Abstract:
A method for preparing silver halide emulsion which comprises silver halide grains containing an average iodide content of not more than 2 mol % comprising the steps of (i) preparing a seed emulsion containing silver halide seed grains, (ii) introducing the seed emulsion into a reaction vessel containing a hydrophilic colloid solution and (iii) introducing into the reaction vessel a silver salt and a halide salt to grow the silver halide grains from the seed grains, wherein in the step (iii), an emulsion containing silver iodide fine grains previously formed is supplied into the reaction vessel as a source of silver iodide; said seed grains are contained in an amount of 0.5 to 5.0% by volume in the hydrophilic colloid solution in the reaction vessel prior to introduction of silver and halide salts.

Description:
FIELD OF THE INVENTION 
     The present invention relates to a method of producing a silver halide photographic emulsion, more specifically a method of producing a silver halide photographic emulsion of low fogging and high sensitivity showing improved storage stability under high-temperature, high-humidity conditions. 
     BACKGROUND OF THE INVENTION 
     In recent years, there has been increased consumption of silver halide photographic light-sensitive materials. Accordingly, the number of silver halide photographic light-sensitive material films processed has increased; there is a need for more rapid processing, i.e., increased processing-capacity per unit time period. 
     This trend is seen in all fields of light-sensitive materials. In the field of medical X-ray light-sensitive materials, for example, the rapid increase in medical examinations and testing parameters is increasing the number of X-ray photographs taken, while the diagnostic results must be informed for the subject as soon as possible. To meet this requirement, rapid processing is required. In angiographic picture taking and perioperative picture taking, in particular, it is necessary to obtain the picture in minimum time. 
     To meet the above demand from the medical field, it is necessary to more rapidly process X-ray films, as well as to promote diagnostic automation (picture taking, film transport, etc.). 
     Ultrarapid processing, however, can pose a problem of image quality deterioration because it is often performed under high-pH, high-temperature (30° to 40° C.) conditions. 
     To meet the above demand for rapid processing and high image quality, tabular silver halide grains have recently been used. With high specific surface area, tabular silver halide grains are unique in that they can adsorb large amounts of sensitizing dyes and can therefore have improved spectral sensitivity, that they significantly reduce crossover light as in X-ray light-sensitive materials, and that images of high resolution with little light scattering are obtained. The use of such tabular grains is expected to offer silver halide photographic light-sensitive materials of high sensitivity and high image quality. Investigations by the present inventors showed, however, that tabular grains have a major drawback that their storage stability under high-temperature, high-humidity conditions is poor so that they are liable to be fogged and desensitized. 
     SUMMARY OF THE INVENTION 
     The object of the present invention is to provide a method of producing a silver halide photographic emulsion having low fog and high sensitivity and showing improved storage stability under high-temperature, high-humidity conditions, 
     The above object of the present invention is accomplished by a method of producing a silver halide photographic emulsion having an average silver iodide content of not more than 2.0 mol %, wherein said emulsion is subjected to a grain growing process in which fine silver iodide grains are supplied to a hydrophilic colloid solution containing previously prepared silver halide seed grains, and wherein the seed grain concentration by volume in the hydrophilic colloid solution containing seed grains, in the reaction vessel, is not less than 0.5% and not more than 5%. 
     In a preferred embodiment of the present invention, the above silver halide emulsion comprises monodispersed twin crystal silver halide grains each having a core consisting of a silver iodobromide having a silver iodide content of not less than 10 mol %, and a shell consisting of a silver iodobromide having a silver iodide content of not more than 7 mol %. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The present invention is hereinafter described in detail. 
     Silver halide grains are usually produced and used in the form of a silver halide emulsion containing them. The silver halide grains used for the present invention may have any shape, whether spherical or tabular, for instance. Preferably, the silver halide grains are monodispersed twin crystal grains wherein at least 50% of the total projected area is occupied by monodispersed twin crystal grains having a thickness of less than 0.3 μm and a grain diameter/thickness ratio of not less than 2:1, more preferably those having a thickness of less than 0.2 μm and a grain diameter/thickness ratio of 5:1 to 8:1 account for at least 50% of the total projected area. 
     In the present invention, grain size is defined as the diameter of a circle converted from a projected image of the grain of the same area. Grain thickness is defined as the distance between two mutually facing principal planes of a tabular grain. The projected area of grains can be obtained by summing the areas of grains thus obtained. The projected area of each grain for determination of total projected area and grain diameter can be obtained by measuring the diameter of the grain or the projected area of a circle on an electron micrograph of a silver halide crystal sample spread over the sample stage to the extent that no grain overlapping occurs, taken at x 10000 to 50000 magnification; the number of subject grains should not be less than 1000 randomly. 
     Grain thickness can be determined by obliquely observing the sample using an electron microscope. 
     A highly monodispersed emulsion preferred for the present invention has a distribution width of not more than 30%, more preferably not more than 20%, as defined by the equation: 
     
