EP0513748A1

EP0513748A1 - Silver halide color photographic light sensitive material

Info

Publication number: EP0513748A1
Application number: EP92108027A
Authority: EP
Inventors: Yukio Konica Corporation Ohya; Shuji Konica Corporation Murakami
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1991-05-14
Filing date: 1992-05-13
Publication date: 1992-11-19
Also published as: JPH04336537A

Abstract

A silver halide color photographic light-sensitive material which is lowered reciprocity failure and increased in speed. The light-sensitive material comprises a support and a silver halide emulsion layer provided on the support. The emulsion layer contains silver halide grains which are formed in the presence of a metal complex having an oxidation potential of from -1.34 V to +1.66 V and a reduction potential of lower than -1.34 V and are chemically sensitized in the presence of a gold-containing compound.

Description

FIELD OF THE INVENTION

This invention relates to a silver halide color photographic light sensitive material and, particularly, to a silver halide color photographic light sensitive material substantially high in photosensitive speed and less in reciprocity law failure.

BACKGROUND OF THE INVENTION

The requirements for silver halide photographic light sensitive materials have become more serious with the years. In addition to the serious requirements for high photosensitive speeds and high image qualities particularly, graininess and image-sharpness, the rapid processing aptitudes for rapid finishing have been seriously required, These requirements can mostly be achieved in the cases where silver halide grains can be achieved to make the photosensitive speeds thereof higher. Therefore, it is not too much to say that how to make the photosensitive speeds of silver halide grains higher must be the most serious problem for the field of the art.
For satisfactorily meeting the requirements for rapidly finishing, it is required to make the yields of print-finishing higher. It is, therefore, essential to improve the characteristics such as those of the reciprocity law failure, latent-image fading and raw-stock preservability of light-sensitive materials.
As for one of the methods of making the photosensitive speeds of silver halides higher, Japanese Patent Publication Open to Public Inspection (hereinafter referred to as 'JP OPI Publication') No. 51-139323(1976) or 59-171947(1984) describes that a processing variation and a reciprocity law failure can be improved by containing a metal compound belonging to the VIII group of the periodic law table in silver halide grains.
JP OPI Publication Nos. 2-20853(1990), 2-20854(1990) and 2-20855(1990) describe each that high-speed photosensitive emulsions can be prepared by making use of the cyan complexes of Rc, Ru, Ir and Os. Even in the techniques, it was found that not only the photosensitive speeds cannot be made satisfactorily higher but the reciprocity law failure is rather deteriorated. JP OPI Publication No.1-121844(1989) describes that highly photosensitized grains can be prepared by doping divalent iron ions in the narrow bandgap portion of the composition of silver halide grains and it is, however, found that the reciprocity law failure characteristics are deteriorated.
JP OPI Publication No. 1-183647(1989) describes that, when containing iron ions in a highly silver chloride containing silver halide having a silver bromide phase having a high silver bromide content, both of high photosensitive speeds and reciprocity law failure characteristics can be improved and the variations of photosensitive speed and gradation each can also be improved even if the variations should be produced by the temperature variations in the course of making an exposure. However, there is a problem still remaining unsolved that a photosensitive speed is seriously varied by the intervals between the time of making an exposure and the time of carrying out a processing (i.e., a latent-image stability).
In JP OPI Publication Nos. 60-196747(1985), 61-103149(1986), 61-205929(1986), 62-56949(1987), 62-253165(1987), 63-41849(1988) and 63-259654(1988), there is the description that the characteristics of an emulsion can be improved by making a sensitizing dye present at a time during grawing in the grains, but there is neither any description that the oxidation-reduction potentials are particularly specified for sensitizing dyes nor that a high sensitization and a reciprocity law failure can each be improved.
As mentioned above, a high sensitization and a reciprocity law failure improvement are contrary to each other in the characteristics. Therefore, a technique capable of improving these characteristics at the same time has strongly been demanded.

SUMMARY OF THE INVENTION

It is an object of the invention to provide a silver halide color photographic light sensitive material high in photosensitive speed and improved in reciprocity law failure.
The object of the invention can be achieved with a silver halide color photographic light-sensitive material which comprises a support having thereon a silver halide emulsion layer containing the following silver halide grains. The silver halide grains are formed in the presence of a metal complex having an oxidation potential of from -1.34 V to +1.66 V and a reduction potential not higher than -1.34 V and are chemically sensitized in the presence of a gold-containing compound.

