (JP, A) JP-A-53- 147529 (JP, A) Japanese Patent Sho 49-8334 (JP, B2) Japanese Patent 50-36978 (JP, B2)

Claims (1)

[Claims] 1. In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the average content of silver iodide in all light-sensitive silver halide emulsions is 1. A compound represented by the following general formula [I], [II], [III] or [IV] in at least one photosensitive silver halide emulsion layer or its adjacent layer. A silver halide photographic light-sensitive material containing at least one of the following. General formula [I] General formula (II) General formula (III) General formula (IV) In the formula, R represents a linear or branched alkylene group, a linear or branched alkenylene group, a linear or branched aralkylene group, or an arylene group, and R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, It represents a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group. Z represents a polar substituent. However, Z
Is not a sulfonic acid group, a carboxylic acid group, a hydroxy group, or an alkoxycarbonyl group. Further, in the general formula [I] or [II], Z is not a substituted or unsubstituted amino group. X represents a hydrogen atom, a cation or a precursor for neutralizing the molecule. n represents 0 or 1.