Silver halide photosensitive color photographic material, image forming method, image information forming method

Abstract

 A silver halide photosensitive photographic material and an image information forming method are disclosed. The silver halide photosensitive photographic material comprises a dye which is decomposed by a color developer. The image forming method comprises steps of color development of the silver halide photosensitive photographic material followed by no bleaching, and converteing the image information to electrical image information.

Description

FIELD OF THE INVENTION

[0001] The present invention relates to a silver halide photosensitive photographic material which can provide electrical image information employing simple and convenient processing, an image forming method, an image information forming method and a resource recovery method.

BACKGROUND OF HE INVENTION

[0002] Conventionally, silver halide photosensitive photographic materials (hereinafter occasionally referred to as photosensitive material) have generally required processing consisting of color development, bleaching, and fixing each employing a specific processing solution, and it has long been desired to develop a method in which image information is obtained using simple and convenient processing.

[0003] Conventional photosensitive materials comprise a yellow filter layer which prevents the deterioration of color reproduction due to the fact that green-sensitive layers and red-sensitive layers are sensitive to blue light on account of blue light absorption properties of silver halides. Furthermore, in order to minimize halation, generally, a layer comprising dyes has been provided. In the present invention, these layers are hereinafter referred to as a yellow filter layer and an antihalation layer, respectively. Conventional photosensitive materials are generally subjected to bleaching and fixing after development. Though colloidal silver is incorporated into the yellow filter and the antihalation layer, it is removed during the bleaching and fixing processes. Therefore, there has been no problem with remaining colors after processing.

[0004] When conventional photosensitive materials are subjected to bleaching, so-called chelating agents such as EDTA, PDTA, etc. are employed. However, these chelating agents are not readily biodegradable and cause an increase in treatment cost of solution waste. Accordingly, countermeasures have been sought.

[0005] It is common knowledge that yellow dyes are incorporated into the yellow filter, which are described, for example, in Japanese Patent Publication Open to Public Inspection Nos. 2-1839, 3-72340, 4-362634, etc. However, photosensitive materials disclosed in these patent publications are premised on bleaching and fixing. Therefore, when these patents are applied to the photosensitive material of the present invention, which is not subjected to bleaching, there are problems in which decomposition properties are insufficient and undesired yellow coloring remains after processing. Further, in those patent publications, technical concept is not at all disclosed in which processing is accomplished without carrying out bleaching as described in the present invention, and image information of the photosensitive photographic material which has been subjected to such processing is converted to electrical image information. In addition, no technical problem is described nor suggested in which, when processing is terminated without carrying out bleaching, the dye decomposition is insufficient and improvement is required to overcome this disadvantage.

[0006] A method in which neither fixing nor bleaching is carried out after color development has been known as one applied to the product introduced by 3M Co. as Dry Silver. However, in this product, bleaching and fixing for the silver halide photosensitive material comprising no yellow filter only are eliminated. There has been no disclosure of technical concepts such that in accordance with it, it is desired to improve decomposition properties of the dyes and there has also been no description at all on the presence of such a problem.

SUMMARY OF THE INVENTION

[0007] The first object of the present invention is to provide a photosensitive material which is capable of being subjected to simple and convenient processing.

[0008] The second object of the present invention is to provide an image information forming method in which electrical image information can be provided using simple and convenient processing.

[0009] The third object of the present invention is to provide a image forming method which minimizes environmental pollution.

[0010] The fourth object of the present invention is to provide a photosensitive material which allows for easy and efficient resource recovery, and a processing method thereof.

[0011] The invention and the embodiments are described below:

1. An image information forming method wherein a silver halide photosensitive photographic material comprising a dye which is decomposed by a color developer is subjected to color development, followed by no bleaching, and image information is converted to electrical image information.

2. A resource recovery method wherein a silver halide photosensitive photographic material comprising a dye which is decomposed by a color developer is subjected to color development, followed by no bleaching; image information is converted to electrical image information, and the silver halide photosensitive photographic material is not returned to a customer, but is recovered.

3. An image forming method wherein processing is carried out by supplying a processing solution with an soaking amount onto a silver halide photosensitive photographic material comprising a dye which is decomposed by a color developer.

4. An image information forming method wherein a silver halide photosensitive photographic material comprising a dye dispersed in the solid state which is decomposed by a color developer is subjected to color development, followed by no bleaching, and image information is converted to electrical image information.

5. A silver halide photosensitive photographic material wherein the silver halide photosensitive photographic material comprises a dye which is decomposed by a color developer and silver in an amount of not more than 2 g/m².

6. An image information forming method described in the above-mentioned item 1. or 4., characterized in that a silver halide photosensitive photographic material comprises silver in an amount of not more than 2 g/m².

7. A resource recovery method described in the above-mentioned item 2., wherein a silver halide photosensitive photographic material comprises silver in an amount of not more than 2 g/m²

8. An image forming method described in the above-mentioned item 3., wherein a silver halide photosensitive photographic material comprises silver in an amount of not more than 2 g/m².

