Abstract:
For incorporation of substantially water-insoluble photographic additives such as couplers into hydrophilic organic colloid layers of silver halide photographic materials, a phthalic acid ester of a formula (I): ##STR1## where R 1  and R 2  may be same or different and each represents a branched alkyl group having no more than 7 carbon atoms, is used so that said additives can effectively be dispersed in the colloid layers. Accordingly, the solubility and dispersibility of the additives is improved; the long-term stability of the additive dispersion is improved, and further and latent image storability and color-forming properties of the photographic material are also improved over the prior art photographic materials.

Description:
FIELD OF THE INVENTION 
     The present invention relates to a silver halide photographic material, and in particular, to one or more substantially water-insoluble photographic additives have been dispersed in a specific phthalic acid ester and the resulting dispersion incorporated into a hydrophilic organic colloid layer. More precisely, it relates to a silver halide color photographic material which exhibits excellent solubility and dispersability with respect to the substantially water-insoluble photographic additives and excellent long-term storability properties of the dispersions with respect to said additives, as incorporated into the hydrophilic organic colloid layer. The photographic materials of the present invention also have excellent color-forming properties and latent image storability. 
     BACKGROUND OF THE INVENTION 
     Substantially water-insoluble photographic additives, for example, oil-soluble couplers, antioxidants to be used for prevention of color fading, color fog or color mixing (such as alkylhydroquinones, alkylphenols, chromans and coumarones), hardeners, oil-soluble filter dyes, oil-soluble ultraviolet absorbents, DIR compounds (such as DIR hydroquinones and colorless DIR compounds), developing agents, dye developing agents, DDR redox compounds DDR couplers, are dissolved in a suitable high boiling point solvent, and the resulting solution is dispersed in a hydrophilic organic colloid, such as a gelatin solution, in the presence of a surfactant, whereby said additives are incorporated into the hydrophilic organic colloid layer. Examples of hydrophilic organic layers include light-sensitive emulsion layers, filter layers, backing layers, anti-halation layers, interlayers and protective layers. As the high boiling point organic solvent, phthalic acid ester series compounds and phosphoric acid ester series compounds are preferred. 
     Phthalic acid ester series compounds, known in the photographic arts, display excellent coupler-dispersability properties and have a high affinity for various organic colloid layers such as gelatin. Moreover, they have been known to favorably influence both the stability and the hue of the color images formed as well as the stability of the chemicals in the photographic material prior to development. The phthalic acid esters are readily available at a low cost. Examples of these compounds are described Japanese Patent Application (OPI) Nos. 91325/79, 149348/84, 216245/83, 109053/84, and 171953/84. (The term &#34;OPI&#34; as used herein means a &#34;published unexamined Japanese patent application.) However, these known phthalic acid ester series compounds have been found to be insufficient for use in the recently  developed high-quality light-sensitive photographic materials with respect to their solubility, dispersibility and long-term stability of the dispersion, color forming property and latent image storability. 
     SUMMARY OF THE INVENTION 
     Accordingly, an object of the present invention is to provide a silver halide color photographic material comprising at least one specific phthalic acid ester compound which exhibits excellent solubility, dispersability and long-term storability of the dispersion with respect to the photographic additives but which is free from the drawbacks of other known phthalic acid esters such as poor solubility, dispersibility, long-term stability of the dispersion, color-forming ability and latent image storability. 
     Another object of the present invention is to provide a high boiling point organic solvent suitable for photographic materials which prevents the color fading of color images caused by light, heat and moisture; which has a large preventative effect against stains and which exhibits excellent solubility, dispersibility and long-term storability of the dispersion with respect to the additive incorporated in the photographic material and excellent color forming property and latent image storability. 
     The present inventors earnestly studied have discovered that the objects of the present invention can be attained by a silver halide color photographic material comprising one or more hydrophilic organic colloid layers which layers contain photographic additives as dispersed therein with a phthalic acid esters of the general formula (I): ##STR2## wherein R 1  and R 2 , which may be same or different, each represents a branched alkyl group having 7 carbon atoms. 
     DETAILED DESCRIPTION OF THE INVENTION 
     Specific examples of the esters of the formula (I) are represented below as formulae S-1 to S6. The esters can be used singly or in the form of a mixture thereof. ##STR3## 
     The amount of the esters of the formula (I) used in the present invention is from 0.02 g to 3 g per g of coupler used in the photographic material of the invention. 
     Examples of photographic additives for use in the present invention include color couplers (more preferably cyan couplers) which are substantially water-insoluble (or easily soluble in organic solvents) and other photographic additives as described below. 
     Examples of various kinds of color couplers are described in the patent publications as referred to in Research Disclosure (RD) No. 17643, VII-C to G. 
     As yellow couplers, for example, those described in U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024 and 4,401,752; Japanese Patent Publication No. 10739/83; and British Pat. Nos. 1,425,020 and 1,476,760 are preferred. 
     As magenta couplers, 5-pyrazolone series and pyrazoloazole series compounds are preferred. Those couplers described in U.S. Pat. Nos. 4,310,619, 4,351,897, 3,061,432, 3,725,067, 4,500,630 and 4,540,654; European Pat. No. 73,636; Research Disclosure No. 24220 (June, 1984) and ibid., No. 24230 (June, 1984); Japanese Patent Application (OPI) Nos. 33552/85 and 43659/85 are especially preferred. 
     As cyan couplers, there are phenol series and naphthol series couplers. Those couplers described in U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011 and 4,327,173, West German Patent Application (OLS) No. 3,329,729, European Pat. No. 121,365A, U.S. Pat. Nos. 3,446,622, 4,333,999, 4,451,559 and 4,427,767, European Pat. No. 161,626A are preferred. 
     As colored couplers for correcting the unnecessary absorption of colored dye, those described in Research Disclosure No. 17643 VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 39413/82, U.S. Pat. Nos. 4,004,929 and 4,138,258, and British Pat. No. 1,146,368 are preferred. 
     As couplers capable of forming colored dyes having an appropriate diffusibility, those described in U.S. Pat. No. 4,366,237; British Pat. No. 2,215,570; European Pat. No. 96,570; and West German Patent Application (OLS) No. 3,234,533 are preferred. 
     Specific examples of polymerized color-forming couplers are described in U.S. Pat. Nos. 3,451,820, 4,080,211 and 4,367,282, and British Pat. No. 2,102,173. 
     Couplers which release a photographically useful residue with coupling reaction can also preferably be used in the present invention. As DIR couplers which release a development inhibitor, those described in the patent publication mentioned in the aforesaid Research Disclosure No. 17643, VII-F, as well as in Japanese Patent Application (OPI) Nos. 151944/82, 154234/82 and 184248/85, and U.S. Pat. No. 4,248,962 are preferred. 
     As couplers which image-wise release a nucleating agent or a development accelerator during development, those described in British Pat. Nos. 2,097,140 and 2,131,188, and Japanese Patent Application (OPI) Nos. 157638/84 and 170840/84 are preferred. 
     Other couplers which can be used in the photographic light-sensitive materials of the present invention are the competing couplers described in U.S. Pat. No. 4,130,427; the polyvalent couplers described in U.S. Pat. Nos. 4,283,472, 4,338,292 and 4,310,618; the DIR redox compound-releasing couplers described in Japanese Patent Application (OPI) No. 185950/85 and the couplers releasing a dye which may reproduce the color after released, as described in European Pat. No. 173,302A. 
     An illustrative but not exhaustive list of color couplers for use in the present invention are represented below in the formulae C-(1) through C-(59). ##STR4## 
     Photographic additives other than the above-mentioned couplers are described in Research Disclosures, and the related parts are shown in the following Table. 
     
