JPH0516578B2 - - Google Patents

Description

[Detailed description of the invention]

<<Industrial Application Field>> The present invention relates to a silver halide color photographic light-sensitive material. More specifically, the present invention relates to a silver halide color photographic material having excellent image sharpness and color reproduction. <<Prior Art>> In recent years, with the spread of small cameras, there has been a demand for image quality enlarged from a small size screen to be equivalent to image quality enlarged from a larger normal size screen. In order to satisfy these needs, it is necessary to develop a color photographic material that has enough graininess and sharpness that the printed image quality is not impaired even when the enlargement magnification is increased. Various methods have been known to improve the sharpness of images, but it is widely known that great effects can be obtained by increasing the edge effect and reducing light scattering in photographic materials. . Among these, the edge effect utilizes the concentration gradient of a development inhibiting substance present during development. In this case, known development inhibiting substances include, for example, iodide ions and prom ions released when silver halide is developed in a developer, or substances produced by oxidation of a developing agent. Effects similar to those of these development inhibitors are described in U.S. Patent No.
Compounds described in No. 3227554, No. 3615506, No. 3617291, No. 3701783, etc., or
It is also known that it can be actively enhanced by using further improved so-called DIR compounds and DIR couplers as described in US Pat. No. 34933 (including DIR couplers with so-called timing groups as described in US Pat. ing. However, even when using the above-mentioned DIR couplers, a large amount of DIR color must be used if a strong edge effect is required, and this inevitably greatly inhibits development. Therefore, there is a limit to the amount of DIR coupler that can be used, and there is also a limit to the edge effect caused by the above-mentioned DIR coupler. The drawback was that there was no. Increasing the coating amount of silver to solve this problem not only increases product cost but also increases light scattering due to silver halide, which causes problems in high spatial frequency regions.
The MTF curve decreases, resulting in deterioration of the sharpness of not only the DIR coupler-added layer but also the underlying layer (for more information on the MTF curve, see Mies's “The
Theory of Photographic Process”, 3rd
Edition, published by Macmillan). The present inventors have developed and filed an application for a DIR coupler which improves the conventional drawbacks and can particularly enhance the edge effect while ensuring a constant maximum image density (Japanese Patent Application No. 7150/1982). This invention is a diffusible development inhibitor-releasing coupler (hereinafter referred to as a diffusible DIR coupler) that can react with the oxidation product of a developing agent during development and release a development inhibitor with a diffusivity of 0.4 or more. The invention relates to a silver halide color photographic light-sensitive material characterized by containing. The present invention relates to an improvement of the above invention.
In other words, the above-mentioned diffusive DIR coupler certainly has a remarkable effect on improving sharpness due to the edge effect, but this cannot be achieved by using diffusive DIR compounds that exhibit corresponding colors in all of the color-sensitive layers. However, in conventional light-sensitive materials, in order to maintain the color forming coupler concentration in each layer, it is necessary to increase the amount of silver halide and main coupler, which increases the film thickness and inhibits the diffusion effect of the diffusive DIR coupler. In addition to this, it also had the disadvantage that the color image of each layer became cloudy and the color reproducibility became insufficient. For example, in a publicly available silver halide photosensitive material in which all color-sensitive layers contain a yellow-producing diffusive DIR, yellow color is produced in addition to the respective colors of the magenta and cyan layers, resulting in color turbidity. In order to reduce this effect, it is necessary to increase the amount of silver applied, which is not only uneconomical, but also increases the thickness of the green and red sensitive layers, so it is necessary to increase the amount of silver applied. This is undesirable because it reduces the effect of the diffusible DIR compound and at the same time reduces the interlayer effect. <<Object of the Invention>> Therefore, the first object of the present invention is to provide a silver halide color that does not impair the image quality of prints even when the enlargement magnification increases, has good graininess, and has extremely excellent image sharpness. Our objective is to provide photographic materials. A second object of the present invention is to provide a silver halide color photographic light-sensitive material which has a high film thickness to enhance the multilayer effect and image sharpness. <<Structure of the Invention>> The above objects are to provide a color photographic light-sensitive material having one or more red-sensitive silver halide emulsion layers, green-sensitive silver halide emulsion layers, and blue-sensitive silver halide emulsion layers on a support, The red-sensitive silver halide emulsion layer contains a cyan color-forming diffusive DIR compound, and the green-sensitive silver halide emulsion layer contains a magenta color-forming diffusive DIR compound.
This was achieved by a silver halide color photographic light-sensitive material characterized by containing a yellow color-forming and diffusive DIR compound in the blue-sensitive silver halide emulsion layer. <<Disclosure of the Invention>> The diffusible DIR compound as used in the present invention means a compound that can release a diffusible development inhibitory substance during development, and the diffusivity of the development inhibitory substance can be measured by the following method. I can do it. A multilayer color photosensitive material having the following composition was prepared on a transparent support and designated as Sample B. 1st layer: Red-sensitive silver halide emulsion layer Sensitizing dye 1 of Example 1 was added to a silver iodobromide emulsion (silver iodide 5 mol%, average grain size 0.4 μ) at 6×10 ^-5 per mol of silver. Emulsion that gives red sensitivity using moles,
A gelatin coating solution containing 0.0015 mol of coupler F per mol of silver was coated so that the amount of coated silver was 1.8 g/m ² (film thickness: 2 μm). Coupler F 2nd layer; Silver iodobromide emulsion used in the 1st layer (no red color) polymethyl methacrylate grains (diameter approx.
1.5 μ) gelatin layer (applied silver amount 2 g/m ² , film thickness
1.5μ). In addition to the above composition, each layer contains a gelatin hardening agent and a surfactant. A photosensitive material was prepared as Sample A, which did not contain the silver iodobromide emulsion in the second layer of Sample B, but had the same structure as Sample B except for this. The obtained samples A and B were subjected to wedge exposure and then processed according to certain conditions. A development inhibitor was added to the developer until the concentration of Sample A was reduced to 1/2. The degree of decrease in density of Sample B at this time was used as a measure of the diffusivity in the silver halide emulsion film. The results are shown in Table 1.

