JPH1165044A - Silver halide photographic sensitive material and its processing method and picture image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to provide eco-friendly and high-grade picture information conveniently and rapidly, by making optical density by transmitting light a specific value. SOLUTION: Optical density by transmitting light is 1.0 or less. As for the optical density, 1.0 or less being preferable from the viewpoint of easy use of picture information, 0.8 or less being more preferable, 0.7 or less being preferable in particular, and 0.6 or less is the most preferable. There is no special limit on types of silver halide color photographic sensitive material, and a color negative film, a color reversal film, or a direct positive photosensitive material can be used. Preferably, the silver halide color photographic sensitive material has a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer, which are capable of recording red, green, and blue light, respectively. As for sensitivity of the silver halide color photographic sensitive material, ISO 30 or more is preferable, ISO 100 or more is much preferable, and ISO 400 or more is more preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, a method for processing the same, and an image forming method.

[0002]

2. Description of the Related Art In recent years, with the rapid spread of personal computers (PCs) and the spread of the Internet, it has become common to import image information into a personal computer, process it, and use it. To capture image information into a personal computer, there are methods of shooting with a digital camera and reading image information of a conventional color photographic material with a scanner, but the former has a small number of pixels, narrow latitude, and gradation is not smooth. There is a problem that the latter requires the color photographic light-sensitive material to be developed in a photo store, and it takes a long time to obtain image information. still,
The method of reading image information of a color photographic light-sensitive material with a scanner is excellent in that high-quality image data can be obtained and image information of a conventional photographic light-sensitive material accumulated for many years can be effectively used.

On the other hand, awareness of environmental protection has been increasing in recent years, and there is a demand for reduction of hazardous waste and effective use of limited resources. The silver halide photographic light-sensitive material uses silver halide as an image recording material, and uses silver resources which are valuable resources. Silver is a limited precious metal resource, and its effective use is demanded. Silver is also a heavy metal,
Since the effluent standards are strict, the burden of recovery is large.

However, in the current silver resource recovery method, silver is recovered after transporting a photographic processing solution or a concentrated solution thereof to a recovery factory. In this case, not only energy is required for concentrating the photographic waste liquid, expensive equipment required for the concentration is required, but also in transporting the photographic waste liquid, the weight of which is hundreds of times the weight of silver is worthless. There was inefficiency due to carrying water together, and the problem was significant from the viewpoint of energy saving and cost reduction. Furthermore, it was also difficult to completely recover the silver resources dissolved in the solution. For these reasons, the silver resources contained in the photosensitive material were diluted in the processing solution,
It was required to recover without spreading.

EDTA and PDTA used in photographic processing
Since complex forming compounds such as are difficult to be decomposed by microorganisms, the load on wastewater treatment is large.

As described above, there has been a demand for an environment-friendly system that can easily and inexpensively obtain high-quality image information, can make use of image information of conventional photographic materials accumulated over many years, and is friendly to the environment. Known systems have never been able to satisfy all these requirements.

That is, digital cameras are inferior in the quality of image information, and the method of reading a photographic photosensitive material with a scanner takes a long time to obtain the image information, and has a large burden on the environment due to the problem of treating wastewater containing heavy metals. was there.

Japanese Patent Application Laid-Open No. 9-146247 discloses a technique in which after processing, the processing is terminated without bleaching or fixing, and image information is obtained by reading the image with a scanner. The optical density of the light-sensitive material described in this publication is 2.0 or more, and the method described in this publication further causes a significant desensitization due to an optical filter effect of a coloring material at the time of exposure, making it difficult to obtain high sensitivity. However, it is difficult to apply to a photographic material requiring high sensitivity. If image information or a hard copy already exists, it can be simply taken into a personal computer or read by a scanner, and the technology disclosed in this patent is not effective for the purpose of taking image information, that is, photographing.

Further, according to studies by the present inventors, when a commonly used photographic color negative film is read by a scanner without being bleached or fixed after development processing, the yellow filter layer and the antihalation layer become obstacles. It turned out that only part of the image could be read. That is, when reading with transmitted light, the antihalation layer is blue,
All three primary colors of red and green light were absorbed, and it became clear that image information could not be read. When reading with reflected light, green and red light can be read, but blue light is not reflected because it is absorbed by the yellow filter layer and cannot be read.