         (Grain size standard deviation/average grain size)×100=distribution width or coefficient of variation (%) 
    
     Here, grain size is determined by the method described above, and average grain size is obtained as an arithmetic mean. 
     
         Average grain size=Σdini/Σni 
    
     In the present invention, a twin crystal grain is defined as a silver halide crystal grain having one or more twin planes. The morphological classification of twin crystals is described in detail by Klein and Meuzer (Photographishe Korrespondenz, Vol. 99, p. 99; ibid., Vol. 100, p. 57). The two or more twin planes of the twin crystal may be mutually parallel or not. Although a twin plane may be directly observed using an electron microscope, it may be observed on a cross-section of an ultrathin sectional sample of resin-dispersed, fixed silver halide. 
     The above-described silver halide grains constituting the silver halide emulsion relating to the present invention mainly comprise twin crystal grains having two or more parallel twin planes, preferably even number of twin planes, more preferably two twin planes. 
     In the present invention, &#34;to mainly comprise twin crystal grains having two or more parallel twin planes&#34; means that the percent ratio by number of twin crystal grains having two or more parallel twin planes is not less than 50%, preferably not less than 60%, and more preferably not less than 70%. 
     A monodispersed twin crystal in the present invention has a grain size distribution width of not more than 30%, preferably not more than 20%. 
     The silver halide composition of the silver halide emulsion of the present invention may be silver iodobromide or silver iodochlorobromide containing not more than 2.0 mol %, preferably 2.0 to 0.05 mol % of silver iodide. 
     Concerning the halogen distribution within the grain, the halogen composition may be uniform or different between the inner and outer portion, and may be of a layer structure (core/shell structure). A more preferable structure comprises an inner phase consisting of a silver iodobromide having a silver iodide content of not less than 10 mol % and an outer phase consisting of a silver iodobromide having a silver iodide content of not more than 7 mol %. 
     The silver halide emulsion of the present invention is formed by growing grains using a previously formed silver halide emulsion as a seed emulsion. Although a silver halide photographic emulsion of the present invention can be prepared by any one of the acidic method, the neutral method, the ammoniacal method and other methods, the double jet method is used to react a soluble silver salt and a soluble halogen salt. As a modification of the double jet method, the controlled double jet method can be used, in which the pAg of the liquid phase where silver halide is formed is kept constant. This method makes it possible to prepare a silver halide emulsion containing grains having regular crystal shape and nearly uniform grain size distribution. 
     In the present invention, the seed grain concentration by volume in the hydrophilic colloid solution containing seed grains, previously contained in the reaction vessel is not less than 0.5% and not more than 5%, preferably not less than 1.0% and not more than 3%, as silver halide. 
     Here, the seed grain concentration is defined by the following equation: 
     
         Seed grain concentration (%)=[total volume (ml) of silver halide seed grains×100]/[volume (ml) of hydrophilic colloid solution in reaction vessel] 
    