         ______________________________________Additives            RD 17643   RD 18716______________________________________1.  Chemical sensitizer                p. 23      p. 648, right                           column2.  Sensitivity elevating       &#34;    agent3.  Spectral sensitizer,                pp. 23-24  from p. 648,    Super color sensitizer      right column to                           p. 649, left                           column4.  Brightening agent                p. 245.  Anti-foggant,    pp. 24-25  p. 649, right    Stabilizer                  column6.  Light absorbent, pp. 25-26  from p, 649,    Filter dye,                 right column to    UV absorbent                p. 650, left                           column7.  Stain preventing agent                p. 25, right                           p. 650, from                column     left to right                           column8.  Color image stabilizer                p. 259.  Hardener         p. 26      p. 651, left                           column10. Binder           p. 26      &#34;11. Plasticizer, Lubricant                p. 27      p. 650, right                           column12. Coating assistant,                pp. 26-27  &#34;    Antistatic agent p. 27      &#34;______________________________________ 
    
     The couplers for use in the present invention can be introduced into the photographic light-sensitive materials by various known dispersion methods. Examples of the dispersion methods include a solid dispersion method, an alkali dispersion method, a latex dispersion method and an oil-in-water dispersion method. The latter  two methods are preferred; the latter method is especially preferred. According to the oil-in-water dispersion method where substantially water-insoluble couplers and other photographic additives are introduced into photographic light-sensitive materials, the couplers and/or additives together are first dissolved in a solution comprising either a high boiling point organic solvent having a boiling point of at least 175° C. or an auxiliary solvent having a low boiling point or in a solvent solution comprising a mixture of both types of solvents. The resulting solution is finely dispersed in an aqueous medium such as water or gelatin-aqueous solution in the presence of a surfactant. Examples of the high boiling point organic solvents are described in U.S. Pat. No. 2,322,027. The dispersion may be accompanied by phase inversion. The auxiliary solvent, if used, may be removed or reduced in amount by distillation, noodle washing or ultrafiltration prior to coating the resulting emulsion onto a support. 
     Specific examples of the high boiling point organic solvents include, in addition to the compounds of the formula (I), phthalic acid esters (e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate); phosphoric acid or phosphonic acid esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate.); benzoic acid esters (e.g., 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate); amides (e.g., diethyldodecanamide, N-tetradecylpyrrolidone, etc.); alcohols or phenols (e.g., isostearyl alcohol, 2,4-di-tert-amylphenol); aliphatic carboxylic acid esters (e.g., dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate); aniline derivatives (e.g., N,N-dibutyl-2-butoxy-5-tertoctylaniline) and hydrocarbons (e.g., paraffin, dodecylbenzene, diisopropylnaphthalene). One or more of these can be used in combination with at least one compound of the formula (I). The auxiliary solvent that can be used consists of organic solvents having a boiling point of about 30° C. or higher, preferably from about 50° C. to about 160° C. Specific examples thereof are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide. 
     Latex dispersion means and methods and specific examples of latex to be used for impregnation are described in U.S. Pat. No. 4,199,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230, the disclosures of which are incorporated herein by reference. 
     Examples of supports which are suitable for use in the present invention are described in the aforesaid Research Disclosure No. 17643, page 28 and ibid., No, 18716, from page 647, right-hand column to page 648, left-hand column. 
     Preferred silver halide to be contained in the photographic emulsion layers in the photographic light-sensitive materials of the present invention are silver iodobromide, silver iodochloride or silver iodochlorobromide, containing silver iodide in an amount of about 30 mol% or less. An especially preferred silver halide is silver iodobromide containing silver iodide in an amount of from about 2 mol% to about 25 mol%. 
     The silver halide grains in the photographic emulsion may have a regular crystal form such as a cubic, octahedral or tetradecahedral from, or an irregular crystal form such as a spherical or tabular form, or may also have a crystal defect such as twin plane, or may have a composite crystal form comprising the said crystal forms. 
     The silver halide grains may be fine grains having a grain size of about 0.2μ or less or may be large grains having a grain size, as a diameter of the project area, of up to about 10μ. The emulsion may be either a polydispersed emulsion or a monodispersed emulsion. 
     The silver halide photographic emulsions for use in the present invention can be prepared by various methods, for example, those described in Research Disclosure No. 17643 (December, 1978), pages 22-23, &#34;I. Emulsion Preparation and Types&#34;; ibid., No. 18716 (November, 1979), page 648; P. Glafkides, Chemie et Phisique Photographique (published by Paul Montel, 1967); G. F. Duffin, Photographic Emulsion Chemistry (published by Focal Press, 1966) and V. L. Zelikmann et al, Making and Coating Photographic Emulsion (published by Focal Press, 1964). 
     The monodispersed emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Pat. No. 1,413,748 are also preferred. 
     In addition, tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains can easily be prepared by the methods described in Gutoff, Photographic Science and Engineering, Vol. 14, pages 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048 and 4,439,520 and British Pat. No. 2,112,157. 
     The crystal structure of the silver halide grains may be uniform throughout the whole grain, or the inside part and the outside part of the crystal structure may have different halogen compositions. The grain may also have a layered crystal structure. Different silver halide compositions may be joined by epitaxial junction in one grain. In addition, the silver halide grain may have a multiphase junction structure, as joined with other compounds than silver halide, such as silver rhodanide and lead oxide. 
     Further, a mixture comprising grains of various crystal forms can also be used in the present invention. 
     The silver halide emulsions for use in the present invention are generally physically ripened, chemically ripened or spectrally sensitized. Additive for use in such ripening and sensitizing steps are described in Research Disclosure Nos. 17643 and 18716. 
     The color photographic materials of the present invention can be developed by conventional methods such as those described in the aforesaid Research Disclosure No. 17643, pages 28-29 and ibid., No. ;b 18716, page 651, from left to right column. 
     The color photographic materials of the present invention, after development, bleach-fixation or fixation, generally are subjected to either rinsing with water or a stabilization procedure. 
     The rinsing step is generally carried out by countercurrent system using two or more rinsing tanks, for economy of water. As the stabilization process, the multistage countercurrent stabilization described in Japanese Patent Application (OPI) No. 8543/82 is typical, and the process can be performed in place of the water-rinsing step. 
     When the photographic light-sensitive materials of the present invention are black-and-white silver halide photographic materials, these can be developed by the methods described in Research Disclosure, Vol. 176, No. 17643, pages 28 to 29, ibid., Vol. 187, No. 18716, page 651, left and right columns, etc. 
     The photographic light-sensitive materials of the present invention which are color photographic materials include, for example, color negative films, color reversal films, color papers, color reversal papers, color negative films for movies and color positive films for movies. 
     The photographic light-sensitive materials of the present invention which are black-and-white photographic materials include, for example, black-and-white negative photographic materials, X-ray photographic materials, printing photographic materials and black-and-white photographic papers. 
     As mentioned above, the silver halide photographic materials of the present invention are characterized by the excellent solubility and dispersibility of the substantially water-insoluble photographic additives, the excellent long-term storability of the dispersions of said additives and the excellent color-forming property and the latent image storability. 
     These attributes can be attained only by the use for the specific high boiling point organic solvents of the present invention, which are surprinsing and unexpected. 
    
    
     The following examples are intended to illustrate the present invention but to limit it in any way. 
     EXAMPLE 1 
     Various kinds of emulsified dispersions were prepared, whereupon the coupler, the coupler solvent and the ratio of coupler/coupler solvent were varied as shown in Table 1 below. The dispersions were coated onto a polyethylene-coated paper support to form a first layer, and a protective layer was coated thereover as the second layer. Sample Nos. 1 to 27 were obtained. 
     