The yellow filter layer is a layer provided so that the green and red light-sensitive layers of the light-sensitive material are not exposed to blue light. When ordinary processing is performed, the color is lost by bleaching and fixing. The above-mentioned problem that it becomes an obstacle does not occur.

The antihalation layer is usually a black layer used to prevent sharpness deterioration due to light reflected by the lowermost layer, and is bleached and fixed to lose color when subjected to ordinary processing. Therefore, the above problem does not occur.

[0012]

SUMMARY OF THE INVENTION A first object of the present invention is to provide an environment-friendly silver halide photographic light-sensitive material capable of providing high-quality image information simply and promptly, a processing method thereof, and an image forming method. Is to do.

A second object of the present invention is to provide, after development, developed silver,
It is an object of the present invention to provide a silver halide photographic light-sensitive material capable of reading image information using a scanner while holding the silver halide in the light-sensitive material, a processing method thereof, and an image forming method.

A third object of the present invention is to facilitate silver recovery,
An object of the present invention is to provide a silver halide photographic light-sensitive material that can contribute to environmental protection.

A fourth object of the present invention is to provide a silver halide photographic material which can be processed quickly.

[0016]

The above objects of the present invention are as follows. 1. a silver halide color photographic material having an optical density of 1.0 or less due to transmitted light; It has a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, each of which contains a coupler and has no optical density of 0.3 or more. 2. A silver halide color photographic light-sensitive material having an ISO sensitivity of 50 or more; 3. The silver halide color photographic light-sensitive material according to the above 1 or 2, wherein the material contains a developing agent or a developing agent precursor. 4. A method for processing a silver halide color photographic light-sensitive material, wherein the silver halide photographic light-sensitive material is not desilvered after the silver halide photographic light-sensitive material is subjected to development processing. 5. A method for processing a silver halide color photographic light-sensitive material, which comprises thermally developing the silver halide photographic light-sensitive material according to the above 1, 2, or 3. 4. An image characterized by reading image information using a scanner or a CCD after developing the silver halide photographic light-sensitive material according to the above 1, 2, or 3, while developing silver and silver halide are held in the light-sensitive material. 6. forming method; 7. The image forming method according to the above item 6, wherein the image information is read optically using coherent light.

[0017]

DETAILED DESCRIPTION OF THE INVENTION The details of the present invention will be described. In the present invention, the spectral transmittance refers to a status M obtained by measuring a photographic photosensitive material before exposure including a support.
B concentration. The measuring method is ISO5 / 3, Photog
raphy Density measurement
s, Part3: Spectral condition
ns (1984). The optical density is preferably 1.0 or less in that image information can be easily used,
It is more preferably 0.8 or less, particularly preferably 0.7 or less, and most preferably 0.6 or less.

In the present invention, desilvering means silver halide,
This is to remove at least a part of the metallic silver from the photosensitive material, and includes bleaching, fixing, and bleach-fixing processes.

The type of the silver halide color photographic light-sensitive material of the present invention is not particularly limited, and may be a color negative film, a color reversal film, or a direct positive light-sensitive material.

The silver halide color photographic light-sensitive material of the present invention can record red, green and blue light in a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer. It is preferable to have

The sensitivity of the silver halide color photographic light-sensitive material of the present invention is preferably ISO 30 or more.
It is preferably 100 or more, and more preferably ISO 400 or more.

In the present invention, the method and system of development processing
Known conditions and methods can be freely applied regardless of conditions. C- which is the standard processing condition for color negatives for general use
The development conditions of 41 processing can be preferably applied.
It is preferable not to perform bleaching and fixing processing in terms of shortening of processing time, recovery of silver resources, and easy disposal of processing waste liquid. Further, it is also possible to spray (for example, ink jet development) or apply an amount of a developing solution that substantially permeates the photosensitive material to develop the photosensitive material. Regardless of the method of ejecting the developer, the developer may be ejected while moving a single movable nozzle, or may be ejected using a plurality of fixed nozzles. The injection may be performed while the photosensitive material is fixed and the nozzle is moved, or the injection may be performed while the nozzle is fixed and the photosensitive material is moved. A combination of these may be used.

In the case of performing a developing process for supplying an amount of the developing solution that can substantially penetrate the photosensitive material through the medium carrying the developing solution to the photosensitive material, there is no limitation on the medium carrying the developing solution. Alternatively, felt, woven fabric, metal having slits or holes, or the like can be preferably used. It is also preferable to apply the developing solution to the photosensitive material with the medium while spraying the developing solution onto the photosensitive material or the medium.