     where the total volume of seed grains is defined as the product of an average volume of the seed grains and total number thereof. 
     An average grain size of the seed grains is 0.3 μm or less in a sphere-equivalent diameter, and preferably, 0.1 to 0.25 μm, wherein the sphere-equivalent diameter is referred to as the average diameter when the volume of the seed grain is converted into a sphere having an equivalent volume. 
     The fine silver iodide grains of the present invention (hereinafter referred to as fine grains) are hereinafter described. Although preferable fine grain size varies depending on the size and halogen composition of the host silver halide grains because fine grain size affects the rate of iodide ion supply, fine grains having an average sphere-equivalent diameter of not more than 0.3 μm, more preferably not more than 0.1 μm are used. For precipitating silver halide on host grains by recrystallization of fine grains, it is preferable that the fine grain size be smaller than the sphere-equivalent diameter of the host grains, more preferably smaller than one-tenth of the sphere-equivalent diameter. The halogen composition of the fine grains has a silver iodide content of not less than 95 mol %, preferably 100 mol %. 
     The silver halide emulsion relating to the present invention incorporates various hydrophilic colloids for silver halide enclosure as binders. For this purpose, gelatin and other photographic binders such as synthetic polymers, e.g., polyvinyl alcohol and polyacrylamide, and colloidal albumin, polysaccharides and cellulose derivatives may be used. 
     The silver halide emulsion used in the present invention may be treated by an appropriate method of removing soluble salt to obtain a Ag ion concentration suitable for chemical sensitization. Available methods include those described in Research Disclosure No. 17643 (December 1978), such as the flocculation method and the noodle washing method. Preferable washing methods include the method described in Japanese Patent Examined Publication No. 16086/1960, which uses an aromatic hydrocarbon aldehyde resin containing sulfonic acid, and the method described in Japanese Patent Publication Open to Public Inspection No. 158644/1988, which uses example compounds G-3 and G-8 and other polymeric flocculants. 
     The photographic light-sensitive material incorporating the silver halide photographic emulsion of the present invention may incorporate various photographic additives added before or after physical or chemical ripening of the emulsion. 
     Examples of such photographic additives include the compounds described in Research Disclosure (hereinafter referred to as RD) Nos. 17643, 18716 (November 1979) and 308119 (December 1989). The compounds and portions where they are described are given below. 
     
         __________________________________________________________________________      RD-17643              RD-18716  RD-308119Additive   Page          Section              Page  Section                        Page  Section__________________________________________________________________________Chemical   23      648 upper 996sensitizer         rightSensitizing dye      23      648-649   996-998Desensitizing dye      23                998   BDye        25-26   649-650   1003Developing 29  XXI 648 upperaccelerator        rightAntifoggant agent and      24      649 upper 1006-1007stabilizer         rightBrightening agent      24                998Hardener   26      651 left  1004-1005Surfactant 26-27          XI  650 right 1005-1006                              XIPlasticizer      27  XXI 650 right 1006  XXILubricant  27  XXIMatting agent      28  XVI 650 right 1008-1009                              XVIBinder     26  XXII          1003-1004Support    28  XVII          1009  XVII__________________________________________________________________________ 
    
     Examples of supports which can be used in the silver halide photographic light-sensitive material of the present invention include those specified on the above-mentioned Research Disclosures. Appropriate supports are plastic films etc., whose surface may be subbed or treated by corona discharge or ultraviolet irradiation to enhance coating layer adhesion. 
     The light-sensitive material of the present invention may be processed with processing solutions such as those described on pages 29-30, XX-XXI, RD-17643 above and pages 1011-1012, XX-XXI, RD-308119 above. 
     As developing agents for black-and-white photographic processing, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, aminophenols such as N-methyl-aminophenol and others may be used singly or in combination. The developer of the present invention may incorporate as necessary known additives such as preservatives, alkalis, pH buffers, antifoggants, hardeners, developing accelerators, surfactants, antifoaming agents, toning agents, hard water softening agents, dissolution aids and thickener. 
     The fixer may incorporate a fixing agent such as a thiosulfate or thiocyanate, and may also contain a water-soluble aluminum salt as a hardener, such as aluminum sulfate or potassium alum. Preservatives, pH regulators, hard water softening agents and other additives may also be incorporated in the fixer. 
     EXAMPLES 
     The present invention is hereinafter described in more detail by means of the following examples, but the invention is not by any means limited by them. 
     Example 1 
     Preparation of seed emulsion 
     A hexagonal tabular seed grain emulsion was prepared as follows: 
     
