JP2955682B2 - Silver halide color photographic materials - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a silver halide color photographic light-sensitive material containing a novel coupler for forming a yellow image.

(Prior Art) In a silver halide color photographic light-sensitive material, an image is formed by reacting an oxidized aromatic primary amine developer with a coupler by exposing the material to light and then developing the color. It is formed. In this method, a color reproduction method using a subtractive color method is used, and yellow, magenta, and cyan color images having complementary colors are formed to reproduce blue, green, and red, respectively.

By the way, conventionally, as a yellow coupler, for example,
Acylacetanilide-type couplers or malondianilide-type couplers are known.

(Problems to be Solved by the Invention) The above-mentioned known couplers exhibit a certain degree of performance and have been used conventionally, but further improvements have been desired. For example, the larger the molecular extinction coefficient (ε) of a dye obtained from a coupler is, the more advantageous it is. That is, in the case of a coupler that forms a dye having a large molecular extinction coefficient, the same image density as before can be obtained even if the amount used is small, so that the emulsion layer can be made thinner and the sharpness of the image can be improved. I can do it. Further, the absorption waveform of the dye obtained from the conventional coupler is not always ideal, and there is a tail on the long wave side, which is not preferable in color reproduction.

Accordingly, an object of the present invention is to use a coupler that forms a yellow dye having a large molar extinction coefficient (ε) and an absorption waveform with a small tail on the long wavelength side to achieve image quality,
In particular, it is an object of the present invention to provide a silver halide color photographic material having improved sharpness and color reproducibility.

(Means for Solving the Problems) The object of the present invention has been attained by a silver halide color photographic light-sensitive material containing a coupler represented by the following general formula (1).

Wherein R1 is a nitrogen, oxygen or carbon atom and is> C
= X1 represents a group bonded to X1, X1 is a nitrogen or carbon atom bonded to = C <, an oxygen atom or a sulfur atom, R2 represents a carbamoyl group or a sulfonyl group, and Ar
Represents an aromatic group or a heterocyclic group.

However, R1 and X1 may be combined to form a cyclic structure or not.

The yellow coupler of the present invention reacts with an oxidized product of a commonly used color developing agent (for example, paraphenylenediamines) to form a yellow dye. The reaction mechanism (estimated mechanism) and the structure of the formed yellow dye are shown in the following scheme.

In the formula, R ₁ , R ₂ , X ₁ and Ar represent the same meaning as described in the general formula (1), and QDI represents quinone diimine (oxidized developing agent). The above is a color developing agent This is an example using. The same applies when other developing agents are used.

Synthesis Example 1 Synthesis of Exemplified Compound (3) The compound was synthesized by the following synthesis method.

25 g of 1 was dissolved in 250 ml of N, N dimethylacetamide. 1.34g of sodium hydride (60%) at room temperature
Was added and stirred for 2 hours. During this time, hydrogen gas was generated. 5.39 g of 2 was added dropwise to this solution at room temperature. Dropping was performed over 10 minutes. After reacting for 3 hours, add 500 ml of ethyl acetate,
500 ml of dilute hydrochloric acid was added. The mixture was transferred to a separating funnel, the oil layer was removed, and the mixture was washed twice with water until the mixture became neutral. The oil layer was removed and the solvent was distilled off under reduced pressure. The target product was separated and purified by column chromatography (filler: silica gel, eluent: ethyl acetate / chloroform = 1/30). 18.3g
The exemplary compound (3) was obtained. The melting point was 116 to 119 ° C (resolvent: acetonitrile / chloroform = 1/1).

Synthesis Example 2 Synthesis of Exemplified Compound (4) The compound was synthesized in the same manner as in Synthesis Example 1. However, instead of para-chlorophenyl isocyanate 2, an equimolar amount of 2,4-dichlorophenyl isocyanate 3 was used. Others were performed similarly. 15.4 g of Exemplified Compound (4) was obtained. Melting point 112-117 ° C.

Synthesis Example 3 Synthesis of Exemplified Compound (5) Synthesis was performed in the same manner as in Synthesis Example 2. However, the following 4 was used in place of 1 in an equimolar amount. Others were performed similarly.

10.9 g of Exemplified Compound (5) was obtained. Melting point 128-130 ° C
(Crystallized from ethyl acetate / hexane).

The yellow coupler of the present invention can be added to a light-sensitive silver halide emulsion layer in a light-sensitive material or a layer adjacent thereto. Particularly, it is preferable to add it to the photosensitive silver halide emulsion layer.

The total amount to the sensitive material in is 0.001~1.20g / m ^2, preferably 0.01~1.00g / m ^2, more preferably 0.10 to
It is 0.80g / m ^2.

(Reference Experiment) In order to clarify the characteristics of the dye obtained from the coupler of the present invention, a dye was synthesized, and the absorption characteristics in an ethyl acetate solvent were compared.

A dye was synthesized as described below using the exemplified compound (1).