         ______________________________________First Layer: Green-sensitive Emulsion LayerSilver iodobromide as spectrally sen-                     0.20 g/m.sup.2sitized with green sensitizing dye (*14)                     as Ag(silver iodide 3.5 mol %, grain size 0.9μ)Gelatin                   1.60 g/m.sup.2Magenta coupler (See Table 1)                     0.20 g/m.sup.2Anti-fading agent (*16)   0.20 g/m.sup.2Stain preventing agent (*17)                     0.02 g/m.sup.2Stain preventing agent (*18)                     0.002 g/m.sup.2Coupler solvent (See Table 1)                     See Table 1Second Layer: Protective LayerGelatin                   2.00 g/m.sup.2Gelatin hardener (*26)    0.11 g/m.sup.2______________________________________ 
    
     These samples were exposed in a conventional manner and then processed as follows: 
     
         ______________________________________Processing Steps______________________________________First developement            38° C.                        1 min 15 sec(Black-and-white development)Rinsing with water            38° C.                        1 min 30 secReversal exposure            100 lux or more                        1 sec or moreColor development            38° C.                        2 min 15 secRinsing with water            38° C.                        45 secBleach-fixation  38° C.                        2 min 00 secRinsing with water            38° C.                        2 min 15 sec______________________________________ 
    
     The compositions of the processing solutions used were as follows: 
     
         ______________________________________First Developer______________________________________Nitrilo-N,N,N--trimethylenephosphonic acid                    0.6 gpentasodium saltDiethylenetriaminepentaacetic acid                    4.0 gpentasodium saltPotassium sulfite        30.0 gPotassium thiocyanate    1.2 gPotassium carbonate      35.0 gHydroquinone-monosulfonate                    25.0 gpotassium saltDiethylene glycol         15.0 ml1-Phenyl-4-hydroxymethyl-4-methyl-3-                    2.0 gpyrazolidonePotassium bromide        0.5 gPotassium iodide          5.0 mgWater to make            1 l                    (pH 9.70)______________________________________ 
    
     
                                           TABLE 1__________________________________________________________________________           Coupler/           Coupler                Dispersion Stability                          Latent Image      Coupler           Solvent                Dispers-  StabilitySample No. Coupler      Solvent           (g/g)                ibility                     Stability                          ΔS0.7                                 Remarks__________________________________________________________________________1     C-(53)      O-1  0.5  0.233                     1.11 0.10   Comparison2     &#34;    O-2  &#34;    0.220                     1.10 0.11   &#34;3     &#34;    O-3  &#34;    0.251                     1.13 0.09   &#34;4     &#34;    S-1  &#34;    0.232                     1.10 0.01   Invention5     &#34;    S-2  &#34;    0.235                     1.09 0.02   &#34;6     &#34;    O-4  &#34;    0.309                     1.18 0.12   Comparison7     &#34;    O-5  &#34;    0.301                     1.15 0.11   &#34;8     &#34;    O-6  &#34;    0.332                     1.30 0.10   &#34;9     &#34;    O-7  &#34;    0.325                     1.25 0.09   &#34;10    C-(9)      O-1  &#34;    0.350                     1.21 0.15   &#34;11    &#34;    O-2  &#34;    0.347                     1.20 0.16   &#34;12    &#34;    O-3  &#34;    0.340                     1.25 0.14   &#34;13    &#34;    S-1  &#34;    0.349                     1.21 0.03   Invention14    &#34;    S-2  &#34;    0.350                     1.22 0.03   &#34;15    &#34;    O-4  &#34;    0.363                     1.28 0.13   Comparison16    &#34;    O-5  &#34;    0.360                     1.26 0.14   &#34;17    C-(9)      O-6  0.5  0.380                     1.31 0.13   Comparison18    &#34;    O-7  &#34;    0.378                     1.30 0.13   &#34;19    &#34;    O-1  1.0  0.253                     1.13 0.09   &#34;20    &#34;    O-2  &#34;    0.251                     1.13 0.09   &#34;21    &#34;    O-3  &#34;    0.280                     1.18 0.08   &#34;22    &#34;    S-1  &#34;    0.290                     1.15 0.00   Invention23    &#34;    S-2  &#34;    0.289                     1.16 0.00   &#34;24    &#34;    O-4  &#34;    0.298                     1.20 0.08   Comparison25    &#34;    O-5  &#34;    0.290                     1.19 0.08   &#34;26    &#34;    O-6  &#34;    0.306                     1.24 0.07   &#34;27    &#34;    O-7  &#34;    0.298                     1.22 0.08__________________________________________________________________________ 
    
     The latent image storability and the dispersion stability of the samples were tested as mentioned below. 
     (1) Dispersion Stability: 
     The dispersion was stored at 40° C. for 72 hours, and the turbidity (D 500 ) of the fresh sample (immediately after emulsification) and that of the aged sample (after 72 hrs. storage) were measured by a spectrophotometer. The dispersability and stability were calculated by the following formulae. 
     Dispersibility=Turbidity of fresh sample immediately after emulsified ##EQU1## (2) Latent Image Storability: 
     The sensitivity difference between the two samples wherein after exposure, one sample was stored under the conditions of 35° C. and 65% RH for 10 days or another sample was stored in a freezer was observed. 
     ΔS 0 .7 =(sensitivity at density 0.7 of the sample stored in freezer)-(sensitivity at density 0.7 of the sample stored under 35° C., 65% RH, for 10 days) ##STR5## 
     The results of Table 1 indicate that the organic solvents of the formula (I) exhibit excellent dispersibility properties as the turbidity of the fresh samples (immediately after emulsified) was low and also exhibit excellent dispersion stability as the variation of the turbidity in the aged samples was also small. 
     In addition, the latent image storability of the samples formed using the organic solvents of the formula (I) was also excellent. 
     EXAMPLE 2 
     A twelve-layered color photographic material was prepared, on a paper support, both surfaces of which were coated with polyethylene. The polyethylene on the side of the first layer contained titanium white as white pigment and a slight amount of ultramarine as a bluish dye. 
     The compositions of the layers were as follows. 
     