         __________________________________________________________________________Solution AOssein gelatin                  60.2                               gDistilled water                 20.0                               l10% methanol solution of        5.6 mlHO(CH.sub.2 CH.sub.2 O).sub.n --[(CH(CH.sub.3)CH.sub.2 O].sub.m --(CH.sub.2 CH.sub.2 O).sub.n --H.sub.n+m=5.7KBr                             26.8                               g10% H.sub.2 SO.sub.4            144 mlSolution B2.5 N aqueous AgNO.sub.3 solution                           3500                               mlSolution CKBr                             1029                               gKI 29.3 gWater was added to make a total quantity of 3500 ml.Solution D1.75 N aqueous KBr solution     Amount required to                           obtain the silver                           potential shown                           below.__________________________________________________________________________ 
    
     Using the mixer stirrer described in Japanese Patent Examined Publication Nos. 58288/1983 and 58289/1983, solutions B and C, each 64.1 ml, were added to solution A at 35° C. by the double jet method over a period of 2 minutes to form nuclei. 
     After stopping the addition of solutions B and C, the temperature of solution A was increased to 60° C. over a period of 60 minutes, and solutions B and C were again added by the double jet method at a flow rate of each 68.5 ml/min over a period of 50 minutes, while keeping the silver electrode potential (determined using a silver ion selective electrode in combination with a saturated silver-silver chloride electrode as a reference electrode) at +6 mV using solution D. After completion of the addition, 3% KOH was added to obtain a pH of 6, followed by immediate desalinization and washing. The resulting emulsion was designated as seed emulsion EM-0. Electron microscopy revealed that this emulsion comprised hexagonal tabular silver halide grains not less than 90% by projected area of which had a maximum adjacent edge ratio of 1.0 to 2.0 and which tabular grains had an average thickness of 0.07 μm and an average diameter of 0.5 μm in circle-equivalent diameter and 0.24  μm in sphere-equivalent diameter. Preparation of fine silver iodide grain emulsion 
     A fine silver iodide grain emulsion was prepared as follows: 
     
         ______________________________________  Solution A  Ossein gelatin           100 g  KI 8.5 gDistilled water was added to make a total quantity of 2000 ml.  Solution B  AgNO.sub.3           360 gDistilled water was added to make a total quantity of 605 ml.  Solution C  KI       352 gDistilled water was added to make a total quantity of 605______________________________________ml. 
    
     While stirring solution A at 40° C. in the reaction vessel, solutions B and C were added at constant rate by the double jet precipitation method over a period of 30 minutes. 
     During the addition, pAg was kept at 13.5 by a conventional means of pAg control. The resulting silver iodide was a mixture of β-AgI and γ-AgI having an average grain size of 0.06 μm. 
     This emulsion is referred to as a fine silver iodide grain emulsion. 
     Preparation of comparative tabular emulsions EM-1 through EM-6 
     Using the three solutions shown below, comparative tabular silver iodobromide emulsions EM-1 through 6 were prepared, which had a silver iodide content of 1.53 mol %. 
     
         __________________________________________________________________________Solution AOssein gelatin                  29.4                              gSeed emulsion EM-0              Equivalent to                           0.588                              mol10% methanol solution of        2.5                              mlHO(CH.sub.2 CH.sub.2 O).sub.n --[(CH(CH.sub.3)CH.sub.2 O].sub.m --(CH.sub.2 CH.sub.2 O).sub.n --H.sub.n+m=5.7Distilled water was added to make a total quantity shown in Table 1.Solution BAgNO.sub.3                      1404                              gDistilled water was added to make a total quantity of 2360 ml.Solution CKBr                             968                              gKI 20.6 gDistilled water was added to make a total quantity of 2360__________________________________________________________________________ml. 
    