2.9 g of Exemplified Compound (1) in 100 ml of tetrahydrofuran
And 80 ml of ethanol, and 80 ml of an aqueous solution in which 4.3 g of sodium carbonate was dissolved was added. 1.8 g of 5 was added to this solution. At room temperature and under stirring, 70 ml of an aqueous solution in which 1.7 g of ammonium persulfate was dissolved was added dropwise. After 3 hours of reaction, 1.2 g of 5 was further added, and 50 ml of an aqueous solution containing 1.2 g of ammonium persulfate was added dropwise.

After reacting for 2 hours, 500 ml of ethyl acetate and diluted hydrochloric acid were added, and the mixture was transferred to a separating funnel. The oil layer was removed, washed with water until neutral, and the oil layer was separated. The solvent was distilled off under reduced pressure. Separation and purification were performed by column chromatography (filler: silica gel, eluent: ethanol / chloroform = 1/30) to synthesize the desired dye of (D-1). Melting point 261-262 ° C
Met.

The following dyes were synthesized in the same manner. Λmax and ε in the ethyl acetate solvent are shown in the table.

As a comparative example, (D-8) was synthesized from a conventional coupler.

As can be seen from the table, the dye obtained from the coupler of the present invention has a high ε and is very useful. In particular, the dyes (D-1) to (D-5) have particularly high ε and λmax
Is also moderate. (D-1), (D-2), (D-3),
The absorption spectra of (D-5) and (D-8) are shown in the drawing. From this, it is clear that the dye obtained from the coupler of the present invention has excellent sharpness in absorption on the long wavelength side and is excellent.

The light-sensitive material of the present invention comprises at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer of a silver halide emulsion layer on a support.
The number of layers and the order of the silver halide emulsion layer and the non-photosensitive layer are not particularly limited as long as the layers are provided. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, generally, The arrangement is such that a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

Non-light-sensitive layers such as various intermediate layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer is described in JP-A-61-43748 and JP-A-59-113438.
No. 59-113440, No. 61-20037, couplers as described in the specification of JP 61-20038, DIR compounds and the like may be contained, and contains a color mixing inhibitor as usually used. You may go out.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045.
No. 2 of the high-speed emulsion layer and the low-speed emulsion layer
A layer configuration can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also, JP-A-57-112751, 62-127
As described in 200350, 62-206541, 62-206543, etc., a low-speed emulsion layer may be provided on the side remote from the support and a high-speed emulsion layer may be provided on the side near the support.

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

Also, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL / RL is selected from the side farthest from the support.
Can be arranged in this order. JP-A-56-25738
As described in JP-A-62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the less sensitive silver halide emulsion layer, and the lower layer is more sensitive than the middle layer. A silver halide emulsion layer having a low degree is arranged,
There is an array composed of three layers having different sensitivities in which the sensitivities are sequentially decreased toward the support. Even in the case of three layers having different sensitivities, Japanese Patent Application Laid-Open No.
As described in JP-A-202464, a medium-speed emulsion layer / a high-speed emulsion layer / a low-speed emulsion layer may be arranged in the same color-sensitive layer from the side remote from the support.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.

The arrangement may be changed as described above even in the case of four or more layers.

No. 4,663,271 to improve color reproduction
No. 4,705,744, No. 4,707,436, JP-A-62-16
No. 4,448,63-89850, a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of a main photosensitive layer such as BL, GL, RL is disposed adjacent to or close to the main photosensitive layer. Is preferred.

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

When the photographic light-sensitive material of the present invention is a color negative film or a color reversal film, a preferable silver halide contained in the photographic emulsion layer is silver iodobromide, iodobromide containing about 30 mol% or less of silver iodide. It is silver chloride or silver iodochlorobromide. Particularly preferred is from about 2 mol% to about 25 mol%
Silver iodobromide or silver iodochlorobromide containing up to silver iodide.

When the photographic material of the present invention is a color photographic paper,
As the silver halide contained in the photographic emulsion layer, those composed of silver chlorobromide or silver chloride substantially free of silver iodide can be preferably used. Here, the phrase "contains substantially no silver iodide" means that the silver iodide content is 1 mol%.
Or less, preferably 0.2 mol% or less. Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide / silver chloride emulsion can be used. Although this ratio can take a wide range depending on the purpose, the silver chloride ratio is 2 mol%.
Those described above can be preferably used. A so-called high silver chloride emulsion having a high silver chloride content is preferably used as a light-sensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably at least 90 mol%, more preferably at least 95 mol%. For the purpose of reducing the replenishment amount of the developing solution, an emulsion of substantially pure silver chloride having a silver chloride content of 98 to 99.9 mol% is also preferably used.

The silver halide grains in the photographic emulsion are cubic, octahedral,
It may be one having regular crystals such as tetradecahedron, one having irregular crystal forms such as spherical or plate-like, one having crystal defects such as twin planes, or a complex form thereof.

