JPH07109498B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a color photographic material containing a novel azo dye precursor. More specifically, it relates to a silver halide color light-sensitive material containing a hydrazone compound having a color forming property or a hydrazine compound which is a tautomer thereof.

(Prior Art) In a subtractive color photographic light-sensitive material, a method of forming a color image using a coupler (hereinafter, simply referred to as a coupler) that develops yellow, magenta and cyan is general. In this method, a dye is formed by a coupling reaction between an oxidized color developing agent and a coupler. Therefore, the coupler is necessarily selected from those in which the coupling reaction can occur. However, due to this restriction, there is a limit to the purpose of increasing the speed of the coupling reaction,
Furthermore, the search for couplers with high color development is not easy. Therefore, a compound for forming a color image having higher color development has been desired for a high-sensitivity light-sensitive material or a light-sensitive material suitable for rapid processing.

(Problems to be Solved by the Invention) An object of the present invention is to provide a color photographic light-sensitive material excellent in color forming property by using a novel azo dye precursor.

(Means for Solving the Problems) The object of the present invention has been achieved by a silver halide color photographic light-sensitive material characterized by containing a compound represented by the following general formula (Ia) or (Ib).

General formula (Ia) General formula (Ib) In the formula, A ₁ and A ₂ represent a hydrogen atom or a group which cleaves a bond with a nitrogen atom during photographic processing, Y and Z represent a methine group or a nitrogen atom, n represents an integer of 0 to 2, and R ₁ represents an aromatic group or an unsaturated heterocyclic group, and X is Or Represents an organic atomic group or a mere bond to form a 5-membered or 6-membered ring together. When n is plural, n Y and n Z respectively represent the same or different.

The compounds represented by the general formulas (Ia) and (Ib) react with the oxidized form of the developing agent by the development treatment to form the following azo dye.

The compounds represented by formulas (Ia) and (Ib) will be described in detail below.

When Y and Z represent a methine group, the methine group is a substituted or unsubstituted methine group. When a substituted methine group, for example an aliphatic group as a substituent group, an aromatic group, a halogen atom, R ₂ O-group, R ₂ S- group, A cyano group, a nitro group, a sulfo group, and R ₂ CO- group or a heterocyclic group. Here, R ₂ and R ₃ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and R ₄ represents an aliphatic group,
Represents an aromatic group and a heterocyclic group.

In the present invention, the aliphatic group is a linear or branched, chain or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic group. Specific examples include methyl, ethyl, butyl, t-acyl, cyclohexyl, hexyl, dodecyl, 2-ethylhexyl, hexadecyl, octadecyl and the like. Examples of the substituent include the substituents listed above as the substituents of the methine group. The number of carbon atoms of such an aliphatic group is usually 1 to 32, preferably 1 to 20.
Is.

In the present invention, the aromatic group usually has 6 to 32 carbon atoms,
Preferred are 6 to 15 substituted or unsubstituted aromatic groups. Specifically, a phenyl group or a naphthyl group is a preferred example. Examples of the substituent include the substituents listed above as the substituents of the methine group.

In the present invention, the heterocyclic group is preferably selected from an oxygen atom, a nitrogen atom or a sulfur atom as a hetero atom, and usually has 1 to 64 carbon atoms, preferably 1 to 32, a 3 to 8 membered ring, a substitution or It is an unsubstituted heterocyclic group. Specifically, imidazolyl group, pyrazolyl group, pyrrolidino group,
Examples thereof include a pyridyl group and a triazolyl group. Examples of the substituent include the substituents listed above as the substituents of the methine group.

In formulas (Ia) and (Ib), X is preferably the following example. In the following, * indicates a bond with a nitrogen atom,
The * mark bonds with the carbon atom.

In the above formula, R ₅ represents a group having the same meaning as the substituents enumerated above as a substituent when Y represents a substituted methine group, 1 represents 0 or 1, and m represents an integer of 0 to 2.
When there are two or more R _5, they represent the same or different. W represents a sulfur atom, an oxygen atom or an N—R ₆ group. Here, R ₆ is preferably an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. The definitions of an aliphatic group, an aromatic group and a heterocyclic group have the same meaning as explained above.

In formulas (Ia) and (Ib), R ₁ is preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group. The substituent is selected from the substituents listed above as the substituent when Y represents a substituted methine group.