     Using the mixer-stirrer disclosed in Japanese Patent Examined Publication Nos. 58288/1983 and 58289/1983, the entire amounts of solutions B and C were added to solution A at 60° C. by the double-jet precipitation method at flow rates such that the final flow rate would triple the initial flow rate over a period of 110 minutes, to grow grains. 
     During this operation, silver electrode potential was controlled at +25 mV using a 1.75N aqueous solution of potassium bromide. 
     After completion of the addition, the following sensitizing dyes A and B were added at 300 mg/mol Ag and 15 mg/mol Ag, respectively, after which the mixture was precipitated and desalinized to remove excess salts, using an aqueous solution of Demol (produced by Kao Atlas) and an aqueous solution of magnesium sulfate. The mixture was then stirred and re-dispersed in an aqueous gelatin solution containing 92.2 g of ossein gelatin to a total quantity of 2500 ml. 
     Sensitizing dye A: 5,5&#39;-dichloro-9-ethyl-3,3&#39;-di-(3-sulfopropyl)oxacarbocyanine salt anhydride 
     Sensitizing dye B: 5,5&#39;-di-(butoxycarbonyl)-1,1&#39;-diethyl-3,3&#39;-di-(4-sulfobutyl)benzimidazolocarbocyanine sodium salt anhydride 
     About 3000 grains of each dispersion were observed and morphologically analyzed using an electron microscope. The results are given in Table 1. 
     Preparation of comparative or inventive tabular emulsions EM-7 through 12 
     Using the four solutions shown below, comparative or inventive tabular silver iodobromide emulsions EM-7 through 12 were prepared, which had a silver iodide content of 1.53 mol %. 
     
         __________________________________________________________________________Solution AOssein gelatin                  29.4                              gSeed emulsion EM-0              Equivalent to                           0.588                              mol10% methanol solution of        2.5                              mlHO(CH.sub.2 CH.sub.2 O).sub.n --[(CH(CH.sub.3)CH.sub.2 O].sub.m --(CH.sub.2 CH.sub.2 O).sub.n --H.sub.n+m=5.7Distilled water was added to make a quantity shown in Table 1.Solution BAgNO.sub.3                      1382                              gDistilled water was added to make a total quantity of 2322 ml.Solution CKBr                             968                              gDistilled water was added to make a total quantity of 2322 ml.Solution DFine silver iodide emulsion     Equivalent to                           0.124                              mol.__________________________________________________________________________ 
    
     Using the mixer-stirrer disclosed in Japanese Patent Examined Publication Nos. 58288/1983 and 58289/1983, the entire amounts of solutions B, C and D were added to solution A at 60° C. by the triple-jet precipitation method at an accelerated flow rate such that the final flow rate would triple the initial flow rate over a period of 110 minutes, to grow grains. 
     During this operation, silverel potential was controlled at +25 mV using a 1.75N aqueous solution of potassium bromide. 
     After completion of the addition, sensitizing dyes A and B were added in amounts of 300 mg/mol Ag and 15 mg/mol Ag, respectively, in the same manner as for EM-1, after which the emulsion was coagulated and desalinized to remove excess salts, using an aqueous solution of Demol (produced by Kao Atlas) and an aqueous solution of magnesium sulfate. The mixture was then stirred and re-dispersed in an aqueous gelatin solution containing 92.2 g of ossein gelatin to a total quantity of 2500 ml. 
     About 3000 grains of each emulsion were observed and morphologically analyzed using an electron microscope. The results are given in Table 1. 
     
                                           TABLE 1__________________________________________________________________________Solution A        Average     Seed grain             grain                  AverageEmulsionVolume     concentration             diameter                  thickness                          DistributionNo.  (ml) (%) by volume             d (μm)                  h (μm)                       d/h                          width (%)                                 Remark__________________________________________________________________________EM-1 4000 0.43    1.05 0.25 4.2                          18     Comp.EM-2 3000 0.58    1.03 0.26 4.0                          18     Comp.EM-3 1500 1.15    1.02 0.27 3.8                          18     Comp.EM-4 1000 1.73    1.03 0.26 4.0                          18     Comp.EM-5  500 3.46    1.02 0.27 3.8                          18     Comp.EM-6  250 6.92    1.01 0.28 3.6                          18     Comp.EM-7 4000 0.43    1.05 0.25 4.2                          18     Comp.EM-8 3000 0.58    1.03 0.26 4.0                          18     Inv.EM-9 1500 1.15    1.02 0.27 3.8                          18     Inv. EM-101000 1.73    1.03 0.26 4.0                          18     Inv. EM-11 500 3.46    1.02 0.27 3.8                          18     Inv. EM-12 250 6.92    1.01 0.28 3.6                          18     Comp.__________________________________________________________________________ Comp.: Comparative Inv.: Inventive 
    
     Preparation of Samples 
     To each emulsion, sensitizing dyes A and B were added at 140 mg/mol Ag and 1.4 mg/mol Ag, respectively, after which the emulsion was chemically ripened with 7.0×10 -4  mol per mol silver of ammonium thiocyanate and appropriate amounts of chloroauric acid and hypo. After 6×10 -4  mol/mol Ag of a fine silver iodide emulsion having an average grain size of 0.06 μm was added, the mixture was stabilized with 3×10 -2  mol of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene. 
     To each emulsion, the following various additives were added. 
     The additives incorporated in the emulsion (light-sensitive silver halide coating solution) are as follows: The amount of addition is expressed per mol of silver halide. 
     