The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion that can be used in the present invention is described in, for example, Research Disclosure (RD) No. 17643 (1978).
December, p. 22-23, "I. Emulsion preparatio
n and types) ”, No. 18716 (November 1979), p.648,
No. 307105 (November 1989), pp. 863-865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P.
Glafkides, Chemie et Phisique Photographique, Paul M
ontel.1967), by Duffin, "Photographic Emulsion Chemistry", Focal Press (GFDuffin, Photographic Emulsion Che)
mistry (Focal Press, 1966)), "Production and Coating of Photographic Emulsion" by Zelikuman et al., Focal Press (VLZeli)
kmanetal., Making and Coating Photographic Emulsio
n, Focal Press, 1964).

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

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineerin.
g), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4,434,2
No. 26, 4,414,310, 4,433,048, 4,439,520 and British Patent No. 2,112,157 can be easily prepared.

The crystal structure may be uniform, the inside and the outside may have different halogen compositions, may have a layered structure, or may have silver halides of different compositions joined by epitaxial junction. Also, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is Research Disclosure No. 1
No. 7643, No. 18716, and No. 307105, and the relevant portions are summarized in the table below.

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is not exposed during imagewise exposure to obtain a dye image,
It is preferable that the silver halide fine particles are not substantially developed in the developing process and are not fogged in advance.

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably 0.5 to 10 mol% of silver iodide
It contains.

The fine grain silver halide preferably has an average grain size (average value of the circle equivalent diameter of the projected area) of 0.01 to 0.5 μm, and 0.02 to 0.2 μm.
μm is more preferred.

Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, before adding this to the coating solution, a triazole-based, azaindene-based,
It is preferable to add a known stabilizer such as a benzothiazolium-based or mercapto-based compound or a zinc compound.

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

Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Patent Nos. 4,411,987 and 4,435,503
It is preferable to add a compound capable of being fixed by reacting with formaldehyde described in (1) to the photosensitive material.

U.S. Pat.Nos. 4,740,454 and
No. 4,788,132, JP-A-62-18539 and JP-A-1-283551 preferably contain a mercapto compound.

In the light-sensitive material of the present invention, described in JP-A-1-106052,
It is preferable to include a compound that releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, irrespective of the amount of developed silver generated by the development processing.

In the light-sensitive material of the present invention, International Publication W088 / 04794, dyes dispersed by the method described in JP-A-1-502912 or
EP317,308A, U.S. Pat.No.4,420,555, JP-A-1-25935
The dye described in No. 8 is preferably contained.

Various color couplers can be used in the present invention, and specific examples thereof are described in the aforementioned Research Disclosure.
No. 17643, VII-CG and No. 307105, VII-C
G.

As the yellow coupler, in addition to those of the present invention, for example, U.S. Patent Nos. 3,933,501, 4,022,620, 4,
No. 326,024, No. 4,401,752, No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476,76
No. 0, U.S. Pat.Nos. 3,973,968, 4,314,023,
Preferred are those described in 4,511,649, EP 249,473A and the like.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
Nos. 6,19,4,351,897, European Patent No. 73,636, U.S. Patent Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984),
No. 2, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-35
No. 730, No. 51-118034, No. 60-185951, U.S. Pat.
Particularly preferred are those described in 4,500,630, 4,540,654, 4,556,630, and WO088 / 04795.

Cyan couplers include phenolic and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200,
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, No. 249,453
A, U.S. Pat.Nos. 3,446,622, 4,333,999,
No. 4,775,616, No. 4,451,559, No. 4,427,767, No. 4,690,889, No. 4,254,212, No. 4,296,199,
Preferred are those described in JP-A-61-42658. Furthermore, JP-A Nos. 64-553, 64-554, 64-555, and 6
Pyrazoloazole couplers described in 4-556 and imidazole couplers described in U.S. Pat. No. 4,818,672 can also be used.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 4,409,320, No. 4,576,910, British Patent 2,10
2,137, EP 341,188A and the like.

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent (Published) No. 3,234,533.

Colored couplers for correcting unwanted absorption of coloring dyes are described in Research Disclosure No. 17643 VII.
Section G, Section VII-G of No. 307105, U.S. Pat.
No. 0, Japanese Patent Publication No. 57-39413, U.S. Pat. Nos. 4,004,929 and 4,138,258, and British Patent No. 1,146,368 are preferred. Further, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181 and a dye that can form a dye by reacting with a developing agent described in U.S. Pat.No.4,777,120 It is also preferable to use a coupler having a precursor group as a leaving group.

Compounds that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers releasing a development inhibitor are disclosed in the aforementioned RD17643, Sections VII-F and Nos. 307105 and VII-F.
57-151944, 57-154234, 60-184248, 63
-37346, 63-37350, U.S. Pat.
Those described in 4,782,012 are preferred.