In the present invention, "after the development processing, the developed silver and the silver halide are kept in the photosensitive material" means that the developed silver produced by the development processing or the silver halide originally contained in the photosensitive material is used. Means that substantially all of the silver resources are left in the photosensitive material so as not to dissolve or diffuse in the processing solution. Here, "substantially" means a state in which 70% or more of the silver resources contained in the light-sensitive material before processing are left in the light-sensitive material. It is more preferable that 99% or more of the silver resources remain in the photosensitive material from the viewpoint of resource recovery and waste liquid treatment.

In the present invention, the scanner is a device which optically scans a photosensitive material and converts reflection or transmission optical density into image information. When scanning, it is common to move the optical part of the scanner in a direction different from the direction of movement of the photosensitive material to scan the required area of the photosensitive material, and it is recommended that the photosensitive material be fixed. Alternatively, only the optical part of the scanner may be moved, or only the photosensitive material may be moved to fix the optical part of the scanner.
Alternatively, a combination of these may be used.

Light sources for reading image information include a tungsten lamp, a fluorescent lamp, a light emitting diode, a laser beam, and the like.
Tungsten lamps are preferable because they can be used without any particular limitation and are inexpensive. Laser light (coherent light source) because they are stable, have high brightness, and are not easily affected by scattering.
Is preferred. The reading method is not particularly limited, but it is preferable to read transmitted light in terms of sharpness.

In the present invention, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are emulsions which have been spectrally sensitized to blue light, green light and red light, respectively. Say layers. Regarding the couplers contained in these layers, any known couplers can be used irrespective of their types. The optical density is a transmission density before the development processing.

The application of heat development to the present invention is preferable in terms of shortening the processing time and improving environmental suitability. It is preferable that the silver halide photographic light-sensitive material of the present invention contains a developing agent or a developing agent precursor, since the management of the developing solution becomes easy.

The materials that can be used in the present invention are all described in known documents, and those skilled in the art can easily synthesize or obtain them with reference to them. Examples of known documents include, for example, JP-A-8-166644 and JP-A-8-20.
No. 2002, No. 8-286340, No. 8-29253
No. 1, No. 8-227131, No. 8-292529,
8-234388, 8-234390, 9-
No. 34081, No. 9-76570, No. 9-11406
No. 2, No. 9-152686, No. 9-152691,
Nos. 9-152692, 9-152693, and 15
No. 2700, No. 9-152701, No. 9-15970
No. 2, No. 9-159703, No. 9-150794,
No. 9,150,795.

Hereinafter, representative examples will be described. The silver halide emulsion used in the present invention is not particularly limited, and a known silver halide emulsion can be used. The grain size, aspect ratio, halide composition (type and amount of halogen in silver halide), halide distribution (distribution of various silver halides in silver halide grains) of silver halide emulsion, presence or absence of transition lines, etc. There are no restrictions. The particle size of the silver halide grains (converted to the length of one side of a cube of the same volume) is preferably 0.05 to 2 microns. The aspect ratio is preferably 4 or more from the viewpoint of sharpness, more preferably 8 or more,
It is particularly preferred that the number be 12 or more. The halide composition preferably contains silver bromide as a main component. Of all silver halide, silver bromide is preferably 80 to 99 mol%, and silver iodide is 1 to 20 mol%. preferable.
Having a transition line is preferred in terms of sensitivity.

In constructing the light-sensitive material of the present invention, a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization is generally used. The additives used in such a process are Research Disclosure N
o. 17643, no. 18716 and no. 3081
19 (hereinafter referred to as RD17643 and RD18716, respectively)
And RD308119).

The places to be described are shown below. [Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Section 23 648 Spectral sensitizer 996 IV-A, B, 23-24 648-9C, D, H, I, Section J Supersensitizer 996 IV-AE, 23-24 648-9 Section J Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649

More specifically, the chemical sensitization of the emulsion used in the present invention is carried out by chemicals containing sulfur capable of reacting with silver ions,
A sulfur sensitization method using active gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or another noble metal compound, or the like can be used alone or in combination.

In the present invention, for example, a chalcogen sensitizer can be used as the chemical sensitizer, and among them, a sulfur sensitizer and a selenium sensitizer are preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide, thiourea, allyl isothiocyanate, cystine, p-trienethiosulfonate, rhodanine and the like.

