JP2607063B2 - Multilayer silver halide color photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a multilayer silver halide color photographic light-sensitive material, and more particularly, to a multilayer silver halide color photographic light-sensitive material having excellent sharpness and storage stability. .

[Prior Art] In general, a silver halide color photographic light-sensitive material (hereinafter referred to as a light-sensitive material) comprises a support, a red-sensitive silver halide emulsion layer containing a cyan coupler, and a green-sensitive silver halide containing a magenta color coupler. It has an emulsion layer and a blue-sensitive silver halide emulsion layer containing a yellow color coupler, and further has an antihalation layer, an intermediate layer, a filter layer, a protective layer and the like as required.

In recent photosensitive materials, on the one hand, the demand for image quality by users has increased, and on the other hand, progress has been made in small format conversion. For this reason, higher quality images are desired than ever before, and many efforts have been made so far.

In order to improve the sharpness, studies have been made from both the optical and development effects.

 As an optical surface, the transmittance of irradiation light
From the viewpoint, monodisperse silver halide grains are attracting attention,
Considering thinning from the viewpoint of the scattering path. Special
In the case of a silver halide emulsion layer closer to the support
Since the light scattering path from the material surface becomes longer, the binder
Thinning by reducing the amount is an effective means of improving sharpness
It is known. [For example, Journal of the
・ Optical Society of America (Jour
nal of the Optical Society of America)58
(9), 1245 to 1256 (1968), photographic
Jens and Engineering (Photographic
Science and Engineering)16(3), 181-191 (197
2) etc.].

Further, as specific means thereof, it is known to simply reduce the amount of gelatin applied, to reduce the amount of coupler applied, to reduce the amount of a high boiling solvent for dispersing the coupler, and to use a so-called polymer coupler. However, all of these methods lead to deterioration in graininess, storage stability, and deterioration in coupler color development, and are not preferable in photographic performance.

For example, if the amount of gelatin applied is simply reduced, when a high-boiling organic solvent is used as the coupler solvent, an undesirable phenomenon called sweating tends to occur. Sweating is a phenomenon in which an oily component oozes out on the surface of a light-sensitive material when the light-sensitive material is placed under high temperature and high humidity. For preventing sweating, a polymer coupler obtained in the case of a coupler monomer can be used. If a polymer coupler is used, the use of a high-boiling organic solvent is not required, or the use of a small amount is sufficient, and the occurrence of sweating can be prevented inevitably. However, the polymer coupler has a disadvantage that photographic performance is greatly deteriorated under high temperature and high humidity.

In addition, the reduction in the amount of the coated coupler generally leads to a reduction in the color density, and therefore, the point is to develop a coupler having high color development. In general, a reduction in the amount of the high-boiling-point solvent is also a means that cannot be simply employed because it generally causes a decrease in the color developing property of the coupler.

Under these circumstances, the present inventors have improved the sharpness by using a polymer coupler in the green light-sensitive silver halide emulsion layer in a color negative light-sensitive material to reduce the thickness of the emulsion surface to 18 μm or less, A new problem has arisen.

That is, when the film thickness of the emulsion surface is 18 μm or less, the stability with time (particularly under high temperature and high humidity) is deteriorated, and the increase of fog, desensitization, and breakdown of gradation are increased.

The present inventors have found that this is caused by the coupler in the green-sensitive silver halide emulsion layer, and have developed a light-sensitive material which does not cause the above problems when the total thickness of the emulsion surface is 18 μm or less. The research was advanced to arrive at the present invention.

[Object of the Invention] An object of the present invention is to provide a light-sensitive material having excellent sharpness and improved stability over time.

[Constitution of the Invention] An object of the present invention is to provide a red light-sensitive silver halide emulsion layer containing a cyan coupler, a green light-sensitive silver halide emulsion layer containing a magenta color coupler and a blue light-sensitive layer containing a yellow color coupler on a support. In a multilayer silver halide color photographic light-sensitive material having a silver halide emulsion layer, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is 18 μm or less, and the photosensitive silver halide emulsion layer is A multilayer silver halide having a thickness of 14 μm or less from the outermost surface on the side having the photosensitive layer to the lower end of the photosensitive silver halide emulsion layer closest to the support, and at least one of the magenta color-forming couplers is a pyrazolotriazole-based magenta coupler Achieved by color photographic materials.

Here, the dry film thickness means a film thickness measured at 23 ° C. under 55% humidity control. As for the thickness of each layer, a cross section of the dried sample is enlarged and photographed with a scanning electron microscope, and the thickness of each layer is measured. The lower limit of the total of the dry film thicknesses of all the hydrophilic colloid layers having the emulsion layer (hereinafter referred to as the emulsion surface film thickness) is as follows.
There is a limit depending on the volume occupied by a silver halide emulsion, an oil agent such as a coupler, an additive, a binder such as gelatin, and the like, and the preferable thickness of the emulsion surface is 5 μm to 18 μm, and more preferably 10 μm to 16 μm. The distance from the outermost surface of the emulsion surface to the lower end of the emulsion layer closest to the support is 14
The color sensitivity is different from that of the emulsion layer, and it is preferably 10 μm or less up to the lower end of the emulsion layer next to the support.

The thickness of the layer containing the pyrazolotriazole-based magenta coupler is preferably 0.5 μm to 5 μm per layer.

The emulsion layer of the light-sensitive material of the present invention undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer (for example, a p-phenylenediamine derivative or an aminophenol derivative) in a color development process to form a dye. Dye-forming couplers are used. The dye-forming couplers are usually selected such that, for each emulsion layer, a dye is formed that absorbs the light in the sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler in the blue-sensitive emulsion layer. A magenta dye-forming coupler is used for the green-sensitive emulsion layer, and a cyan dye-forming coupler is used for the red-sensitive emulsion layer.

The pyrazolotriazole magenta coupler used in the present invention is represented by the general formulas [I] and [II].

General formula [I] General formula [II] In the above general formulas [I] and [II], R ₁ and R ₂ represent an alkyl, an aryl or a hetero ring, and the alkyl, aryl or hetero ring may be bonded via an oxygen atom, a nitrogen atom or a sulfur atom. Good. Further, the above-mentioned alkyl, aryl and hetero ring may be bonded via the following bonding groups. That is, acylamino, carbamoyl, sulfonamide, sulfamoylcarbonyl, carbonyloxy, oxycarbonyl, ureido, thioureido, thioamide, sulfone, and sulfonyloxy.