         __________________________________________________________________________First Layer: Gelatin LayerGelatin                           1.30                                g/m.sup.2Second Layer: Antihalation LayerBlack colloidal silver            0.10                                g/m.sup.2                                as AgGelatin                           0.70                                g/m.sup.2Third Layer: Low Sensitive Red-sensitive Emulsion LayerSilver iodobromide spectrally sensitized                             0.15                                g/m.sup.2with red sensitizing dyes (*1/*2 = 1/2                                as Agby weight)(silver iodide 5.0 mol %, meangrain size 0.4μ)Gelatin                           1.00                                g/m.sup.2Cyan coupler (*3)                 0.14                                g/m.sup.2Cyan coupler (*4)                 0.07                                g/m.sup.2Anti-fading agents                0.10                                g/m.sup.2(*5/*6/*7 = 1/2/2.5 by weight)Coupler solvents                  0.06                                g/m.sup.2(*8/*9 = 2/1 by weight)Fourth Layer: High Sensitive Red-sensitive Emulsion LayerSilver iodobromide emulsion spectrally                             0.15                                g/m.sup.2sensitized with red sensitizing dyes as Ag(*1/*2 = 1/2 by weight) (silver iodide6.0 mol %, meangrain size 0.7μ)Gelatin                           1.00                                g/m.sup.2Cyan coupler (*3)                 0.20                                g/m.sup.2Cyan coupler (*4)                 0.10                                g/m.sup.2Anti-fading agents                0.15                                g/m.sup.2(*5/*6/*7 = 1/2/2.5 by weight)Coupler solvents (*8/*9 = 2/1 by weight)                             0.10                                g/m.sup.2Fifth Layer: InterlayerBlack colloidal silver            0.02                                g/m.sup.2                                as AgGelatin                           1.00                                g/m.sup.2Color mixing preventing agent (*10)                             0.08                                g/m.sup.2Color mixing preventing agent solvents                             0.16                                g/m.sup.2(*11/*12 = 1/1 by weight)Polymer latex (*13)               0.10                                g/m.sup.2Sixth Layer: Low Sensitive Green-sensitive Emulsion LayerSilver iodobromide emulsion spectrally                             0.10                                g/m.sup.2sensitized with green sensitizing dye                                as Ag(*14) (silver iodide 2.5 mol %, grainsize 0.4μ)Gelatin                           0.80                                g/m.sup.2Magenta coupler (*15)             0.10                                g/m.sup.2Anti-fading agent (*16)           0.10                                g/m.sup.2Stain preventing agent (*17)      0.01                                g/m.sup.2Stain preventing agent (*18)      0.001                                g/m.sup.2Coupler solvent                   0.15                                g/m.sup.2(*11/*19 = 1/1 by weight)Seventh Layer: High Sensitive Green-sensitive Emulsion LayerSilver iodobromide emulsion spectrally                             0.10                                g/m.sup.2sensitized with green sensitizing dye                                as Ag(*14) (silver iodide 3.5 mol %, grainsize 0.9μ)Gelatin                           0.80                                g/m.sup.2Magenta coupler (*15)             0.10                                g/m.sup.2Anti-fading agent (*16)           0.10                                g/m.sup.2Stain preventing agent (*17)      0.01                                g/m.sup.2Stain preventing agent (*18)      0.001                                g/m.sup.2Coupler solvents                  0.15                                g/m.sup.2(*11/*19 = 1/1 by weight)Eighth Layer: Yellow Filter LayerYellow colloidal silver           0.20                                