In addition, US Pat. Nos. 1,574,944 and 2,410,689 and 2,2
Nos. 78,947, 2,728,668, 3,501,313, and 3,653.
No. 6,955, West German Application Publication (OLS) 1,42
2,869, JP-A-56-24937,
Sulfur sensitizers described in JP-A-55-45016 and the like can also be used.

The addition amount of the sulfur sensitizer varies over a considerable range under various conditions such as pH, temperature, and the size of silver halide grains.
About ^10-7 mol to about ^{10 -1} moles per mole are preferred.

As selenium sensitizers, aliphatic isoselenocyanates such as allyl isoselenocyanate, selenureas, selenides such as selenoselenide and diethyl selenide, and the like can be used. U.S. Pat. Nos. 1,574,944 and 1,6
Nos. 02,592 and 1,623,499. Further, a reduction sensitizer can be used in combination.

Examples of the reduction sensitizer include stannous chloride, thiourea dioxide, hydrazine, polyamine and the like.
Also, a noble metal compound other than gold, for example, a palladium compound or the like can be used in combination.

The silver halide grains of the emulsion used in the present invention are preferably chemically sensitized by a gold compound.
The gold compound preferably used in the present invention may have a gold oxidation number of +1 or +3, and various kinds of gold compounds are used.

Representative examples include potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide, gold selenide and the like. .

The amount of the gold compound to be added varies depending on various conditions. As a guide, the amount is from 10 ^-8 mol to 10 ^-1 mol, preferably from 10 ^-7 mol to 10 ^-2 per mol of silver halide.

The compound may be added at any time during the formation of silver halide grains, during physical ripening, during chemical ripening, and after the completion of chemical ripening.

Known photographic additives which can be used in the present invention are also described in the above-mentioned Research Disclosure.

In the following, relevant places are shown. [Item] [RD308119 page] [RD17643] [RD18716] Anti-turbidity agent 1002 VII-I 25 650 Dye image stabilizer 1001 VII J-J 25 Brightener 998 V 24 UV absorber 1003 VIII-C, 25 26 XIIIC light scattering agent 1003 VIII binder 1003 IX 26651 static 1006 XIII 27 650 inhibitor hardener 1004 X 26 651 plasticizer 1006 XII 27 650 lubricating oil 1006 XII 27 650 activator 1005X6 Agent Matting agent 1007 XVI Developer 1011 XXB

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,98
It is preferable to add a compound that can be fixed by reacting with formaldehyde described in JP-A Nos. 7 and 4,435,503 to the photosensitive material.

Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure (RD) No. No. 17643, VII-C ~
G.

As the coupler, for example, US Pat.
Nos. 933,051, 4,022,620, 4,326,024 and 4,40.
No. 1,752, No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,
Nos. 425,020, 1,476,760, U.S. Pat. Nos. 3,973,968, 4,314,023, and 4,511,649.
And those described in European Patent No. 279,473A and the like.

Examples of 5-pyrazolone and pyrazoloazole compounds are described in US Pat. No. 4,310,619.
No. 4,351,897, European Patent No. 73,636, U.S. Pat. No. 3,061,43.
No. 2, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984
), JP-A-60-43659, and JP-A-61-722.
No. 38, No. 60-35730, No. 55-11
Nos. 8034, 60-185951, U.S. Pat. Nos. 4,500,630 and 4,540,6.
No. 54, No. 4,556,630, International Publication WO88 / 04795 and the like are particularly preferable.

Examples of phenolic and naphthol couplers are described in US Pat. No. 4,052,212,
Nos. 4,146,396 and 4,228,2
No. 33, No. 4,296,200, No. 2,369,929, No. 2,801,171
No. 2,772,162, No. 2,
No. 895,826, No. 2,772,002, No. 3,758,308, No. 4,33
Nos. 4,011, 4,327,173, German Patent Publication No. 3,329,729, European Patent No. 121,365A, and 249,453A.
No. 4,446,622, U.S. Pat. No. 4,333,999, U.S. Pat. No. 4,775,61.
No. 6, specification No. 4,451,559, specification No. 4,427,767, specification No. 4,690,889
No. 4,254,212, No. 4,254,212
Preferred are those described in 296,199, JP-A-61-42658 and the like.