DETAILED DESCRIPTION OF THE INVENTION

In the silver halide color photographic light sensitive materials of the invention, the silver halide grains contained in at least one of the silver halide emulsion layers thereof are preferable to comprise silver chlorobromide having a silver chloride content of not less than 90 mol% but not substantially containing silver iodide. For displaying the effects of the invention more remarkably, the above-mentioned silver chloride content thereof is to be, desirably, not less than 95 mol% and, preferably, not less than 98 mol%.
The expression, '-- silver halide grains do not substantially contain silver iodide --', means that the silver halide grains are silver chlorobromide having a silver iodide content not more than 0.5 mol% and, preferably, silver chlorobromide not containing any silver iodide at all. In other words, it is particularly preferable for the invention to use silver chlorobromide containing silver bromide within the range of 0.01 to 2 mol%.
The silver halide emulsions relating to the invention may be comprised of either grains having a single composition or the mixture of silver halide grains each having the different compositions. In the silver halide emulsion layers containing the silver halide grains of the invention, the proportion of the silver halide grains having a silver chloride content of not less than 90 mol% to the whole silver halide grains of the emulsion layers is, desirably, not less than 60% by weight and, preferably, not less than 80% by weight.
The metal complexes each applicable to the invention have an oxidation potential, hereinafter referred to as Eox, within the range of -1.34V to +1.66V and a reduction potential, hereinafter referred to as Ered, of a base value of not higher than -1.34V.
The above-mentioned Eox and Ered can readily be measured by the skilled in the art. The methods of measuring them are detailed in, for example, A. Stanlenda, "Naturwissenschaften" Vol.47, 1960, p.353 and p.512; P. Delahay, "New Instrumental Methods in Electrochemistry", 1954, Interscience Publishers Co.; and L. Meites, "Polarographic Techniques", 2nd Ed., 1965, Interscience Publishers Co.
The values of Ered mean each a potential at which a subject compound is reduced upon injection of an electron from the cathode in a voltammetry, and the values of Eox mean each a potential at which the electrons of a subject compound are abstracted at the anode in a voltammetry.
A cyclic voltammetry for measuring an oxidation potential and a reduction potential will briefly be described below.
In an acetonitrile solvent and at a temperature of 20°C, a platinum electrode is used as a counter electrode and a saturated calomel electrode is used as a reference electrode, respectively, so that a cyclic voltamgram can be measured at a scanning speed of 50 mV/sec.

The typical metal complexes of the invention will now be given below. It is, however, to be understood that the metal complexes of the invention shall not be limited thereto.

	Eox	Ered
(1) K₄[Ru(CN)₆]	0.89	-3.30
(2) K₄[Os(CN)₆]	0.63	-3.59
(3) K₄[Re(CN)₆]	0.44	-3.56
(4) K₄[Re(NCS)₆]	-0.04	-3.14
(5) K₄[Fe(CN)₆]	0.36	-3.63
(6) K₄[Os(NCS)₆]	0.11	-3.00
(7) K₄[Ru(NCS)₆]	0.35	-2.90
(8) K₂[Pd(NCS)₄]	0.51	-1.97
(9) K₂[Pt(NCS)₄]	0.63	-2.01
(10) K₄[Os(SeCN)₆]	0.19	-2.96
(11) K₂[Fe(EDTA)]	0.12	-3.68
(12) K₂[Pd(CN)₄]	0.61	-2.34