         ______________________________________Compound A                 150    mgt-butyl-catechol           400    mgPolyvinylpyrrolidone (molecular weight 10,000)                      1.0    gStyrene-maleic anhydride copolymer                      2.5    gTrimethylolpropane         10     gDiethylene glycol          5      gNitrophenyl-triphenyl-phosphonium chloride                      50     mg1,3-ammonium dihydroxybenzene-4-sulfonate                      4      gSodium 2-mercaptobenzimidazole-5-sulfonate                      1.5    mgCompound B                 70     mgn-C.sub.4 H.sub.9 OCH.sub.2 CH(OH)CH.sub.2 N(CH.sub.2 COOH).sub.2                      1      gCompound A ##STR1##Compound B ##STR2##______________________________________ 
    
     The additives incorporated in the protective layer coating solution are as follows: The amount of addition is expressed per gram of gelatin. 
     
         ______________________________________Matting agent consisting of polymethyl methacrylate                       7      mggrains having an area-average grain size of 7 μmColloidal silica (average grain size 0.013 μm)                       70     mg2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt                       30     mg(CH.sub.2 CHSO.sub.2 CH.sub.2 ).sub.2 O                       36     mgCompound C                  12     mgCompound D                  2      mgCompound E                  7      mgCompound F                  15     mgCompound G                  5      mgF.sub.19 C.sub.9 O(CH.sub.2 CH.sub.2 O).sub.10 CH.sub.2 CH.sub.2 OH                       3      mgCompound C ##STR3##Compound D ##STR4##Compound E ##STR5##Compound F ##STR6##A mixture wherein n is 2 to 5.Compound G ##STR7##______________________________________ 
    
     The above coating solutions were uniformly coated and dried on both faces of a subbed blue-colored polyethylene terephthalate film base of 180 μm in thickness to yield samples 1 through 12 as listed in Table 2. 
     For all samples, the amount of grain coated was adjusted to 3.0 g/m 2 , and the amount of silver coated 2.0 g/m 2  for each face. 
     The samples thus obtained were evaluated as follows: 
     Sensitometry and storage stability 
     The samples were kept standing at room temperature (20° C.) for 3 days (natural aging) or subjected to a accelerated aging test at 50° C. temperature and 80% humidity for 3 days. Each sample was then inserted between two sheets of sensitized paper KO-250 for X-ray photography and exposed to an X-ray via a penetrometer B, after which it was photographically processed with XD-SR developer at 35° C. for 45 seconds, using an automatic processing machine SRX-501. All materials and equipment used here were products of Konica Corporation. 
     Each sample thus processed was subjected to sensitometry. Sensitivity was obtained as a percent ratio to the reciprocal of the amount of exposure energy required for sample 1 to provide a density of fog+1.0. 
     Gamma was expressed as the gradient of the linear portion of the characteristic curve, and the fog value included a base density of 0.15. 
     The results are given in Table 2. 
     
                                           TABLE 2__________________________________________________________________________    Natural aging                Accelerated agingSample    Emulsion       Sensi-      Sensi-No. No.  Fog       tivity           Gamma                Fog                   tivity                       Gamma                            Remark__________________________________________________________________________1   EM-1 0.26       100 2.8  0.45                    93 2.5  Comparative2   EM-2 0.23       107 2.9  0.43                    95 2.6  Comparative3   EM-3 0.17       147 3.0  0.36                   120 2.8  Comparative4   EM-4 0.17       147 3.1  0.36                   121 2.8  Comparative5   EM-5 0.17       147 3.1  0.37                   119 2.8  Comparative6   EM-6 0.26        69 2.8  0.46                    50 2.5  Comparative7   EM-7 0.26       104 2.8  0.43                    93 2.5  Comparative8   EM-8 0.19       135 3.1  0.21                   136 3.0  Inventive9   EM-9 0.17       152 3.1  0.18                   152 3.1  Inventive10   EM-10    0.17       151 3.2  0.18                   152 3.2  Inventive11   EM-11    0.17       150 3.1  0.18                   150 3.1  Inventive12   EM-12    0.27        72 2.8  0.43                    54 2.5  Comparative__________________________________________________________________________ 
    