In the general formulas (Ia) and (Ib), when A ₁ and A ₂ represent a group other than a hydrogen atom, it is preferably an acyl group (eg acetyl, benzoyl), an alkoxycarbonyl group (eg ethoxycarbonyl), an aryloxycarbonyl. Groups (eg, phenoxycarbonyl), carbamoyl groups (eg, N, N-diethylcarbamoyl), sulfonyl groups (eg, methanesulfonyl), and other hydrolyzable groups, of the type utilizing the reverse Michael reaction described in US Pat. No. 4,009,029. Precursor group, precursor group of the type that utilizes anions generated after the ring opening reaction described in U.S. Pat. No. 4,310,612 as an intramolecular nucleophilic group, U.S. Pat.
4,478, 3,932,480 or 3,993,661 a precursor group that causes electron transfer through a conjugated system and thereby causes a cleavage reaction, U.S. Pat.
Precursor group which causes a cleavage reaction by electron transfer of anion reacted after ring cleavage described in U.S. Pat.
Precursor groups utilizing an imidomethyl group described in 363,865 and 4,410,618 are mentioned.

When adjacent Ys and Zs in formulas (Ia) and (Ib) each represent a substituted methine group, and when those substituents are linked to form a ring structure, for example, a benzene ring and the like can be mentioned. When X represents N—R ₆ and R ₆ and A ₁ each represent a substituent, those substituents may be linked to each other to form a ring structure.

A preferable example of the compound of the present invention is that it is diffusion resistant, and at least one of X, Y, Z, A ₁ , A _{2 and} R ₁ represents a group having a total carbon number of 10 or more. preferable. This immobilizes the compounds of this invention in the added photographic layer.

The azo dye precursors represented by the general formulas (Ia) and (Ib) produce yellow, magenta and cyan dyes by photographic processing. Examples of such dyes are the Journal of
The Society of Dyers and Colorist
s) 356 pages in 1979, 507 pages in 1969, 284 pages in 1977, JP-A-62-71951, and Berichte 1957 143.
It is described in the page etc.

Among the azo dye precursors used in the present invention, a particularly preferred compound is represented by the following general formula (IIa) or (IIb).

General formula (IIa) General formula (IIb) In the formula, A ₁ , A ₂ , R ₁ , R ₅ and m have the same meanings as described above, and X ₁ is a sulfur atom, an oxygen atom or N-
Represents an R ₆ group. R ₆ has the same meaning as described above.

Next, the general formula (Ia) or (I
Specific examples of the compound represented by b) are shown below, but the invention is not limited thereto.

The compound represented by the general formula (Ia) or (Ib) used in the present invention is, for example, J. Amer. Chem. Soc., 70 , 2843 (19
48), Chem.Ber., 92 , 1105 (1959), same 83 , 247 (1950),
92 , 1447 (1959) and the like or a similar method.

Specific synthetic examples of typical compounds are described below. Other compounds can be similarly synthesized.

Synthesis Example (1) Synthesis of Exemplified Compound (1) α-chloro-α-pivaloyl-2′-chloro-5′-
{2- (2,4-di-t-amylphenoxy) butanamide} acetanilide 6.1 g and 1-phenylthiosemicarbazide 1.8 g were dissolved in 50 ml of N, N-dimethylformamide, and further at room temperature (25 ° C.) for 1 hour, The reaction was carried out at 45 ° C for 30 minutes. The reaction mixture was poured into 500 ml of water and extracted with ethyl acetate. The oil layer was separated and the solvent was distilled off under reduced pressure. The residue was recrystallized from a mixed solvent of ethanol and hexane to obtain 5.3 g of Exemplified compound (1). The melting point was 137-140 ° C.

Synthesis Example (2) Synthesis of Exemplified Compound (4) α-Bromo-α-cyano-3 ′-(2,4-di-t-amylphenoxyacetamido) acetophenone 15 g and 1-phenylthiosemicarbazide 3.9 g were added to N, N. -Dissolved in 100 ml of dimethylformamide and reacted at room temperature (25 ° C) for 2 hours. The reaction mixture was poured into 500 ml of water and extracted with ethyl acetate. The oil layer was separated and the solvent was distilled off under reduced pressure to obtain 15.8 g of an oily exemplified compound (4).