*: EDTA: Ethylenediaminetetra acetic acid

The above-given metal complexes may be used in an amount within the range of, suitably, 1x10⁻⁹ to 1x10⁻³ mols per mol of silver used and, more effectively for the invention, 1x10⁻⁸ to 1x10⁻⁴ mols per mol of silver used.
In the invention, it is preferred to use the above-given metal complexes and an iridium-containing compound in combination, because the effects of the invention can greatly be displayed. The typical examples of the compounds include, an iridium (III) chloride, an iridium (III) bromide, iridium (IV) chloride, a potassium hexachloroiridate (III), a potassium hexachloroiridate (IV), a hexaamine iridium (III) salt, a hexaamine iridium (IV) salt, a trioxalate iridium (III) salt and a trioxalate iridium (IV) salt.
The iridium-containing compounds may be used in an amount within the range of 1x10⁻¹² to 5x10⁻⁶ mols per mol of silver used and, preferably, 1x10⁻¹⁰ to 5x10⁻⁷ mols per mol of silver used.
In the invention, the metal complexes and iridium compounds each applicable to the invention may be contained in silver halide grains by making the above-mentioned metal complexes and iridium compounds present when forming the silver halide grains. The may be contained therein in any one of rash, continuous and separate addition methods.
In the invention, the silver halide grains are chemically sensitized in the presence of a gold-containing compound.
As for the gold sensitizers, i.e., the gold-containing compounds, for the above-mentioned gold sensitization, it is allowed to use those having a gold oxidation number of either +1 valency or +3 valency and the gold compounds ordinarily used as the gold sensitizers may be used. The typical examples thereof include a chloroauric acid, a potassium chloroaurate, an auric trichloride, a potassium auro thiocyanate, a potassium iodoaurate, a tetracyanoauric acid, an ammonium aurocyanate and a pyridyl trichlorogold.
The amounts of the gold sensitizers to be added may be so varied as to meet the various conditions. The are, however, added in an amount within the range of, desirably, 5x10⁻⁷ to 5x10⁻³ mols per mol of silver used, more desirably, 2x10⁻⁶ to 1x10⁻⁴ mols and, preferably, 2.6x10⁻⁶ to 4x10⁻⁵ mols.
When embodying the invention, the preferable chemical sensitization means is to use both of a chalkogen sensitization and a gold sensitization in combination. Thereby a remarkable sensitization effect can be displayed. Among the above-mentioned sensitization means, the combination of a sulfur sensitization and a gold sensitization is more useful, because the combination used thereof can display not only the sensitization effects but also the effect of inhibiting any fog from production.
For the above-mentioned sulfur sensitization, any one of the well-known sulfur sensitizers can be used. The sulfur sensitizers may be added in an amount good enough to effectively increasing the photosensitive speed of an emulsion. Such an amount as mentioned above may be varied over a considerably wide range under various conditions such as the variations of pHs, temperatures and AgX grain sizes. As the rough standard, however, they may be added in an amount within the range of, desirably,, 10⁻⁷ to 10⁻¹ mols per mol of AgX.
In the preparation of silver halide emulsion of the invention, any temperatures may be applied for carrying out a chemical ripening, provided, a subject sensitization can be achieved. The temperatures are, however, within the range of, desirably, 90°C to 20°C, more desirably, 80°C to 30°C and, preferably, 70°C to 35°C.
There is no special limitation to the grain sizes of the silver halide grains applicable to the invention. However, when taking a rapid processability, a photosensitive speed and other photographic characteristics into consideration, the grain sizes thereof are to be within the range of, desirably, 0.2 to 1.6 µm and, preferably, 0.25 to 1.2 µm.
The grain sizes of silver halide grains may be distributed either monodispersewise or polydispersewise. In the grain size distribution of silver halide grains, however, the preferable grains are those of monodisperse silver halide having a grain size distribution variation coefficient of, desirably, not more than 0.22 and, more desirably, not more than 0.15.
The above-mentioned variation coefficient means a ratio (σ/r_M) of a standard deviation of grain size distribution (σ) to an average grain size (r_M).
In the invention, any types of silver halide grains may be applied to emulsions, provided they are prepared in an acid, neutral or ammoniacal method. The grains are also allowed to be grown either at the same time or after preparing the seed grains thereof.
The silver halide grains applicable to the invention are allowed to have any desired configurations. One of the preferable examples thereof is a cube having {100} planes as the crystal faces thereof. The grains having an octahedral, tetradecahedral or dodecahedral configuration and, besides, the grains having twinned crystal faces may also be used.
The silver halide emulsions applicable to the invention can be optically sensitized to any desired wavelength regions by making use of a sensitizing dye. The silver halide photographic light sensitive materials applicable to the invention are comprised of at least one of silver halide emulsion layers containing silver halide grains having a maximum spectral sensitivity in the wavelength region of not longer than 720 nm and, preferably, within the range of not shorter than 400 nm to not longer than 700 nm. The above-mentioned sensitizing dyes may be used independently or in combination. It is also allowed to contain in an emulsion a sensitizing dye and a dye having no sensitizing function in itself or a compound substantially incapable of absorbing any visible rays of light, that is so-called a super-sensitizer for enhancing the sensitizing function of the sensitizing dye.
It is further allowed to use the above-mentioned sensitizing dyes for their own inherent sensitizing function and, besides, for gradation and development controls.
The sensitizing dyes applicable thereto include, for example, a cyanine dye, a melocyanine dye, a complex cyanine dye, a complex melocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye and a hemioxanol dye.
The sensitizing dyes preferably applicable to the invention include, for example, those denoted by BS-1 to BS-15, GS-1 to GS-6 and RS-1 to RS-7 described in JP OPI Publication No. 2-162332(1990), pp.13∼21. However, the sensitizing dyes preferably applicable to the invention shall not be limited thereto.