The groups represented by R ₁ and R ₂ are linear or branched alkyl groups having 1 to 20 carbon atoms (eg, methyl, ethyl, propyl,
i-propyl, sec-butyl, n-butyl, t-butyl, n-octyl, t-octyl, dodecyl, octadecyl, etc.). These groups may further have a substituent (eg, a halogen atom, nitro, cyano, alkoxy, aryl,
It may have oxy, amino, acylamino, carbamoyl, sulfonamide, sulfamoyl, imide, alkylthio, arylthio, aryl, alkoxycarbonyl, acyl. Specifically, chloromethyl, bromomethyl, trichloromethyl, β-nitroethyl, δ-cyanobutyl, methoxymethyl, ethoxyethyl, phenoxyethyl, N-methylaminoethyl, dimethylaminobutyl, acetaminoethyl, benzoylamino, propyl, ethylcarbamoylethyl , Methanesulfonamidoethyl, ethylthioethyl, p-methoxyphenylthiomethyl, phenylmethyl, p-chlorophenylmethyl,
Naphthylethyl, ethoxycarbonylethyl, acetylethyl, etc.).

Further, the aryl group represents a phenyl or naphthyl group, and may have a substituent described in the section of the alkyl group.

The hetero ring represents a 5- or 6-membered ring having at least one of a nitrogen atom, an oxygen atom and a sulfur atom, and may or may not have aromaticity. For example, pyridyl, quinolyl, pyrrolium, morpholyl, furanyl, tetrahydrofuranyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl,
Oxazolyl, imidazolyl, thiadiazolyl and the like. Further, these may have the substituents described in the section of the alkyl group.

R ₁ ′ and R ₁ ″ may combine with each other to form a carbon ring (eg, cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl, etc.) and a hetero ring (eg, piperidyl, pyrrolidyl, dioxanyl, morpholinyl, etc.).

Examples of the alkyl, aryl, or heterocyclic ring represented by R ₁ or R ₂ bonded through the above-mentioned bonding group or a nitrogen atom, an oxygen atom, or a sulfur atom include, for example, —OR ₂ ′, −SR ₂ ′, −COR ₂ ′, −OCOR ₂ ′, −COOR ₂ ′, —SO ₂ R ₂ ′, —OSO ₂ R ₂ ′ and the like. Here, R ₂ ′ represents an alkyl, an aryl, or a hetero ring, and R ₂ ″, R ₂ represents a hydrogen atom, an alkyl, an aryl, or a hetero ring.

When the heterocyclic group is a pyrazolotriazolyl compound, the compound is a magenta coupler included in the present invention as well as forming a bis-type pyrazolotriazole compound.

Next, specific examples of R ₁ and R ₂ represented by the general formula will be shown.

_{CH 3 - C 2 H 5 -} (n) C 3 H 7 - (n) C 8 H 17 - (n) C 15 H 31 - _{(T) C 4 H 9 -} (t) C 5 H 11 - (t) C 8 H 17 - -C 17 H 35 -CH 2 CH 2 CH 2 OC 12 H 25 -CH 2 CH 2 CONHC 14 H 29 - OC ₁₂ H ₂₅ −NHC ₁₄ H ₂₉ -S-C ₁₆ H ₃₃ -CONHC ₁₄ H ₂₉ -NHSO ₂ C ₁₆ H ₃₃ -SO ₂ NHC ₁₆ H ₃₃ -COC ₁₁ H ₂₃ -OCOC ₁₅ H ₃₁ −COOC ₁₂ H ₂₅ −SO ₂ C ₁₆ H ₃₃ Z represents a hydrogen atom or a group which is released when a dye is formed by coupling with an oxidized form of an aromatic primary amine color developing agent.

Specifically, for example, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an arylthio group, an alkylthio group, (Z ₂ is a carbon atom, an oxygen atom, a nitrogen atom,
Represents the group of atoms required to form a 5- or 6-membered ring with atoms selected from sulfur atoms. The following is a specific example.

Halogen atom: chlorine, bromine, fluorine Alkoxy group: ethoxy group, benzyloxy group, methoxyethylcarbamoylmethoxy group, tetradecylcarbamoylmethoxy group, etc. Aryloxy group: phenoxy group, 4-methoxyphenoxy group, 4-nitrophenoxy group, etc. acyloxy Group: acetoxy group, myristoyloxy group, benzoyloxy group, etc. Arylthio group: phenylthio group, 2-butoxy-5
Octylphenylthio group, 2,5-dihexyloxyphenylthio group, etc. alkylthio group: methylthio group, octylthio group, hexadecylthio group, benzylthio group, 2- (diethylamino) ethylthio group, ethoxycarbonylmethylthio group,
Ethoxyethylthio group, phenoxyethylthio group, etc. Pyrazolyl group, imidazolyl group, triazolyl group, tetrazolyl group, etc. For example, And the like.

Hereinafter, specific examples of the pyrazolotriazole coupler of the present invention will be shown, but the present invention is not limited thereto.

When the green-sensitive silver halide emulsion layer comprises two or more emulsion layers, the pyrazolotriazole-based magenta coupler must be contained in at least one emulsion layer. This is the case when it is contained in the above emulsion layer.

The coupler of the present invention usually contains 1 × / mol of silver halide.
10 ^-3 mol to 1 mol, preferably 1 × 10 ^-2 mol to 8 ×
It can be used in the range of 10 ^-1 mol.

Further, the magenta coupler of the present invention can be used in combination with another type of magenta coupler. That is, the green photosensitive silver halide emulsion layer containing the magenta coupler of the present invention contains magenta couplers other than the present invention and / or
Alternatively, a colored magenta coupler may be contained. However, the content of these magenta couplers and / or colored magenta couplers outside the present invention is preferably less than 30 mol% of the total coupler amount, and particularly preferably.
Less than 15 mol%.

As the magenta coupler that can be used in combination with the green light-sensitive silver halide emulsion layer of the present invention, pyrazolone-based compounds, indazolone-based compounds, cyanoacetyl-based compounds, pyrazoloazole-based compounds other than the present invention, and the like can be used. Based compounds are advantageous.

Specific examples of the magenta coupler that can be used are described in JP-A-49-11.
No. 1631, No. 56-29236, No. 57-94752, JP-B-48-27
No. 930, U.S. Pat.Nos. 2,600,788, 3,062,653, 3,4
08,194, 3,519,429 and Research Disclosure 12443.

Colored magenta couplers that can be used in combination with the green light-sensitive silver halide emulsion layer of the present invention include U.S. Pat.
No. 1, 3,519,429 and JP-B-48-27930.