【table】

[Table] The DIR coupler (hereinafter simply referred to as DIR coupler) that can release a highly diffusive development inhibiting substance with a diffusivity of 0.4 or more used in the present invention is represented by the following general formula [] . 1 General formula [] A-(-Y)m In the formula, A represents a coupler component, and m is 1 or 2
Y represents a group that binds to the coupling position of the coupler component A and leaves upon reaction with the oxidized product of the color developing agent, and represents a highly diffusible development inhibitor or a compound capable of releasing a development inhibitor. 2 In the general formula [], Y represents the following general formula [] to []. In general formulas [a], [b] and [],
R ₁ is an alkyl group, an alkoxy group, an acylamino group, a halogen atom, an alkoxycarbonyl group, a thiazolilideneamino group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl group, an N-alkylcarbamoyl group, an N,N-dialkylcarbamoyl group, Nitro group, amino group, N-arylcarbonyloxy group, sulfamoyl group, N-alkylcarbamoyloxy group, hydroxy group, alkoxycarbonylamino group, alkylthio group,
Represents an arylthio group, an aryl group, a heterocyclic group, a cyano group, an alkylsulfonyl group, or an aryloxycarbonylamino group. General formula [a],
In [b] and [], n represents 1 or 2, and when n is 2, R ₁ may be the same or different, and the total number of carbons contained in n R ₁ is and ranges from 0 to 10. In the general formula [], R ₂ represents an alkyl group, an aryl group or a heterocyclic group. In the general formula [], R ₃ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,
R ₄ represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkanesulfonamide group, a cyano group, a heterocyclic group, an alkylthio group, or an amino group. When R ₁ , R ₂ , R ₃ or R ₄ represents an alkyl group, it may be substituted or unsubstituted, chain or cyclic. Substituents include halogen atoms, nitro groups, cyano groups, aryl groups, alkoxy groups,
Aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group,
Examples include carbamoyl group, hydroxy group, alkanesulfonyl group, arylsulfonyl group, alkylthio group, and arylthio group. When R ₁ , R ₁ , R ₃ or R ₄ represents an aryl group, the aryl group may be substituted. Substituents include alkyl groups, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, halogen atoms, nitro groups, amino groups, sulfamoyl groups, hydroxy groups, carbamoyl groups, aryloxycarbonylamino groups, alkoxycarbonylamino groups, acylamino groups, cyano group or ureido group. When R ₁ , R ₁ , R ₃ or R ₄ represents a heterocyclic group, it represents a 5- or 6-membered monocyclic ring or fused ring containing a nitrogen atom, oxygen atom, or sulfur atom as a hetero atom, a pyridyl group, quinolyl group, furyl group,
These selected from a benzothiazolyl group, an oxazolyl group, an imidazolyl group, a thiazolyl group, a triazolyl group, a benzotriazolyl group, an imido group, an oxazine group, etc., are further substituted with the substituents listed for the above aryl group. Good too. In the general formula [], the number of carbon atoms contained in R ₂ is 1 to 15. In the general formula [], the total number of carbon atoms contained in R ₃ and R ₄ is 1 to 15. 3 In the general formula [], Y can also be represented by the following general formula []. General formula [] -TIME-INHIBIT In the formula, the TIME group is a group that is bonded to the coupling position of the coupler and can be cleaved by reaction with a color developing agent, and after being cleaved by the coupler,
This is a group that can release the INHIBIT group in a moderately controlled manner. The INHIBIT group is a development inhibitor. 4 In the general formula [], −TIME−INHIBIT
The group represents the following general formulas [] to []. In the general formulas [] to [], R ₅ is a hydrogen atom, halogen atom, alkyl group, alkenyl group, aralkyl group, alkoxy group, alkoxycarbonyl group, anilino group, acylamino group, ureido group, cyano group, nitro group, sulfone Amide group, sulfamoyl group, carbamoyl group, aryl group, carboxy group, sulfo group, hydroxy group,
Represents an alkanesulfonyl group, with the general formula [],
In [], [], [] and [],
represents 1 or 2, and the general formula [], [], [
] and [], k represents an integer of 0 to 2, and in the general formulas [], [] and [], R ₆ represents an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, or an aryl group,
In general formulas [] and [], B is an oxygen atom or

[Formula] (R ₆ represents the same meaning as already defined), and the INHIBIT group represents the general formula [
It has the same meaning as the general formula defined in a], [b], [], [], and [] except for the number of carbon atoms. However, in general formulas [a], [b] and [], the total number of carbons contained in each R ₁ in one molecule is 1.
~32, the number of carbons contained in R ₂ in the general formula [] is 1 to 32, and the total number of carbons contained in R ₃ and R ₄ in the general formula [] is 1 to 32
It is. When R ₅ and R ₆ represent an alkyl group, it may be substituted or unsubstituted, chain-like or cyclic. Examples of the substituent include the substituents listed when R ₁ to R ₄ are alkyl groups. When R ₅ and R ₆ represent an aryl group, the aryl group may be substituted. As a substituent, R ₁
- The substituents listed when R ₄ is an aryl group can be mentioned. Among the above diffusible DIR compounds, the general formula [
Particularly preferred are those having leaving groups represented by a], [b] to []. The yellow image forming color residue represented by 5A includes pivaloylacetanilide type, benzoylacetanilide type, malondiester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, and malonester monoamide type. , benzothiazolylacetate type, benzoxazolyl acetamide type, benzoxazolyl acetate type, malon diester type, benzimidazolylacetamide type or benzimidazolylacetate type coupler residue, heterocycle contained in U.S. Pat. No. 3,841,880 Coupler residues derived from substituted acetamides or heterocyclic substituted acetates, or US Pat. No. 3,770,446, UK Pat.