For the purposes of preventing any fog production and stabilizing photographic characteristics in the courses of preparing, storing or photographically processing a light sensitive material, an antifoggant or a stabilizer may be added to the silver halide emulsions of the invention, in the course of chemical ripening, after completing the chemical ripening and/or at the point of time between the completion of chemically ripening and the starting a coating the silver halide emulsion.
As for the binders of the silver halide photographic light sensitive materials applicable to the invention, gelatin ca advantageously be used for.
In the silver halide photographic light sensitive materials relating to the invention, a dye-forming coupler such as a yellow coupler, magenta coupler and cyan coupler can be used.
The yellow couplers preferably applicable to the invention include, for example, acylacetoanilide type couplers. Among them, a benzoylacetoanilide type and pyvaloylacetoanilide type compounds may advantageously be used. In particular, the following compounds may preferably be used; namely, the exemplified compounds Y-1 through Y-146 each given in JP OPI Publication No.63-85631(1988), the exemplified compounds Y-1 through Y-98 given in JP OPI Publication No.63-97951(1988) and the exemplified compounds Y-1 through Y-24 given in JP OPI Publication No. 1-156748(1989), pp.67∼78.
The magenta couplers preferably applicable to the invention include, for example, a pyrazoloazole type and 3-anilino-5-pyrazolone type couplers.
The typical examples of the pyrazoloazole type couplers include; the compounds M-1 through M-61 given in JP OPI Publication No. 63-167360(1988), pp.5 (in the right lower column) ∼ 9 (in the left lower column); and the compounds No. 1∼4, 6, 8∼17, 19∼24, 26∼43, 45∼59, 61∼104, 106∼121, 123∼162 and 164∼223 each given among the compounds given in JP OPI Publication No. 62-166339(1987), pp.18 (in the right upper column)∼32 (in the right upper column). The 3-anilino-5-pyrazolone type couplers include, for example, the exemplified compounds No.218 to No.244 each given in JP OPI Publication No. 63-52138(1988) and, besides, the compounds given in, for example, U.S. Patent Nos. 2,600,788, 3,061,432, 3,062,653, 3,127,269, 3,311,476, 3,152,896, 3,419,391, 3,519,429, 3,555,318, 3,684,514, 3,888,680, 3,907,571, 3,928,044, 3,930,861, 3,930,866 and 3,933,500; JP OPI Publication Nos. 49-29639(1974), 49-111631(1974), 49-129538(1974), 50-13041(1975), 52-58922(1977), 55-62454(1980), 55-118034(1980), 56-38043(1981), 57-35858(1982), 60-2953(1985), 60-23855(1985) and 60-60644(1985); British Patent No. 1,247,493; Belgian Patent Nos. 789,116 and 792,525; West German Patent No. 2,156,111; and JP Examined Publication Nos. 46-60479(1971) and 57-36577(1982).
The cyan couplers preferably applicable to the invention include, for example, a 2-acylaminophenol type and 2,5-diacylaminophenol type couplers.
The typical examples of the former type couplers include; the exemplified compounds PC-1 through PC-19 given in JP OPI Publication No. 1-156748(1989), pp.116∼119; the exemplified compounds C-1 through C-28 given in JP OPI Publication No. 62-249151(1987) and the couplers given in JP Examined Publication No. 49-11572(1974), JP OPI Publication Nos. 61-3142(1986), 61-9652(1986), 61-9653(1986), 61-39045(1986), 61-50136(1986), 61-99141(1986) and 61-105545(1986). The typical examples of the latter type couplers include; the exemplified compounds C-1 through C-25 given in JP OPI Publication No. 63-96656(1988); the exemplified compounds PC-II-1 through PC-II-31 given in JP OPI Publication No. 1-156748(1989), pp.124∼127; and, besides, the cyan couplers given in JP OPI Publication No. 62-178962(1987), pp. 7 (in the right lower column) ∼ 9 (in the left lower column); those given in JP OPI Publication No. 60-225155(1985) pp. 7 (in the left lower column) ∼ 10 (in the right lower column); those given in JP OPI Publication No. 60-222853(1985), pp. 6 (in the left upper column) ∼ 8 (in the right lower column); and those given in JP OPI Publication No. 59-185335(1984), pp. 6 (in the left lower column) ∼ 9 (in the left upper column).
The hydrophobic compounds such as the above-mentioned dye-forming couplers may be usually added into an objective hydrophilic colloidal layer in the following manner. The hydrophobic compound is dissolved in a high boiling organic solvent having a boiling point of approximately not lower than 150°C or a water-insoluble macromolecular compound together with, if required, a low boiling and/or water-soluble organic solvent in combination. The resulting solution is emulsified with a surfactant in a hydrophilic binder such as an aqueous gelatin solution by making use of a dispersing means such as a stirrer, a homogenizer, a colloid mill, a flow-jet mixer or a supersonic homogenizer, so that the resulting emulsified dispersion may be added into the objective hydrophilic colloidal layers.
The typical examples of the high boiling organic solvents include the exemplified organic solvents 1 through 22 each given in JP OPI Publication No. 62-166331(1987).
To the silver halide photographic light sensitive materials relating to the invention, it is allowed to freely apply a water-soluble dye, a color-staining inhibitor, an image stabilizer, a layer hardener, a plasticizer, a polymer latex, a UV absorbent, a formalin scavenger, a mordant, a development accelerator, a development retarder, a fluorescent whitening agent, a matting agent, a lubricant, an antistatic agent and a surfactant.
In the silver halide photographic light sensitive materials relating to the invention, the photographic component layers thereof are coated over any one of various kinds of supports which have ordinarily been used in the field of the art. If required, the photographic component layers may be coated directly or through a sublayer after the support surfaces are subjected to a corona-discharge treatment, a UV-irradiation treatment and/or a flame treatment.
When coating a photographic light sensitive material applied thereto with the silver halide emulsion relating to the invention, a thickener may also be used for improving the coatability. The useful coating methods include, particularly, an extrusion coating method and a curtain coating method, in which two or more layers can be coated at the same time.
In the invention, the processes for developing the silver halide photographic light sensitive material include, for example, the well-known processes having widely been applied to various color photographic processes.