g/m.sup.2                                as AgGelatin                           1.00                                g/m.sup.2Color mixing preventing agent (*10)                             0.06                                g/m.sup.2Color mixing preventing agent solvent                             0.15                                g/m.sup.2(*11/*12 = 1/1 by weight)Polymer latex (*13)               0.10                                g/m.sup.2Ninth Layer: Low Sensitive Blue-sensitive Emulsion LayerSilver iodobromide emulsion spectrally                             0.15                                g/m.sup.2sensitized with blue sensitizing dye (*20)                                as Ag(silver iodide 2.5 mol %, grain size 0.5μ)Gelatin                           0.50                                g/m.sup.2Yellow coupler (*21)              0.20                                g/m.sup.2Stain preventing agent (*18)      0.001                                g/m.sup.2Coupler solvent (*9)              0.05                                g/m.sup.2Tenth Layer: High Sensitive Blue-sensitive Emulsion LayerSilver iodobromide emulsion spectrally                             0.25                                g/m.sup.2sensitized with blue sensitizing dye (*20)                                as Ag(silver iodide 2.5 mol %, grain size 1.2μ)Gelatin                           1.00                                g/m.sup.2Yellow coupler (*21)              0.40                                g/m.sup.2Stain preventing agent (*18)      0.002                                g/m.sup.2Coupler solvent (*9)              0.10                                g/m.sup.2Eleventh Layer: Ultraviolet Absorbing LayerGelatin                           1.50                                g/m.sup.2Ultraviolet absorbents            1.00                                g/m.sup.2(*22/*6/*7 = 1/0.2/1 by weight)Color mixing preventing agent (*23)                             0.06                                g/m.sup.2Color mixing preventing agent solvent (*9)                             0.15                                g/m.sup.2Anti-irradiation dye (*24)        0.02                                g/m.sup.2Anti-irradiation dye (*25)        0.02                                g/m.sup.2Twelfth Layer: Protective LayerSilver chlorobromide fine grains  0.07                                g/m.sup. 2(silver chloride 97 mol %, mean grain                                as Agsize 0.2μ)Gelatin                           1.50                                g/m.sup.2Gelatin hardener (*26)            0.17                                g/m.sup.2__________________________________________________________________________ (*1) 5,5Dichloro-3,3di(3-sulfobutyl)-9-ethylthiacarbocyanine Nasalt (*2) Triethylammonium3-[2{2[3(3-sulfopropyl)-naphtho(1,2-d)-thiazolin-2-indeneethyl1-butyl3-naphtho(1,2-d)-thiazolino]propane sulfonate (*3) 2[(2,4-di-t-Amylphenoxy)hexanamido4,6-dichloro-5-ethylphenol (*4) 2[2Chlorobenzamido4-chloro-5-[(2-chloro-4-t-amylphenoxy)octanamido]phenol (*5) 2(2-Hydroxy-3-sec-5-t-butylphenyl)benzotriazole (*6) 2(2-Hydroxy-5-t-butylphenyl)benzotriazole (*7) 2(2-Hydroxy-3,5-di-t-butylphenyl)-6-chlorobenzotriazole (*8) Di(2ethylhexyl) phthalate (*9) Trinonyl phosphate (*10) 2,5Di-t-octylhydroquinone (*11) Tricresyl phosphate (*12) Dibutyl phthalate (*13) Polyethyl acrylate (*14) 5,5Diphenyl-9-ethyl-3,3disulfopropyloxacarbocyanine Nasalt (*15) 7Chloro-6-methyl-2-[2{2octyloxy-5-(2-octyloxy-5-t-octylbenzene-sulfonamid)benzenesulfonamido1-methylethyl1Hpyrazolo[1,5b][1,2,4]triazole (*16) 3,3,3&#39;,3Tetramethyl-5,6,5&#39;,6tetrapropoxy-1,1bisspiroindane (*17) 3(2-Ethylhexyloxycarbonyloxy)-1-(3-hexadecyloxyphenyl)-2-pyrazoline (*18) 2Methyl-5-t-octylhydroquinone (*19) Trioctyl phosphate (*20) Triethylammonium 3[2(3-benzylrhodanin-5-ylidene)-3-benzoxazolinyl]propane sulfonate (*21) Pivaloyl-[(2,4dioxo-1-benzyl-5-ethoxyhydantoin-3-yl)-2-chloro-5-(2,4-di-tamylphenoxy)nutanamido]acetanilide (*22) 5Chloro-2-(2-hydroxy-3-t-butyl-5-t-octyl)phenylbenzotriazole (*23) 2,5Di-sec-octylhydroquinone ##STR6## ##STR7##? (*26) 1,2Bis(vinylsulfonylacetamido)ethane 
    