Examples include coupler residues derived from acylacetamides described in JP-A No. 50-139738 or Research Disclosure No. 15737, and heterocyclic coupler residues described in US Pat. No. 4,046,574. The magenta image-forming coupler residue represented by A includes a coupler residue having a 5-oxo-2-pyrazoline nucleus, a pyrazolo-[1,5-a]benzimidazole nucleus, or a cyanoacetophenone type coupler residue. is preferred. The cyan image-forming coupler residue represented by A is preferably a coupler residue having a phenol nucleus or an α-naphthol nucleus. 6 In the general formula [], A is the general formula [A],
[A], [A], [A], [A], [A] and [A] are represented. In the formula, R ₁₁ represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R ₁₂ and R ₁₃ each represent an aromatic group or a heterocyclic group. In the formula, the aliphatic group represented by R ₁₁ preferably has 1 to 22 carbon atoms and may be substituted or unsubstituted, chain-like or cyclic. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an amino group, an acylamino group, a halogen atom, and the like, which themselves may further have a substituent. Specific examples of aliphatic groups useful as R ₁₁ are as follows. : Isopropyl group, isobutyl group, tert-butyl group, isoamyl group, tert
-amyl group, 1,1-dimethylbutyl group, 1,1
-dimethylhexyl group, 1,1-diethylhexyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, 2-methoxyisopropyl group, 2-phenoxyisopropyl group, 2-p
-tert-butylphenoxyisopropyl group, α-
Aminoisopropyl group, α-(diethylamino)
Isopropyl group, α-(succinimido)isopropyl group, α-(phthalimido)isopropyl group,
α-(benzenesulfonamido)isopropyl group, etc. When R ₁₁ , R ₁₂ or R ₁₃ represents an aromatic group (particularly a phenyl group), the aromatic group may be substituted. Aromatic groups such as phenyl groups include alkyl groups having 32 or less carbon atoms, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups, alkylsulfamoyl groups, alkylsulfonamide groups, and alkylureido groups. , an alkyl-substituted succinimide group, etc., and in this case, the alkyl group may have an aromatic group such as phenylene interposed in the chain. It may be substituted with a phenyl group or an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, etc., and the aryl group of these substituents The moieties may be further substituted with one or more alkyl groups having a total of 1 to 22 carbon atoms. The phenyl group represented by R ₁₁ , R ₁₂ or R ₁₃ includes an amino group, a hydroxy group, a carboxy group, a sulfo group, a nitro group, a cyano group, including those substituted with a lower alkyl group having 1 to 6 carbon atoms. , a thiocyano group or a halogen atom. or,
R ₁₁ , R ₁₂ or R ₁₃ may represent a substituent in which a phenyl group is fused with another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group, a tetrahydronaphthyl group, etc. These substituents may themselves have further substituents. When R ₁₁ represents an alkoxy group, the alkoxy moiety represents a linear or branched alkyl group, alkenyl group, cyclic alkyl group, or cyclic alkenyl group having 1 to 40 carbon atoms, preferably 1 to 22 carbon atoms,
These may be substituted with a halogen atom, an aryl group, an alkoxy group, or the like. When R ₁₁ , R ₁₂ or R ₁₃ represents a heterocyclic group, the heterocyclic group is the carbon atom of the carbonyl group of the acyl group in α-acylacetamide or the amide thereof, respectively. Bonds with the nitrogen atom of the group. Such heterocycles include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, imidazole, thiazole,
Examples include oxazole, triazine, tidiazine, oxazine, etc. These may further have a substituent on the ring. In general formula [A], R ₁₅ has 1 to 1 carbon atoms
40, preferably 1 to 22 linear or branched alkyl groups (e.g. methyl, isopropyl, tert-butyl, hexyl, dodecyl, etc.), alkenyl groups (e.g. allyl group, etc.), cyclic alkyl groups (e.g. cyclopentyl group, cyclohexyl group, norbornyl group), aralkyl group (e.g. benzyl, β-
phenylethyl group, etc.), cyclic alkenyl group (e.g. cyclopentenyl, cyclohexenyl group, etc.), and these represent a halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, carboxy group, alkylthiocarbonyl group,
Arylthiocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group,
Sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, thiourethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkyl Amino group, anilino group, N
It may be substituted with -arylanilino group, N-alkylanilino group, N-acylanilino group, hydroxy group, mercapto group, etc. Furthermore, R ₁₅ is an aryl group (e.g. phenyl group,
(α- or β-naphthyl group, etc.) may also be represented.
The aryl group may have one or more substituents,
Examples of substituents include alkyl groups, alkenyl groups,
Cyclic alkyl group, aralkyl group, cyclic alkenyl group, halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group,
Carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N -Alkylanilino group, N-arylanilino group, N-acylanilino group, hydroxy group, mercapto group, etc. may be included. More preferred as _R15 is phenyl in which at least one ortho position is substituted with an alkyl group, an alkoxy group, a halogen atom, etc. This is because the coupler remaining in the film undergoes coloration due to light or heat. It is useful because there are few. Furthermore, R ₁₅ is a heterocyclic group (for example, a 5- or 6-membered heterocyclic ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom, a fused heterocyclic group, a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group) , oxazolyl group, imidazolyl group, naphthoxazolyl group, etc.), a heterocyclic group substituted with the substituents listed for the above aryl group, an aliphatic or aromatic acyl group, an alkylsulfonyl group,
It may represent an arylsulfonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group. In the formula, R ₁₄ is a hydrogen atom, a linear or branched alkyl, alkenyl, cyclic alkyl, aralkyl, or cyclic alkenyl group having 1 to 40 carbon atoms, preferably 1 to 22 carbon atoms (these groups are the same as those listed for R ₁₅ above). aryl groups and heterocyclic groups (which may have the substituents listed above for _R15 ), alkoxycarbonyl groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, stearyl group) oxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, naphthoxycarbonyl group, etc.), aralkyloxycarbonyl group (e.g., benzyloxycarbonyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, heptadecyl group, etc.) oxy group, etc.), aryloxy group (e.g., phenoxy group, tolyloxy group, etc.), alkylthio group (e.g., ethylthio group, dodecylthio group, etc.), arylthio group (e.g., phenylthio group, α-naphthylthio group, etc.), carboxy group, acylamino group ( For example, acetylamino group, 3-[(2,4-di-tert-amylphenoxy)acetamide]benzamide group, etc.), diacylamino group, N-alkylacylamino group (e.g. N-methylpropionamide group, etc.), N-aryl Acylamino group (e.g. N-phenylacetamide group, etc.), ureido group (e.g. ureido, N-
aryl ureido, N-alkylureido groups, etc.),
Urethane group, thiourethane group, arylamino group (e.g. phenylamino, N-methylanilino group,