The compound represented by the general formula (Ia) or (Ib) used in the present invention is oxidized or is oxidized through hydrolysis to form an azo dye. Among these, the case where the dye is cross-oxidized by the reaction with the oxidized product of the developing agent to form a dye is a preferable example. In this case, as a developing agent, a color developing agent of para-phenylenediamines, hydroquinones, phenidones and the like are preferable examples.

In another embodiment, the dye may be formed by being oxidized in the bleaching process step. In this case the dye can be formed independently of the area where the silver halide was exposed.

The compound of the present invention can be used for various purposes as described above. The substituents of the compound can be selected according to their purpose, and the type of developer, development conditions (temperature, pH, processing time, etc.) and bleaching conditions (type of oxidizing agent, pH, temperature, time, etc.) You can choose.

The present invention can be applied to a multilayer color photographic light-sensitive material having at least three different spectral sensitivities and a single-color photographic light-sensitive material having one or more emulsion layers on a support.

A multilayer color photographic light-sensitive material usually has at least one red-sensitive emulsion layer, green-sensitive emulsion layer and blue-sensitive emulsion layer on a support. The order of these layers is arbitrarily selected as needed.

The compound represented by formula (Ia) or (Ib) used in the present invention can be used in the above-mentioned color-sensitive emulsion layer or an intermediate layer adjacent thereto and containing no photosensitive emulsion.

When the color-sensitive emulsion layer is composed of two or more identical color-sensitive layers having different sensitivities, a high-sensitivity layer, an intermediate-sensitivity layer,
It can be added to any layer such as a low-sensitivity layer.

The addition amount of the compound represented by the general formula (Ia) or (Ib) is preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻¹ mol / m ² , particularly 1 × 10 7
^-6 to 1 × 10 ^-3 mol / m ² is preferable.

The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer provided on a support. There is no particular limitation on the number of layers of the emulsion layer and the non-photosensitive layer and the layer order. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red color-sensitive layer and the green color. The color-sensitive layer and the blue color-sensitive layer are installed in this order.
However, depending on the purpose, the installation order may be reversed, or the installation order may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers.

A non-photosensitive layer such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748, 59-113438 and 5
No. 9-113440, No. 61-20037, No. 61-20038 may contain a coupler as described in the specification, DIR compounds and the like, may also contain a color mixing inhibitor as is commonly used Good.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer,
As described in West German Patent No. 1,121,470 or British Patent No. 923,045, a two-layer structure of a high sensitivity emulsion layer and a low sensitivity emulsion layer can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Further, JP-A-57-112751 and 62-2003.
No. 50, No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support. .

As a specific example, from the side farthest from the support, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL / GL
It can be installed in the order of / GH / RH / RL or BH / BL / GH / GL / RL / RH.

Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. In addition, JP-A-56-25738 and 62-6
As described in 3936, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support.

Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. A silver halide emulsion layer having a low degree of sensitivities is arranged, and the sensitivities are gradually reduced toward the support.
An example is an array composed of layers. Even in the case of being composed of three layers having different sensitivities as described above, JP-A-59-20246
As described in No. 4, in the same light-sensitive layer, a medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer may be arranged in this order from the side distant from the support.

As described above, various layer configurations and arrangements can be selected according to the purpose of each sensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. . Particularly preferred is about 2 mol% to about 25 mol%
Up to silver iodobromide or silver iodochlorobromide.

Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof.

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

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD), No. 17643 (1978.
December), pp. 22-23, "I. Emulsion preparati
on and types) ”, and No. 18716 (November 1979),
P. 648, "The Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Glafkides, Chemie et Phisique Photogr
aphique Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographi
c Emulsion Chemistry (Focal Press, 1966)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., VLZelikman et al. Making and Coating Photog.
uraphic Emulsion, Focal Press, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutoff Photoguraphic Science and Engineerin by Gaft.
g), Vol. 14, pp. 248-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,433,048, 4,439,520
It can be easily prepared by the method described in Japanese Patent No. 2,112,157 and the like.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with a compound other than silver halide such as silver rhodanide and lead oxide.

Also, a mixture of particles having various crystal forms may be used.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. The additive used in such a process is the research disclosure mentioned above.
It is described in No.17643 and No.18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Pat. Nos. 4,411,987 and 4,435,503
It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde described in No.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG.