A colored coupler for correcting unnecessary absorption of a coloring dye can be used within the range of the spectral transmittance of the present invention. Research Disclosure No. 17
No. 643, section VII-G, U.S. Pat. No. 4,163,67.
No. 0, JP-B-57-39413, U.S. Pat. No. 4,004,929, and JP-A-4,138,25.
No. 8 and British Patent No. 1,146,368 are preferred. No. 4,774,1.
A coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in JP-A No. 81,
It is preferable to use a coupler having a dye precursor group capable of forming a dye by reacting with a developing agent described in U.S. Pat. No. 4,777,120 as a leaving group.

A typical example of a polymerized dye-forming coupler that can be used in the present invention is described in US Pat.
No. 1,820, No. 4,080,211, No. 4,367,282, No. 4,40
No. 9,320, No. 4,576,910 and British Patent No. 2,102,173.

Couplers which release a photographically useful residue upon coupling can also be preferably used in the present invention.
The DIR coupler releasing the development inhibitor is RD1 described above.
7643, Patent VII-F, JP-A-57
JP-151944, JP-A-57-154234,
Nos. 60-184248 and 63-37346; U.S. Pat. Nos. 4,248,962 and 4,
What is described in the specification of 782,012 etc. is preferable.

As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,099
7,140. No. 2,131,188, JP-A-59-157638, and JP-A-59-170.
Those described in JP-A-840-840 are preferred.

Other couplers usable in the light-sensitive material of the present invention include those described in US Pat. No. 4,130,42.
7, No. 4,28.
Multi-equivalent couplers described in 3,427, 4,338,393 and 4,310,618, JP-A-60-185950, JP-A-62.
DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound, or DIR redox compound releasing redox compound described in JP-A--24252 and the like, European Patent No. 173,3
No. 02A, a coupler which releases a dye that recolors after release, RDNo. 11440, 24241, bleaching accelerator releasing couplers described in JP-A-61-201247 and the like, ligand releasing couplers described in U.S. Pat. No. 4,553,477 and the like, JP-A-63-75747.
And couplers emitting a fluorescent dye described in U.S. Pat. No. 4,774,181 and the like.

Further, various couplers can be used in the present invention, and specific examples thereof are described in the following RD. The relevant parts are shown below.

[Items] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D VII CG-G Magenta coupler 1001 VII-D VIIC-G Cyan coupler 1001 VII-D VIIC-G Colored coupler 1002 VII-G VII G DIR coupler 1001 VII-F VIIF BAR coupler 1002 VII-F Other useful residues Emission coupler 1001 VII-F The additive used in the present invention is RD308119XIV. It can be added by the described dispersion method or the like.

The additives used in the present invention can be used within the range of the optical density of the present invention.

In the present invention, the aforementioned RD 1764
3, page 28, RD18716, pages 647-8 and RD
The support described in XIX of 308119 can be used in the optical density range of the present invention.

The light-sensitive material of the present invention includes the above-mentioned RD308
An auxiliary layer such as a filter layer or an intermediate layer described in section 119 VII-K can be provided.

The pH of the outermost surface of the photographic constituent layer of the light-sensitive material of the present invention is preferably from 5.0 to 7.0, more preferably from 5.0 to 7.0.
5 to 6.5, and can be measured by the method described in JP-A-61-245153.

As the support, polyethylene terephthalate, cellulose triacetate film and the like can be preferably used. The thickness of the support is usually 50 to 200 μm.

When the light-sensitive material of the present invention is used in the form of a roll, it is preferable to take the form housed in a cartridge. The most common cartridge is the current 135 format cartridge. Other cartridges proposed in the following patent documents can also be used. That is, Japanese Utility Model Laid-Open No. 58-67329 and Japanese Patent Laid-Open No. 58-18
Nos. 1035, 58-182634, 58-195236, U.S. Pat. No. 4,221,4.
No. 79, Japanese Patent Application No. 63-57785, 63
-183344, 63-25638,
Japanese Patent Application Nos. 1-21862, 1-225362, 1-320246, 1-202222, 1-21863, 1-37181, 1-333108. No. 1-85198, No. 1-172595, No. 1-172594, No. 1-172593, U.S. Pat.
6,418, 4,848,693, 4,832,275 and the like.

The processing time of the light-sensitive material in the present invention is not particularly limited. The standard processing time and processing temperature are shown below.