Diphenylamino group, N-methylanilino group, diphenylamino group, N-acetylanilino group, 2
-chloro-5-tetradecanamide anilino group, etc.), alkylamino group (e.g. n-butylamino group, methylamino group, cyclohexylamino group, etc.), cycloamino group (e.g. piperidino group, pyrrolidino group, etc.), heterocyclic amino group groups (e.g., 4-pyridylamino group, 2-benzoxazolylamino group, etc.), alkylcarbonyl groups (e.g., methylcarbonyl group, etc.), arylcarbonyl groups (e.g., phenylcarbonyl group, etc.), sulfonamide groups (e.g., alkylsulfonamide group, etc.) group, arylsulfonamide group, etc.), carbamoyl group (e.g., ethylcarbamoyl group, dimethylcarbamoyl group,
N-methyl-phenylcarbamoyl, N-phenylcarbamoyl, etc.), sulfamoyl group (e.g. N-alkylsulfamoyl, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-alkyl-N -arylsulfamoyl group, N,N-diarylsulfamoyl group, etc.),
Represents any one of a cyano group, a hydroxy group, a mercapto group, a halogen atom, and a sulfo group. In the formula, R ₁₇ represents a hydrogen atom or a linear or branched alkyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, an alkenyl group, a cyclic alkyl group, an aralkyl group, or a cyclic alkenyl group, and these are the above-mentioned It may also have the substituents listed for R ₁₅ . Further, R ₁₇ may represent an aryl group or a heterocyclic group, and these may have the substituents listed for R ₁₅ above. In addition, R ₁₇ is a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, or a ureido group. group, urethane group, sulfonamide group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-arylanilino group, N-alkylanilino group, N- It may also represent an acylanilino group, a hydroxy group or a mercapto group. R ₁₈ , R ₁₉ and R ₂₀ each represent a group used in a typical 4-equivalent phenol or α-naphthol coupler, and specifically R ₁₈ is a hydrogen atom, a halogen atom, an aliphatic hydrocarbon residue, an acylamino Group -O-R ₂₁ or -S-R ₂₁ (However, R ₂₁
is an aliphatic hydrocarbon residue), and when two or more R18s exist in the same molecule, two or more _R18s are present in the same molecule.
R ₁₈ may be a different group, and aliphatic hydrocarbon residues include those having substituents. R ₁₉ and
Examples of R ₂₀ include groups selected from aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues, or one of these groups may be a hydrogen atom, and these groups may have substituents. Including those that have. Further, R ₁₉ and R ₂₀ may jointly form a nitrogen-containing heterocyclic nucleus. is an integer from 1 to 4, m is from 1 to
An integer of 3, n is an integer of 1 to 5. The aliphatic hydrocarbon residue may be either saturated or unsaturated, and may be linear, branched, or cyclic. and preferably alkyl groups (e.g. methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl,
cyclohexyl, etc.), alkenyl groups (for example, allyl, octenyl, etc.). Aryl groups include phenyl groups, naphthyl groups, etc.
In addition, heterocyclic residues include pyridinyl, quinolyl,
Representative groups include thienyl, piperidyl, imidazolyl and the like. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues include halogen atoms, nitro, hydroxy, carboxyl, amino, substituted amino, sulfo, alkyl, alkenyl, aryl, heterocycle, alkoxy, Examples include groups such as aryloxy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpholino. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₇ of the substituents of the coupler represented by general formulas [A] to [A],
R ₁₈ , R ₁₉ and R ₂₀ may be bonded to each other, or any one of them may be a divalent group to form a symmetrical or asymmetrical composite coupler. Specific examples of the above-mentioned diffusible couplers are shown below. These compounds according to the invention are covered by British Patent No.
No. 3227554, No. 3617291, No. 3933500, No. 3958993, No. 4149886, No. 4234678,
JP-A-51-13239, JP-A No. 57-56837, British Patent No.
It can be easily synthesized by the methods described in Research Disclosure No. 2070266, No. 2072363, Research Disclosure No. 21228, December 1981, etc. The amount of the diffusible DIR compound used in the present invention is 0.001 mol to 0.5 mol, preferably 0.005 mol to 0.1 mol, per mol of the main coupler for color image formation for each color. In the present invention, a known method such as the method described in US Pat. No. 2,322,027 can be used as a method for introducing a coupler used in a light-sensitive material into a silver halide emulsion layer. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. tributyl trimesate) or organic solvents with a boiling point of 30 to 150 degrees, such as lower alkyl acetates such as ethyl acetate and butyl acetate, propionic acid esters, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc. After dissolving, it is dispersed into hydrophilic colloids. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination. Also, Special Publication No. 51-39853,
The polymer dispersion method described in No. 51-59943 can also be used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. As an engaging agent or protective colloid for photographic emulsion,
Although gelatin is advantageously used, other hydrophilic colloids can also be used. For example, derivatives of gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; Multiple synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used. Gelatin includes lime-processed gelatin, acid-processed gelatin, Bu11.Soc.Sci.Phot.Japan.No16,
Enzyme-treated gelatin as described on page 30 (1966) may be used, and hydrolyzed or enzymatically decomposed products of gelatin may also be used. As gelatin derivatives, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used. A specific example is U.S. Patent No.
No. 2614928, No. 3132945, No. 3186846, No. 3312553, British Patent No. 861414, No. 1005784
No. 1033189, Special Publication No. 42-26845, etc. The gelatin graft polymer is a gelatin grafted with a single (homo) or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, their esters, derivatives such as amides, acrylonitrile, styrene, etc. can be used. In particular, polymers which are compatible to some extent with gelatin, such as acrylic acid, methacrylic acid, acrylamide, methacrylamide,
Graft polymers with polymers such as hydroxyalkyl methacrylates are preferred. These examples are:
U.S. Patent No. 2763625, U.S. Patent No. 2831767, U.S. Patent No.
It is described in No. 2956884 etc. Typical synthetic hydrophilic polymer substances include, for example, West German Patent Application (OLS) No. 2312708 and U.S. Patent No.
It is described in No. 3620751, No. 3879205, and Japanese Patent Publication No. 43-7561. Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention. Preferred silver halide is silver iodide containing up to 15 mole percent silver iodide. Particularly preferable is 2
Silver iodobromide containing from mol% to 12 mol% silver iodide. The average grain size of the silver halide grains in the photographic emulsion (grain diameter in the case of spherical or approximately spherical grains,
In the case of cubic particles, the particle size is defined as the edge length and is expressed as an average based on the projected area), but there is no particular restriction on the particle size.