EXAMPLES

Now, the examples of the invention will be given below. However, the invention shall not be limited thereto.

EXAMPLE-1

Into 1000 ml of an aqueous 2% gelatin solution being kept to be 40°C, the following Solution A and Solution B were added at the same time by taking 30 minutes, with controlling the pAg and pH of the mixed solutions to be 6.5 and 3.0, respectively. Further, the following Solution C and Solution D were added at the same time by taking 120 minutes, with controlling the pAg and pH of the mixed solution to be 7.3 and 5.5, respectively.
In the above-mentioned addition of the solutions, the pAg thereof was controlled in the method described in JP OPI Publication No. 59-45437(21984) and the pH thereof were controlled with an aqueous sulfuric acid or sodium hydroxide solution.

(Solution A)

Sodium chloride 3.42 g

Potassium bromide 0.03 g

Add water to make 200 ml

(Solution B)

Silver nitrate 10 g

Add water to make 200 ml

(Solution C)

Sodium chloride 102.7 g

Potassium bromide 1.0 g

Add water to make 600 ml

(Solution D)

Silver nitrate 300 g

Add water to make 600 ml
After completing the addition of the above-mentioned solutions, the resulting mixed solution was desalted with an aqueous 5% solution of Demol-N (manufactured by Kao-Atlas Corp.) and an aqueous 20% solution of magnesium sulfate. After that, the desalted solution was mixed with an aqueous gelatin solution, so that a monodisperse type cubic grain emulsion having an average grain size of 0.40 µm, a variation coefficient of size distribution (σ/r_M) of 0.07 and a silver chloride content of 99.5 mol% could be prepared. The resulting emulsion is hereinafter referred to as Em-A.
The resulting emulsion Em-A was subjected to an optimum chemical sensitization at 60°C by making use of sodium thiosulfate in an amount of 1.5 mg/mol of AgX, the following compound SB-5 in an amount of 6x10⁻⁴ mols/mol of AgX and sensitizing dye GS-6 in an amount of 2x10⁻⁴ mols/mol of AgX. The resulting chemically sensitized emulsion is hereinafter referred to as Em-1.
Em-2 was prepared in the same manner as in Em-1, except that Em-A was chemically sensitized with sodium chloroaurate in an amount of 1.5 mg/mol of AgX, the following compound SB-5 in an amount of 6x10⁻⁴ mols/mol of AgX and sensitizing dye GS-1 in an amount of 2x10⁻⁴ mols/mol of AgX.