When the magenta coupler and other couplers of the present invention are added, they can be incorporated into the green-sensitive silver halide emulsion layer by the above-described oil protect dispersion or latex dispersion method, and when the coupler is alkali-soluble. It may be added as an alkaline solution.

The layer constitution preferably used in the present invention is a layer constitution comprising a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer in order from the method close to the support ( This is the case of a so-called normal layer configuration) or a reverse layer configuration (described in Japanese Patent Application Nos. 59-193609 and 59-202065).

In the case of the forward layer structure, the same color-sensitive layer may be composed of two or more layers having different sensitivities, and in the case of the reverse layer structure, the same color-sensitive layer is formed of three or more layers having different sensitivities. It may be made up.

Further, a non-photosensitive hydrophilic colloid layer may be provided between the photosensitive silver halide emulsion layers, and particularly, the non-photosensitive hydrophilic colloid layer is provided between the photosensitive silver halide emulsion layers having different color sensitivity. Is preferred. Further, it is preferable to provide an antihalation layer, a filter layer, and a protective layer.

In a preferred embodiment of the present invention, at least one photosensitive silver halide emulsion layer contains a compound which releases a development inhibitor or a precursor thereof by reacting with an oxidized form of a color developing agent (hereinafter referred to as a DIR compound). Is to include
More preferably, it is contained in a green-sensitive silver halide emulsion layer containing a pyrazolotriazole-based magenta coupler.

The DIR compound that can be preferably used in the present invention is represented by the following general formula.

Formula (1) AY) m In the formula, A represents a coupler component, m represents 1 or 2, and Y is bonded to the coupling position of the coupler component A and released by reaction with an oxidized color developing agent. And a group which becomes a compound capable of releasing a development inhibitor having a large diffusibility after release.

A only needs to have the property of a coupler, and it is not always necessary to form a dye by coupling.

In the general formula (1), Y represents the following general formulas (2A) to (5)
Represents

General formula (2A) General formula (2B) General formula (2C) General formula (2D) General formula (2E) General formula (3) General formula (4) General formula (5) In the above general formulas (2A) to (2D) and (3), R ₃ is an alkyl group, an alkoxy group, an acylamino group, a halogen atom, an alkoxycarbonyl group, a thiazolylideneamino group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl Group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, nitro group, amino group, N-arylcarbamoyloxy group, sulfamoyl group, N-
Represents an alkylcarbamoyloxy group, a hydroxy group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group, an aryl group, a heterocyclic group, a cyano group, an alkylsulfonyl group, or an aryloxycarbonylamino group. n represents 1 or 2, and when n is 2, R ₃ may be the same or different, and the total number of carbon atoms contained in n R ₃ is 0 to 10.

R _{4 in the} above general formula (2E) has the same meaning as R _{3 in} (2A) to (2D), and X represents an oxygen atom or a sulfur atom.

In the general formula (4), R ₄ represents an alkyl group, an aryl group or a heterocyclic group.

In the general formula (5), R ₅ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₆ represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonyl Represents an amino group, an alkane sulfonamide group, a cyano group, a heterocyclic group, an alkylthio group or an amino group.

When R ₃ , R ₄ , R ₅ or R ₆ represents an alkyl group, it may be substituted or unsubstituted, linear or branched, or a cyclic alkyl group. Substituents are halogen, nitro, cyano, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, sulfamoyl, carbamoyl, hydroxy, alkanesulfonyl, arylsulfonyl, alkylthio Or an arylthio group.

When R ₃ , R ₄ , R ₅ or R ₆ represents an aryl group, the aryl group may be substituted. As a substituent, an alkyl group,
Alkenyl group, alkoxy group, alkoxycarbonyl group, halogen atom, nitro group, amino group, sulfamoyl group, hydroxy group, carbamoyl group, aryloxycarbonylamino group, cyano group or ureido group.

When R ₃ , R ₄ , R ₅ or R ₆ represents a heterocyclic group, a 5- or 6-membered monocyclic or condensed ring containing at least one selected from a nitrogen atom, an oxygen atom and a sulfur atom as a hetero atom Represents a ring, selected from a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group, an oxazolyl group, an imidazolyl group, a thiazolyl group, a triazolyl group, a benzotriazolyl group, an imide group, an oxazine group, and the like; May be substituted by the substituents listed for

In the general formulas (2E) and (4), R ₄ has 1 to 15 carbon atoms.

In the general formula (5), the total number of carbon atoms contained in R ₅ and R ₆ is 1 to 15.

In the above general formula (1), Y is the following general formula (6)
Represents

General formula (6) -TIME-INHIBIT In the formula, the TIME group is bonded to the coupling position of the coupler,
It is a group that can be cleaved by reaction with a color developing agent, and can release an INHIBIT group appropriately after being cleaved from a coupler. The INHIBIT group is a group that becomes a development inhibitor by the release.

In the general formula (6), the -TIME-INHIBIT group represents the following general formulas (7) to (13).

General formula (7) General formula (8) General formula (9) General formula (10) General formula (11) General formula (12) General formula (13) In the general formulas (7) to (13), R ₇ is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aralkyl group,
Alkoxy group, alkoxycarbonyl group, anilino group,
Acylamino group, ureido group, cyano group, nitro group, sulfonamide group, sulfamoyl group, carbamoyl group,
Represents an aryl group, a carboxy group, a sulfo group, a hydroxy group or an alkanesulfonyl group; and in the general formulas (7), (8), (9), (11) and (13), l represents an integer of 1 or 2. In general formulas (7), (11), (12) and (13),
k represents an integer of 1 or 2, and in the general formulas (7), (10) and (11), R ₈ represents an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group or an aryl group; ) And (13), B is an oxygen atom or (R ₈ represents the same meaning as defined above.), And the INHIBIT group is represented by the general formula (2A), (2B), (3), (4)
And the same meaning except for the number of carbon atoms and the general formula defined in (5).

However, in general formulas (2A), (2B) and (3),
The number of carbon atoms contained in each R ₃ in one molecule is 1 to 32 in total, and in the general formula (4), the number of carbon atoms contained in R ₄ is 1
And the total number of carbon atoms contained in R ₅ and R ₆ in the general formula (5) is 0 to 32.

When R ₇ and R ₈ represent an alkyl group, they may be substituted or unsubstituted, linear or cyclic. Examples of the substituent include the substituents listed when R _{3 to} R ₆ are an alkyl group.

When R ₇ and R ₈ represent an aryl group, the aryl group may be substituted. Examples of the substituent include the substituents listed when R _{3 to} R ₆ are an aryl group.