     The sample thus prepared was designated as Sample No. 101. 
     Next, sample Nos. 102 to 110 were prepared in the same manner as the preparation of the Sample No. 101, except that the coupler solvents and the color mixing preventing agent solvents in the third to eleventh layers were varied as shown in Table 2 below. 
     These samples were exposed in a conventional manner and then processed in the same manner as Example 1. The latent image storability was ested for each sample. The results obtained are shown in Table 2. 
     The results of Table 2 indicate that the organic solvents of the formula (I) impart excellent latent image storability to the photographic material. 
     
                       TABLE 2______________________________________          Latent Image Storability                BL     GL   RLSample No.   Organic Solvent                S.sub.0.7                       S.sub.0.7                            S.sub.0.7                                 Remarks______________________________________101     --           0.04   0.04 0.04 Comparison102     O-1          0.06   0.07 0.07 &#34;103     O-2          0.05   0.04 0.05 &#34;104     O-3          0.03   0.03 0.04 &#34;105     S-1          0.00   0.00 0.00 Invention106     S-2          0.00   0.00 0.00 &#34;107     O-4          0.03   0.04 0.03 Comparison108     O-5          0.03   0.03 0.03 &#34;109     O-6          0.02   0.02 0.03 &#34;110     O-7          0.03   0.02 0.03 &#34;______________________________________ 
    
     EXAMPLE 3 
     A multilayered photographic paper (Sample No. 201) was prepared by forming the layers having the compositions shown below on a paper support, both surfaces of which were coated with polyethylene. The coating compositions for the layers were prepared as follows. 
     Coating Composition for First Layer: 
     27.2 cc of ethyl acetate and 7.7 cc (8.0 g) of High Boiling Point Solvent (Solv-1) were added to Yellow Coupler (C-58) (10.2 g), Yellow Coupler (C-59) (9.1 g) and 4.4 g of Color Image Stabilizer (Cpd-1) and dissolved, and the resulting solution was dispersed by emulsification in 185 cc of an aqueous 10 wt% gelatin solution containing 8 cc of a 10 wt% sodium dodecylbenzenesulfonate solution. The emulsified dispersion thus prepared was blended and dissolved in Emulsions EM1 and EM2 mentioned below, whereupon the gelatin concentration was adjusted as shown below, to provide the coating composition for the first layer. Coating compositions for the second layer to the seventh layer were prepared in the same manner as in the first layer. As a gelatin hardening agent for each layer, 1-hydroxy-3,5-dichloro-s-triazine sodium salt was used. 
     The compositions of the layers were as follows. 
     