The bleaching accelerator releasing couplers described in RD Nos. 11449, 24241, JP-A-61-201247, etc. are effective in shortening the processing time of a processing step having bleaching ability. The effect is great when added to a photosensitive material using silver particles. Examples of couplers that release a nucleating agent or a development accelerator in the form of an image during development include British Patent Nos. 2,097,140 and 2,131,188, and JP-A-59-157638.
And No. 59-170840 are preferred. Also, JP-A-60-1007029, JP-A-60-252340, JP-A-1-44940
And compounds capable of releasing a fogging agent, a development accelerator, a silver halide solvent, and the like by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A Nos. 1-45687 and 1-45687.

Other compounds 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 and the like, multi-equivalent couplers described in U.S. Pat.Nos. 4,283,472, 4,338,393, and 4,310,618. , JP-A-60-1
No. 85950, DIR redox compound releasing couplers described in JP-A-62-24252, etc., DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, European Patent Nos. 173,302A and 313,
No. 308A, couplers releasing dyes that recolor after release, U.S. Pat.No. 4,555,477, ligand releasing couplers described in JP-A-63-75747, couplers releasing leuco dyes described in JP-A-63-75747, U.S. Pat. And couplers that release the fluorescent dye described in (1).

The coupler used in the present invention can be introduced into a 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 high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl 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) phthalate, etc., phosphoric acid or phosphonic acid ester (Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-
2-ethylhexylphenylphosphonate, etc.), benzoates (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N, N-diethyllaurylamide) , N-tetradecylpyrrolidone), alcohols or phenols (isostearyl alcohol, 2,4-di-tert)
-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-ter
t-octylaniline, etc.), and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-hexane. Ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

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

These couplers may be impregnated with a loadable latex polymer (for example, U.S. Pat.No. 4,203,716) in the presence or absence of the high-boiling organic solvent, or dissolved in a water-insoluble and organic solvent-soluble polymer to form a hydrophilic polymer. It can be emulsified and dispersed in a water-soluble colloid aqueous solution.

Preferably, International Publication No.W088 / 00723, twelfth
Homopolymers or copolymers described on pages 30 to 30 are used. In particular, use of an acrylamide-based polymer is preferred for stabilizing a color image.

In the color light-sensitive material of the present invention, phenethyl alcohol and 1,2-benzisothiazoline-3 described in JP-A-63-257747, JP-A-62-272248 and JP-A-1-80941 may be used.
-One, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2
It is preferable to add various preservatives or fungicides such as phenoxyethanol and 2- (4-thiazolyl) benzimidazole.

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, those described above.
No. 17643, page 28, No. 18716, page 647 right column to page 648 left column, and No. 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and particularly preferably 16 μm or less. The film swelling speed T
_1/2 is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example,
Photographic Science and Engineering by A. Green et al. (Photogr.
Sci. Eng.), Vol. 19, No. 2, pp. 124-129, and can be measured by using a serometer (swelling meter) of the type described below.
T _1/2 is defined as 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds.
Defined as the time to reach 2.

The film swelling speed T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is
150-400% is preferred. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness-film thickness).
/ Can be calculated according to the film thickness.

The color photographic light-sensitive material according to the present invention is described in RD.
Development can be carried out by the usual methods described on pages 28 to 29 of 17643, No. 18716, left column to right column of 651, and No. 307105, pages 880 to 881.

The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent.
Phenylenediamine compounds are preferably used, and typical examples thereof are 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-β
-Methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof.
Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred. These compounds can be used in combination of two or more depending on the purpose.

Color developing solutions include pH buffers such as alkali metal carbonates, borates or phosphates, chlorides, bromides,
It generally contains a development inhibitor or an antifoggant such as an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and 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, N-tetramethylenephosphonic acid And ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts.

When the reversal process is performed, color development is usually performed after black and white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 l or less per square meter of the light-sensitive material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air.

The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below.

That is, The above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, 63-216050 can be mentioned.
The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the following various steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for the color development processing is usually set between 2 and 5 minutes, but the processing time can be further reduced by using a high temperature and high pH and using a high concentration of the color developing agent.