Of the diffusible DIR compounds represented by the general formula (1), those having a leaving group represented by the general formulas (2A) and (2B) to (5) are particularly preferable.

In the general formula (1), the yellow image forming coupler residue represented by A is a pivaloyl acetanilide type, a benzoyl acetanilide type, a malon diester type, a malon diamide type, a dibenzoyl methane type, a benzothiazolylacetamide type , Malonester monoamide type, benzothiazolyl acetate type, benzoxazolylacetamide type, benzoxazolyl acetate type,
Malon diester type, benzimidazolylacetamide type or benzimidazolyl acetate type coupler residue, heterocyclic substituted acetamide or coupler residue derived from heterocyclic substituted acetate contained in U.S. Patent No. 3,841,880 or U.S. Patent No. 3,770,446, UK Patent 1, Four
No. 59,171, West German Patent (OLS) 2,503,099, JP-A-50-13
Examples include coupler residues derived from acylacetamides described in 9738 or Research Disclosure No. 15737, and heterocyclic coupler residues described in US Pat. No. 4,046,574.

The magenta color image coupler residue represented by A is 5
-Oxo-2-pyrazolyl nucleus, pyrazolo- [1,5-a]
Coupler residues having a benzimidazole nucleus or cyanoacetophenone type coupler residue are preferred.

As the cyan image forming coupler residue represented by A, a coupler residue having a phenol nucleus or an α-naphthol nucleus, an indazolone-based or pyrazolotriazole-based coupler residue is preferable.

Further, after the coupler couples with the oxidized form of the developing agent and releases the development inhibitor, the effect as a DIR coupler is the same even when substantially no dye is formed. A coupler residue of this type represented by A is disclosed in U.S. Pat. No. 4,052,213.
And coupler residues described in JP-A Nos. 4,088,491, 3,632,345, 3,958,993 and 3,961,959.

Preferred diffusable DIR compounds used in the present invention include, but are not limited to, the following compounds.

These compounds are disclosed in U.S. Pat.Nos. 4,234,678 and 3,227,554.
Nos. 3,617,291, 3,958,993, 4,149,886,
No. 3,933,500, JP-A-57-56837, 51-13239, U.S. Pat. Nos. 2,072,363 and 2,070,266, and Research Disclosure, December 21, 1981, No. 21228, can be easily synthesized.

The DRI compound used in the present invention is usually 1 × 10 ^-6 mol to 5 × 10 ^-2 mol, preferably 1 × 10 ^-5 mol to 1 × 10 ^-2 per mol of silver halide.

In the light-sensitive material of the present invention, together with the diffusive DIR, a DIR compound having a low diffusivity can be used. They may be used in the same emulsion layer as the diffusible DIR or in a different emulsion layer.

In the silver halide emulsion, silver bromide as silver halide,
Any of silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, silver chloride and the like can be used. Silver bromide and silver chloroiodobromide are preferred.

The silver halide grains used in the silver halide emulsion are:
Any of the acidic method, neutral method and ammonia method may be used. The particles may be grown at a time, or may be grown after the seed particles have been made. The method of producing the seed particles and the method of growing may be the same or different.

In the silver halide emulsion, a halide ion and a silver ion may be mixed at the same time, or one of them may be mixed in a liquid in which one is present. Alternatively, it may be formed by sequentially and simultaneously adding halide ions and silver ions while controlling the pH and pAg in the mixing vessel while taking into account the critical growth rate of silver halide crystals. According to this method, silver halide grains having a regular crystal form and a nearly uniform grain size can be obtained. The halogen composition of the grains may be changed using a conversion method in any step of the formation of AgX.

Known silver halide solvents such as ammonia, thioether, and thiourea can be present during the growth of silver halide grains.

In the course of forming and / or growing the silver halide grains, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt) and iron salt ( Metal ions by using at least one member selected from the group consisting of a complex salt and a metal ion, and these metal elements can be contained inside the particles and / or on the surface of the particles. A reduction sensitization nucleus can be provided inside the grains and / or on the grain surface.

In the silver halide emulsion, unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or may be kept contained. When removing the salts, use Research Disclosure (hereinafter referred to as R).
(Abbreviated as D) 17643 No. II.

The silver halide grains may have a uniform silver halide composition distribution within the grains, or may be core / shell grains having different silver halide compositions between the inside of the grains and the surface layer.

The silver halide grains are preferably such that a latent image is mainly formed on the surface.

The silver halide grains may have a regular crystal form such as cubic, octahedral, or tetradecahedral, or may have an irregular crystal form such as spherical or plate-like. In these particles, the ratio between the {100} plane and the {111} plane can be arbitrarily used. Further, those having a composite form of these crystal forms may be used, and particles of various crystal forms may be mixed.

The silver halide grains may have a size of 0.05 to 30 μm, preferably 0.1 to 20 μm.

The silver halide emulsion having any grain size distribution may be used. Emulsions having a wide grain size distribution (referred to as polydisperse emulsions) may be used, and emulsions having a narrow grain size distribution (referred to as monodisperse emulsions). When the value is divided by the average grain size, it means that the value is 0.20 or less, where the grain size is the diameter in the case of spherical silver halide, and the projected image in the case of grains other than spherical. The diameter when converted to a circular image of the same area is shown.) Or a mixture of several types. Further, a polydisperse emulsion and a monodisperse emulsion may be used in combination.

The silver halide emulsion may be a mixture of two or more kinds of silver halide emulsions formed separately.

The silver halide emulsion can be chemically sensitized by a conventional method. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or another noble metal compound, or the like can be used alone or in combination.

The silver halide emulsion can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dye may be used alone or in combination of two or more. A dye which has no spectral sensitizing effect by itself together with the sensitizing dye, or a compound which does not substantially absorb visible light, and which contains a supersensitizer which enhances the sensitizing effect of the sensitizing dye is contained in the emulsion. Is also good.

As the sensitizing dye, a cyanine dye, a merocyanine dye, a composite cyanine dye, a composite merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a steryl dye, and a hemioxanol dye are used.

Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

Silver halide emulsions may be used during chemical ripening, at the end of chemical ripening, and / or at the end of chemical ripening in order to prevent fog during the production process, storage, or photographic processing of the light-sensitive material, or to maintain stable photographic performance. After ripening and before coating the silver halide emulsion, compounds known as antifoggants or stabilizers in the photographic industry can be added.