Yellow couplers include, for example, U.S. Pat.
No. 1, No. 4,022,620, No. 4,326,024, No. 4,401,7
52, Japanese Examined Patent Publication No. 58-10739, British Patents 1,425,020, 1,476,760, U.S. Patents 3,973,968, 4,314,02
Those described in No. 3, No. 4,511,649 and European Patent No. 249,473A are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. No. 4,310,61
No. 9, No. 4,351,897, European Patent No. 73,636, US Pat. No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552.
Issue, Research Disclosure No. 24230 (June 1984
Mon), JP-A-60-43659, 61-72238, 60-35730
No. 55-118034, No. 60-185951, U.S. Pat.No. 4,500,
Those described in No. 630, No. 4,540,654, No. 4,556,630 and the like are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and U.S. Pat.
4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162,
No. 2,895,826, No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,173, West German Patent Publication No.
3,329,729, European Patents 121,365A, 249,453A
U.S. Pat.Nos. 3,446,622, 4,333,999, and 4,
No. 451,559, No. 4,427,767, No. 4,690,889, No.
Those described in 4,254,212, 4,296,199, JP-A-61-42658 and the like are preferable.

Colored couplers to correct unwanted absorption of colored dyes are Research Disclosure No. 17643 VII-
Section G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Patent Nos. 4,004,929, 4,138,258, British Patent No. 1,
Those described in No. 146,368 are preferable.

As the coupler in which the color forming dye has an appropriate diffusibility, those described in U.S. Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570 and West German Patent (Publication) 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 4,409,320, No. 4,576,910, British Patent No. 2,
No. 102,173, etc.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the above-mentioned RD17643, VII-F patents, JP-A-57-151944 and 57-154234.
Nos. 60-184248 and US Pat. No. 4,248,962 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,13.
Those described in 1,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427, multi-equivalent couplers described in U.S. Pat.Nos. 4,283,472, 4,338,393, and 4,310,618. , JP-A-60-18
5950, DIR redox compound releasing coupler or DIR coupler releasing coupler or DIR coupler releasing redox compound or DIR redox compound releasing redox described in JP-A-62-24252, etc. Dye releasing coupler, RD No.1144
9, 24241, bleaching accelerator releasing couplers described in JP-A-61-2201247 and the like, and ligand releasing couplers described in US Pat. No. 4,553,477 and the like.

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

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

Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used for the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohesyl phthalate,
Di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) Phthalates), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl) Phosphate, di-
2-ethylhexyl phenylphosphonate, etc., benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecane amide, N, N-diethyllaurylamide) , N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-t-)
Amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2) -Butoxy-5-t-
Octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. As the auxiliary solvent, a boiling point of about 30 ° C. or higher, preferably an organic solvent of 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-. Examples include ethoxyethyl acetate and dimethylformamide.

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

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

Suitable supports that can be used in the present invention include, for example, the aforementioned R
Page 28 of D.No.17643 and page 647 of the same No.18716 From right column 6
See page 48, left column.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD.
The development processing can be carried out by a usual method described on pages 28 to 29 of 643 and 651 left column to right column of No. 18716.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3 -Methyl-4-amino-N-ethyl-N
-Β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
Examples include -β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound or a development inhibitor or a fog. Generally, it contains an inhibitor and the like. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, and coupler agents such as sodium boron hydride. , 1-
Auxiliary developing agents such as phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylforphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid. , Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N , N ', N'-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

When the reversal process is performed, black and white development is usually performed before color development. In this black-and-white developer, a known black-and-white developing agent such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol is used alone. Alternatively, they can be used in combination.