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. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing processing before bleach-fixing processing or bleaching processing after bleach-fixing processing can be arbitrarily performed according to the purpose.
As the bleaching agent, for example, compounds of a polyvalent metal such as iron (III), peracids, quinones, and nitro compounds are used. Representative bleaching agents include organic complex salts of iron (III) such as aminoamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Among these, iron aminopolycarboxylates (II) including iron (III) complex salts of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate
I) Complex salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution.
The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but the processing can be carried out at a lower pH for speeding up the processing.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary. Specific examples of useful cleansing accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and 2,059,98.
No. 8, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418
No. 53-72623, No. 53-95630, No. 53-95631,
Nos. 53-104232, 53-124424, 53-141623,
53-28426, Research Disclosure No.17129
Having a mercapto group or a disulfide group described in JP-A No. (July 1978); thiazolidine derivatives described in JP-A-50-140129;
No. 20832, No. 53-32735, U.S. Pat. No. 3,706,561; thiourea derivatives; West German Patent No. 1,127,715, JP-A-5
8-16,235; iodide salts described in West German Patent No. 966,410;
Polyoxyethylene compounds described in 2,748,430;
Polyamine compounds described in JP-B-45-8836; and JP-A-49-40,943; JP-A-49-59,644; JP-A-53-94,927;
Compounds described in Nos. 54-35,727, 55-26,506 and 58-163,940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable in view of a large accelerating effect, and in particular, US Patent No. 3,893,858
And compounds described in West German Patent No. 1,290,812 and JP-A-53-95,630. Further, the compounds described in U.S. 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 photographic material for photography.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids have an acid dissociation constant (pKa) of 2
And acetic acid, propionic acid and the like.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, a large amount of iodides, and the like. In particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether compound, thiourea, or the like. As a preservative for fixer and bleach-fixer,
Sulfites, bisulfites, carbonyl bisulfite adducts or the sulfinic acid compounds described in EP-A-294769A are preferred. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixing solution or the bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0 for adjusting pH, preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methylimidazole. It is preferable to add 0.1 to 10 mol / l.

The total time of the desilvering step is preferably shorter as long as the desilvering failure does not occur. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ℃ ~ 50
° C, preferably 35 ° C to 45 ° C. In the preferred temperature range, the desilvering speed is improved, and the generation of stain after browning is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening stirring,
JP-A-62-183460 describes a method of impinging a jet of a processing solution on the emulsion surface of a light-sensitive material, JP-A-62-183461, a method of increasing the stirring effect by using a rotating means, There are a method of moving the photosensitive material while bringing the emulsion surface in contact with the provided wiper blade to make the emulsion surface turbulent, thereby improving the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is disclosed in
It is preferable to have the photosensitive material conveying means described in JP-A-60-191257, JP-A-60-191258 and JP-A-60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing solution from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, calcium ion described in JP-A-62-288838,
The method of reducing magnesium ions can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc.
(1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Antifungal Activities, "Encyclopedia of Antimicrobial and Antifungal Agents" (1986) The bactericides described can also be used.

In the processing of the light-sensitive material of the present invention, the pH of the washing water is from 4 to
9, preferably 5 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but in general, 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Patent Application Laid-Open
Known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can all be used.

Further, after the water washing treatment, a stabilization treatment may be further carried out. As an example, a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography, is exemplified. be able to. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat.No. 3,342,597, 3,342,599, Schiff base compounds described in Research Disclosure Nos. 14,850 and 15,159, aldol compounds described in 13,924, U.S. Pat. The metal salt complex described,
Urethane compounds described in JP-A-53-135628 can be exemplified.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-1444547, and
No. 15438.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to.

The silver halide light-sensitive material of the present invention is disclosed in U.S. Pat.
No. 500,626, JP-A-60-133449, JP-A-59-218443, JP-A-6
It is also applicable to the photothermographic materials described in 1-238056, European Patent 210,660A2, and the like.

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

Example 1 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further applied to form a layer structure shown below. Was produced. The coating solution was prepared as follows.

Preparation of first layer coating solution Yellow coupler ExY-17.0 g, ExY-26.0 g, color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (Cpd-7) 0.7 g
27.2 cc of ethyl acetate and solvent (Solv-3) and (So
lv-7) 4.1 g of each was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate to prepare an emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cubic, 3: 7 mixture of large-size emulsion A having an average grain size of 0.88 μm and small-size emulsion A having an average grain size of 0.80 μm (silver molar ratio), the coefficient of variation of the grain size distribution being 0.08 0.10 and 0.10 for each size emulsion.
3 mol% was locally contained on a part of the particle surface).
In this emulsion, blue-sensitive sensitizing dyes A and B shown below were added in an amount of 2.0 × 10 ^-4 to large-size emulsion A per mole of silver.
2.5 × 1 for mol and small size emulsion A
0 to ⁴ moles are added. The emulsion was chemically ripened by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion A and the silver chlorobromide emulsion A were mixed and dissolved to prepare a first layer coating solution having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardener for each layer, 1-
Oxy-3,5-dichloro-s-triazine sodium salt was used.

The total amount of Cpd-10 and Cpd-11 in each layer was 25.0% each.
It was added to a mg / m ² and 50.0 mg / m ^2.

The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer.

(Per mole of silver halide, 2.0 × 10 ^-4 mol for large-size emulsion A and 2.5 × 10 ^-4 mol for small-size emulsion A, respectively) (Per mol of silver halide, 4.0 × 10 ^-4 mol for large-size emulsion B, and for small-size emulsion B,
5.6 × 10 ^-4 mol) and (Per mol of silver halide: 7.0 × 10 ^-5 mol for large-size emulsion B, 1.0 × ^10-5 mol for small-size emulsion B
10 ^-5 mol) (Per mole of silver halide, 0.9 × 10 ^-4 mole for large-size emulsion C, and 0.9 × 10 ^-4 mole for small-size emulsion C, respectively)
1.1 × 10 ⁻⁴ mol) The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mole of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

Also, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ^-4 mol and 2 × 10 mol, respectively, per mol of silver halide. ×
10 ^-4 mol was added.