Em-3 and Em-5 were each prepared in the same manner as in emulsion Em-1, except only that the compounds shown in Table-1 were added into Solution C. Besides, Em-4 and Em-7 through Em-12 were each prepared in the same manner as in emulsion Em-2, except only that the compounds shown in Table-1 were added into Solution C.

Table-1

Em No.	Additive to (Solution C)	Amount added^*1 (mol %)	Chemical^*3 sensitization
Em-1	-	-	A
Em-2	-	-	B
Em-3	K₃[RhCl₆]^*2	5x10⁻⁶	A
Em-4	K₃[RhCl₆]	5x10⁻⁶	B
Em-5	Exemplified compound (1)	5x10⁻⁶	A
Em-6	Exemplified compound (1)	5x10⁻⁶	B
Em-7	Exemplified compound (2)	5x10⁻⁶	B
Em-8	Exemplified compound (12)	5x10⁻⁶	B
Em-9	Exemplified compound (6)	5x10⁻⁶	B
Em-10	Exemplified compound (7)	5x10⁻⁶	B
Em-11	Exemplified compound (11)	5x10⁻⁶	B
Em-12	Exemplified compound (2)	5x10⁻⁶	B
	K₂[IrCl₆]	2x10⁻⁸
Em-13	Exemplified compound (7)	5x10⁻⁶	B
	K₂[IrCl₆]	2x10⁻⁸

^*1 indicates an amount added per mol of silver used,
^*2 indicates Eox = 1.31 V and Ered = -1.30 V,
^*3 indicates A standing for a sulfur sensitization and B for a gold-sulfur sensitization, respectively.

Sample 101 was prepared by coating the following layers on a polyethylene-laminated paper support having polyethylene layer on one of the surface thereof and titanium oxide-containg polyethylene lay on the other surface, onto which a photographic component layers are to be coated.
Samples 102 through 112 were prepared in the same manner as in Sample 101, except that Em-2 of Sample 101 was replaced by Em-2 through Em-12, respectively.
The characteristics of the resulting emulsions were tested by making use of the samples thus prepared.

(1) Sensitometry

The samples each was wedgewise exposed to green light for 0.05 seconds, and was processed for color development in accordance with the the following processing steps. The density of resulting image was measured by making use of an optical densitometer (Model PDA-65 manufactured by Konica Corp.) The photosensitive speed (hereinafter referred simply as speed) was expressed by the reciprocal of an exposure quantity required for obtaining a density 0.8 higher than the fog density, and the speed values of the samples were expressed in terms of a speed relative to that of Sample 101 which was regarded as a value of 100.

(2) Reciprocity law failure characteristics

Each wedgewise exposure was made to green rays of light for 10 seconds so as to have the same exposure quantity as in the above-mentioned sensitometry, and the sensitometry was carried out in the same manner as in the above-mentioned case. The difference between the speeds, or the values of speed variations obtained when each sample was exposed to light for 0.05 seconds and 10 seconds, and the values of the speed differences of the sample were each expressed in terms of a relative value to that of Sample 101 which was regarded as a value of 100.

(3) Latent image stability

Each sensitometry was carried out in the same manner as in the above-mentioned sensitometry, except that the periods from the time when exposing each sample to light to the time when processing each sample were set for 1 minute and for 24 hours, respectively. so as to obtain the difference between the speeds or the values of speed variations and the values of the speed differences of the sample were each expressed in terms of a relative value to that of Sample 101 which was regarded as a value of 100.
The results thereof are shown in Table-2.

The processing conditions were as follows.

Processing step	Temperature	Time
Color developing	35.0 ± 0.3°C	45 sec.
Bleach-fixing	35.0 ± 0.5°C	45 sec.
Stabilizing	30 to 34°C	90 sec.
Drying	60 to 80°C	60 sec.

Color developer
Pure water	800 ml
Triethanol amine	10 g
N,N-diethylhydroxyl amine	5 g
Potassium bromide	0.02 g
Potassium chloride	2 g
Potassium sulfite	0.3 g
1-hydroxyethylidene-1,1-diphosphonic acid	1.0 g
Ethylenediaminetetraacetic acid	1.0 g
Disodium catechol-3,5-diphosphonate	1.0 g
N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate	4.5 g
Fluorescent whitening agent (a 4,4'-diaminostilbene disulfonic acid derivative)	1.0 g
Potassium carbonate	27 g
Add water to make in total of	1 liter
Adjust pH to be	pH=10.10