         ______________________________________Support:Polyethylene-coated Paper, containing white pigment(TiO.sub.2) and blueish dye in the polyethylene on the sideof the first layer.First Layer: Blue sensitive Emulsion LayerMonodispersed silver chlorobromide                       0.13 g/m.sup.2emulsion (EM1) spectrally sensitized with                       as Agsensitizing dye (ExS-1)Monodispersed silver chlorobromide                       0.13 g/m.sup.2emulsion (EM2) spectrally sensitized with                       as Agsensitizing dye (ExS-1)Gelatin                     1.86 g/m.sup.2Yellow coupler (C-58)       0.44 g/m.sup.2Yellow coupler (C-59)       0.39 g/m.sup.2Coupler image stabilizer (Cpd-1)                       0.19 g/m.sup.2Solvent (Solv-1)            0.35 g/m.sup.2Second Layer: Color Mixing Preventing LayerGelatin                     0.99 g/m.sup.2Color mixing preventing agent (Cpd-2)                       0.08 g/m.sup.2Third Layer: Green-sensitive Emulsion LayerMonodispersed silver chlorobromide                       0.05 g/m.sup.2emulsion (EM3) spectrally sensitized with                       as Agsensitizing dyes(ExS-2/ExS-3 = 1:0.2 by weight)Monodispersed silver chlorobromide                       0.11 g/m.sup.2emulsion (EM4) spectrally sensitized with                       as Agsensitizing dyes(ExS-2/ExS-3 = 1:0.2 by weight)Gelatin                     1.80 g/m.sup.2Magenta coupler (C-9)       0.38 g/m.sup.2Color image stabilizer (Cpd-3)                       0.20 g/m.sup.2Solvent (Solv-2)            0.12 g/m.sup.2Solvent (Solv-3)            0.25 g/m.sup.2Fourth Layer: Ultraviolet Absorbing LayerGelatin                     1.60 g/m.sup.2Ultraviolet absorbents      0.70 g/m.sup.2(Cpd-4/Cpd-5/Cpd-6 = 3/2/6 by weight)Color mixing preventing agent (Cpd-7)                       0.05 g/m.sup.2Solvent (Solv-4)            0.27 g/m.sup.2Fifth Layer: Red-sensitive Emulsion LayerMonodispersed silver chlorobromide                       0.07 g/m.sup.2emulsion (EM5) spectrally sensitized                       as Agwith sensitizing dyes(ExS-4/ExS-5 = 1/50 by weight)Monodispersed silver chlorobromide                       0.16 g/m.sup.2emulsion (EM6) spectrally sensitized                       as Agwith sensitizing dyes(ExS-4/ExS-5 = 1/50 by weight)Gelatin                     0.92 g/m.sup.2Cyan coupler (C-49)         0.32 g/m.sup.2Color image stabilizers     0.17 g/m.sup.2(Cpd-5/Cpd-6/Cpd-8 = 3/4/2 by weight)Polymer for dispersion (Cpd-9)                       0.28 g/m.sup.2Solvent (Solv-2)            0.20 g/m.sup.2Sixth Layer: Ultraviolet Absorbing LayerGelatin                     0.54 g/m.sup.2Ultraviolet absorbents      0.21 g/m.sup.2(Cpd-4/Cpd-6/Cpd-8 = 1/5/3 by weight)Solvent (Solv-2)            0.08 g/m.sup.2Seventh Layer: Protective LayerGelatin                     1.33 g/m.sup.2Acryl-modified copolymer of polyvinyl                       0.17 g/m.sup.2alcohol (modification degree 17 mol %)Liquid paraffin             0.03 g/m.sup.2______________________________________ 
    
     (Cpd-10) and (Cpd-11) were used as anti-irradiation dyes. Alkanol XC (by E. I. Du Pont de Nemours and Company), sodium alkylbenzenesulfonate, succinic acid ester and Magefacx F-120 (by DAI NIPPON INK &amp; CHEMICALS, Inc.) were used as emulsification and dispersing agent and coating assistant in each layer. (Cpd-12) and (Cpd-13) were used as silver halide stabilizers. The silver emulsions used in Example 3 are as follows. 
     
         ______________________________________            Grain   Shape of Size      Br Content                              FluctuationEmulsion   Grain    (μ)    (mol %) Coefficient______________________________________EM1     Cubic    1.0       80      0.08EM2     Cubic     0.75     80      0.07EM3     Cubic    0.5       83      0.09EM4     Cubic    0.4       83      0.10EM5     Cubic    0.5       73      0.09EM6     Cubic    0.4       73      0.10______________________________________ 
    
     The compounds used in Example 3 are mentioned below. ##STR8## Solv-1: Dibutyl Phthalate Solv-2: Tricresyl Phosphate 
     Solv-3: Trioctyl Phosphate 
     Solv-4: Trinonyl Phosphate 
     Samples Nos. 202 to 208 were prepared in the same manner as the preparation of the Sample 201, except that the couplers and/or the high boiling point solvents in the Sample 201 were replaced by others as shown in Table 3 below. 
     