It is preferably 3μ or less. The particle size distribution may be narrow or wide. Silver halide grains in photographic emulsions may have regular crystal shapes such as cubic or octahedral shapes, or irregular crystal shapes such as spherical or plate shapes. or a composite form of these crystal forms.
It may also consist of a mixture of particles of various crystalline forms. The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.
Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particle. The photographic emulsion used in the present invention is P. Glafkides
Author “Chimie et Physique Photographique” (Paul Montel, 1967), GFDuffin
Author “Photographic Emulsion Chemistry” (The
Focal Press, 1966), VLZelikman et al.
al “Making and Coating Photographic”
Emulsion" (The Focal Press, 1964). In other words, any of the acid method, neutral method, ammonia method, etc. may be used, and soluble silver salt and soluble halogen As a method for reacting the salt, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. may be used. A method in which particles are formed in an excess of silver ions (so-called back mixing method) may also be used.
As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled 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. Two or more types of silver halide emulsions formed separately may be mixed and used. 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. In order to remove soluble salts from the emulsion after precipitation or physical ripening, a nude water washing method in which gelatin is gelatinized may be used, and inorganic salts, anionic surfactants, anionic polymers (e.g. A precipitation method (flocculation) using gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin, etc.) may also be used. Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see, for example, H. Frieser, ed.
Die Grundlagen der Photographischen
Prozessmit Silberhalogeniden” (Akademische
Verlagsgesellschft. 1968) pages 675-734 can be used. Namely, sulfur sensitization using sulfur-containing compounds that can react with activated gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts); , amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g., gold complex salts as well as Pt, It, Pd
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table, such as complex salts of metals in Group 1 of the periodic table, etc., can be used alone or in combination. Specific examples of these include U.S. Patent No. 1574944, U.S. Pat.
No. 2728668, No. 3656955, etc., and U.S. Pat.
The precious metal sensitization method is described in US Pat. No. 2,399,083, US Pat. No. 2,448,060, British Patent No. 618,061, etc. The photographic emulsion used in the present invention contains the following ingredients for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or for stabilizing photographic performance.
Various compounds can be included. Namely, azoles such as benzothiazolium salts, nitroimidazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen substituted); heterocyclic mercapto compounds such as mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group thioketo compounds, such as oxadorinthione; azaindenes, such as triazaindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a,7) tetraazaindenes); benzenethiosulfones; Many compounds known as antifoggants or stabilizers can be added, such as acids; benzenesulfuric acid; and the like. For more detailed examples of these and how to use them, see, for example, U.S. Pat. No. 3,954,474.
No. 3982947 and No. 4021248,
Alternatively, the description in Japanese Patent Publication No. 52-28660 can be referred to. The photographic emulsion layer or other hydrophilic colloid layer of the photographic light-sensitive material of the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast, sensitization). ) may contain various surfactants for various purposes. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol,
polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, polyethylene oxide adducts of silicone), Nonionic surfactants such as glycidol derivatives (e.g. alkenyl succinic acid polyglycerides, alkyl phenol polyglycerides) fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylates, alkyl sulfonates, alkyl benzene sulfates Foonate, alkylnaphthalene sulfonate,
Alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphate esters, alkyl betaines, amines Ampholytic surfactants such as oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings. Cationic surfactants such as can be used. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, and quaternary ammonium salts for the purpose of increasing sensitivity, increasing contrast, or accelerating development. compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, US Patent No. 2400532,
Same No. 2423549, Same No. 2716062, Same No. 3617280,
No. 3772021, No. 3808003, British Patent No.
Those described in No. 1488991 etc. can be used. The photographic material of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)
Acrylamide, vinyl esters (e.g. vinyl acetate), acrylonitrile, olefins, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulfoalkyl (meth)acrylates, etc. ) Polymers containing a combination of acrylate, styrene sulfonic acid, etc. as monomer components can be used. For example, US Patent No. 2376005, US Patent No. 2739137, US Patent No. 2853457,
Same No. 3062674, Same No. 3411911, Same No. 3488708,
Same No. 3525620, Same No. 3607290, Same No. 3635715,
British Patent No. 3645740, British Patent No. 1186699, British Patent No.
The one described in No. 1307373 can be used. For photographic processing of the photographic light-sensitive material of the present invention, for example, research
Any of the known methods and known treatment liquids as described in No. 176 (RD-17643) may be used. This photographic processing may be either a development processing for forming a silver image (black and white photographic processing) or a photographic processing for forming a dye image (color photographic processing) depending on the purpose. or,
The treatment temperature is usually chosen between 18°C and 50°C, but it may also be lower than 18°C or above 50°C. As a special type of development processing, a method may be used in which a developing agent is contained in the light-sensitive material, for example, in an emulsion layer, and the light-sensitive material is processed in an aqueous alkaline solution to perform development. Among the developing agents, hydrophobic ones are used in Research Disclosure No. 169 (RD-
16928), US Patent No. 2739890, UK Patent No.
They can be incorporated into the emulsion layer by various methods such as those described in No. 813253 or West German Patent No. 1547763. Such development treatment may be combined with silver salt stabilization treatment with thiocyanate. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain an aqueous aluminum salt as a hardening agent. When forming a dye image, conventional methods can be applied.
For example, negative-positive method (e.g. “Journal of the
Society of Motion Picture and Television
Engineers, Vol. 61 (1953), pp. 667-701); color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer. , for example phenylene diamines (e.g. 4-amino-N,
N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3
-Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamidoethylaniline, 4-amino-3-methyl-N -ethyl-N-β-methoxyethylaniline, etc.) can be used. In addition, “Photographic” by LFA Mason
“Processing Chemistry” (The Focal Press
(1966) pp. 226-229, U.S. Patent No. 2193015,
Those described in JP-A No. 2592364, JP-A-48-64933, etc. may be used. The color developer may also contain a PH buffer, a development inhibitor, an antifoggant, and the like.