DETAIL DESCRIPTION OF THE INVENTION

[0012] In the present invention, the dyes which can be decomposed by a color developer denote dyes which are decomposed at a decomposition ratio of at least 50 percent during color development reaction employing the color developer. In terms of color reproduction, the decomposition ratio is preferably at least 70 percent and is more preferably at least 90 percent. The dye decomposition ratio was obtained using the formula described below in comparison to the optical density of a sample prior to color development, which is prevented from interference due to dyes formed by color development.

[0013] Dyes as described in the present invention may include organic compounds or inorganic compounds, irrespective of their structure. Organic compounds are preferred because they result in relatively rapid decomposition reaction in a color developer. In the scope of the present invention, organic compounds such as organic dyes and inorganic compounds such as colloidal silver may be employed in combination.

[0014] Investigation performed by the inventors of the present invention revealed that when a photosensitive material, prepared by using dyes which were not decomposed by a developer, was subjected to color development followed by no bleaching and the resulting image was read, reading the image information was hindered due to the presence of the absorption of the dyes, colloidal silver, etc., due to insufficient decomposition of these dyes. It was found that, particularly, when the image information formed by a yellow dye forming coupler was read, the remaining yellow color caused major problem.

[0015] As for the processing solutions employed in the present invention, it is preferred that processing in which almost all the supplied processing solution is absorbed by photosensitive material, is carried out because no solution waste is generated. Examples of methods to supply the processing solution to the photosensitive material, spray development or coating development is preferable.

[0016] The spray development as described herein denotes a development in which a developer is supplied onto a photosensitive material as a spray in an amount substantially capable of soaking the photosensitive material. Irrespective of spray methods and types, the number of nozzles, shapes of nozzles, spraying may be carried out during movement of a single movable nozzle or employing a plurality of fixed nozzles. The spraying may also be carried out by moving a nozzle while stopping a photosensitive material or may be carried out by moving a photosensitive material, or in a combination thereof.

[0017] The coating development as described herein denotes a development in which a developer is supplied onto a photosensitive material in an amount substantially capable of soaking the photosensitive material via a means of carrying the developer. As for the means of carrying the developer, felt, fabrics, metal sheets with holes or slits, etc. are preferably employed. While spraying a developer onto a photosensitive material or a medium, a method is preferred in which the developer is coated onto the photosensitive material employing the medium.

[0018] The present invention is preferably applied to a photosensitive material having a silver amount of not more than 2 g/m². In the photosensitive material having a silver amount of not more than 2 g/m², yellow coloration and light scattering due to silver halides themselves are minor. As a result, when colloidal silver and non-decomposable dyes are incorporated into a yellow filter layer and an antihalation layer, coloration after processing is excessive and causes major problems. Accordingly, the embodiments of the present invention are preferably applied.

[0019] The dyes employed in the present invention exhibit decomposable properties. Preferred examples include pyrazolidinediones, isoxazolones, pyrazolopyridones, barbituric acid series, pyrazolones, indandiones, pyridones, closed chain methylenes, etc. Particularly preferred examples include pyrazolidinediones and isoxazolones. Pyrazolidinediones are described in Japanese Patent Publication Open to Public Inspection Nos. 3-208046, 3-167546, and 9-106041; isoxazolones are described in Japanese Patent Publication Open to Public Inspection Nos. 3-208044, 3-72340, 4-362634, 5-209133, 7-92613, and 8-6196; pyrazolopyridones are described in Japanese Patent Publication Open to Public Inspection Nos. 2-282244, 3-7931, 3-167546, 8-6196, and 9-106041; barbituric acid series are described in European Patent No. 274723, Japanese Patent Publication Open to Public Inspection Nos. 3-223747, 3-167546, 8-6196, and 9-106041; pyrazolones are described in U.S. Pat No. 4,092,168, and Japanese Patent Publication Open to Public Inspection Nos. 3-23441, 3-19544, 3-206441, 3-206442, 3-208043, 4-151651, 3-144438, 3-167546, 5-50345, 5-53241, 5-86056, 8-6196, and 8-50345, and Japanese Patent Publication No. 55-155351; indandiones are described in European Patent No. 524593, and Japanese Patent Publication Open to Public Inspection Nos. 5-289239 and 8-6190; pyridones are described in Japanese Patent Publication Open to Public Inspection Nos. 55-155351, 4-37841, 2-277044, and 8-6196; closed chain methylenes are described in Japanese Patent Publication Open to Public Inspection No. 3-182742 and European Patent No. 762198. However, in these specifications, technical concept are not at all disclosed in which processing is completed without carrying out bleaching as mentioned in the present invention and image information of a photosensitive material which has been subjected to such processing being converted to electrical image information. Furthermore, technical problems are neither described nor noted in which, when processing is completed without carrying out bleaching, the resulting insufficient dye decomposition retires improvement.

[0020] Dyes of the present invention may be incorporated into a photosensitive material, employing conventional methods. Namely, other than addition as a solid dispersion, dyes may be dissolved in a high boiling point solvent and then added.

[0021] High boiling point solvents of the present invention are most preferably organic compounds having a boiling point of not less than 100 °C at one atmospheric pressure, and for example, phosphoric acid esters, phthalic acid esters, alkyl phenols, and amides are preferably employed.