                                           TABLE 3__________________________________________________________________________    1st Layer 3rd Layer 4th Layer                              5th Layer 6th Layer    Coupler         Solvent              Coupler                   Solvent                        Solvent                              Coupler                                   Solvent                                        Solvent__________________________________________________________________________201 (Comparison)    C-(58)         Solv-1              C-(9)                   Solv-2                        Solv-4                              C-(49)                                   Solv-2                                        Solve-2    C-(59)         Solv-3202 (Invention)    C-(58)         S-1  C-(9)                   S-1  Solv-4                              C-(49)                                   S-1  Solv-2    C-(59)203 (Comparison)    C-(57)         O-2  C-(52)                   O-2  O-2   C-(39)                                   O-2  O-2204 (Invention)    C-(57)         S-2  C-(52)                   S-2  S-2   C-(39)                                   S-2  S-2205 (Comparison)    C-(59)         Solv-1              C-(51)                   Solv-2                        Solv-4                              C-(50)                                   Solv-2                                        Solv-2206 (Invention)         S-1       S-2  Solv-4     S-1  Solv-2207 (Comparison)    C-(58)         O-3  C-(9)                   O-3  O-3   C-(49)                                   O-3  O-3    C-(59)    C-(27)          C-(47)208 (Invention)    C-(58)         S-1  C-(9)                   S-1  S-1   C-(49)                                   S-1  S-1    C-(59)    C-(27)          C-(47)__________________________________________________________________________ 
    
     The latent image storability of each of the thus prepared samples was tested in the same manner as in Example 1. (After exposure, the samples were developed as mentioned below.) 
     The latent image storability of the samples of the present invention was found superior to that of the comparative samples. 
     The development process was as follows: 
     The samples exposed were processed by running development with Fuji Color Paper Processor FPRP 115, under the conditions mentioned below. 
     
         ______________________________________                        Amount ofProcessing    Tempera-            Replenisher                                TankStep     ture     Time       (*)     Capacity______________________________________Color    37° C.             3 min 30 sec                        200 ml  60 litersdevelopmentBleach-fixation    33° C.             1 min 30 sec                         55 ml  40 litersRinsing (1)    24-34° C.             1 min      --      20 litersin waterRinsing (2)    24-34° C.             1 min      --      20 litersin waterRinsing (3)    24-24° C.             1 min      10 liters                                20 litersin waterDrying   70-80° C.             1 min______________________________________ (*)This means the amount per m2 of the photographic material as being processed. The rinsing was carried out by three tank cascade system from the tank (3) to the tank (1). 
    
     The compositions of the processing solutions used are as follow. 
     
         ______________________________________                 TankColor Developer       Solution Replenisher______________________________________Water                 800 ml   800 mlDiethylenetriaminepentaacetic acid                 1.0 g    1.0 gNitrilo-triacetic acid                 2.0 g    2.0 gBenzyl alcohol        15 ml    23 mlDiethylene glycol     10 ml    10 mlSodium sulfite        2.0 g    3.0 gPotassium bromide     1.2 g    --Potassium carbonate   30 g     25 gN--ethyl-N--(β-methanesulfonamido-                 5.0 g    9.0 gethyl)-3-methyl-4-aminoanilinesulfateHydroxylamine sulfate 3.0 g    4.5 gFluorescent brightening agent                 1.0 g    2.0 g(WHITEX 4B of Sumitomo ChemicalCo., Ltd.)Water to make         1000 ml  1000 mlpH (at 25° C.) 10.20    10.80______________________________________                 TankBleach-fixing Solution                 Solution Replenisher______________________________________Water                 400 ml   400 mlAmmonium thiosulfate (70 wt %)                 150 ml   300 mlSodium sulfite        13 g     26 gAmmonium ethylenediaminetetraacetato                 55 g     110 gferrateEthylenediaminetetraacetic acid                 5 g      10 gdisodiumWater to make         1000 ml  1000 mlpH (at 25° C.) 6.70     6.30______________________________________ 
    
     EXAMPLE 4 
     The samples 201 to 208 of Example 3 were processed in accordance with the processing procedure as mentioned below, and the latent image storability of each of the Samples thus processed was tested in the same manner as Example 3. 
     As a result, an especially preferred result was obtained by the process of Example 4 where no benzyl alcohol was used. 
     
         ______________________________________Processing Step  Temperature                       Time______________________________________Color Development            35° C.                       45 secBleach-fixation  30-35° C.                       45 secRinsing (1) in Water            30-35° C.                       20 secRinsing (2) in Water            30-35° C.                       20 secRinsing (3) in Water            30-35° C.                       20 secRinsing (4) in Water            30-35° C.                       30 secDrying           70-80° C.                       60 sec______________________________________ 
    
     The compositions of the processing solutions used are as follows: 
     
         ______________________________________Color DeveloperWater                     800    mlEthylenediamine-N,N,N&#39;,N&#39;--tetra-                     1.5    gmethylene-phosphonic acidGlutamic acid             6.0    gSodium chloride           l.4    gPotassium carbonate       25     gN--ethyl-N--(β-methanesulfonamidoethyl)-                     5.0    g3-methyl-4-aminoaniline sulfateN,N--diethylhydroxylamine 4.2    gFluorescent brightening agent                     2.0    g(4,4&#39;-diaminostilbene)Water to make             1000   mlpH (at 25° C.)     l0.10Bleach-fixing SolutionWater                     400    mlAmmonium thiosulfate (70 wt %)                     100    mlSodium sulfite            18     gAmmonium ethylenediaminetetraacetato                     55     gferrateEthylenediaminetetraacetic acid                     3      gdisodiumAmmonium bromide          40     gGlacial acetic acid       8      gWater to make             1000   mlpH (at 25° C.)     5.5Rinsing SolutionIon Exchanged Water (Ca-content andMg-content each were 3 ppm or less.)______________________________________ 
    
     While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.