The pH of these color developing solution and black-and-white developing solution is generally 9 to 12. The replenishment amount of these developers depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and is 500 ml or less by reducing the bromide ion concentration in the replenisher. You can also When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually set to 2 to 5 minutes, but the processing time can be further shortened by setting the temperature and the pH to high and using the color developing agent at a high concentration.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out depending on the purpose. Examples of bleaching agents include iron (III), cobalt (II
I), compounds of polyvalent metals such as chromium (IV) and copper (II), peracids, quinones, nitro compounds and the like are used.
Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3- Aminopolycarboxylic acids such as dianopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salts and persulfates are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution containing these aminopolycarboxylic acid iron (III) complex salts is usually
5.5-8 but lower p due to faster processing
It can also be treated with H.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988.
No. 53-32736, No. 53-57831, No. 53-37418,
53-72623, 53-95630, 53-95631, 53-104
No. 323, No. 53-124424, No. 53-141623, No. 53-28426
No. 17129 (July 1978) and the like, compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506, JP-A-45-8506. Sho 52-20832, 5
3-32735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715, iodide salts described in JP-A-58-16235; Poly German compounds described in West German Patents 966,410 and 2,748,430. Oxyethylene compounds; polyamine compounds described in JP-B-45-8836; other JP-A-49-42434,
49-59644, 53-94927, 54-35727, 55-26506
No. 58-163940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and the compounds described in US Pat. No. 3,893,858, West German Patent 1,290,812 and JP-A-53-95630 are particularly preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used, and ammonium thiosulfate is most widely used. Can be used for As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process.
The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, and the temperature of rinsing water, the number of rinsing tanks (number of stages), replenishment method such as countercurrent and forward flow, and various other conditions. It can be set in a wide range. this house,
The relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is
urnal of the Society of Motion picture and Televis
ion Engineers, Volume 64, p.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In processing the color light-sensitive material of the present invention, as a solution to such a problem,
The method of reducing calcium and magnesium ions described in Japanese Patent Application No. 61-131632 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" The sterilizing agents described in "Microbial Sterilization, Sterilization, and Antifungal Technology" edited by the Society of Hygiene Technology and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9
And preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics and uses of the light-sensitive material, but in general, the range of 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C for 30 seconds to 5 minutes is selected. To be done. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such a stabilizing process, the method disclosed in
All known methods described in Nos. 57-8543, 58-14834, and 60-220345 can be used.

Further, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. it can. Various chelating agents and antibacterial agents can be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline compounds described in U.S. Pat. Salt complex, JP-A-5
The urethane compounds described in 3-135628 can be mentioned.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-containing compounds, if necessary, for the purpose of promoting color development.
3-pyrazolizones may be incorporated. Typical compounds are JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.
No. etc. are listed.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

The silver halide light-sensitive material of the present invention is described in US Pat.
0,626, JP-A-60-133449, 59-218443, 61-23
It can also be applied to the photothermographic materials described in 8056 and European Patent 210,660A2.

(Effect of the Invention) In the silver halide color photographic light-sensitive material of the present invention,
The azo dye is easily produced by photographic processing, and it has an excellent effect that it has high sensitivity, good color development, and is suitable for rapid processing.

Example 1 On a subbed cellulose triacetate film support,
A sample 101, which is a multi-layer color light-sensitive material having the following composition, was prepared.

(Composition of photosensitive layer) The coating amount of silver halide and colloidal silver is silver.
The amount represented in units of g / m ^2, also couplers, moles per 1 mol of silver halide in the same layer for the amount for the additives and gelatin represented in units of g / m ^2, also the sensitizing dye Indicated by.

The symbols indicating additives have the following meanings. However, if it has multiple functions, one of them is listed as a representative.