Silver halide emulsion binder (or protective colloid)
It is advantageous to use gelatin, but a gelatin derivative, a graft polymer of gelatin and another polymer,
Other hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic high molecular substances such as homopolymers and copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention may comprise one or more hardeners for increasing the film strength by crosslinking the binder (or protective colloid) molecules. By using it, it can be hardened. The hardener can be added in such an amount that the light-sensitive material can be hardened to such an extent that it is not necessary to add the hardener to the processing solution, but it is also possible to add the hardener to the processing solution.

For example, aldehydes, (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxy dioxane, etc.), active vinyl compounds (1,3,5 -Triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol and the like, active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine and the like), mucohalic acids (mucochloric acid, And the like can be used alone or in combination.

A plasticizer can be added to the silver halide emulsion layer and / or another hydrophilic colloid layer of the light-sensitive material for the purpose of enhancing flexibility. Preferred plasticizers are the compounds described in RD17643, section XII, A.

A photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or hardly-soluble synthetic polymer for the purpose of improving dimensional stability and the like.

For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (eg, vinyl acetate), acrylonitrile, olefin, ethylene alone or in combination, or acrylic acid, A polymer having a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid or the like as a monomer component can be used.

It is desirable that these yellow and cyan dye-forming couplers have, in the molecule, a group having 8 or more carbon atoms that makes the coupler non-diffusible. Also, these dye-forming couplers need only reduce two molecules of silver ions, even if they are four-equivalent, in which four molecules of silver ions need to be reduced in order to form one molecule of dye. 2
Both may be equivalent. Dye-forming couplers are colored couplers having a color correcting effect and development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, toning agents by coupling with oxidized developing agents. ,
Compounds that release photographically useful fragments such as hardeners, foggants, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included. A colorless coupler that performs a coupling reaction with an oxidized form of an aromatic primary amine developer but does not form a dye (also referred to as a competitive coupler) can be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler, a known acylacetanilide-based coupler can be preferably used. Of these, benzoylacetanilide and pivaloylacetoanilide compounds are advantageous. Specific examples of yellow color couplers that can be used include, for example, U.S. Pat.
No. 5,057, No. 3,265,506, No. 3,408,194, No. 3,5
No. 51,155, No. 3,582,322, No. 3,725,072, No. 3,
891,445, West German Patent 1,547,868, West German Application Publication 2,219,
No. 917, No. 2,261,361, No. 2,414,006, UK Patent No. 1,4
No. 25,020, JP-B-51-10783, JP-A-47-26133,
No. 48-73147, No. 50-6341, No. 50-87650, No. 50-12
No. 3342, No. 50-130442, No. 51-21827, No. 51-10263
No. 6, No. 52-82424, No. 52-115219, No. 58-95346 and the like.

As the cyan dye-forming coupler, a phenol or naphthol coupler is generally used. Specific examples of cyan coloring couplers that can be used include, for example, U.S. Pat.
No. 730, No. 2,474,293, No. 2,801,171, No. 2,895,8
No. 26, No. 3,476,563, No. 3,737,326, No. 3,758,
No. 308, No. 3,893,044, JP-A-47-37425,
No. 50-10135, No. 50-25228, No. 50-112038, No. 50
Preferred are couplers described in JP-A-117422 and JP-A-50-130441 and couplers described in JP-A-58-98731.

Of the dye-forming couplers, colored couplers, DIR couplers, DIR compounds, image stabilizers, color fogging inhibitors, ultraviolet absorbers, fluorescent brighteners, etc. that do not need to be adsorbed on the silver halide crystal surface, hydrophobic compounds are solid Various methods such as a dispersion method, a latex dispersion method and an oil-in-water type emulsification dispersion method can be used, and these can be appropriately selected according to the chemical structure of a hydrophobic compound such as a coupler. The oil-in-water type emulsification dispersion method can be applied by a conventionally known method of dispersing a hydrophobic additive such as a coupler, and usually, a low boiling point organic solvent having a boiling point of about 150 ° C. or higher, if necessary, having a low boiling point, and / or an aqueous solution. Dissolve using a hydrophilic organic solvent, using a surfactant in a hydrophilic binder such as an aqueous gelatin solution using a stirring device, a homogenizer, a colloid mill, a flow mixer, using a dispersing means such as an ultrasonic device, After emulsification and dispersion, it may be added to the target hydrophilic colloid layer. A step of removing the low boiling organic solvent at the same time as the dispersion or dispersion may be included.

Organic solvents having a boiling point of 150 ° C or higher such as phenol derivatives, alkyl phthalates, phosphates, citrates, benzoates, alkylamides, fatty acid esters and trimesic acid esters which do not react with the oxidized form of the developing agent as high boiling solvents A solvent is used.

A low boiling or water-soluble organic solvent can be used with or instead of a high boiling solvent. Organic solvents having a low boiling point and substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene.

When the dye-forming coupler, DIR coupler, colored coupler, DIR compound, image stabilizer, color fogging inhibitor, ultraviolet absorber, fluorescent whitening agent, etc. have an acid group such as carboxylic acid and sulfonic acid, they are used as an alkaline aqueous solution. It can also be introduced into a hydrophilic colloid.

Dissolve the hydrophobic compound in a solvent having a low boiling point solvent alone or in combination with a high boiling point solvent, as a dispersing aid when dispersing in water using mechanical or ultrasonic, anionic surfactant,
Nonionic surfactants, cationic surfactants and amphoteric surfactants can be used.

The oxidized developing agent or the electron transfer agent migrates between the emulsion layers (the same color-sensitive layer and / or different color-sensitive layers) of the light-sensitive material, causing color turbidity, degraded sharpness, and granularity. A color antifoggant can be used to prevent the property from being noticeable.

The color antifoggant may be contained in the emulsion layer itself, or an intermediate layer may be provided between adjacent emulsion layers to be contained in the intermediate layer.

An image stabilizer for preventing deterioration of a dye image can be used in the photosensitive material. Compounds that can be preferably used are those described in RD17643, Section VII J.

The hydrophilic colloid layer such as the protective layer and the intermediate layer of the photosensitive material may contain an ultraviolet absorber to prevent fogging due to discharge caused by the photosensitive material being charged by friction or the like and to prevent deterioration of an image due to ultraviolet rays. Good.

In order to prevent deterioration of the magenta dye-forming coupler and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used for the light-sensitive material.

When the hydrophilic colloid layer of the light-sensitive material contains a dye or an ultraviolet absorber, it may be mordanted with a mordant such as a cationic polymer.