Bleach-fixer
Ferric ammonium enthylenediaminetetraacetate, dihydrate	60 g
Ethylenediaminetetraacetic acid	3 g
Ammonium thiosulfate (in an aqueous 70% solution)	100 ml
Ammonium sulfite (in an aqueous 40% solution)	27.5 ml
Add water to make in total of	1 liter
Adjust pH with potassium carbonate or glacial acetic acid to be	pH=5.7

Stabilizer
5-chloro-2-methyl-4-isothiazoline-3-one	1.0 g
Ethylene glycol	1.0 g
1-hydroxyethylidene-1,1-diphosphonic acid	2.0 g
Ethylenediaminetetraacetic acid	1.0 g
Ammonium hydroxide (in an aqueous 20% solution)	3.0 g
Fluorescent whitening agent (a 4,4'-diaminostilbene disulfonic acid derivative)	1.5 g
Add water to make in total of	1 liter
Adjust pH with sulfuric acid or potassium hydroxide to be	pH=7.0

From the results shown in Table-2, the remarkable effects of the invention can be proved. In other words, about Samples 103 and 104 applied each with a metal complex K₃[RhCl₆] having the other Eox and Ered than those of the invention, they were improved in reciprocity law failure characteristics to some extent, but were still low in speed and not improved in latent-image stability.
About Sample 105 applied with a metal complex K₂[Rh(CN)₆] having the Eox and Ered of the invention and sulfur-sensitized, it was proved to be increased in speed, but still not quite satisfactory in reciprocity law failure characteristics and latent-image stability.
In contrast to the above, it was proved that Samples 106 through 113 each of the invention were high in speed and were also excellently improved in reciprocity law failure characteristics and latent-image stability.
As compared to Samples 112 and 113, the sample in which K₂[IrCl₆]²⁻ was used in combination is preferable, because the reciprocity law failure characteristics and latent-image stability were further improved.

EXAMPLE-2

The monodisperse type cubic grain emulsion, Em-14 through Em-25, shown in Table-3 were each prepared in the same manner as in Example-1, except that the periods of time for adding Solution A through Solution D were adjusted and the compounds shown in Table-3 were added into Solution C.
Each of Em-14 through Em-19 had an average grain size of 0.65 µm, a variation coefficient of 0.06 and a silver chloride content of 98.5 mol%; and each of Em-20 through Em-25 had an average grain size of 0.47 µm, a variation coefficient of size distribution of 0.07 and a silver chloride content of 99.8 mol%. The resulting emulsions were each optically and chemically sensitized as shown in Table-3.
Next, Sample 201 of multilayered silver halide color photographic light sensitive materials was prepared by coating each of the layers having the following compositions on a polyethylene-laminated paper support the same as used in Example 1. The coating solutions were prepared in the following manners.

Coating solution for Layer 1

Ethyl acetate of 60 ml was added and dissolved into yellow coupler (YY-1) of 26.7 g, dye-image stabilizers (ST-1) of 10.0 g and (ST-2) of 6.67 g, additive (HQ-1) of 0.67 g and high-boiling organic solvent (DNP) of 6.67 g. The resulting solution was dispersed in 220 ml of an aqueous 10% gelatin solution containing 7 ml of an aqueous solution of 20% surfactant (SU-1) by making use of a supersonic homogenizer, so that a yellow coupler dispersed solution could be prepared. In the dispersed solution, antimold (B-1) was added. The resulting solution was mixed with the blue-sensitive silver halide emulsion containing 10 g of silver prepared under the following conditions, so that the coating solution for Layer 1 could be prepared.
The coating solutions for Layers 2 through 7 were each prepared in the manner similar to in the above-mentioned coating solution for Layer 1.
Further, water-soluble dyes, AI-1, AI-2 and AI-3 were each added to the coating solutions for Layers 1, 3 and 6, respectively.
The structures of the additives used therein were as follows.
As the hardeners, each of H-2 was added (in 0.07 g/m²) to Layers 2 and 4; and H-1 was added (in 0.05 g/m²) to Layer 7.

Samples 202 through 206 were each prepared in the same manner as in Sample 201, except that the emulsions used in the light sensitive silver halide emulsion layers were replaced by those shown in Table-4.