Also, if necessary, water softeners, preservatives, organic solvents, development accelerators, dye-forming couplers, competitive couplers, fogging agents, auxiliary developers, viscosity imparting agents, polycarboxylic acid chelating agents, and antioxidants. It may also include. Specific examples of these additives include Research Disclosure (RD-17643),
It is described in US Pat. No. 4,083,723, West German Publication No. 2,622,950, etc. The photographic emulsion layer of a color developer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As a bleach,
For example, iron (), cobalt (), chromium (),
Compounds of polyvalent metals such as copper, peracids, quinones, nitroso compounds, etc. are used. for example,
Ferricyanide, dichromate, organic complex salts of iron () or cobalt (), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or citric acid, tartaric acid, Complex salts of organic acids such as malic acid; persulfates, permanganates; nitrosophenols, etc. can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. Bleach or bleach-fix solutions are manufactured by U.S. Patent No.
No. 3042520, No. 3241966, Special Publication No. 45-8506,
Bleaching accelerator described in JP-A No. 45-8836, etc., JP-A-53
In addition to the thiol compound described in No.-65732, various additives can also be added. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments,
Included are complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Useful sensitizing dyes include, for example, German patent no.
929080, US Patent No. 2493748, US Patent No. 2503776
No. 2519001, No. 2912329, No. 2912329, No. 2519001, No. 2912329, No.
Examples include those described in No. 3656959, No. 3672897, No. 4025349, British Patent No. 1242588, and Japanese Patent Publication No. 44-14030. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.
Representative examples are U.S. Patent No. 2688545 and U.S. Patent No. 2977229.
No. 3397060, No. 3522052, No. 3522052, No. 3397060, No. 3522052, No.
No. 3527641, No. 3617283, No. 3628964, No. 3666480, No. 3672898, No. 3679428,
No. 3814609, No. 4026707, British Patent No.
No. 1344281, Special Publication No. 43-4936, No. 53-12375,
It is described in JP-A-52-109925 and JP-A-52-110618. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains a color-forming coupler, that is, an aromatic 1
Compounds that can develop color by oxidative coupling with class amine developers (e.g., phenylene diamine derivatives, aminophenol derivatives, etc.) may be used in conjunction with polymer coupler latexes, or compounds that can be used without polymer coupler latexes. It may be used alone in the layer. For example, magenta couplers include 5-pyrazolone couplers, pyrazolonebenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides), etc.,
Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ions.
It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). Also, DIR
In addition to couplers, the products of the coupling reaction are colorless DIRs that release development inhibitors.
A coupling compound may also be included. A specific example of a magenta coloring coupler is a U.S. patent
No. 2600788, No. 2983608, No. 3062653, No. 3127269, No. 3311476, No. 3419391,
Same No. 3519429, Same No. 3558319, Same No. 3582322,
Same No. 3615506, Same No. 3834908, Same No. 3891445,
West German Patent No. 1810464, West German Patent Application (OLS) No.
No. 2408665, No. 2417945, No. 2418959, No. 2424467, Japanese Patent Publication No. 1973-6031, Japanese Patent Publication No. 1973-49-
No. 74027, No. 49-74028, No. 49-129538, No. 50
-60233, 50-159336, 51-20826, same
No. 51-26541, No. 52-42121, No. 52-58922,
This is described in No. 53-55122. A specific example of a yellow coupler is shown in U.S. Patent No.
No. 2875057, No. 3565506, No. 3408194, No. 3551155, No. 3582322, No. 3725072,
West German Patent No. 3891445, West German Patent No. 1547868, West German Published Application No. 2219917, West German Patent No. 2261361, West German Patent No. 2414006
No., British Patent No. 1425020, Special Publication No. 51-10783,
JP-A-47-26133, JP-A No. 48-73147, JP-A No. 50-6341
No. 50-87650, No. 50-123342, No. 50-
No. 130442, No. 51-21827, No. 51-102636, No. 51-102636, No. 51-21827, No. 51-102636, No.
It is described in No. 52-82424, No. 52-115219, etc. A specific example of a cyan coupler is described in U.S. Patent No.
No. 2369929, No. 2434272, No. 2474293, No. 2521908, No. 2895826, No. 3034892,
Same No. 3311476, Same No. 3458315, Same No. 3476563,
Same No. 3583971, Same No. 3591383, Same No. 3767411,
No. 4004929, West German Patent Application (OLS) No.
No. 2414830, No. 2454329, JP-A-48-5055,
No. 48-59838, No. 51-26034, No. 51-146828
No. 52-69624 and No. 52-90932. Examples of colored couplers include U.S. Patent Nos. 2521908, 3034892, 3476560,
Special Publication No. 38-22335, No. 42-11304, No. 44-2016
No. 44-32461, JP-A No. 51-26034, No. 52-
42121, those described in West German Patent Application (OLS) No. 2418959 can be used. As a DIR coupler, for example, the US patent
3227554, 3617291, 3632345, 3701783, 3790384, West German Patent Application (OLS) No. 2414006, 2454301,
No. 2454329, British Patent No. 953454, Japanese Unexamined Patent Publication No. 1973-
Those described in No. 122335, No. 52-69624, and Japanese Patent Publication No. 51-16141 can be used. In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor upon development; for example, U.S. Pat. No. 3,297,445, U.S. Pat.
No., West German Patent Application (OLS) No. 2417914, JP-A-Sho
Those described in No. 52-15271 and No. 53-9116 can be used. The photographic material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,3-dihydroxydioxane, etc.), (4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination. In the photographic material of the present invention, when the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc., they may be mordanted with a cationic polymer or the like. For example, UK Patent No. 685475, US Patent No. 2675316, US Patent No. 2839401, US Patent No. 2882156.
No. 3048487, No. 3184309, No. 3184309, No. 3048487, No. 3184309, No.
No. 3445231, West German Patent Application (OLS) No. 1914362,
Polymers described in JP-A-50-47624, JP-A-50-71332, etc. can be used. The photosensitive material of the present invention uses hydroquinone derivatives, aminophenol derivatives,
It may also contain gallic acid derivatives, ascorbic acid derivatives, etc. The photographic material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, a benzotriazole compound substituted with an aryl group, a 4-thiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, a benzoxazole compound, and an ultraviolet absorbing polymer can be used. These ultraviolet absorbers may be fixed in the hydrophilic colloid layer. Specific examples of ultraviolet absorbers include U.S. Patent No. 3314794.