On the other hand, the processing time of the color negative processing which is a typical processing of the conventional photosensitive material for photography is shown below.

[0065]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited to these. Comparative Example 1 A person and a Macbeth color chart were photographed using a color negative film JX-100 manufactured by Konica Corporation. The B density according to status M of this negative film was 2.8.
This negative film was developed under the specified conditions using a developer of color negative processing C-41, and then subjected to a stop treatment with a 1% acetic acid solution, washed with water and dried to obtain Comparative Sample 1. When an image of Comparative Sample 1 was read using a Konica Scanner Q-scan, it was found that image information to be read by blue light could not be read.

As a result, it has been clarified that only a part of the image information can be read out in the state where the development processing is performed using the conventional color negative film and the silver resources are kept in the photosensitive material.

Example 1 Sample 10 was prepared by providing a photographic component layer having the following composition on a triacetylcellulose support which had been previously subjected to an undercoating treatment.
It was set to 1. The addition amount is expressed in grams per 1 m ^2. However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes (indicated by SD) were shown in moles per mole of silver.

First layer UV-1 0.3 OIL-1 0.044 Gelatin 1.33

Second layer (intermediate layer) Polyethyl acrylate latex 0.20 Gelatin 1.40

Third layer (low-sensitivity red-sensitive layer) Silver iodobromide a 0.12 Silver iodobromide b 0.50 SD-1 3.0 × 10 ⁻⁵ SD-4 1.2 × 10 ^{− 4} SD-3 2.0 × 10 ^-4 SD-6 3.0 × 10 ^-6 C-1 0.51 OIL-2 0.45 Gelatin 1.40

Fourth layer (medium-speed red-sensitive layer) Silver iodobromide c 0.64 SD-1 3.0 × 10 ^-5 SD-2 1.2 × 10 ^-4 SD-3 2.0 × 10 ^-4 C-2 0.22 OIL-2 0.21 Gelatin 0.84

Fifth layer (high-sensitivity red-sensitive layer) Silver iodobromide c 0.13 Silver iodobromide d 1.14 SD-1 3.0 × 10 ⁻⁵ SD-2 1.2 × 10 ^{− 4} SD-3 2.0 × 10 ^-4 C-1 0.085 C-2 0.084 OIL-2 0.23 Gelatin 1.23

Sixth layer (intermediate layer) Polyethyl acrylate latex 0.23 Gelatin 1.00

Seventh layer (low-sensitivity green color-sensitive layer) Silver iodobromide a 0.245 Silver iodobromide b 0.105 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 (Medium Speed Green Sensitive Layer) Silver iodobromide e 0.87 SD-7 2.0 × 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 (highly sensitive green color-sensitive layer) Silver iodobromide f 1.19 SD-7 2.8 × 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 (intermediate layer) Polyethyl acrylate latex 0.20 Gelatin 1.00

Eleventh layer (low-sensitivity blue-sensitive layer) Silver iodobromide g 0.29 Silver iodobromide h 0.19 SD-10 4.0 × 10 ^-4 SD-11 2.0 × 10 ^{− 4} Y-1 0.91 OIL-1 0.37 Gelatin 1.29

Twelfth layer (high-sensitivity blue-sensitive layer) Silver iodobromide h 0.13 Silver iodobromide i 1.00 SD-10 2.2 × 10 ^-4 SD-11 0.8 × 10 ^{− 4} Y-2 0.48 OIL-1 0.21 Gelatin 1.55

Thirteenth layer (first protective layer) Silver iodobromide j 0.30 UV-1 0.055 UV-2 0.110 OIL-2 0.63 gelatin 1.32

Fourteenth layer (second protective layer) PM-1 0.15 PM-2 0.04 WAX-1 0.02 D-1 0.001 Gelatin 0.55

In addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersing aid, SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, antifoggant weight average molecular weight: 10,000 (AF-1) And two kinds of polyvinylpyrrolidone having a weight average molecular weight of 1,100,000 (AF-2), inhibitors AF-3, AF-4 and AF
-5, hardeners H-1 and H-2 were added. The structure of the compound used in the above sample is shown below.

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Table 1 shows the features of the silver iodobromide.

[0091]

[Table 1]

As a preferred example of forming silver halide grains of the present invention, a production example of silver iodobromide d and f is shown below.