     From Table 2, it is seen that the samples according to the present invention have high levels of sensitivity and gamma value with low fog and show excellent storage stability under high-temperature, high-humidity conditions. 
     Example 2 
     Preparation of comparative tabular grain emulsions EM-13 through 18 
     Using the five solutions shown below, comparative tabular silver iodobromide grain emulsions EM-13 through 18 were prepared, which had an average silver iodide content of 2.0 mol %. 
     
         __________________________________________________________________________Solution AOssein gelatin                  29.4                              gSeed emulsion EM-0              Equivalent to                           0.588                              mol.10% methanol solution of        2.5                              mlHO(CH.sub.2 CH.sub.2 O).sub.n --[(CH(CH.sub.3)CH.sub.2 O].sub.m --(CH.sub.2 CH.sub.2 O).sub.n --H.sub.n+m=5.7Distilled water was added to a final quantity shown in Table 3.Solution BAgNO.sub.3                      187                              gDistilled water was added to make a total quantity of 314 ml.Solution CKBr                             111                              gKI 27.7 gDistilled water was added to make a total quantity of 314 ml.Solution DAgNO.sub.3                      1217                              gDistilled water was added to make a total quantity of 2045 ml.Solution EKBr                             852                              gDistilled water was added to make a total quantity of 2045__________________________________________________________________________ml. 
    
     Using the mixer-stirrer disclosed in Japanese Patent Examined Publication Nos. 58288/1983 and 58289/1983, the entire amounts of solutions B and C were added to solution A by the double-jet precipitation method at a constant flow rate over a period of 30 minutes, to grow grains. Subsequently, the entire amounts of solutions D and E were added by the double-jet precipitation method at an accelerated flow rate such that the final flow rate would double the initial flow rate (3 × from start to final) over a period of 90 minutes, to grow grains. 
     During this operation, silver electrode potential was controlled at +25 mV using a 1.75N aqueous solution of potassium bromide. 
     After completion of the addition, sensitizing dyes A and B were added in amounts of 300 mg/mol Ag and 15 mg/mol Ag, respectively, in the same manner as in Example 1, after which the emulsion was coagulated and desalinized to remove excess salts, using an aqueous solution of Demol (produced by Kao Atlas) and an aqueous solution of magnesium sulfate. The mixture was then stirred and re-dispersed in an aqueous gelatin solution containing 92.2 g of ossein gelatin to a total quantity of 2500 ml. 
     About 3000 grains of each dispersion were observed and morphologically analyzed using an electron microscope. The results are given in Table 3. 
     Preparation of comparative or inventive tabular grain emulsions EM-19 through 24 
     Using the six solutions shown below, comparative or inventive tabular silver iodobromide emulsions EM-19 through 24 were prepared, which had an average silver iodide content of 2.0 mol %. 
     
         __________________________________________________________________________Solution AOssein gelatin                  29.4                              gSeed emulsion EM-0              Equivalent to                           0.588                              mol.10% methanol solution of        2.5                              mlHO(CH.sub.2 CH.sub.2 O).sub.n --[(CH(CH.sub.3)CH.sub.2 O].sub.m --(CH.sub.2 CH.sub.2 O).sub.n --H.sub.n+m=5.7Distilled water was added to a final quantity shown in Table 3.Solution BAgNO.sub.3                      159                              gDistilled water was added to make a total quantity of 267 ml.Solution CKBr                             111                              gDistilled water was added to make a total quantity of 267 ml.Solution DAgNO.sub.3                      1217                              gDistilled water was added to make a total quantity of 2045 ml.Solution EKBr                             852                              gDistilled water was added to make a total quantity of 2045 ml.Solution FFine silver iodide emulsion     Equivalent to                           0.167                              mol.__________________________________________________________________________ 
    