The following dyes were added to the emulsion layer to prevent irradiation (the number in parentheses indicates the coating amount).

(Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ ) and bluish dye (ultra blue)] Second layer (color mixture preventing layer) Gelatin 0.99 Color mixture inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion (cube, 1: 3 mixture (Ag molar ratio) of large-size emulsion B having an average grain size of 0.55 μm and small-size emulsion B having an average grain size of 0.59 μm.
0.10 and 0.08, and each size emulsion contained 0.8 mol% of AgBr locally on part of the grain surface.) 0.12 Gelatin 1.24 Magenta coupler (ExM) 0.23 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer ( Cpd-3) 0.16 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorbing agent (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, large emulsion C having an average grain size of 0.58 μm and small emulsion of 0.45 μm 1: 4 mixture (Ag mole ratio) with size emulsion C. Coefficient of variation of grain size distribution is 0.09 and 0.1.
11. In each size emulsion, 0.6 mol% of AgBr was locally contained in a part of the grain surface.) 0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd- 4) 0.02 color image stabilizer (Cpd-6) 0.18 color image stabilizer (Cpd-7) 0.40 color image stabilizer (Cpd-8) 0.05 solvent (Solv-6) 0.14 sixth layer (ultraviolet absorbing layer) gelatin 0.53 UV absorber (UV-1) 0.16 Color mixture inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification)
17%) 0.17 Liquid paraffin 0.03 Sample 101 for evaluation was produced by the method described above. Samples 102 to 110 were prepared by changing the couplers used in 101 to those shown in Table 1 in an equimolar amount.

Next, each sample was subjected to gradation exposure of a three-color separation filter for sensitometry using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K). The exposure at this time was performed so that the exposure amount was 250 CMS with an exposure time of 0.1 second.

The exposed samples were subjected to continuous processing (running test) using a paper processor using a solution having the following processing step and processing solution composition, until the replenishment was twice the tank capacity of color development.

The composition of each processing solution is as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Add 40 g water 1000ml pH (25 ° C) 6.0 Rinse solution (same as tank solution and replenisher) Ion-exchanged water (Calcium and magnesium are 3ppm or less each) A measurement was made. At this time, the maximum value of the optical density measured through the blue filter was defined as Dmax. Also where the optical density measured through a blue filter of 1.0, the optical density as D _G / D _B is measured through a green filter,
The amount of the magenta component of the dye mixed into the yellow image was evaluated. It can be considered that the smaller this value is, the smaller the redness of the yellow color image and the better the hue. The results are shown in Table 1.

The number of the coupler of the present invention is indicated by the number shown in the compound examples of the present invention.

As is clear from Table 1, the coupler (3) of the present invention,
It can be said that (4), (5), (6), (8), (11) and (14) are couplers which have a higher Dmax than the comparative compound and have excellent coloring properties. In particular, (3) (4) (5)
(6) has high coloring properties. The couplers of the present invention can be said to show a comparative example ExY-2 equivalent D _G / D _B values that are to be excellent in color reproducibility conventionally, is excellent in color reproducibility. Since the absorption wavelength of the coupler ExY-2 of the comparative example is shifted to the shorter wavelength side, it is known that the visual density becomes lower and the amount of the coupler must be increased accordingly, but the coupler of the present invention has a longer wavelength. These disadvantages are improved because the harmful absorption edge of the side is sharply cut.

As described above, since the coupler of the present invention has a high molar extinction coefficient of the resulting dye, it can be said that the coupler exhibits high color development and is also an excellent coupler having an improved hue.

Example 2 A sample 201, which is a multilayer color photographic material comprising the following layers, was prepared on an undercoated cellulose triacetate film support.

The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dyes are shown in terms of moles per mole of silver halide in the same layer.