Preparation of Seed Emulsion-1 A seed emulsion was prepared as follows. 5-58
288 and 58-58289, a silver nitrate aqueous solution (1.161 mol) and a mixed aqueous solution of potassium bromide and potassium iodide (potassium iodide) were added to the following solution A1 prepared at 35 ° C. 2 mol%) was added over 2 minutes by a double jet method while keeping the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV to perform nucleation. Subsequently, the temperature of the solution was raised to 60 ° C. over a period of 60 minutes, and the pH was adjusted to 5.0 with an aqueous sodium carbonate solution.
2 mol) and a mixed aqueous solution of potassium bromide and potassium iodide (potassium iodide 2 mol%) was added over 42 minutes by a double jet method while keeping the silver potential at 9 mV. After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing were immediately performed using a normal flocculation method.

The resulting seed crystal emulsion had an average sphere-equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and a maximum side ratio of 1.0% or more of 90% or more of the total projected area of silver halide grains.
~ 2.0 hexagonal tabular grains.
This emulsion is referred to as seed emulsion-1.

[Solution A1] Ossein gelatin 24.2 g Potassium bromide 10.8 g HO (CH₂CH₂O)_m(CH (CH₃) CH₂O)_19.8(CH₂CH ₂ O)_nH (m + n = 9.77) (10% ethanol solution) 6.78 ml 10% nitric acid 114 ml H₂O 9657ml

Preparation of silver iodide fine grain emulsion SMC-1 While stirring vigorously 5 L of a 6.0% by weight gelatin aqueous solution containing 0.06 mol of potassium iodide, 7.06 mol
2 liters of an aqueous silver nitrate solution and 2 liters of a 7.06 mol aqueous potassium iodide solution were added over 10 minutes. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles are prepared, the pH is adjusted using an aqueous sodium carbonate solution.
Was adjusted to 5.0. The average particle size of the obtained silver iodide fine particles was 0.05 μm. This emulsion is designated as SMC-1.

Preparation of silver iodobromide d Seed emulsion-1 equivalent to 0.178 mol and HO (CH ₂ CH
₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂
CH _{2 O)} n containing 10% ethanol solution 0.5ml of H (m + n = 9.77) , maintaining the 4.5 wt% of inert gelatin solution 700ml to 75 ° C., the pAg 8.4,
After adjusting the pH to 5.0, particles were formed by the simultaneous mixing method with vigorous stirring according to the following procedure. 1) 2.1 mol of silver nitrate aqueous solution and 0.195 mol of SM
C-1 and potassium bromide aqueous solution, pAg 8.4,
It was added while maintaining the pH at 5.0. 2) Subsequently, the temperature of the solution was lowered to 60 ° C., and the pAg was adjusted to 9.8. Thereafter, 0.071 mol of SMC-1 was added and aging was performed for 2 minutes (introduction of dislocation lines). 3) 0.959 mol of silver nitrate aqueous solution and 0.03 mol of S
MC-1 and an aqueous solution of potassium bromide, pAg of 9.
8. It was added while maintaining the pH at 5.0.

Each solution was added at an optimum rate throughout the particle formation so as to prevent formation of new nuclei and Ostwald ripening between particles. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The obtained emulsion had a particle size (cubic 1 of the same volume).
The emulsion was composed of tabular grains having a halogen composition of 0.75 μm in side length, an average aspect ratio of 5.0, and a halogen composition of 2 / 8.5 / X / 3 mol% (X is a dislocation line introduction position) from the inside of the grains. . When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 6.7 mol%.

Preparation of silver iodobromide f In the preparation of silver iodobromide d, pAg was adjusted to 8. in step 1).
8, and silver iodobromide f was prepared in exactly the same manner as silver iodobromide d except that the amount of silver nitrate added in step 3) was 0.92 mol and the amount of SMC-1 was 0.069 mol. .

The obtained emulsion had a particle size (cubic 1 of the same volume).
An emulsion comprising tabular grains having a halogen composition of 0.65 μm, an average aspect ratio of 6.5, and a halogen composition of 2 / 8.5 / X / 7 mol% (X is a dislocation line introduction position) from the inside of the grains. . When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 11.9 mol%.

After the above-mentioned sensitizing dyes were added to each of the above emulsions and ripened, triphosphine selenide, sodium thiosulfate, chloroauric acid and potassium thiocyanate were added, and the fogging and sensitivity were optimized according to a conventional method. It was subjected to chemical sensitization to obtain a photosensitive material.