[0022] In the present invention, when image information is converted to electrical image information, a device, generally referred to as a scanner, may be employed. Generally, when such a scanner scans a photosensitive material, it is recommended that the necessary area of the photosensitive material is scanned by moving the optical portion of the scanner in a direction different from the motion of the photosensitive material. However, the photosensitive material is fixed and the optical portion of the scanner may only be moved, or the photosensitive material may only be moved, while the optical portion of the scanner is fixed.

[0023] Light sources, which are employed to read image information include tungsten-filament lamps, fluorescent lamps, light emitting diodes, laser light, etc. The tungsten-filament lamps are preferred in terms of low cost, while laser light (coherent light source) is preferred in terms of stability, high intensity, and minimum influence from scattering. Reading methods are not particularly specified, however, reading is preferably carried out employing transmitted light in terms of color reproduction and sharpness.

[0024] Thermal development is preferably applied to the color development of the present invention in terms of a decrease in processing time and less adverse impact on the environment.

[0025] Incorporation of a developing agent precursor into the photosensitive material of the present invention is preferred for easier management of the developer.

[0026] Materials employed in the present invention other than dyes mentioned above are described in publications, and referring to these, those skilled in the art can readily synthesize or purchase such materials. As the publications, cited can be, for example, Japanese Patent Publication Open to Public Inspection Nos. 8-166644, 8-202002, 8-286340, 8-292531, 8-227131, 8-292529, 8-234388, 8-234390, 9-34081, 9-76570, 9-114062, 9-152686, 9-152691, 9-152692, 9-152693, 9-152700, 9-152701, 9-159702, 9-159703, 9-150794, and 9-150795.

[0027] Various types of silver halide emulsions may be employed. Regarding the silver halide emulsion, the grain diameter, aspect ratio, silver halide composition (types and amounts of halogens in silver halide), halide distribution (distribution of each silver halide in silver halide grains), presence of dislocation lines, etc are selected for the characteristics of the recording material. The grain diameter (converted to the one edge length of a cube having the same volume) of silver halide grains is preferably between 0.05 and 2 microns. The aspect ratio is preferably 4 or more in terms of sharpness; is more preferably 8 or more, and is most preferably 12 or more. The dominant component of halides is preferably silver bromide. Of the total silver halide, silver bromide is preferably between 80 and 99 mole percent, and silver iodide is preferably between 1 and 20 mole percent. The presence of dislocation lines is preferred in terms of sensitivity.

[0028] When the materials of the present invention are constituted, a silver halide emulsion subjected to physical ripening, chemical sensitization, and spectral sensitization is generally employed. Additives employed in these processes are described in Research Disclosure Nos. 17643, 18716, and 308119 (hereinafter, each is referred to respectively as RD 17643, RD 18716, and RD 308119).

[0029] Specific pages which describe additives are listed below:

(Item)	(page in RD 308119)		(RD 17643)	(RD 18716)
Chemical Sensitizers	996	Section III-A	23	648
Spectral Sensitizers	996	IV-A, B Section C, D, H, I, J	23 and 24	648 and 649
Supersensitizers	996	Section IV-A to E, J	23 and 24	648 and 649
Antifoggants	998	VI	24 and 25	649
Stabilizers	998	VI	24 and 25	649

[0030] For the chemical sensitization of the silver halide emulsion employed in the present invention, more specifically, employed can be, individually or in combination, sulfur-containing compounds capable of reacting with silver ions, a sulfur sensitization method using active gelatin, a selenium sensitization method using selenium compounds, a reduction sensitization method using reducing compounds, a noble metal sensitization method using gold and other noble metals, etc.

[0031] In the present invention, as chemical sensitizers, for example, chalcogen sensitizers may be employed, and of these, sulfur sensitizers and selenium sensitizers are preferred.

[0032] Cited as the sulfur sensitizers, are, for example, thiosulfates, allythiocarbamide, thiourea, allylisothiocyanate, cystine, p-trienthiosulfonate salts, rhodanine, etc.

[0033] In addition to these, employed may be sulfur sensitizers described in U.S. Pat. Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668, 3,501,313, and 3,656,955; West German OLS Patent No. 1,422,869; Japanese Patent Publication Open to Public Inspection Nos. 56-24937 and 55-45016; etc.

[0034] The added amount of the sulfur sensitizer varies in a fairly large range, depending on various conditions such as pH, temperature, silver halide size, etc., but as the standard, it preferably is between about 1 × 10^-7 and about 1 × 10^-1 mole per mole of silver halide.

[0035] As the selenium sensitizers, employed can be aliphatic isoselenocyantes such as allylisoselenocyanates, selenoureas, selenides such as selenoselenide, and diethylselenide, etc. Specific examples of these are described in U.S. Pat. Nos. 1,574,944, 1,602,592, and 1,623,499. Furthermore, reduction sensitizers may also be employed in combination.

[0036] As reduction sensitizers, cited can be stannous chloride, thiourea dioxide, hydrazine, polyamine, etc. Furthermore, noble metal compounds other than gold, for example, palladium compounds, etc. can be employed together with these previously listed.

[0037] Silver halide grains of the emulsion employed in the present invention preferably undergo chemical sensitization employing gold compounds.

[0038] As gold compounds preferably employed in the present invention, are those in which the gold oxidation number may have a valence of +1 or +3, and many types of gold compounds may be employed.