First layer (antihalation layer) Black colloidal silver 0.15 gelatin 1.90 ExM-1 5.0 × 10 ^-3 Second layer (intermediate layer) gelatin 2.10 UV-1 3.0 × 10 ^-2 UV-2 6.0 × 10 ^-2 UV-3 7,0 × 10 ^-2 ExF-1 4.0 × 10 ^-3 Solv-2 7.0 × 10 ^-2 Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, Ball equivalent diameter 0.
3 μm, coefficient of variation of sphere equivalent diameter 29%, normal crystal, twin mixed particles, diameter / thickness ratio 2.5) Silver coating amount 0.50 gelatin 1.50 ExS-1 1.0 × 10 ^-4 ExS-2 3.0 × 10 ^-4 ExS-3 1.0 × 10 ^-5 ExC-1 0.11 ExC-3 0.11 ExC-4 3.0 × 10 ^-2 ExC-7 1.0 × 10 ^-2 Solv-1 7.0 × 10 ^-3 4th layer (medium sensitivity red-sensitive emulsion layer) Silver halide emulsion (AgI 4 mol%, internal high AgI type, equivalent sphere diameter 0.
55 μm, coefficient of variation of equivalent sphere diameter 20%, normal crystal, twin mixed particles, diameter / thickness ratio 1.0) Silver coating amount 0.85 gelatin 2.00 ExS-1 1.0 × 10 ^-4 ExS-2 3.0 × 10 ^-4 ExS-3 1.0 × 10 ^-5 ExC-1 0.16 ExC-2 8.0 × 10 ^-2 ExC-3 0.17 ExC-7 1.5 × 10 ^-2 ExY-1 2.0 × 10 ^-2 ExY-2 1.0 × 10 ^-2 Cpd-10 1.0 × 10 ^-4 Solv-1 0.10 Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent sphere diameter)
0.7 µm, coefficient of variation of equivalent sphere diameter 30%, twin mixed particles, diameter / thickness ratio 2.0) Silver coating amount 0.70 Gelatin 1.60 ExS-1 1.0 × 10 ^-4 ExS-2 3.0 × 10 ^-4 ExS-3 1.0 × 10 ^-5 ExC-5 7.0 × 10 ^-2 ExC-6 8.0 × 10 ^-2 ExC-7 1.5 × 10 ^-2 Solv-1 0.15 Solv-2 8.0 × 10 ^-2 6th layer (intermediate layer) Gelatin 1.10 P- 2 0.17 Cpd-1 0.10 Cpd-4 0.17 Solv-1 5.0 × 10 ^-2 7th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, equivalent sphere diameter 0.
3 μm, coefficient of variation of sphere equivalent diameter 28%, normal crystal, twin mixed particles, diameter / thickness ratio 2.5) Silver coating amount 0.30 Gelatin 0.50 ExS-4 5.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-6 0.3 × 10 ^-4 ExM-1 3.0 × 10 ^-2 ExM-2 0.20 ExY-1 3.0 × 10 ^-2 Cpd-11 7.0 × 10 ^-3 Solv-1 0.20 8th layer (medium speed green-sensitive emulsion layer) Silver halide emulsion (AgI 4 mol%, internal high AgI type, equivalent sphere diameter 0.
55 μm, coefficient of variation of sphere equivalent diameter 20%, normal crystal, twin mixed particles, diameter / thickness ratio 4.0) Silver coating amount 0.70 gelatin 1.00 ExS-4 5.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-6 3.0 × 10 ^-5 ExM-1 3.0 × 10 ^-2 ExM-2 0.25 ExM-3 1.5 × 10 ^-2 ExY-1 4.0 × 10 ^-2 Cpd-11 9.0 × 10 ^-3 Solv-1 0.20 Layer 9 (high Sensitive green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent sphere diameter)
0.7 μm, sphere equivalent diameter variation coefficient 30%, normal crystal, twin mixed particles, diameter / thickness ratio 2.0) Silver coating amount 0.50 Gelatin 0.90 ExS-4 2.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS- 6 2.0 × 10 ^-5 ExS-7 3.0 × 10 ^-4 ExM-1 1.0 × 10 ^-2 ExM-4 3.9 × 10 ^-2 ExM-5 2.6 × 10 ^-2 Cpd-2 1.0 × 10 ^-2 Cpd-9 2.0 × 10 ^-4 Cpd-10 2.0 × 10 ^-4 Solv-1 0.20 Solv-2 5.0 × 10 ^-2 10th layer (yellow filter layer) Gelatin 0.90 Yellow colloid 5.0 × 10 ^-2 Cpd-1 0.20 Solv-1 0.15 11 layers (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, equivalent sphere diameter 0.
5 μm, coefficient of variation of sphere equivalent diameter 15%, octahedral particles) Silver coating amount 0.40 Gelatin 1.00 ExS-8 2.0 × 10 ^-4 ExY-1 9.0 × 10 ^-2 ExY-3 0.90 Cpd-2 1.0 × 10 ^-2 Solv -1 0.30 12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent sphere diameter)
1.3 μm, coefficient of variation of sphere equivalent diameter 25%, normal crystal, twin mixed particles, diameter / thickness ratio 4.5) Silver coating amount 0.50 Gelatin 0.60 ExS-8 1.0 × 10 ^-4 ExY-3 0.12 Cpd-2 1.0 × 10 ^-3 Solv-1 4.0 × 10 ^-2 13th layer (1st protective layer) Fine grain silver iodobromide (average grain size 0.07 μm, AgI 1 mol%) 0.20
Gelatin 0.80 UV-2 0.10 UV-3 0.10 UV-4 0.20 Solv-3 4.0 × 10 ^-2 P-2 9.0 × 10 ^-2 14th layer (second protective layer) Gelatin 0.90 B-1 (1.5 μm diameter) 0.10 B-2 (1.5 μm in diameter) 0.10 B-3 2.0 × 10 ^-2 H-1 0.40 Furthermore, in order to improve the preservability, processing property, pressure resistance, fungicidal / antibacterial property, antistatic property, and coating property. The following Cpd-
3, Cpd-5, Cpd-6, Cpd-7, Cpd-8, P-1, W
-1, W-2 and W-3 were added.