To the silver halide emulsion layer and / or other hydrophilic colloid layers of the light-sensitive material, a development retarder, a compound which changes the developability such as a development retarder, or a bleaching accelerator can be added. A compound that can be preferably used as a development retarder is RD17643
And the development retarder is a compound described in 17643, Item XXI, Item E. Development acceleration,
A black-and-white developing agent and / or a precursor thereof may be used for other purposes.

The emulsion layer of the photographic light-sensitive material contains a polyalkylene oxide or a derivative thereof such as an ether, ester, or amine, a thioether compound, a thiomorpholine, a quaternary ammonium compound, a urethane derivative, for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may contain a urea derivative or an imidazole derivative.

Photosensitive materials include filter layers, antihalation layers,
An auxiliary layer such as an irradiation prevention layer can be provided. In these layers and / or the emulsion layers, dyes which flow out or bleach from the light-sensitive material during the development processing may be contained. Examples of such dyes include oxonol dyes, hexoxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes.

A matting agent can be added to the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material for the purpose of reducing the gloss of the light-sensitive material, improving the writability, preventing sticking between the light-sensitive materials, and the like. As the matting agent, any can be used. For example, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate,
Examples include polymers of calcium carbonate, acrylic acid and methacrylic acid and their esters, polyvinyl resins, polycarbonates, and polymers of styrene and their copolymers. The matting agent preferably has a particle size of 0.05 μm to 10 μm. The amount to be added is preferably 1 to 300 mg / m ² .

A lubricant can be added to the light-sensitive material to reduce sliding friction.

An antistatic agent for antistatic purposes can be added to the photosensitive material. The antistatic agent may be used in the antistatic layer on the side of the support where the emulsion is not laminated, and a protective colloid layer other than the emulsion layer and / or the emulsion layer on the side where the emulsion layer is laminated on the support. May be used. Antistatic agents preferably used are compounds described in RD17643 XIII.

In the photographic emulsion layer and / or other hydrophilic colloid layer of the photosensitive material, coating property improvement, antistatic property, slip property improvement, emulsification dispersion, adhesion prevention, photographic properties (development acceleration, hardening, sensitization, etc.)
Various surfactants can be used for the purpose of improvement and the like.

The support used in the light-sensitive material of the present invention includes cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate,
Films made of semi-synthetic or synthetic polymers such as polyamides are included.

The photosensitive material is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support as necessary, and then directly or on the surface of the support, adhesion, antistatic property, dimensional stability, abrasion resistance, hardness, It may be applied via one or more subbing layers to improve antihalation, friction properties, and / or other properties.

When coating the photosensitive material, a thickener may be used to improve the coating property. In addition, for example, for a hardener such as a hardener, which causes gelation before coating when added to a coating solution in advance due to its high reactivity, it is recommended to mix it immediately before coating using a static mixer or the like. preferable.

As an application method, extrusion coating and curtain coating, which can simultaneously apply two or more layers, are particularly useful, but bucket coating is also used depending on the purpose. The application speed can be arbitrarily selected.

The surfactant is not particularly limited, for example, natural surfactants such as savonin, alkylene oxides, glycerin, nonionic surfactants such as glycidol,
Including higher alkyl amines, quaternary ammonium salts, pyridine and other heterocycles, cationic surfactants such as phosphonium or sulfonium, and acidic groups such as carboxylic acid, sulfonic acid, phosphoric acid, sulfuric acid ester, and phosphoric acid ester You may add an amphoteric surfactant, such as an anionic surfactant, amino acids, aminosulfonic acid, and sulfuric acid or phosphoric acid ester of amino alcohol. For the same purpose, it is also possible to use a fluorine-based surfactant.

To obtain a dye image using the light-sensitive material of the present invention, color photographic processing is performed after exposure. The color processing includes a color development processing step, a bleaching step, a fixing step, a washing step, and a stabilizing step as required. Instead of the bleaching step and the fixing step, In addition, a bleach-fixing process can be performed using a one-bath bleach-fixing solution, or a monobath processing process using a one-bath developing bleach-fixing solution capable of performing color development, bleaching, and fixing in one bath. Can also be performed.

A pre-hardening treatment step, a neutralization step thereof, a stop fixing treatment step, a post-hardening treatment step and the like may be performed in combination with these treatment steps. In these processes, instead of the color developing process, an activator process in which a color developing agent or a precursor thereof is contained in the material and the developing process is performed with an activator solution may be performed, or the activator may be used in the mono bath process. Processing can be applied. Among these processes, representative processes are shown below. (These processes are any of a water-washing process, a water-washing process, and a stabilization process as a final process.)-Color developing process-Bleaching process-Fixing process-Color developing process-Bleaching-fixing process Process-Pre-hardening process-Color developing process-Stop fixing process-Rinsing process-Bleaching process-Fixing process-Rinsing process-Post-hardening process-Color developing process-Rinsing process-Supplement Color development processing step-Stop processing step-Bleaching processing step-Fixing processing step-Activator processing step-Bleaching fixing processing step-Activator processing step-Bleaching processing step-Fixing processing step-Mono bath processing step The processing temperature is usually 10 ° C. ~ 65 ° C, but 65 ° C
The temperature may exceed ℃. The treatment is preferably performed at 25 ° C to 45 ° C.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol-based and p-phenylesinamine-based derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, for example, salt acid, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate, etc. it can.

These compounds are generally used in an amount of about 0.
It is used at a concentration of 1 to 30 g, more preferably about 1 to 15 g for the color developing solution 1. If the amount is less than 0.1 g, a sufficient color density cannot be obtained.

Examples of the aminophenol-based developer include o-
Aminophenol, p-aminophenol, 5-amino-2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene and the like are included.

Particularly useful primary aromatic amine color developing agents are N-
N′-dialkyl-p-phenylenediamine compound, wherein the alkyl group and the phenyl group are substituted,
Alternatively, it may not be substituted. Among them, particularly useful compounds are NN-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N, N-dimethyl-p-phenylenediamine hydrochloride, 2-amino- 5- (N-ethyl-N-dodecylamino) -toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylamino Examples include aniline, 4-amino-3-methyl-N, N-diethylaniline, 4-amino-N- (2-methoxyethyl) -N-ethyl-3-methylaniline-p-toluenesulfonate.

The color developing agents may be used alone or in combination of two or more. Further, the color developing agent may be incorporated in a color photographic material.

In this case, the silver halide color photographic light-sensitive material can be processed with an alkali solution (activator solution) instead of the color developing solution, and bleach-fix processing is performed immediately after the alkali solution processing.