[0039] As representative examples, listed are potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurous thiocyanate, pyridyltrichlorogold, gold sulfide, gold selenide, etc.

[0040] The added amount of the gold compound varies depending on ambient conditions, but as the standard, it is usually between 1 × 10^-8 and 1 × 10^-1 mole per mole of silver halide, and is preferably between 1 × 10^-7 and 1 × 10^-2 mole.

[0041] Furthermore, these compounds may be added during formation of silver halide grains, physical ripening, chemical ripening and during any process after chemical ripening.

[0042] Photographic additives, which can be employed in the present invention, are also described in the above-mentioned Research Disclosures.

[0043] Pages which describe related additives are shown below.

(Item)	(Page of RD 308119		(RD 17643)	(RD 18716)
Color Contamination Preventing Agents	1002	Section VII-I	25	650
Dye Image Stabilizing Agents	1001	Section VII J	25
Brightening Agents	998	V	24
UV Absorbers	1003	VIII-C, Section XIIIC	25 to 26
Light Scattering Agents	1003	VIII
Binders	1003	IX	26	651
Antistatic Agents	1006	XIII	27	650
Hardeners	1004	X	26	651
Plasticizers	1006	XII	27	650
Lubricating Oil	1006	XII	27	650
Active Agents and Coating Aids	1005	XI	26 to 27	650
Matting Agents	1007	XVI
Developing Agents	1011	Section XXB

[0044] Furthermore, in order to minimize the degradation of photographic properties due to formaldehyde gas, compounds which react with formaldehyde to result in fixation, described in U.S. Pat. Nos. 4,411,987 and 4,435,503, are preferably incorporated into the photosensitive material.

[0045] Various types of colored couplers may be employed in the present invention. Specific examples are described in patents described in the above-mentioned Research Disclosure (RD) Item No. 17643, Sections VII-C to G.

[0046] As examples of 5-pyrazolone series and pyrazoloazole series compounds, those are particularly preferred which are described in U.S. Pat. Nos. 4,310,619 and 4,351,897; European Patent No. 73,636; U.S. Pat. Nos. 3,061,432 and 3,725,067; Research Disclosure Item No. 24230 (June 1984); Japanese Patent Publication Open to Public Inspection Nos. 60-43659, 61-72238, 60-35730, 55-118034, 60-185951; U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630; International Patent Publication Open to Public Inspection WO 88/04795; etc.

[0047] As phenol series and naphthol series couplers, those which are preferred are 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, 2,772,002, 3,758,908, 4,334,011, and 4,327,173; West German Patent Publication Open to Public Inspection No. 3,329,729; European Patent Nos. 121,365A, 249,453A; U.S. Pat. Nos. 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4,690,889, 4,254,212, and 4,296,199; Japanese Patent Publication Open to Public Inspection Nos. 61-42658 and 63-88551; etc.

[0048] Typical examples of polymerized dye-forming couplers which can be employed in the present invention are described in U.S. Pat. Nos. 3,451,820, 4,080,211, 4,367,282, and 4,409,320, 4,576,910; U.K. Patent No. 2,102,173; etc.

[0049] Couplers which release a photographically useful residual group upon coupling are also preferably employed. As DIR couplers which release a development inhibitor, those which are preferred are described in patents in the above-mentioned RD 17643, VII-F; Japanese Patent Publication Open to Public Inspection Nos. 57-151944, 57-154234, 60-184248, and 63-37346; U.S. Pat. Nos. 4,248,962, and 4,782,012; etc.

[0050] As couplers which release imagewise nucleation agents or development accelerators, preferred which are those described in U.K. Patent Nos. 2,097,140 and 2,131,188; Japanese Patent Publication Open to Public Inspection Nos. 59-157638 and 59-170840.

[0051] In addition to those, couplers which can be employed in the photosensitive material of the present invention include competing couplers described in U.S. Pat. No. 4,130,427; polyequivalent couplers described in U.S. Pat. Nos. 4,283,427, 4,338,393, and 4,310,618; DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox compound releasing redox compounds described in Japanese Patent Publication Open to Public Inspection Nos. 60-185950 and 62-24252, etc.; couplers which form no leuco dye after being released, described in European Patent No. 173,302A; bleach accelerator releasing couplers described in RD Nos. 11440 and 24241, and Japanese Patent Publication Open to Public Inspection No. 61-201247, etc.; ligand releasing couplers described in U.S. Pat. No 4,553,477, etc.; leuco dye releasing couplers described in Japanese Patent Publication Open to Public Inspection No. 63-757747; fluorescent dye releasing couplers described in U.S. Pat. No. 4,774,181; etc.

[0052] Furthermore, various other couplers can be employed in the present invention. The specific examples are described in the RDs described below. The related pages are listed below.

(Item)	(Page of RD 308119)		(RD 17643)
Yellow Couplers	1001	Section VII-D	Section VII C to G
Magenta Couplers	1001	Section VII-D	Section VII C to G
Cyan Couplers	1001	Section VII-D	Section VII C to G
Colored Couplers	1002	Section VII-G	Section VII G
DIR Couplers	1001	Section VII-F	Section VII F
BAR Couplers	1002	Section VII-F
Couplers releasing other useful residual groups	1001	Section VII-F

[0053] Additives employed in the present invention can be added using a dispersion method described in RD 308119 XIV, and the like.