UV: UV absorber, Solv: High boiling organic solvent, ExF: Dye, Ex
S: Sensitizing dye, ExC: Cyan coupler, ExM: Macenta coupler, ExY: Yellow coupler, Cpd: Additive 1st layer (antihalation layer) Black colloidal silver …… 0.2 Zalatin …… 1.3 ExM-9 …… 0.06 UV-1 ...... 0.03 UV-2 ...... 0.06 UV-3 ...... 0.06 Solv-1 …… 0.15 Solv-2 …… 0.15 Solv-3 …… 0.05 Second layer (intermediate layer) Gelatin …… 1.0 UV-1 …… 0.03 ExC-4 …… 0.02 ExF-1 …… 0.004 Solv-1 …… 0.1 Solv-2 …… 0.1 Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform) AgI type, sphere equivalent diameter 0.5
μ, coefficient of variation of equivalent spherical diameter 20%, plate-like particles, diameter / thickness ratio
3.0) Coating silver amount …… 1.2 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, spherical equivalent diameter 0.3
μ, coefficient of variation of equivalent spherical diameter 15%, spherical particles, diameter / thickness ratio
1.0) Coated silver amount …… 0.6 Gelatin …… 1.0 ExS-1 …… 4 × 10 ^-4 ExS-2 …… 5 × 10 ^-5 ExC-1 …… 0.05 ExC-2 …… 0.50 ExC-3 …… 0.03 ExC-4 …… 0.12 ExC-5 …… 0.01 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core shell 1: 1 internal height)
AgI type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 15%, plate-like particles, diameter / thickness ratio 5.0) Coating silver amount …… 0.7 Gelatin …… 1.0 ExS-1 …… 3 × 10 ^-4 ExS- 2 …… 2.3 × 10 ^-5 ExC-6 …… 0.11 ExC-7 …… 0.05 ExC-4 …… 0.05 Solv-1 …… 0.05 Solv-3 …… 0.05 Fifth layer (intermediate layer) Gelatin …… 0.5 Cpd -1 ...... 0.1 Solv-1 ...... 0.05 6th layer (low sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core shell ratio 1: 1 surface height)
AgI type, equivalent sphere diameter 0.5μ, variation coefficient of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 4.0) Silver coating amount …… 0.35 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, sphere) Equivalent diameter 0.3
μ, coefficient of variation of equivalent spherical diameter 25%, spherical particles, diameter / thickness ratio
1.0) Amount of coated silver …… 0.02 Gelatin …… 1.0 ExS-3 …… 5 × 10 ^-4 ExS-4 …… 3 × 10 ^-4 ExS-5 …… 1 × 10 ^-4 ExM-8 …… 0.4 ExM− 9 …… 0.07 ExM-10 …… 0.02 ExY-11 …… 0.03 Solv-1 …… 0.3 Solv-4 …… 0.05 7th layer (high sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, Internal height of core shell ratio 1: 3
AgI type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter / thickness ratio 5.0) Coating silver amount …… 0.8 Gelatin …… 0.5 ExS-3 …… 5 × 10 ^-4 ExS- 4 …… 3 × 10 ^-4 ExS-5 …… 1 × 10 ^-4 ExM-8 …… 0.1 ExM-9 …… 0.02 ExY-11 …… 0.03 ExC-2 …… 0.03 ExM-14 …… 0.01 Solv- 1 …… 0.2 Solv-4 …… 0.01 8th layer (intermediate layer) Gelatin …… 0.5 Cpd-1 …… 0.05 Solv-1 …… 0.02 9th layer (donor layer of the multi-layer effect for the red sensitive layer) Iodobromide Silver emulsion (AgI 2 mol%, core shell ratio 2: 1
AgI type, equivalent sphere diameter 1.0μ, variation coefficient of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 6.0) Coating silver amount …… 0.35 Silver iodobromide emulsion (AgI 2 mol%, core shell ratio 1: 1) Internal height of
AgI type, equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 20%, plate-shaped particles, diameter / thickness ratio 6.0) Silver coating amount …… 0.20 gelatin …… 0.5 ExS-3 …… 8 × 10 ^-4 ExY− 13 …… 0.11 ExM-12 …… 0.03 ExM-14 …… 0.10 Solv-1 …… 0.20 10th layer (yellow filter layer) Yellow colloidal silver …… 0.05 Gelatin …… 0.5 Cpd-2 …… 0.13 Solv-1… ... 0.13 Cpd-1 ... 0.10 11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type, spherical equivalent diameter 0.
7μ, coefficient of variation of equivalent sphere diameter 15%, tabular grains, diameter / thickness ratio 7.0) Coating amount of silver ... 0.3 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3)
μ, coefficient of variation of equivalent spherical diameter 25%, plate-shaped particles, diameter / thickness ratio
7.0) Silver coating amount …… 0.15 Gelatin …… 1.6 ExS-6 …… 2 × 10 ^-4 ExC-16 …… 0.05 ExC-2 …… 0.10 ExC-3 …… 0.02 ExY-13 …… 0.07 ExY-15 …… 1.2 Solv-1 0.40 12th layer (high sensitivity blue emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent spherical diameter)
1.0μ, 25% variation coefficient of equivalent spherical diameter, multiple twin plate-like particles,
Diameter / thickness ratio 2.0) Coating silver amount …… 0.5 Gelatin …… 0.5 ExS-6 …… 1 × 10 ^-4 ExY-15 …… 0.24 ExY-13 …… 0.01 Solv-1 …… 0.08 13th layer (1st layer) Protective layer) Gelatin …… 0.8 UV-4 …… 0.1 UV-5 …… 0.15 Solv-1 …… 0.01 Solv-2 …… 0.01 14th layer (second protective layer) Fine grain silver bromide emulsion (AgI 2 mol%) , Uniform AgI type, sphere equivalent diameter 0.07μ) …… 0.5 gelatin ・ ・ ・ 0.45 polymethylmethacrylate particles 1.5μ …… 0.2 H-1 …… 0.4 Cpd-5 …… 0.5 Cpd-6 …… 0.5 Each layer has the above In addition to the components of Emulsion Stabilizer Cpd-3 (0.0
4 g / m ² ) Surfactant Cpd-4 (0.02 g / m ² ) was added as a coating aid.