No. 3352681, No. 3499762, No. 3499762, No. 3352681, No. 3499762, No.
No. 3533794, No. 3700455, No. 3705805, No. 3707375, No. 4045229, JP-A-46-2784
No. 1, West German Patent Application Publication No. 1547863, etc. The photographic material of the present invention may contain an aqueous solution dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes,
Included are merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include, for example:
U.S. Patent No. 2360290, U.S. Patent No. 2418613, U.S. Patent No.
No. 2675314, No. 2701197, No. 2704713, No. 2710801, No. 2728659, No. 2732300,
No. 2735765, No. 2816028, British Patent No.
Hydroquinone derivatives described in No. 1363921 etc.
Gallic acid derivatives described in U.S. Patent Nos. 3,069,262 and 3,457,079, p-alkoxyphenols described in U.S. Pat. U.S. Patent No. 3432300, U.S. Patent No. 3573050, U.S. Patent No. 3574627
No. 3764337, JP-A-52-35633, No. 52-
Examples include p-oxyphenol derivatives described in No. 147434 and No. 52-152225, and bisphenols described in US Pat. No. 3,700,455. The photographic support used in the present invention includes cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, cellulose acetate propionate film, polystyrene film, and polyethylene terephthalate film, which are usually used in photographic light-sensitive materials. , polycarbonate film,
Other materials include laminates of these materials, thin glass, and paper.
Baryta or paper coated or laminated with an α-olefin polymer, especially a polymer of α-olefin having 2 to 10 carbon atoms, such as polyethylene, polypropylene, ethylene butene copolymer, etc.; Supports such as plastic films whose surfaces are roughened to improve adhesion to other polymeric substances give good results. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion with photographic emulsion layers and the like.
The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment. In the photographic light-sensitive material, the photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener. These water-soluble brighteners may be used, or water-insoluble brighteners may be used in the form of a dispersion. The photographic material of the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. The following known antifading agents can be used in the photographic material of the present invention, and color image stabilizers can be used alone or in combination of two or more. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-
These include oxyphenol derivatives and bisphenols. When exposing the silver halide color photographic light-sensitive material of the present invention, not only exposure times of 1/1000 seconds to 1 second, which are used in cameras, but also exposure times shorter than 1/1000 seconds, such as xenon flash lamps or cathode ray tubes, can be used. There was 1/
Exposures of 10 ⁴ to 1/10 ⁶ seconds can also be used;
Exposures longer than seconds can also be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. Laser light can also be used for exposure. Also, electron beams, X-rays, gamma rays,
It may be exposed to light emitted from a phosphor excited by alpha rays or the like. <<Effects of the Invention>> Since the present invention can fully exhibit the function of the diffusive DIR coupler, the multilayer effect can be greatly improved, and the sharpness and graininess of images can be improved. Furthermore, since each of the color forming couplers used in the present invention contributes to image reproduction, not only does color turbidity not occur, but also the amount of coated silver can be reduced and the film thickness of the photosensitive material can be reduced. This not only reduces the manufacturing cost of the photosensitive material, but also makes it easier to diffuse the diffusive DIR coupler, which also improves the sharpness of the image, which is the significance of the present invention. is big. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. <<Example>> A multilayer color photosensitive material 101 consisting of each layer having the composition shown below was prepared on a polyethylene terephthalate film support. 1st layer; antihalation layer (AHL) gelatin layer containing black colloidal silver; 2nd layer; intermediate layer (ML); 3rd gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone; 1st layer. Red-sensitive emulsion layer (RL ₁ ) Silver iodobromide...1.6g/ ^m2 (silver iodide 4 mol%, average grain size 0.5μ) Sensitizing dye...6.0×10 ^-5 mol per mol of silver Sensitizing dye...1.5×10 ^-5 mol per mol of silver Coupler Ec-1...0.04 mol per mol of silver Coupler Ec-2...0.004 mol per mol of silver Coupler D-2... ...0.003 mol per mol of silver Fourth layer; second red-sensitive emulsion layer (PL ₂ ) Silver iodobromide emulsion...2.0 g/m ² (silver iodide 7 mol %, average grain size 1.2 μ) Increase Sensitizing dye... 3.5 x 10 ^-5 mol per mol of silver Sensitizing dye... 1.0 x 10 ^-5 mol per mol of silver Coupler Ec-4... 0.02 mol per mol of silver Coupler Ec- 2...0.002 mol per mol of silver 5th layer; intermediate layer (ML) 6th layer, same as the 2nd layer; 1st green-sensitive emulsion layer (CL ₁ ) Silver iodobromide emulsion... 1.5 g/m ² (Silver iodide 4 mol%, average grain size 0.5μ) Sensitizing dye...3.0 x 10 ^-5 mol per mol of silver Sensitizing dye...1.0 x 10 ^-5 mol per mol of silver Coupler Ec-5...12.0g per mol of silver Coupler Ec-6...0.01 mol per mol of silver Coupler D-2...0.005 mol per mol of silver 7th layer; 2nd green-sensitive emulsion Layer (GL ₂ ) Silver iodobromide emulsion...1.6g/ ^m2 (silver iodide 4 mol%, average grain size 1.2μ) Sensitizing dye...2.5×10 ^-5 mol per mol of silver Sensitization Dye: 0.8×10 ^-5 mol per mol of silver Coupler Ec-7: 0.02 mol per mol of silver Coupler Ec-6: 0.003 mol per mol of silver 8th layer: Yellow filter layer (YFL) Yellow colloidal silver and 2,5-
Ninth gelatin layer containing di-t-octylhydroquinone emulsion dispersion; first blue-sensitive emulsion layer (BL ₁ ) Silver iodobromide emulsion...1.5 g/m ² (silver iodide 6 mol%, average grain Size: 0.4μ) Coupler Ec-8...0.25 mol per mol of silver Coupler D-2...0.015 mol per mol of silver 10th layer; 2nd blue-sensitive emulsion layer (BL ₂ ) Silver iodobromide ...1.1g/m ² (silver iodide 6 mol%, average grain size 0.8μ) Coupler Ec-8...0.06 mol per 1 mol of silver 11th layer; 1st protective layer (PL ₁ ) Iodobromide Silver...0.5g/ ^m2 (silver iodide 1 mol%, average particle size 0.07μ) 12th gelatin layer containing an emulsified dispersion of ultraviolet absorber UV-1; second protective layer ( _PL2 ) trimethyl methacrylate Apply a gelatin layer containing particles (1.5 μ in diameter). In addition to the above composition, each layer contains a gelatin hardening agent H.