In addition to the above, n-butyl-p-hydroxybenzoate was added. Further, B-4, F-1, F-4, F-
5, F-6, F-7, F-8, F-9, F-10, F-1
1, and iron, lead, gold, platinum, iridium, and rhodium salts.

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

Next, the compound (3) of the present invention was used for ExY-3 in the eleventh layer,
Samples 202 and 203 replaced in (5) to be equimolar
Further, Samples 204 and 205 were prepared by reducing the amount of (3) and (5) used to 70%.

The sample prepared as described above was cut into a width of 35 mm, subjected to imagewise exposure, and processed by an automatic developing machine. Processing is 35
A sample having a width of mm was continuously measured for 500 m. The processing steps and the composition of the processing solution are shown below.

The washing water was of a countercurrent type from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath. Replenishment to the bleach-fixing bath is achieved by connecting the top of the bleaching tank and the bottom of the bleach-fixing tank and the top of the fixing tank and the bottom of the bleach-fixing tank with pipes, and supplying the replenisher to the bleaching tank and fixing tank. All of the generated overflow liquid was allowed to flow into the bleach-fix bath. Incidentally, the amount of carryover of the developing solution into the bleaching step, the amount of carryover of the bleach-fixing step of the bleaching solution, bring volume to the washing step to carry amount and fixing solution to the fixing step of the bleach-fixing solution photographic material 1 m ² per 65ml, 50ml, 50ml, 5 respectively
It was 0 ml. The crossover time is 5 seconds in each case, and this time is included in the processing time of the previous process.

 The composition of the treatment liquid is shown below.

(Bleaching fixer mother liquor) A mixture of the above bleaching solution mother liquor and the following fixing solution mother liquor in a ratio of 15 to 85. Tap water is passed through a mixed-bed column filled with H-type strongly acidic cation exchange resin (Rohm and Haas Amberlite IR-120B) and OH-type strongly basic anion exchange resin (Amberlite IRA-400). To lower the calcium and magnesium ion concentration to 3 mg / l or less, followed by sodium diisocyanurate 20 mg / l and sodium sulfate 150 mg / l.
l was added. The pH of this solution was in the range of 6.5-7.5.

(Fixing solution) Common to mother liquor and replenisher (unit: g) Formalin (37%) 1.2 ml Sodium p-toluenesulfinate 0.3 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetate Salt 0.05 water was added and 1.01 pH 7.2 Samples 202 and 203 were found to give higher color density than Sample 201 of Comparative Example. In addition, it was found that Samples 204 and 205 with the reduced amount of couplers provided the same coloring density as Sample 201.

From the above results, it was found that the compound of the present invention gives a high color-forming density, and it is clear that the blue-sensitive emulsion layer can be made thinner and the sharpness can be improved.

[Brief description of the drawings]

1 and 2 show absorption spectra in an ethyl acetate solvent. FIG. 1 shows D-1 and D-2 of the dye obtained from the coupler of the present invention, and D-8 of the dye for comparison, and FIG. 2 shows D-3 and D of the dye obtained from the coupler of the present invention.
-5 is indicated.

Continuation of the front page (56) References JP-B-51-26038 (JP, B2) JP-B 60-18979 (JP, B2) JP-B-49-12661 (JP, B1)

Claims (4)

(57) [Claims] 1. A silver halide color photographic light-sensitive material comprising a coupler represented by the following general formula (1). Wherein R1 is a nitrogen, oxygen or carbon atom and> C =
X1 represents a group bonded to X1, X1 represents a nitrogen or carbon atom bonded to と C <, an oxygen atom or a sulfur atom, R2 represents a carbamoyl group or a sulfonyl group, and Ar
Represents an aromatic group or a heterocyclic group. However, R1 and X1 may be combined to form a cyclic structure or not. 2. The silver halide color photograph according to claim 1, wherein the group represented by R1 in the general formula (1) is a group bonded to> C = X1 by a nitrogen atom. Photosensitive material. 3. The silver halide color photographic material according to claim 1, wherein the group represented by R2 in the general formula (1) is a carbamoyl group. 4. The silver halide color photographic light-sensitive material according to claim 1, wherein the coupler represented by the general formula (1) is a coupler represented by the following general formula (2). In the formula, R2 and Ar have the same meanings as described in formula (1), R3 represents a substituent, and X2 represents an oxygen atom or an imino group. When X2 is a substituted imino group, it may or may not bond with R3 to form a cyclic structure.