Next, the chemical structural formulas or chemical names of the compounds used in this example are shown.

Solv-1 Tricresyl Phosphate Solv-2 Diptyl Phthalate (Preparation of Samples 102 to 106) In place of ExY-15 (Compound 1 of the present invention) in the 11th and 12th layers of Sample 101, equimolar amounts of the compounds shown in Table 1 were added, and the same as in Sample 101. It was made.

As described above, the samples 101 to 106 produced with white light,
After wedge exposure, the following development processing was performed to evaluate the color developability, wet heat fastness and light fastness. The results are summarized in Table 1.

 Processing method Processing time Processing temperature Color development 2 minutes 30 seconds 38 ℃ Bleaching 1 minute 00 seconds 38 ℃ Bleaching fixing 3 minutes 15 seconds 38 ℃ Washing with water (1) 40 seconds 35 ℃ Washing with water (2) 1 minute 00 seconds 35 ℃ Cheap Constant 40 seconds 38 ℃ Drying 1 minute 15 seconds 55 ℃ Next, describe the composition of the treatment liquid.

(Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- (N- Ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 Add water 1.0 l pH 10.05 (bleaching solution) (Unit: g) Ethylenediaminetetraacetic acid Ferric ammonium dihydrate 120.0 Ethylenediaminetetraacetic acid dihydrate Natrium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol Ammonia water (27%) 15.0 ml Add water 1.0 l pH 6.3 (Bleach fixer) (Unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0 Ethylenediaminetetraacetic acid dinatrium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate Aqueous solution (70%) 240.0 ml Ammonia water (27%) 6.0 ml Water is added to 1.0 l pH 7.2 (washing solution) Tap water is used as H type strong acid cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas). , OH type anion exchange resin (Amberlite IR-400) was passed through a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / l or less, followed by sodium isocyanurate dichloride 20 mg / l and 150 mg / l sodium sulfate were added.

The pH of this solution is in the range 6.5-7.5.

(Stabilizing liquid) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononyl phenyl ether (Average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid di sodium salt 0.05 Water added 1.0l pH 5.0-8.0 As can be seen from the results in Table 1, the light-sensitive material of the present invention is superior in color forming property to the light-sensitive material using the conventional yellow coupler.

Example 2 A sample similar to the one produced in Example 1 was cut into a width of 35 mm, and a subject considered to be standard was photographed. The obtained sample was processed by Fuji Photo Film Co., Ltd., Color Negative Processor, FP-350 by the following processing method,
After the treatment, the same evaluation as in Example 1 was performed, and the same result was obtained.

Next, the composition of the treatment liquid will be described.

(Bleach-fixing solution) Common for mother liquor and replenisher (Unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite, 12.0 Ammonium thiosulfate aqueous solution (70%) 260.0 ml Acetic acid (98%) ) 5.0 ml bleaching accelerator 0.01 mol 1.0 l pH 6.0 (washing solution) with water added Common for mother liquor and replenisher Tap water is H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite). Water is passed through a mixed-bed column packed with IR-400) to treat calcium and magnesium ions at a concentration of 3 mg / l or less, and then 20 mg / l sodium diisocyanurate dichloride and 1.5 mg / l sodium sulfate are added. did.

The pH of this solution is in the range 6.5-7.5.

(Stabilizer) Common for mother liquor and replenisher (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononyl phenyl ether (Average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid dinatrium salt 0.05 Add 1.0 l of water pH 5.8-8.0

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material containing an azo dye precursor represented by the following general formula (Ia) or (Ib). General formula (Ia) General formula (Ib) (In the formula, A ₁ and A ₂ represent a hydrogen atom or a group that cleaves a bond with a nitrogen atom during photographic processing, Y and Z represent a methine group or a nitrogen atom, and n represents an integer of 0 to 2, R ₁ represents an aromatic group or an unsaturated heterocyclic group, X 1
Is Or Represents an organic atomic group or a mere bond to form a 5-membered or 6-membered ring together. When n is plural, n Y and n Z respectively represent the same or different. )