Silver iodobromide a, b, c, e, g, h, i, j
Was also subjected to spectral sensitization and chemical sensitization according to d and f above.

The composition of the processing solution is shown below. Color developer Water 800 ml Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxyamine sulfate 2.5 g Sodium chloride 0.6 g 4-amino-3- Methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 liter, add potassium hydroxide or 20
The pH is adjusted to 10.06 using% sulfuric acid. Sample 101
Was 0.7 in optical density.

Using the sample 101, a person and a Macbeth color chart were photographed. Develop and stop the photographed sample (1
% Acetic acid aqueous solution), washed with water and dried to obtain a sample 102.

Samples 101 and 102 are absorbed by X-rays.
As a result of measuring the amount of silver,
It was found that 9.8% of silver was contained.
As a result, it was possible to realize a state in which silver resources could be easily collected without diffusing into the processing solution. The processing time required for the conventional negative processing was 510 seconds until the end of drying, but was reduced to 240 seconds, and the processing time was reduced to half or less.

The sample 102 was prepared using a scanner Qs manufactured by Konica Corporation.
When the image was read using can, a high-quality image was obtained. From Example 1, it was found that high-quality image information can be obtained easily and quickly by using the technology of the present invention. It has been found that silver resources can be easily collected and contribute to environmental protection.

Example 2 In the third, fourth, fifth, seventh, eighth, ninth, eleventh and twelfth layers of Example 1, hot solvent-1 (equal in weight to the coupler in each layer), developing agent precursor-1 (each layer) Sample 201 was prepared in the same manner as in Example 1 except that the amount of the coupler was twice as large as that of the coupler in the medium and silver benzotriazole (the same mol as the coupler in each layer) was added. Sample 2
01 and a person and a Macbeth color chart were photographed. The photographed sample was heat-developed with a heat roll preheated to 140 ° C. for 60 seconds to obtain a sample 202.

The photographed image was clearly recorded on the sample 202. Sample 202 was scanned by Konica Scanner Q-s
When the image was read using can, a high-quality image was obtained. From Example 2, it was found that the use of the technique of the present invention enables high-quality image information to be obtained simply and quickly, without producing any waste such as processing waste liquid.

[0110]

Embedded image

Example 3 The developed sample 101 prepared in Example 1 was bleached with the bleaching solution used in Example 1, immersed in a 5% sodium hypochlorite solution, and the emulsion layer was peeled off. The silver concentration in the solution was 35 g /
Liter, and the silver content was greater than the silver concentration of 7 g / liter in the processing waste liquid from the conventional system, which was advantageous for silver recovery. When the remaining support was washed with water, it was sufficiently pure to be used as a raw material for a photographic support, and the support could be recycled.

[0112]

According to the present invention, it is possible to provide high-quality image information simply and quickly, and it is environmentally friendly. After development, the developed silver and silver halide are kept in the photosensitive material using a scanner. It is possible to provide a silver halide photographic light-sensitive material capable of reading image information, easily recovering silver, contributing to environmental protection, and performing rapid processing, a processing method thereof, and an image forming method.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 7/42 G03C 7/42 H04N 1/00 H04N 1/00 G

Claims (7)

[Claims] 1. A silver halide color photographic light-sensitive material having an optical density of 1.0 or less due to transmitted light. 2. A silver halide emulsion layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, each of which contains a coupler and has a layer having an optical density of 0.3 or more. A silver halide color photographic light-sensitive material having an ISO sensitivity of 50 or more, characterized by having no silver halide color photographic material. 3. A silver halide color photographic light-sensitive material according to claim 1, which contains a developing agent or a developing agent precursor. 4. A method for processing a silver halide color photographic light-sensitive material, wherein the silver halide photographic light-sensitive material according to claim 1, 2 or 3 is not desilvered after development processing. 5. A method for processing a silver halide color photographic light-sensitive material, comprising thermally developing the silver halide photographic light-sensitive material according to claim 1, 2 or 3. 6. A scanner or CCD after the silver halide photographic light-sensitive material according to claim 1, 2 or 3 is developed, and the developed silver and silver halide are held in the light-sensitive material.
An image forming method, wherein image information is read using a computer. 7. The image forming method according to claim 6, wherein image information is read optically using coherent light.