[0054] In the present invention, supports can be employed which are described on page 28 of the above-mentioned RD 17643, on pages 647 and 648 of RD 18716, and in XIX of RD 308119.

[0055] In the photosensitive material of the present invention, filter layers and supplementary interlayers can be provided which are described in Section VII-K of the above-mentioned RD 308119.

[0056] The pH of the topmost surface of the photographic constituting layers of the photosensitive material of the present invention is preferably between 5.0 and 7.0, and is more preferably between 5.5 and 6.5. The pH can be measured by a method described in Japanese Patent Publication Open to Public Inspection No. 61-245153.

[0057] As supports, employed preferably are polyethylene terephthalate film, cellulose triacetate film, etc. A support with a thickness of 50 to 200 µm is generally employed.

[0058] When rolled photosensitive material of the present invention is used, it is preferred to be loaded in a cartridge. At present, the most common cartridge is a case in the 135 format. Other cartridges which are proposed in patent publications described below may be employed. Namely, cartridge techniques may be referred to those which are disclosed in Japanese Patent Publication Open to Public Inspection Nos. 58-67329, 58-181035, 58-182634, and 58-195236; U.S. Pat. No. 4,221,479; Japanese Patent Application Nos. 63-57785, 63-183344, 63-325638, 1-21862, 1-25362, 1-30246, 1-20222, 1-21863, 1-37181, 1-33108, 1-85198, 1-172595, 1-172594, and 1-172593; U.S. Pat. Nos. 4,846,418, 4,848,693, and 4,832,275; etc.

EXAMPLES

[0059] The present invention is described with reference to Examples below.

Example 1

[0060] Exemplified Compound 27, Comparative Dye 1 solid dispersion, and colloidal silver were added to an aqueous gelatin solution, hardener H-1 was then added, and the resulting mixture was coated onto a cellulose triacetate support. The resulting samples were termed Sample 101, Sample 102, and Sample 103, respectively.

Measurement of Decomposition Ratio

[0061] Sample 101, Sample 102, and Sample 103 were subjected to color development employing color negative photosensitive material process C-41 and dried. The optical density of each processed Sample was measured and the dye decomposition ratio was obtained by comparing it to the optical density of the Sample previously measured prior to processing.

[0062] The decomposition ratio of Sample 101 of the present invention was 0.96, while the decomposition ratios of Comparative Sample 102 and Comparative Sample 103 were 0.03 and 0.01, respectively.

Measurement of Nondiffusion Ratio

[0063] Sample 101, Sample 102, and Sample 103 were washed in 25 °C water for 30 seconds and dried. The optical density of the washed Sample was measured and the nondiffusion ratio of a dye was obtained upon comparing it to the optical density of the Sample previously measured, prior to washing.

[0064] The nondiffusion ratios of Sample 101 of the present invention and Comparative Sample 103 were 0.99, while that of Comparative Sample 102 was 0.03.

[0065] Based on these results, it is clear that the Sample of the present invention is quickly decomposed by a developer and can achieve the objects of the present invention, while in Comparative Sample 102, diffusion to the other layer results in adverse effects such as desensitization of the blue-sensitive layer and color contamination, while in Comparative Sample 103, decomposition is not sufficiently carried out and is not suitable for quick and simple processing.

[0066] Further, the green-sensitive layer of Sample 101 comprised of the dye of the present invention was preferable because it exhibited less fog, compared to Comparative Sample 103.

Example 2

[0067] On a cellulose triacetate support previously subjected to subbing treatment, the photographic constitution layers having compositions described below were provided and was designated Sample 201. The addition amount is expressed in the number of grams per m². However, the amounts of silver halide and colloidal silver are expressed in terms of silver amount and the amount of the sensitizing dye (hereinafter referred to as SD) is expressed in the number of moles per mole of silver. First layer (UV absorbing layer)

UV-1	0.3
OIL-1	0.044
Gelatin	1.33

Second layer (interlayer)

[0068] 

Polyethyl acrylate latex	0.20
Gelatin	1.40
AS-1	0.05

Third layer (slow red-sensitive layer)

[0069] 

Silver iodide "a"	0.04
Silver iodide "b"	0.12
SD-1	3.0 × 10-5
SD-4	1.5 × 10-4
SD-3	3.0 × 10-4
SD-6	3.0 × 10-6
C-1	0.51
OIL-2	0.45
Gelatin	1.40

Fourth layer (intermediate red-sensitive layer)

[0070] 

Silver iodide "c"	0.18
SD-1	3.0 × 10-5
SD-2	1.5 × 10-4
SD-3	3.0 × 10-4
C-2	0.22
OIL-2	0.21
Gelatin	0.84

Fifth layer (fast red-sensitive layer)

[0071] 

Silver iodide "c"	0.10
Silver iodide "d"	0.33
SD-1	3.0 × 10-5
SD-2	1.5 × 10-4
SD-3	3.0 × 10-4
C-1	0.085
C-2	0.084
OIL-2	0.23
Gelatin	1.23

Sixth layer (interlayer)

[0072] 

Polyethyl acrylate latex	0.23
Gelatin	1.00
AS-1	0.08

Seventh layer (slow green-sensitve layer)