Table-4

Sample No.	Emulsion for
	Blue sensitive layer	Green sensitive layer	Red sensitive layer
201	Em-14	Em-1	Em-20
202	Em-15	Em-3	Em-21
203	Em-16	Em-4	Em-22
204	Em-17	Em-5	Em-23
205	Em-18	Em-6	Em-24
206	Em-19	Em-12	Em-25

After the resulting samples were each exposed and then processed in the same manner as in Example-1, except that the exposures were made to white light, and they were each evaluated in the same manner as in Example-1.
The speeds obtained were each expressed by a value relative to the speed of Sample 201 which was regarded as a value of 100; and the values of the reciprocity law failure characteristics and the latent-image stabilities were each expressed by a value relative to the value of the speed variation of Sample 201, which was regarded as a value of 100.
The results of the evaluation are shown in Table-5.
As is obvious from the above-given Table-5, the effects of the invention were remarkable also in multilayered silver halide color photographic light sensitive materials. Words, the samples applied thereto with a metal complexes having other Eox and Ered than those of the invention and the samples applied thereto with the metal complexes having Eox and Ered of the invention, but not sensitized with the compounds containing gold, each of these samples was not satisfactorily improved in photosensitive speed, reciprocity law failure and latent-image stability.
In contrast to the above, the samples of the invention were proved to be excellent in all of the photosensitive speed, reciprocity law failure improvement and latent-image stability.
It can be estimated that the effects of the invention can be displayed by the synergistic effect of the metal complex having the specific Eox and Ered contained in silver halide grains and the gold complex salt introduced in the course of carrying out a chemical sensitization. These effects were unexpected from the conventional combination thereof.

Claims

A silver halide color photographic light-sensitive material comprising a support having thereon a silver halide emulsion layer containing silver halide grains wherein said silver halide grains are formed in the presence of a metal complex having an oxidation potential of from -1.34 V to +1.66 V and a reduction potential not higher than -1.34 V and are chemically sensitized in the presence of a gold-containing compound.
The light-sensitive material of claim 1, wherein said silver halide grains comprises not less than 90 mol% of silver chloride.
The light-sensitive material of claim 2, wherein said silver halide grains comprises not less than 95 mol% of silver chloride.
The light-sensitive material of claim 1, wherein said metal complex is K₄[Ru(CN)₆], K₄(Os(CN)₆], K₄[Re(CN)₆], K₄[Re(CNS)₆], K₄[Fe(CN)₆], K₄[Os(CNS)₆], K₄[Ru(CNS)₆], K₂[Pd(CNS)₄], K₂[Pt(CNS)₄], K₄[Se(CNS)₆], K₂[Fe(EDTA)] or K₂[Pd(EDTA)], in which EDTA is ethylenediaminetetraacetic acid.
The light-sensitive material of claim 1, wherein the amount of said metal complex is 1 x 10⁻⁹ moles to 1 x 10⁻³ moles per mole of silver contained in said silver halide grains to be formed.
The light-sensitive material of claim 5, wherein the amount of said metal complex is 1 x 10⁻⁸ moles to 1 x 10⁻⁴ moles per mole of silver contained in said silver halide grains to be formed.
The light-sensitive material of claim 1, wherein said silver halide grains are formed in the presence of said metal complex and an iridium-containing compound.
The light-sensitive material of claim 7, wherein the amount of said iridium-containing compound is 1 x 10⁻¹² moles to 1 x 10⁻⁶ moles per mole of silver contained in said silver halide grains to be formed.
The light-sensitive material of claim 8, wherein the amount of said iridium-containing compound is 1 x 10⁻¹⁰ moles to 1 x 10⁻⁷ moles per mole of silver contained in said silver halide grains to be formed.
The light-sensitive material of claim 1, wherein the amount of said gold-containing compound is 5 x 10⁻⁷ moles to 5 x 10⁻³ moles per mole of silver contained in said silver halide grains to be sensitized.
The light-sensitive material of claim 10, wherein the amount of said gold-containing compound is 5 x 10⁻⁶ moles to 5 x 10⁻⁴ moles per mole of silver contained in said silver halide grains to be sensitized.
A silver halide color photographic light-sensitive material comprising a support having thereon a silver halide emulsion layer containing silver halide grains wherein said silver halide grains are formed in the presence of K₄[Ru(CN)₆], K₄[Os(CN)₆], K₄[(Re(CN)₆], K₄[Re(CNS)₆], K₄[Fe(CN)₆], K₄[Os(CNS)₆], K₄[Ru(CNS)₆], K₂[Pd(CNS)₄], K₂[Pt(CNS)₄], K₄[Se(CNS)₆], K₂[Fe(EDTA)] or K₂[Pd(EDTA)] in an amount of 1 x 10⁻⁸ mol to 1 x 10⁻⁴ mol per mol of silver halide, wherein EDTA is ethylenediamine- tetraacetic acid; and are chemically sensitized in the presence of a gold-containing compound.