The color developing solution used in the present invention may contain an alkali agent usually used in the developing solution, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or borax. And further contains various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or development regulators such as citrazic acid, and preservatives such as hydroxylamine or sulfite. May be. Furthermore, various antifoaming agents and surfactants, and organic solvents such as methanol, dimethylformamide and dimethylsulfoxide can be appropriately contained.

The pH of the color developer used in the present invention is usually 7 or more,
Preferably it is about 9-13.

In the color developer used in the present invention, diethyloxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, an aromatic secondary alcohol, hydroxamic acid, bentose or Hexose, pyrogallol-1,
3-dimethyl ether and the like may be contained.

In the color developing solution used in the present invention, various chelating agents can be used in combination as a sequestering agent. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminopentaacetic acid;
Organic phosphonic acids such as -hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acids such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane 1, Examples thereof include polyhydroxy compounds and the like, such as phosphonocarboxylic acids such as 2,4-tricarboxylic acid, and polyphosphoric acids such as tripolyphosphoric acid and hexametaphosphoric acid.

The bleaching step may be performed simultaneously with the fixing step as described above, or may be performed individually. As the bleaching agent, a metal complex salt of an organic acid is used, and for example, an organic acid such as polycarboxylic acid, aminopolycarboxylic acid or oxalic acid or citric acid, which is coordinated with a metal ion such as iron, cobalt, or copper is used. . The most preferred organic acids among the above organic acids include polycarboxylic acids and aminopolycarboxylic acids. Specific examples thereof include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N, N ′, N ′
-Triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediamine Tetraacetic acid and the like can be mentioned.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

These bleaching agents are 5-450 g /, more preferably 20-2 g
Use at 50g /.

As the bleaching solution, a solution having a composition containing a sulfite as a preservative, if necessary, in addition to the bleaching agent as described above, is required.
Further, a bleaching solution containing an ethylenediaminetetraacetate iron (III) complex bleach and having a composition in which a large amount of a halide such as ammonium bromide is added may be used. As the halide, besides ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can also be used. it can.

The bleaching solution used in the present invention includes JP-A-46-280,
JP-B-45-8506 and JP-B-46-556, Belgian Patent No. 770,9
No. 10, JP-B-45-8836, JP-B-53-9854, JP-A-54-71
Various bleaching accelerators described in JP-A Nos. 634 and 49-42349 can be added.

Although the pH of the bleaching solution is used at 2.0 or more, it is generally 4.0 to
It is used at 9.5, preferably at 4.5-8.0, most preferably at 5.0-7.0.

A fixing solution having a commonly used composition can be used. As a fixing agent, a compound capable of forming a water-soluble complex salt by reacting with silver halide used in a usual fixing process, for example, thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, and potassium thiocyanate And thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea, thioether and the like. These fixing agents are 5g /
As described above, use in an amount that can be dissolved, but generally 70
Use at ~ 250g /. A part of the fixing agent can be contained in the bleaching tank, and conversely, a part of the bleaching agent can be contained in the fixing tank.

The bleaching solution and / or the fixing solution include various pH buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. The agents can be used alone or in combination of two or more. Furthermore, various fluorescent whitening agents, defoaming agents or surfactants can be added. Also, hydroxylamine, hydrazine, preservatives such as bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acid or nitro alcohol, stabilizers such as nitrates, hardening agents such as water-soluble aluminum salts, methanol,
An organic solvent such as dimethylsulfonamide and dimethylsulfoxide can be appropriately contained.

The pH of the fixer is used at 3.0 or higher, but generally 4.5 to
It is used at 10, preferably 5 to 9.5, most preferably 6 to 9.

Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the above-mentioned bleaching step, and preferred compounds and the concentrations in the processing solution are the same as those in the above-mentioned bleaching step.

To the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the bleaching agent as described above and, if necessary, a sulfite as a preservative is applied. Also, a bleach-fixing solution having a composition in which a small amount of a halide such as ammonium bromide is added to the above-mentioned silver halide fixing agent and a bleach-fixing agent of ethylenediaminetetraacetate (III) complex salt, or conversely, a halogen such as ammonium bromide. Bleach-fixing solution having a composition containing a large amount of a halide, and a special bleach-fixing solution having a composition comprising a combination of an iron (III) complex salt of ethylenediaminetetraacetate and a large amount of a halide such as ammonium bromide. Can do things. As the halide, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid,
Lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can also be used.

Examples of the silver halide fixing agent that can be contained in the bleach-fixing solution include the fixing agents described in the above fixing processing step. The concentration of the fixing agent and the pH buffer and other additives that can be contained in the bleach-fixing solution are the same as those in the above-mentioned fixing process.

The pH of the bleach-fix solution is used at 4.0 or higher.
Used in 5.0-9.5, preferably used in 6.0-8.5,
Most preferably, it is 6.5 to 8.5.

Example 1 Hereinafter, specific examples of the present invention will be described, but embodiments of the present invention are not limited thereto.

In all of the following examples, the addition amount in the silver halide photographic light-sensitive material is based on 1 m ² unless otherwise specified. Further, silver halide and colloidal silver are shown in terms of silver.

On a triacetylcellulose film support, each layer having the composition shown below was sequentially formed from the support side to prepare a multilayer color photographic element sample 1.