-1 and a surfactant were added. The sample prepared as described above was designated as sample 101. The compounds used to prepare the samples are shown below. Sensitizing dye: Anhydro 5,5'-dichloro-
3,3'-di-(γ-sulfopropyl)-9-ethyl-thiacarbocyanine hydroxide pyridinium salt. Sensitizing dye: anhydro-9-ethyl-3.
3'-di-(γ-sulfopropyl)-4,5,4'-
5′-dibenzothiacarbocyanine hydroxide triethylamine salt. Sensitizing dye: anhydro-9-ethyl-5.
5'-Dichloro-3,3'-di-(γ-sulfopropyl)oxacarbocyanine sodium salt. Sensitizing dye: Anhydro 5, 6, 5', 6'-tetrachloro-1, 1'-diethyl-3, 3'-di-
{β-[β-(γ-sulfopropoxy)ethoxy]
Ethylimidazolocarboxyanine} hydroxide sodium salt. Preparation of sample 102 Instead of coupler D-2 in the third layer of sample 101,
Coupler Ec-11 was added to 1/2 (mole) of the amount added in the case of coupler D-2, coupler Ec-9 was added in place of coupler D-2 in the sixth layer, and the amount added was 1/2 (mole) of the amount added in the case of coupler D-2. Sample 102 was prepared in the same manner as Sample 101 except that coupler D-2 in the ninth layer was replaced with coupler Ec-10. Preparation of Samples 103 to 105 The coupler D-2 in the third layer of sample 101 was replaced with the diffusive cyan DIR couplers exemplified herein as C-15, C-14, and C-16, respectively, and the sixth layer was replaced with coupler D-2 in the third layer. of……
Coupler D-2 is exemplified herein as a diffusive magenta DIR coupler M-14, M-13, respectively.
Replaced with M-15 and changed the coating amount of the third layer to 7.
%, sample 101 except that the coating amount of the 6th layer was lowered by 5%.
Samples 103 to 105 were prepared in the same manner as in the case of . The structural formulas of the compounds newly used to prepare samples 102 to 105 are shown below. These samples 101 to 105 were exposed to white imagewise light and subjected to color development as shown below. Table 1
The results shown are obtained. The development process in this case was carried out at 38°C as described below. 1 Color development... 3 minutes 15 seconds 2 Bleaching... 6 minutes 30 seconds 3 Washing... 3 minutes 15 seconds 4 Fixing... 6 minutes 30 seconds 5 Washing... 3 minutes 15 seconds 6 Stabilization... 3 minutes 15 seconds each The composition of the treatment liquid used in the process is as follows. Color developer Sodium nitrilotriacetate...1.0g Sodium sulfite...4.0g Sodium carbonate...30.0g Potassium bromide...1.4g Hydroxylamine sulfate...2.4g 4-(N-ethyl-N-β-hydroxy Ethylamino)-2-methylaniline sulfate...4.5g Add water...1.0 Bleach solution Ammonium bromide...160.0g Aqueous ammonia (28%)...25.0cc Ethylenediamine-tetraacetic acid sodium iron salt
…130.0g Glacial acetic acid …14.0cc Add water …1.0 Fixer Sodium tetrapolyphosphate …2.0g Sodium sulfite …4.0g Ammonium thiosulfate (70%) …175.0cc Sodium bisulfite …4.6g Add water......1.0g Stabilizing solution Formalin...8.0cc Add water...1.0 In addition, samples 101 to 105 were exposed to uniform red light, and then imagewise exposed to green light, followed by white exposure. same

When color development was performed as shown in Table 1, magenta and cyan images having characteristic curves similar to those shown in FIG. 1 were obtained. Here, Δx is the area where the green-sensitive emulsion layer is unexposed (point A)
It shows the extent of the multilayer effect that is suppressed by the uniformly fogged cyan emulsion layer when the exposed area (point B) is developed. That is, in FIG. 1, the curve A-B represents the characteristic curve regarding the magenta color image of the green-sensitive layer, and the curve a
-b represents the cyan image density of the red-sensitive layer upon uniform red exposure. Point A represents the fogged portion of the magenta color image, and point B represents the exposure amount portion that provides a magenta color image density of 2.0. The difference (a-b) between the cyan density a at the exposure amount A and the cyan density b at the same exposure amount B was taken as a measure of the interlayer effect from the green-sensitive layer to the red-sensitive layer. Similarly, Table 1 also shows the results when uniform green light was applied and wedge exposure was performed with red light.
It was shown to. Also, the measurement of MTF value is based on “The Theory of
The method described in "Photographic Process" 3rd edd. (published by Macmillan, written by Mies) was followed.The specific sensitivity was set as 1.0 for sample 101, and the others were expressed in relative terms.The results in Table 1 show that the Photosensitive material (sample 103~
105) has a larger multilayer effect and superior sharpness expressed by MTF compared to conventional samples (comparative samples 101 and 102).

[Brief explanation of drawings]

FIG. 1 shows the multilayer effect of the photosensitive material of the present invention.
In the figure, the curve A-B represents the characteristic curve for the magenta color image of the green-sensitive layer, and the curve a-b represents the cyan color image density of the red-sensitive layer due to uniform red exposure.
Point A represents the fogged portion of the magenta color image, and point B represents the exposure amount portion that provides the magenta color image density of 2.0.

Claims (1)

[Claims] 1. In a color photographic light-sensitive material having one or more red-sensitive silver halide emulsion layers, one or more green-sensitive silver halide emulsion layers, and one or more blue-sensitive silver halide emulsion layers on a support, the red-sensitive silver halide emulsion layer is coated with cyan. A silver halide color photographic material characterized by containing a color-forming diffusive DIR compound, a magenta color-forming diffusive DIR compound in a green-sensitive silver halide emulsion layer, and a yellow color-forming diffusive DIR compound in a blue-sensitive silver halide emulsion layer. .