     Using the mixer-stirrer disclosed in Japanese Patent Examined Publication Nos. 58288/1983 and 58289/1983, the entire amounts of solutions B, C and F were added to solution A at 60° C. by the triple-jet precipitation method at a constant flow rate over a period of 30 minutes, to grow grains. Subsequently, the entire amounts of solutions D and E were added at an accelerated flow rate such that the final flow rate would double the initial flow rate over a period of 90 minutes, to grow grains. 
     During the process, silver electrode potential was controlled at +25 mV using a 1.75N aqueous solution of potassium bromide. 
     After completion of the addition, sensitizing dyes A and B were added at 300 mg/mol Ag and 15 mg/mol Ag, respectively, in the same manner as in Example 1, after which the emulsion was coagulated and desalinized to remove excess salts, using an aqueous solution of Demol (produced by Kao Atlas) and an aqueous solution of magnesium sulfate. The mixture was then stirred and re-dispersed in an aqueous gelatin solution containing 92.2 g of ossein gelatin to a total quantity of 2500 ml. 
     About 3000 grains of each emulsion were observed and morphologically analyzed using an electron microscope. The results are given in Table 3. 
     
                                           TABLE 3__________________________________________________________________________Solution A        Average     Seed grain             grain                  AverageEmulsionVolume     concentration             diameter                  thickness                          DistributionNo.  (ml) (%) by volume             d (μm)                  h (μm)                       d/h                          width (%)                                 Remark__________________________________________________________________________EM-134000 0.43    0.90 0.34 2.6                          23     Comp.EM-143000 0.58    0.89 0.35 2.5                          22     Comp.EM-151500 1.15    0.85 0.39 2.2                          25     Comp.EM-161000 1.73    0.84 0.40 2.1                          25     Comp.EM-17 500 3.46    0.83 0.41 2.0                          26     Comp.EM-18 250 6.92    0.80 0.44 1.8                          27     Comp.EM-194000 0.43    0.94 0.31 3.0                          20     Comp.EM-203000 0.58    0.92 0.32 2.9                          20     Inv.EM-211500 1.15    0.91 0.33 2.8                          20     Inv.EM-221000 1.73    0.91 0.33 2.8                          20     Inv.EM-23 500 3.46    0.90 0.34 2.6                          20     Inv.EM-24 250 6.92    0.89 0.35 2.5                          24     Comp.__________________________________________________________________________ Comp.: Comparative Inv.: Inventive 
    
     Preparation of Samples 
     Each emulsion was chemically ripened in the same manner as in Example 1 and then coated in the presence of various additives, to yield samples 13 through 24. Each sample was subjected to sensitometry and an accelerated deterioration test for storage stability in the same manner as in Example 1. 
     The results are given in Table 4. 
     
                                           TABLE 4__________________________________________________________________________    Natural aging                Accelerated agingSample    Emulsion       Sensi-      Sensi-No. No.  Fog       tivity           Gamma                Fog                   tivity                       Gamma                            Remark__________________________________________________________________________13  EM-13    0.26       110 2.5  0.46                   93  2.2  Comparative14  EM-14    0.23       108 2.6  0.45                   92  2.3  Comparative15  EM-15    0.25       109 2.5  0.44                   90  2.2  Comparative16  EM-16    0.25       108 2.4  0.45                   86  2.0  Comparative17  EM-17    0.26       100 2.4  0.46                   82  2.0  Comparative18  EM-18    0.27        65 2.3  0.46                   45  1.8  Comparative19  EM-19    0.26       115 2.8  0.43                   93  2.5  Comparative20  EM-20    0.17       145 3.0  0.20                   146 2.9  Inventive21  EM-21    0.17       160 3.0  0.18                   160 3.0  Inventive22  EM-22    0.17       159 3.1  0.18                   159 3.1  Inventive23  EM-23    0.17       155 3.0  0.18                   154 3.0  Inventive24  EM-24    0.27        80 2.8  0.46                   64  2.5  Comparative__________________________________________________________________________ 
    
     From Tables 2 and 4, it is seen that the samples according to the present invention have high levels of sensitivity and gamma value with low fog and undergo little performance deterioration over time under high-temperature, high-humidity conditions.