[0073] 

Silver iodide "a"	0.08
Silver iodide "b"	0.02
SD-6	5.0 × 10-4
SD-5	5.0 × 10-4
M-1	0.21
OIL-1	0.25
Gelatin	0.98

Eighth layer (intermediate green-sensitive layer)

[0074] 

Silver iodide "e"	0.18
SD-7	3.0 × 10-4
SD-8	6.0 × 10-5
SD-9	4.0 × 10-5
M-2	0.17
OIL-1	0.29
Gelatin	1.43

Ninth layer (fast green-sensitive layer)

[0075] 

Silver iodide "f"	0.40
SD-7	4.0 × 10-4
SD-8	8.0 × 10-5
SD-9	5.0 × 10-5
M-1	0.09
OIL-1	0.11
Gelatin	0.78

Tenth layer (interlayer)

[0076] 

Yellow colloidal silver	0.02
Polyethyl acrylate latex	0.20
Gelatin	1.00
AS-1	0.08

Eleventh layer (slow blue-sensitive layer)

[0077] 

Silver iodide "g"	0.08
Silver iodide "h"	0.03
SD-10	8.0 × 10-4
SD-11	3.0 × 10-4
Y-1	0.91
OIL-1	0.37
Gelatin	1.29

Twelfth layer (fast blue-sensitive layer)

[0078] 

Silver iodide "h"	0.08
solver iodide "i"	0.30
SD-10	4.4 × 10-4
SD-11	1.5 × 10-4
Y-1	0.48
OIL-1	0.21
Gelatin	1.55

Thirteenth layer (first protective layer)

[0079] 

Silver iodide j	0.05
UV-1	0.055
UV-2	0.110
OIL-2	0.63
Gelatin	1.32

Fourteenth layer (second protective layer)

[0080] 

PM-1	0.15
PM-2	0.04
WAX-1	0.02
D-1	0.001
Gelatin	0.55

[0081] Further, other than the above-mentioned compositions, added were coating aids SU-1, SU-2, and SU-3, dispersing aid SU-4, viscosity controlling agent V-1, stabilizers ST-1 and ST-2, antifoggant two types of polyvinylpyrrolidone with a weight average molecular weight of 10,000 (AF-1) and a weight average molecular weight of 1,100,000 (AF-2), retarders AF-3, AF-4, and AF-5, and hardeners H-1 and H-2.

[0082] The structures of compounds employed in the above-mentioned Samples are illustrated below.

[0083] Table 1 shows advantages of the above-mentioned silver iodide.

Table 1

Emulsion No.	Average Grain Diameter (µm)	Average AgI Amount (mole percent)	Diameter/Thickness Ratio
Silver Iodobromide "a"	0.30	2.0	1.0
Silver Iodobromide "b"	0.40	8.0	1.4
Silver Iodobromide "c"	0.60	7.0	3.1
Silver Iodobromide "d"	0.75	7.0	5.0
Silver Iodobromide "e"	0.60	7.0	4.1
Silver Iodobromide "f"	0.65	9.0	6.5
Silver Iodobromide "g"	0.40	2.0	4.0
Silver Iodobromide "h"	0.65	8.0	1.4
Silver Iodobromide "i"	1.00	8.0	2.0
Silver Iodobromide "j"	0.05	2.0	1.0

[0084] Further, as preparation examples of preferred silver halide grains of the present invention, preparation examples of silver iodobromide "d", "f", etc. are described below.

Preparation of Seed Crystal Emulsion-1

[0085] A seed crystal emulsion was prepared as described below.

[0086] Employing a mix-stirring machine described in Japanese Patent Publication Nos. 5-58288 and 58-58289, nuclei were formed by adding during 2 minutes an aqueous silver nitrate solution (1.161 moles) and an aqueous potassium bromide and potassium iodide solution (2 mole percent of potassium iodide) to the following solution A1 regulated at 35 °C employing a double-jet method, while maintaining the silver potential at 0 mV (measured by a silver ion selection electrode employing a saturated silver-silver chloride electrode as the reference electrode). Subsequently, the resulting mixture was warmed to 60 °C over 60 minutes and the pH was adjusted to 5.0 employing an aqueous sodium carbonate solution. Thereafter, an aqueous silver nitrate solution (5.902 moles) and an aqueous potassium bromide and potassium iodide solution (2 mole percent of potassium iodide) were added over 42 minutes, while maintaining the silver potential at 9 mV. After completing the addition, after lowering the temperature to 40 °C, the resulting mixture was immediately desalted and washed employing an ordinary flocculation method.

[0087] The resulting seed crystal emulsion was an emulsion comprised of hexagonal tabular grains having an average spherical converted diameter of 0.24 µm, an average aspect ratio of 4.8, and a maximum edge length ratio of the total projection area of not less than 90 percent of 1.0 to 2.0.