Sample-1 (Comparative) First Layer: Antihalation Layer (HC-1) A gelatin layer containing black colloidal silver. Second layer: Intermediate layer (IL) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone. 1.0 μm thick Third layer: low-sensitivity red-sensitive silver halide emulsion layer (RL-1) Monodisperse emulsion (emulsion I) composed of Ag Br I containing an average grain size (r) of 0.30 μm and 6 mol% of Ag I Silver coating amount 1.8 g / m ² Sensitizing dye I: 6 × 10 ⁻⁵ mol per mol of silver Sensitizing dye II: 1.0 × 10 ⁻⁵ mol per mol of silver Cyan coupler (C-1) 0.06 mole per mole of silver Colored cyan coupler (CC-1) ... per mole of silver
0.003 mol DIR compound (A-1): 0.0030 mol per mol of silver
2.7 μm thick Fourth layer: high-sensitivity red-sensitive silver halide emulsion layer (RH-1) Average particle size (r) 0.5 μm, Ag Br I containing 7.0 mol% of Ag I
Monodisperse emulsion (emulsion II): silver coating amount 1.3 g / m ² sensitizing dye I: 3 × 10 ^-5 mol per mol of silver sensitizing dye II: 1.0 × 10 ⁵ mol per silver ^-5 mol Cyan coupler (C-1): 0.02 mol per 1 mol of silver Colored cyan coupler (CC-1): 1 mol per silver
0.0015 mol DIR compound (A-1) 0.001 mol per mol of silver
1.3 μm thickness 5th layer: Intermediate layer (IL) Same as 2nd layer, gelatin layer. Thickness: 1.5 μm Sixth layer: low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion-I: Silver coating amount 1.5 g / m ² Sensitizing dye III: 2.3 × 10 ⁻⁵ per mol of silver Mole Sensitizing dye IV: 2.5 × 10 ⁻⁵ mol per mol of silver Magenta coupler (M-1): 0.050 per mol of silver
Mol Colored magenta coupler (CM-1): 0.009 mol per mol of silver DIR compound (A-1): 0.0025 mol per mol of silver
Film thickness 2.5 μm Seventh layer: High-sensitivity green-sensitive silver halide emulsion layer (GH-1) Emulsion-II: coated silver amount: 1.4 g / m ² Sensitizing dye III: 1.5 × 10 ^-5 per mol of silver Mole Sensitizing dye IV: 1.0 × 10 ^-5 mol per mol of silver Magenta coupler (M-1): 0.020 per mol of silver
Mol Colored magenta coupler (CM-1): 0.002 mol per mol of silver DIR compound (A-1): 0.0010 mol per mol of silver
Eighth layer: yellow filter layer (YC-1) A gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone. Ninth layer: low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) Monodisperse emulsion composed of Ag Br I containing an average particle diameter of 0.48 μm and containing 6 mol% of Ag I (emulsion III): silver coating Amount 0.9 g / m ² Sensitizing dye V: 1.3 × 10 ^-5 mol per mol of silver Yellow coupler (Y-1): 0.29 mol per mol of silver Film thickness 3.0 μm 10th layer: high sensitivity blue Sensitive emulsion layer (BH-1) Monodisperse emulsion composed of Ag Br I having an average particle diameter of 0.8 μm and containing 15 mol% of Ag I (emulsion IV): Silver coating amount 0.5 g / m ² Sensitizing dye V: 1 mol of silver 1.0 × 10 ⁻⁵ mol with respect to yellow coupler (Y-1): 0.08 mol per mol of silver DIR compound (A-1): 0.0015 mol with respect to 1 mol of silver
Film thickness 1.5 μm Eleventh layer: first protective layer (Pro-1) Gelatin layer containing ultraviolet absorbers UV-1 and UV-2. Film thickness 1.
0 μm 12th layer: 2nd protective layer (Pro-2) Gelatin layer containing polymethyl methacrylate particles (1.5 μm in diameter) and formalin scavenger (HS-1)
Each layer has a gelatin hardener (H-
1) and a surfactant were added.

 The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye I: anhydro 5,5'-dichloro-9-ethyl-
3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II: anhydro 9-ethyl-3,3'-di- (3-
Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide Sensitizing dye III: anhydro 5,5'-diphenyl-9-ethyl-3,3'-di- (3-sulfopropyl) Oxacarbocyanine hydroxide Sensitizing dye IV: Anhydro 9-ethyl-3,3'-di- (3-
Sulfopropyl) -5,6,5 ', 6'-dibenzoxacarbocyanine hydroxide Sensitizing dye V: anhydro 3,3'-di- (3-sulfopropyl) -4,5-benzo-5'-methoxy Thiacyanine Next, Sample 1 to Sample changed from Sample 1 as shown in Table 1.
24 created.

The thickness of each layer was adjusted by changing the amount of gelatin applied.

Each of the samples Nos. 1 to 24 thus prepared was exposed to wedges using white light and red light, and then subjected to the following development processing.

Processing step (38 ° C) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying Used in each processing step The composition of the processing solution is as follows.

[Color developing solution] 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline sulfate 4.75 g Sodium sulfite anhydrous 4.25 g Hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1

[Bleaching solution] Iron ammonium salt of ethylenediaminetetraacetic acid 100 g Diammonium salt of ethylenediaminetetraacetic acid 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Add water to adjust the pH to 1, and adjust the pH to 6.0 using aqueous ammonia.

[Fixing solution] Ammonium thiosulfate 175.0 g Sodium sulfite anhydrous 8.5 g Sodium metasulfite 2.3 g Water was added to 1 to adjust the pH to 6.0 using acetic acid.

[Stabilizing solution] Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konishi Roku Kogyo Co., Ltd.) 7.5 ml Make up to 1 by adding water.

For each of the obtained samples, sensitometry and sharpness (MTF) were measured using red light (R).

From the results of the sensitometry, the magnitude of the interimage effect (IIE) was expressed by the following equation.

The sharpness improvement effect was obtained by using a white light-exposed sample and calculating the MTF (Modulation Transfer Function) of the dye image.
It is shown as a relative value of MTF at 100 / mm (sample No. 1 is 100).

 Table 2 shows the above results.

As is clear from Table 2, when the pyrazolotriazole-based magenta coupler of the present invention is used, IIE and sharpness cannot be expected to be improved when the film thickness is large. It can be seen that the improvement in IIE and sharpness due to the
It can be seen that the combination has greatly improved.

Next, a part of each of the prepared samples 1 to 24 was left for 10 days in an atmosphere of 40 ° C. and 80% RH, and another part was left for 2 days in an atmosphere of 23 ° C. and 55% RH, using white light (W). Exposure was performed, and the development processing described above was performed.

The relative sensitivity of each of the obtained samples was measured using green light.

The relative sensitivity (S) is the relative value of the reciprocal of the exposure amount that gives fog density +0.1, and is a sample left at 23 ° C and 55% RH.
The values are shown with the W sensitivity of No. 1 as 100.

 Table 3 shows the results.

As is clear from Table-3, when the pizolotriazole-based magenta coupler of the present invention is used, when the film thickness is large, the desensitization of the green photosensitive layer is larger than that in the comparison (No. 1). On the other hand, it can be seen that the desensitization width becomes smaller by making the film thinner, contrary to the comparative coupler.

Claims (1)

(57) [Claims] 1. A red-sensitive silver halide emulsion layer containing a cyan coupler, a green-sensitive silver halide emulsion layer containing a magenta color-forming coupler and a blue-sensitive silver halide emulsion layer containing a yellow-coloring coupler on a support. In the multi-layer silver halide color photographic light-sensitive material, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is 18 μm or less, and further from the outermost surface on the side having the photosensitive silver halide emulsion layer. Up to the bottom of the photosensitive silver halide emulsion layer closest to the support
A multilayer silver halide color photographic light-sensitive material having a size of 14 μm or less, and wherein at least one of the magenta color-forming couplers is a pyrazolotriazole-based magenta coupler.