(Solution A1)

[0088] 

Ossein gelatin	24.2 g
Potassium bromide	10.8 g
HO(CH2CH2O)m(CH(CH3)CH2O)19.8(CH2CH2O)nH ( ) (10% ethanol solution)	6.78 ml
10% nitric acid	114 ml
H2O	9657 ml

Preparation of Fine Silver Iodide Grain Emulsion SMC-1

[0089] To 5 liters of an aqueous 6.0 weight percent gelatin solution containing 0.06 mole of potassium iodide, 2 liters of an aqueous 7.06 mole silver nitrate solution and 2 liters of an aqueous 7.06 mole potassium iodide solution were added with vigorous stirring over 10 minutes. During the addition, the pH was adjusted to 2.0 using nitric acid and the temperature was regulated at 40 °C. After grain formation, the pH was adjusted to 5.0 using an aqueous sodium carbonate solution. The resulting fine silver iodide grains had an average grain diameter of 0.05 µm. The resulting emulsion was designated SMC-1.

Preparation of Silver Iodobromide "d"

[0090] The temperature of 700 ml of an aqueous 4.5 weight percent inert gelatin solution containing Seed Crystal Emulsion-1 equivalent to 0.178 mole and 0.5 ml of a 10 percent ethanol solution of HO(CH₂CH₂O)_m(CH(CH₃)CH₂O)_19.8(CH₂CH₂O)_nH (

) was maintained at 75 °C, and the pAg and pH were adjusted to 8.4 and 5.0, respectively. After that, grains were formed under vigorous stirring employing a double-jet method according to the following steps:

1) an aqueous 2.1 mole silver nitrate solution, an 0.195 mole SMC-1 solution and an aqueous potassium bromide solution were added, while maintaining the pAg at 8.4 and the pH at 5.0.

2) subsequently, the solution was cooled to 60 °C, and the pAg was adjusted to 9.8. After that, 0.071 mole of SMC was added and ripening (introduction of dislocation lines) was carried out for 2 minutes

3) an aqueous 0.959 mole silver nitrate solution, an aqueous 0.03 mole SMC-1 solution, and an aqueous potassium bromide solution were added while maintaining the pAg at 9.8 and the pH at 5.0.

[0091] Further, during grain formation, each solution was added at an optimum rate so that neither new nuclei formation nor Ostwald ripening among grains was carried out. After the completion of the above addition, a washing treatment was carried out at 40 °C employing an ordinary flocculation method. After that, dispersion was repeated by the addition of gelatin and the pAg and pH were adjusted to 8.1 and 5.8, respectively.

[0092] The resulting emulsion was an emulsion comprised of tabular grains having a grain diameter (one edge length of a cube having the same volume) and an average aspect ratio of 5.0. Electron microscopic observation of the emulsion revealed the formation of at least 5 dislocation lines in both the fringe portion (external portion of not less than 50 percent from the center of a grain in terms of a silver halide amount) of grains of not less than 60 percent of the total projection area of grains in the emulsion, and also in the grain interior. The surface silver iodide content ratio was 6.7 mole percent. Preparation of Silver Iodobromide "f"

[0093] Silver Iodobromide "f" was prepared in the entirely same manner as in Silver Iodobromide "d", except that in the preparation of Silver Iodobromide "d", in 1) step, pAg was adjusted to 8.8 and in step 3), the amount of silver nitrate was adjusted to 0.92 and the amount of SMC-10 was adjusted to 0.069 mole.

[0094] The resulting emulsion was comprised of tabular grains having a grain diameter (one edge length of a cube having the same volume) of 0.65 µm and an average aspect ratio of 6.5. Electron microscopic observation of the emulsion revealed the formation of at least 5 dislocation lines in both the fringe portion (external portion of not less than 60 percent from the center of a grain in terms of a silver halide amount) of grains of not less than 60 percent of the total projection area of grains in the emulsion, and also in the grain interior. The surface silver iodide content ratio was 11.9 mole percent.

[0095] After adding the above-mentioned sensitizing dyes and carrying out ripening, added were triphosphine selenide, sodium thiosulfate, chloroauric acid, and potassium thiocyanate, and according to a common method, chemical ripening was carried out so that the relationship between the fog and the sensitivity became optimum.

[0096] Further, silver iodobromides "a", "b", "c", "e", "g", "h", and "i" underwent spectral sensitization and chemical sensitization in the same manner as the above-mentioned "d" and "f" so as to have the properties described in the above Table 1.

[0097] Image information was subjected to subjective evaluation by 10 judges. The image information was printed using a post chelate type sublimation thermal transfer printer CHC-S845-5C manufactured by Konica Corp. Each of the resulting prints was subjectively evaluated by 10 judges. Unless otherwise specified, evaluation was carried out using a method in which two samples were compared to make a discrimination. Furthermore, the reasons for rating a better image quality were listed by the judges.

[0098] Sample 202 was prepared in the same manner as Sample 201, except that yellow colloidal silver contained in the tenth layer of Sample 201 was replaced with exemplified Compound 17 so that the absorbance became the same at 440 nm.

[0099] Sample 201 and Sample 202 were subjected to exposure of a Macbeth color chart and a human subject; after that, were subjected to color development employing a C-41 process; to washing at 25 °C for 10 seconds using an aqueous 1 percent acetic acid solution; to washing using water at 25 °C for 30 seconds, and to drying. The resulting Samples were designated Sample 211 and Sample 212. The image information on Sample 211 and Sample 212 was read employing a film scanner Q-Scan manufactured by Konica Corp.

[0100] As compared to Sample 212 employing colloidal silver, the image data obtained from Sample 211, comprising the dyes of the present invention, were preferred due to excellent color reproduction. According to the subjective evaluation results, nine of ten judges responded that Sample 211 exhibited better color reproduction than Sample 212. The other judge responded that there was no difference in image quality between them. The image data obtained from Comparative Sample 212 using the colloidal silver exhibited poor color reproduction and satisfactory image data were not obtained from the Comparative Sample.

[0101] The time necessary for processing the Sample of the present invention was shortened up to 270 seconds while the conventional negative processing took 510 seconds until drying was finished. The processing solution of the present invention contains no chelating agent, to minimize pollution of the environment.

Example 3

[0102] Sample 101 prepared in Example 1 was treated with a 1% sodium hypochlorite solution and the emulsion layers were removed from the support. The obtained support exhibited quality sufficient for recycling upon remelting. According to the constitution of the present invention, recovery of the resources employed for the support are now possible.

Example 4

[0103] Sample 101 and Sample 102 were subjected to development by spraying only enough developer to completely soaking the Sample. The resulting Samples were designated Sample 401 and Sample 402. The image information of each of these Samples was read employing a scanner Q-Scan manufactured by Konica Corp. The image information obtained from Sample 401 of the present invention exhibited high and satisfactory image quality. On the other hand, the image information obtained from Comparative Sample 402 was unsatisfactory due to the deterioration in color reproduction, sharpness and graininess. According to the subjective evaluation results, all 10 judges responded that the color reproduction of Sample 401 was better than Sample 402. This processing generated absolutely no solution waste to result in minimum pollution to the environment, and was therefore the preferred one. The image quality difference between Sample 401 of the present invention obtained by this processing and Comparative Sample 402 was greater than that between Sample 211 of the present invention in Example 2 and Comparative Sample 212. It was confirmed that when spray development was carried out, the advantages of the present invention were obtained more effectively.

Example 5

[0104] Samples were prepared in the same manner as in Sample 201 and Sample 202, except that the silver amount of each of Sample 201 and Sample 202 was decreased to 1/4. The resulting samples were designated Sample 501 and Sample 502. Sample 501 and Sample 502 were subjected to the same processing as Example 2 and the resulting samples were designated Sample 511 and Sample 512. The image information of each of these Samples was read employing a scanner Q-Scan manufactured by Konica Corp. The image information obtained from Sample 511 exhibited preferred excellent sharpness compared to the image information obtained from Sample 512, which only resulted in dark image information, being inferior in color reproduction and sharpness. According to the subjective evaluation results, 9 of the 10 judges responded that the image quality of Sample 511 was better than Sample 512. The other judge responded that there was no difference in image quality.

[0105] Based on Example 5, it is found that according to the constitution of the present invention, preferred characteristics are obtained for the variation of the silver amount and the image information with particularly preferred image quality is obtained in the case of the lower silver amount. On the contrary, it is found that in the Comparative Sample, image information with satisfactory image quality is not obtained, irrespective of the silver amount.

Comparative Example 1

[0106] Color negative film JX-100 manufactured by Konica Corp. was subjected to exposure of a human subject and a Macbeth color chart. The resulting film was subjected to development under the specified conditions employing a color negative photosensitive material process C-41 developer; then, to stop processing, 1% acetic acid solution was employed, followed by washing and drying. The processed film was designated Comparative Sample-1. When trying to read the image of Comparative Sample-1, it was found to be absolutely impossible to read the image information using blue light.

[0107] Based on this, it was clarified that when conventional color negative film was employed and was subjected to development while retaining silver resources in the photosensitive material, only one part of the image information was readable.

[0108] According to the present invention, it is possible to provide a silver halide photosensitive color photographic material which can be applied to simple and convenient processing; and which generates minimum pollutants to the environment, and further allows for easy and efficient resource recovery, an image forming method, and provides an image information forming method, and a silver recovery method.

Claims

1. An image information forming method comprising steps of

exposing a silver halide photosensitive photographic material according to image information,

developing the exposed silver halide photosensitive photographic material by color development, and

followed by no bleaching, conversion of image information to electrical image information,
wherein a silver halide photosensitive photographic material comprising a dye which is decomposed by a color developer.

2. An image forming method comprising steps of

exposing a silver halide photosensitive photographic material according to image,

developing the exposed silver halide photosensitive photographic material by color development,
wherein a silver halide photosensitive photographic material comprising a dye which is decomposed by a color developer, and the processing is carried out by supplying a processing solution with an soaking amount onto a silver halide photosensitive photographic material comprising a dye which is decomposed by a color developer.

3. An image information forming method of claim 1 wherein the dye which is decomposed by a color developer is dispersed in a solid state in the silver halide photosensitive photographic material.

4. A silver halide photosensitive photographic material having a light sensitive silver halide emulsion leyer provided on a support, wherein the silver halide photosensitive photographic material comprises a dye which is decomposed by a color developer and an converted amount of silver in the silver halide photosensitive photographic material is not more than 2 g/m².

5. The image information forming method of claim 1, wherein the silver halide photosensitive photographic material comprises silver in an amount of not more than 2 g/m².

6. The image forming method of claim 2, wherein the silver halide photosensitive photographic material comprises silver in an amount of not more than 2 g/m².